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TECHNICAL FIELD
[0001] The present invention relates to a network router and a method of configuring network routing information in a network router.
BACKGROUND
[0002] Existing Internet Protocol (IP) routers operate based on a hop-by-hop forwarding principle. The base function of this is realised in a table containing destinations or destination prefixes and corresponding next hops, i.e. outgoing interfaces. This way, each node receiving a packet data unit (PDU) is capable of searching the next-hop to which it should forward the packet. In the forwarding engine hardware, this table is often referred to as a forwarding table.
[0003] The internet is currently organised in a hierarchical manner, meaning that an intra-domain routing protocol or Interior Gateway Protocol (IGP)—typically Open Shortest Path First (OSPF), or Intermediate System to Intermediate System IS-IS—calculates the shortest paths inside a local domain, and a separate protocol takes care of inter-domain routing. This Exterior Gateway Protocol (EGP) in IP networks is typically implemented as Border Gateway Protocol (BGP). In practice, BGP identifies and returns the edge-router (i.e. the inter-domain next-hop) that should be used to reach the destination prefix. Subsequently recursive lookup is used in the router in order to find the local next-hop (i.e. the outgoing interface) leading towards this particular edge router.
[0004] IP router implementations often contain a separate forwarding table for each incoming interface, although in practice the tables are often filled with the same values. However, some recent proposals already utilise the possibility that these tables may be filled with different values (Zifei Zhong, et al.: “Failure Inferencing based Fast Rerouting for Handling Transient Link and Node Failure”, Infocom 2005.)
[0005] If a link or node goes down in the network, the appropriate routing protocols propagate this information and the router calculates a new route to the destinations. During this so-called routing re-convergence, i.e. as long as not all routers have installed the new routes (i.e. new next-hops), the network may experience transient routing loops and lost packets.
[0006] Normally, forwarding tables are recalculated in each router by a control element (the routing engine). However, in some other concepts, like in the distributed router system described in “Performance Evaluation of Control Plane Modularization and Decentralisation for BGP”, Markus Hidell et al., Usenix 2006, the forwarding tables are calculated on distributed control elements and are downloaded to the physically separate forwarding elements over the regular IP network.
[0007] Some solutions for IP-based fast re-route (IP-FRR) are based on putting alternative “virtual” IP addresses per node (also known as “not-via addresses”) into each router's forwarding table. These virtual addresses are then allocated a different next-hop than the normal IP address of the destination. This way, in case of a failure, a detour path can be used leading to the same destination.
[0008] Existing forwarding tables are nowadays very long. It has been observed by M. Hidell et al. (supra) that the number of entries can be higher than 100,000. Currently the forwarding table of a router is set up in such a way that it contains an entry for each destination or each destination prefix the router is aware of.
[0009] Using not-via addresses further increases the entries in forwarding tables. Aiming at the repair of single node or link failures, the increase is a number of additional entries equal to the number of links in the network. With double failure protection the increase is a square function of links.
[0010] The growth of forwarding tables slows down the forwarding, because the lookup from a large database takes longer than from a small one.
[0011] Calculating the routes for external prefixes takes more time than required due to the lookup of irrelevant prefixes in recursive lookup.
[0012] A major part of re-convergence time of link state routing protocols is spent with the download of the next-hops into the forwarding engines of line cards.
[0013] In the distributed router concept, a high number of destination prefixes also increases the signalling bandwidth overhead required to download the forwarding tables to the forwarding elements.
SUMMARY
[0014] It is an object of the present invention to obviate at least some of the above disadvantages and provide an improved network router and an improved method of configuring a network router.
[0015] According to a first aspect of the present invention there is provided a method of configuring a network router. The network router comprises a plurality of ingress interfaces, and an interface forwarding table assigned to each ingress interface. The method comprises the step of determining if the ingress interface may be used as part of a route from any source node to any destination node in the network. The forwarding table entries that are not used are removed from at least one of the interface forwarding tables.
[0016] According to a second aspect of the present invention there is provided a method of configuring a network router. The network router comprises a node forwarding table for the node itself. The method comprises the step of determining if the node may be used as part of a route from any source node to any destination node in the network. The forwarding table entries that are not used are removed from the node forwarding table.
[0017] In a first configuration of the second aspect the network router may further comprise a plurality of ingress interfaces, and an interface forwarding table assigned to each ingress interface. The method may further comprise removing the forwarding table entries that are not used from at least one of the interface forwarding tables.
[0018] In a configuration of the first or second aspect, the routing tables of all nodes and interfaces in the network may be known. The step of removing the forwarding table entries which are not used may comprise for all destination entries in the forwarding table, checking for all source nodes in the network whether the route from the source node to the destination node comprises a link directed towards the network router. The entry for a destination may be removed from the forwarding table, if for no source node the route to the destination node comprises a link directed towards the network router.
[0019] In another configuration of the first or second aspect the topology of the network and the link weights of the network may be known. The step of removing the forwarding table entries which are not used may comprise for all destination entries in the forwarding table, comparing for all source nodes in the network (a) the length of the shortest path from a node directly linked to the network router to a destination with (b) the sum of the length of the direct link and the length of the shortest path from the network router to the destination. The entry for a destination may be removed from the forwarding table, if the lengths of the paths are not equal.
[0020] In a further configuration of the first and second aspect at least some of the destinations may be inter-domain addresses. The method may further comprise the step of removing the inter-domain destinations from the forwarding table, if the edge node through which the inter-domain destination is reachable has been removed from the forwarding table.
[0021] In yet another configuration of the first and second aspect an entry from the node forwarding table is not removed if it is part of a static route.
[0022] According to a third aspect of the present invention a network router comprises a plurality of ingress interfaces, and an interface forwarding table assigned to each ingress interface. At least one of the interface forwarding tables comprises only forwarding table entries that are used.
[0023] According to a fourth aspect of the present invention a network router comprises a node forwarding table assigned to the router itself. The forwarding table comprises only forwarding table entries that are used.
[0024] According to a first configuration of the fourth aspect, the network router may further comprise a plurality of ingress interfaces, and an interface forwarding table assigned to each ingress interface. At least one of the interface forwarding tables is a copy of the reduced node forwarding table.
[0025] According to a configuration of the third or fourth aspect the forwarding table of at least one of its interfaces may comprise an entry for a destination, if for at least one source node the route to the destination node goes through the corresponding interface.
[0026] According to another configuration of the third or fourth aspect the forwarding table of the node or at least one of its interfaces may comprise an entry for a destination, if for at least one source node the route to the destination node comprises a link directed towards the network router.
[0027] According to a fifth aspect of the present invention a network router comprises a node forwarding table assigned to the router itself, a plurality of ingress interfaces, an interface forwarding table assigned to each ingress interface, and means for removing the forwarding table entries that are not used from at least one of the interface forwarding tables.
[0028] According to a sixth aspect of the present invention a network router comprises a node forwarding table assigned to the router itself and means for removing the forwarding table entries which are not used.
[0029] In a first configuration of the sixth aspect the network router may further comprise a plurality of ingress interfaces, an interface forwarding table assigned to each ingress interface, and means for copying the reduced node forwarding table to at least one of the interface forwarding tables.
[0030] In a configuration of the fifth or sixth aspect the network router may further comprise means for reducing a forwarding table in accordance with the method of the first or second aspect.
[0031] According to a seventh aspect of the present invention a computer program product comprises data processing device program code means adapted to perform the method of the first or second aspect when said program is run on a data processing device.
[0032] According to an eighth aspect of the present invention a computer-readable medium comprises computer-executable instructions to reduce any forwarding table of a network router in accordance with the first or second aspect.
[0033] The smaller size of the forwarding tables obtained by the present invention may significantly improve the performance of a router. The lookup of the next-hop may take less time. Fewer recursive lookups may allow the processing capacity requirement of the routing engine to be reduced. The smaller size of the forwarding tables may also reduce traffic by the control messages. Moreover, routing convergence time may be reduced. Furthermore, the present invention may be applied to each node individually without influencing the behaviour of the rest of the network.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 illustrates schematically the logical view of the forwarding tables in a router.
[0035] FIG. 2 is a schematic of a network illustrating per-interface forwarding table reduction according to the present invention.
[0036] FIG. 3 illustrates a method of reducing an interface forwarding table according to the present invention.
[0037] FIG. 4 is a schematic of a network illustrating a method of node forwarding table reduction according to the present invention.
[0038] FIG. 5 illustrates a method of reducing a node forwarding table according to the present invention.
DETAILED DESCRIPTION
[0039] A router has a forwarding table assigned to each ingress interface, referred to as interface forwarding table. Another table is assigned to the router itself, referred to as node forwarding table. The interface forwarding tables may be identical copies of the node forwarding table. This would serve the purpose of decreasing the forwarding delay. Packets arriving at the router at an ingress interface are routed according to the corresponding interface forwarding table, while packets originating from the router itself (e.g., ping commands from the command line interface, or higher level protocol messages) are routed based on the node forwarding table.
[0040] Many of the forwarding entries are actually never used during the routing. In a certain routing configuration, packets headed to a certain destination may never go through some nodes, or—more frequently—may never go through some links. These destinations are superfluous in the forwarding tables since they are never used.
[0041] However, as with normal destinations, most of the “not-via” destinations are also not used since the detour paths corresponding to a failure do not pass through a lot of links and nodes. These nodes do not need to have these not-via addresses in their forwarding tables.
[0042] A lot of the recursive lookups are not required because their results are never used during forwarding, but they place a processing burden on the routing engine. It makes no sense to stretch re-convergence time by the download of a lot of unneeded entries into the forwarding engine. Knowing that a lot of the entries are never used, this is a waste of bandwidth and processing capacity.
[0043] In a particular routing configuration, routes headed to a certain destination usually never go through some nodes, or—more frequently—may never go through some links. In these cases such destinations may safely be removed from the forwarding table of the corresponding node or interface, respectively.
[0044] With reference to FIG. 1 , a logical view of the forwarding tables in a router is shown in a schematic manner. A router 1 has a number of line cards for the ingress interfaces 2 and 3 as well as egress interfaces 4 and 5 . For reasons of simplicity, however, only two interfaces of each kind are depicted in FIG. 1 . Moreover, the router has a forwarding table assigned to each ingress interface, referred to as interface forwarding tables 6 , 7 , 8 , 9 . The router also has another forwarding table assigned to the router itself, referred to as node forwarding table 11 . The interface forwarding tables 6 , 7 , 8 , 9 may be identical copies of the node forwarding table 11 . This would serve the purpose of reducing the forwarding delay. Packets arriving at the router at one of the ingress interfaces 2 or 3 are routed according to the corresponding interface forwarding table 6 or 7 , while the packets originating from the router 1 itself, e.g. ping commands from the command line interface (CLI) 10 , or higher level messages, are routed based on the node forwarding table 11 .
[0045] In a first scenario, the actual routing in the network is known, i.e. the routing tables of all nodes and interfaces are known. This is a realistic assumption if
the routing tables are computed in a centralised way, or each node runs the same routing algorithm and the output of it is deterministic and predictable by the other nodes, i.e. deterministic tie-breaking rules are used if multiple equivalent paths are used.
[0048] An exemplary network that fulfils these conditions may consist of the same kind of routers.
[0049] In a second scenario, the routing is on shortest paths. While the nodes know the topology and the actual link weight, it cannot be predicted which shortest path was actually chosen by the intermediate routers. The most prominent example for this is OSPF or IS-IS, where the tie-breaking rules are vendor dependent, so that a router cannot always guess which alternative paths are used. In fact, in the case of Equal-Cost Multi-Path (ECMP) routing all of the shortest paths are in use.
[0050] In some cases, the administrator may also statically configure explicit forwarding table entries having precedence over the OSPF based routes. These will be referred to as explicit paths.
[0051] FIG. 2 is a schematic of a network illustrating per-interface forwarding table reduction according to the present invention. S 1 and S 2 are source nodes, A and B are nodes in the network linked by link L, and D is a destination node. The forwarding tables at the incoming interfaces signed with a cross do not need to contain an entry to destination D, because arriving traffic will not be directed towards destination D. Utilising the fact that in an advanced router, the forwarding tables of each interface can be set individually, it is possible that one interface of node A must list destination D, while two other interface of node A do not need this destination.
[0052] According to the present invention, the unused destination addresses are removed from the ingress interface forwarding table of node B at link L, where L is the link between node A and node B. Further, link L is considered a directed link going from node A to node B, and carrying traffic only in this direction. In order to determine whether a destination D may be removed from this forwarding table, it needs to be checked if link L may be used by any traffic arriving at the ingress interface of link L at node B heading towards destination D. If link L is not used by any possible traffic, it may safely be removed from the forwarding table at node B.
[0053] In the first scenario described above the exact routes are known. As shown in FIG. 3 it is determined in step 310 whether the route from a certain source S to D contains the link L. This is repeated for each possible source node S within the autonomous system or routing area and the unused destinations are removed from the forwarding table in step 320 . After reducing the table, the forwarding table of the ingress interface of L at node A comprises an entry for destination node D if and only if there exists a source node S for which the traffic from S to D may go through link L.
[0054] With respect to the second scenario, let w(L) denote the administrative weight (length) of the link L and let d(X,Y) be the length of the shortest path from node X to node Y, i.e.
[0000]
d
(
X
,
Y
)
:=
min
{
∑
L
∈
P
w
(
L
)
}
[0000] where P is a path from X to Y. If node A generates or forwards traffic towards destination D, then this traffic may use link L if and only if
[0000] d ( A,D )= w ( L )− d ( B,D ).
[0055] However, if explicit paths are given, it also needs to be checked whether there is an explicit table entry in node A suppressing the default shortest path behaviour. This can be done in many ways:
[0056] 1. If static routes are distributed with OSPF or IS-IS, the information is present.
[0057] 2. Otherwise, it may be assumed that the node forwarding tables are always filled with all potential destination prefixes, since the user may wish to send traffic to any destination. If an interface receives a packet headed towards a destination that is not listed in the respective interface forwarding table, it may divert this packet to the node forwarding table to obtain a valid outgoing (egress) interface.
[0058] 3. Alternatively, the FIB of node A must be queried, e.g. via SNMP. This, however, requires a new function in the routers and is a slower process that could cause longer transient times with packet losses during updates of the static routing tables.
[0059] Finally, in order to determine the necessary routing table entries, the set of interfaces which may forward traffic to D needs to be identified. Let this set be denoted by FD. The result can be found by dynamic programming:
The edge nodes must be in set FD. If a node A is in FD, and A can forward the traffic to node B, then B (i.e. the ingress interface coming from A) must also be in FD.
[0062] Also note that the prefix or prefixes of the directly connected interfaces are never removed from the forwarding tables.
[0063] Assuming that the router itself does not generate packets to arbitrary destinations and that there are no explicit paths configured into the network that are not learnt by any of the means (1. to 3.) listed above, an alternative to the interface forwarding table reduction would be to remove the unnecessary destination addresses from the node forwarding table of any node. If one wishes to reduce the node forwarding table of a node N, the functionality of making an identical copy of the node forwarding table for the interface remains unchanged, thus reducing the required new functionality and processing.
[0064] FIG. 4 is a schematic of a network illustrating a node forwarding table reduction according to the present invention. S represents a source node, N A , N B and N C are network nodes, and D is a destination node. This example shows that the upper node N A does not need to contain an entry towards destination D as normally traffic from source S will not pass through this node, i.e., the shortest path between source S and destination D does not pass the upper node N A through any interface.
[0065] With reference to FIG. 5 , in step 510 it is determined whether a node N may be used by the traffic from any source S toward D. If node N is not used, destination D may be removed from the node forwarding table in step 520 .
[0066] In the first scenario described above the actual routing in the network, and thus the exact routes, are known. It is therefore trivial to check whether the route from S to D contains node N.
[0067] In the second scenario mentioned above routing is on shortest paths. Hence, the dynamic programming procedure described in the previous section may be used.
[0068] It is well known that the majority of the forwarding table entries come from external prefixes (i.e. inter-domain routes). These are generally propagated by BGP. However, BGP only determines the edge router to use in order to reach a given prefix. The intra-domain route is left for the IGP protocol; hence the actual egress (outgoing) interface towards an external prefix is learnt by recursive lookup.
[0069] However, if an interface or node B is not along the IGP route towards an edge node D from any other node S, then this edge node D is not listed as a destination in the corresponding interface forwarding table or node forwarding table at node B. This also means that the forwarding table of B does not need to contain any external prefixes which would use edge node D. Therefore, the number of external prefixes may also be greatly reduced, and the routing engine does not even need to perform a recursive lookup on these prefixes.
[0070] The smaller size of the forwarding tables obtained by the present invention may significantly improve the performance of a router: when a packet is to be forwarded, the lookup of the next-hop takes less time because the number of entries in the forwarding table is smaller.
[0071] Such a reduction is particularly important when the network nodes propagate several virtual addresses for failure protection or other purposes. According to the present invention, a lot of these virtual addresses do not need to be stored in each router and can be removed.
[0072] Furthermore, by needing less recursive lookups the processing capacity requirement of the routing engine may be reduced.
[0073] Using centralised router configuration, the smaller size of the forwarding tables also means that less traffic is generated by the control messages and reduces the management complexity.
[0074] According to the present invention, routing convergence time may be reduced with OSPF or IS-IS, since the major part of the re-routing time with fast IGPs is the time needed to download and install the forwarding table to the linecard.
[0075] The method according to the present invention may be applied to each node individually without influencing the behaviour of the rest of the network.
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Disclosed is a method of configuring routing information in a network router linked into a network. The network router has a forwarding table. The method comprises removing the forwarding table entries which are not used. A network router configured in accordance with the method has a forwarding table comprising only forwarding table entries that are used.
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This is a continuation of application Ser. No. 797,519, filed on Nov. 22, 1991, now abandoned.
TECHNICAL FIELD
The present invention relates to compositions which provide both a skin cleansing and skin moisturizing benefit from the same product. These compositions provide improved lathering and cleansing characteristics, are extremely mild to the skin, and upon rinse-off deliver a moisturizing agent to the skin. These compositions comprise at least one anionic surfactant, a dispersed, insoluble oil phase, at least one additional surfactant selected from nonionic, zwitterionic and amphoteric surfactants, an optional suspending agent, and water. This invention also relates to methods for providing combined cleansing and moisturization, and to methods for delivering these compositions as a foam.
BACKGROUND OF THE INVENTION
Cleansing compositions must satisfy a number of criteria including cleansing power, foaming properties, and mildness/low irritancy with respect to the skin, hair and the occular mucosae.
Skin is made up of several layers of cells which coat and protect the keratin and collagen fibrous proteins that form the skeleton of its structure. The outermost of these layers, referred to as the stratum corneum, is known to be composed of 250 Å diameter protein bundles surrounded by 80 Å thick bilayers of epidermal lipids and water. Anionic surfactants can penetrate the stratum corneum membrane and, by delipidization (i.e. removal of the lipids from the stratum corneum), destroy its integrity. This destruction of the stratum corneum bilayers can lead to dry rough skin and may eventually permit the surfactant to interact with the viable epidermis, creating irritation.
Ideal cosmetic cleansers should cleanse the skin gently, causing little or no irritation without defatting and or drying the skin and without leaving skin taut after frequent use. Most lathering soaps, liquids and bars fail in this respect. Also, most current cleansing products do not deliver an adequate moisturizing benefit during cleansing. Therefore, users typically must moisturize their skin in a separate step following cleansing.
Certain synthetic surfactants are known to be mild. However, a major drawback of most mild synthetic surfactant systems, when formulated for skin cleansing, is poor lather performance compared to the highest bar soap standards (bars which are rich in coconut soap and superfatted). On the other hand, the use of known high sudsing anionic surfactants with lather boosters can yield acceptable lather volume and quality. Unfortunately, however, the highest sudsing anionic surfactants are, in fact, poor in clinical skin mildness. Surfactants that are among the mildest, such as sodium lauryl glyceryl ether sulfonate, (AGS), are marginal in lather. These two facts make the balancing of the surfactant selection and the lather and skin feel benefit a delicate process. Rather stringent requirements for cosmetic cleansers limit the choice of surface-active agents, and final formulations represent some degree of compromise. Mildness is often obtained at the expense of effective cleansing, or lathering may be sacrificed for either mildness, product stability, or both.
Furthermore, it would be highly desirable to also deliver skin moisturizers from cleansing compositions, because this would provide users with the convenience of obtaining both a cleansing and a moisturizing benefit from a single product. However, such dual cleansing and moisturizing compositions are difficult to formulate because the cleansing ingredients, in general, tend to be incompatible with the moisturizing ingredients.
Thus a need exists for cleansing compositions which will produce a foam which is abundant, stable and of high quality (compactness), which are effective skin cleansers, which are very mild to the skin and occular mucosae, and which can also deliver a moisturizing agent to the skin. These combined skin cleansing and moisturizing compositions would be termed two-in-one cleansers because of the dual cleansing and moisturizing benefits they would provide.
One highly successful solution to this dilemma of delivering both a cleansing and conditioning benefit from the same product has been in the shampoo area. Two-in-one conditioning shampoos have been developed which deliver suspended silicone hair conditioning agents in the presence of various cleansing surfactants. See U.S. Pat. No. 4,788,006, to Bolich, Jr. et al., issued Nov. 29, 1988; U.S. Pat. No. 4,741,855, to Grote et al, issued May 3, 1988; and U.S. Pat. No. 4,704,272, to Oh et al., issued Nov. 3, 1987. Shampoos, though, generally contain higher levels of more potent surfactants than are needed or desirable for gently cleansing the skin, because the hair has a larger surface area compared to the skin and tends to become soiled with higher levels of sebum, dirt, and other debris. Conversely, the hair generally requires much lower levels of conditioners than the skin, because the hair is easily overconditioned resulting in limp, unmanageable, and resoiled hair. Thus, it is seen that cleansing and moisturizing the skin is different from cleansing and conditioning the hair. Therefore, it would be highly desirable to develop effective, yet gentle, skin cleansing compositions which would also provide a skin moisturizing benefit.
It is therefore an object of the present invention to provide improved personal cleansing compositions which thoroughly cleanse the skin and which also moisturize the skin, i.e. to provide combined skin cleansing and moisturizing compositions.
It is a further object of the present invention to provide combined cleansing and moisturizing compositions which are very mild to the skin and occular mucosae.
It is an even further object of the present invention to provide combined cleansing and moisturizing compositions which will produce a foam which is abundant, stable, and of high quality.
It is a still further object of the present invention to provide methods for cleansing and moisturizing the skin.
It is a yet further object of the present invention to provide methods for delivering combined cleansing and moisturizing compositions as foams.
These and other objects will become readily apparent from the detailed description which follows.
SUMMARY OF THE INVENTION
The present invention relates to a personal cleansing composition comprising:
(a) from about 1% to about 10% of at least one anionic surfactant,
(b) from 0.4% to about 15% of a suspending agent,
(c) from about 0.1% to about 10% of a dispersed, insoluble, oil phase,
(d) from about 1% to about 10% of at least one additional surfactant selected from the group consisting of nonionic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof, and
(e) the remainder water.
The present invention further relates to methods for cleansing and moisturizing the skin and to methods for delivering these cleansing compositions as a dense, compact foam.
All percentages and ratios used herein are by weight or by a solids weights basis and all measurements are at 25° C., unless otherwise indicated.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to compositions which provide both a skin cleansing and skin moisturizing benefit from the same product. It has been found that compositions comprising certain anionic surfactants in combination with at least one additional surfactant selected from nonionic, zwitterionic, and amphoteric surfactants, provide good cleansing and foaming and yet are mild to the skin. Further, it has been found that insoluble, oil phase moisturizing agents can be dispersed in these compositions employing an optional suspending agent to provide a moisturizing benefit from the cleanser.
Essential Ingredients
Anionic Surfactants
The combined personal cleansing and moisturizing compositions herein comprise at least from about 0.1% to about 70%, preferably from about 1% to about 10%, and most preferably from about 2% to about 7.5% of at least one anionic surfactant.
Anionic surfactants useful herein include ethoxylated alkyl sulfates, alkanoyl sarcosinates, and mixtures thereof. The ethoxylated alkyl sulfates correspond to the formula RO(C 2 H 4 O) x SO 3 M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 10, and M is a water-soluble cation such as ammonium, sodium, potassium and trialkanolamine (e.g., triethanolamine). The preferred ethoxylated alkyl sulfates useful in the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, R has about 14 to about 18 carbon atoms. The alcohols can be derived from fats, e.g. coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil are preferred herein. Such alcohols are reacted with about 1 to about 10, and especially about 3, molar proportions of ethylene oxide and the resulting mixture of molecular species is sulfated and neutralized. An especially preferred ethoxylated alkyl sulfate for use herein is sodium laureth-3 sulfate.
The alkanoyl sarcosinates correspond to the formula RCON(CH 3 )CH 2 CH 2 CO 2 M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, and M is a water-soluble cation such as ammonium, sodium, potassium and trialkanolamine (e.g., triethanolamine). Preferably, R has about 14 to about 18 carbon atoms. An especially preferred alkanoyl sarcosinate for use herein, is sodium lauroyl sarcosinate.
Additional Surfactants
The combined personal cleansing and moisturizing compositions herein comprise at least from about 0.1% to about 70%, preferably from about 1% to about 10%, and most preferably from about 2% to about 8% of at least one additional surfactant selected from the group consisting of nonionic surfactants, zwitterionic surfactants, ampohteric surfactants, and mixtures thereof.
Suitable surfactants are disclosed in McCutcheon's, Detergents and Emulsifiers, North American Edition (1986), published by Allured Publishing Corporation; U.S. Pat. No. 5,011,681, to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No. 4,788,006, to Bolich, Jr. et al., issued Nov. 29, 1988; U.S. Pat. No. 4,741,855, to Grote et al., issued May 3, 1988; U.S. Pat. No. 4,704,272, to Oh et al., issued Nov. 3, 1987; U.S. Pat. No. 4,421,769, to Dixon et al, issued Dec. 20, 1983; and U.S. Pat. No. 3,755,560, to Dickert et al, issued Aug. 28, 1973; each of which is incorporated herein by reference in its entirety.
Preferred additional surfactants include ethoxylated glyceryl esters, alkanoylamidopropyl betaines, alkanoylamido hydroxysultaines, and mixtures thereof. Especially preferred are the PEG glyceryl fatty acid derivatives such as PEG-20 glyceryl stearate, PEG-80 glyceryl tallowate, PEG-30 glyceryl cocoate, PEG-80 glyceryl cocoate, and PEG-200 glyceryl tallowate (available as the Varonic LI series from Sherex); betaines such as cocamidopropyl betaine (available as Velvetex BK-35 and BA-35 from Henkel); hydroxysultaines such as cocamidopropyl hydroxysultaine (available as Mirataine CBS from Rhone-Poulenc), and mixtures thereof.
Dispersed, Insoluble Oil Phase
The combined personal cleansing and moisturizing compositions herein comprise at least from about 0.1% to about 10%, preferably from about 0.5% to about 5%, and most preferably from about 0.75% to about 2% of a dispersed, insoluble oil phase.
Without being limited by theory it is believed that this oil phase of the compositions of the instant invention provides a skin moisturizing benefit by depositing upon the skin during the cleansing and rinsing processes. By "dispersed" is meant that the oil phase can exist as a separate and distinct phase of fine particles, aggregates, or liquid crystals within the water phase of the compositions of the instant invention. By "insoluble" is meant that the oil phase has a solubility of less than about 5.0 grams per 100 grams of water at 25° C., preferably less than about 1.0 gram per 100 grams of water at 25° C.
A wide variety of oil type and emollient type materials and mixtures of materials are suitable for use in the oil phase of the compositions of the present invention. Preferably, the oil phase is selected from the group consisting of silicones, hydrocarbons, fatty acids, fatty acid derivatives, cholesterol, cholesterol derivatives, vegetable oils, vegetable oil derivatives, and mixtures thereof.
Examples of silicones include non-volatile silicones such as dimethicone copolyol; dimethylpolysiloxane; diethylpolysiloxane; high molecular weight dimethicone (average molecular weight from about 200,000 to about 1,000,000 and, preferably, from about 300,000 to about 600,000) which can have various end-terminating groups such as hydroxyl, lower C 1 -C 3 alkyl, lower C 1 -C 3 alkoxy and the like; mixed C 1 -C 3 alkyl polysiloxane (e.g., methylethylpolysiloxane); phenyl dimethicone and other aryl dimethicones; dimethiconol; fluorosilicones; and mixtures thereof.
Preferred are non-volatile silicones selected from the group consisting of dimethicone copolyol, dimethylpolysiloxane, diethylpolysiloxane, high molecular weight dimethicone, mixed C 1 -C 30 alkyl polysiloxane, phenyl dimethicone, dimethiconol, and mixtures thereof. More preferred are non-volatile silicones selected from dimethicone, dimethiconol, mixed C 1 -C 30 alkyl polysiloxane, and mixtures thereof. Especially preferred is dimethiconol which is a dimethyl silicone polymer terminated with hydroxyl groups. Dimethiconol is available as Q2-1401 Fluid, a solution of 13 percent ultra-high-viscosity dimethiconol in volatile cyclomethicone fluid as a carrier; as Q2-1403 Fluid, a solution of ultra-high-viscosity dimethiconol fluid in dimethicone (both sold by Dow Corning Corporation); and as other custom blends (e.g. 10% dimethiconol in dimethicone). Nonlimiting examples of silicones useful herein are described in U.S. Pat. No. 5,011,681, to Ciotti et al., issued Apr. 30, 1991, which has already been incorpoated by reference.
Examples of hydrocarbons include materials such as petrolatum, mineral oil (e.g., USP light or heavy), and branched hydrocarbons (e.g., isohexadecane, available as Permethyl 101A from Presperse).
Examples of fatty acids and fatty acid derivatives include esters such as diisopropyl adipate, isopropyl myristate, isopropyl palmitate, ethylhexyl palmitate, isodecyl neopentanoate, C12-15 alcohols benzoate, diethylhexyl maleate, PG-14 butyl ether, PG-2 myristyl ether propionate, and the like. Especially preferred are long chain esters of long chain fatty acids, e.g. cetyl ricinoleate.
Examples of cholesterol and cholesterol derivatives include cholesterol, and cholesterol esters and ethers (e.g., cholesterol stearate, cholesterol isosterate, cholesterol acetate, and the like).
Examples of vegetable oils and vegetable oil derivatives include, soybean oil, derivatized soybean oils such as maleated soybean oil, coconut oil and derivatized coconut oil, cottonseed oil and derivatized cottonseed oil, jojoba oil, cocoa butter, and the like.
Examples of other materials useful in the oil phase include other natural and synthetic triglycerides, lanolin, lanolin esters and derivatives, animal fats, and other synthetic fats and oils. Examples of other suitable materials, including emollients, are disclosed in U.S. Pat. No. 4,919,934, to Deckner et al., issued Apr. 24, 1990; which is incorporated herein by refernce.
Water
The moisturizing and cleansing compositions of the present invention comprise water as an essential component. The water is present from about 50% to about 99.7%, preferably from about 60% to about 80%, and most preferably from about 65% to about 75%.
Optional Ingredients
Suspending Agent
A highly preferred optional component of the present compositions is a suspending agent or mixture of suspending agents. The suspending agent or mixture of agents is present at a level of from about 0% to about 15%, preferably from about 0.4% to about 15%, and more preferably from about 5% to about 15%. The optional suspending agent serves to assist in suspending the insoluble oil phase and may also give pearlescence to the product. Preferred materials are long chain acyl derivatives as well as other long chain materials, and xanthan gum. Especially preferred are long chain acyl derivatives as well as other long chain materials.
Suspending agents useful in the present compositions are any of several long chain (C 16-22 ) acyl derivative materials such as those selected from the group consisting of ethylene glycol long chain esters, alkanolamides of long chain fatty acids, long chain esters of long chain fatty acids, glyceryl long chain esters, long chain esters of long chain alkanolamides, and mixtures thereof. Included are ethylene glycol esters of fatty acids having from about 16 to about 22 carbon atoms. Preferred are the ethylene glycol stearates, both mono and distearate, but particularly the distearate containing less than about 7% of the monostearate. Other suspending agents found useful are alkanol amides of fatty acids, having from about 16 to about 22 carbon atoms, preferably about 16 to 18 carbon atoms. Preferred alkanol amides are stearic monoethanolamide, stearic diethanolamide, stearic monoisopropanolamide and stearic monoethanolamide stearate.
Another suspending agent useful in the present compositions is xanthan gum. This biosynthetic gum material is commercially available and is a heteropolysaccharide with a molecular weight of greater than 1 million. It contains D-glucose, D-mannose and D-glucuronate in the molar ratio of 2.8:2.0:2.0. The polysaccharide is partially acetylated with 4.7% acetyl. This information and other information is found in Whistler, Roy L. Editor Industrial Gums-Polysaccharides and Their Derivatives New York: Academic Press, 1973, which is incorporated herein by reference. Kelco, a Division of Merck & Co., Inc. offers xanthan gum as Keltrol®.
Useful suspending agents are described in U.S. Pat. No. 4,788,006, to Bolich, Jr. et al., issued Nov. 29, 1988; U.S. Pat. No. 4,741,855, to Grote et al., issued May 3, 1988; and U.S. Pat. No. 4,704,272, to Oh et al., issued Nov. 3, 1987; all of which have already been incorporated herein by reference.
Humectants
The compositions of the instant invention can optionally contain one or more humectants and/or skin moisturizers. A variety of humectants and/or moisturizers can be employed and can be present at a level of from about 0.1% to about 20%, more preferably from about 0.5% to about 5%, and most preferably from about 2% to about 4%. These materials include, but are not limited to, urea; guanidine; glycolic acid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium); lactic acid and lactate salts (e.g. ammonium and quaternary alkyl ammonium); polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol, propylene glycol, hexylene glycol and the like; polyethylene glycol; sugars and starches; sugar and starch derivatives (e.g. alkoxylated glucose); panthenol (including D-, L-, and the D,L-forms); pyrrolidone carboxylic acid; hyaluronic acid; lactamide monoethanolamine; acetamide monoethanolamine; and mixtures thereof.
Preferred humectants for use in the compositions of the present invention are the C 3 -C 6 diols and triols. Especially preferred is the triol, glycerol.
Optional Surfactants
The compositions of the instant invention can optionally contain one or more additional surfactant materials. A variety of additional surfactants can be employed and can be present at a level of from about 0.1% to about 10%, more preferably from about 0.5% to about 5%, and most preferably from about 2% to about 4%.
Suitable optional surfactants can include any of a wide variety of nonionic, cationic, anionic, and zwitterionic surfactants, such as those disclosed in McCutcheon's, Detergents and Emulsifiers, North American Edition (1986), published by Allured Publishing Corporation; U.S. Pat. No. 5,011,681, to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No. 4,421,769, to Dixon et al, issued Dec. 20, 1983; and U.S. Pat. No. 3,755,560, to Dickert et al, issued Aug. 28, 1973; each of which has already been incorporated herein by reference.
Other Optional Components
A variety of additional ingredients can be incorporated into the compositions of the present invention. Nonlimiting examples of these additional ingredients include vitamins and derivatives thereof (e.g., ascorbic acid, vitamin E, tocopheryl acetate, and the like); sunscreens; thickening agents (e.g., polyol alkoxy ester, available as Crothix from Croda); cationic polymers and thickeners (e.g., cationic guar gum derivatives such as guar hydroxypropyltrimonium chloride and hydroxypropyl guar hydroxypropyltrimonium chloride, available as the Jaguar C series from Rhone-Poulenc); carboxylic copolymers (e.g., carbomers); emulsifiers; emollients; preservatives for maintaining the antimicrobial integrity of the compositions; anti-acne medicaments (resorcinol, salicylic acid, and the like); antioxidants; skin soothing and healing agents such as aloe vera extract, allantoin and the like; chelators and sequestrants; and agents suitable for aesthetic purposes such as fragrances, essential oils, skin sensates pigments, pearlescent agents (e.g., mica and titanium dioxide), lakes, colorings, and the like (e.g., clove oil, menthol, camphor, eucalyptus oil, and eugenol). Nonlimiting examples of suitable carboxylic copolymers, emulsifiers, emollients, and other additional ingredients are disclosed in U.S. Pat. No., 5,011,681, to Ciotti et al., issued Apr. 30, 1991, which has already been incorporated by reference herein.
Methods for Cleansing and Moisturizing the Skin
The compositions of the instant invention are useful for cleansing and moisturizing the skin. Typically, a suitable amount of the composition is directly applied to the skin, which has optionally been premoistened with water. Alternatively, a suitable amount of the composition can be applied to the skin via intermediate application to the hands, a washcloth, a sponge, or other application device. It has been found that the compositions of the instant invention provide their optimal cleansing performance when combined with water during the cleansing process. To complete the cleansing process, the compositions of the instant invention are thoroughly rinsed from the skin with water, thereby leaving behind the moisturizing ingredients. Suitable amounts of the composition for use in cleansing range from, but are not limited to, about 0.5 mg/cm 2 to about 5.0 mg/cm 2 of skin area.
Other Product Forms
The compositions of the instant invention can be suitably formulated as foaming gels, foaming lotions, foaming scrubs, and the like.
Delivery of the Compositions as a Foam
In further embodiments, the compositions of the instant invention can be delivered as a foam. Preferably the foam has a density of from about 0.01 gms/cm 3 to about 0.25 gms/cm 3 , more preferably from about 0.05 gms/cm 3 to about 0.20 gms/cm 3 , and most preferably from about 0.08 gms/cm 3 to about 0.11 gms/cm 3 .
For delivery as a foam, the compositions of the instant invention can be delivered, for example, from a hand-held device such as a nonaerosol pump foamer or from an aerosol container charged with a suitable propellant system.
Non-aerosol squeeze foamer packages are well known as exemplified by the disclosures in the following patents that are incorporated herein by reference. U.S. Pat. No. 3,709,437, to Wright, issued Jan. 9, 1973; U.S. Pat. No. 3,937,364, to Wright, issued Feb. 10, 1976; U.S. Pat. No. 4,022,351, to Wright, issued May 10, 1977; U.S. Pat. No. 4,147,306, to Bennett, issued Apr. 3, 1979, U.S. Pat. No. 4,184,615, to Wright, issued Jan. 22, 1980; U.S. Pat. No. 4,598,862, to Rice, issued Jul. 8, 1986; U.S. Pat. No. 4,615,467, to Grogan et al., issued Oct. 7, 1986; and French Patent No. 2,604,622, to Verhulst, published Apr. 8, 1988. These containers (packages) do not use any propellant. They create a foam from almost any surfactant composition. The composition is placed in the container reservoir (plastic squeeze bottle). Squeezing the container with the hand forces the composition through a foamer head, or other foam producing means, where the composition is mixed with air and then through a homogenizing means that makes the foam more homogeneous and controls the consistency of the foam. The foam is then discharged as a uniform, non-pressurized aerated foam.
Pressurized aerosol delivery systems are also well-known in the art. When the compositions of the instant invention are delivered from such pressurized systems, the compositions further comprise from about 25% to about 80%, preferably from about 30% to about 50%, of suitable propellants. Examples of such propellants are the chlorinated, fluorinated, and chlorofluorinated lower molecular weight hydrocarbons; nitrous oxide; carbon dioxide; butane; propane; and the like. These propellants are used at a level sufficient to expel the contents of the container.
When the compositions of the instant invention are optionally delivered as a foam, it is preferable that the composition used for such delivery has a viscosity in the range from about 0.1 cPs to about 40 cPs, preferably from about 1 cPs to about 30 cPs, and most preferably from about 10 cPs to about 20 cPs. These viscosities are determined at 25° C. using a Brookfield RVT (Brookfield Instruments, Stoughton, Mass.) equipped with a spindle No. 1 at 100 rpm.
EXAMPLES
The following examples further describe and demonstrate the preferred embodiments within the scope of the present invention. The examples are given solely for the purpose of illustration, and are not to be construed as limitations of the present invention, since many variations thereof are possible without departing from its spirit and scope.
Ingredients are identified by chemical or CTFA name.
Example I
A combined cleansing and moisturizing composition containing a dispersed oil phase comprising a mixture of a hydrocarbon and a fatty acid derivative is prepared by combining the following ingredients.
______________________________________Ingredients Weight Percent______________________________________Phase AWater QS100Guar Hydroxypropyltrimonium chloride 0.75Citric Acid 0.00-2.00Phase BSodium Lauroyl Sarcosinate 3.94Cocamidopropyl Hydroxysultaine 1.31Cocamidopropyl Betaine 0.70PEG-80 Glycerol Cocoate 4.38Citric Acid 0.17Ethylene Glycol Distearate 10.0Phase CPEG-80 Glycerol Cocoate 1.40Phase DPetrolatum 0.50Cetyl Ricinoleate 0.50Sodium Laureth Sulfate 0.26Sodium Chloride 0.05Phase ERicinoleoamidopropyltrimonium Chloride (and) 1.28Propylene GlycolPolyquaternium-2 0.75Phase FCocamidopropyl Hydroxysultaine 1.02Phase GCocamidopropyl Betaine 1.02Phase HPhenoxyethanol 0.40DMDM Hydantoin 0.08Mica (and) Titanium Dioxide 0.10Fragrance 0.15Phase ISodium Hydroxide 0.00-2.00______________________________________
The water and guar hydroxypropyltrimonium chloride are combined to form a homogeneous solution and heated to 70° C. Next the pH is adjusted to 3.0-6.0 with citric acid as needed and the mixture (Phase A) is cooled to room temperature. Next, the Phase B ingredients are combined with heating to 80° C. until homogeneous, cooled to room temperature, and added to Phase A. Each of Phases C through H is then separately prepared by mixing at room temperature and sequentially added to the composition with mixing. Finally, the resulting mixture is adjusted to pH 6.0-7.0 with sodium hydroxide as needed.
The resulting combined cleansing and moisturizing composition is useful for cleansing and moisturizing the skin.
EXAMPLE II
A combined cleansing and moisturizing composition containing a dispersed oil phase comprising maleated soybean oil is prepared by combining the following ingredients.
______________________________________Ingredients Weight Percent______________________________________Phase AWater QS100Guar Hydroxypropyltrimonium chloride 0.75Citric Acid 0.00-2.00Phase BSodium Lauroyl Sarcosinate 3.94Cocamidopropyl Hydroxysultaine 1.31Cocamidopropyl Betaine 0.70PEG-80 Glycerol Cocoate 4.38Citric Acid 0.17Ethylene Glycol Distearate 10.0Phase CPEG-80 Glycerol Cocoate 1.40Phase DMaleated Soybean Oil 1.00Sodium Laureth Sulfate 0.26Sodium Chloride 0.05Phase ERicinoleoamidopropyltrimonium Chloride (and) 1.28Propylene GlycolPolyquaternium-2 0.75Phase FCocamidopropyl Hydroxysultaine 1.02Phase GCocamidopropyl Betaine 1.02Phase HPhenoxyethanol 0.40DMDM Hydantoin 0.08Mica (and) Titanium Dioxide 0.10Fragrance 0.15Phase ISodium Hydroxide 0.00-2.00______________________________________
The composition is prepared using the general procedure given in Example I.
The resulting combined cleansing and moisturizing composition is useful for cleansing and moisturizing the skin.
EXAMPLE III
A combined cleansing and moisturizing composition containing a dispersed oil phase comprising nonvolatile silicones is prepared by combining the following ingredients.
______________________________________Ingredients Weight Percent______________________________________Phase AWater QS100Guar Hydroxypropyltrimonium chloride 0.75Citric Acid 0.00-2.00Phase BSodium Lauroyl Sarcosinate 3.94Cocamidopropyl Hydroxysultaine 1.31Cocamidopropyl Betaine 0.70PEG-80 Glycerol Cocoate 4.38Citric Acid 0.17Ethylene Glycol Distearate 10.0Phase CPEG-80 Glycerol Cocoate 1.40Phase DDimethicone (and) Dimethiconol.sup.1 1.00Sodium Laureth Sulfate 0.26Sodium Chloride 0.05Phase ECocamidopropyl Hydroxysultaine 1.02Phase FCocamidopropyl Hydroxysultaine 1.02Phase GCocamidopropyl Betaine 1.02Phase HPhenoxyethanol 0.40DMDM Hydantoin 0.08Mica (and) Titanium Dioxide 0.10Fragrance 0.15Phase ISodium Hydroxide 0.00-2.00______________________________________
The composition is prepared using the general procedure given in Example I, with the only change being one less phase to be added.
The resulting combined cleansing and moisturizing composition is useful for cleansing and moisturizing the skin.
EXAMPLE IV
A combined cleansing and moisturizing composition, without a suspending agent, and containing a dispersed oil phase comprising maleated soybean oil is prepared by combining the following ingredients.
______________________________________Ingredients Weight Percent______________________________________Phase AWater QS100Phase BSodium Lauroyl Sarcosinate 2.25Cocamidopropyl Hydroxysultaine 3.25Cocamidopropyl Betaine 2.25PEG-80 Glyceryl Cocoate 2.25Phase CMaleated Soybean Oil 1.25Linoleamidopropyl PG-Dimonium 1.00Chloride PhosphatePhase DWater 2.00Polyquaternium-2 0.75Cocamidopropyl Hydroxysultaine 0.25Cocamidopropyl Betaine 0.25Phase EPolyol alkoxy ester 1.00Phase FPhenoxyethanol 0.40DMDM Hydantoin 0.08Mica (and) Titanium Dioxide 0.10Fragrance 0.15Phase ITriethanolamine 0.00-2.00______________________________________
Phases A, B, and C are each prepared at room temperature, and these three phases are combined with mixing until clear. Phase D is prepared and added to the mixture, which is then heated to 80° C. Next, Phase E is added with mixing, and the mixture is then cooled to room temperature. Phase F is prepared and added with mixing. Finally, the mixture is adjusted to pH 6.0-7.0 with the triethanolamine as needed.
The resulting combined cleansing and moisturizing composition is useful for cleansing and moisturizing the skin.
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The present invention relates to compositions which provide both a skin cleansing and skin moisturizing benefit from the same product. These compositions provide improved lathering and cleansing characteristics, are extremely mild to the skin, and deliver a moisturizing agent to the skin. These compositions comprise at least one anionic surfactant, a dispersed, insoluble oil phase, at least one additional surfactant, an optional suspending agent, and water. This invention also relates to methods for providing combined cleansing and moisturization, and to methods for delivering these compositions as a foam.
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This is a divisional of application Ser. No. 08/507,224, filed Oct. 27, 1995, which is a National Stage of PCT/EP94/00417, filed Feb. 14, 1994, which has issued as U.S. Pat. No. 5,820,971.
BACKGROUND OF THE INVENTION
1. Field of the Invention
A security document and method of producing it The present invention relates to security documents such as bank notes, identity cards or the like, with multilayer security elements having a layer in which diffraction structures, in particular holographic structures, are embossed in the form of a relief structure and which are combined with a reflective layer, and to a method for producing the same.
2. Discussion of Related Technology
Optically variable elements such as holograms, diffraction grids or interference layer elements have been preferably used for some time as protection against forgery or copying due to their optical properties that vary with the viewing angle. For mass production of such elements it is customary to produce so-called master holograms which have the particular phase information in the form of a three-dimensional relief structure. Starting with the master hologram one produces by duplication so-called press dies for embossing the required holograms in large numbers of units.
The embossing can also be done directly on the document material as described in EP-A 0 338 378. In a continuous process bank note paper in a roll form is first printed on both sides and then provided in certain areas with a holographic structure. The lacquer to be embossed and the relief structure are simultaneously transferred to the paper by covering the surface structure of the press die with a radiation-curable lacquer. As soon as paper and press die are brought in contact the lacquer is cured. The lacquer now adheres to the paper surface and has the holographic relief structure. Then the embossed structure is given a thin vacuum metalized layer that permits the holographic information to be observed in reflection.
Since paper is virtually impermeable to UV radiation the curing of the lacquer can in this case only take place with the aid of electron radiation, a very elaborate and expensive method that furthermore damages the paper. For this reason the production of embossed holograms directly on the document material has not become accented in practice, although this procedure has great advantages with respect to resistance to forgery since the hologram is connected virtually undetachably with the substrate. Due to the much more cost-effective production and more versatile applicability embossed holograms are therefore usually prepared as multilayer elements on a separate carrier and transferred to the document by means of an adhesive layer. The layer structure is dimensioned, or prepared by additional measures, in such a way that the hologram can be removed from the carrier layer after being glued to the document.
The multilayer element applied to the carrier material can be produced e.g. by the method known from U.S. Pat. No. 4,758,296. A matrix in web form wound on rolls is provided with a liquid resin and brought in contact with a plastic carrier material. The liquid resin is simultaneously cured by UV or electron radiation. In a further step the relief structure is provided with a thin metal layer so that the hologram can be observed in reflection. To be transferred to a document the layer structure is finally provided with a hot-melt adhesive layer that is activated under the action of heat and pressure.
However this security element has the disadvantage that the hologram element might be detached from the document by reheating the hot-melt adhesive, and transferred to another.
In general, so-called transfer embossing foils have more than the layers described in U.S. Pat. No. 4,758,296. For example EP-A 0 170 832 describes a transfer embossing foil comprising a carrier material, a first layer of lacquer permitting subsequent detachment of the carrier material, a second layer of lacquer in which the diffraction structures are embossed, a metal layer and a layer of bonding agent. Such a foil can be glued to a document by the method known from EP-A 0 433 575. The embossing foil in which the hologram structure is embedded is applied to a document locally in the form of a marking. For this purpose the document is printed at a certain place with an adhesive which only becomes viscous and sticky through UV, gamma or electron radiation. This activation takes place either before or after the transfer foil and document are brought together.
Although this security element offers irreversible adhesion to the document since the cured adhesive is not reactivable, the embossed structure can be exposed if the layer bordering the relief structure or the metal layer has a different chemical base.
BRIEF SUMMARY OF THE INVENTION
Interestingly enough, the prior art also contains proposals for preventing embossed layers from being exposed by using chemically homogeneous materials or permeable metal layers (GB-A 2 093 404). But since these elements are applied with reversibly activable adhesives in all such proposals these elements are still detachable from the substrate and thus insufficiently protected from manipulation. The invention is therefore based on the problem of providing a security document with an embossed hologram, whereby the embossed hologram has a simple layer structure with a good laminar compound that is cost-effective and simple to produce, and the hologram is furthermore connected with the document irreversibly.
The invention offers many-sided advantages involving both the production of embossed holograms directly on the document material and the production and application of transferred embossed holograms.
For example it is possible to produce embossed holograms directly on the antifalsification Caper with the aid of light-curing substances in very uncomplicated fashion. Such substances are e.g. blue light-curing or delayed-curing lacquers.
These substances can of course be used just as advantageously for producing or applying transferred embossed holograms.
Along with this simple production or transfer, the inventive security documents also offer the crucial advantage that the security elements have a simple layer structure and an intensive laminar compound within the element or between element and document.
This is because the materials selected for plastic layers that are adjacent in the element layer structure are chemically homogeneous and therefore ensure a much more intensive compound in the boundary layers than chemically different substances. The firm compound with the document arises from the use of reaction lacquers or adhesives (i.e., lacquers and adhesives that polymerize or cross-link upon physical and/or chemical activation) which adhere irreversibly to the document.
To obtain a layer structure as simple as possible even in the case of the transferred embossed holograms, the metal layer disposed above the embossed layer is not covered with an additional foil layer which is then equipped with an adhesive layer but, according to the invention, is coated directly with the adhesive, the adhesive being selected so as to have a foil-like character in the cured state (on the substrate). These requirements are met by all reaction adhesives that polymerize by physical and/or chemical activation. To counteract manipulation of all kinds the embossed layer of the transfer element and the adhesive layer are formed according to the invention as chemically homogeneous layers. The metal layer located between these layers is designed so thin that it already has microcracks or pores with normal handling so that the embossed layer and adhesive layer are in contact through these randomly present openings and form a largely inseparable compound at these places. Exposure of the relief structure cr detachment of the security element therefore leads inevitably to destruction of the stated layer structure. Alternatively or additionally the metal layer can also be provided with openings systematically.
In a preferred embodiment the transfer element comprises a carrier material preferably bearing a UV-curable layer of lacquer in which the hologram structure is embossed, and a metal layer whose thickness is much smaller than 1 micron, preferably in the range of 0.01 microns. Transfer to the document takes place by means of a UV-activable adhesive having a chemical composition similar to that of the UV-curable lacquer, whereby the adhesive and layer of lacquer are in direct contact with each other in some areas. This security element has a simple layer structure in which the layers themselves adhere in optimal fashion.
Depending on the case of application the inventive layer structure can be varied. The above-described transfer structure is particularly useful when extremely thin security elements are required that add as little buildup as possible on the later substrate or paper of value and also have low inherent stability after the carrier foil is removed, thereby additionally preventing removal of the security element.
If the security element is to be mechanically stable itself the invention offers two alternatives, namely to use a mechanically stressable foil in which the relief structure is embossed, or a carrier foil remaining on the later security element together with the embossed layer of lacquer or a foil layer bearing the embossing. Such a structure is to be equipped according to the invention with a permeable metal layer and with a curing adhesive layer. Such embodiments are of special interest in particular when the security element is designed as a strip and applied to the paper as a safeguarding thread.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages and variants will be explained with reference to the figures. It is pointed cut that the figures do not offer a true-to-scale representation of the invention but are only for the sake of illustration. The term “reaction adhesive” or “reaction lacquer” used in the following text include all types of adhesives or lacquers that “cure” (i.e., polymerized or cross-link) irreversibly under specific physical or chemical action. Both UV-curable and two-component adhesives and lacquers are thus referred to here as reaction adhesives and reaction lacquers.
FIG. 1 shows an inventive security document,
FIG. 2 shows a transfer embossing foil according to the invention,
FIG. 3 shows a method for producing the inventive security document of FIG. 1,
FIG. 4 shows a variant of the production method of FIG. 3,
FIG. 5 shows a variant of the production method of FIG. 3,
FIG. 6 shows a further variant of the production method of FIG. 3,
FIG. 7 shows a further variant of the production method of FIG. 3,
FIG. 8 shows a variant of the inventive security document,
FIG. 9 shows a method for producing the inventive security document of FIG. 8,
FIG. 10 shows a variant of the production method of FIG. 9 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
FIG. 1 shows a cross section through a security document according to the invention. Security element 9 is disposed on security document 1 in a predetermined area. Depending on the requirements, element 9 can have the form of a thread or band or be formed as a mark with certain contour shapes. It comprises UV-curable or chemically curable layer of reaction lacquer 2 in which diffraction structures are embossed in the form of a relief, and thin reflective layer 3 , preferably a metal layer. Element 9 is inseparably connected with security document 1 via reaction adhesive layer 4 . Adhesive layer 4 consists of a material that is largely homogeneous chemically with the material of embossed layer 2 . This has the advantage that a very firm compound arises in areas where the metal layer contains pores or microcracks (which is unavoidable with layer thicknesses in the range of about 1 micron) and where layer of lacquer 2 and adhesive layer 4 thus adjoin directly. This is very desirable with respect to protection against forgery by reembossing the relief structure, and resistance wear. Since UV-curable or chemically curable layers of reaction lacquer and adhesive are irreversibly curable it is impossible to detach the layers later. In case of thermal or chemical attacks both layers are furthermore always affected so that such measures necessarily destroy the total security element.
In this embodiment of the invention security element 9 is produced separately as transfer embossing foil 10 whose structure is shown in FIG. 2 . Carrier material 5 is expediently designed as an endless plastic band to which lacquer 2 is applied in a continuous process. A matrix whose surface structure corresponds to the interference stripe pattern of any desired diffraction structure is used to emboss the relief structure in reaction lacquer 2 , which is cured e.g. by UV radiation during the embossing process. Such a method is described for example in the abovementioned U.S. Pat. No. 4,758,296.
Alternatively one can of course also use a delayed-curing lacquer, i.e. a lacquer in which polymerization is initiated by irradiation with suitable light and then takes place with a time lag, or a blue light-curing lacquer. More detailed information about such lacquers can be found elsewhere.
After this the embossed structure in layer 2 is provided with an either uninterrupted or screened reflective layer 3 , preferably a metal layer. Screening offers the advantage that the compound between adhesive layer 4 and embossed layer 2 can be made even firmer. The size of the metal-free areas can be selected as one chooses; it is thus conceivable to make the metal-free areas so small that they cannot be resolved by the eye and thus do not impair the general impression of the information shown. Alternatively the metal-free areas could be used as design elements so that the diffraction information is observable visually within the security element area only at certain places.
Metalizing methods to be used may be e.g. the customary vacuum metalizing method or else a photolytic method.
The metalized layer can optionally be provided with a protective layer, in which case the latter should be made of a material chemically homogeneous with embossed layer 2 .
The finished transfer embossing band 10 can be stored on rolls as a semifinished product and used on demand in a production method as described in the following with reference to FIGS. 3 to 5 .
FIG. 3 shows part of a continuous method for producing security documents according to the invention. Security document material 1 , preferably bank note paper already printed, exists here in web form and is coated locally with a special reaction adhesive in printing unit 6 .
This reaction adhesive is for example a cationically reacting UV adhesive that can be treated like an ink before activation. Unlike customary radically reacting UV adhesives which only cure during irradiation, so-called cationically curing adhesives have the property of being only activated by irradiation with UV light and curing further after irradiation. Such cationically curing UV lacquer systems are sold e.g. by Herberts under type designation ISS 1202.
After adhesive 4 has been transferred to substrate 1 in printing unit 6 it is irradiated in the next unit with UV lamp 7 , as shown in FIG. 3, to activate its bonding ability. In the following step transfer embossing foil 10 with elements 9 is fed from supply roll 11 according to FIG. 2 . Element 9 (FIG. 2) adheres to the adhesive layer and is removed from carrier band 5 in the form of the reaction adhesive coating. Carrier band 5 and the non-transferred remains of element layer structure 9 are wound onto transfer band roll 12 . In a last method step not shown, substrate 1 provided with security elements 9 is cut up into suitable formats, e.g. individual bank notes.
In a variant, adhesive 4 can also be printed on transfer embossing foil 10 and activated there. This possibility is shown in FIG. 4 . Before embossing foil 10 removed from roll 11 is brought together with substrate 1 , UV-activatable adhesive 4 is applied to metal layer 3 of embossing foil 10 in any desired patterning in printing unit 6 and then activated with UV lamp 7 . In this case too carrier band 5 is removed from substrate 1 via roll 12 directly after foil 10 and element 9 join substrate 1 .
Instead of delayed-curing (cationically cured) adhesives one can of course also use the abovementioned blue light-curing reaction adhesives. This method variant is shown in FIG. 5 . Paper web 1 is provided with the blue light-curing reaction adhesive in printing unit 6 . This reaction adhesive is e.g. an acrylate from Imperial Chemical Industries PCL with the designation LCR 0603B.
In the area of pressing cylinder 16 transfer material 10 and paper web 1 are brought in contact and irradiated with blue light 17 . The reaction adhesive thereby cures within seconds since the paper is permeable to blue light. The transfer foil can then be removed from the hologram-paper compound in the usual way.
Departing from the embodiments shown in FIGS. 3 to 5 it is also possible to leave carrier foil 5 on substrate 1 temporarily or permanently. This may be useful as additional protection from mechanical loads temporarily, e.g. for a period of storage or transport, or for the entire life e.g. of safeguarding threads. It is important in this connection that the protective layer function performed by carrier foil 5 should in this case be regarded only as additional to the protective layer function of layer of reaction lacquer 2 . Removal of carrier foil 5 opens up no possibilities of manipulation since it does not yet make the relief structure accessible.
The methods shown in FIGS. 3 to 5 are wonderfully simple and require no elaborate protective measures, as are necessary for example when electron-beam curing or solvent-containing adhesives are used. Furthermore one thus obtains both a firm laminar compound within the security element and firm adhesion to the document, so that it is not possible either to separate the embossed structure from the element layer structure or to detach the element from the document.
Although it is preferable to use radiation-curing reaction adhesives for reasons of process engineering, in particular due to their simple and extremely fast curing, one can alternatively use mixed reaction adhesives which are related chemically with the embossed layer. According to the invention the embossed layer need not necessarily be a radiation-curable layer of lacquer, it can also be a chemically curing layer that has the same chemical base as the adhesive layer.
This variant is shown in FIG. 6 . One component of the reaction adhesive is applied in printing unit 13 directly to transfer embossing foil 10 removed from roll 11 , while the second component is applied in printing unit 14 to substrate 1 . When substrate 1 and transfer embossing foil 10 are brought together a self-curing layer arises in the area of the adhesive components to ensure the compound between substrate 1 and embossed layer 2 . Carrier material 5 can of course here too be removed directly after joining substrate 1 , as shown in the figure, or else be left on substrate 1 as a temporary protective layer.
The separate application of the adhesive components shown in FIG. 6 makes the functional principle particularly clear. However this procedure is not permissible with any two-component adhesive since these adhesives generally develop their adhesive properties only when intimately mixed. Departing from the principle shown in FIG. 6 one can, if necessary, replace pair of rolls 13 or 14 by a mixing apparatus (not shown) for first mixing the two components and then applying them jointly in the way customary for the expert. The other pair of rolls is then omitted in this embodiment.
FIG. 7 shows a further possibility for producing the inventive security element. This method corresponds substantially to the production method of FIG. 4 only that security element carrier 10 supplied by roll 11 is completely fixed to substrate 1 here, i.e. no transfer band is removed. As already mentioned at the outset such an embodiment is useful in cases where the security elements have sufficient inherent stability (stable relief foil), or one desires increased protection from mechanical loads by providing an additional protective layer (additional protective layer instead of transfer carrier foil).
FIG. 8 shows a variant of reaction inventive security document 1 . In this case security element 9 comprises layer of lacquer 20 in which the diffraction structures are embossed in the form of a relief, thin reflective layer 3 , preferably a metal layer, and layer of protective lacquer 21 . Here too element 9 can have the form of a thread or band or else be formed as a mark with certain contour shapes, depending on the requirements. Embossed layer of lacquer 20 consists according to the invention of a reaction lacquer, in particular a UV-initiated delayed-curing or a blue light-curing lacquer, as were already explained. Layer of protective lacquer 21 protects the sensitive embossed structure and metal layer 3 from outside environmental influences and mechanical impairment. It is preferably made of a material chemically homogeneous with layer of reaction lacquer 20 to form a firm compound with layer of lacquer 20 in the area of microcracks or pores in the metal layer.
In contrast to the security document shown in FIG. 1 security element 9 is produced directly on the document in this embodiment. The various procedures permitting simple and cost-effective production of this security document will be explained in more detail with reference to FIGS. 9 and 10.
In FIG. 9 a blue light-curing reaction adhesive, e.g. the abovementioned acrylate LCR-0603B, is applied by means of printing unit 18 to paper substrate 1 in the desired form of later security element 9 , possibly all over. The pretreated paper is then fed to an embossing unit, here embossing cylinder 22 . The surface of the embossing cylinder has holographic relief structure 23 which is transferred upon contact with the layer of reaction lacquer. During the embossing process the reaction lacquer is cured within seconds through the paper layer with the aid of blue light 17 . In following method steps not shown in the figure the metalizing or protective lacquer coating is performed.
Alternatively the embossing roll can be provided with the reaction lacquer instead of paper web 1 . After irradiation with blue light the cured embossed layer adheres to the paper and is removed from the embossing roll.
FIG. 10 shows a similar method in which a delayed-curing (cationically cured) reaction lacquer is used for the layer to be embossed. In this case the layer of reaction lacquer applied to the paper is irradiated shortly before the embossing unit. The exposure to UV light only initiates polymerization reaction and does not cause complete curing of the reaction lacquer. The still formable layer of reaction lacquer is then provided with relief structure 23 by being brought in contact with embossing cylinder 22 . When substrate web 1 leaves the embossing unit the layer of reaction lacquer is completely crosslinked and can be processed further in the conventional way.
It is of course also possible in this embodiment example to apply the delayed-curing reaction lacquer to the embossing roll, partially activate it there and finally bring it in contact with the paper during the final curing process.
The described methods thus permit simple production of a security element very resistant to forgery having a minimum of element layers and thus requiring very few method steps for its production, and can furthermore dispense with complicated, cost-intensive techniques.
A further method variant is to provide the embossing roll as shown in FIGS. 9 and 10 with a metalized layer before it is brought in contact with the layer of reaction lacquer. More details of this procedure can be found in EP-A 0 563 992.
Since particularly antifalsification papers frequently have great surface roughness which might impair the effectiveness of the diffraction structures the paper can, if necessary, be glazed in the area of the security element before lacquering by additional measures, as are described in EP-A 0 440 045.
It is also evident that any desired combinations of reaction adhesives lacquers can be used for the embossed layer and the adhesive layer in the case of the transferred embossed hologram. The same holds for the embossed or protective layer of the hologram produced directly on the document.
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A transfer foil for use in a safety document includes a multilayer structure having a carrier layer and a plastic layer in which diffraction structures, for example holographic structures, are embossed in the form of a relief structure and which is combined with a reflective layer. The plastic layer includes a reaction lacquer layer selected from the group consisting of cationical curing lacquers, blue light-curing lacquers and chemical curing multicomponent lacquers.
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[0001] This application is the US National Stage of International Application No. PCT/EP2007/064347, filed Dec. 20, 2007 and claims the benefit thereof. The International Application claims the benefits of European Patent Office application No. 06026683.0 EP filed Dec. 22, 2006, both of the applications are incorporated by reference herein in their entirety.
FIELD OF THE INVENTION
[0002] The invention relates to a cooling channel and improvements in the regulation of the cooling flow for increased lifetime of a gas turbine engine and for the further diminishment of air pollution such as nitrogen oxides (NOx).
BACKGROUND OF THE INVENTION
[0003] In gas turbine engines parts deal with high material temperatures making it usually necessary to provide cooling to these parts. Due to uneven heating, cooling needs to be adjusted.
[0004] Typically, a worst case map of hot-spots is established from calculations and with highly expensive experimental testing. The cooling system is designed to cope with this hot-spot map. Where the position of the hot-spot(s) is known and doesn't move significantly during operation, similar parts with varying cooling passages can be applied at the expense of standardization with effects on lead times and spares stocks.
[0005] However, the heating patterns cannot be established over all combinations of the variation of parameters, like inlet temperature and pressure, fuel type, quality and composition, or machine load, which will be experienced in service. Manufacturing variation can also lead to variation between nominally identical parts. Furthermore, service replacement and equipment wear can also change the heating patterns during the operating life of the equipment.
[0006] Therefore, robust design usually involves the use of more cooling air than is strictly necessary with impact on engine efficiency and thermal stresses between joined hotter and cooler areas of the cooled part which reduces life of the engine.
[0007] Other, dynamic approaches adjust cooling during operation relying on (failure-prone) sensors and valves with contact surfaces between parts in relative motion (subject to wear).
[0008] SU 726428 describes a device for controlling the flow as a function of the temperature of the flowing medium.
[0009] U.S. Pat. No. 2,763,433 describes L-shaped plates redirecting exhaust gas by closing and opening of an orifice as a function of the exhaust gas temperature flowing through a conduit.
[0010] U.S. Pat. No. 2,673,687 describes a so-called “duck bill” type valve for controlling and directing the flow of hot exhaust gases as a function of the temperature of the exhaust gases.
[0011] U.S. Pat. No. 4,245,778 describes a vent control arrangement for energy conservation having bimetallic damper elements mounted in a draft hood, the bimetallic damper elements having alternate bimetal reeds of different initial tension, or alternate orientations, or different flexibility.
[0012] U.S. Pat. No. 4,441,653 describes a thermally actuated damper for a furnace exhaust gas flue.
[0013] U.S. Pat. No. 6,039,262 describes a bimetallic actuator for heat transfer applications between a hot stream and a coolant stream.
SUMMARY OF THE INVENTION
[0014] An object of the invention is to provide a new cooling channel for an adjusted cooling of uneven heated parts of a gas turbine engine or other equipment dealing with high material temperatures.
[0015] This objective is achieved by a flow distribution regulation arrangement in a cooling channel, the flow distribution regulation arrangement comprising a plurality of bimetallic elements adapted to adjust a local flow of a cooling medium in the cooling channel in response to a heat load onto the bimetallic elements, wherein the heat load originates from local boundary sub areas of the cooling channel.
[0016] An inventive flow distribution regulation arrangement comprises bimetallic elements. These elements are formed from two materials with different expansion coefficients so that heating causes them to differentially bend away from or into the flow channel depending on their arrangement.
[0017] In a first advantageous embodiment, bimetallic elements are arranged on a cold wall of the cooling channel facing a hot wall of the cooling channel, the bimetallic elements reacting differentially to radiation from a hot-spot and the rest of the hot wall to divert coolant preferentially towards the hot-spot in increasing the cross-section where the hot-spot is located by bending away from the flow channel. This results in the cooling flows self-adjusting to reduce the hot-spot temperature and raise the temperature of the rest of the hot wall (usually overcooled) until the two temperatures approach each other.
[0018] Another advantageous embodiment is the use of a bimetallic element to uncover or enlarge an inlet port or ports which feed a cooling system. This may prove extremely valuable in the context of nozzle guide vane (NGV) blading cooling.
[0019] It is advantageous when an upstream end of the bimetallic elements relative to a cooling air flow is fixed to the cold wall of the cooling channel in order to constrain as little as possible the aerodynamics of the cooling flow.
[0020] An additional advantageous refinement involves limiting the thermal contact between the cold wall and bimetallic elements by using an air gap or low conductivity coating.
[0021] In a further advantageous embodiment bimetallic elements are arranged on the hot wall of a convective cooling channel to enhance coolant turbulent heat transfer preferentially towards the hotter spots. This will result in the cooling flows self-adjusting to reduce the hot-spot temperature. The movement of bimetallic strips into the convection flow in response to conduction received from the heated part has two effects. Firstly, the strips act as turbulators. The further they protrude, the higher is the turbulent heat transfer in their wake on the hot part. Secondly, due to the conduction, the strips themselves form a heat convection path to the coolant which will be more effective as they bend and protrude further into the flow.
[0022] One advantage of the inventive flow distribution regulation arrangement is the finer resolution achievable which means that the inventive cooling channel will save more air than a typical “active” control approach. This finer resolution results from the fact that multiple small elements can be applied rather than the “single valve” of other embodiments. The total cooling air in a gas turbine can be reduced with an increase in thermal efficiency of the cycle for the same maximum hot gas and material temperatures. Furthermore, if part of the cooling air which is economised is used for reducing the maximum hot gas temperature, pollutant emissions can be reduced.
[0023] Despite a finer spatial resolution than any of the adjustable prior art solutions the method of construction of the inventive flow distribution regulation arrangement is simple and efficient since it uses masking, coating and stamping, which are readily adaptable to many different sizes of parts, so the variable cooling can be made economically. The variable elements can be formed into various shapes for application to different components. For a can combustor, for instance, the coated, punched and formed sheet would be rolled into a tube for placing within the convective channel between the combustor liner and the cooling sleeve which surrounds it.
[0024] Against the prior art of using variants of similar parts for predictable varying heating environments, the inventive flow distribution regulation arrangement allows full standardization to be maintained so eliminating the possibility of mis-assembly and giving the usual standardization advantages of large production runs and smaller spares stocks.
[0025] Another advantage of the inventive flow distribution regulation arrangement, where a problem hot spot automatically activates the appropriate bimetallic element is the threefold increased reliability. Firstly, reducing (or even eliminating) thermal stresses between hotter and cooler areas of the same part can significantly increase part life. Secondly, avoiding contact surfaces between parts in relative motion improves reliability compared to actuator valve cooling adjustment systems. Thirdly, there is no need for a (failure-prone) sensor and control system to decide which actuator to operate and by how much.
[0026] The strips can be so designed as to lay flat against the surface in cold (non-operating) conditions so that removal is eased and the chances of accidental damage is minimized. Unlike most coolant control systems, the failure modes do not cause catastrophic failure. A first possible mode is that a strip becomes detached. If the strip is arranged on the cold side, the cross-section and the coolant flow would increase. If the strip is arranged on the hot side, this hot surface would then lie more exposed which compensates partially for the reduced cooling turbulence. A grid needs to be put at the end of the cooling channel to prevent the fugitive strips from entering the moving parts of the engine. A second possible mode is that a strip gets stuck in extended mode. If the bimetallic strip is arranged on the cold side, the surface facing that strip would then be cooled less at this point than surrounding surfaces with a life reduction similar to current practice. If the strip is arranged on the hot side, the corresponding surface is then overcooled. A third possible mode is that the strip gets stuck in down mode. If the bimetallic strip is arranged on the cold side, the surface facing that strip would then be overcooled. If the strip is arranged on the hot side, the surface would then be cooled less at this point than surrounding surfaces with a life reduction similar to current practice.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The invention will now be further described, with reference to the accompanying drawings in which:
[0028] FIG. 1 is a sectional view of part of a combustor can with bimetallic strips arranged on the cold side of a flow distribution regulation arrangement in a cooling channel;
[0029] FIG. 2 is an axial view of the combustor shown in FIG. 1 ;
[0030] FIG. 3 is a sectional view of a nozzle guide vane with almost covered inlet openings;
[0031] FIG. 4 is a sectional view of a nozzle guide vane at higher temperature than in FIG. 3 with uncovered inlet openings;
[0032] FIG. 5 is a sectional view of part of a combustor can with bimetallic strips arranged on the hot side of a cooling channel;
[0033] FIG. 6 is an axial view of the combustor shown in FIG. 5 ;
[0034] FIGS. 7 to 18 show the process of manufacture by coating; and
[0035] FIGS. 19 to 23 show the process of manufacture by fabricating.
[0036] In the drawings like references identify like or equivalent parts.
DETAILED DESCRIPTION OF THE INVENTION
[0037] Referring to the drawings, FIG. 1 shows a part of a combustor can of a gas turbine engine with a flow distribution regulation arrangement in a cooling channel 1 .
[0038] The cooling channel 1 is defined by a combustor liner 6 and a cooling sleeve 5 surrounding the combustor liner 6 . Bimetal strips are arranged on the cold wall of the cooling sleeve 5 . A local boundary sub area 4 of the combustor liner 6 is hotter than the surrounding area. The bimetal strip facing this hot spot 7 moves out of the convection air flow in response to radiation received from the hot spot 7 . The cross-section 3 of the cooling channel 1 is enlarged relative to colder sub areas like on the left hand side of FIG. 1 and the amount of on-rushing cooling air is increased.
[0039] FIG. 2 shows a different view on the flow distribution regulation arrangement in a combustor can. Looking in the axial direction of the combustor can is best to describe the functional principle of the inventive flow distribution regulation arrangement in a cooling channel 1 . The bimetal strips facing a hot spot 7 move out of the convection air flow in response to the radiation received. Coolant flow is diverted preferentially to the hot spot 7 increasing the throughput of coolant to reduce the hot spot 7 temperature while the rest of the hot wall is cooled less.
[0040] FIG. 3 shows a section through a nozzle guide vane 9 (NGV) comprising a leading edge 15 , a trailing edge 16 with openings 24 , a first part of a coolant metering plate 11 with first openings 12 and a bimetal strip 23 close to the leading edge 15 anchored at one end (anchor point 17 ) and having a second part of a metering plate 13 with second openings 14 at the far end. The first and second openings 12 , 14 of the first and second parts of metering plates 11 , 13 hardly overlap, so that the inlet port 10 is almost closed. Only a little cooling air can enter the nozzle guide vane 9 and exhaust from the trailing edge 16 .
[0041] The hottest part of the nozzle guide vane 9 is typically the leading edge 15 . FIG. 4 shows a bimetal strip 23 bending towards the leading edge 15 due to increased temperature radiation received from the leading edge 15 , thereby sliding the second part of the metering plate 13 to the left and increasing the overlap of first and second openings 12 , 14 of the first and second parts of the metering plate 11 , 13 to let more cooling air enter the nozzle guide vane 9 . The hotter a nozzle guide vane 9 , the larger the coolant flow 8 , thus equalizing the temperature of all similar nozzle guide vanes 9 on a ring.
[0042] FIG. 5 shows part of a convective channel between a combustor liner 6 and a cooling sleeve 5 which surrounds it. Bimetallic elements 2 of a flow distribution regulation arrangement are arranged with their downstream end relative to a coolant flow on the hot side, i.e. on the combustor liner 6 and protrude into the convective cooling channel 1 . The bimetallic element 2 in the centre is in “normal” position. The left-most bimetallic element 2 is in “hot” position and protrudes deeper into the cooling channel 1 thereby inducing more coolant turbulence and thus additional heat conduction and convection over the hot spot 7 . The right-most bimetallic element 2 is in “cold” position where it hardly protrudes into the cooling channel 1 thereby reducing the coolant convective heat transfer over the “cold” spot.
[0043] FIG. 6 shows the same arrangement as FIG. 5 with a different perspective looking along an axial direction of the combustor can. The bimetal strips at hot spots 7 move into the convection air flow in response to the radiation received, thus increasing the turbulence and heat conduction over the hot spot 7 .
[0044] FIGS. 7 to 18 show the process of manufacturing a part of a flow distribution regulation arrangement in a cooling channel 1 supporting bimetallic elements 2 as a coating on a shell 21 . Figures with even numbers are side views on shells 21 cut along the indicated dashed-dotted lines shown in the respective preceding Figures. FIGS. 7 and 8 show the masking of areas where the bimetallic strips 23 shall detach from the shell 21 . FIGS. 9 and 10 show the shell 21 after a first coating with a base material 19 . FIGS. 11 and 12 show the arrangement of second masks 18 on top of the first masks 18 along three edges of the first masks 18 to allow the formation of strips in the next step shown in FIGS. 13 and 14 , where again base material 19 is applied. After this, a mask 18 with cut-outs for the second material of the bimetallic strips 23 is applied as shown in FIGS. 15 and 16 . Once the second material of the bimetallic strips 23 has been applied, the masks 18 are dissolved to release the bimetallic strips 23 . The end-product is shown in FIGS. 17 and 18 .
[0045] The strips can alternatively be formed by masking, coating and stamping a separate substrate layer which is then welded or brazed to a part of the gas turbine engine, for instance a shell 21 , at suitable points as shown in FIGS. 19 to 23 . This has the advantage that the bimetallic strips 23 and the mentioned part of the gas turbine engine can be manufactured in parallel, reducing lead time, and may permit a more robust bimetallic strip 23 . The masking and coating sequence is also simplified compared to the procedure shown in FIGS. 7 to 18 . FIG. 19 shows a stamped out strip pattern in a substrate. The substrate is then masked 18 on both sides as shown in FIG. 20 . On one side a second part 20 of the material for bimetallic elements 2 is applied as shown in FIG. 21 . On the other side, a braze material 22 is applied. FIG. 22 shows the result after having resolved the masks 18 . The substrate is then brazed together with a shell 21 as shown in FIG. 23 .
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A flow distribution regulation arrangement in a cooling channel is provided. The flow distribution regulation arrangement includes a plurality of bimetallic elements adapted to adjust a local flow of a cooling medium in the cooling channel in response to a heat load onto the bimetallic elements, wherein the heat load originates from local boundary sub areas of the cooling channel.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This patent application is the U.S. national phase, under 35 USC 371, of PCT/DE03/01330, filed Apr. 24, 2003; published as WO 03/097359 A1 on Nov. 27, 2003 and claiming priority to DE 102 22 294, filed May 18, 2002, the disclosures of which are expressly incorporated herein by reference.
FIELD OF THE INVENTION
The present invention is directed to dampening systems with devices for the inflow and for the return flow of a dampening agent. The dampening system includes at least one dampening ductor, a dampening agent tank, an inflow device and a return flow device.
BACKGROUND OF THE INVENTION
Dampening systems are used in offset printing presses and in other printing systems. A dampening system consists of, for example, a dampening ductor, which may also be called a water tank roller, a dampening agent tank, and devices for supplying and returning dampening agent to and from the dampening agent tank. The dampening ductor or roller is typically partially immersed in the dampening agent contained in the dampening agent tank, picks up the dampening agent by a rotating movement, and transfers the dampening agent to further rollers of the printing group. To prevent interferences with the printing operation, it is important that the dampening agent taken up by the dampening ductor or roller has identical physical and chemical properties over the entire length of the roller.
A dampening system in an offset printing press is described in DE 198 53 362 C1. A supply system for dampening agent, which has a plurality of spray nozzles over the roller length, is assigned to the dampening ductor in the axial direction of the ductor.
A dampening system is known from DE 196 16 198 A1, which system has at least one dampening agent pickup roller. A dampening agent supply line is arranged above the dampening agent pickup roller, parallel with this roller, and extends over the roller's full length. On its underside, the supply line is provided with outlet openings, by the use of which a water curtain is formed when the supply line is charged with dampening agent.
For use in removing deposits, such as ink particles, for example, from a dampening ductor or roller, DD 247 414 A1 proposes to press a stripping element against the surface of the roller with a pressure which is equal over the entire length of the roller.
A dampening agent recirculating system for offset printing presses is described in EP 0 638 417 A1. In this case, a dampening agent supply line, with hole-shaped cutouts, and a dampening agent catch rod, which is situated at a defined small distance from the dampening ductor, are positioned parallel to the dampening ductor or roller.
DE 94 20 343 U1 shows a dampening system, whose dampening agent tank has an inflow line with several openings. A return conduit, having a weir, extends over the entire length of the dampening agent tank.
DE 199 09 262 A1 describes a dampening agent tank with a dam for limiting the return flow of the dampening agent. A filter has been installed between this dam and a return flow line.
DE 38 31 741 A1 discloses a dampening agent tank with several inflow lines and with several return flow lines.
DE 17 61 908 A discloses an adjustable dampening supply device.
SUMMARY OF THE INVENTION
The object of the present invention is directed to providing dampening systems with dampening agent inflow and return flow devices.
In accordance with the present invention, the object is attained by the provision of a dampening system having at least one dampening fluid ductor or roller, a dampening agent tank, an inflow device and a return flow device. The inflow device has several distributing tubes, each typically with several openings, that are assigned to the ductor. At least one inflow line of the distributing tube is arranged between last openings of first and second ends of the distributing tube. The return flow device has a collecting tank that is connected with the dampening agent tank, which collecting tank extends in the longitudinal direction of the ductor and is double walled.
The advantages to be gained by the present invention consist, in particular, in that the dampening ductor or roller is arranged in the dampening agent tank between the inflow device and the return flow device for the dampening agent. The inflow device and the return flow device are configured in such a way that the inflow and the return flow of the dampening agent in the area of the dampening ductor are both distributed to several locations. In the course of conducting new or fresh dampening agent from a dampening agent reservoir to the dampening agent tank, uneven intermixing of newly supplied dampening agent with dampening agent already present in the dampening agent tank can occur at some locations in the dampening agent tank. Areas of the dampening agent tank, in which little intermixing takes place, can heat up and can have a temperature which is higher, by up to 10° C., in comparison with areas of the dampening agent tank in which a constant exchange between newly supplied dampening agent with the dampening agent already present in the dampening agent tank takes place. Since the viscosity of the dampening agent depends greatly on the temperature of the dampening agent, and since the print quality, in turn, depends greatly on the viscosity of the dampening agent, the dampening agent taken up from the tank by the dampening ductor must be substantially at the same temperature level over the entire length of the dampening ductor.
The present invention is directed to the provision of a dampening system wherein a uniform exchange of dampening agent takes place substantially over the entire length of the area of the dampening ductor.
This objective is achieved in accordance with the present invention because several locations for the inflow of dampening agent, called dampening agent inflow locations, are assigned to the front of the dampening ductor, and several locations for the return of dampening agent, called dampening agent return flow locations, are assigned to the rear of the dampening ductor. Thus, the dampening ductor is located in the area of a flow of dampening agent which is formed by both the inflow and the return flow of the dampening agent into or out of the dampening agent tank. The locations for the inflow and for the return flow are matched to each other in such a way that a uniform intermixing of newly supplied dampening agent with that already present in the dampening agent tank takes place in the area of the dampening ductor and over its entire roller length. In this way, it is possible, for example, to match the spatial arrangement of the inflow and return flow locations among or between each other.
A further possibility resides in the configuration of the inflow and of the return flow locations themselves, such as, for example, their geometry, shape and/or diameter. It would also be possible to cause uniform intermixing by a suitable distribution of the charging pressure at the dampening agent inflow locations. In actual use, a combination of these various possibilities will result, wherein the actual configuration will have to be determined by empirical tests. In connection with the principle of uniform intermixing of dampening agent, such as water, in the area of the dampening doctor blade over its entire length, it is important that, on the one hand, that dampening agent is supplied at several locations in the area of the dampening ductor and, on the other hand, dampening agent is returned at several locations in the area of the dampening doctor blade in order to assure a continuous exchange of dampening agent in the area of the dampening ductor.
In accordance with a preferred embodiment of the present invention, the dampening agent inflow device is arranged at the dampening agent tank as a separate component. This is of particular advantage if the inflow device must periodically be disassembled, for example because it has become damaged or dirty. In the present case, it is then possible to remove the inflow device, embodied as a separate component, in a simple and cost-effective manner from the dampening agent tank. Thus, a more cost-intensive disassembly of the entire dampening agent tank is not necessary.
The dampening agent inflow line is attached substantially at the center of the inflow device. This has the advantage that, following the charging of the inflow line with dampening agent, an almost identical dampening agent pressure prevails at all of the dampening agent inflow locations of the inflow device. In this way, a pressure drop, as is the case when the inflow line is located on one side of the inflow device, is clearly reduced.
To minimize interference effects of the dampening agent flow in the dampening agent tank, it would be sensible to arrange the tubes of the dampening agent inflow line at the side of the dampening agent tank. At the same time, it is conceivable to use the inflow line as a support for the inflow device. This allows a simple and a cost-effective configuration of the inflow line and the inflow device.
It is of no importance, for the principle of the invention, in which way the inflow device is configured. It is thus possible, for example, to configure the inflow device as a hollow conductor, such as a round tube, for example.
To provide dampening agent to the dampening agent tank, uniformly distributed over the entire length of the dampening ductor, it is practical for the dampening agent inflow locations, which are embodied as either circular or rectangular cutouts, to be arranged over the entire length of the hollow conductor and to be evenly spaced apart from each other. A further possibility lies in providing a rectangular cutout for the passage of the dampening agent in the hollow conductor, which rectangular cutout extends substantially over the entire length of the hollow conductor.
In connection with dampening ductors of great length it is not as possible to provide a uniform pressure at all of the dampening agent inflow locations available, even with a central inflow of the dampening agent into the inflow device, which is embodied as a hollow conductor. In this case, it would be sensible for the inflow device to consist of at least two hollow conductors, which are arranged one behind the other in the longitudinal direction. Each one of these hollow conductors may be separately provided with dampening agent by the use of an inflow line and wherein the two hollow conductors are functionally separated from each other.
In accordance with a further preferred embodiment, the return flow device consists of at least two cutouts which are arranged in the bottom of the dampening agent tank, and through which the dampening agent can be returned from the dampening agent tank to the dampening agent reservoir. To achieve a uniform removal of the dampening agent from the dampening agent tank it would furthermore be appropriate to arrange the cutouts so that they are parallel with respect to the longitudinal axis of the dampening ductor. A return flow device configured in this way can be accomplished in a particularly simple and cost-effective manner.
It is particularly advantageous, in accordance with the present invention, if the return flow device has a comb-shaped component which is arranged upstream of the cutouts in the bottom of the dampening agent tank. The comb shape of the component is constituted by alternating areas of tooth-shaped elevations and indentations, wherein a cutout in the bottom of the dampening agent tank is assigned to each indentation area. The comb-shaped component is arranged parallel with respect to the longitudinal axis of the dampening ductor. The comb-shaped component extends over the entire length of the dampening doctor blade, and the tooth-shaped elevations point vertically upward. A type of increase of the cross section of this area is accomplished by the provision of the indentations, because of which increase the dampening agent can preferably flow into the cutouts arranged downstream of the indentations and is removed in this way, from the dampening doctor blade over the entire length of the latter.
Due to the large temperature difference between the dampening agent and the ambient air it would be prudent to configure the lines for the inflow and for the return flow of the dampening agent into or out of the dampening agent reservoir to be double-walled to achieve some sort of thermal disconnection between the lines conducting dampening agent and the ambient air. Without a thermal disconnection, any moisture contained in the air can condense on the lines charged with dampening agent. Drops of condensate are formed, which drops can settle, for example, in the area of the printing group and/or onto the web of material to be imprinted, which drops can also lead to interference with the printing operation.
The hollow space of the double-walled inflow and return flow lines is filled with an insulative foam.
To match the temperature of the new dampening agent supplied from the dampening agent reservoir, in particular in such a way that the dampening agent received on the dampening doctor blade over its entire length has substantially the same temperature, it would be beneficial for a temperature measuring device to be provided in the area of the dampening agent doctor blade in at least two locations. The temperature measuring device can be coupled with a control and/or with a regulating device, by the use of which, the temperature of the supplied dampening agent is regulated.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention are represented in the drawings and will be described in what follows.
Shown are in:
FIG. 1 , a side elevation view, partly in cross-section, of a preferred embodiment of a dampening system with a dampening agent tank, a dampening ductor and devices for the inflow and return flow of dampening agent in accordance with the present invention, in
FIG. 2 , a front view, partly in cross-section, of a first preferred embodiment of a dampening system in accordance with FIG. 1 and taken in the sectional direction A shown in FIG. 1 , and without the comb-shaped component, in
FIG. 3 , a front view, partly in cross-section of a dampening system in accordance with FIG. 1 in the sectional direction B shown in FIG. 1 and without the dampening ductor, and in
FIG. 4 . a front view, partly in cross-section of a second preferred embodiment of a dampening system in accordance with the present invention, also taken in the sectional direction as shown in FIG. 1 and without the comb-shaped component.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A dampening system in accordance with the present invention, with devices for accomplishing the inflow and the return flow of a dampening agent 01 into or out of a dampening agent tank 02 , is represented in FIG. 1 . A dampening ductor or roller 03 is attached between an inflow device 04 , as seen in FIG. 2 , and a return flow device 06 . The inflow device 04 is arranged opposite the front side of the dampening ductor 03 .
For improved understanding it should be pointed out at this juncture that the inflow device 04 consists of at least one distributing tube 18 with several openings 07 . This is shown most clearly in FIG. 2 and also in FIG. 4 which shows two such distributing tubes 18 , each with several openings 07 .
In the present preferred embodiment, each distributing tube 18 is provided as a separate component in the dampening agent tank 02 , as represented in FIG. 2 and in FIG. 4 , and is preferably substantially located completely below the liquid level of the dampening agent 01 . Moreover, each distributing tube 18 is embodied as a hollow conductor 18 in the form of a round tube 18 and has an interior tube diameter of approximately 10 mm to 20 mm, and in particular has a diameter of 12 mm. A longitudinal axis of each distributing tube 18 extends parallel with a longitudinal axis of the dampening ductor 03 . The length of the distributing tube or the distributing tubes 18 extends substantially over the length of the dampening ductor 03 .
As can also be seen by referring to FIG. 2 , the dampening agent inflow locations 07 , which are embodied as circular cutouts 07 , are arranged over the entire length of the distributing tube 18 . These circular cutouts 07 point or face in a direction toward the dampening ductor 03 . By charging the distributing tube 18 with dampening agent 01 , this dampening agent 01 can then exit through the dampening agent inflow locations 07 , so that dampening agent 01 is supplied to the dampening agent tank 02 substantially over the entire length of the dampening ductor 03 . The distal ends of the distributing tube 18 are each closed, so that no dampening agent 01 can flow out of them. In the present preferred embodiment, the circular cutouts 07 are spaced at equal distances from each other and all have the same diameter. The diameter of each of the circular cutouts 07 lies, for example, within a range of from 1 mm to 5 mm, and is, in particular, 3 mm.
The cross section or area of each of the circular cutouts 07 corresponds to approximately 25% of the diameter of the round tube 18 .
The flow path of the dampening agent 01 between the distributing tube or tubes 18 and the dampening ductor 03 is identical over the entire length of the dampening ductor 03 because of the parallel orientation of the dampening ductor 03 and the distributing tube or tubes 18 . Because the plurality of dampening agent inflow locations 07 are arranged opposite the dampening ductor 03 over substantially its total length, it is possible to supply the dampening agent tank 02 uniformly with dampening agent 01 over substantially the entire length of the dampening ductor 03 .
Each distributing tube 18 is provided with dampening agent 01 from a dampening agent reservoir, which is not specifically represented, through an inflow line 08 . As seen in FIG. 1 , this inflow line 08 can be a double-walled hollow conductor filled with an insulative foam 10 . To achieve a substantially uniform pressure of the newly supplied dampening agent 01 arriving at all of the dampening agent inflow locations 07 of each distributing tube 18 , embodied as a round tube 18 , and flowing into the dampening agent tank 02 to mix with the dampening agent 01 already in tank 02 , each inflow line 08 is arranged centered along the length of its associated distributing tube 18 . In contrast to a one-sided inflow of the dampening agent 01 into the distributing tube 18 , with the length of the distributing tube 18 being the same, the dampening agent 01 travels over a substantially shorter flow path before exiting through the dampening agent inflow locations 07 . Moreover, with the inflow line 08 arranged in the center of the distributing tube 18 , and with an identical number of dampening agent inflow locations 07 , only approximately half as many of the dampening agent inflow locations 07 are arranged in series one behind the other in comparison to the orientation that would exist in a one-sided inflow. Because of this configuration, a considerably reduced pressure difference between dampening agent inflow locations 07 spaced far apart from each other, and thereby a substantially identical pressure of the outflowing dampening agent, can be achieved at all dampening agent inflow locations 07 .
In the present preferred embodiment, the dampening agent inflow line 08 is embodied in the form of a bent round tube 08 , which is either of one piece construction, or which can consist of several components, which are, for example screwed together, welded together or hard-soldered. The connection between the distributing tube 18 and the inflow line 08 can also be provided by a screw connection, a welded connection or a hard-soldered connection. The inflow line 08 at the same time takes on the function of a support for the distributing tube 18 , so that a separate frame for holding the distributing tube 18 in the dampening agent tank 02 can be omitted. In order not to negatively affect the essential function of the dampening system, which could be the case if, for example, the flow of the dampening agent 01 through the tubes of the inflow line 08 were interfered with, the inflow line 08 runs on the side of the dampening agent tank 02 adjacent the bottom of the dampening agent tank 02 .
In a further preferred embodiment, which is represented in FIG. 4 , several distributing tubes 18 can be assigned to the dampening ductor 03 . Each one of these several distributing tubes 18 has its own inflow line 08 .
At least one inflow line 08 of the distributing tube 18 is arranged between a last opening 07 of a first distal end and a last opening 07 of a second distal end of the distributing tube 18 . The inflow line 08 is, in particular centered along the length of the distributing tube 18 . In the case of several inflow lines 08 for a single distributing tube 18 , these several inflow lines 18 are arranged approximately uniformly distributed in relation to the longitudinal direction of the distributing tube 18 .
The two last openings 07 of the distal ends of the distributing tube 18 are spaced at a distance I 01 from each other, as seen in FIG. 2 . A further distance 102 is defined between the last opening 07 and the inflow line 08 .
The following relationship applies: I 02 = I01 / N+1′ wherein N is the number of inflow lines 08 , and I 01 is the spacing between the two last openings of the distributing tube 18 .
For a distance I 03 between two inflow lines 08 the following applies: I 03 ≠ I01 / N+1′ wherein N is the number of inflow lines 08 , and I 01 is the spacing between the two last openings of the distributing tube 18 .
The openings 07 of the distributing tube 18 are arranged below the surface level of the dampening agent 01 in the dampening agent tank 01 , i.e. within the body of the dampening agent 01 . The inflow lines 08 are also arranged, from the side of the dampening agent tank 02 to the center of the distributing tube 18 , within the dampening agent 01 .
The inflow line 08 of each distributing tube 18 is arranged, at least in part, in the longitudinal direction of the dampening ductor 03 within the dampening agent. This may be seen most clearly in FIG. 2 and also in FIG. 4 .
The return flow device 06 has a double-walled collecting tank 16 . Collecting tank 16 is connected with the dampening agent tank 02 and extends in the longitudinal direction of the dampening ductor or roller 03 , as is seen in FIG. 1 . This longitudinal extension of the collecting tank 16 can also be seen in FIG. 3 .
The return flow device 06 is arranged in the dampening agent tank 02 opposite to the rear of the dampening ductor 03 . In the depicted embodiment, the return flow device 06 consists of two components, namely cutouts 09 which are located in the bottom of the dampening agent tank 02 for the return flow of the dampening agent 01 which was carried out of the area of the dampening ductor 03 , and a comb-shaped component 12 , which has been placed upstream of the cutouts 09 . The cutouts 09 , which may be formed as circles, have a diameter of from 10 mm to 30 mm, and in particular of 23 mm. The comb-shaped component 12 is oriented parallel with the longitudinal axis of the dampening ductor 03 and extends over the entire width of the dampening agent tank 02 . In the same way, the downstream located cutouts 09 , formed on the bottom of the dampening agent tank 02 , are also arranged parallel with the longitudinal axis of the dampening ductor 03 and extend substantially over the entire length of the dampening ductor 03 .
The dampening system, in the area of the return flow device 06 , is represented in FIG. 3 , in the cross-sectional direction B and without the dampening ductor 03 . The comb-shaped component 12 and the cutouts 09 arranged in the bottom of the dampening agent tank 02 can be seen in this cross-sectional front elevation view. The comb-shaped component 12 is mounted on the bottom of the dampening agent tank 02 and is oriented perpendicularly with respect to it. In the present preferred embodiment, the comb-shaped component 12 is embodied in the form of a comb plate 12 with tooth-shaped elevations 13 . The tooth-shaped elevations 13 each have a linear extension of from 100 mm to 300 mm, in particular of 200 mm. The elevations 13 , in the form of teeth, are formed so that dampening agent return flow locations 14 , which are substantially embodied by incisions 14 , formed in the top of the comb-shaped plate 12 , are open at the top of plate 12 and are extending parallel to each other, and with rectangular and/or triangular and/or curved bottom transitions. The incisions 14 , as well as the alternating tooth-shaped elevations 13 , are located below the liquid level of the dampening agent 01 in the dampening agent tank 02 . The dampening agent 01 coming from the dampening ductor 03 can flow out of the tank 02 over the entire length of the comb-shaped component 12 . However, a sort of a cross-sectional flow volume increase takes place in the area of each incision 14 , because of which flow volume increase, flowing off dampening agent 01 is conducted out of the area of the dampening ductor 03 preferably in the respective areas of the incisions 14 . A separate cut-out 09 in the bottom of the dampening agent tank 02 is assigned downstream of each incision 14 in the comb plate 12 , and through which cut-out 09 the dampening agent 01 is conducted out of the dampening agent tank 02 into a collecting tank 16 . It is assured by this that in the area of each incision 14 , the dampening agent 01 can flow off unhindered. The dampening agent 01 that flows out of the dampening agent tank 02 , is returned from the collecting tank 16 to the dampening agent reservoir through one return line 11 , as seen in FIG. 2 , or through two such return lines 11 , as seen in FIG. 4 . Each such return line 11 is also a double-walled line with the hollow space being filled with insulative foam 10 , in a manner similar to that which was discussed previously in connection with each inflow line 08 . The collecting tank 16 extends in the longitudinal direction of the dampening ductor 03 , as seen in FIG. 3 , and extends, in the transverse direction of the tank 02 and the ductor 03 , at a fraction of the width of the dampening agent tank 02 . The collecting tank 16 has double walls defining a space which is filled with an insulative foam 20 , as seen in FIGS. 1 and 3 . The incisions 14 in the comb plate 12 , as well as the cutouts 09 in the bottom of the dampening agent tank 02 , are spaced apart from each other at equal distances and extend over the entire length of the dampening ductor 03 . The distance between the tooth-shaped elevations 13 is from 1 mm to 20 mm, and in particular is 5 mm. By the arrangement of the incisions 14 in the comb plate 12 and by the respectively arranged downstream cutouts 09 in the bottom of the dampening agent tank 02 , it is possible to remove dampening agent 01 from the area of the dampening ductor 03 substantially over the entire length of the dampening ductor 03 .
Analogous to the geometric conditions in the area of the inflow device 04 , the return flow path of the dampening agent 01 between the dampening ductor 03 and the return flow device 06 is also uniform over the entire length of the dampening ductor 03 . This is because of the parallel arrangement of the dampening ductor 03 and the return flow device 06 . Because the dampening agent return flow locations 09 , 14 are arranged opposite each other, over substantially the entire length of the dampening ductor 03 , dampening agent 01 , coming from the direction of the dampening ductor 03 , can be removed from the area of the dampening ductor 03 uniformly over the entire length of the dampening ductor 03 .
Since the longitudinal axes of the inflow device 04 and of the return flow device 06 extend substantially parallel with respect to the longitudinal axis of the dampening ductor 03 , and to each other, and because the dampening agent inflow locations 07 are arranged on the front and dampening agent return flow locations 09 , 14 are arranged on the back of, and substantially opposite the dampening ductor 03 , and extending over the entire length of the dampening ductor 03 , and further because of the substantially uniform charging with pressure of all of dampening agent inflow locations 07 , it is possible, in a simple way, in accordance with the present invention, to supply dampening agent 01 to the dampening ductor 03 over its entire length and to uniformly remove dampening agent 01 . This means that identical flow conditions prevail for both inflowing and outflowing dampening agent 01 over the entire roller length, so that a uniform intermixing of freshly supplied, inflowing dampening agent 01 , with dampening agent 01 already present in the dampening agent tank 02 can take place over the entire roller length. A uniform exchange of dampening agent 01 is thus assured over the entire roller length. The uniform, equal exchange of dampening agent 01 is additionally aided by setting the direction of rotation 17 of the dampening ductor 03 to be the same as the flow direction of the dampening agent 01 , as seen in FIG. 1 . Because of the even intermixing of new, inflowing dampening agent with dampening agent 01 already present in the dampening agent tank 02 , the dampening agent 01 picked up by the dampening ductor 03 has identical physical and chemical properties over the entire length of the dampening ductor 03 . In addition, to match the temperature of the new dampening agent supplied from the dampening agent reservoir, temperature measuring devices 22 , 23 are provided in the area of the dampening agent doctor blade 03 in at least two locations, as seen in FIG. 1 . The temperature measuring devices 22 , 23 are coupled with a control or regulating device 24 . The temperature of the dampening fluid can be regulated or controlled using the control or regulating device 24 in response to the dampening fluid temperature measured by the temperature measuring devices 22 , 23 .
In place of the cutouts 09 in the bottom of the dampening agent tank 02 , it is also possible to, for example, arrange an additional separating wall, with cutouts 09 , between the dampening agent tank 02 and the collecting tank 16 .
The size of the inflow and of the return flow at the respective dampening agent inflow locations 07 and at the dampening agent return flow locations 09 , 14 can be adjusted.
While preferred embodiments of dampening systems having a dampening agent feeding and return device, in accordance with the present invention, are set forth fully and completely hereinabove, it will be apparent to one of skill in the art that various changes in, for example, a drive source for the ductor, the specific constituency of the dampening fluid, and the like could be made without departing from the true spirit and scope of the present invention which is accordingly to be limited only by the following claims.
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A dampening system has at least one dampening ductor or roller; a dampening agent bin or trough, which holds a dampening agent, a feeding device, and a return device. The feeding device includes at least one dampening agent distributing pipe that has a number of spaced openings. A number of these dampening agent distributing pipes are assigned to the dampening ductor or roller.
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FIELD OF THE INVENTION
This invention is directed to the making of all porcelain dental prosthetic restorations.
BACKGROUND OF THE INVENTION
Heretofore, porcelain type dental prosthetic restorations, such as used for crowns, bridges and the like, comprised a restoration consisting of a metallic form or cast which was veneered with a porcelain coating or layer. The metal cast was generally formed of metal such as gold, silver, platinum and/or alloys thereof. Subsequently, the metallic cast portion of a porcelain restoration was made from less expensive base metal alloys of chrome, cobalt, nickel or the like, to which the porcelain was applied and thereafter fired to vitrification under vacuum at temperatures ranging between 1600°-2200° F. While the metal based porcelain restorations were effective, all porcelain restorations are esthetically preferable. However, the forming of all porcelain restorations presented a number of problems distinct from those encountered in making the metal-porcelain restorations.
The making of all porcelain restorations required the making of a die or mold of a suitable refractory material that could withstand the firing temperatures at which porcelain is required to be vitrified. A serious problem heretofore encountered with making all porcelain restorations was the difference in the thermal coefficient of expansion of the refractory material of the die and the porcelain material. This difference in the relative expansion and contraction rate upon heating and cooling of the die or mold and the porcelain cause the porcelain to either separate from the die and/or crack, thereby rendering the predictability of attaining a properly fitting porcelain restoration very uncertain. The problem in achieving a properly fitting all porcelain restoration was further aggrevated when a multiple tooth porcelain restoration was required, e.g., a bridge.
Because of the cracking and/or separation of the porcelain from the die or mold, it was heretofore necessary to effect the necessary repairs after firing and then refire the porcelain. Consequently, with the prior known techniques, repeated repairs and refirings were required. Oftentimes, as many as four, five or more firings were required before a satisfactory all porcelain restoration was achieved. Such numerous firings necessarily increased the overall cost, time and labor involved to fabricate a satisfactory all porcelain restoration.
To obviate some of the problems encountered in making all porcelain type restorations, there is disclosed in U.S. Pat. No. 3,453,756 the concept of utilizing hollow dowels or pins to compensate for the difference of thermal expansion encountered in making all porcelain restorations. It was also noted in this patent that the use of solid pins or dowels was not desirable, as such pins would stress and fracture the refractory die or mold during firing. However, the concept described therein has not, to my knowledge, achieved commercial acceptance and it is not known to be widely used or in use.
It is also known that dowel pins have been widely used in making stone does or molds, which are not subject to firing or used in making porcelain restorations. Dowels used for making stone dies or molds, which are not subjected to high temperatures, are generally formed of plastic or low temperature materials. An example of such dowel as used in a non-firing die or mold is evidenced in U.S. Pat. No. 4,139,943 granted Feb. 20, 1979.
Other examples of pins, posts or dowels as used in various dental procedures, which are not considered to be related to the making of porcelain restorations, are evidenced by U.S. Pat. Nos. 1,639,782; 1,867,300; 3,153,283; 3,541,688; 4,174,570; 4,398,884; 4,443,192; and 4,449,931.
OBJECTS
An object of this invention is to provide a technique for forming all porcelain dental prosthetic restorations which is relatively simple and positive in operation.
Another object is to provide for making a satisfactory all porcelain dental prosthetic restoration in a minimum number of firings.
Another object of this invention is to fabricate a die or mold of a phosphate bonded investment and having disposed therein a thermal conducting pin or pins for uniformly distributing the heat therethrough on heating and cooling.
Another object of this invention is to provide a specifically constructed pin or dowel that will optimize the distribution of heat through the die or mold and the porcelain material thereon in a manner that will minimize cracking and/or separation of the porcelain from the die at the interface thereof.
SUMMARY OF THE INVENTION
The foregoing objects, features and other advantages are attained by forming a die or mold, in preparation of forming an all porcelain restoration, of a phosphate bonded investment which includes a silicate filler and magnesium oxide mixed with ammonia and water. The phosphate bonded investment, when mixed, is poured into the wax or rubber impression which has been formed of a patient's teeth. Prior to the setting of the investment material, a pair of thermal conducting pins are inserted in the mold material. After the mold material has set, a second pour is made to form a base for the die mold, the base forming material being poured about the pins or dowels extending beyond the die. Prior to pouring the base material, the interface and pin extension are suitably lubricated or coated so as to render the pins readily releasable from the base material.
The dowel pins are specially constructed from high temperature metal which are structured so as to function as a heat sink for effecting generally uniform heating and cooling of the refractory material and the porcelain material. Preferably, each die or tooth configuration is provided with a matched pair of pins. The respective pins or dowels include an extended base portion which is slightly tapered inwardly toward its free end which extends into the mold base. The intermediate or other portion adapted to extend into the mold or die is serrated to provide a mechanical bond between the die and the pin. At least one of the matched pair of pins is provided with an extended portion arranged to transmit heat to a tip end of the die or mold. The arrangement is such that when a particular die or mold is fired to vitrify the porcelain thereon, that the dowel or pin will effect uniform heating and cooling of the die and porcelain thereon, whereby the mass of the pin effectively transmits the heat to and from the interior of the die in a rapid and uniform manner.
FEATURES
A feature of this invention resides in the provsiion of utilizing a phosphate bonded investment in conjunction with thermal conducting pins in fabricating the dies or mold on which an all porcelain dental porsthetic can be formed in a minimum of firings.
Another feature resides in the specific construction of solid high temperature dowels or pins for use in a die or mold for making porcelain dental prosthetics.
Other features and advantages will become more readily apparent when considered in view of the drawings and specifications in which:
FIG. 1 is a partial prospective view of a mold or die formed of a phosphate bonded investment for making all porcelain dental prosthetic restorations.
FIG. 2 is a perspective view of a matched pair of thermo conducting pins of this invention.
FIG. 3 is a detail sectional view through a single die mold.
FIG. 4 is a schematic view of a die embodying the invention during a firing operation.
FIG. 5 is a schematic view of the die mold of FIG. 4 during a cooling thereof.
DETAILED DESCRIPTION
Referring to the drawings, there is shown in FIG. 1, the mold or die construction for making an all porcelain dental porsthetic in accordance with this invention.
Referring to the drawing, there is shown therein a model or die 10 formed of a phosphate bonded investment embodying the invention. It will be understood that the mold or die is formed by first mixing a slurry of phosphate bonded investment which comprises a phosphate material with a silicate filler and magnesium oxide, ammonia and water. Such phosphate bonded investment is of the type which is sold under the name Austenal Inlay Investment, product no. 2410-06, manufactured by Austenal International Co.
The slurry so formed is poured into a wax or rubber impression of a patient's teeth, which has been previously prepared by a dentist or a lab technician in the manner well known in the art.
With the phosphate investment bonded material placed in the wax or rubber teeth impression, a pair of thermo-conducting pins are placed in the slurry mix before it has fully set within the wax or rubber teeth impression.
Referring to FIG. 2, the pin or dowels 11 and 12 are formed as matched pairs, each of which are formed as a solid pin of a high temperature resistant material such as stainless steel, and more specifically 303 stainless steel or the like, which can withstand temperatures of at least 2200° F. with a minimum oxidation and/or deterioration. As shown, pin 11 includes a tapered lower end portion 11A, which tapers inwardly toward the free end thereof. Intermediate the ends of pin 11 there is provided a knurled intermediate portion 11B. Beyond the end of the knurled portion 11B there is provided an extension or extended portion 11C. As noted, the intermediate portion 11B and the extended portion 11C are each provided with a progressively reduced cross-sectional area.
The other pin 12 of the matched pair comprises a relatively shorter pin which comprises a similar tapered lower end portion 12A which is somewhat shorter than taper portion 11A of pin 11 and an upper portion 12B which is knurled as indicated. The knurled portions 11B and 12B of the respective pins 11 and 12 provide the means whereby the phosphate bonded investment of the mold or die representing the formed tooth model 10A may be mechanically bonded to the respective pins or dowels upon curing. In accordance with this invention, a pair of matched pins 11 and 12 are inserted into a slurry mix placed in the wax or rubber impression so that the tapered end portions of the respective pins project beyond the surface of the phosphate investment that is poured into the impression.
Upon the curing of the phosphate bonded investment within the impression mold, the surfaces of the extended pin portions and the surface of the cured investment are lubricated or coated and a second pour is made to form the base 10B for the teeth mold or dies 10A. As best seen in FIG. 3, the second pour which defines the base 10B is poured to a level where the tapered end of the respective pins project slightly beyond the surface which forms the bottom of the base 10B.
As shown in FIGS. 3 to 5, the longer of the pins, e.g. pin 11, is inserted into the tooth die so that the extended portion 11C extends toward the high point of the tooth die, whereas the shorter pin 12 is disposed in the bulk or base portion of the tooth die.
When the second pour or base portion 10B has cured, the molded refractory or phosphate investment mold is removed from the impression mold. Thereafter, the individual teeth die, or group of teeth die, are severed or cut as indicated at 13 whereby one or more teeth die can be readily separated from the base 10B of the mold; as seen in FIG. 1.
It will be understood that the tooth or teeth to be restored by an all porcelain prosthesis restoration had been prepared by a dentist before the tooth impression was made. Thus, the die of the tooth to be restored upon the removal thereof from the wax impression is readied for receiving the coating of porcelain material. The die D, which is the replica of the treated tooth to be restored with an all porcelain restoration, is provided with a layer of porcelain material 14. In the illustrated embodiment, an all porcelain cap is shown.
The die or group of teeth die which define the mold for the porcelain restoration is then coated with the raw porcelain material M as best indicated in FIGS. 3 to 5. The die or group of teeth die so coated with the raw porcelain material is then placed in a kiln, oven or heater 14 and is subjected to a temperature ranging between 1800° to 2200° F., under a vacuum, so as to effect vitrification of the porcelain layer M.
As shown in FIG. 3, the provision of the high temperature dowel pins 11 and 12 function as a heat sink for conducting heat to the interior of the refractory die during a firing operation as indicated by arrows A. Simultaneously, the die D with the porcelain layer M thereon is being heated externally as indicated by arrows B. The arrangement is such that the internal surfaces of the die or mold D is being heated at substantially the same rate that the external surfaces of the porcelain layer M is being vitrified. Thus, the temperature of the die and the porcelain is being brought up to temperature in a substantially optimum uniform manner so as to resist any cracking or separation of the porcelain layer M.
Also, on cooling, the termo conducting pins 11 and 12 tend to effect uniform cooling of the refractory die D and the vitrified layer of porcelain thereon. The pins 11 and 12 thus control the cooling down of the refractory die at substantially the same rate as the cooling of the vitrified porcelain. The function of the pins 11 and 12 as a heat sink to effect the uniform heating and cooling of the refractory die D and porcelain coating M thereon, effectively enables the vitrified porcelain prosthetic to resist cracking and/or separating from its die D. In this manner, the number of firings otherwise required to construct a satisfactory all porcelain restoration is reduced to a minimum of possibly one or two firings, as distinguished from four, five or more firings required by the prior known techniques.
From the foregoing, it will be noted that a refractory die D formed of an ammonia phosphate bonded investment material having a silicate filler in the presence of magnesium oxide, when used in conjunction with solid thermo conducting pins in the manner herein set forth, results in suprisingly reducing the numer of firings otherwise required to form a satisfactory all porcelain porsthetic dental restoration. By effecting the reduction in the number of firings otherwise required, a more economical restoration is achieved as the cost of time, labor and effort is substantially reduced.
While the invention has been described with respect to the illustrated embodiment herein, it will be understood and appreciated that variations and modifications can be made without departing from the spirit or scope of the invention.
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This disclosure is directed to the use of phosphate bonded investment with solid high temperature dowels or pins for the preparation or making of all porcelain dental prosthetic restorations. More specifically, the solid, high temperature pin type dowels, when used in dies and models formed of phosphate bonded investment material for making porcelain restorations, when fired to a temperature range between 1600°-2200° F. functions as a heat sink to effect a more uniform heating and cooling of refractory model and porcelain restoration thereon so that the form and shape of the vitrified porcelain restoration may be more accurately maintained.
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FIELD OF INVENTION
[0001] This invention relates to cosmetic methods and products concerned with decreasing the acidity of sweat secreted from human eccrine glands, decreasing body malodour, and decreasing perspiration.
BACKGROUND OF INVENTION
[0002] Cosmetic deodorant compositions are known. Typical deodorant compositions comprise one or more agents that mask or inhibit the formation of unpleasant body odours; perfumes and/or antimicrobial agents are widely used for this purpose. Some deodorant compositions also reduce perspiration and are termed deodorant antiperspirant compositions, or antiperspirant compositions. Typical antiperspirant compositions comprise a metal antiperspirant salt, such as an astringent aluminium or aluminium/zirconium salt, in combination with a cosmetically suitable vehicle. Such cosmetic deodorant and antiperspirant products are available in a variety of product forms, for example as sticks, roll-on lotions, aerosols and pump spray formulations.
[0003] We have discovered a method of gaining a range of benefits, including improved deodorancy and antiperspirancy, by reducing the acidity of sweat secreted by human eccrine glands by topical application of a vacuolar (H + )-ATPase (or V-ATPase) inhibitor. Decreased acidity may result in any of the following benefits: increased desquamation and hence smoother skin (see M. M. Brysk et al, Experimental Cell Research, 214(1), 22-26, September 1994); reduced volatility of odiferous short chain fatty acids on the skin surface and hence decreased body malodour; reduced acid-induced damage of cosmetic ingredients applied to the skin, in particular perfumes; and improved performance of antiperspirant compositions comprising an antiperspirant salt.
[0004] A method of elevating the pH of human sweat has previously been reported in WO 00/15185 (Beck et al). In this publication, the agent used to increase the pH was a bicarbonate reabsorption inhibitor. The present invention, in contrast, uses a V-ATPase inhibitor. V-ATPase inhibitors are disclosed in numerous publications, including WO 95/20043 (Stein and Tonkinson) and WO 00/51589 (Boyd); however, none of these publications disclose the methods or compositions of the present invention.
[0005] The present invention takes advantage of the recent discovery of vacuolar-type H + -ATPases (V-ATPases) in the luminal membrane of eccrine sweat ducts (Bovell D. L., et al, The Histochemical Journal, 32, 2000, 409-413).
SUMMARY OF INVENTION
[0006] We have found a new method for reducing the acidity of human sweat. The method involves the topical application of a vacuolar (H + )-ATPase (or V-ATPase) inhibitor. Such materials inhibit proton pumps in the luminal membrane of the sweat gland and thereby reduce the sweat gland's ability to acidify the sweat. Significantly, Example 1 of the present patent suggests that not all eccrine sweat ducts have active V-ATPases in the luminal membrane; hence, the present invention discloses a ‘selective’ method for increasing the pH of sweat secreted from eccrine sweat ducts. Unlike the prior art method involving bicarbonate reabsorption inhibitors (WO 00/15185, Beck et al)., it is believed that the present invention may target sweat ducts producing particularly low pH sweat.
[0007] Thus, according to a first aspect of the present invention, there is provided a cosmetic method of reducing the acidity of sweat excreted from human eccrine glands, said method comprising the topical application of a V-ATPase inhibitor to the skin in the vicinity of the eccrine glands.
[0008] The higher sweat pH resulting from the use of a V-ATPase inhibitor can lead to enhanced performance of an antiperspirant salt also applied.
[0009] Thus, according to a second aspect of the present invention, there is provided a cosmetic method of reducing perspiration, said method comprising the topical application of an antiperspirant salt and a V-ATPase inhibitor to the human skin.
[0010] According to a third aspect of the present invention, there is provided a method of enhancing the efficacy of a topically-applied antiperspirant salt, said method comprising the co-application of a V-ATPase inhibitor to the human skin.
[0011] According to a fourth aspect of the present invention, there is provided a deodorant product comprising a V-ATPase inhibitor and an antiperspirant salt.
[0012] According to a fifth aspect of the present invention, there is provided a method of manufacture of a deodorant composition, said method comprising the mixing of an antiperspirant salt and a V-ATPase inhibitor with a carrier material.
[0013] The higher sweat pH resulting from the use of a V-ATPase inhibitor may also lead to enhanced appreciation of topically-applied perfume. This may arise as a result of the perfume smelling better at the higher pH attained; as a result of reduced body malodour resulting from decreased volatility of odiferous fatty acids on the skin surface; as a result of reduced acid-induced damage of said perfume; or as a result of any other mechanism.
[0014] Thus, according to a sixth aspect of the present invention, there is provided a cosmetic product comprising a V-ATPase inhibitor and a perfume.
[0015] According to a seventh aspect of the present invention, there is provided a method of manufacture of a cosmetic composition, said method comprising the mixing of a perfume and a V-ATPase inhibitor with a carrier material.
DETAILED DESCRIPTION OF THE INVENTION
[0016] The elevation of sweat pH brought about by the V-ATPase inhibitor can lead to numerous benefits, as mentioned hereinbefore. For the benefits requiring the co-application of a perfume or an antiperspirant salt, it is not essential that the perfume or antiperspirant salt be applied as part of the same composition as the V-ATPase inhibitor. The benefit may be derived from independent application of the antiperspirant salt or perfume and the V-ATPase inhibitor. Co-application may be concurrent or consecutive, although it is preferred that the V-ATPase inhibitor is applied before or at the same time as the perfume or antiperspirant salt.
[0017] In one particular embodiment of the invention, the V-ATPase inhibitor is applied first, such as from a night-time product, for example a cosmetic cream or spray, and a perfume or antiperspirant salt is applied after the luminal membrane proton pump has been inhibited, for example the following morning, from a deodorant composition. In a related embodiment of the invention, the V-ATPase inhibitor is applied from a personal cleansing composition and, after drying, a perfume or antiperspirant salt is applied from a deodorant composition. In a further related embodiment of the invention, the V-ATPase inhibitor and a perfume or antiperspirant salt are simultaneously applied from independent cosmetic compositions. In all products of these types, where the V-ATPase inhibitor and the perfume or antiperspirant salt are applied from independent cosmetic compositions, it is preferred that the product also comprises a means for, and/or instruction for, both of the compositions to be applied to the body.
[0018] In another embodiment of the invention, the V-ATPase inhibitor and a perfume or antiperspirant salt are present in the same composition.
[0019] Preferred compositions comprising the products of the invention are deodorant compositions, in particular deodorant antiperspirant compositions.
[0020] In products comprising a V-ATPase inhibitor and a perfume and/or antiperspirant salt, and in methods of their use, the product is of particular benefit when used on an often malodorous region of the human body, for example the underarm areas or the feet.
[0021] Other compositions comprising the products of the invention are skin-care compositions, in particular creams, lotions, and gels.
[0022] The V-ATPase Inhibitor
[0023] The V-ATPase inhibitor may be any of the materials known in the art to function in this manner. Examples include the V-ATPase inhibitors described in the references cited hereinbefore and incorporated herein by reference. In the present invention, the V-ATPase inhibitor serves to inhibit V-ATPase in the luminal cells of the eccrine sweat gland, particularly the cells of the reabsorptive duct. This leads to a reduction in the rate of proton transfer from within such cells, leading to a decrease in the acidity of the sweat exiting said sweat ducts. When assessed according to the method described in Example 1, preferred materials have a significant effect when present at a level of less than 300 μg/ml, particularly preferred materials have a significant effect when present at a level of less than 100 μg/ml, and especially preferred materials have a significant effect when present at a level of less than 50 μg/ml.
[0024] Particular V-ATPase inhibitors are selected from the group comprising bafilomycins, concanamycins, olygomycins, oligonucleotides as disclosed in WO 95/20043 (Stein and Tonkinson), prodigiosine, fusiococcin, fusidic acid, suramin, omeprazole, felodipine, and compounds, as described in WO 00/51589 (Boyd), of the formula:
[0025] wherein R 1 and R 2 are the same or different and each is H, a straight-chain or branched saturated or unsaturated alkyl, an aryl, R CH 2 —, R CO—, or R SO 2 —, wherein R is H, a straight-chain or branched saturated or unsaturated alkyl, or an aryl; R 3 is H, a straight-chain or branched saturated or unsaturated alkyl, an aryl, an oxime, or an oxime methyl ether; the aromatic ring is unsubstituted or substituted with at least one substituent selected from the group consisting or a halogen, a nitro, an amino, a hydroxyl, a thio, an acyl, an alkyl, and a cyano; the saturated alkyl, unsaturated alkyl and aryl substituents defined in R 1 -R 3 and R are unsubstituted or substituted with at least one substituent selected from the group consisting of a halogen, a nitro, an amino, a hydroxyl, a thio, an acyl, an alkyl, and a cyano; and Z is a contiguous linker comprising a chain of 0-12 atoms which, together with the five atoms beginning with the carbon or the aromatic ring in meta-relationship with OR 1 and ending with the carbon directly attached to the alkyl oxygen of the lactone, said carbons being covalently bonded to either end of linker Z, integrally form a 5-17 membered ring; or a salt or ester thereof. Preferred V-APTase inhibitors of this formula are salicylihalamides A and B, lobatamides A-F, and apicularen A and B.
[0026] Preferred V-ATPase inhibitors are bafilomycins (especially bafilomycin A 1 ), concanamycins (especially concanamycin A,) and olygomycin. Preferred materials having large-scale commercial availability are omeprazole and felodipine.
[0027] In some circumstances, it is preferred that the V-ATPase inhibitor is present in or derived from a natural extract. The preferred level of incorporation of V-ATPase inhibitor into a composition greatly depends upon the effectiveness of the V-ATPase inhibitor employed and the dose typically delivered to the skin by said composition. Typical levels are from 0.05% to 10% by weight of the composition of which it is a part. (In calculating the level of V-ATPase inhibitor present in a composition, any volatile propellant present is not taken into account in the calculation). It is preferred that the aforementioned level is 0.1% or greater and it is particularly preferred that the level is 0.5% or greater. With regard to the maximum amount employed, it is preferred that this is no greater than 5% and particularly preferred that the level is no greater than 1% by weight.
[0028] Additional Components
[0029] Antiperspirant Salt
[0030] Conventional inorganic antiperspirant salts may be used in the products of the invention. Examples include astringent active salts, in particular, aluminium, zirconium and mixed aluminium/zirconium salts, including both inorganic salts, salts with organic anions and complexes. Preferred astringent salts include aluminium, zirconium and aluminium/zirconium halides and halohydrate salts, such as chlorohydrates. Preferred levels of incorporation are from 0.5% to 60%, particularly from 5% to 30% or 40% and especially from 5% or 10% to 30% or 35% by weight of the composition of which it is a part. In non-aqueous formulations, the above weight percentages exclude any water of hydration bound to the antiperspirant salt. Especially preferred aluminium halohydrate salts, known as activated aluminium chlorohydrates (ACCH), are described in EP 6,739 (Unilever PLC and NV). Zirconium aluminium chlorohydrate (ZACH) salts are also preferred materials, as are the so-called ZAG (zirconium-aluminium-glycine) complexes, for example those disclosed in U.S. Pat. No. 3,792,068 (Procter and Gamble Co.) and activated versions called AZAG.
[0031] When an antiperspirant salt is employed, the weight ratio of antiperspirant salt to V-ATPase inhibitor is generally quite high: typically between 300:1 and 2:1. Preferably the weight ratio is between 100:1 and 5:1 and particularly preferred is a ratio between 50:1 and 10:1.
[0032] Carrier Material
[0033] A carrier material for the antiperspirant salt and/or the V-ATPase inhibitor, is a preferred additional component in the products of the invention. The carrier material may be hydrophobic or hydrophilic, solid or liquid. Preferred carrier materials are liquids at ambient temperature and atmospheric pressure. Hydrophobic liquids suitable for use include liquid silicones, that is to say, silicone oils. Such materials have desirable sensory properties, making them particularly preferred, especially in skin-care compositions. The liquid silicones may be cyclic or linear, examples include Dow Corning silicone fluids 344, 345, 244, 245, 246, 556, and the 200 series; Union Carbide Corporation Silicones 7207 and 7158; and General Electric silicone SF1202. Alternatively, non-silicone hydrophobic liquids may be used. Such materials include mineral oils, hydrogenated polyisobutene, polydecene, paraffins, isoparaffins of at least 10 carbon atoms, and aliphatic or aromatic ester oils (eg. isopropyl myristate, lauryl myristate, isopropyl palmitate, diisopropyl sebecate, diisopropyl adipate, or C 8 to C 18 alkyl benzoates).
[0034] Hydrophilic liquid carrier materials, for example water, may also be employed. Systems employing water are often emulsion systems having an aqueous phase (typically 40 to 80% by weight) and a non-aqueous phase (typically 20 to 60% by weight).
[0035] Particularly preferred liquid carrier materials comprise organic solvents. Preferred organic solvents have a melting point of less than 10° C., preferably less than 50° C.; this can benefit both low temperature storage stability and ease of manufacture. A class of preferred organic solvents are aliphatic alcohols (monohydric or polyhydric, preferably having 2 to 8 carbon atoms) and polyglycol ethers, preferably oligoglycol ethers having only 2 to 5 repeat units. Examples include dipropylene glycol, glycerol propylene glycol, butylene glycol, ethanol, propanol, isopropanol, and industrial methylated spirits. The most preferred organic solvents are aliphatic alcohols, in particular those having 2 to 3 carbon atoms, especially ethanol and isopropanol.
[0036] Mixtures of carrier materials may also be used. The amount of carrier material employed is preferably from 30% to 99%, more preferably 60% to 98%, of the composition, excluding any volatile propellant that may be present.
[0037] When organic solvent is present in a composition, it is often present at from 30% to 98% by weight of the total weight of the liquid components of the composition; in particular, the organic solvent often comprises from 60% to 97% by weight of the total liquids present.
[0038] Additional Anti-Microbial Agent
[0039] An additional component that can sometimes augment the ability of the compositions of the invention to reduce body odour is an anti-microbial agent. Most of the classes of agents commonly used in the art can be incorporated into compositions of the invention. Levels of incorporation are preferably from 0.01% to 3%, more preferably from 0.03% to 0.5% by weight of the composition, excluding any volatile propellant that may be present.
[0040] Preferred anti-microbial agents have a minimum inhibitory concentration (MIC) of 1 mg.ml −1 or less, particularly 200 μg.ml −1 or less, and especially 100 μg.ml −1 or less. The MIC of an anti-microbial agent is the minimum concentration of the agent required to significantly inhibit microbial growth. Inhibition is considered significant if an 80% or greater reduction in the growth of an inoculum of a relevant micro-organism is observed, relative to a control medium without an anti-microbial agent, over a period of 16 to 24 hours at 37° C. A relevant micro-organism that may be used is Staphylococcus epidermidis. Details of suitable methods for determining MICs can be found in Antimicrobial Agents and Susceptibility Testing, C. Thornsberry, (in Manual of Clinical Microbiology, 5 th Edition, Ed. A. Balows et al, American Society for Microbiology, Washington D.C., 1991). A particularly suitable method is the Macrobroth Dilution Method, as described in Chapter 110 of above publication (pp. 1101-1111) by D. F. Sahm and J. A. Washington II. MICs of anti-microbials suitable for inclusion in the compositions of the invention are triclosan: 0.01-10 μg.ml −1 (J. Regos et al., Dermatologica (1979), 158: 72-79) and farnesol: ca. 25 μg.ml −1 (K. Sawano, T. Sato, and R. Hattori, Proceedings of the 17 th IFSCC International Conference, Yokahama (1992) p.210-232). By contrast ethanol and similar alkanols have MICs of greater than 1 mg.ml −1 . Preferred anti-microbials are bactericides, in particular organic bactericides, for example quaternary ammonium compounds, like cetyltrimethylammonium salts; chlorhexidine and salts thereof; and diglycerol monocaprate, diglycerol monolaurate, glycerol monolaurate, and similar materials, as described in Deodorant Ingredients, S. A. Makin and M. R. Lowry, in Antiperspirants and Deodorants, Ed. K. Laden (1999, Marcel Dekker, New York). More preferred anti-microbials for use in the compositions of the invention are polyhexamethylene biguanide (PHMB) salts (also known as polyaminopropyl biguanide salts), an example being Cosmocil CQ available from Zeneca PLC, preferably used at up to 1% and more preferably at 0.03% to 0.3% by weight; 2′,4,4′-trichloro, 2-hydroxy-diphenyl ether (triclosan), preferably used at up to 1% by weight and more preferably at 0.05-0.3% by weight of the non-volatile components of the composition; and 3,7,11-trimethyldodeca-2,6,10-trienol (farnesol), preferably used at up to 1% and more preferably at up to 0.5% by weight of the non-volatile components of the composition.
[0041] Inorganic antimicrobial agents may also be employed, for example zinc phenol sulphonate, preferably at up to 3% by weight of the non-volatile components of the composition.
[0042] Structurants and Emulsifiers
[0043] Structurants and emulsifiers are further additional components of the compositions of the invention that are highly desirable in certain product forms. Structurants, when employed, are preferably present at from 1% to 30% by weight of the composition, whilst emulsifiers are preferably present at from 0.1% to 10% by weight of the composition. In roll-ons, such materials help control the rate at which product is dispensed by the roll ball. In stick compositions, such materials can form gels or solids from solutions or suspensions of the chelator salt in a carrier fluid. Suitable structurants for use in such compositions of the invention include cellulosic thickeners such as hydroxypropyl cellulose and hydroxy ethyl cellulose, and dibenzylidene sorbitol. Emulsion pump sprays, roll-ons, creams, and gel compositions according to the invention can be formed using a range of oils, waxes, and emulsifiers. Suitable emulsifiers include steareth-2, steareth-20, steareth-21, ceteareth-20, glyceryl stearate, cetyl alcohol, cetearyl alcohol, PEG-20 stearate, and dimethicone copolyol. Suspension aerosols, roll-ons, sticks, and creams require structurants to slow sedimentation (in fluid compositions) and to give the desired product consistency to non-fluid compositions. Suitable structurants include sodium stearate, stearyl alcohol, cetyl alcohol, hydrogenated castor oil, synthetic waxes, paraffin waxes, hydroxystearic acid, dibutyl lauroyl glutamide, beta-sitosterol, oryzanol, acylated cellobiose, alkyl silicone waxes, quaternium-18 bentonite, quaternium-18 hectorite, silica, and propylene carbonate. Some of the above materials also function as suspending agents in certain compositions.
[0044] Further emulsifiers desirable in certain compositions of the invention are perfume solubilisers and wash-off agents. Examples of the former include PEG-hydrogenated castor oil, available from BASF in the Cremaphor RH and CO ranges, preferably present at up to 1.5% by weight, more preferably 0.3 to 0.7% by weight. Examples of the latter include poly(oxyethylene) ethers or esters, often comprising 5 to 30 oxyethylene units and a C10 to C22 alkyl or acyl chain.
[0045] Sensory Modifiers
[0046] Certain sensory modifiers are further desirable components in the compositions of the invention. Such materials are preferably used at a level of up to 20% by weight of the composition. Emollients, humectants, volatile oils, non-volatile oils, and particulate solids which impart lubricity are all suitable classes of sensory modifiers. Examples of such materials include cyclomethicone, dimethicone, dimethiconol, isopropyl myristate, isopropyl palmitate, talc, finely-divided silica (eg. Aerosil 200), polyethylene (eg. Acumist B18), polysaccharides, corn starch, C12-C15 alcohol benzoate, PPG-3 myristyl ether, octyl dodecanol, C7-C14 isoparaffins, di-isopropyl adipate, isosorbide laurate, PPG-14 butyl ether, glycerol, hydrogenated polyisobutene, polydecene, titanium dioxide, phenyl trimethicone, dioctyl adipate, and hexamethyl disiloxane. Liquid emollients, including silicone oils, and humectants, are of particular benefit in compositions of the present invention, especially in skin-care compositions.
[0047] Perfume
[0048] Perfume is a key component in many of the products of the invention. Suitable materials include conventional perfumes, such as perfume oils and also include so-called deo-perfumes, as described in EP 545,556 and other publications. Levels of incorporation are preferably up to 4% by weight, particularly from 0.1% to 2% by weight, and especially from 0.7% to 1.7% by weight of the composition in which the perfume is present, excluding any volatile propellant that may be present in said composition. In certain embodiments, these preferred levels of perfume incorporation apply by weight of the total composition, that is to say, including any volatile propellant that may also be present.
[0049] Additional pH Modifiers
[0050] In some products it may be preferred to incorporate an additional pH modifier, in order to assist the V-ATPase inhibitor in reducing the acidity of the sweat upon the skin surface. Simple bases, such as bicarbonate, may be employed. Alternatively, or additionally, a bicarbonate reabsorption inhibitor as described in WO 00/15185 (Beck et al) may be employed.
[0051] Further Additional Components
[0052] Further additional components that may also be included are colourants and preservatives, for example C 1 -C 3 alkyl parabens.
[0053] Product Forms
[0054] The compositions comprising the products of the invention may take any form. Examples include wax-based sticks, soap-based sticks, compressed powder sticks, roll-on suspensions or solutions, emulsions, gels, creams, squeeze sprays, pump sprays, and aerosols. Each product form contains its own selection of additional components, some essential and some optional. The types of components typical for each of the above product forms may be incorporated in the corresponding compositions of the invention. Roll-on compositions particularly suited to the invention are simple solutions in organic solvents, although water can be tolerated in such compositions. In addition, emulsion compositions, for example oil-in-water and water-in-oil emulsions, are not excluded. Stick compositions of the invention are preferably based on either a monohydric or polyhydric alcohol organic solvent base. They are often gelled with sodium stearate, although dibenzylidene sorbitol (DBS) may alternatively be used, preferably in combination with hydroxypropyl cellulose.
[0055] Aerosol compositions of the invention may comprise from 30 to 99 parts by weight, and particularly 30 to 60 parts by weight of propellant and the remainder (respectively 70 to 1 and particularly 70 to 40 parts by weight) of the antiperspirant/deodorant base composition.
[0056] The propellant in the aerosol compositions may be selected from liquified hydrocarbons or halogenated hydrocarbon gases (particularly fluorinated hydrocarbons such as 1,1-difluoroethane and/or 1-trifluoro-2-fluoroethane) that have a boiling point of below 10° C. and especially those with a boiling point below 0° C. It is especially preferred to employ liquified hydrocarbon gases, and especially C 3 to C 6 hydrocarbons, including propane, isopropane, butane, isobutane, pentane and isopentane and mixtures of two or more thereof. Preferred propellants are isobutane, isobutane/isopropane, isobutane/propane and mixtures of isopropane, isobutane and butane. Other propellants that can be contemplated include alkyl ethers, such as dimethyl ether or compressed non-reactive gasses such air, nitrogen or carbon dioxide.
[0057] The means of application of the V-ATPase inhibitor and/or other optional components of the invention may be directly from one of the aforementioned product forms or it may be indirect, via preliminary application to paper towelling or fabric. Thus, the V-ATPase inhibitor could be applied from a paper or fabric wipe, drawn across the skin surface and thereby transferring V-ATPase inhibitor from the wipe to the skin. Alternatively, the V-ATPase inhibitor could be applied by some other means and a composition comprising a perfume or an antiperspirant salt applied via a wipe.
[0058] Methods of Manufacture
[0059] The compositions comprising the products of the invention may be manufactured by any convenient method. In a particular embodiment of present invention, a suitable composition is manufactured by the mixing of a V-ATPase inhibitor and a perfume and/or antiperspirant salt with an appropriate carrier material, the components being agitated to give a homogeneous mixture. Said mixture may be used in any of the product forms described above, with the incorporation of the appropriate additional components.
EXAMPLES
Example 1
[0060] Proton Transfer Inhibition by a V-ATPase Inhibitor
[0061] Human eccrine sweat ducts were isolated using the Kealey shearing technique (Lee C. M., Jones C. J., and Kealey T., J. Cell. Sci., 72, 1984, 259-274). Isolated portions of reabsorptive duct were mounted on a conventional microperfusion apparatus, between glass pipettes. One end of the duct was cannulated with a microperfusion pipette. The ducts were perfused at 37° C. with a control solution containing N-methyl-D-glucamine chloride (114 mM), potassium hydrogenphosphate (2.5 mM), magnesium chloride (1 mM), calcium chloride (1 mM), glucose (5 mM), and N-methyl-D-glucamine lactate (4 mM). Osmolality was adjusted to 300 mOsm/kg with mannitol and the pH adjusted to 7.4 with tris-HEPES. Intracellular pH was measured using the pH sensitive fluorescent probe BCEFC (bis-2-carboxyethyl-carbfluorescein) at 5 μM.
[0062] In order to investigate the effect of V-ATPase inhibitors, the intracellular pH was first rapidly decreased from its equilibrium value by a 20 mM basolateral pulse of ammonium chloride (pulse duration: 30 to 60 sec.). Intracellular pH was monitored and two kinds of response were observed: either the sweat duct exhibited a steady pH recovery or the sweat duct exhibited no significant pH recovery. The former response was most prevalent. The sweat ducts exhibiting this behaviour were selected for the next part of the procedure.
[0063] In the next part of the procedure, the indicated sweat ducts were subjected to acidification by a 20 mM basolateral pulse of ammonium chloride, with the additional presence of a V-ATPase inhibitor. The results, as indicated in Table 1, show that ATPase inhibitors lead to a significant reduction in the rate of pH recovery, compared with the control. Hence, olygomycin (at 20 μg/ml), bafilomycin-A 1 (at 6.2 μg/ml), and concanamycin-A (at 0.1 μg/ml) all inhibit proton transfer out of the cells of the reabsorptive duct. These results are all significant at the 95% level (as determined by the Student t-test).
TABLE 1 V-ATPase Inhibitor Conc. (μg/ml) Rate of pH recovery (%) None (control) — 100 Olygomycin 20 12 Bafilomycin-A 1 6.2 27 Concanamycin-A 0.1 5
Examples 2 to 7
[0064] Deodorant Compositions
[0065] The following represent typical deodorant compositions incorporating a V-ATPase at a level of 0.1% to 5% by weight of the composition, excluding any volatile propellant that may be present. The figures refer to percentages by weight of the total composition.
TABLE 2 Aerosol Compositions Example: 2.1 2.2 2.3 2.4 2.5 2.6 Cyclomethicone (DC245) 3.47 11.8 14.4 3.55 4.1 5.2 Ethanol 20 Isopropyl palmitate 10.3 8.5 Isopropyl myristate 0.31 PPG-14 butyl ether 9.7 0.7 9.1 Octyldodecanol 0.25 Polydecene 0.3 Dibutyl phthalate 4.5 Bentone 38 (ex Rheox) 1 1 1.5 1 0.95 0.7 Propylene carbonate 0.15 Methylpropanolamine 0.08 Silicone gum (Q2-1401) 0.2 AACH 10 4 Milled AACH 10 2 ACH 9.2 9.3 Silica 0.1 0.01 Talc 3 Micronised polyethylene 9.3 Perfume 0.5 0.7 0.7 0.7 1 Allantoin 1.5 Palmitoyl ethanolamide 0.3 0.3 0.3 0.3 0.3 0.3 V-ATPase inhibitor 0.03 0.15 0.6 0.25 1.4 1 n-Pentane 20 C3/C4 hydrocarbons 75 75 40 70 60 80
[0066] [0066] TABLE 3 Lotion Compositions Example: 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 Ethanol 30 60 28 Isopropanol 30 30 30 60 30 Hydroxypropyl- 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 cellulose ACH 4 4 20 ZACH 20 AZAG 18 PHMB 0.2 0.2 Triclosan 0.1 Suspending Agent 3 Propylene Carbonate 1 Talc 6 V-ATPase inhibitor 0.2 0.4 0.6 0.8 1 2 3 4 5 Water + minors 69.1 64.9 64.7 38.3 68.1 37.2 46.3 47.3 Cyclomethicone + 67 minors
[0067] [0067] TABLE 4 Cream and Soft Solid Compositions Example: 4.1 4.2 4.3 4.4 4.5 C18-C36 acid glycol ester 2.5 3.75 Castor wax 7.5 1.25 Triacontenyl vinyl pyrrolidone 5 copolymer Paraffin wax 5 Silica 1 0.2 Cyclopentasiloxane and 64.05 cetearyl-dimethicone/vinyl dimethicone co-polymer C12-15 alkyl benzoate 64.3 63.1 62.9 63.7 4 Dextrin palmitate 10 5 Neopentyl glycol diheptanoate 5 PEG-8 distearate 2 Stearyl dimethicone 0.75 AACH 25 25.5 Milled AACH 25.5 26 AZAG 22 V-ATPase inhibitor 0.2 0.4 0.6 0.8 1.5 Perfume 0.5 0.5 0.5
[0068] [0068] TABLE 5 Further Cream and Soft Solid Compositions Examples: 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 Silicone wax 2.5 3 N-lauroyl glutamic acid 1 dibutylamide C18-C36 acid glycol 5 ester C18-C36 acid 1.25 triglyceride Castor wax 4 Stearyl alcohol 6 Paraffin wax 7.5 Candelilla wax 7 C24/28 alkyl dimethicone 3.5 wax Silica 1.5 1.5 Talc 1.75 6 5 Bentone 38 3 0.5 Anhydrous aluminium 6 silicate Microthene powder 6 Propylene carbonate 1.5 Cyclomethicone 64.4 61 62.5 36.3 56 43 47.8 Tetraphenyl 52.7 tetramethylsiloxane C12-15 Alkyl benzoate 10 11.7 Dextrin palmitate 5 9 Octyldodecanol 15 PPG14 butyl ether 4.5 Dimethicone (10 cst.) 5 10 Dimethicone (350 cst.) 24 POE-100 stearyl ether 2 POE-100 stearate 1 AACH 25.5 22 Milled AACH 25.5 ACH 18 AZAG 25 25.7 20 26.5 V-ATPase inhibitor 0.1 0.3 0.5 1 2 3 4 5 Perfume 0.5 0.5 0.5
[0069] [0069] TABLE 6 Solid Stick Compositions Examples: 6.1 6.2 6.3 6.4 6.5 6.6 Cyclomethicone (DC245) 40.7 37.3 40.1 39.7 45.5 5 Permethyl 103A 16 12 PPG-14 Butyl ether 4 10 Propylene glycol 47.8 Ethanol 13 Isostearyl alcohol 12 Stearyl alcohol 14 14 17 11.5 Castor wax 2 5 2.5 5 12-hydroxystearic acid 6 N-lauroyl glutamic acid 2 dibutylamide Dibenzyilidene sorbitol 3 Eicosanol 0.2 0.2 Octyldodecanol 14 14 C20-40 alcohols 0.5 C20-40 pareth-3/C20-40 1.75 pareth-20 PEG-8 distearate 0.6 5 Amino-2-methyl-1-propanol 0.2 Al—Zr Gly antiperspirant 23 25 24 26 26 22.5 salt Glycerol 2 EDTA 1 Talc 3 Fumed silica 1 2 Perfume 1 1 1 V-ATPase inhibitor 0.1 0.5 0.8 1 1 1.5
[0070] [0070] TABLE 7 Further Solid Stick Compositions Examples: 7.1 7.2 7.3 7.4 7.5 7.6 Cyclomethicone 36.3 49.25 10 37 (DC245) Mineral oil 11.5 Polydecene 12.7 PPG-14 butyl ether 2.5 C12-15 alkyl benzoate 15 Dimethicone (50 cst.) 1.5 Propylene glycol 31 53.5 Ethanol 50 Water 8.7 20 Stearyl alcohol 14 1 Castor wax 4.5 Dextrin palmitate 10 Cellobiose 3.8 octanonanoate Beta sitosterol 2.5 Oryzanol 2.5 Sodium stearate 5.8 7.7 Eicosanol 0.2 Isopropyl myristate 10 Cetyl dimethicone 1 1 copolyol Amino-2-methyl-1- 0.5 propanol Poloxamer 407 6 Cocamide DEA 7 Aluminium 26 30 chlorohydrate Zirkonal 50 51.7 40 Triclosan 0.3 Glycerol 2 17.3 Talc 1.5 Fumed silica 1 Perfume 1 V-ATPase inhibitor 0.5 0.75 1 2 3.5 5
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A cosmetic method of reducing the acidity of sweat excreted from human eccrine glands, said method comprising the topical application of a V-ATPase inhibitor to the skin in the vicinity of the eccrine glands. Said method may result in a range of benefits, including enhanced appreciation of topically-applied perfume and enhanced efficacy of topically-applied antiperspirant salt. Cosmetic products and compositions comprising a V-ATPase inhibitor and selected other components are also claimed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of, and claims priority under 35 U.S.C. 120 to, application Ser. No. 11/175,602, filed on Jul. 5, 2005, and now U.S. Pat. No. 7,234,722, issued on Jun. 26, 2007, which is incorporated herein by reference, and which is a nonprovisional of, and claims priority under 35 U.S.C. 119(e) to, application Ser. No. 60/584,991, filed Jul. 2, 2004, which application is incorporated herein by reference.
FIELD OF THE INVENTION
present invention relates to an improved baby stroller, and more particularly to a baby stroller in which the baby may transported selectively in a standing, sitting, or reclining position.
BACKGROUND OF THE INVENTION
An age-old problem for parents with small children is in transporting them without having to carry them. Historically, the perambulator or baby carriage was used; devices of this type resembled a crib with wheels, a handle, and a cover, and the baby was laid in the carriage for transport. More recently, parents typically employ a stroller for this purpose. Strollers of a wide variety of styles have been developed, but the basic stroller generally includes a cloth seat, suspended within a wheeled frame, and a restraint of some type to keep the child in the seated position. Other solutions include front carriers, sling carriers, and backpack carriers, all of which have their own drawbacks, primarily because the parent must bear the burden of the child's weight. As the child grows older, comfort for the parent becomes an issue.
While the stroller is indispensable to modern parents, there are drawbacks to its use as well. Babies spend a great deal of time confined in a sitting position—in a high chair at the dinner table, and in a car seat while traveling—and the time spent restrained in a stroller adds to that seated time. Most young children can only tolerate the restrained seated position for a short time before becoming antsy, irritable, and bored. For older babies and toddlers, who have begun to pull up or stand, the tolerance for a restrained seated position may be quite short, because of their inherent desire to stand.
Additionally, recently published reports correlate the confining of babies to seated positions with the later sedentary preferences linked to childhood obesity, as well as to delayed development. As noted by the National Association for Sport and Physical Education, “Confining babies and young children to stroller, playpens, and car and infant seats for hours at a time may delay development such as rolling over, crawling, walking, and even cognitive development.” Consequently, there is a need to encourage physical activity and to discourage restraint to a seated position, where it is feasible to do so.
The use of high chairs is certainly reasonable and valid for a child who is eating, and the proper restraint of a child into a car seat is legally required when the child is traveling by car. However, there is a distinct need for an improved stroller that permits the child to be safely restrained and strolled, while being kept in a supported, upright position, and in a safe, entertaining environment, so that the baby is afforded the opportunity to use developing muscles. Such a stroller would be an alternative to constant seated restraint, but would also ideally retain the familiar and convenient features of a conventional stroller. These features typically include the ability quickly and easily to fold the stroller into a compact configuration for storage and transport, the availability of adjustable, comfortable handles for parents of different heights, the availability of storage space for a diaper bag or the like, fully pivotable wheels, a canopy for shielding the baby from the elements, and a structurally sturdy design.
SUMMARY OF THE INVENTION
In accordance with the aforementioned goals and needs, the present invention is an improved stroller for transporting a child selectively in a standing, seated, or reclined position.
Specifically, the present invention includes a stroller that has a frame that includes in principle at least three elements for sturdy construction: base rails interconnected by a cylindrical hub; a spine connected to the cylindrical hub by a concentric cylindrical sleeve that surrounds the hub, and from which the spine extends generally upward; and a bracing linkage, which is rotatably attached to the base rails and can be placed against the spine in order to support the spine.
A plurality of wheels, typically at least four, are attached to the frame. These wheels are preferably attached at each end of each of the base rails and may pivot about a vertical axis in addition to rolling in the usual manner.
A basket for supporting the child is attachable to and supported on at least the spine and in some embodiments attachable and supported on the bracing linkage. The basket includes a ring for confining the child and a sling for supporting the child in the standing position. Additionally a seat is attached to the spine below the basket. The seat includes a seat base member that is retractable for clearance when the child is in the standing position and may be extended to provide support for the child in the seated and reclined positions.
The frame is movable between unfolded and folded positions by rotation of the sleeve about the hub.
In another feature of the present invention, a handle is attached to the spine. Generally, the spine will included a sleeve member and a handle member, with the handle member being slidable along and generally interior of the sleeve member in order to lengthen or shorten the spine. This feature permits the handle height to be adjusted to a higher or lower position within a reasonable range to permit parents of different heights to place the handle at a comfortable position. Preferably the handle may be placed at one of a series of positions corresponding to varied handle heights. Because the spine will generally form an arc, the sleeve member and the handle member will be curved along the same arc. This specific arrangement and other arrangements belong generally to a class of telescoping spine configurations.
In yet another feature of the present invention, the seat also includes a back member for providing back support to the child in both the seated and reclining positions. Depending upon the specific configuration of these positions, the seat back may recline and return to upright as desired. Regardless, however, the seated position is defined by positioning the seat base member proximate the back member and/or the spine, and the reclined position is defined by articulating the seat base member away from the back member and/or the spine.
The present invention also includes a standing support member that is attached to the frame, usually in the region of the hub, and that extends generally parallel to and between the base rails. The purpose of this standing support member is to support the feet of the child when the child is in the standing position. While this member may be a rigid surface, it is preferably to some degree a soft, springy (or otherwise resilient) support surface, such as a trampoline, soft goods, or an air pillow, for example.
In still another feature of the present invention, the spine and the bracing linkage define between themselves a storage area. Because of the generally triangular configuration of the frame, the storage area is ample for storing an article such as a diaper, a travel bag, or a purse in a manner in which the article is supported on the frame. A hook or other hanging structure may be provided for this purpose.
Another feature of the ring and the sling, or more generally of the seating support for the child, is that the child is able to rotate through a significant arc of rotation at least while in the standing position. For example, at least a portion of the right and the sling may be co-rotatable from center in order to provide the child with the ability to turn to the left and right. This feature permits a greater range of motion for the child.
The basket or some portion of it may include a port into which the bracing linkage may be inserted, against the spine, in order to complete the support structure when the stroller is in the “in use” position. This port retains the bracing linkage in a manner that ensures the structural integrity of the stroller when it is in use, and an interference fit, a press fit, a positive lock, or another suitable retention mechanism may be used.
In another feature of the present invention, a canopy is provided in order to shade the child from elements such as sun, wind, or precipitation exposure. This canopy may include a series of individually adjustable canopy struts for full or partial coverage.
In another feature of the present invention, one or more of the wheels may be lockable against rotation.
BRIEF DESCRIPTION OF THE DRAWINGS
Further features, embodiments, and advantages of the present invention will become apparent from the following detailed description with reference to the drawings, wherein:
FIG. 1 is a general perspective view of a stroller according to the present invention;
FIG. 2 is a plan view of a base of a stroller as in FIG. 1 ;
FIGS. 2A and 2B are detail views of wheels of a stroller as in FIG. 2 ;
FIG. 3 is a side perspective view of a spine of a stroller;
FIG. 4 is a detail perspective view of a seat and basket of a stroller;
FIG. 5A is a side perspective view of interior components of a seat of a stroller;
FIG. 5B is a perspective view of the underside of a seat as in FIG. 5A ;
FIG. 6 is a rear perspective view of a stroller as in FIG. 1 ; and
FIG. 7 is a perspective view of a stroller as in FIG. 1 , but in the folded position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, a stroller 10 according to the present invention, transportable along a path 8 , is shown in FIG. 1 in a general perspective view. The stroller generally includes a frame 12 ; four wheel sets 14 attached to and supporting the frame 12 to permit the stroller to be rolled along to transport a child therein; a basket 16 for supporting the child; and a seat 18 . Each of these components will be discussed in greater detail below, in connection with FIG. 1 and subsequent figures.
In a preferred embodiment of the invention, the frame 12 includes at least two base rails 102 , 104 , which are interconnected by a cylindrical hub 106 . This hub 106 extends laterally interbetween the base rails 102 , 104 and joins with each of the base rails 102 , 104 each at a point 105 approximately midway along the base rails 102 , 104 , between rear ends 102 R, 104 R and forward ends 102 F, 104 F, to form a generally H-shaped base 100 . The frame 12 also includes a spine 120 , which includes a cylindrical sleeve 122 that is disposed concentrically about the hub 106 , such that the sleeve 122 may slide along the radius of the hub 106 while remaining supported on the hub 106 . The frame 12 further includes a bracing linkage 170 that is rotatably attached to the base rails 102 , 104 in the region of the rear ends 102 R, 104 R, and which may be disposed against the spine 120 at a support location 124 in supporting relation to the spine 120 . The bracing linkage 170 and its operation will be described in greater detail below. In this manner, a triangular support frame 12 is established.
Referring now to FIG. 2 , a plan view of the base 100 shows the two base rails 102 , 104 , joined by the cylindrical hub 106 as described above. The base rails 102 , 104 are formed of a metal, plastic, or composite tubing which is selected and configured to provide sufficient strength to bear the weight of the remaining component parts of the stroller 10 , plus the weight of any child carried therein and any other materials carried thereon. The base 100 is itself supported on several (preferably four) sets 14 of wheels 108 , 109 attached to the base 100 , or more specifically to the forward and rear ends 102 F, 104 F, 102 R, 104 R of the base rails 102 , 104 .
As will be seen by a person having ordinary skill in the art, these wheel sets 14 may take a number of different forms without departing from the scope of the invention, and not merely the form illustrated in the figures. For example, as is shown in FIG. 2 , in a preferred embodiment the front wheel set 14 is mounted to the base rail end 102 F in a manner that permits the free revolution of the front wheel 108 about a vertical axis A (see FIG. 2A ). Specifically, the base rail end 102 F is provided with a caster end 112 , which houses an axis pin 114 . The axis pin 114 freely rotates within an aperture 113 in the caster end 112 and is attached to a wheel fork 116 , onto which the wheel 108 is mounted. This configuration allows the stroller 10 to be turned rather easily, with a minimal turning radius, because the wheel 108 freely rotates with two degrees of freedom, being mounted upon an axis which is horizontal and parallel to the path 8 (see FIG. 1 ), while also revolving about axis A. Alternatively, as is illustrated in the preferred embodiment shown in FIG. 2B , the rear wheel 109 is mounted with axis directly on the rail 102 R, in a configuration that does not permit the free revolution of the rear wheels 109 about a vertical axis and therefore promotes lineal transport stability along the path 8 (see FIG. 1 ). Those skilled in the art will recognize that for optimal stability and maneuverability, front wheels of the type illustrated in FIG. 2A and rear wheels of the type illustrated in FIG. 2B are preferred to be selected. However, this is merely one of many different configurations that are possible without departing from the scope of the invention.
In a preferred embodiment of the invention, the base rails 102 , 104 are configured with an inward central bend, and the hub 106 has a width profile that is significantly narrower than the overall width of the stroller 10 . The base rails 102 , 104 are preferably curvilinear in appearance and configured in a way that simultaneously promotes quad-point stability, structural support of the central spine 120 , and a folding action (to be described in greater detail below). Specifically, the symmetrical inward central and upward bend of the base rails 102 , 104 provides for a four-way quasi-footed arrangement of the wheels, a central footing for the spine 120 , and a region 110 between the base rails 102 , 104 that is of sufficient size to accommodate motion of the basket 16 therethrough during folding for storage.
Referring again to FIG. 2 , it should be noted that different configurations of the connection between the base rails 102 or 104 are possible. In FIG. 2 , the base rails 102 , 104 are formed as two pieces which are attached, by welding or any other suitable attachment mechanism, to the hub 106 . Alternatively, the base rails 102 , 104 could be formed as a single piece, to each of which the hub 106 is attached on its ends by welding or any other suitable attachment mechanism. Depending on various configurations of the base rails 102 , 104 and the hub 106 , and depending on other manufacturing and durability considerations, either of these connections, or any similar connection, may prove suitable for an embodiment of the invention, without departing from the scope thereof.
Additional features of the base also illustrated include an optional footrest stretcher 118 , which extends between the base rails 102 , 104 posterior of the hub 106 . This stretcher 118 , though optional, can be useful in certain embodiments to assist in maneuvering the stroller, such as to lift the stroller onto a curb.
Also visible in FIG. 2 is the cylindrical sleeve 122 , the purpose and construction of which will be described more fully below. The sleeve 122 surrounds the hub 106 , and in the embodiment shown, is formed for manufacturing reasons (because of the permanent connection between the base rails 102 , 104 and the hub 106 ) as upper and lower half-cylinders, which mate to form the cylindrical sleeve 122 . The two half-cylinders are held in place, potentially both in mated relationship and with side-to-side confinement, by a pair of collars 119 .
A support surface 115 , which may be a resilient support surface such as a trampoline, is preferably rotatably mounted upon the. cylindrical sleeve 122 at attachment points 139 (see FIG. 3 ), and releasably attachable to the base rails 102 , 104 with a pair of posts 117 (shown in FIG. 2 in phantom). These posts 117 may be formed with an upper surface curved concavely to mate with the base rails 102 , 104 , and may feature a connection of sufficient precision and resiliency to hold the trampoline 115 in place during operation of the stroller in the standing position, yet be easily dislodged during folding. A magnetic connection may be preferred for this purpose. The support surface 115 is provided as a location for the child to stand and (if a trampoline is provided) to bounce lightly. The trampoline 115 may also be attached to the basket 18 by trampoline linkages 121 , as shown in FIGS. 1 and 7 . These linkages 119 may be rigid metal or plastic, or they may be cables.
Referring now to FIG. 3 , a spine 120 of the stroller 10 is shown in greater detail in a side perspective view. In a preferred embodiment, the spine 120 comprises a pair of spine tube members 130 , 131 , preferably made of the same material selected for the base rails 102 , 104 , which are fixedly attached to and extend upward from a generally cylindrical sleeve 122 that is sized to surround the hub 106 of the base 100 , in sliding relation along the curved surface of the hub 106 . Trampoline attachment points 139 are disposed on the underside of the sleeve 122 . In a preferred embodiment, the spine 120 forms the support structure for the basket area 16 and the seat 18 (see FIG. 1 ) in which the child is to ride. The spine 120 is preferably formed in a slight arc that in the unfolded, operational position extends generally vertically from the sleeve 122 and back toward the operator (not shown), ending in a handle mechanism 140 which is disposed at a height of comfortable hand operation.
In a preferred embodiment, the spine tube members 130 , 131 include spine outer tubes 132 , 133 extending from the sleeve 122 to a point at or above the seat mounting location 200 , and spine inner tubes 134 , 135 of slightly smaller diameter, which are sidably disposed within the outer tubes 132 , 133 to increase or decrease the length of the spine 120 , which therefore disposes the handle mechanism 140 at a variable location to accommodate operators of varying hand heights. In this embodiment, the spine outer tubes 132 , 133 are referred to as sleeve members, and the inner tubes 134 , 135 are referred to as handle members. The sleeve members 132 , 133 and the handle members 134 , 135 are for operational reasons bent on the same arc, which permits a telescoping action.
The particular handle height desired is set by a locking cuff 136 , disposed at the juncture of the sleeve members 132 , 133 and the handle members 134 , 135 , which may be released to permit the handle members 134 , 135 to be slid within the sleeve members 132 , 133 to the desired handle height, and engaged to retain the handle members 134 , 135 in the desired location. Ideally, the locking cuff 136 has a handle release mechanism 137 and additionally serves, in a two-tube or multi-tube system, as a spacer to assist in retaining the spine members 130 , 131 substantially mutually parallel throughout their respective lengths. Additionally, the top ends of the spine members 130 , 131 may be permanently affixed to the handle mechanism 140 to keep them parallel near the top ends. Alternatively, the handle members 134 , 135 could be bent severely to form handles and kept appropriately spaced by one or more spacer members.
In a preferred embodiment, the handle mechanism may be provided with auxiliary mechanisms, such as a handle arc 138 for hanging articles, a cup or bottle holder, or similar members designed to be within easy reach of the stroller operator. These features may contribute significantly to the usability of the invention, but their presence or absence does not create a departure from the scope of the present invention.
Referring again to FIGS. 1 , 2 , and 3 , it has been noted that the frame 12 generally features three components that relate to the stability of the stroller: the base 100 , the spine 120 , and the bracing linkage 170 , which together cooperate to form a generally triangular frame structure 12 . The benefits of this simplified frame structure 12 will become apparent in connection with the discussion of the seat 18 and basket 16 below. The base 100 and frame 120 have been previously discussed. The bracing linkage 170 is comparatively simple in operation.
In a preferred embodiment as shown in FIG. 2 , the bracing linkage 170 includes a curvilinear tube 172 having left and right ends 174 , 176 and formed into a U or scoop shape with a third-dimensional outward bend 178 in the central region. The left and right ends 172 , 174 are each pivotally attached to the axes 180 of the left and right rear wheels 109 , or thereabouts on the rear ends 102 R, 104 R of the base rails, so that the bracing linkage tube 172 may be pivoted into or out of contact with the spine 120 .
Although the spine 120 may itself be provided with a receiving port for receiving the attachment section 184 of the bracing linkage tube 172 , in the preferred embodiment shown in FIG. 3 , the port 220 may be formed integrally with the basket 18 such that the linkage tube 172 is received in supporting abutment to the spine 120 . The bracing linkage tube 172 will ideally be provided with a positive locking mechanism 182 , for preventing spontaneous disengagement of the linkage tube 172 from the port 220 , for as will be seen in connection with the discussion of the operation of a device according to the invention, disengagement of the linkage tube 172 from the port 220 begins the process of folding the stroller for storage. Alternatively, the port 220 may be configured to provide a resilient interference-type fit or press fit with the linkage tube 172 , such that some significant force is required to dislodge the tube 172 from the port 220 . For example, a spring-loaded mechanism disposed on the linkage tube 172 between the members of the port 220 may be compressed by the locking mechanism 182 to facilitate quick release or insertion into the port 220 , then released to exert a spring force that retains the tube 172 within the port 220 . In this embodiment, the locking mechanism 182 comprises a lever that engages to compress the spring-loaded mechanism for release or insertion, and is configured with an arc profile to match the tube 172 , thus allowing the locking mechanism 182 to clip onto the tube 172 for securement once inserted.
Regardless of the particular details of reception, however, the triangular arrangement provides support for the basket 18 (as will be described below) while maximizing the free space in the region of and below the basket 18 .
Referring now to FIG. 4 , a basket 18 and seat 16 mechanism is shown in a detail view. A seat 16 according to the present invention presents the user with three possible positions: a standing position, a seated position, and a reclined position, each of which is defined according to a position and configuration of the seat 16 .
The basket 18 is generally round or ovoid when viewed from above, with a generally void center section, and thus forms a confinement ring 201 , a portion of which extends around the spine 120 and in a preferred embodiment provides a port 220 for receiving the bracing linkage tube 172 (see FIG. 3 ). The child may be placed into the remainder of the confinement ring 201 for transport. Viewed from the side, as can be most easily seen in FIGS. 1 or 5 A, the basket 18 is saucer-shaped, with a fairly substantial undersection 202 that extends downward from the saucer portion 203 near the spine 120 . On this undersection 202 the basket 18 is pivotally mounted upon the spine 120 at a seat mounting location 200 (see FIG. 3 ), such that during folding the basket may be rotated down so that its forward portion is in contact with or near to the lower portion of the spine 120 .
The seat 16 is in a preferred embodiment provided with three principal members: A seat back 204 , a seat base 206 , and a two-level seat ring 208 .
Referring now also to FIG. 5A , the basket 18 is optimally molded so as to provide a pair of tracks 210 , 212 for supporting and guiding a rotating motion of the seat ring 208 . The upper track 210 is disposed along the inner rim of the confinement ring 201 , in approximately the front half of the saucer section 203 of the basket 18 , and is co-radial with the upper level of the two-level seat ring 208 . The lower track 212 is disposed along the inner radius of the undersection 202 , but forward of the spine 120 , and is co-radial with the lower level of the seat ring 208 . The tracks 210 , 212 provide support for mounting the seat ring 208 in rotative sliding relation therealong.
The seat ring 208 is provided with a number of friction-reducing members 230 , which may be wheels, ball bearings, rounded knobs, or a material of a low coefficient of sliding friction, or any other suitable material or construction that permits the seat ring 208 to rotate upon the basket 18 . As a specific alternative equivalent, the friction-reducing members 230 may be set into the basket 18 , and the seat ring 208 may be provided on its underside with a concave arc profile configured to mate and cooperate with the friction-reducing members 230 , all without departing from the scope of the invention. In a preferred embodiment, the seat ring 208 has two levels, one upper and one lower, which are concentric arcs having different radii. This configuration allows the seat ring 208 to form a mounting location for the seat back 204 that permits the seat back to rotate through a significant range (as much as 100° from center in either direction). This permits the child to be positioned, or to self-position, in a location other than a straight-forward view.
Referring now to FIGS. 5A and 5B , it can be seen that the seat back 204 is pivotally mounted upon the lower radius of the seat ring 208 , or more specifically on a short extension therefrom, so that the seat back 204 may be positioned in a straight-up “chair” position or in a reclined position. Depending upon the particular arrangement of the seat ring 208 and the basket 18 , the reclining action may only be available in the center-forward position, at which the seat back 204 is directed to face the front of the stroller directly.
The seat base 206 includes a platform 232 that is disposable generally in the center of the seat ring 208 , and that is rotatably attached by a strut 234 to the spine 120 , independently of the remainder of the seat 16 . The strut 234 is mounted upon an axis 236 (perhaps coaxial with the lower point of attachment of the basket 18 to the spine 120 ) that by a ridge-and-detent system, a positive lock, an interference fit, or some other appropriate system may be locked into a firm “up” position that corresponds to a “sitting” or “reclining” position of operation. Upon release of this locking mechanism, however, the seat base 206 may be rotated in the direction of arrow B into a “down” position against the spine 120 , such that full clearance is provided to allow the child to stand in the “standing” position. In order to maximize the clearance, the platform 232 may be provided on its underside with a pair of recesses 238 that correspond to and cooperate with the spine tube members 130 , 131 . An optional handle (not shown) may be provided to facilitate the upward or downward motion.
In an alternative embodiment of the present invention, the platform 232 may be configured to be rotatable along with the seat ring 208 , in a barstool-like configuration.
As can be seen in FIG. 5B , an optional but preferred seat sling 240 (shown in phantom indicated by dashed lines) is provided. The sling 240 is co-rotational with the seat ring 208 , and provides support for the child in all positions, but most necessarily in the standing position. The sling is provided with leg holes 242 , and is preferably formed of breathable Neoprene or a similar material.
Additionally, the seat back 204 and seat base 206 may be provided with soft goods (not shown), which provide for extra comfort for the child in the seated and reclining positions.
Referring again to FIG. 4 , another optional feature found in the preferred embodiments of the present invention is an extendable canopy 250 . The canopy 250 provides optional shade for the child and includes a set of canopy struts 252 that support a fabric canopy cover, which is stretched across the struts 252 but not shown in the figures. The canopy struts 252 are U-shaped and attached to stackable discs 254 , which are rotatably mounted to either side of the basket 18 . The stackable discs 254 are configured with stops that prevent the extension of the associated struts 252 beyond a point predetermined for that strut 252 . In the retracted position, the struts 252 are “stacked,” to minimize the extension of the canopy cover, and the struts 252 telescope outward over the basket 18 to maximize the extension of the canopy cover. The presence of three struts 252 as shown in FIG. 4 permits four degrees of canopy extension: no extension (full retraction), one strut's extension, two struts' extension, and three struts' extension (full extension).
Referring now to FIG. 6 , a stroller according to the present invention is shown in a rear perspective view, with reference numerals corresponding generally to those used in figures already described. The rear view shows an optional hook 270 , which in the figure extends from the locking mechanism 136 , but which could be placed at a different point on the spine 120 as desired. The hook 270 permits a diaper bag 272 , or a purse or backpack or other similar article, to be hung within a storage area 274 that is generally defined and bounded by the rear portions of the base rails 102 , 104 and the U of the bracing linkage 170 . The hook 270 could include any suitable mechanism for hanging such an article and may take a form specialized to a particular kind of article; thus, the term “hook” may include any support surface suitable for hanging or supporting such an article.
Those skilled in the art to which the present invention relates will recognize the need to restrain the child within the confinement ring, in at least the sitting and reclining positions. In addition to the sling described above, the use of a safety belt, a harness, shoulder straps, or another similar conventional mechanism to restrain the child is recommended. The design of embodiments of the present invention is suited to the use of virtually any of these devices without restraining the operation of the stroller in any fashion.
Another element essential to the utility of the present invention is in its capacity to be folded into a more compact unit for storage or transport in a car. As can be seen in FIG. 7 , a stroller 10 according to the present invention is foldable into a folded position first by placing the seat base 206 in the “standing” position and lowering the handles to their minimum extension. Next, releasing the bracing linkage 170 from its port 220 permits the basket 18 to be rotated downward so that its forward end is proximate the spine 120 . By the nature of the trampoline linkages 121 , the trampoline 115 will also be rotated “under” (the stroller may need to be lifted for this purpose). The spine 120 may then be rotated forward, with the sleeve 122 slidably rotating about the hub 106 , into a “flat” configuration, and the bracing linkage 170 rotated forward into contact with the spine 120 .
In view of the aforesaid written description of the present invention, it will be readily understood by those persons skilled in the art that the present invention is susceptible of broad utility and application. Many embodiments and adaptations of the present invention other than those herein described, as well as many variations, modifications, and equivalent arrangements, will be apparent from or reasonably suggested by the present invention and the foregoing description thereof, without departing from the substance or scope of the present invention. Accordingly, while the present invention has been described herein in detail in relation to preferred embodiments, it is to be understood that this disclosure is only illustrative and exemplary of the present invention and is made merely for purposes of providing a full and enabling disclosure of the invention. The foregoing disclosure is not intended nor is to be construed to limit the present invention or otherwise to exclude any such other embodiments, adaptations, variations, modifications and equivalent arrangements, the present invention being limited only by the claims appended hereto and the equivalents thereof.
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A stroller for transporting a child includes a wheeled frame including at least two base rails interconnected by a cylindrical hub, a spine, and a bracing linkage. A basket attaches to the spine, confining the child and supporting a seat ring. The seat ring includes upper and lower connected concentric arcs having different radii and supports a seat back on its lower arc. The seat back reclines, and the seat ring rotates from center. A seat base is supported on the frame and includes a platform movable between an extended position disposed inside the seat ring and a retracted position withdrawn from the seat ring. The stroller permits the child to be safely and comfortably transported in a standing, seated, or reclined position.
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CROSS-REFERENCE TO RELATED APPLICATIONS
Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
TECHNICAL FIELD
This invention relates to the field of routing, protecting, and concealing cabling. More specifically, the present invention is relevant to the action of dropping cables from raceway duct systems.
BACKGROUND OF THE INVENTION
Raceway duct systems are used to route, protect and conceal cabling. This cabling may comprise data, voice, video, fiber optic, or power cabling. This type of duct system can have numerous configurations. The most typical kind of ducting occurs in longitudinal sections which have a trough and a lid. There are also a variety of other types of sections included with these systems, such as 90° elbows, 45° elbow fittings, t-fittings, four way intersections (or x-sections), and others. These systems often times run the cable through ducts which are run along the ceiling in a facility. The type of facility referred to might be, e.g., a telecommunications facility, or a computer equipment center office. These types of facilities often include numerous, often time hundreds or thousands of computing equipment racks. The duct work is used to deliver the cables to the appropriate pieces of equipment in these racks. Because the cabling is run along the ceiling of such facilities, the cabling must be “dropped” to the equipment.
The prior art techniques for dropping cable to equipment from a ceiling duct system are labor intensive and costly. The most common technique used to accomplish this is disclosed in prior art FIG. 1 . Referring to the figure, we see a prior art fiber optic raceway system with a cable drop assembly 10 . These types of prior art systems are used to drop cabling between two standard ducts. These ducts are first standard duct 12 and second standard duct 14 . Each of these will be well known to those skilled in the art as common 4 inch trough-type ducts which are usually sold in 6 foot sections. These trough sections have 4 inch sides and a four inch floor (all in cross section). They are typically constructed in durable plastic and are rather thick. In fact, they are usually manufactured with a thickness of ⅛ inch, which makes this type of duct very durable. This protects the cable from trauma and fire. But its thickness makes it virtually impossible to cut with a standard utility knife, or other cutting equipment which might be available to technicians in the field.
The prior art methods involve the time consuming method of creating a drop at a junction between two existing in the ducts. Referring to FIG. 1 , first and second ducts, 12 and 14 respectively, are normally connected using a single connector.
This kind of connector is often referred to as a junction kit by those skilled in the art. Junction kits are used snap fit two longitudinal sections together. For example, two 6 foot sections can be snapped together to form a continuous 12 foot section.
Occasionally, it will be necessary to access some of the cables running through the two sections and deliver them to equipment below. This equipment is usually located in what are known as telco or server racks.
FIG. 1 shows a prior art technique of dropping cables in such a circumstance. When it is necessary to drop a group of cables (a subcomponent of the plurality presently included in the duct) the technician will install a drop unit 16 in between ducts 12 and 14 . Drop unit 16 is T-shaped and is used to drop the cables which have been separated from the bundle to be delivered to equipment below. The dropping occurs through a lower portion 18 . Lower portion 18 enables the cable to run down to the equipment, e.g., server racks, routers, and other telecommunications or computing equipment. The techniques for doing this will be well known to those skilled in the art. T-shaped drop units like that shown as drop unit 16 are readily available in the market. Both ends of the “T” in junction 16 are connected to ducts 12 and 14 using a first junction kit 22 and a second junction kit 24 , respectively. First junction kit 22 and second junction kit 24 are commercially available. They are each used to snap the junction in between the ducts. A third junction kit 26 may be used to connect the lower part of the T to a vertical duct 20 . Vertical duct 20 may be used to direct the cabling downward to protectively access it to the equipment it is designated for.
After vertical duct 20 , the cabling being dropped will be inserted into what is known to those skilled in the art as corrugated (or ribbed) split tubing. Corrugated split tubing comes having a one inch, two inch, or sometimes even three inch inside diameter. Thus, it forms a conduit having a smaller cross sectional smaller size than the ducts have. This split tubing is also split along its length to allow access for inserting and removing cables therefrom. It is used to direct the cables to their particular destinations in smaller bundles.
The installation of the drop cabling systems such as that shown in FIG. 1 is extremely time consuming. It may take the average technician over 24 hours to complete the drop of a small number of cables. This creates significant human resource issues and costs.
Another negative is the cost of these systems. The drop unit 16 , and the three junction kits 22 , 24 , and 26 are somewhat expensive. Much more expansive than the simple straight ducting and split tubing. This in many cases, makes the FIG. 1 process, though effective in protecting the cabling, unreasonably expensive.
Besides the FIG. 1 system, another prior art technique exists. This alternative system is known commercially as an Express Exit™ system. It is sold by ADC, Inc. This ADC system lifts the selected cables, which are intended to be dropped out from above the duct. Once the dropped cables are raised out from above the duct, they are directed to specified equipment below in protective ducting or ribbed split tubing. The ADC product, however, has proved to be a difficult system to use. Especially in situations in which the space within the technician is allowed to work above the duct is limited. In many situations, the technician will be precluded from using the ADC system because there is insufficient work space above the duct (which typically runs along the ceiling of the facility). Furthermore, the installation of the ADC system has proven to be labor intensive, and it has significant part costs—much like the system disclosed in FIG. 1 .
Therefore, there is a need in the art for a system that is much easier and less time consuming to use, but still allows for the adequate protection of cables being dropped out of an overhead, or otherwise placed duct.
SUMMARY OF THE INVENTION
The present invention overcomes the above-stated disadvantages in the prior art systems by providing a cable duct with apertures along its sides. The cable duct system of the present invention may also involve the use of knockout sections which form the apertures. The cable duct system (like most) is adapted to receive a plurality of cables. The duct itself has a longitudinal floor, a first longitudinally extending side, and a second longitudinally extending side opposing the first side, wherein one of the sides or the floor define an aperture for dropping a bundle of cables from the duct to equipment below it. The holes may be in the sides or floor of the duct, but preferably, are in the sides spaced apart so that cables can optionally be dropped at different positions.
Another novel feature of the cable duct system of the present invention is a downspout which is inserted through each of the holes in the duct. This downspout has first and second ends, the first end which is adapted to be inserted through the holes provided in the ducting and then cause to depend from the ducting. The downspout is also adapted to receive and guide at least one cable there through to make the dropping of the cables more convenient. The second end of the downspout has a grommet. The grommet retains the second end of the downspout by bearing against an internal surface of the duct. The first end of the downspout is sized so that it can be force fit into the internal surface of a standard piece of ribbed split tubing. Ribbed split tubing is standard in the industry, and the forced fit enables this tubing to be suspended along with the downspout from the duct. The fiber optic (or other kind of cable) is protectively held in all of these devices. The downspout can alternatively have any radius of curvature to meet the specifics of its environment. In one preferred embodiment disclosed herein, however, two downspouts are provided. One having a two-inch radius of curvature. The other having a three-inch radius of curvature. The two different sizes may be used together or separately to meet industry ideals.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
The present invention is described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a side view of a conventional system for dropping cable from a fiber-optic cable raceway.
FIG. 2 is a side view of the duct of the present invention.
FIG. 3 is a perspective view of one end of the duct of the present invention in use enabling the dropping of cables to computing equipment.
FIG. 4 is an end view of one end of the duct of the present invention in use enabling the dropping of cables to computing equipment.
FIG. 5 is a side view of one end of the duct of the present invention in use enabling the dropping of cables to computing equipment.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides a system and method for managing the dropping of fiber-optic, or other sorts of cabling from a duct or other systems to the equipment with minimal cost and effort.
The subject matter of the present invention is described with specificity to meet statutory requirements. However, the description itself is not intended to limit the scope of this patent. Rather, the inventors have contemplated that the claimed subject matter might also be embodied in other ways, to include different steps or combinations of steps similar to the ones described in this document, in conjunction with other present or future technologies. Moreover, although the term “step” may be used herein to connote different elements of methods employed, the term should not be interpreted as implying any particular order among or between various steps herein disclosed unless and except when the order of individual steps is explicitly described. Further, the present invention is described in detail below with reference to the attached drawing figures, which are incorporated in their entirety by reference herein.
You will note the use of the terms aperture and hole throughout this application. Each of these terms is to be given it's broadest meaning. The terms are intended to include any type of opening. E.g., holes, gaps, or slits would all fall within the definitions of each of these terms. The use of either term should not be construed as imparting any specific shape unless otherwise specified.
FIGS. 2 through 5 show the duct system of the present invention. FIG. 2 shows a side view of one section of a duct 40 of the present invention. This duct will be very similar to ducts known to those skilled in the art, except that it is provided with knockout portions (see 64 and 68 ) which may be physically removed by force to form apertures (not pictured in FIG. 2 ). These resulting apertures may be seen in FIG. 3 . Referring to FIG. 3 , we see the apertures 66 and 86 exist, in the depicted embodiment, in the sides of the duct. They will be used to remove and drop cables from the duct 40 in a method to be described hereinafter.
Structurally speaking, the duct has a trough shape. As can be seen from FIGS. 2–5 , the duct 40 comprises an upper portion 42 and a lower portion 44 . It also has two ends 54 and 56 . In cross section, the duct can be seen to have a first side 43 and a second side 45 . The duct also has a floor 46 which along with sides 43 and 45 defines the trough shape of the duct. The bulk of the cabling will be run through the trough. The trough is defined by three longitudinal walls—the sides 43 and 45 and the floor 46 .
Provided on top of the duct, a lid is installed (not pictured). The lid snaps onto and closes off the top of the trough along its entire length. It can be snapped on or off to create access to the cables included in the trough. These lids are well known to those skilled in the art, and are the most conventional way to top off the duct. The snapping in of the lid is done into lid-receiving channels. A first lid receiving channel 48 travels along the top of longitudinally extending side 45 . An identical lid receiving channel extends along the upper part of the longitudinally extending opposite side 43 of the duct. Channel 48 is defined by a first ridge 50 and a second ridge 52 formed on the second side 45 of the duct. An identical arrangement is disposed on the other side 43 (not specifically labeled). In inwardly formed member on each side of the lid is used to snap in on top of the duct in a fashion that will be well known to those skilled in the art.
Side 45 also has a first plurality of reinforcing ribs 58 and a second plurality of reinforcing ribs 60 below the first plurality. These are used to reinforce the duct and give it more structural integrity.
In FIG. 2 it may be seen that a knock out portion 64 in side 45 is provided by creating an outline of weakness around the portion 64 to define it. Here, in the preferred embodiment, perforations 62 have been used. The perforations 62 make knock out portion 64 easily removable form the ⅛ inch duct wall by a users fingers. The user simply pushes against portion 64 to snap it out of the duct.
It is import ant to note that other methods of weakening the duct wall, other than perforating it, could be employed to form the outline of weakness. For example, the wall could simply be thinned out along the outline. Chemical agents could also be employed to chemically weaken the outline.
Alternatively still, simple holes could be drilled into the duct instead of creating knocked out portions. These holes could simply be pre-manufactured as part of the molding process, or actively removed through drilling. Other cutting processes could be used instead.
Portion 64 is not the only knockout portion in the duct of the present invention. There are also a plurality of knocked out portions with weakened outlines 68 which run down the rest of side 45 of the duct. These knock outs are the same as portion 64 .
There are also knockouts on back side 43 . Though not pictured in FIG. 2 , the opposite side 43 of duct 40 possesses the same kinds of knock out portions shown on side 45 . formed by weakened outlines. Though these are not pictured in FIG. 2 , there are evident in FIGS. 3 through 5 . The embodiment shown in FIGS. 2 through 5 shows the same duct 40 of FIG. 2 , except that the knock-out portions (alternatively preformed holes) on both sides 43 and 45 of duct 40 have been removed.
Though FIGS. 2–5 show an embodiment in which both sides of the duct have knockouts, it will be recognized that knockouts or simple holes could be placed on only one side of the duct rather than both. It is also possible that fewer numbers or more of these knock out portions or holes could be provided on either side of the duct. Knockouts could even be provided in the floor 46 of the duct 40 .
Duct 40 of the present invention could be used alone, as it is pictured in FIG. 2 with cables being removed through the duct through the holes directly into split tubing and then run to the equipment as desired.
The preferred embodiment is provided, however, with optional downspouts. These downspouts are used to protectively conduct the cabling into the split tubing. A first downspout 70 is disclosed in FIGS. 3 through 5 . This downspout has a 3 inch radius of curvature. This particular radius of curvature enables the spout to be more practical for use in common cable running applications. E.g., for use with particular server-rack arrangements.
Downspout 70 has essentially two parts. A grommet 71 (see FIG. 4 , grommet 71 is not shown in FIGS. 3 and 5 ) and a spout 74 . Grommet 71 defines a hole through which the dropped cables will be run. This hole, though not particularly visible in the figures, is the same as a hole 79 defined through an opposite downspout 77 . The grommet 71 serves to retain downspout 70 into the duct from within. To do so, grommet 71 bears against the inside surface of the duct to hold the downspout within it. Spout 74 is used to fit through aperture 62 and includes a guide channel defined by a surface 76 . The top of spout 76 has been removed, thus the cable or cables will be exposed above where enter into corrugated split tubing 90 as shown. The selected fibers/cables will be slid down this channel defined by surface 76 and thus partially exposed before being dropped into corrugated split-tubing in a manner which will be described hereinafter. It also protects the cable which is run through it.
Downspout 70 is installed into the duct by inserting a first end 75 of the downspout through hole 66 and sliding the downspout through the hole until the inside surface of grommet 71 engages the inside surface of the duct, as can be seen in FIG. 4 .
FIG. 4 , as well as FIGS. 3 and 5 shown that the opposite side 43 of the duct 40 includes a downspout 77 which extends from the other side of the duct. See FIG. 4 . It has a grommet 72 , just like grommet 71 of downspout 70 . In fact, downspout 77 is essentially a mirror image of downspout 70 , and is installed in the same manner as well.
The spout 74 of downspout 70 has a cable receiving inside surface 76 . The downspout 70 is adapted to receive the cable and drop it into a split tubing 90 shown below. First end 71 of the spout is adapted with a radius which makes it able to be force fit within the standard inside diameter of a typical split tubing, e.g., split tubing 90 . For installation purposes, the downspout is slid into through hole 66 , then the selected cables to be dropped at that point are slid down cable receiving inside surface 76 into split tubing 90 , and then an outside surface 78 of spout 74 is forcibly slid into the split tubing 90 . Because the radius of outside surface 78 is slightly greater than the inner diameter of split tubing 90 , the force fit will be enabled.
A second downspout 80 with a 2 inch radius of curvature is disclosed being installed through a second hole 86 in duct 40 . This downspout 80 , like the first downspout, will have a grommet like that disclosed for downspout 70 . Though the grommet on downspout 80 is not shown, it would be the same as grommet 82 shown on a downspout opposite (in side 43 ). This not-pictured grommet will retain downspout 80 within the duct in the same manner disclosed for downspout 70 already. Essentially, downspout 80 is identical to downspout 70 , except that its radius of curvature has been minimize. This makes it more apt for different applications. For example, it may be advantageous with some server-rack configurations to drop the cabling more tightly to the duct. One skilled in the art will recognize that different radii of curvature for different downspouts could be used for different kinds of applications in order to drop cabling at different distances from duct 40 . All of these different curvatures and displacements should be considered within the scope of the present invention, and the present invention is not of course limited to the two radii of curvature identified here. Other radii or even configurations could be used and still fall within the scope of the present invention.
Though the installation techniques used with the present invention may be already somewhat evident, they are essentially the steps of first creating the apertures (or knockouts) in one of said sides or floor. You could put the apertures anywhere. In one of the sides, or in the floor. But as can be seen in FIGS. 2–5 , the preferred embodiment has holes spaced along both sides ( 43 and 45 ) of the duct 40 . These holes may be formed as premanufactured or drilled holes, or as the result of knockouts described above.
Once the duct is installed, normally at the ceiling of a facility, it will be likely that a systems administrator will eventually have to drop groups of cables from the duct. To do so, the user will simply physically remove a knockout proximate a location into which a single, or a plurality of cables need to be dropped. The knocked out portion of the duct, when removed, will create an aperture at the place a group of cables is to be dropped. If the holes are premanufactured or predrilled into the duct walls, this step will not be necessary.
After the hole has been created, in the preferred method, a downspout will be installed. This is done by removing the lid, if this has not yet been done, and then inserting the spout portion, e.g., first end 75 of spout 70 through the aperture 66 created. The insertion is done by first positioning the downspout 70 such that it is curved upward. After its full insertion, it will then be curved downward such that it depends from the duct. It will be held in by the grommet 71 .
Once the downspout 70 has been fully inserted, the split tubing 90 can be forced fit around the spout at first end 75 . As described above, this is a forced fit. The spout will then be securely held within the tubing. Tubing 90 will then be run to the equipment in a manner known to those skilled in the art.
Now that the spout and tubing have been installed, the user is ready to run the cable intended to be dropped. This is done by simply snaking it from inside the duct, though the spout, down the tubing, and to the equipment where it will be connected.
Once the necessary connections have been made, the remaining cables from the duct are resituated in the duct, and the lid is reinstalled. The process is then complete.
Again, the ducting system of the present invention is a significant improvement over the prior art available. The ducting of such systems is typically of such a thickness, e.g., at least ⅛ inch thick, such that it is difficult if not impossible to cut through it with a utility knife of other tool used by a technician in the field. The knock outs, or alternatively drilled holes, enable the user to gain access at any point along the duct if necessary in order to drop fibers. This gives the technician great levity in terms of accessing different cables at different points and then dropping them to equipment as desired.
As can be seen, the present invention and its equivalents are well adapted to provide a new and useful equipment housing which may be used to monitor equipment. Many different arrangements of the various components depicted, as well as components not shown, are possible without departing from the spirit and scope of the present invention.
The present invention has been described in relation to particular embodiments, which are intended in all respects to be illustrative rather than restrictive. Alternative embodiments will become apparent to those skilled in the art that do not depart from its scope. Many alternative embodiments exist but are not included because of the nature of this invention. A skilled programmer may develop alternative means of implementing the aforementioned improvements without departing from the scope of the present invention.
It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations and are contemplated within the scope of the claims. Not all steps listed in the various figures need be carried out in the specific order described.
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A ducting system for managing fiber optic, or other sorts of cabling. The duct has perforated circular punchouts in its sides. To drop cables to equipment below, the user simply punches out one of the circular perforated sections in the duct. This will leave a hole, which is sized to receive a downspout. Instead of punchouts, holes for the downspout could simply be drilled in the initial product. Regardless, the downspout is dropped to its full extent through and out of the duct through the hole, and is then retained by a grommet which bears against the interior of the duct. Once the downspout is secured in the hole, the selected cables are dropped from the duct through the hole, down the downspout, and into standard ribbed flex tubing, which may be force fit onto the downspout.
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FIELD OF THE INVENTION
[0001] The present invention relates to the use of the Lotus plant and especially Lotus extract in oral and topical applications. In addition, the present invention concerns the addition of methyl donors and other antioxidants to the formulation to protect the body from free radicals, a key factor contributing to aging.
BACKGROUND
[0002] The human body is assaulted on a daily basis by factors that accelerate the aging process—diet, stress, sun, heat, environment, and the formation of free radicals, which damage the skin cell membrane and DNA by various pathways.
[0003] The free radicals originate from many reactions. For example, molecular oxygen can be stripped of an electron by photons of light (solar radiation), heat, or an oxidant. Thus formed, singlet oxygen is highly reactive and short lived; it quickly adds another electron, producing the super oxide anion radical and the hydroxyl radical. All of these radicals are toxic to cells and highly reactive, causing a cascade of damage that accumulates over the years and contributes to aging.
[0004] In addition, free radicals are produced by normal metabolism, where oxygen is used to convert food for energy, as well as in certain diseases, such as infection and inflammation, in which the immune cells use free radicals, such as nitric oxide and superoxide radicals, to destroy bacteria and viruses. However, these free radicals, if in excess, can produce more damage, in particular to DNA, causing mutations and fragmentations.
[0005] The damage doesn't stop at the cell or molecule that is oxidized, since the oxidized component within the cell or molecule becomes unstable and highly reactive due to its need for an electron, it becomes a free radical attacking other cells or molecules, thereby causing a chain reaction.
[0006] For general health, oxidation of lipids and proteins injures cell membranes, weakens blood vessels, modifies enzymes and damages many other molecules. These injuries alter cell functions and increase the risk of heart disease, stroke, and cancers.
[0007] The effects of free radicals on the skin is reflected in accelerated aging; that is, a loss of tone and elasticity and formation of wrinkles and lines. These effects are due to the damage free radicals have on collagen levels and chemical changes to the collagen molecule itself by various pathways.
[0008] In addition to the aging factors, as discussed above, skin is also subject to other aging factors. Within the dermis are highly stable fibers of collagen and elastin. Collagen, the most abundant protein in the body, has a high tensile strength thus preventing skin from being torn by over stretching. Elastin, also a protein, allows movement. As skin ages, elastic tissue increases until it loses the ability to stretch and recover. This loss of resiliency and elasticity is accompanied by increased stiffness, sagging and wrinkling. Changes in collagen solubility and cross-linking contribute to loss of elasticity. Cell renewal, skin thickness and circulation decrease with aging, affecting the skin's ability to withstand stress from UV radiation and free radicals.
[0009] On the cellular level, aspartyl and asparaginyl residues are prominent sites of age-related damage in proteins. These damaged sites have been characterized in a variety of proteins, but are particularly common in the long-lived proteins. Enzymatic mechanisms for reversing damage to DNA are well established and have been shown to be essential for extended lifespan.
[0010] Experiments performed in vitro with recombinant and chemically modified polypeptides have shown that the presence of an L-isoaspartyl residue may alter both enzymatic activity and the binding of other molecules.
[0011] Limiting the accumulation of these residues within cells is currently believed to be important; all human cells examined thus far contain an L-isoaspartyl/D-aspartyl protein methyltransferase that has been proposed to serve this function. It is also believed that this methyltransferase can recognize both D-aspartyl and L-isoaspartyl residues. In addition, it is thought that this enzyme may have the ability to reverse at least part of the damage to protein molecules.
[0012] Although the human isoaspartyl protein repair methyltransferase has been purified from red blood cells and had its protein sequence determined, in addition to harvesting a variant in a bacterial system, the availability and use of methyltransferase has been limited.
[0013] On or around Nov. 14, 1995, however, it was reported that scientists germinated a 1,288 year old Sacred Lotus seed. The research reported in the November issue of the American Journal of Botany, began in 1982, when Jane Shen-Miller, a plant physiologist at the University of California at Los Angeles (UCLA) obtained seven brown, oval-shaped Sacred Lotus seeds from the Beijing Institute of Botany.
[0014] In 1983, Jane Shen-Miller filed through the hard shells of four of the ancient Sacred Lotus seeds and watched three of them sprout. She then dried and burned the seedlings so she could use radiocarbon dating to establish the ages, the oldest of which was 1,288 years old. It has been postulated as a result of this research that Sacred Lotus seeds act as live embryos until such seeds are germinated. Up until this point, geneticists knew only about proteins that repaired damaged DNA. But findings have suggested that the L-isoaspartyl methyltransferase (MT) enzyme, found in the Sacred Lotus seeds and nearly all other organisms, may have the ability to repair other proteins—those that make up cells and tissues, thus slowing tissue decay.
[0015] In these ancient Sacred Lotus seeds, the MT enzyme was present at levels comparable to modern day Sacred Lotus seeds. Damaged proteins did not accumulate within the ancient Sacred Lotus seeds, suggesting that the MT enzyme, possibly along with other constituents, such as methyl donors and antioxidants, kept the ancient Sacred Lotus seeds alive for so many years.
[0016] Notwithstanding the above, it is unknown as to whether use of methyltransferase or extracts or components of the Sacred Lotus plant in topical or oral compositions would be effective in combating aging, repairing damaged skin and/or restoring skin to a more youthful appearance. Moreover, there are no known acceptable products available which incorporate methyltransferase or extracts or components of the Sacred Lotus for combating dermatological aging, repairing damaged skin and/or restoring skin to a more youthful appearance.
SUMMARY OF THE INVENTION
[0017] The present invention alleviates and overcomes certain of the above-mentioned problems and shortcomings of the present state of the art through the discovery of novel acceptable oral and topical delivery systems and compositions for effectively treating and preventing signs of aging, repairing damaged skin and restoring skin to a more youthful appearance and methods of using the same.
[0018] Accordingly it is the object of the invention to provide a general method for prevention or alleviation of age-related damage to the skin and associated decline of body function and appearance from aging through the topical and/or internal use of a composition in combination with a suitable carrier or vehicle.
[0019] Another object is to enhance a cosmetic composition to make the skin appear younger by adding Sacred Lotus and methyl donors.
[0020] Another object is to restore the skin to a more youthful appearance.
[0021] Another object is the formulation of dietary supplements to nourish and protect skin from within.
[0022] Another object is to have the person taking the supplement experience improvement in physical attributes helping the person to feel younger and look younger; have increased stamina; have increased sexual function; have improved circulation; have improved hair and nail strength and growth; have improved vision; have improved mental focus, performance and memory; have improved overall health; have improved immune function; have improved body composition, with greater muscle tone; have improved body composition, with less body fat; have improved ability to sleep; have improved vitality; have improved energy; have improved mood; restore skin to a more youthful appearance; improve the vibrancy of skin; improve the smoothness of skin; improve the tone of skin; improve the elasticity of skin; and have less wrinkles.
[0023] Another object is to use additional antioxidants to counter the deleterious effects of free radicals.
[0024] Another object is to add Lotus extract and methyl donors to existing preparations to reduce the appearances of lines and wrinkles.
[0025] Another object is to use the extract of Sacred Lotus ( Nelumbo nucifera ) as a natural source of methyltransferase. It has now been observed, surprisingly and unexpectedly, that by using an extract of Lotus in combination with methyl donors by topical application or oral ingestion, signs of aging can be reduced, eliminated or even reversed.
[0026] Until the present invention, there were no acceptable vehicles utilizing Lotus extract in combination with synergistic acting methyl donors in an elegant cosmetic and/or basic pharmaceutical composition. Thus another object of the present invention are formulations of Lotus extract in combination with methyl donors in dermatologicals, such as gels, lotions, powders, tablets, capsules, creams, sunscreens, cleansers, and various skin care formulas to repair the damage from aging, reduce further damage and restore skin to a more youthful appearance.
[0027] These and other objects are achieved by the present invention which is directed to a topical or oral formulation for the protection of the skin against free radical damage contributing to aging and a method for preventing or alleviating such damage and restoring skin to a more youthful appearance by employing such in a topical or oral formulation.
[0028] The formulation is a suitable cosmetic or dermatologically or orally acceptable non-toxic, non-allergenic carrier containing a variety of components.
[0029] The above features and advantages of the present invention will be better understood with reference to the detailed description and examples. It should also be understood that the particular methods and topical and oral formulations illustrating the present invention are exemplary only and not to be regarded as limitations of the present invention.
DETAILED DESCRIPTION
[0030] By way of illustrating and providing a more complete appreciation of the present invention and many of the attendant advantages thereof, the following detailed description and examples are given concerning the novel topical and oral delivery systems which contain a combination of Lotus extract and methyl donors for effectively treating and preventing aging, repairing damaged skin and restoring skin to a more youthful appearance and improving overall health and methods of using same.
[0031] The present invention uses Lotus extract in skin and dietary formulas to combat aging. It is believed that the use of Lotus extract in cosmetics and dietary supplements accomplish anti-aging effects based on anti-aging factors (enzymes such as methyltransferase) which are present in the Lotus plants and seeds.
[0032] Moreover, Lotus extracts contain certain anti-oxidants such as vitamin C and glutathione which may contribute to anti-aging effects on skin along with methyltransferase and may even contain other beneficial factors.
[0033] In accordance with the present invention, methyltransferase and/or the natural compounds found in an extract of Lotus plants may be used in an effort to repair age related signs of the skin such as lines, spots, wrinkles, and/or loss of elasticity. Other sources of methyltransferase that may be used in the invention are extracts of Sacred Lotus seeds or other components of the Sacred Lotus plants, extracts of Yellow Lotus seeds or components of Yellow Lotus plants, extracts of Purple Lotus seeds or other components of Purple Lotus plants, extracts of Blue Lotus seeds or other components of Blue Lotus plants, extracts of White Lotus seeds or other components of White Lotus plants, extracts of other Lotus seeds or components of other Lotus plants where methyltransferase may be present, wheat germ oil, liver, brain, other animal parts including glands, and bio-fermentation or chemical synthesis for example.
[0034] An extract is prepared, for example, as follows. Maceration is the preferred process, since no heat is used which may destroy or alter temperature sensitive components; however percolation, digestion, infusion and decoction are within the scope of the invention as more scientific information becomes available.
[0035] A twenty percent extract of Nelumbo nucifera is used and prepared by placing 200 grams of finely milled untreated whole seeds, including husks and piths, in a stoppered container with about 750 mL of a 50/50 wt/wt mixture of purified water and propylene glycol USP and allowed to stand for a period of at least three days in a warm place with frequent agitation, until soluble matter is dissolved. The mixture is filtered and, after most of the liquid has drained, the residue on the filter is washed with sufficient quantity of solvent mixture; the filtrates are combined to produce 1000 mL.
[0036] It is also within the scope of the present invention to use different amounts of the seed, other parts of the plant, as well as other species, solvents and mixtures.
[0037] The present inventor has been experimenting with the use of Lotus seed extract in oral and topical formulations since 1996. Ongoing research has revealed that colorful fruits and vegetables, such as carrots and broccoli, contain excellent antioxidant properties. As evidenced by their names (Blue Lotus, Yellow Lotus, Purple Lotus, etc.), the flowers of the Nelumbo family are also very colorful. The present inventor realized that the pigments contained in the Lotus flower would act similarly to antioxidants and that the combination of Lotus seed extract and Lotus flower extract may prevent free radical damage and extend the youthfulness of the skin.
[0038] While it is believed that Sacred Lotus ( Nelumbo nucifera ) is a preferred species and the seed and flower are the preferred parts, other parts of the plant or other species, such as the Yellow Lotus ( Nelumbo lutea ), Blue Lotus ( Nelumbo caerulea ), White Lotus or other Lotus varieties containing these anti-aging enzymes or constituents are believed to be suitable alternatives for accomplishing the objectives of the present invention.
[0039] As discussed above, methyltransferase and/or the natural compounds found in the extract of the Lotus is used to combat the natural aging process. However, the skin is also subject to external factors that contribute to accelerating the aging process. The present invention combats these external factors utilizing extract of the Lotus in combination with methyl donors. It is believed that this mixture provides added protection from external factors that damage the skin.
[0040] The present invention combines Lotus extract with methyl donors. As discussed above, it is believed that Lotus extract contains the L-isoaspartyl methyltransferase enzyme. In general, the methyltransferase enzyme catalyzes the transfer of a methyl group to an acceptor molecule. Many different methyltransferase reactions have been documented in the literature, including 1-phenanthrol methyltransferase activity, 5,10-methylenetetrahydrofolate-dependent methyltransferase activity, 5-methyl-5,6,7,8-tetrahydromethanopterin-dependent methyltransferase activity, to name a few. According to the theory of the present invention, the Lotus extract contains the L-isoaspartyl methyltransferase enzyme, which transfers a methyl group to damaged L-isoaspartyl residues. This mechanism serves to repair cell damage to all human cells.
[0041] As discussed above, Applicant has discovered that the addition of methyl donors to topical and oral compositions containing Lotus extract results in improved skin benefits by the repair of age-related damage in proteins by limiting the accumulation of L-isoaspartyl residues. Methyl donors include any compounds that have a methyl (—CH 3 ) side chain. Some suitable examples include methionine, betain (aka trimethylglycine), dimethylglycine, choline, polyenyphosphatidylcholine, phosphatidylserine, phosphatidyl choline (lecithin), glycerylphosphoryl choline, and S-adenosyl-L-methionine (“SAMe”). The methyl donor provides the methyl group needed by the L-isoaspartyl methyltransferase to repair the damaged cell.
[0042] The present invention is directed to the use of a combination of Lotus extract and methyl donors in oral and topical formulations. It is theorized that this combination may act in concert with or perhaps synergistically with one or more of the following ingredients:
[0000] Vitamins
[0043] Any known vitamins or their derivatives are useful in the present invention. Vitamins, by definition, are any of a group of organic substances essential in small quantities to normal metabolism. Synthetic vitamins are also available and may be utilized in the present invention. It is believed that the addition of one or more vitamins to the proposed combination would benefit the end user by providing components that may be needed in the cell repair process.
[0044] Vitamin A, or retinol, is a fat soluble vitamin. Vitamin A has been demonstrated to aid bone development, strengthen the immune system and promote wound healing. Sources of Vitamin A include broccoli, cantaloupe, cod, halibut, kale, red peppers, spinach and watercress. The addition of natural or synthetic Vitamin A and derivatives thereof to the present invention would prove beneficial.
[0045] Vitamin B-1, or thiamine, is a water soluble vitamin. Vitamin B-1 has been demonstrated to assist in the metabolism of proteins and fats. Sources of Vitamin B-1 include chick peas, pinto beans, soybeans, nuts, and salmon.
[0046] Vitamin B-2, or riboflavin, is a water soluble vitamin. Vitamin B-2 is essential for normal cell growth. Sources of Vitamin B-2 include almonds, walnuts and dairy products, such as cottage cheese, milk and yogurt. The addition of natural or synthetic Vitamin B-2 and derivatives thereof to the present invention would prove beneficial.
[0047] Vitamin B-3, or niacin, is a water-soluble vitamin. Vitamin B-3 has been demonstrated to protect against carcinogens and is useful in maintaining healthy skin. Sources of Vitamin B-3 include almonds, sunflower seeds, hazelnuts and yogurt.
[0048] Vitamin B-6, or pyridoxine, is a water-soluble vitamin. Vitamin B-6 is essential for the proper functioning of over sixty enzymes. Sources of Vitamin B-6 include eggs, salmon, pinto beans and lentils.
[0049] Vitamin B-12, or cyanocobalamin, is a water-soluble vitamin. Vitamin B12 helps maintain healthy cells. Sources of Vitamin B-12 include eggs, yogurt, salmon and halibut.
[0050] Vitamin C, or ascorbic acid, is one of several antioxidants shown to be essential for reducing free-radical induced cellular and molecular events when skin or cells are exposed to substantially high doses of ultraviolet B radiation. Vitamin C has also been shown to inhibit ultraviolet radiation-induced immunosuppression in vitro. Sources of Vitamin C include broccoli, cantaloupe, citrus, red peppers, strawberries and tomatoes.
[0051] Vitamin D is a fat soluble vitamin. Vitamin D is essential in calcium absorption and metabolism. Sources of Vitamin D include fish, such as cod.
[0052] Vitamin E is the α-form of tocopherol. There are four stereoisomers of tocopherol and four stereolsomers of tocotrienol. The tocopherols and the tocotrienols both contain a central aromatic chromanol nucleus and a 16-carbon member side chain. The side chain in the tocopherols is saturated. The side chain in the tocotrienols is not. Vitamin E is found in palm oil, soy bean oil, corn oil, canola oil, cranberry oil, rapeseed oil, rice bran oil, sunflower oil, safflower oil and cottonseed oil. However, of these, only cranberry oil, palm oil and rice bran oil contain tocotrienols. α-tocopherol is one of several antioxidants shown to be essential for reducing free-radical induced cellular and molecular events when skin or cells are exposed to substantially high doses of ultraviolet B radiation. α-tocopherol has also been shown to inhibit ultraviolet radiation-induced immunosuppression in vitro. Sources of Vitamin E include almonds, hazelnuts, pecans, sunflower seeds, asparagus, olives, and spinach.
[0053] Vitamin F, also known as Essential Fatty Acids or EFA, is a fat-soluble vitamin. Vitamin F consists of unsaturated fatty acids with two or more double bonds, such as linoleic acid and linolenic acid. The term Vitamin F was discredited by the American Medical Association in 1937. Sources of Vitamin F include vegetable oils, such as olive oil.
[0054] Vitamin H, also known as biotin, is a water soluble vitamin. Sources of biotin include liver, kidney, pancreas, yeast and milk.
[0055] Vitamin K is a general term that refers to a group of naphthoquinone derivatives required for the bioactivation of proteins involved in blood coagulation or stagnation. Sources of Vitamin K include green plants and intestinal bacteria.
[0000] Minerals
[0056] Any known minerals or their derivatives are useful in the present invention. There are several definitions for minerals, including, “any substance that is neither animal nor vegetable.” However, the use of the term in the present invention is directed to any of a group of inorganic substances essential to the functioning of the human body and that are usually obtained from foods. It is believed that the addition of one or more minerals to the proposed combination would benefit the end user by providing components that may be needed in the cell repair process.
[0057] Minerals useful in the present invention include copper, zinc, and manganese, for their role in forming the antioxidant, superoxide dismutase, and selenium and glutathione, for their role in function of glutathione peroxidase. Other minerals involved in cell function maintenance include calcium, magnesium and potassium. Other useful minerals include sulfur, chromium, iron, phosphorous and iodine.
[0000] Antioxidants
[0058] Antioxidants protect skin cells and collagen from free radical damage. The present invention combines Lotus and methyl donors with antioxidants to provide stronger damage protection. Some of the antioxidants useful in the present invention include glycyrrhiza glabra, quercetin, rosemary, sage, ginger, tumeric, carnosine, curcumin, limonene, silymarin, isoflavones, carotenoids, asaxanthin, lycopene, lutein, superoxide dismutase, aloe vera, carnosine, CoEnzyme Q10, hawthorne berry, hawthome berry extract, acerola, acerola extract, apricot, apricot extract, bilberry, bilberry extract, blackberry, blackberry extract, black currant, black currant extract, blueberry, blueberry extract, chaste berry, chaste berry extract, cherry, cherry extract, cranberry, cranberry extract, elderberry, elderberry extract, mulberry, mulberry extract, raspberry, raspberry extract, strawberry, strawberry extract, ubiquinone, acerola berry, olive pulp extract, including hydroxytyrosol, broccoli sprouts, ginko biloba, ginseng, carnitine, pycnogenol, oregano, inositol, choline, willow bark extract, acetylsalicylic acid, meadowsweet flower, and DMAE (dimethylamino ethanol). The berries listed above can be used as the fruit, as a powder or as an extract.
[0000] Amino Acids
[0059] Amino acids, such as glycine, glutamine, proline, and lysine, are components of collagen and therefore useful in compositions of the present invention. Valine, arginine, and alanine are vital to skin repair. Collagen is one part of connective tissue and the major component of the skin. 4-hydroxyproline is found mainly in collagen. Serine is a non-essential amino acid for human development.
[0000] Hormones
[0060] Hormones are vital to the skin's natural metabolism. With age, hormone levels decline in the body and the skin. Cell function declines as hormonal levels drop. It is known that estrogen and testosterone can restore some youthfulness to the skin's appearance. This invention encompasses these and other compounds with hormonal activity that rejuvenate the skin's youthful appearance. Some of the hormones useful in the present invention include estrogen and its components (estradiol, estriol and estrone), testosterone, pregnenolone, progesterone, melatonin, and DHEA. Phytoestrogens from plants are also useful in the present invention and include soy and its constituents, yam, polygonum cuspidatum, black cohosh, licorice, grapes/resveratrol, dongquai, red clover, and vitex agnus castus.
[0061] Growth factors, such as EGF (Epidermal Growth Factor), FGF (Fibroblast Growth Factor) or IGF (Insulin-like Growth Factor), appear to act in concert with or perhaps synergistically with Lotus.
[0000] Compounds Commonly Used in Cosmetics as Skin Beautifiers
[0062] The present invention may also include the following conventional ingredients:
[0063] α-hydroxy acids, also known as fruit acids, are well-known skin rejuvenating agents for photoaged and aged skin. Some examples of α-hydroxy acids include citric, glycolic (sugar cane extract) and lactic acids.
[0064] Glycerin is a common humectant in both topical and oral formulations. It is used to dissolve non-water soluble substances. It is also used to provide a moisture barrier between the skin and the environment.
[0065] Rice bran oil, walnut oil, almond oil, pumpkin seed oil, sunflower seed oil, safflower seed oil, fish oil, omega 3 fatty acids, omega 6 fatty acids, DNA/RNA, vitamin D, policosanol,
[0066] The term surfactant is used to describe an additional group of additives to the present invention. Surfactants are solubilizers which are used to promote solubility. Surfactants for use in the present invention are pharmaceutically acceptable and include polysorbates and partial esters of common fatty acids, to name two of many available.
[0067] Sunscreen agents are also within the scope of the present invention. Titanium dioxide is a well-known cosmetic ingredient used topically to protect the skin from photo-aging. Octylmethoxycinnamate, benzophenone, octylsalicylate, and parsol 1789 can also be used in combination with Lotus and/or methyl donors to increase the skin's defense against sun damage.
[0068] It should be understood that the topical or oral compositions of the present invention may be used at any appropriate daily intervals, depending of course upon the particular type of composition formulated. For instance, the Firming Antioxidant Serum, as set forth in Example 2 hereinafter, is to be used anytime when desired, i.e., at night, under make-up, by itself, or before using or with other preparations. Whereas anyone skilled in the art, obviously can formulate a myriad of products for special needs that would be within the scope of this invention.
[0069] A composition according to the present invention may be in any of the cosmetic, pharmaceutical or dietary forms which are generally used for topical application such as liquids (both aqueous and non-aqueous solutions), creams (both oil-in-water and water-in-oil, O/W & W/O, emulsions), gels (both aqueous and non-aqueous), lotions, serums, ointments, paste, powders, liposomes, laminates, microspheres, capsules, and tablets.
[0070] Compositions of the present invention may also contain additives such as water, alcohols, oils (mineral vegetable, animal and synthetics), glycols, colorants, preservatives, emulsifiers, gelling agents, gums, esters, silicones, polymers, fragrances, flavors, active ingredients, acids, bases, buffers, salts, polyols, proteins and their derivatives, essential oils, tonics, waxes, lipids, stabilizers, fillers, celluloses, glycans, amines, solubilizers, thickeners, sugars and sugar derivatives, ceramides, sweeteners and the like, so long as such additives do not defeat the objectives of the present invention.
[0071] Other items such as lecithin, squalene, panthenol, jojoba oil, vegetable oils, saccharide isomerate, glycerin, dimethicone, aloe, saccharide isomerate and other moisturizers also appear to benefit the present invention in holding moisture in the skin, enhancing its repair process, protecting the skin barrier function and making the skin appear younger.
[0072] The following examples are given for illustrative purposes only to delineate some of the features of the invention and are not intended to be limiting. As to exemplary formulations set forth below, the quantities are given in percent weight (% wt) or international units (I.U.), unless otherwise noted, based on the total weight of the composition. The term qs means to use a sufficient quantity by weight to bring the entire composition to 100%. Whenever possible, International Nomenclature Cosmetic Ingredient (INCI) names are used.
EXAMPLE 1
[0073]
DAILY NUTRIENTS
Vitamin A Palmitate
1750
IU
Natural Beta Carotene
750
IU
Lycopene
0.375
mg
Lutein
0.375
mg
Vitamin E (d-alpha tocopheryl acetate and
50
IU
mixed tocopherols and tocotrienols)
Cholecalciferol (Vitamin D3)
200
IU
Vitamin C
150
mg
Thiamine HCl
4
mg
Riboflavin
5
mg
Niacinamide
20
mg
Pyridoxine HCl
6
mg
Folic Acid
200
mcg
Vitamin B-12
5
mcg
Pantothenic Acid
7.5
mg
Biotin
75
mcg
Calcium (Carbonate & Citrate)
12.5
mg
Magnesium Oxide
18.75
mg
Iron (Fumarate)
7.5
mg
Zinc (Sulfate & Gluconate)
7.5
mg
Manganese Gluconate
2
mg
Selenium (L-Selenomethionine & Citrate)
35
mcg
Chromium Nicotinate
37.5
mcg
Copper Gluconate
0.5
mg
Green Tea Extract
7.5
mg
Grape Seed Extract
7.5
mg
N-Acetyl Glucosamine
15
mg
Citrus Bioflavanoids
37.5
mg
N-Acetyl Cysteine
5
mg
Sacred Lotus seed extract
500
mcg
S-adenosylmethionine
500
mcg
Magnesium Stearate (lubricant)
8.4
mg
Stearic Acid (binder)
42
mg
Microcrystalline Cellulose (tablet aide) qs
840
mg
[0074] Procedure:
[0075] All of the above were mixed in a powder blender until completely homogenous. The mixed powder was fed into a tablet press and compressed into tablets.
[0076] A unique blend of protective antioxidants and essential nutrients with the entire Sacred Lotus seed (in food preparations the pithe (embryo) or lumule is removed due to bitter taste) used to promote good health and radiant skin is provided. This product may be taken, for example, twice per day.
EXAMPLE 2
[0077]
FACE THERAPY
Water
50-75
Carbomer 940
0.1-1
Diazolidnyl Urea
0.1-0.5
Glycerine
0.1-5
Methylparaben
0.1-0.3
Panthol Powder
0-1
Triethanolamine
0.5-2
Stearic Acid
0.5-5
Glycol Stearate SE
0.5-5
Cetyl Alcohol
0.5-4
PPG-3 Myristal Ether
0-3
Isopropyl Myristate
0.5-5
Cocoa Butter
0-3
Rose Hip Seed Oil
0-1
Soybean Oil
0-2
Tocopheryl Acetate
0-5
Retinyl Palmitate
0-1
Propylparaben
0.05-0.2
Lecithin
0-1
Lipogard
0-5
Pregnenolene Acetate
0-0.5
Progesterone
0-0.018
Water
0-10
Glucosamine
0-5
Soy Isoflavones
0-1
Carnosine
0-5
Polygonum Cuspidatum
0-1
Propylene Glycol
0-5
Aloe Extract 10×
0-5
Ascorbyl Palmitate
0-1
Superoxide Dismutase
0-2
Fermalcase 1000
0-2
Coneflower Extract/Hydrocotyl extrct
0-5
Green Tea Extract (GTP)
0-5
Grape Seed Extract
0-5
Pine Bark Extract
0-5
Lotus Seed Extract
0-5
Folate
0-5
Saccharide Isomerate
0-5
Ginseng Extract
0-5
Wild Yam Extract
0-5
Algea Extract
0-5
Tenox 6
0.05-0.8
Vanilla 371B
0-2
Lycopene
0-0.25
Lutein
0-0.25
[0078] Procedure
[0079] The ingredients are mixed together using standard mixing techniques. A pleasant cream results.
EXAMPLE 3
[0080]
LOTUS FIRMING SERUM
Water
50-85
Panthenol Powder
0-1
Mg Ascorbyl Phosphate
0-15
Superoxide Dismutase
0-2
Catalase
0-2
Lotus Seed Extract
0-15
S-adenosylmethionine
0-5
Saccharide Isomerate
0-8
Na4EDTA
0.01-0.5
Glucosamine
0-10
Lipogard
0-5
Germaben II
0.5-1.5
Sodium Hyaluronate
0-10
Pine Bark Extract
0-10
Green Tea Extract
0-10
Coneflower Extract/Hydrocotyl extract
0-10
Vitamin A/D3
0-1.5
Tocopheryl Acetate
0-5
Cyclomethicone
0-10
Sepigel 305
0-10
Fragrance
0-1
Lutein
0.001-0.5
Lycopene
0.001-0.5
[0081] Procedure
[0082] The ingredients are mixed together using standard mixing techniques. A pleasant serum results.
EXAMPLE 4
[0083]
ANTI-AGING MOISTURIZER
Water
50-75
Carbomer 940
0.1-1
Diazolidnyl Urea
0.1-0.5
Glycerine
0-10
Allantoin
0-10
Methylparaben
0.1-0.3
Panthenol Powder
0.1-1
Triethanolamine
0.5-3
Stearic Acid
1-5
Glycol Stearate SE
1-5
Cetyl Alcohol
0.5-5
PPG-3 Myristal Ether
0.5-5
Isopropyl Myristate
0.1-5
Cocoa Butter
0-5
Rose Hip Seed Oil
0-1
Soybean Oil
0-2
Tocopheryl Acetate
0-5
Retinyl Palmitate
0-1
Tocotrienol Oil
0.001-0.5
Tumeric Oil
0-5
CoQ10
0-0.5
Propylparaben
0.1-0.2
Aloe Extract 10×
0-5
Beta-Carotene
0-5
Superoxide Dismutase
0-2
Fermalcase 1000
0-2
Coneflower Extract/Hydrocotyl extract
0-10
Green Tea Extract (GTP20)
0-10
Grape Seed Extract
0-10
Pine Bark Extract
0-10
Lotus Seed Extract
0-10
S-adenosylmethionine
0-5
Ascorbyl Palmitate
0-1
Saccharide Isomerate
0-5
Ginkgo Biloba Extract
0-10
Ginseng Extract
0-10
Bilberry Extract
0-10
Rosemary Extract
0-10
Milk Thistle Extract
0-10
Olive leaf Extract
0-10
Tetrahydrodiferuloymethane
0-5
Carnosine
0-5
Alpha-Lipoic Acid
0-1
Water
2-10
Lutein
0-0.25
Lycopene
0-0.25
[0084] Procedure
[0085] The ingredients are mixed together using standard mixing techniques.
EXAMPLE 5
[0086]
EYE THERAPY
Water
20-65
Glycerin
0-5
NA4 EDTA
0-0.5
Panthenol
0-1
Diazolidinyl Urea
0.1-0.5
Methylparaben
0.1-0.3
Tween 20
0-2
Veegum 5%
10-20
Sunflower Oil
5-15
Mineral Oil
5-15
Arlacel 165
1-5
Cetyl Alcohol
1-5
Phenyl Dimethicone
1-5
Olive Oil
0-5
Propylparaben
0.05-0.2
Tocopheryl Acetate
0-5
2 POE Stearyl Stearate
0-5
Lecithin
0-2
Glyceryl Dilaurate
0-2
Sodium Lauryl Sulfate
0-0.5
Retinyl Palmitate
0-2
Magnesium Ascorb Phos
0-5
Fermocalase 1000
0-2
Superoxide Dismutase BT
0-2
Aloe 10×
0-5
Algae Extract APT
0-5
Hydro Soy Protien
0-5
Coneflower Extract/Hydrocotyl extract
0-8
Glucosamine
0-5
Lotus Seed Extract
0-10
Trimethylglycine
0-5
Polygonum Cuspidatum
0-0.5
Propylene Glycol
0-5
Wild Yam Extract
0-5
Glycosaminoglycans
0-10
Pregnenolone Liposome
0-2
Progesteone Liposome
0-2
Soy Isoflavones
0-0.3
Squalane Ubiquinone
0-5
Tenox 6
0.05-0.5
Lycopene
0.001-0.8
Lutein
0.001-0.3
Sodium Hydroxide 25%
0-5
[0087] Procedure
[0088] The ingredients are mixed together using standard mixing techniques.
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Cosmetic, dermatological and dietary compositions for treatment of aging of the skin are provided that contain a compound useful in promoting skin health and youthful appearance, such as extract of Lotus in combination with methyl donors, in a suitable carrier or vehicle along with methods of treatment to reduce signs of aging such as loss of elasticity, age spots, enlarged pores, fine lines, wrinkles and to promote over-all younger looking skin by using said compositions to help repair damage and to help neutralize free radicals.
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RELATED APPLICATIONS
This application claims priority under 35 U.S.C. 119 from Provisional Applications 60/643,001, 60/643,002, 60/643,003 and 60/643,004 all filed Jan. 12, 2005.
Reference is made to co-pending applications filed on the same date as this application by the same inventors, the disclosures of which are incorporated herein by reference as follows:
application Ser. No. 11/152,679 entitled AN INTRUSION DETECTION SYSTEM FOR USE ON SINGLE MODE OPTICAL FIBER USING FRESNEL REFLECTIONS.
application Ser. No. 11/152,772 entitled AN INTRUSION DETECTION SYSTEM FOR USE ON SINGLE MODE OPTICAL FIBER USING A STORAGE REGISTER FOR DATA.
application Ser. No. 11/152,681 entitled AN INTRUSION DETECTION SYSTEM FOR USE ON SINGLE MODE OPTICAL FIBER USING A POLARIMETER.
application Ser. No. 11/152,680 entitled AN INTRUSION DETECTION SYSTEM FOR USE ON SINGLE MODE OPTICAL FIBER USING A SIMPLIFIED POLARIMETER.
application Ser. No. 11/152,768 entitled AN INTRUSION DETECTION SYSTEM FOR USE ON SINGLE MODE OPTICAL FIBER USING POLARIZERS AT 90 DEGREES.
FIELD OF THE INVENTION
The present invention relates to the detection of movement of a single mode optical fiber.
The present invention as described in more detail hereinafter includes both to embodiments of the invention which allow location of the intrusion event by analysis at the same end as the transmitted light of reflected light and to embodiments of the invention which do not provide location of the intrusion event by analysis of light at a remote end of the fiber.
BACKGROUND OF THE INVENTION
Single mode fiber optic backbone cables are being deployed to connect sections of high-speed networks together, and for long distance communications. To secure these high-speed networks, software based Intrusion Detection Systems (IDSs) have been introduced. These systems capture and analyze all packets for unusual patterns that point to an intrusion as well as monitor systems accessing a network. However, this adds to the complexity of the network and burdens processing power. Current IDSs are hampered by Base-Rate Fallacy limitation, which is the inability to suppress false alarms. Additionally, software-based IDSs do not provide protection against passive optical fiber tapping, which can go undetected by the network hardware. Software IDS is the de-facto standard for intrusion detection, however it is oblivious to actual physical layer intrusion and perturbation such as tapping or the attendant fiber handling.
It is well known, by those skilled in the technology, that optical fibers are easily tapped and the data stream monitored. One relatively simple non-interruptive tapping method involves placing a bend coupler on the fiber to be tapped. A controlled bend of a critical radius is placed on the fiber. This causes a small spatial distortion in the core/cladding guiding properties and a fraction of the light escapes the fiber. A detector is located at the point of the light leakage and the data steam observed. Bend couplers typically introduce a loss of light power of up to 1 dB or more. Power measuring intrusion detection systems are available to detect this loss in optical power and provide warning alarms.
With care and skill, more insidious methods are available to the skilled intruder. With a sufficiently sensitive receiver and care in preparation, a fiber can be successfully tapped without introducing a telltale bend in the optical fiber. A successful tap can be achieved by carefully removing a few inches of the protective outer coating of the target fiber and polishing, etching, or otherwise reducing the outer cladding down by a few microns to form a flat coupling region. A cladding-to-cladding coupling is then made using a special intercept fiber. This method intercepts a portion of the weak but measurable evanescent power that propagates along the tapped fiber. In this case, the intercepted light, which is detected by a sensitive receiver, can easily be 20 or 30 dB down from the power in the fiber core. This results in a loss of received optical power of only 0.04 or 0.004 dB and is impossible to detect reliably by power measurement methods. Using a similar stripping mechanism and a high sensitivity photo detector, Rayleigh Scattering from within the fiber can be detected.
Reference is made to Hernday, P. Polarization Measurements. In D. Derickson (Ed.), (1998). Fiber Optic Test and Measurement (pp. 220-245). New Jersey: Prentice Hall PTR, the disclosure of which is incorporated herein by reference.
Reference is also made to US pending Application 2005/0002017 published Jan. 6, 2005 by Haran which discloses primarily a method for utilizing an optical fiber for use in detection of intrusion through a perimeter fence but also mentions in passing that similar techniques can be used in optical fibers in transmission systems.
Reference is also made to PCT pending Application WO 02/095349 published Nov. 28, 2002 by Rogers which discloses a method for optical fiber backscatter polarimetry.
In U.S. Pat. No. 5,384,635 (Cohen) published Jan. 24, 1995 is disclosed a method for detecting vibration of an optical fiber caused by digging equipment where the method detects polarization changes in back-scattered light.
In U.S. Pat. No. 4,904,863 (McDearmon) published Feb. 27, 1990 is disclosed a pressure sensor which uses an optical fiber where the method detects polarization changes in back-scattered light.
In U.S. Pat. No. 4,840,481 (Spillman) published Jun. 20, 1989 is disclosed a strain sensor which uses an optical fiber where the method detects polarization changes in back-scattered light.
In U.S. Pat. No. 6,724,469 (LeBlanc) published Apr. 20, 2004 is disclosed a method of polarization optical time-domain reflectometry.
SUMMARY OF THE INVENTION
It is one object of the present invention to provide an arrangement for detecting movement of an optical fiber which overcomes the limitations with power loss detection methods and can detect intrusion activity before any optical power loss occurs.
According to the invention there is provided a method for detecting movement of an optical fiber comprising:
providing a optical fiber having a first end and a second end;
detecting movement of a portion of the fiber along the length thereof by:
injecting polarized light into one end of the optical fiber;
detecting at one end of the fiber a series of received light signals which have been transmitted along the fiber;
comparing at least some of the received light signals relative to data obtained from previously received ones of the received light signals to detect changes of polarization of the received light signals relative to the previously received light signals;
analyzing the changes in polarization to determine any changes which are indicative of manipulation of the optical fiber causing movement of a portion thereof along the length thereof;
and generating an alarm in response to the detection of any such changes which are indicative of manipulation of the optical fiber causing movement of a portion thereof along the length thereof;
wherein the changes in polarization are detected by splitting the received light signals into a plurality of paths including first and second paths and using the first path to detect an amplitude of the light in the path when polarized in a linear direction and using the second path to detect an amplitude of the light in the path when polarized in a circular direction;
wherein the splitter is selected such that the state of polarization (SOP) of the signals in the separate paths are NOT maintained relative to an absolute reference as would be required in a standard polarimeter.
Preferably the changes in polarization are detected by splitting the received light signals into only first and second and third paths and using the first path to detect an amplitude of the light in the path when linearly polarized and using the second path to detect an amplitude of the light in the path when circularly polarized and using the third path to detect an amplitude of the light in the path when un-polarized.
Preferably the changes in polarization are detected by splitting the received light signals into only first and second paths and using the first path to detect an amplitude of the light in the path when linearly polarized and using the second path to detect an amplitude of the light in the path when circularly polarized.
Preferably the circularly polarized light in the second path is isolated by a quarter wave retarder and a linear polarizer.
Preferably the light signals are split into the separate paths by an optical switch which separates the signals in time division such that the paths are selected sequentially.
Preferably the light signals are split into the separate paths by an optical switch which separates the signals in time division such that the paths are selected sequentially.
Preferably the light signals are split into the separate paths by an optical switch which separates the signals in time division such that the paths are selected sequentially.
Preferably there is provided a second optical switch or a coupler for supplying the signals from the separate paths to a single receiving system for analyzing the amplitude.
Preferably the light in the second path is circularly polarized by a quarter wave retarder and a linear polarizer and wherein the second path is fed back to the optical switch so as to use a single linear polarizer for both the first and second paths.
Preferably an absolute value is obtained of the change in amplitude in each path between a signal and previous signals and the absolute values are summed together to provide an output for analysis.
Preferably an absolute value is obtained of the change in amplitude in each path between a signal and previous signals and the absolute values are summed together to provide an output for analysis.
Preferably an absolute value is obtained of the change in amplitude in each path between a signal and previous signals and the absolute values are summed together to provide an output for analysis.
Preferably the signals are detected at the opposite end of the optical fiber from which the light is injected.
Preferably the method includes determining the location along the fiber of the said manipulation by:
detecting the signals at the same end as the light pulses are injected such that the signals contain reflected and/or Rayleigh backscattered components;
detecting polarization of a series of the light signals from the Rayleigh backscattering components in discrete time steps to generate for each time step data relating to the polarization;
such that the stored data is time dependent and thus indicative of a time of travel of the light signals and thus of a location of the position from which the Rayleigh backscattering components have originated along the fiber;
storing the data in a register for a period of time and discarding the data after the period of time and replacing it with fresh data;
and in the event that movement is detected of the optical fiber, extracting the data from the register and analyzing the polarization of the series of signals to detect the location of the movement.
Preferably the register is a FIFO.
Preferably the scattering signal level is typically orders of magnitude lower than the Fresnel Reflections and the Fresnel Reflections are typically infrequent and wherein the reflections are integrated along with the scattering such that the Fresnel Reflections integrate into a manageable signal and the total integrated signal is monitored for indication of fiber manipulation.
Preferably the scattering signal level is typically orders of magnitude lower than the Fresnel Reflections and the Fresnel Reflections are typically infrequent and wherein the large Fresnel reflections are sampled using a storage technique, this stored sample is compared to other dynamic or stored samples and this comparison is monitored for indication of fiber manipulation.
According to the present invention there is provided an intrusion detection system that can sense and alarm any attempt to access the optical fibers in a single mode fiber optic communication cable. The present method monitors the active signal of a single mode optical fiber strand for signal degradation and disturbances in polarization that could indicate fiber damage, handling, or physical intrusion.
The system uses the polarized light output signal from a light source such as, but not limited to, a laser transmitter that is coupled to the single mode fiber; standard semiconductor lasers such as DFB and Fabry-Perot are inherently highly polarized. At the receive end of the link, a detection system determines the state of polarization (SOP) of the light. Mechanical disturbances such as handling of the fiber cable cause shifts in the SOP that is detected by the system and signals a possible intrusion attempt before an actual tap occurs.
Using adaptive filtering, normal background disturbances from environmental heating/cooling systems, road traffic, and background disturbances can be learned and filtered out. This will allow maximum sensitivity to intrusion attempt signatures while minimizing the probability of false alarm events. The design objective is to identify intrusion attempts while the attack is still at the outer layer of the cable structure. This will allow for rapid location and interception of any intruder.
Further claimed is the detection of fiber handling and/or intrusion by method of monitoring state of polarization, degree of polarization, or of other parameters related to SOP and DOP. This includes detection or measurement of the handling or disturbance of the optical fiber or cable, either as a prelude to, incident of, or as a result of an intrusion, as detected by any shift in the degree or state of polarization of any portion of the light contained herein, originating from, or propagating through the optical fiber or cable being monitored.
Further claimed is a means for directing the optical transmission of information into any of a plurality of optical fibers. This could be, but is not limited to an optical switch. Significant to this embodiment is the monitoring of all secondary fibers for intrusion, such as with this invention. The intention is to maintain the security and integrity of all possible fibers from intrusion in order to prevent a pre-emptive intrusion prior to the re-routing of data.
For illustration, if a perpetrator had unmonitored access to the secondary fiber, a fiber tap could be installed undetected. The primary fiber could then be perturbed, and when data is switched to the secondary, the data security is compromised. According to this invention, when an intrusion is attempted on any fiber, it will be detected; guaranteeing for the future the security of the system.
This summary describes a number of embodiments of this invention:
An embodiment which utilizes only the signals corresponding to S 0 and S 1 , or any other configuration using fewer than the 4 signals required for a full polarimeter. This trade off enables benefits including, but not limited to, a simplified manufacturing process in exchange for impact including, but not limited to, decreased sensitivity.
A secondary embodiment on the above theme utilizing a second optical coupler summing the intrusion and attenuation signals together, by a configurable mix amount. This allows a single optical receiver/detector. The obvious financial advantage of this implementation must be weighed against the extreme sensitivity to interference between the two coherent light paths being combined.
A third embodiment which utilizes a single linear and a single circular polarization sensitive detectors. This does not yield absolute SOP measurements, but will indicate a change in the SOP sufficient for intrusion detection.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following drawings, a first set of embodiments is disclosed in which the detector is at the remote end of the fiber for detection of the intrusion events without locating the events in position along the fiber:
FIG. 1 illustrates a polarized light source launched into a length of single mode fiber. The single mode fiber is connected to an optical polarimeter, which feeds a processor.
FIG. 2 is a variation on FIG. 1 above with the following distinctions: the polarimeter block is detailed as a full polarimeter with four receivers detecting signals for a Jones Matrix of Stokes Parameters, and the addition of a 2:1 fiber optic coupler and an additional receiver for monitoring the non-intrusion signal.
FIG. 3 is a block diagram of a simplified polarimeter intrusion detection system. The output of the individual polarimeter sections of the optics are summed in order to detect changes rather than absolute polarization measurements.
FIG. 4 is a block diagram of a Greatly Simplified SM IDS using a single polarizer to detect change in SOP.
FIG. 5 is a block diagram of a Single Receiver SM IDS uses a secondary coupler to rejoin the multiple light paths into one detector/receiver.
FIG. 6 is a block diagram of a Simplified Polarimeter using one linear polarizer for detection of linearly polarized light, and one % wave retarder feeding a linear polarizer for detection of circularly polarized light.
FIG. 7 is a block diagram of a further Simplified Polarimeter.
In the following drawings, a second set of embodiments is disclosed in which the detector is at the transmit end of the fiber for detection of the intrusion events while locating the events in position along the fiber by using reflected and backscattered light.
FIG. 8 illustrates a block diagram of a polarimeter used on an optical fiber to detect and locate manipulation of the fiber leading to a potential intrusion event.
FIG. 9 is a block diagram of the Polarization Receiver from FIG. 8 .
FIG. 10 is a block diagram of a preferred embodiment of detection system using a simplified polarimeter for detection of intrusion events and for locating those intrusion events along the fiber.
FIG. 11 is a block diagram of an alternative embodiment to that of FIG. 10 .
FIGS. 12 , 13 and 14 show block diagrams of arrangements in which a wavelength selective reflection can be used, such as a printed Bragg Grating, a reflective connector, or a fiber loop back, as shown respectively for increasing or controlling the level of the Fresnel reflections from the remote end.
In the following drawings, a third set of embodiments is disclosed in which the detector is at the remote end of the fiber for detection of the intrusion events utilizing two polarizers arranged at 90 degrees:
FIG. 15 illustrates a polarized light source launched into a length of single mode fiber. The single mode fiber is connected to an optical polarizer, which feeds an optical receiver.
FIG. 16 is a block diagram for an installation in an active fiber which is being used for data. This is similar to FIG. 1 above, with the addition of a fiber optic coupler samples a portion of the signal for analysis, routing the remaining signal to the end user's receiver.
FIG. 17 is similar to FIG. 1 above, with the addition of a 2:1 fiber optic coupler and a second receiver for monitoring the non-intrusion signal.
FIG. 18 is a block diagram for a combination of FIGS. 16 and 17 above, the coupler for feeding the end-user equipment, and a dual receiver configuration.
FIG. 19 is a block diagram for a variation on FIG. 1 with the substitution of a rotatable polarizer under a closed feedback loop.
FIG. 20 is a block diagram of one embodiment of the invention.
DETAILED DESCRIPTION
Fundamental to the present invention is the mechanics or more simply by launching a light source of stable polarization 1 into a single mode fiber 2 . At the remote or receive end the single mode fiber is connected to the input of an optical polarimeter 3 . This polarimeter measures the SOP of the monitored light. The output of this polarimeter is connected to a processor unit 4 ; such as, but not limited to, a microcomputer. Handling of the fiber cable causes a local mechanical disturbance to the fiber. This mechanical disturbance, while not introducing detectable macro or micro bending losses, causes the polarization orientation to change. This is detected by the polarimeter and reported to the processor.
A more comprehensive view is now described in conjunction with FIG. 2 . Optical signal feeds the polarimeter 9 , which converts it to the four so-called Stokes Parameters: S 0 , S 1 , S 2 , and S 3 as detected by receivers Rx 0 -Rx 3 10 , 11 , 12 , and 13 . These parameters collectively describe all possible states of polarization and degrees of polarization (DOP) (Hernday 1998). This is forwarded to the processor 14 where the SOP and DOP are calculated, and the signal is filtered to eliminate normal environmental background noise. The filtered signal is then analyzed for transient signatures and level changes that are characteristic of cable and fiber handling. At a pre-set detection condition the circuit activates the alarm response.
The optical signal can be split by an optional optical coupler 7 . The main portion of the signal can be brought back out to an optical connector ( 8 ) and be made available for the communication or data receiver, sending a sample to the polarimeter for monitoring. Additionally, the S 0 parameter of the polarimeter directly measures optical power without polarization effects. This can be used to monitor the received power for perturbations which are detectable in the non-polarization domain.
A simplified embodiment is depicted in FIG. 3 . In an intrusion detection system, actual SOP is not required as information, only the change in that state. Such an instrument as shown.
Rather than use extensive DSP to calculate DOP, orientation, and angle, a system is presented here for pragmatically determining polarization changes only.
The outputs from a polarimeter 15 are individually monitored in addition to being sent to processors such 20 , 21 , 22 as differentiators and precision full wave rectifiers (absolute value circuits). These three rectified lines are then summed in a summing amp 19 , the output of which is monitored.
Whenever any change in polarization properties occurs, the distribution of power between the polarimeter outputs (which we will refer to as s 1 , s 2 , and s 3 16 , 17 , 18 ) which lead to the calculation of Stokes Parameters S 1 , S 2 , and S 3 changes; as one increases, it is at the expense of one or both of the others decreasing. If all three lines are differentiated and full wave rectified by the processors 20 , 21 , 22 , the increase on one line will appear as a positive signal into the summing amp, as will the decreases on the other two lines. This is further illustrated in FIG. 7 . This additive action increases sensitivity of the system, always positive going and of level representative of the disturbance of the intrusion. Also, by monitoring both S 0 and the three non-processed lines s 1 , s 2 , and s 3 , disturbances not related to intrusion, such as a shift in laser power, could be recognized and processed. One possible way to analyze that condition would be, when the S 0 changes, to confirm that the ratio of the s 1 -s 3 remains the same (its polarization “signature”) and confirm that total power changes the same degree as S 0 .
Alternatively, processors 20 , 21 , 22 can convert the s parameters to Stokes Parameters S. Summing the three processed S parameters of S 1 , S 2 , and S 3 and monitoring the summed level gives an indication of polarization shifting indicating a possible intrusion.
The differentiation and precision rectification can be performed in software if desired.
The embodiment in FIG. 4 is for a limited implementation of a polarimeter. This device will detect light that is fully or partially linear polarized. Ease of manufacture and low cost are among the advantages, inability to detect light with circular polarization is a disadvantage. As before, light is injected by a polarized light source 23 into the fiber under test 24 . This delivers light into a splitter 25 that directs a portion of the light unaltered to a detector/receiver 26 , and the other portion passes through a polarization filter such as a linear polarizer 27 and into a receiver/detector 28 . The advantage of this embodiment is that a mixture of polarization sensitive and insensitive signals are combined. By adjusting the relative intensities, as with series resistors on the detectors, or amplifiers of differing gain, the system sensitivity can be optimized for the application.
The signals from the two are monitored and compared by a processor 29 . Variations in light amplitude which are not related to an intrusion, and therefor a shift in SOP, will appear on Rx 1 26 . Shifts in SOP will be detected by Rx 2 28 . The inability to detect non-linear SOP is not as significant as might first seem because cable handling causes dramatic changes in SOP, with frequent motion between circular, elliptical, and linear states.
The embodiment in FIG. 5 is a variation on this: the two optical signals, rather than feeding dual detectors, are joined in a coupler 30 and feed a single receiver/detector 31 . A significant advantage with this arrangement is a simple one detector feeding the analysis system. The ratio of polarization sensitive to polarization insensitive can be adjusted by varying the split ratios of the two couplers 25 and 30 . This allows significant attenuation monitoring with slight polarization sensitivity, strong polarization sensitivity with slight attenuation sensitivity, and every combination in between.
The embodiment in FIG. 6 will detect both linear and circular polarized light. Light is split by a coupler or splitter 32 . One leg feeds a linear polarizer 33 , which allows the receiver/detector to detect linear polarized light. The light exiting the other leg of the splitter feeds a Y 4 wave retarder 35 which, as in a full polarizer, converts circular polarized light to linear polarized and vice versa. This feeds linear polarizer 36 , which allows receiver/detector 37 to detect that which was originally circular polarized light. In operation, it is similar to a full polarimeter, with two primary differences:
1. The lack of the 45-degree offset 2 nd linear polarizer limits resolution of linear polarized light. This causes a decrease in “intrusion gain” under some conditions.
2. This device does not measure polarization in absolute terms; rather it detects changes in polarization, as such an absolute alignment of the system is not required. This greatly reduces manufacturing costs. Thus the splitter 32 is selected such that it can be manufactured economically. Preferably, the two legs of splitter 32 should be of identical SOP.
Note that couplers do not need to be polarization maintaining because only change in SOP is important, not absolute SOP. This technique can be applied to a full polarimeter design while neglecting calibration and alignment. In these configurations, absolute SOP measurements are inconsequential, only change in SOP is required for IDS.
Rather than use extensive DSP to calculate DOP, orientation, and angle, a system is shown in FIG. 7 for pragmatically determining polarization changes only.
The outputs from S 1 through S 3 are individually monitored in addition to being sent to differentiators and precision full wave rectifiers (absolute value circuits). These three rectified lines are then summed in a summing amp, the output of which is monitored.
Whenever any change in polarization properties occurs, the distribution of power between S 1 , S 2 , and S 3 changes; as one increases, it is at the expense of one or both of the others decreasing. If all three lines are differentiated and full wave rectified, the increase on one line will appear as a positive signal into the summing amp, as will the decreases on the other two lines. This additive action increases sensitivity of the system, always positive going and of level representative of the disturbance of the intrusion. Also, by monitoring both S 0 and the three non-processed lines S 1 , S 2 , and S 3 , disturbances not related to intrusion, such as a shift in laser power, could be recognized and processed. One possible way to analyze that condition would be, when the S 0 changes, to confirm that the ratio of the S 1 -S 3 remains the same (its polarization “signature”) and confirm that total power changes the same degree as S 0 . Because of the hardware rectification, this analysis would be approximate. In implementations which do not first rectify the signal, the above process can be performed.
The differentiation and precision rectification can be performed in software if desired.
Turning now to the locating system shown in FIGS. 8 to 14 , the arrangement shown and described herein use the techniques described above.
Fundamental to the invention is the mechanics, or more simply by launching polarized light pulses from a light source 51 into an optical splitter or coupler 52 . The output of the coupler is attached to the monitored fiber 54 . Optical reflections caused by Rayleigh Backscattering and Fresnel Reflections from the fiber pass through splitter 52 and are fed into a polarization sensitive receiver 53 . The signal is then processed by the processor 55 : such as, but not limited to, an A/D connected to a microprocessor.
Handling of the fiber cable causes a local mechanical disturbance to the fiber. This mechanical disturbance, while not introducing detectable macro or micro bending losses, causes the polarization orientation to change. This is detected by the polarimeter and reported to the processor. A more comprehensive view is now described.
The optical signal feeds the polarimeter 56 , which converts it to the four so-called Stokes Parameters: S 0 , S 1 , S 2 , and S 3 as detected by receivers Rx 0 -Rx 3 57 , 58 , 59 , and 60 . These parameters collectively describe all possible states of polarization and degrees of polarization (DOP) (Hernday 1998). This is forwarded to the processor 61 where the SOP and DOP are calculated, and the signal is filtered to eliminate normal environmental background noise. The filtered signal is then analyzed for transient signatures and level changes that are characteristic of cable and fiber handling. At a pre-set disturbance level or slope change the circuit activates the alarm response.
Present art consists of the Polarization OTDR as described by Anderson and Bell (1997), which presented a characterization of the static polarization condition of the light as a function of distance. It did not address intrusion, and was only intended to measure a fundamental characteristic of the light within a fiber.
The invention described in this document builds upon the Polarization OTDR by analyzing dynamic distribution of SOP throughout a fiber as an intrusion detection system. It is intended for characterizing transient SOP behavior, which was not addressed at all in prior art.
It is possible to use a single set of detection optics and electronics when configuring a full or partial polarimeter for applications including, but not limited to, intrusion detection in optical fiber.
In the first configuration shown in FIG. 10 , an optical switch 71 , of the simplified type described hereinbefore, selects between direct measurement on line 72 , measurement of circular polarized light on line 73 , and measurement of linear polarized light on line 74 . This allows one to time division multiplex (TDM) the data, using a further optical switch 75 scanning a fiber under test (FUT). This design allows the use of a 1×3 coupler/splitter rather than switch; potentially offering a cost advantage, although with the disadvantage of several dB of insertion loss in the coupler/splitter. It is critical that either 71 or 76 , or both, be a switch as two couplers will not allow TDM. Since intrusions tend to be very slow occurrences, on the order of hundreds of milliseconds, there is ample time to average readings under each measurement state.
A second configuration exists in FIG. 11 , which can be chosen for cost as well as other reasons. Significant to the design is the use of a time division switch 77 to route the signal first to a quarter wave retarder 78 and then to the linear polarizer. This design also allows the use of a 1×2 coupler/splitter 80 rather than switch; potentially offering a cost advantage, although with the disadvantage of switch; potentially offering a cost advantage, although with the disadvantage of several dB of insertion loss in the coupler/splitter.
The truth table for this configuration follows:
S0
I→A
a→1
S1
I→B
b→1
S2
I→C, II→B
b→1
One technique for minimizing/streamlining this is to collect and store distance data in a register 81 or other similar device such as, but not limited to, a FIFO; but to only analyze the quasi-CW signal from the Fresnel reflections in real time. This “quasi-CW” signal is comprised of the Fresnel reflections from the trace with a minor Rayleigh scattering component. These Fresnel reflections, on the order of 20-25 dB above the scattering are high in amplitude but low in duty cycle. They can be integrated along with the scattering, or captured by peak detecting sample and hold (or other technique). This quasi-CW signal is analyzed for an intrusion. When one is detected, the time dependant data in the register 81 is analyzed for location information.
The processing required for signal analysis of an intrusion detection system is not insignificant, algorithms which analyze the environment and filter out disturbances to be ignored are highly computationally intensive. When configuring a locating IDS, the task becomes much more complex. The signal analysis normally used for non-locating might need to be applied to every location in time along the vertical axis of the imaginary OTDR trace, perhaps 2000 locations or more. The CPU burden of applying conventional finite DSP to each of these elements is extreme. Thus the above technique of storing the data in the register until an intrusion event is detected can be used. While the intrusion event can be most effectively detected from the Fresnel reflections, other techniques using the other data such as data corresponding to a specific location in the fiber can be used to detect the intrusion event in real time; and only when the event has been detected is the bulk of the remaining data from the register used for location. The scattering signal level is typically orders of magnitude lower than the Fresnel Reflections and the Fresnel Reflections are typically infrequent so that the reflections are integrated along with the scattering such that the Fresnel Reflections integrate into a manageable signal and the total integrated signal is monitored for indication of fiber manipulation. Also the large Fresnel reflections can be sampled using a storage technique, this stored sample is compared to other dynamic or stored samples and this comparison is monitored for indication of fiber manipulation.
One variation is to add a reflection at the far end of the cable, such as a connector with a gold deposition.
It will be appreciated that the monitoring system can be used with dark fiber either which are available as spare fibers or which are specifically dedicated as monitoring fibers. However in other cases, the monitoring system can be used with active fibers carrying data. In this case, if the monitor is to be used concurrently with data, a wavelength selective reflection can be used at the remote end to increase and/or control the intensity of the Fresnel reflections, such as a printed Bragg Grating 90 , a wave length division multiplexer (WDM) 91 and a reflective connector 92 , or a WDM 93 and fiber loop back 94 , as shown in FIGS. 12 , 13 and 14 respectively.
Turning now to the third set of embodiments shown in FIGS. 15 to 20 , the arrangements are similar to those shown and described above and use many of the same techniques. Thus it will be appreciated that each of the techniques described can be used symmetrically. In addition, in the arrangement shown in FIGS. 15 to 20 , the detections system is located at the remote end from the signal transmission in a non-locating mode similar to that of FIGS. 1 to 7 . However, symmetrically to that of FIGS. 8 to 14 the detection system can be located at the same end as the transmission for a locating arrangement responsive to reflected and backscattered light and may use the same techniques as described.
Thus as shown the arrangement includes a transmitter launching a light source of stable polarization 101 into a single mode fiber 102 . At the remote or receive end the single mode fiber is connected to the input of an optical polarizer 103 . This polarizer passes light with similarly aligned polarization, and blocks light orthogonally aligned. The output of this polarizer is connected to an optical receiver 104 . Handling of the fiber cable causes a local mechanical disturbance to the fiber. This mechanical disturbance, while not introducing detectable macro or micro bending losses, causes the polarization orientation to change. This results in a change in the optical power at the output port 105 which feeds the receiver. The resultant optical signal is proportional in amplitude to the disturbing forces.
In the case of active fiber monitoring, where live traffic is carried on the monitored fiber, as shown in FIG. 16 , the optical signal from the source 106 is split by an optical coupler 107 . The main portion of the signal can be brought back out to an optical connector 108 and be made available for the communication or data receiver. The sampled output 109 feeds the polarizer 110 , which feeds the receiver 111 . The signal can be digitized and forwarded to the processor 112 where the signal is filtered to eliminate normal environmental background noise. The filtered signal is then analyzed for transient signatures and level changes that are characteristic of cable and fiber handling. At a pre-set disturbance level the circuit activates the alarm response.
An enhanced variation of the detection scheme is shown in FIG. 17 . The incoming optical signal from the fiber 113 is connected to the input of a 2×1 coupler 114 where a portion of the light is sampled. One output of the coupler 115 is then connected to the input port of a polarizer 116 as above. The coupler maintains polarization information and it is used to sample a portion of the total optical signal. The other output of the coupler 117 is connected to a second receiver 118 where the absolute throughput power is calculated from the fixed ratio sample. This establishes an absolute power baseline that is compared to the polarization detection sampling. The processor then compares the response in the two channels and is able to calculate any power change as well as changes in polarization. This comparison can be performed in the digital domain including use of equipment such as, but not limited to a computer, or the analog domain using circuitry such as, but not limited to, a differential amplifier. This provides more information on fiber disturbances as a significant change in both channels could indicate a problem with the laser or fiber path while a transient and steady state change in the polarization only would provide a strong indication of an intrusion attempt.
The techniques described above can be combined, as illustrated in FIG. 18 . The tap coupler of FIG. 16 and the dual receiver of FIG. 17 are implemented.
In FIGS. 15 , 16 , 17 , and 18 , the polarizer 103 , 110 , and 116 can be replaced by a polarization controlling device 120 , as shown in FIG. 19 . Under feedback control, the base polarization state can be adjusted to any level within the extinction ratio of the polarizer to optimize the efficiency and sensitivity of the measurement.
An embodiment shown in FIG. 20 consists of launching a light source of stable polarization 121 into a single mode fiber 122 . At the remote or receive end the single mode fiber is connected to the input of an optical splitter or coupler 123 , typically of a non-symmetrical split ratio. One output of this coupler, typically the larger coupling percentage leg, feeds the optical connector 124 to the end receiver. The other leg of coupler feeds an optical splitter or coupler 125 . Typically this would be a 50:50 coupler. One leg of this coupler feeds an optical receiver 126 . The other coupler leg feeds a polarization controller 127 , which alters the state of polarization (SOP) of the exiting light. This feeds the input to an optical coupler or splitter 128 , typically of a 50:50 split ratio. The two output legs of this coupler feeds a pair of optical polarizers 129 and 130 , whose SOP is aligned orthogonal to each other. These feed a pair of optical receivers 131 and 132 . A processor/controller 133 , such as a combination of A/D converters and CPU monitors the outputs of the three receivers 126 , 131 , and 132 , and adjusts the controller 27 accordingly.
In order to maximize detection sensitivity, or “intrusion gain”, the optics must be aligned such that the signal at Rx 3 132 is at a minimum; i.e. Pol 2 130 perfectly orthogonal to the light. This signal is, however, very low in magnitude and difficult to measure. One way of insuring this alignment is to align Polarization Controller 127 for a maximum signal at Rx 2 131 .
The polarization controller 127 is a device that can convert any SOP into any other SOP. Using this, a transmitter laser can be easily converted into a more readily managed linear polarization. The Processor 133 adjusts SOP by monitoring Rx 2 131 for a maximum signal. When this occurs, the SOP is properly aligned and linear. Rx 3 132 then monitors for intrusions.
Additionally, the ratio of signals at Rx 2 131 to Rx 1 126 is an indication of the “tuning” of polarization alignment. When Rx 2 drops in power while Rx 1 remains constant, alignment issues or an intrusion are occurring. If they both change in power, an attenuation event is occurring, such as laser power fluctuation or a failing connector.
Thus in FIG. 20 a polarized light source launched into a length of single mode fiber. The single mode fiber is connected to the optical coupler which splits the signal: the majority going to the system data receiver (if an active fiber unit), a portion sampled to the measurement system. This sampled portion goes to another splitter, one leg of which monitors power, the other leg is monitored for intrusion. This intrusion leg feeds a polarization controller, which both takes whatever stable SOP of the light and converts it to linearly polarized, and aligns it with the orientation of polarimeter Pol 1 . Pol 1 feeds Rx 2 and allows a strong signal for both closing the control loop on the polarization controller, as well as monitoring, with Rx 1 , fluctuations in absolute (non-intrusion dependant) power. Pol 2 feeds Rx 3 ; and, being aligned perpendicular to the SOP of the light, is optimized for intrusion sensitivity.
In summation: Rx 1 measures absolute optical power, Rx 2 monitors maximum polarized power, and Rx 3 monitors intrusion. The combination of Rx 1 and Rx 2 monitor systematic stabilities not related to intrusion. The combination Rx 1 and Rx 3 detect actual intrusions.
Since various modifications can be made in my invention as herein above described, and many apparently widely different embodiments of same made within the spirit and scope of the claims without department from such spirit and scope, it is intended that all matter contained in the accompanying specification shall be interpreted as illustrative only and not in a limiting sense.
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A telecommunications optical fiber is secured against intrusion by detecting manipulation of the optical fiber prior to an intrusion event. This can be used in a non-locating system where the detection end is opposite the transmit end or in a locating system which uses Fresnel reflections and Rayleigh backscattering to the transmit end to detect and then locate the motion. The Rayleigh backscattering time sliced data can be stored in a register until an intrusion event is detected. The detection is carried out by a polarization detection system which includes an optical splitter which is manufactured in simplified form for economic construction. This uses a non-calibrated splitter and less than all four of the Stokes parameters. It can use a polarimeter type function limited to linear and circular polarization or two linear polarizers at 90 degrees.
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FIELD OF THE INVENTION
[0001] The present invention relates to medical devices, and, more particularly, to medical device mechanical pumps for delivering therapeutic agents. Embodiments of the present device are useful for medical drug delivery devices, including small, low cost insulin delivery devices worn on the skin for treating Type 1 and Type 2 diabetes.
BACKGROUND OF THE INVENTION
[0002] Transcutaneous delivery of medicine is an alternative to orally delivered pharmaceuticals, which reach the blood stream by way of the intestines. Some medicines lose their effectiveness when ingested and must be delivered using other means. Parenteral delivery refers to delivery of medicine to the body by means other than via the intestines. Intradermal, subcutaneous, and intravenous injections are examples of parenteral delivery.
[0003] Insulin is an example of a medication that must be administered using parenteral delivery. Insulin is injected by patients with Type 1 diabetes, and some patients with Type 2 diabetes. In Type 1, or juvenile onset diabetes, the pancreas no longer produces insulin, and insulin must be injected to regulate blood sugar. In Type 2 diabetes, the body loses its sensitivity to insulin, and more insulin is required to regulate blood sugar. In the later stages of the disease, the pancreas of a Type 2 diabetic stops producing insulin, and the patient becomes insulin dependent, similar to a Type 1 diabetic.
[0004] Different patients adopt different insulin regimens, depending on many factors, including the type and stage of the disease, access to medical care, support by family members, lifestyle, motivation, and attitude toward the disease. A healthy pancreas secretes insulin at a low, steady basal or background rate, and produces larger boluses of insulin in response to food intake. Injections of long acting insulin (formulated to be taken up by the body slowly and steadily over a period of several hours) are used to mimic basal insulin, and injections of rapid acting insulin (formulated to be taken up quickly) are used for boluses. Type 1 diabetics and insulin dependent Type 2 diabetics typically adopt regimens that include both basal and bolus insulin. Type 2 diabetics new to insulin might start on a relatively low dosage of basal insulin only, with one shot a day of long acting insulin. Alternatively, new to insulin Type 2 diabetics might start on a relatively low dosage of bolus only insulin, taken one to two times a day with meals. With time, Type 2 diabetics will increase their insulin dosage and add bolus or basal insulin to complement their initial insulin regimen.
[0005] Typically, the insulin is drawn up from a vial and injected with a syringe and needle. Insulin therapy with syringes and vials is low in cost but requires significant skill and dexterity to draw up the proper amount of insulin and purge bubbles. Insulin pens are popular in Europe and are beginning to displace syringes in the United States. Insulin pens are comprised of a prefilled insulin cartridge with a plunger, a needle, a mechanism that allows the user to dial in the specific amount of insulin to be delivered, and a button to inject the insulin. Such pens are, in essence, hand-held medical fluid delivery devices. Disposable insulin pens with an integrated insulin cartridge and reusable insulin pens with replaceable insulin cartridges are both available on the market today. Insulin pens are convenient and easy to use, eliminating the need to draw up the insulin into a syringe, allowing the patient to set the dose by turning a dial rather than trying to read a meniscus in a small, finely graduated syringe, and simplifying the elimination of bubbles, which affect delivery accuracy.
[0006] Continuous subcutaneous insulin infusion (CSII), or insulin pump therapy, is a preferred method for delivering insulin to diabetic patients, and is known to have certain advantages over injection of insulin with syringes or pens. Insulin pump therapy consists of a low, steady basal delivery, with larger bolus deliveries taken in conjunction with food intake, a pattern that closely resembles insulin secretion from a healthy pancreas. Instead of using long acting insulin for basal delivery, insulin pumps deliver small shots of rapid acting insulin at regular time intervals to approximate slow continuous delivery. Recently introduced “smart pumps” have features that keep track of insulin injection history, remember commonly used dosages, help calculate bolus size, and allow for fine-tuning of basal and bolus delivery. Insulin pumps also offer increased lifestyle flexibility through frequent, convenient insulin dosing, allowing the user to eat what they want when they want and still maintain control of their blood glucose levels.
[0007] Insulin pumps are comprised of the pump engine, an insulin reservoir, and an infusion set which delivers insulin from the pump across the skin to the patient. The infusion set may be worn for multiple days, allowing infusion of insulin across the skin as required without the need to pierce the skin multiple times with needles for individual injections. The pump may be worn on a belt clip, or placed in a pants pocket, holster, or bra, for example. The pump is connected to the user via an infusion set, comprised of a transcutaneously inserted cannula affixed to the body with an adhesive patch, with a length of plastic tubing linking the cannula to the pump. The cannula is usually attached to the user's abdomen region, although other locations such as the lower back or thigh may be used. A new generation of pumps known as patch pumps is now beginning to appear on the market. These pumps are smaller in size and affix directly to the skin such that the tubing leading to the cannula is shortened or eliminated entirely.
[0008] There are several problems associated with existing approaches to insulin delivery, and insulin therapy in general. Even though insulin therapy is known to be the best way to limit glycemic excursions, Type 2 patients resist starting insulin. Many patients associate insulin with the last stages of the disease leading to death, they are afraid of needles and giving themselves injections, and the therapy is complicated and confusing, involving carbohydrate counting, regulation of food intake, and the relationship between insulin, food, and exercise. Physicians delay putting their Type 2 patients on insulin because the patients are resistant, it is difficult and time-consuming to initiate and manage patients on insulin therapy, and they are afraid of dangerous and potentially fatal hypoglycemic events induced by delivering too much insulin. This delay in starting insulin therapy accelerates the course of the disease.
[0009] As mentioned above, the needles used with syringe and pen injections are intimidating to patients. Some patients have needle-phobia and just the thought of injecting causes anxiety. For both syringes and pens, the patient must remember to carry the insulin and supplies with them if they are going to inject away from home. Syringes require the user to draw up the insulin from a vial and purge bubbles, a multi-step process requiring significant skill, dexterity, and visual acuity to perform accurately. In addition, syringes offer no means for creating a time record of delivery, other than relying on the patient to keep a logbook.
[0010] Insulin pens solve many of the problems associated with syringes, greatly simplifying the injection process. However, they still require the use of needles, and can be inaccurate if the patient does not prime the pen before injecting or does not keep the needle in the skin and hold the button down for a sufficient length of time during the injection. Recently introduced smart pens keep a primitive record of the most recent injections, but cannot distinguish priming shots from regular injections, and do not allow for downloading and analysis of the insulin data in conjunction with blood glucose data.
[0011] While insulin pumps offer many benefits relative to syringes and pens, they also have several problems. Insulin pumps are expensive, complex devices with many features, requiring multiple steps to set up and use. Thus they are difficult for health care providers to learn and teach, and for patients to learn and use. Conventional insulin pumps use indirect pumping in which a motor and gears drive a lead screw, which pushes on a plunger in a syringe-like cartridge to inject the insulin. The indirect pumping approach is susceptible to over-delivery of insulin due to siphoning and pressure differentials.
[0012] Bubbles present a major challenge with conventional insulin pumps, which rely on the user to fill a syringe-like reservoir. It is difficult for the user to purge all of the air out of the system when setting up the pump, and additional bubbles can form when dissolved gas in the insulin comes out of solution due to changes in temperature or pressure. During delivery, bubbles displace insulin and reduce delivery accuracy. For example, a small 10 microliter bubble passing through the pump to the user is equivalent to 1 unit of missed insulin. Pre-filled insulin cartridges come to the user with approximately 20-40 microliters of air in the cartridge, and more gas can come out of solution during use.
[0013] Endocrinologists prescribe most insulin pumps, but many diabetics only see primary care physicians (PCPs). Many physicians, including endocrinologists and PCPs, are unwilling to put their patients on pumps because they don't think their patients can handle it, or because it will cause more work for the physicians that they are not reimbursed for. The pumps are relatively large, making them difficult to wear and operate discretely. Insulin pump therapy is expensive, with conventional pumps costing approximately $5,000 up front. A low cost pump could make insulin pump therapy more accessible, but it is important to provide the accuracy and critical safety benefits of conventional pumps such as occlusion detection and delivery confirmation. Furthermore, it would be beneficial to maintain a delivery record for retrospective analysis by the physician and/or patient.
[0014] For these reasons, currently available insulin pumps are used predominantly by a small class of insulin-using diabetics—sophisticated Type 1 patients who meticulously monitor their blood glucose levels and are proficient at counting carbohydrates to determine insulin dosing. Many people who could benefit from insulin pump therapy, such as Type 2 diabetics, are unable to use them or choose not to use them because of the disadvantages discussed above.
[0015] Thus, it is desirable to have an insulin pump that is low in cost, accurate, safe, and simple enough to teach and use that primary care physicians (PCPs) would put their insulin using Type 1 and Type 2 patients on the pump, allowing more diabetics to benefit from the advantages of insulin pump therapy. The device would have the simplicity and low cost of an insulin pen, combined with the convenience, lifestyle benefits, data logging, and safety features of a pump.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a simplified perspective view depiction of a medical device mechanical pump according to an embodiment of the present invention, an infusion set patch, and a pre-filled cartridge;
[0017] FIG. 2 is a simplified perspective view depiction of the medical device mechanical pump of FIG. 1 with the pre-filled cartridge inserted and attached to the infusion set patch;
[0018] FIG. 3 is a simplified perspective view depiction the medical device mechanical pump of FIG. 1 with the upper housing removed, revealing the inner components of the medical device mechanical pump;
[0019] FIG. 4 is a simplified cross section of a mechanical pump engine (also referred to herein as a “micropump”) with integrated bubble trap that draws fluid from the pre-filled cartridge and can be employed in various embodiments of the present invention.
[0020] FIG. 5 is a simplified exploded perspective view of a micropump actuation triggering mechanism as can be employed in various embodiments of the present invention;
[0021] FIG. 6 is a simplified exploded perspective view of a micropump actuation triggering mechanism as can be employed in various embodiments of the present invention;
[0022] FIG. 7 is a simplified exploded perspective view of the micropump actuation triggering mechanism of FIG. 6 from another viewpoint; and
[0023] FIG. 8 is a simplified depiction of a passive circuit to enable one-way communication from a medical device insulin pump according to an embodiment of the present invention and an associated blood glucose meter.
[0024] FIGS. 9A-9B are simplified cross sectional views of a mechanical pump engine with integrated delivery counter as can be employed in various embodiments of the present invention.
[0025] FIG. 10 is a perspective view of a reset mechanism that can be used with the mechanical pump engine with integrated delivery counter illustrated in FIGS. 9A-9B .
DETAILED DESCRIPTION
[0026] The present invention relates to medical device mechanical pumps, and, more particularly, to medical device mechanical pumps (also referred to herein as a “mechanical pump” and/or a “medical device pump”) for delivering therapeutic agents. Although a simple mechanical patch pump for delivering insulin or other therapeutic agents is described for the purpose of example, one of skill in the art would understand that other embodiments of this device could be used for other devices that would benefit from a mechanical pump, such as hand-held insulin pens (a type of portable user-operated medical fluid delivery device), more complex insulin pumps with additional features, belt or pocket worn insulin pumps, and medical fluid delivery devices for delivering other therapeutic agents such as drugs or other fluids for other applications such as for treating pain.
[0027] One aspect of the present invention is to provide an easy to teach, easy to learn, easy to use mechanical pump for delivering insulin. The simple mechanical pump does not require electronics or battery power for delivering insulin, instead relying on power provided by the user when pressing the delivery button. Another aspect of the present invention is to provide a pump that delivers discrete shots of a fixed size with each button press that can be used to deliver long acting basal insulin, regular or rapid acting insulin for boluses, or a mix of long acting and regular or rapid acting insulin for basal/bolus therapy. Another aspect of the present invention is to provide a low cost insulin patch pump comprised of a disposable patch pump that accepts pre-filled cartridges and attaches to a disposable infusion set. Another aspect of the present invention is to provide a low cost mechanical pump that provides beneficial safety features and accuracy. Another aspect of the present invention is to provide a simple, low cost means of communication from the disposable pump to a blood glucose meter to confirm and record insulin delivery events. Another aspect of the present invention is to provide a simple, low cost means of counting pump deliveries.
[0028] The mechanical pump disclosed herein is useful for delivering insulin to diabetic patients, and also may be used for delivering other drugs, cells, genetic material such as DNA, and biopharmaceuticals including protein-based drugs, for applications such as treatment for diabetes, Parkinson's disease, epilepsy, pain, immune system diseases, inflammatory diseases, and obesity (referred to generally as therapeutic agents).
[0029] The mechanical pump, generally denoted by 100 in FIG. 1 , accepts pre-filled insulin cartridge 170 and docks onto adhesive patch platform 210 . Using a pre-filled insulin cartridge greatly simplifies the pump set up for the patient, eliminating the need to draw up insulin from a vial and purge bubbles. In a preferred embodiment of the present invention, mechanical pump 100 is affixed directly to the skin via adhesive patch platform 210 . Mechanical pump 100 is simple in nature and has minimal features evident from the outside. These include insulin cartridge compartment 150 , cartridge door 130 , lower housing 190 and upper housing 140 , safety release button 120 and delivery button 110 . Upon inserting insulin cartridge 170 into insulin cartridge compartment 150 and closing cartridge door 130 , conduit 160 penetrates septum 180 , providing access to insulin inside cartridge 170 . Attached to adhesive patch platform 210 is flexible cannula inserter 200 with inserter lever 220 and flexible cannula 230 .
[0030] Referring now to FIG. 2 , mechanical pump 100 is shown attached to adhesive patch platform 210 with insulin cartridge 170 inserted into insulin cartridge compartment 150 and cartridge door 130 closed. Flexible cannula inserter lever 220 is in the down position, with flexible cannula 230 protruding from the bottom side of adhesive patch platform 210 .
[0031] FIG. 3 shows mechanical pump 100 with upper housing 140 removed to reveal internal components, which are shown in detail in FIG. 4 , FIG. 5 , and FIG. 6 . Pressing safety release button 120 slides safety release rod 300 forward, allowing delivery button 110 to be pressed in. Pressing delivery button 110 activates trigger mechanism 310 , which in turn generates a single stroke from micropump 320 . Stroke from micropump 320 first generates a pressure drop that sucks in insulin from insulin cartridge 170 via conduit 160 , and through bubble trap 330 , then delivers insulin via delivery conduit 340 to flexible conduit 230 and across the skin to the patient.
[0032] Focusing now on FIG. 4 , a cross section of micropump 320 and bubble trap 330 is provided. Pressing down on flexible diaphragm 430 pressurizes pump chamber 420 , closing inlet valve 440 , which seals pump inlet 500 , opening outlet valve 460 , and delivering fluid through channel 450 to pump outlet 470 . The volume of fluid delivered to pump outlet 470 is equivalent to the volume of pump chamber 420 displaced by flexible diaphragm 430 . Allowing flexible diaphragm 430 to return to the up position as pictured in FIG. 4 causes the pressure in pump chamber 420 to drop. The drop in pressure closes outlet valve 460 , sealing channel 450 , and lifts inlet valve 440 , opening pump inlet 500 and causing fluid to fill pump chamber 420 via pump inlet channel 560 .
[0033] Before entering the pump, fluid passes through bubble trap 330 , which is comprised of bubble trap housing 570 , bubble trap inlet 580 , bubble trap chamber 590 , and porous membrane 530 . In a preferred embodiment, porous membrane 530 is hydrophilic and has an average pore size between approximately 0.05 and 2 microns. Hydrophobic porous material also will work for the bubble trap. Bubble trap 330 prevents bubbles originating in the insulin reservoir from reaching micropump 320 , where they could increase compliance of the system and affect delivery accuracy. Bubble trap 330 also filters particles out of the system before reaching micropump 320 , where they could prevent inlet valve 440 or outlet valve 460 from sealing properly. During priming, micropump 320 pumps air out of the system and fills conduit 160 , bubble trap chamber 590 , pump inlet channel 560 , pump chamber 420 , delivery conduit 340 , and flexible conduit 320 with fluid from cartridge 170 . The process of filling wets porous membrane 530 , and subsequent bubbles released from cartridge 170 become trapped in bubble trap chamber 590 . Bubble trap 330 is designed such that the volume of bubble trap chamber 590 is greater than the volume of bubbles that might exist within cartridge 170 .
[0034] Continuing with FIG. 4 , Pump chamber o-ring 480 seals upper pump housing 510 to valve seat plate 550 , lower housing o-ring 490 seals lower housing 520 to valve seat plate 550 , and bubble trap o-ring 540 seals bubble trap housing 570 to back side of valve seat plate 550 . Upper pump housing 510 , valve seat plate 550 , lower housing 520 , and bubble trap housing 570 are attached to each other using screws, adhesive, pins on one side that interfere with holes on the other, heat staking, or ultrasonic welding.
[0035] Trigger mechanism 310 , shown in FIG. 5 and FIG. 6 , serves to translate presses of delivery button 110 into pumping cycles of micropump 320 . A function of trigger mechanism 310 is to ensure that partial presses of delivery button 110 cannot produce a fraction of a full pump stroke. When delivery button 110 is pushed past a specific distance, trigger mechanism 310 activates a complete pump stroke. When delivery button 110 is pushed less than the specific distance, no pump stroke is produced. Similarly, the triggering mechanism ensures that the patient must fully release delivery button 110 before pressing again to deliver another pump stroke, a feature that likewise prevents activation of a partial pump stroke.
[0036] In FIG. 5 , trigger mechanism 310 is shown in relation to micropump 320 . Trigger mechanism housing 650 is shown removed to reveal trigger mechanism 310 . Piston 610 engages flexible diaphragm 430 . Activation rod 620 is attached to delivery button 110 and is biased in the out position by coil spring 640 which pushes against snap ring 630 . FIG. 6 and FIG. 7 show components of trigger mechanism 310 in more detail from two viewing angles. Piston 610 and leaf springs 720 are shown separated from the trigger mechanism assembly for clarity. In the rest position (delivery button 110 not pressed), trigger mechanism body flat 780 contacts piston flat 790 , maintaining piston 610 in the down position such that micropump diaphragm 430 is biased downwards, such that it presses down on and actively closes inlet valve 440 , providing an extra measure of safety against over-delivery of insulin. Pressing delivery button 110 pushes activation rod 620 , compressing coil spring 640 and pushing trigger mechanism body 730 forward. First pin 710 protrudes outwardly from trigger mechanism body 730 and rides along piston ledge 650 , preventing piston from rising. First pin 710 is biased inwards by one of leaf springs 720 . When first pin 710 is pushed beyond piston ledge 650 , piston 610 rises and first pin 710 slides into ramped piston slot 770 . When delivery button 110 is released, coil spring 640 pushes activation rod 620 back towards the rest position, and ramp 740 on trigger mechanism body 730 engages piston ramp 750 , pushing piston back down to the rest position, where it is held in place with trigger mechanism body flat 780 again contacting piston flat 790 . If the patient tries to re-press delivery button 110 before trigger mechanism has returned to the rest position, second pin 700 , biased inwards by one of leaf springs 720 , engages detent 760 , stopping motion of trigger mechanism body 730 and preventing delivery of a partial bolus. Under normal operating conditions when pressing delivery button 110 , second pin 700 slides over vertical piston ramp 660 , allowing forward motion of trigger mechanism body 730 .
[0037] Mechanical pump 100 includes a simple, low cost, batteryless means for one-way communication to a blood glucose meter. Communication from the pump to the meter is useful for recording and time stamping insulin delivery events for later review by the patient and/or health care provider. This information can be useful to the patient, for example, to remember whether or not they have already delivered their insulin. One embodiment for communicating from mechanical pump 100 to a blood glucose meter is shown in FIGS. 8 A and B. Radio frequency identification (RFID) tag 810 is connected to antenna 800 with switch 820 included in the circuit, and blood glucose meter 840 has an antenna and other electronics required to read RFID tag 810 . When mechanical pump 100 is in the rest state (delivery button 110 not pressed), and blood glucose meter 840 is within range of mechanical pump 110 , blood glucose meter 840 detects the presence of RFID tag 810 due to wireless signal 850 , as shown in FIG. 8A . At this time, blood glucose meter 840 can read information stored on RFID tag 810 , such as the amount of insulin delivered per press of delivery button 110 , the type of insulin, and manufacturing date and identification information for mechanical pump 100 .
[0038] By reading identification information for mechanical pump 100 from RFID tag 810 , blood glucose meter 840 can keep track of how long the patient has used a particular pump, and alert or warn the user when it is time to change pumps to prevent mechanical pump 100 from being used beyond its intended lifetime. Now referring to FIG. 8B , pressing delivery button 110 pushes activation rod 620 in the direction of the arrow, causing switch pin 830 to open switch 820 , and interrupting wireless signal 850 . Blood glucose meter 840 recognizes interruption in wireless signal 850 as an insulin delivery event, and records the event in its memory, along with a time stamp of the event. Blood glucose meter 840 also can display the insulin delivery event to the patient to confirm delivery and to guide the patient regarding how much insulin remains be delivered. The stored insulin delivery data also can be used to display to the patient how much insulin remains in cartridge 170 . The insulin delivery data can be displayed along with blood glucose and food intake data also stored on blood glucose meter 840 to help the patient manage their blood glucose levels.
[0039] Alternatively, RFID 810 , antenna 800 , and switch 820 can be configured such that switch 820 is open when mechanical pump 100 is in the rest state. In this configuration, pressing delivery button 110 closes switch 820 , signaling to blood glucose meter 840 that an insulin delivery event has occurred. If it is desired to increase the range with which information can be sent from mechanical pump 100 to meter 840 , or increase the certainty by which the signal from mechanical pump 100 is received by meter 840 , a battery can be included in the circuit with antenna 800 , RFID tag 810 , and switch 820 , rather than relying entirely on power being supplied by meter 840 to read information from mechanical pump 100 . Alternatively, a piezoelectric or other energy-generating device can be incorporated in mechanical pump 100 such that pressing delivery button 110 generates power that is used to transmit signal 850 to blood glucose meter 840 . Instead of opening or closing a switch, the device could be configured such that pressing activation button 110 shields or unshields RFID tag 810 , making its signal alternately detectable or undetectable by blood glucose meter 840 .
[0040] It may be desirable to improve the reliability of the one-way communication between mechanical pump 100 and blood glucose meter 840 . This can be accomplished by incorporating two or more RFID tags and associated antennas. For example, one RFID tag can be configured such that it can be read (i.e., detected) by meter 840 when delivery button 110 is not pressed, while a second RFID tag can be configured such that it cannot be read (i.e., detected) by meter 840 when delivery button 110 is not pressed. In such an embodiment, pressing delivery button 110 would make the first RFID tag undetectable and would make the second RFID detectable. Meter 840 would be configured to detect transitions in detectability from both tags in order to determine that a delivery event has occurred. By including additional RFID tags, a digital logic communication scheme can be easily implemented in which various tags are activated and deactivated to signal different use events.
[0041] It may be desirable to transmit more detailed information about the delivery event from mechanical pump 100 to meter 840 , for example the sequential number associated with each delivery, or the delivery volume for the case where the bolus delivery volume is variable rather than fixed, for example for an insulin pen. In these cases, a more complex circuit can be included in mechanical pump 100 , and two-way communication between mechanical pump 100 and meter 840 can be implemented.
[0042] In the present example, mechanical pump 100 communicates with blood glucose meter 840 . However, devices other than a blood glucose meter can be used to communicate with mechanical pump 100 , for example a telephone, continuous glucose monitor, remote controller, personal digital assistant, computer, or a network appliance.
[0043] In another embodiment of the present invention, mechanical pump 100 can be configured as an external device, rather than attaching it to the body via an adhesive patch. Similar to an insulin pen, the delivery mechanism can be configured to allow the user to dial in the desired dose before injecting, rather than delivering a fixed shot size with each press of the delivery button, and the mechanism can push on the plunger of the insulin cartridge, rather than using micropump 320 to suck fluid out of the reservoir. For an external device, it is important to prime the system before each use. Priming complicates the storage of bolus data, since the device must distinguish between bolus delivery and priming events. One option to address this issue is to have the blood glucose meter instruct the patient when to prime, and to record the next delivery event as a priming event. Another approach is to include a sensor on the delivery device to sense contact with the skin during a delivery event. This can be accomplished with a switch that closes when the device is brought into contact with the skin. The switch would remain open during a priming event. The status of the switch (and thus the type of event, delivery to the body or prime) would be communicated from the pump to the blood glucose meter to store with the associated delivery event in the data log.
[0044] FIGS. 9A-9B are simplified cross sectional views of a mechanical pump engine with integrated delivery counter 900 , as can be employed in various embodiments of the present invention. FIG. 10 is a perspective view of a reset mechanism that can be used with mechanical pump engine with integrated delivery counter 900 , as illustrated in FIGS. 9A-9B . Mechanical pump engine with integrated delivery counter 900 includes delivery counter 902 . Delivery counter 902 includes teeth 904 , window 906 , first character 908 , and second character 910 . In FIG. 9A , piston 610 engages flexible diaphragm 430 . Activation rod 620 is biased in the rest position by coil spring 640 . In the rest position, trigger mechanism body 730 maintains piston 610 in the down position such that micropump diaphragm 430 is biased downwards, such that it presses down on and actively closes inlet valve 440 , providing an extra measure of safety against over-delivery of insulin. As illustrated in FIG. 9B , pressing activation rod 620 (as illustrated by arrow A 1 ), compresses coil spring 640 , pushing trigger mechanism body 730 forward. Pin 732 protrudes outwardly from trigger mechanism body 730 , and makes contact with tooth 904 , advancing the position of first character 908 and second character 910 in respect to window 906 . As trigger mechanism body 730 moves forward, piston 610 rises into ramp 740 , allowing flexible diaphragm 430 to move upward, inlet valve 440 to open, and fluid to flow into the pump chamber by way of pump inlet 500 . When activation rod 620 is released, coil spring 640 pushes trigger mechanism body 730 back towards the rest position, forcing piston 610 and flexible diaphragm 430 down, and closing inlet valve 440 . Each time trigger mechanism body 730 moves back and forth, pin 732 advances delivery counter 902 in the direction indicated by arrow A 2 , and displays a new character in window 906 . In this way, one can keep track of the number of pump cycles. FIG. 10 illustrates a mechanism for resetting delivery counter 902 . Using a torsion spring 912 and detent 914 , delivery counter 902 is reset by first pressing in the direction indicated by arrow A 3 , then rotating delivery counter 902 in the direction indicated by arrow A 4 until first character 908 is displayed in window 906 . In this way, users can easily reset the delivery counter before delivering a dose of fluid.
[0045] An advantage of the present invention is the ease with which the patient can use it. To set up the pump, the patient loads a pre-filled insulin cartridge 170 into insulin cartridge compartment 150 and closes cartridge door 130 . Next, the patient attaches mechanical pump 100 to adhesive patch platform 210 , establishing a fluid connection between mechanical pump 100 and flexible cannula 230 , and primes the device by holding down safety release button 120 and pressing delivery button 110 until a drop of insulin forms at the tip of flexible cannula 230 . The patient then removes the backing from adhesive patch platform 210 , secures the device to their skin, and pushes down on inserter lever 220 until it clicks in the down position. At this point the patient can deliver a fixed bolus of insulin on demand by holding down safety release button 120 and pressing delivery button 110 . If desired, delivery button 110 can be configured such that upon pressing delivery button 110 , the patient receives tactile and/or audible feedback to confirm that the button was pressed. Other than the simple priming step, the user does not have to perform any special steps to eliminate bubbles during setup or use of mechanical pump 100 , unlike the process for a conventional insulin pump. The design of the device allows for discrete operation through clothing without the need to see the device to deliver a bolus. After depleting insulin cartridge 170 , mechanical pump 100 , cartridge 170 , and adhesive patch platform 210 are removed and disposed of, and a new device is set up and attached to the skin. Alternatively, to reduce system cost, mechanical pump 100 can be re-used several times, reloading it with a new cartridge and attaching it to a new adhesive patch platform as necessary with each use. The device could be configured such that the patient can remove mechanical pump 100 while leaving adhesive patch platform 210 still attached to their body. This feature is useful if the patient wants to remove the pump temporarily for activities such as bathing or exercise, to change out insulin cartridges, or to check the pump if a problem is suspected. The pump can be reattached to adhesive patch platform 210 when desired by the patient.
[0046] In the case where mechanical pump 100 is removed from adhesive patch platform 210 , with adhesive patch platform 210 still attached to the patient's body, it is desirable for fluid outlet from mechanical pump 100 and fluid inlet to flexible cannula 230 to be sealed when mechanical pump 100 is disconnected in order to prevent external fluid, debris, other contamination, or air from entering fluid outlet from mechanical pump 100 or fluid inlet to flexible cannula 230 . In conventional infusion pumps with disconnectable infusion sets, only the infusion set portion is sealed with a septum while the needle that is connected to the pump for piercing the septum remains open and vulnerable to air and contamination. A seal can be provided on both sides by incorporating a septum on both fluid outlet from mechanical pump 100 and fluid inlet to flexible cannula 230 , with a needle on one side that pierces both septums to establish a flow path when mechanical pump 100 is attached to adhesive patch platform 210 .
[0047] Another advantage of the present invention is that it greatly simplifies insulin pump therapy to make it more broadly accessible while still providing beneficial safety features. Using direct micropump 320 to suck fluid from the insulin reservoir eliminates the mechanism that drives a plunger in a conventional indirect insulin pump. This greatly reduces the possibility of inadvertently driving the mechanism and over-delivering insulin. Conventional insulin pumps do not have any metering or flow-regulating device between the reservoir and the patient, making them vulnerable to failure modes such as siphoning and pressure differentials. In the present invention, micropump 320 is positioned between the insulin reservoir and the patient. Two normally closed valves 440 and 460 prevent unintentional insulin delivery. In addition, flexible diaphragm 430 is biased downwards by piston 610 in the rest position such that it presses down on and actively closes inlet valve 440 , providing an extra measure of safety against over-delivery of insulin. If the drive mechanism fails or is inadvertently activated in the present invention, at most one additional bolus will be delivered. In addition, micropump 320 and fluid lines between the pump and the patient have very low compliance; thus, if an occlusion occurs, pressure in the system rises very rapidly, and it will not be possible to press delivery button 110 , signaling the occlusion to the user. Safety release button 120 is an additional safety feature that prevents unintentional delivery.
[0048] Another advantage of mechanical pump 100 is that it is very small compared to existing pumps. For patients undergoing basal/bolus insulin therapy, approximately half of the insulin they inject is basal and half is bolus. If mechanical pump 100 is used to deliver only bolus insulin, or only basal insulin, the insulin reservoir can be approximately half the size of the reservoir from a conventional insulin pump used for basal/bolus therapy. If the pump is used to deliver only basal or only bolus insulin, there will be less pooling of insulin at the infusion site compared to conventional pumps which deliver both basal and bolus insulin to the same site. This may allow for the cannula to be worn longer than the typical 2-3 days before replacement. In addition, mechanical pump 100 does not have electronics, on-board power, an actuator, or a display, allowing for further size reduction. Because mechanical pump 100 is very small, it can be worn comfortably and discretely beneath clothing.
[0049] Another advantage of the present invention is that it is very low in cost compared to conventional insulin pumps, making the therapy accessible to more patients. The present invention is so low in cost that it can be disposable after each use. Thus, the user gets a new pump approximately every three days, improving reliability compared to conventional pumps which typically are expected to last for four years before replacement.
[0050] Embodiments of the present invention also employ only mechanical energy input by a user (via a user activated delivery button) to deliver a therapeutic agent (e.g., insulin) to a user. These embodiments, therefore, do not require expensive electronics or cumbersome batteries.
[0051] These and other objects and advantages of this invention will become obvious to a person of ordinary skill in this art upon reading of the detailed description of this invention including the associated drawings.
[0052] Various other modifications, adaptations, and alternative designs are of course possible in light of the above teachings. Therefore, it should be understood at this time that within the scope of the appended claims the invention might be practiced otherwise than as specifically described herein.
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A medical device pump with a housing with a compartment for removably receiving a cartridge containing a therapeutic agent, a conduit configured to operatively provide a fluid flow path for therapeutic agent to exit from the cartridge, a user activated delivery button, a trigger mechanism, and a mechanical pump mechanism. The trigger mechanism, user activated delivery button and mechanical pump mechanism of the medical device pump are configured such that the trigger mechanism is activated by a user fully activating the user activated delivery button. Moreover, such full activation generates mechanical power employed by, and sufficient for, the mechanical pump mechanism to pump a predetermined volume of therapeutic agent from the cartridge and through the fluid flow path.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention The invention is related to an interconnecting mechanism for a three-dimensional integrated circuit, and, more particularly, to an interconnecting mechanism that reduces the crosstalk effect for a three-dimensional integrated circuit.
[0002] 2. Description of Related Art
[0003] Due to the increasing importance of thinness and compactness of portable electronic device for communications, computing and so on, and due to the fact that such electronic products are increasingly multi-function and high performance, semiconductor process technology is moving toward higher integration, such that package structures with ever greater density are being pursued by manufacturers. Thus, manufacturers of both semiconductors and semiconductor packages have started utilizing three-dimensional package techniques to realize a compact packaging system with higher density.
[0004] Three-dimensional package techniques result in so-called 3D IC's, integrating a plural layers of chips or circuit substrates by various means into a single integrated circuit. In particular, 3D IC techniques commonly interconnect a plurality of chips using a three-dimensional packaging method on a single integrated circuit. Thus, an interconnecting technique with high density is required to install electrical junctions on the active surface and/or reverse surface of chips for providing a three-dimensional stack and/or package with high density.
[0005] Through-silicon via (TSV) technology is currently one of the crucial ways to realize 3D IC's, wherein through-silicon vias are utilized for vertical electrical connections in chips or substrates, allowing the stacking of more chips on a given area to increase the overall package density. Moreover, good use of through-silicon vias can effectively integrate different processes or reduce transmission delays, while reducing power consumption, raising efficiency, and increasing transmission bandwidth due to shorter interconnection pathways. Thus, TSV technology enables stacking of chips to achieve low power consumption, high density packaging and miniaturization.
[0006] However, currently, traditional TSV may generate far-end crosstalk and near-end crosstalk between a plurality of through-silicon vias, causing adverse effects on overall chip functionality. As shown in FIG. 1 , which depicts the level of near-end crosstalk generated by traditional TSV using current technology, traditional TSV exhibits a near-end crosstalk of −55.077 dB under a signal frequency of 1 GHz (curve S 41 ), while exhibiting a near-end crosstalk of −35.478 dB under a signal frequency of 10 GHz (curve S 41 ). Moreover, FIG. 2 depicts far-end crosstalk generated by traditional TSV technology, showing that traditional TSV exhibits a far-end crosstalk of −57.242 dB under a signal frequency of 1 GHz (curve S 31 ), while exhibiting far-end crosstalk of −37.622 dB under a signal frequency of 10 GHz (curve S 31 ).
[0007] Thus, developing an applicable interconnection mechanism that reduces or prevents near-end and far-end crosstalk in a plurality of through-silicon vias in a 3D IC is a highly desirable in the industry.
SUMMARY OF THE INVENTION
[0008] In view of the disadvantages of the prior art, the invention provides an interconnecting mechanism formed in a dielectric layer of a three-dimensional integrated circuit, comprising: a pair of first sub-interconnecting mechanisms including a first spiral conductive element formed in the dielectric layer with a first axis perpendicular to the planar direction of the dielectric layer, and a second spiral conductive element formed in the dielectric layer with a second axis perpendicular to the planar direction of the dielectric layer, wherein the first spiral conductive element is axially symmetrical to the second spiral conductive element; and a pair of second sub-interconnecting mechanisms including a third spiral conductive element formed in the dielectric layer with a third axis perpendicular to the planar direction of dielectric layer, and a fourth spiral conductive element formed in the dielectric layer with a fourth axis perpendicular to the planar direction of dielectric layer, wherein the third spiral conductive element is axially symmetrical to the fourth spiral conductive element, and the third spiral conductive element and the fourth spiral conductive element are located beside the first spiral conductive element and the second spiral conductive element.
[0009] Compared to the prior art, the present invention can not only effectively reduce the crosstalk effect in the signal paths of a 3D IC, reducing possible far-end crosstalk and near-end crosstalk generated between each input port and output port, but also can avoid reduction of the signal integrity with an increase of system complexity, integrate differing semiconductor processes, lower both transmission delays and power consumption through the shortening of interconnection paths, and raise the signal transmission bandwidth, thus further accommodating the next generation of electronic devices.
BRIEF DESCRIPTION OF DRAWINGS
[0010] FIG. 1 shows a simulation of near-end crosstalk generated by a traditional TSV;
[0011] FIG. 2 shows a simulation of far-end crosstalk generated by a traditional TSV;
[0012] FIG. 3 provides a perspective view of an interconnecting mechanism according to an embodiment of the present invention;
[0013] FIG. 4 provides a top view of an interconnecting mechanism according to an embodiments of the present invention;
[0014] FIGS. 5A to 5G provide profile views of steps for manufacturing an interconnecting mechanism according to an embodiment of the present invention;
[0015] FIG. 6 shows a simulation of near-end crosstalk generated by an interconnecting mechanism according to an embodiment of the present invention; and
[0016] FIG. 7 shows a simulation of far-end crosstalk generated by an interconnecting mechanism according to an embodiment of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0017] The following is explanation of the disclosed embodiments by examples, such that those familiar with this technical field can easily understand the advantages and efficacy by the explanation.
[0018] Note that the illustrated structures, ratios and sizes of elements of the disclosed embodiments in the appended figures and in the explanation are only provided for general understanding, particularly by those who are familiar with this technical field. Such details are not intended to limit the implementing conditions of the disclosed embodiments, and such details and illustrations are not directly applicable to realizing the invention. Various modifications of structure, ratio and size will fall within the scope of the disclosed embodiments when the efficacy and purpose of the disclosed embodiments are not affected. Meanwhile, terms in the explanation like “first,” “second,” “third,” “fourth,” “upper,” “lower,” “top,” “bottom,” “a,” and so on are only intended for convenience of description rather than for limiting the feasible scope of the disclosed embodiments. Adjustments of the relative relationships without actual alteration of the essence of the structures and techniques should be seen as within the feasible scope of the disclosed embodiments.
[0019] FIG. 3 provides a perspective view of an interconnecting mechanism 3 according to the present invention. The interconnecting mechanism 3 is formed in a dielectric layer (not shown) and includes a paired first sub-interconnecting mechanism 3 a having a first spiral conductive element 31 and a second spiral conductive element 32 , and a paired second sub-interconnecting mechanism 3 b having a third spiral conductive element 33 and a fourth spiral conductive element 34 . The first, second, third and fourth spiral conductive elements 31 , 32 , 33 and 34 have their axes perpendicular to the planar direction of the dielectric layer.
[0020] The first spiral conductive element 31 is axially symmetrical to the second spiral conductive element 32 . The third spiral conductive element 33 is axially symmetrical to the fourth spiral conductive element 34 . The third spiral conductive element 33 and the fourth spiral conductive element 34 are located beside the first spiral conductive element 31 and the second spiral conductive element 32 .
[0021] The first spiral conductive element 31 has a first upper through-silicon via 311 a, a first lower through-silicon via 311 b, a first connection section 312 , a first upper section 313 a and a first lower section 313 b. The first connection section 312 , the first upper section 313 a and the first lower section 313 b are arc-shaped. The first upper through-silicon via 311 a and the first lower through-silicon via 311 b are perpendicular to the planar direction of the dielectric layer. The first upper section 313 a and the first lower section 313 b are parallel to the planar direction of the dielectric layer.
[0022] The first connection section 312 is connected to the bottom of the first upper through-silicon via 311 a and connected to the top of the first lower through-silicon via 311 b, wherein the first connection section 312 is dislocated with the first upper section 313 a and the first lower section 313 b, such that the first upper section 313 a and the first lower section 313 b form the first spiral conductive element 31 . Likewise, the second, third and fourth spiral conductive elements 32 , 33 and 34 have a similar structure to that of the first spiral conductive element 31 . Therefore, two sets of differential transmission paths are formed, which commonly form two sets of spiral interconnecting mechanisms.
[0023] The second spiral conductive element 32 has a second upper through-silicon via 321 a , a second upper through-silicon via 321 b, a second connection section 322 , a second upper section 323 a and a second lower section 323 b. The second connection section 322 , the second upper section 323 a and the second lower section 323 b are arc-shaped. The second upper through-silicon via 321 a and the second lower through-silicon via 321 b are perpendicular to the planar direction of the dielectric layer. The second connection section 322 , the second upper section 323 a and the second lower section 323 b are parallel to the planar direction of the dielectric layer.
[0024] The second connection section 322 is connected to the bottom of the second upper through-silicon via 321 a and connected to the top of the second lower through-silicon via 32 lb. The second connection section 322 is dislocated with the second upper section 323 a and the second lower second 323 b.
[0025] The third spiral conductive element 33 has a third upper through-silicon via 331 a, a third lower through-silicon via 331 b , a third connection section 332 , a third upper section 333 a and a third lower section 333 b. The third connection section 332 , the third upper section 333 a and the third lower section 333 b are arc-shaped. The third upper through-silicon via 331 a and the third lower through-silicon via 331 b are perpendicular to the planar direction of the dielectric layer. The third connection section 332 , the third upper section 333 a and the third lower section 333 b are parallel to the planar direction of the dielectric layer.
[0026] The third connection section 332 is connected to the bottom of the third through-silicon via 331 a and connected to the top of the third lower through-silicon via 331 b . The third connection section 332 is dislocated with the third upper section 333 a and the third lower section 333 b.
[0027] The fourth spiral conductive element 34 has a fourth upper through-silicon via 341 a, a fourth lower through-silicon via 341 b, a fourth connection section 342 , a fourth upper section 343 a and a fourth lower section 343 b. The fourth connection section 342 , the fourth upper section 343 a and the fourth lower section 343 b are arc-shaped. The fourth upper through-silicon via 341 a and the fourth lower through-silicon via 341 b are perpendicular to the planar direction of the dielectric layer. The fourth connection section 342 , the fourth upper section 343 a and the fourth lower section 343 b are parallel to the planar direction of the dielectric layer.
[0028] The fourth connection section 342 is connected to the bottom of the fourth through-silicon via 341 a and connected to the top of the fourth lower through-silicon via 341 b. The fourth connection section 342 is dislocated with the fourth upper section 343 a and the fourth lower section 343 b.
[0029] FIG. 4 provides a top view of the interconnecting mechanism 3 of an embodiment according to the present invention. The first connection section 312 is axially symmetric to the second connection section 322 , and the first upper section 313 a is axially symmetric to the second upper section 323 a, the first connection section 312 , the second connection section 322 , the first upper section 313 a and the second upper section 323 a commonly forming a spiral structure in the planar direction of the dielectric surface Likewise, the third connection section 332 is axially symmetric to the fourth connection section 342 , and the third upper section 333 a is axially symmetric to the fourth upper section 343 a, the third connection section 332 , the fourth connection section 342 , the third upper section 333 a and the fourth upper section 343 a commonly forming another spiral structure in the planar direction of the dielectric surface.
[0030] FIGS. 5A to 5G provide profile views of steps of manufacturing an interconnecting mechanism of an embodiment according to the present invention. As shown in FIG. 5A , four lower through-silicon vias 511 b are formed in a substrate 501 using etching and deposition processes (the substrate or dielectric layer referenced herein referring to objects composed of silicon, silicon nitride, and other organic or non-organic material).
[0031] As shown in FIG. 5B , a lower section 513 b is formed on the top of the lower through-silicon via 511 b by a deposition technique, for example, wherein the lower section 513 b has four arc-shaped conductive traces ( 313 b, 323 b, 333 b and 343 b, as shown in FIG. 3 ), each of which has one end electrically connected to the lower through-silicon via 511 b.
[0032] As shown in FIG. 5C , the substrate 501 is turned over, such that the lower section 513 b is located beneath the lower through-silicon via 511 b.
[0033] As shown in FIG. 5D , a connection section 512 composed of a conductive material is installed on the lower through-silicon via 511 b by a deposition technique, for example, wherein the connection section 512 has four conductive traces ( 312 , 322 , 332 and 342 , as shown in FIG. 3 ), each of which has one end electrically connected to the lower through-silicon via 511 b.
[0034] As shown in FIG. 5E , a passivation layer 505 or another dielectric layer is formed on the substrate 501 by, for example, a deposition technique. As shown in FIG. 5F , four upper through-silicon vias 511 a are formed on the passivation layer 505 by etching or deposition, for example.
[0035] As shown in FIG. 5G , upper sections 513 a composed of a conductive material are installed on the upper through-silicon vias 511 a by a deposition technique, for example, wherein the upper section 513 a has four arc-shaped conductive traces ( 313 a, 323 a, 333 a and 343 a, as shown in FIG. 3 ), each of which has one end electrically connected to the upper through-silicon via 511 a.
[0036] Notice that in other embodiments of the invention, the connection section 512 , the upper section 513 a and the lower section 513 b may all be installed as a redistribution layer (RDL).
[0037] Referring again to FIG. 3 , the interconnecting mechanism 3 has two sets of differential transmitting structures, including a first port 3001 , a second port 3002 , a third port 3003 and a fourth port 3004 . FIG. 6 shows a simulation result for near-end crosstalk generated by the interconnecting mechanism 3 of an embodiment according to the present invention (curve S 41 ′ : crosstalk from the fourth port to the first port). The interconnecting mechanism 3 has a near-end crosstalk of −63.014 dB under a signal frequency of 1 GHz (curve S 41 ′), and has a near-end crosstalk of −43.498 dB under a signal frequency of 10 GHz (curve S 41 ′). FIG. 7 shows a simulation result for far-end crosstalk generated by the interconnecting mechanism 3 of an embodiment according to the present invention (curve S 31 ′: crosstalk from the third port to first port). The interconnecting mechanism 3 has a far-end crosstalk of −61.205 dB under a signal frequency of 1 GHz (curve S 31 ′), and has a near-end crosstalk of −41.787 dB under a signal frequency of 10 GHz (curve S 31 ′). It can be seen that an interconnecting mechanism disclosed in the present invention provides significant improvements in reducing near-end crosstalk and far-end crosstalk, as compared to the traditional through-silicon via structure (the efficacy of which is illustrated in FIGS. 1 and 2 ).
[0038] In conclusion, a through-silicon via structure in the present invention enables a 3D IC to effectively reduce crosstalk, and reduce far-end crosstalk and near-end crosstalk between input and output ports. As compared to the through-silicon via structure in the prior art, the through-silicon via structure disclosed in the present invention avoids further influence of crosstalk among electrical signals due to an increase of complexity of a system, while integrating different semiconductor processes to effectively lower the negative effects of near-end and far-end crosstalk in transmission between chips or substrates in a very economic way and simultaneously raising reliability of the semiconductor device using the technique and the manufacturing process.
[0039] The above-mentioned exemplary embodiments illustratively reveal the theory and efficacy of the disclosed invention, rather than limit the invention to the particular disclosed embodiments. Those familiar with this technical field will be able to make alterations to the embodiments without departing from the essential spirit and scope of the principles of the invention as defined in the following claims.
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An interconnecting mechanism is provide, which includes paired first sub-interconnecting mechanisms and paired second sub-interconnecting mechanisms. The first pair of sub-interconnecting mechanisms includes first and second axially symmetrical spiral conductive elements. The second pair of sub-interconnecting mechanisms includes third and fourth axially symmetrical spiral conductive elements. Configuring the pairs of sub-interconnecting mechanisms in a differential transmission structure having a spiral shape is used to avert sounds and noise signals between different chips or substrates caused by a miniaturizing fabrication process or an increased wiring density.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates both to an apparatus and method for forming a stretchable strap from a supply of stretchable film material initially having a sheet configuration and once formed to positioning the stretchable strap into securing engagement with an article, package, etc. being bound.
2. Description of the Prior Art
The prior art is replete with "strapping machines" specifically designed to bind an article, package, etc. with a strap formed of a plurality of materials most of which are commonly distinguished by being non-elastic or non-stretchable. While the material from which the prior art strapping is formed is naturally capable of a certain amount of flexibility, required to position the strap about the article being bound, none of the prior art strapping material known is capable of any elastic expansion or stretching. More specifically, strapping machines normally use a variety of materials including but not limited to polypropelene, fiberglass, steel or metal and other such non-elastic material. A lack of elasticity in the prior art materials is in fact a requirement based on the design and structural operation of the prior art machines used to bind the various articles or packages utilizing such materials. More specifically, in the operation of the prior art strapping machines, the strapping is fed into the machine from a coil which has been pre-formed. A free end is directed into some type of directing sleeve or channel and a pushing force is exerted thereon. The free end travels the length of the directing or positioning channel and serves to effectively surround the article or package being bound. Once the non-elastic strap is at its intended position it is disposed into engaging relation with the outer surface thereof and connected to itself by a variety of means dependent on the particular prior art material utilized.
While it is of course to be assumed that the prior art strapping machines, as well as the known and commercially existing strapping materials, are operative for their intended function, it is also recognized in the industry that such non-elastic strapping is at least somewhat inefficient and also more expensive than other materials that could be utilized if in fact the technology were available.
The invention herein, to be described in greater detail hereinafter, utilizes a different, more efficient and less expensive material in the formation of a "stretchable strapping" which is still of high strength but which has certain elastic capabilities allowing it to overcome certain problems existing in the prior art and presently commercially available strapping machines and strapping material.
SUMMARY OF THE INVENTION
The present invention is directed to both an assembly or apparatus as well as a method of forming a stretchable strapping from a sheet of flexible, elastic film material and positioning a "single strand" of the formed stretchable strapping into fixed bound engagement about the exterior surfaces of any one of a plurality of packages, articles, objects, etc. This of course differs from prior art apparatus and techniques which utilize a flexible but non-elastic strapping material normally formed of a metallic, plastic, fiberglass of like prior art material. While the present invention could incorporate numerous materials having certain elastic capabilities, one preferred material now commercially available is a linear, low density, polyethylene material originally supplied to the apparatus of the present invention in a sheet configuration stored on a continuous roll. The apparatus or assembly comprises a support base or frame on which the remaining components of the apparatus are mounted in cooperative, working relation to one another. More specifically, the subject assembly includes a shaping means located in a receiving location to the rolled supply of stretchable material film in a sheet configuration. The sheet is initially guided or "threaded" through a shaping ring or like structure which effectively channels the film down from its sheet configuration into an elongated strap. A stretching means is considered part of the shaping means and is mounted on the support base or frame downstream of the shaping ring and comprises a plurality of driven pulleys or rollers.
In a preferred embodiment, to be described in greater detail hereinafter, the plurality of driven rollers includes a first roller and second roller wherein the first roller is located downstream of the second roller and both rollers serve to drivingly engage the formed, elongated strap. A stretching action occurs by structuring the first, downstream roller or pulley to have a greater peripheral rotating speed than the second or upstream roller. This will in effect provide a pulling force between the first and second rollers to a sufficient degree to effectively stretch the strap. The amount of stretch or linear increase in the overall length is dependent upon the particular, predetermined parameters of the material. Purposely, the material is not stretched to its maximum linear dimension but to a length somewhat less than the maximum longitudinal or linear dimension. This allows the formed stretchable strap to have a certain degree of elasticity remaining therein. This lends greater efficiency and security to the articles once bound by the stretchable strap or "stretch strapping" by allowing it to adapt to any shift in weight or positioning of the articles, objects or packages being bound by the stretch strapping. The formed stretch strapping is then passed along a flow path by a plurality of components including free wheeling pulleys and/or rollers until it reaches a positioning means.
The positioning means includes a gripping structure which serves to removably grasp or grip the free end of the formed stretch strapping. A drive structure preferably in the form of a closed, continuous drive chain, is connected to and drives the gripping structure with the free end of the strap attached thereto. A reversible drive motor serves to force the drive chain along a predetermined path of travel defined by its surrounding placement to an article or object to be bound. More specifically, a supporting yoke assembly having a continuous, closed configuration surrounding a central opening more fully describes the aforementioned path of travel. The object to be bound is positioned within the central aperture and the drive chain and drive motor are activated to exert a pulling force on the strap by virtue of it being gripped by the gripping structure. Once the formed stretch strapping or strap is disposed along the path of travel and in surrounding relation to the object to be bound, but outwardly spaced therefrom, it is further positioned into binding contact with the outer surface or portions of the article to be bound.
Control mechanisms serve to effectively tighten the strap about the outer surfaces to a point where certain segments of the strap are disposed in crossed-over relation to one another. A heat sealing structure is inserted at this cross-over point to heat the temperature of the material from which the strap is formed to an effective melting temperature. Such portions are pressed together to form a tight heat seal or weld and the strap is severed or otherwise disconnected, preferably by a heated wire or the like so as to segregate the length of the strap now bound to the outer portions of the article from the remainder of the strap yet to travel about the aforementioned path of travel. After removal of the article already bound, the next cycle continues after the article is placed within the aperture of the yoke assembly as described above.
An important feature of the present invention, including the method of forming and positioning the stretch strapping includes the exertion of a pulling force on the flexible and elastic material subsequent to its being formed into an elongated strap. This pulling force is exerted on the strap by gripping the free end thereof until it surrounds the article or package to be bound. The flexibility as well as the elasticity of the light but high strength material (linear low density polyethylene) on which the strap is formed prevents it from being positioned and manipulated in the conventional, prior art fashion as with known strapping machines. The increased elasticity and flexibility, even after being subjected to a stretching step, allows it to be securely bound about the outer portions of the article being bound and further allows it to adapt to any shifting or movement of the article, overcoming certain prior art problems.
Other structural components of the assembly including a tensioning means to maintain the strap in a linearly taught condition is described in greater detail hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
For a fuller understanding of the nature of the present invention, reference should be had to the following detailed description taken in connection with the accompanying drawings in which:
FIG. 1 is a front view of the assembly of the present invention.
FIG. 2 is a sectional view along line 2--2 of FIG. 1.
FIG. 3 is a partial sectional view in detail along line 3--3 of FIG. 1.
FIG. 4 is a sectional view along line 4--4 of FIG. 1.
FIG. 5 is a top view along line 5--5 of FIG. 1.
FIG. 6 is a top view of certain components of the assembly to be described in greater detail.
FIG. 7 is a front view of the structure of FIG. 6.
FIG. 8 is a detailed sectional view in partial cut-away of a moving structure associated with the assembly of the present invention.
FIG. 9 is a front view in partial cut-away of the supply of film in a sheet configuration utilized in the assembly and method of the present invention.
FIG. 10 is a sectional view along line 10--10 of FIG. 9.
FIG. 11 is a sectional view of certain components associated with the embodiment of FIG. 9.
FIG. 12 is a perspective view of a yoke assembly of the apparatus of the present invention.
FIG. 13 is a sectional view in partial cut-away of the sealing structure associated with the assembly of the present invention.
Like reference numerals refer to like parts throughout the several views of the drawings.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in the accompanying figures, the present invention is directed towards an assembly generally indicated as 10 for forming a stretchable strap having an elongated configuration from a supply of film having a sheet configuration and rotatably mounted on the assembly 10 in a roll form as generally indicated as 12. As will be explained in greater detail hereinafter, the material from which the stretchable strapping is formed is an elastic material and is preferably a linear, low density polyethylene material. It should be emphasized, however, that other materials can in fact be used as long as their elastic and strength characteristics are applicable for the intended use herewith.
The assembly comprises a support base having an outer housing or frame which serves to support the remainder of the components to be described hereinafter. The base or housing 14 may be permanently or more preferably movably mounted by casters or wheels 15 secured thereto.
With reference to FIG. 9, the assembly 10, with the housing 14 removed, includes a support base as at 16 wherein the supply roll of stretchable film as at 12 is rotatably mounted by a supporting arm 18 at what may be referred to as an input or leading portion generally indicated as 17 of the assembly 10. A shaping means 20 may take the form of a ring, channel, sleeve, etc. or other like structure which serves to shape the film as at 19 from its sheet-like configuration, substantially convergently downwardly into an elongated strip hereinafter referred to as the strap or formed strap 22. The material is pulled through the shaping ring 20 by the stretching means which is generally indicated in FIG. 9 as 24. The stretching means may be considered part of the shaping means and includes a first drive roller 26 and a second driven roller 28 both driven by a drive motor 30 as best shown in FIG. 11. The drive motor 30 serves to forcibly rotate the drive gear as at 32 by means of a drive shaft 33 attached thereto. An elongated drive chain as at 34 serves to interconnect both the first roller or pulley 26 and the second roller or pulley 28 in a manner which causes the forced rotation of both. The first roller is specifically dimensioned, configured and otherwise structurally adapted to rotate at a greater peripheral speed than the second roller 28. This serves to exert a pulling and stretching force on the segment of the strap as at 22' causing it to stretch and thereby be elongated to a length somewhat less than its maximum degree of stretch or longitudinal extension depending upon the particular tension parameters of the material used. In other words, the strap 22 is stretched as at 22' to a degree somewhat less than its maximum stretchable limits so that a certain amount of elasticity or "memory" remains within the strap 22 as it is bound around an object, article, container, etc. generally indicated as 39 in FIG. 12, also to be explained in greater detail hereinafter.
Further with regard to FIG. 9, the strap 22, after leaving the stretching means generally indicated as 24, travels around a predetermined path of travel at least partially defined by spaced apart free wheeling pulleys or rollers as at 41, 43 and 45. This path of travel leads and guides the strap 22 to the yoke assembly generally indicated as 40 and as best shown in FIGS. 1 and 12. In addition, a tensioning means generally indicated as 42 is mounted on the support base 16 downstream of the stretching means 24 but prior to the strap 22 reaching the yoke assembly 40.
The tensioning means 42 comprises a roller or pulley member 44 which, as best shown in FIG. 10, is attached to a weight or like member as at 46 which is adapted to move reciprocally in a substantially vertical orientation, under the influence of gravity, within an elongated guide slot or channel as at 47. The tensioning means 42 includes the member 46 which may in effect define a weight influenced by gravity to be normally biased downwardly towards the lower end as at 47' of the guide slot 47. This will have the effect of always placing an adequate amount of tension on the strap 22 thereby maintaining it in a substantially taut condition. The weighted tension structure 42, 46 due to its constant and continuous engagement with the strap 22 will also serve to force the strap from a predetermined path of travel about the length of the yoke assembly 40 into confronting engagement with the article 39 being bound. Such confronting engagement is indicated in FIG. 12 as 22".
The flow path as generally described and defined with reference to the structure of FIG. 9 should be more clearly defined as the travel of the strap 22 as it is formed from a sheet configuration from the stretchable film 19 into an elongated strap as shown. The flow path is generally defined as the path of travel along which the strap is forced prior to its entering the yoke assembly 40. The yoke assembly includes various components including a substantially continuous, closed frame 49. The frame is further defined by a central receiving opening as at 50 through which the article 39 at least partially passes and is positioned in order to receive the binding strap 22 into binding engagement with outer surface portions thereof as indicated by the strap in FIG. 12 as 22".
The yoke and its closed, continuous configuration of its frame 49 defines a path of travel of the strap as it is forced by being pulled, effectively along the length of the yoke 49, by the positioning means. The positioning means comprises an elongated continuous drive member preferably in the form of a drive chain as at 52. A drive gear as at 54 serves to forcibly drive the chain or drive member 52 continuously about the aforementioned path of travel. As shown in FIG. 4, a drive motor 54 is interconnected to the drive chain or drive member 52 by a linkage assembly including drive shaft and associated gear 56. The drive gear 54 is of course driven thereby through an additional elongated supplementary or original drive member as at 55 also in the form of a drive chain. As should be apparent, continuous operation of the drive motor 54 will cause the elongated drive member or chain 52 to rotate preferably in a clockwise direction. However, the drive motor 54 is reversible so as to at least partially reverse the direction of travel of the drive chain 52 for purposes of beginning a new cycle after an original or first article 39 has been bound as shown in FIG. 12 and is removed from the receiving opening 50 within the frame 49 of the yoke assembly 40.
An additional structure associated with the positioning means is a gripping member or structure 56 secured to the elongated drive member and movable therewith. The gripping structure 56 is specifically structurally adapted to removably grip the strap 22 as it enters into the area of the yoke assembly (see FIG. 7) from a guide roller or pulley 57 which effectively ends the aforementioned flow path as pictured and described with reference to FIG. 9. Once the strap 22 passes about the free wheeling guide roller or pulley 57, it enters into removable gripping engagement with the elongated drive member 52 of the positioning means by virtue of its removable connection to the gripping structure 56 as shown in detail in FIG. 3. The activation of the drive motor 54 causes the elongated drive member 52 to be pulled or travel in a clockwise direction about the yoke assembly 40 and accordingly, pull and engage a free end of the strap 22 therewith by virtue of its connection with the gripping structure 56. Continued driving and activation of the drive motor 54 will cause the continued travel of the drive member 52 in a clockwise direction and a continuous pulling force being exerted on the strap 22 as it travels along the path of travel generally defined by the configuration of the yoke frame 49. The gripping structure 56 is adapted to maintain a gripping force on the free end of strap 22 as long as the drive chain travels in the preferred clock-wise direction. However, travel in the opposite direction serves to automatically release the strap from the gripping structure 56.
As part of this path of travel, a retaining means is provided so as to retain the strap 22 along the length of the path of travel and generally about the periphery of the receiving opening 50. More specifically, the retaining means comprises a plurality of outwardly extending retaining fingers 58 disposed in spaced apart relation to one another. The fingers 58 are reciprocal as indicated by directional arrow 59 in FIG. 2 so that the fingers may be selectively and automatically positioned into an outwardly extended operative position as shown in FIG. 2 or a retracted position by virtue of the automatic operation of fluid (air or hydraulic) operated cylinders as at 60. More specifically, the strap 22 is pulled about the path of travel and engages each of the fingers 58. These fingers, when all in their outwardly extending operative position (FIG. 2) serve to retain the strap 22 in an outward spaced location and in surrounding relation to the article 39 to be bound. Once the fingers are all concurrently retracted into their non-operative position, the strap 22 is directed inwardly into its bound position in engagement with the outer surface of the article 39 as represented in FIG. 12 as 22". The inward gathering of the strap 22 into the position 22" is provided or aided at least in part due to the existence of the tensioning means 42 which exerts a weight, due to gravity, as provided by the weighted roller 46, 44 on the strap 22 (see FIGS. 9 and 10). As the retaining fingers 58 are moved to their retracted, non-supporting position, the pulley and weight 44, 46 fall to the bottom of the elongated slot 47 as at 47'. This takes up the slack of the strap 22 and will allow it to be tightly bound about the outer surface of the article 39 into the bound position 22".
With reference to FIGS. 6 and 7, an additional control mechanism is provided and shown in detail in FIGS. 6 and 7. Such control mechanism and weighted movements of the components to be described in detail hereinafter are moved automatically by a plurality of micro switches, sensors, relays, etc. the details of which are well known in the art and commercially available. FIG. 7 shows that the end of the strap as at 22'" has made a complete travel about the path of travel generally defined by the length of the yoke frame 49. It is brought by the gripping member 56 into a cross-over point wherein the strap 22 and 22'" essentially overlap as best shown in FIG. 13. At the point of cross-over, a heating element generally indicated as 68 moves upwardly through the operation of a fluid-activated piston and cylinder arrangement 66 to a point where the heating element or plate 68 comes between the two segments of the strap 22 and 22'" and into engagement with both for the purpose of heating. Before the heating plate 68 is retracted, the two segments 22 and 22' are forced together by a press plate as at 70 also activated by appropriate fluid piston and cylinder arrangement 72. The press plate forces the two strands 22 and 22'" into engagement with one another and against the heating plate 68 due to the existence of a brace plate 74 which may be considered a part of the support base and/or frame 16. After the two strands 22 and 22'" are forced against the heating plate as described above, the heating plate 68 and the press plate 70 both retract. Once the heating plate 68 is removed from between the two strands 22 and 22'", the press plate is again forced into contact with the now heated strands 22 and 22'" forcing them together into a heat seal or weld. This binds the strap about the outer surface of the article 39 as intended.
This occurs by a spaced apart gripping plate 90 and 91 between which a segment of the strap 22 passes exerting a pulling force on the strap 22 in a direction indicated by arrow 89 in FIG. 7. Activation of the piston and cylinder arrangement generally indicated as 92 serves to reverse the direction of the plates 90 and 91 or more specifically pull back a segment of the strap 22 at a point before the overlapping heat seal engagement as pictured in FIG. 13. This will tighten the strap 22" when in its bound position as shown in FIG. 12. Other features associated with the gripping plates 90 and 91 include a biasing spring as at 93 serving to normally bias the plate 91 away from the plate 90. The forced activation of the piston and cylinder arrangement generally indicated as 95 in FIG. 6, causes an inwardly directed travel of the plate 90 into further engagement with the plate 91 except for the fact that a strap segment is sandwiched therebetween. This all occurs immediately prior to establishing the heat weld between the overlapping strands 22 and 22'".
Once the heat weld has been formed as described above, the strap is removed from the gripping structure 56 through activation, at least in part, of a retaining flange 100. This occurs by an additional fluid activated piston and cylinder arrangement 98 serving to drive the rod 99 and the attached retaining flange 100 in a reciprocal fashion as shown. When the retaining flange is retracted in accordance with directional arrow 106 in FIG. 6, it serves to grip the strand and pull laterally in the same direction as arrow 106.
Once the retaining flange 100 travels in the direction of the arrow 106 in FIG. 6, the drive motor 54, serving to rotate the drive chain 52 in a normally clockwise direction is reversed. This causes the reverse travel of the drive chain 52 in a counter-clockwise direction causing the gripping structure 56 attached thereto to also travel in a counter-clockwise direction. The gripping structure thereby automatically disengages the strand 22 and travels in the aforementioned counter-clockwise direction until it re-engages an aligned portion of the strand 22 at a location downstream of the now established heat weld, wherein such location is generally indicated by the indicator arrow 111 in FIG. 7. The reverse activation of the drive motor 54 continues until the gripping structure 52 again re-engages the strap 22 where indicated. Once the strap 22 is so engaged, the motor 54 is again activated so as to force the continuous rotation and travel of the drive chain 52, the gripping structure 56 and the strap 22 in a clockwise direction by exerting a pulling force on the re-engaged strap 22.
However, the now bound strap is severed by a severing mechanism at a location downstream of the heat weld after the gripping structure 56 re-engages a new portion of the aligned strand 22.
A severing mechanism generally indicated as 76 in FIGS. 6 and 7 is engaged and activated. This severing mechanism includes a heated severing wire 78 mounted on a support 80 and activated into and outwardly severing position as indicated by the directional arrow 81. Such activation and movement occurs automatically through the tripping of a relay or micro switch which in turn activates the fluid activated piston and cylinder assembly 83. The severing of the strap occurs as the last act immediately prior to starting a recycle and a repositioning of the strap 22 about the aforementioned yoke frame 48 and along the designated path of travel as set forth above.
Other features associated with the control mechanism shown in FIGS. 6 and 7 is a guide wire indicated as one of two through which one free end of the strap 22 is originally threaded. The overall configuration and dimension of the guide wire 102 is such as to maintain the strap in a given area so that it can be acted upon by the components as set forth in FIGS. 6 and 7 and as described above.
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This invention relates to both an apparatus and method of forming a thin flexible and to some extent resilient material strap from a supply of sheet film and further wherein the apparatus and method involves the positioning of the formed stretchable strapping about and in binding relation to the exterior of any one of a plurality of various types of packages, articles, etc. The apparatus comprises positioning means which serves to grip a free end of the formed stretch strapping and exert a pulling force thereon to direct it about a predetermined path of travel surrounding the article being bound and subsequently securing a length of the stretch strapping in binding engagement with the exterior surfaces or portions of the article being bound.
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FIELD OF THE INVENTION
[0001] The invention relates generally to braces for reinforcing tubes and to tubes reinforced by said braces, and more particularly to a reinforced roller tube for use with extendible awnings of the roll-up type popularly used with recreational vehicles.
BACKGROUND OF THE INVENTION
[0002] Awnings of the roll-up type are well-known in the recreational vehicle field for providing shade and cover from inclement weather, and also for providing additional living space adjacent to the vehicle.
[0003] Roll-up awnings are also used in a variety of other settings where temporary cover is required. For example, and without limitation, roll-up awnings are used on hotel and shop fronts, and on trailer homes. One edge of the awning is fixed to the vehicle or building and, in the stored position, the other end is wrapped around a spring-loaded roller tube. The awning can be mounted to the roller tube by means of slideways extending longitudinally within the exterior surface of the roller tube. The roller tube can be pivotably supported by arms extending from the vehicle or building, and can be further supported from the ground by poles, or from the vehicle or building by outriggers. The awning is deployed by unrolling the awning from the roller tube against spring resistance, and supporting and locking the unrolled awning in place. Subsequent stowing of the awning onto the roller tube is facilitated by the aforementioned spring-loading.
[0004] In the deployed position, the roller tube must support its own weight, the weight of the awning, and the weight of other attachments such as screens or valances. In addition, the roller tube must resist wind forces acting on the awning, and support any additional weight due to precipitation accumulating on the awning. Because the area of awning and the length of the roller tube can be large (roller tubes of 21 feet or more in length are commonly used), the roller tube must be strongly constructed to minimize bowing or bending in use. A common failure mode of roller tubes is for initial bowing to facilitate further accumulation of precipitation on the awning, leading to complete structural failure of the roller tube.
[0005] In the past, a long roller tube would sag between its end supports. To mitigate this problem, additional supports can be used; the roller tube can be constructed from strong materials such as extruded aluminum or steel; and/or stiffening inserts can be positioned within the roller tube.
[0006] Examples of each of these approaches can be found, for example, in the following patents. U.S. Pat. No. 4,258,778 discloses a roller tube formed from sheet metal, with optional reinforcement provided by inserts or foamed plastic placed within the roller tube; U.S. Pat. No. 4,508,126 discloses partial length stiffeners for a roller tube; U.S. Pat. No. 5,351,736 discloses a roll-formed roller tube with strengthening ridges formed in its surface; and U.S. Pat. No. 6,598,612 B1 discloses an awning having a mansard shape for minimizing the accumulation of precipitation on the awning and aerodynamically reducing the effect of wind on the awning.
[0007] Each of the aforementioned approaches suffers from one or more of the following drawbacks: roll-forming long roller tubes from a sheet metal such as steel has proved to be technically difficult; the stiffeners have a low stiffness to weight ratio; the stiffeners have elaborate shapes that are expensive to make; the stiffeners comprise welds or joints that are expensive to form and which may accumulate stresses and fail in use; or additional supports for the awning are required, which may be cumbersome or obstructive.
[0008] Notwithstanding the existence of a variety of awning roller tube strengthening devices in the prior art, there is a continuing need for improved means for reinforcing awning roller tubes that can be simply and inexpensively manufactured from commonly available, light weight materials without the need for welding or jointing, and which minimize the risk of roller tube bending or failure from precipitation or wind. The present invention substantially fulfills these needs. All this and more will become apparent to one of ordinary skill upon reading the disclosure, drawings, and claims appended hereto.
SUMMARY OF THE INVENTION
[0009] The present invention is directed to a brace for reinforcing a tube, a reinforced tube such as a reinforced roller tube for an awning, and to an awning assembly incorporating said reinforced roller tube. The invention provides an improved brace that is light-weight, resists flexing and twisting, and can be easily and inexpensively manufactured from commonly available sheet materials without the need for welding or jointing.
[0010] In a first embodiment, the invention provides a brace for a tube, the brace comprising a pair of mounted, elongate metal strips. Each metal strip comprises a central longitudinal portion, two longitudinal edge portions, and an intermediate longitudinal portion connecting the central portion and each edge portion. The central portions are mounted to each other, for example by rivets. The intermediate portions extend substantially radially from the central portions, and each edge portion forms an angle with the intermediate portion to which it is connected to form a foot for engaging the interior of the tube.
[0011] When inserted into a tube, the feet of the brace contact the interior surface of the tube to reinforce the tube. Not to be thereby limited by theory, flexing forces applied to the tube are transferred through one or more of the feet to the mounted central portions of the brace, spreading the force over the contact area of the two central portions, which provides high stiffness. The brace is devoid of joints or welds, which could otherwise accumulate stresses and lead to structural failure.
[0012] In a second embodiment, the invention provides a reinforced roller tube for an awning, the roller tube comprising a brace according to the first embodiment disposed within at least a central portion of the roller tube.
[0013] In a third embodiment, the invention provides an improved awning assembly, the awning assembly comprising a reinforced roller tube according to the second embodiment, and further comprising an awning having first and second ends, the first end being attachable to a wall or support, the second end being attached to the roller tube, and the awning being rollable around the roller tube.
[0014] It is therefore an object of the present invention to provide an improved brace exhibiting a high stiffness to weight ratio for reinforcing a tube, wherein the cross-sectional shape of the tube is not particularly limited, and can include, for example, circular, elliptical, square, hexagonal, or octagonal cross-sections.
[0015] It is a further object of the invention to provide a brace for a tube that can be simply and inexpensively manufactured from commonly available, light-weight sheet materials, without the need for welding or jointing.
[0016] It is a further object of the invention to provide a reinforced roller tube for use with awnings that minimizes the risk of roller tube bending or failure from the action of precipitation or wind, without unduly adding to the weight of the roller tube.
[0017] It is a further object of the invention to provide an improved awning assembly for use on hotels, shop fronts, recreational vehicles, and mobile homes, which resists bending and/or collapse due to the action of wind or accumulation of precipitation on the awning, without unduly adding to the weight, complexity, or cost of the awning assembly.
[0018] It is yet a further object of the invention to provide a brace that can be used to reinforce pre-existing tubes, such as existing roller tubes, by subsequent insertion therein of a brace according to the first embodiment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings where:
[0020] FIG. 1 depicts a recreational vehicle incorporating an awning assembly according to the present invention.
[0021] FIG. 2 shows a transverse sectional view of reinforced roller tube according to the prior art.
[0022] FIG. 3 shows an isometric view, partially cut away, of an embodiment of a reinforced roller tube according to the present invention.
[0023] FIG. 4 shows an isometric view of a brace according to the present invention.
[0024] FIG. 5 shows a transverse sectional view of a reinforced roller tube according to the present invention.
[0025] FIG. 6 shows transverse sectional views of several embodiments of reinforced tubes according to the present invention, the tubes having different cross-sectional shapes.
DETAILED DESCRIPTION
[0026] Certain exemplary but non-limiting embodiments of the present invention are now described for illustrative purposes with reference to the attached drawings.
[0027] The present invention is directed to a brace for reinforcing a tube, a reinforced tube such as a roller tube for an awning, and to an awning assembly incorporating said reinforced roller tube.
[0028] Referring now to FIG. 1 , there is shown a recreational vehicle 100 with wall 102 , the vehicle equipped with an awning 104 , such as a canvas or vinyl awning, with which the reinforced roller bar 110 of the present invention is particularly suited. The awning 104 comprises a first end 106 that is secured to the wall 102 of the vehicle 100 , and a second end 108 secured to the roller tube 110 . In an extended state, the awning 104 and roller tube 110 are supported by two or more poles or outriggers, such as one or more outriggers 112 supported against wall 102 , or one or more poles 114 supported by the ground. In typical embodiments, the awning 104 can extend about eight feet from the vehicle 100 and the awning 104 can extend twenty or more feet along the vehicle 100 . In the past, awnings have typically shown some degree of sag at the roller tube 110 , which can be exacerbated by precipitation or debris collecting in the awning 104 and/or by wind action on the awning 104 , which can lead to structural failure of the roller tube 110 .
[0029] Referring now to FIG. 2 , a reinforced roller tube 200 of the prior art comprising roller tube 202 in combination with a brace 206 , and is shown in cross-section. Roller tube 202 can, for example, be an extruded metallic tube, the outer surface thereof optionally comprising a plurality of slideways 204 extending longitudinally along the roller tube 202 for mounting the awning, a screen, or a valance to the roller tube 202 . The brace 206 is disposed within at least a central portion of the roller tube 202 . The prior art brace of FIG. 2 has an offset X cross-section 208 comprising four struts 214 extending approximately radially. Each strut 214 terminates adjacent the inner surface of the roller tube 202 in a foot 210 , 212 . In the embodiment of FIG. 2 , three simple feet 210 , and a foot in the form of an internal receiving channel 212 for engaging slideway 204 , are provided. Bending moments applied to the roller tube 202 are transferred to the brace 206 via the integral feet 210 , 212 whereby the rigidity of the brace 206 opposes bending of the roller tube 202 . The cross-sectional dimensions of the brace 206 are selected so that the feet 210 , 212 are adjacent the inner wall of the roller tube in the assembled state, and so that the brace can be inserted into the roller tube without binding.
[0030] In the prior art brace 206 of FIG. 2 , a plurality of joints are present 216 , 218 , 220 , 222 , 224 , 226 . Bending moments applied to the brace can result in accumulation of stresses at the joints, and, in the extreme case, structural failure.
[0031] As used herein, the term “joint” refers to an integral tee structure in metal, whether formed by welding, extrusion, molding, or the like, and the term “joint” is therefore distinct to and different from the mounting of two sheets of metal by fasteners.
[0032] As shown in FIG. 3 , a reinforced roller tube according to the present invention is shown. Reinforced roller tube 300 comprises a roller tube 302 and a brace 304 disposed within a central portion of the roller tube. Optionally, roller tube 302 comprises one or more slideways 303 such as recessed structures comprising longitudinal grooves extending parallel to the axis of the roller tube and integrally formed within the surface of the roller tube 302 and adapted to retain the edge of an awning, a valance, a screen, or the like. The roller tube 302 can be formed of any sufficiently rigid material, such as extruded aluminum, roll-formed steel sheet, or steel pipe. The dimensions of the roller tube 302 are not particularly limited. For example, roller tubes of from about two to twenty-five or more feet in length are known in the art, and the diameter of a roller tube can be from about one inch to more than six inches. Most preferably, the diameter of the roller tube is about two to three inches in diameter.
[0033] At one or both of a first 306 and second 308 end of the roller tube, optional means 310 , 312 are provided for rotationally coupling the roller tube 302 to its support and preferably for providing spring resistance to unrolling of the awning and assistance in its re-rolling. Such means are well-known in the art and typically comprise at least a spring assembly 314 , head casing 316 , mounts 318 for attaching the roller tube to its support, and a locking means 320 such as a locking pin for holding the awning in an extended configuration.
[0034] The central portion of the roller tube 302 comprises one or more braces 304 . As used herein, the central portion of the roller tube is any portion of the roller tube excluding the optional means 310 , 312 located at a first 306 and second 308 end of the tube. For example, in a preferred embodiment, brace 304 can be disposed within the central ten feet of a fourteen foot roller tube.
[0035] The brace 304 comprises a first 322 and a second 324 elongate metal strip mounted to each other. The metal strips can formed from an aluminum or steel sheet, and can optionally further comprise a coating such as galvanized coating. The longitudinal dimension of the strips is selected according to the length of the required brace. The width of the strip is selected to be commensurate with the inner diameter of the roller tube, when the strip is in the configuration of a brace according to the invention, so that the brace can be inserted into the roller tube without binding, and the feet of the brace can contact or be adjacent to the inner surface of the roller tube.
[0036] Referring now to FIG. 4 , a brace 400 according to the present invention is shown in further detail. First 402 and second metal strip 404 each comprise a central longitudinal portion 406 extending medially and substantially the length of each strip. The two central longitudinal portions are mounted to each other by fasteners 408 . Any suitable fastener or fastening means now or subsequently known in the art can be used to mount the strips. For example, and without limitation, rivets, bolts, screws, adhesive, spot welding, clips, or a combination thereof can be used. It will be readily appreciated by those of ordinary skill that rigidity of the brace does not require that the strips be mounted at every point along the central longitudinal portions 406 , and that substantial rigidity can be obtained using spaced apart fasteners 408 . In a preferred embodiment of a brace of about ten feet in length, rivets are spaced apart at intervals of about 12 to 18 inches.
[0037] Without being thereby limited by theory, the brace of the present invention is substantially stiff in part because bending moments applied to the tube are distributed over the common surface of the mounted central longitudinal portions 406 . Thus, in use, the stress upon the fasteners 408 is low.
[0038] The width of central longitudinal portion 406 is selected according to the width required by fasteners 408 and also to permit the intermediate portions 410 , 412 to extend substantially radially from central longitudinal portions 406 towards the inner surface of the tube. In preferred embodiments, the width of central longitudinal portion 406 is approximately 20% of the inner diameter of the tube.
[0039] The longitudinal outer edge 414 of each intermediate portion 410 , 412 forms an angle with the intermediate portion to which it is contiguous to form a foot for contacting the inner surface of the tube. The feet can be oriented in a clockwise or anti-clockwise direction with respect to a transverse section of the brace, or a single brace can comprise a combination of clockwise and anti-clockwise-oriented feet. The location of the feet is selected to engage the inner wall of the tube, whereby the brace can be freely inserted into the tube without binding, and bending moments applied to the tube are transferred to the brace via the feet. As used herein, the term “engage” encompasses feet that are proximal to or in contact with the inner surface of the tube. It is not required that the feet be mounted or connected to the inner surface of the tube.
[0040] Referring now to FIG. 5 , a transverse section of a reinforced roller tube 500 according to the present invention comprising brace 501 inserted into a roller tube 502 is shown. The feet 506 , 508 , 510 , 512 are preferably positioned with respect to the inner surface of roller tube 502 to avoid slideways 504 or like feature of the tube. The width of the feet 506 , 508 , 510 , 512 is not particularly limited. In preferred embodiments, the width of the feet is approximately 20% of the inner diameter of the tube.
[0041] The brace of the present invention is not limited to tubes of circular cross-section. Referring now to FIG. 6 , reinforced tubes according to the present invention are illustrated having square 602 , oval 604 , and hexagonal 606 cross-sections. It will be readily appreciated that the physical principles upon which the present brace is based permit the brace to be scaled in size for a wide range of tube sizes. Thus, for example and without limitation, very small (less than one-half inch diameter) and very large (more than one foot in diameter) tubes can be reinforced by braces contemplated as falling within the scope of the present invention. In like manner, the brace according to the present invention is not limited in its application to the roller tube applications by which the present invention has been illustrated, but instead can be used in a wide variety of unrelated applications in which a reinforced tube is desired.
[0042] In use, a brace according to the present invention is inserted into at least a portion of a tube or roller tube to achieve reinforcement. For example, a brace can be inserted into the central one-third of a tube, or a plurality of shorter braces can be used, or the full length of a tube excluding end fittings, if any, can be reinforced.
[0043] The device of the present invention provides a number of advantages over the prior art. The brace exhibits a high stiffness to weight ratio for reinforcing tube of essentially any desired cross-section. The brace can be simply and inexpensively manufactured from commonly available, light-weight sheet materials, such as aluminum or steel sheet, without the need for welding or jointing. The brace can be used in a wide variety of applications, including its use to reinforce the roller tube of an awning wherein it minimizes the risk of roller tube bending or failure from the action of precipitation or wind without unduly adding to the weight of the roller tube. Further, the brace of the present invention is readily adaptable for retro-fitting for reinforcement of pre-existing tubes.
[0044] Although the present invention has been described in considerable detail with reference to certain preferred versions thereof, other versions are possible and can be envisaged within the scope and spirit of the present invention. Therefore, the spirit and scope of the appended claims should not be limited to the description of the preferred versions contained herein.
[0045] Now that the invention has been described:
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Brace devoid of joints or welds for reinforcing a tube, such as the roller tube of an awning, the brace being formed from a pair of elongate metal strips mounted to each other along their respective longitudinal central portions, the edges of each strip forming integral feet at angles with respect to the strip, and the strips extending substantially radially from the mounted central portions to engage the interior of the tube at the feet.
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BACKGROUND
[0001] This application relates to a flow meter, and more specifically to dynamic calibration of a flow meter of a beverage brewing apparatus.
[0002] A plurality of factors influence the flavor when brewing a cup of coffee, including the quantity of coffee, the quantity of water, the temperature of the water, and the contact time between the coffee and the water. In many systems configured to brew a beverage such as coffee, a flow meter is used to monitor a volume of water delivered to the coffee. The flow meter generally includes a rotor having opposing polarity magnets embedded therein. The rotor is configured to spin about a central axis as water flows there through. As the flow meter rotates, these magnets pass a Hall Effect sensor, functioning as a switch that it activated and deactivated by the magnetic fields of the magnets. For every rotation of the rotor, a high and low signal is observed by the Hall Effect sensor.
[0003] Under constant conditions, a high quality flow meter may be accurate to within 0.5%, meaning that each toggle in the flow meter signal can be related directly to a volume of water. For example, if a system intends to deliver 1000 mL of water and the flow meter is calibrated to deliver 0.5 mL per pulse, a controller will simply track the total number of pulses until 2000 pulses have been observed. Accuracy of these systems is dependent upon the linearity of the flow meter over the operating range of the system. In order to control the operation conditions of a beverage brewing system a pump is typically used to control the flow rate. However, in systems where the operating conditions are not controlled, the flow rate of fluid through the flow meter may change based on variates in the wall voltage, boiler power, boiler efficiency, water temperature, or other influencing factors. As these factors shift the flow rate away from the nominal target rate, the performance of the flow meter similarly shifts, thereby compromising the accuracy of the system.
SUMMARY
[0004] According to one embodiment, a beverage brewing apparatus is provided including a reservoir, a brew basket configured to container a flavorant for preparing a brewed beverage, and a heating mechanism fluidly coupled to the reservoir and the brew basket. A flow meter is configured to measure a volume of fluid supplied from the reservoir to the brew bask. The flow meter is configured to calibrate dynamically in response to at least one operating parameter of the beverage brewing apparatus.
[0005] In addition to one or more of the features described above, or as an alternative, in further embodiments the at least one operating parameter includes voltage of the beverage system.
[0006] In addition to one or more of the features described above, or as an alternative, in further embodiments the at least one operating parameter includes a temperature of the fluid.
[0007] According to another embodiment, a method of dynamically calibrating a flow meter is provided including identifying a relationship between calibration variance and pulse rate of the flow meter to form an advanced logic calibration and applying the advanced logic calibration to the flow meter.
[0008] In addition to one or more of the features described above, or as an alternative, in further embodiments the advanced logic calibration is applied to each pulse observed by the flow meter.
[0009] In addition to one or more of the features described above, or as an alternative, in further embodiments the relationship between calibration variance and pulse rate is generally linear.
[0010] In addition to one or more of the features described above, or as an alternative, in further embodiments the relationship between calibration variance and pulse rate of the flow meter is determined using data collected during operation of a beverage brewing apparatus.
[0011] In addition to one or more of the features described above, or as an alternative, in further embodiments the advanced calibration logic is based on data collected from a plurality of beverage brewing apparatuses.
[0012] In addition to one or more of the features described above, or as an alternative, in further embodiments the method includes identifying a relationship between calibration variance and flow rate of a fluid through the flow meter to form an advanced logic calibration. A relationship between between flow rate and pulse rate is then determined.
[0013] In addition to one or more of the features described above, or as an alternative, in further embodiments an average pulse rate per time interval is calculated for the plurality of beverage brewing apparatuses. The advanced logic calibration is then applied to the average pulse rate.
[0014] In addition to one or more of the features described above, or as an alternative, in further embodiments an operating condition of at least one of the plurality of beverage brewing apparatuses is different.
BRIEF DESCRIPTION OF THE FIGURES
[0015] The accompanying drawings incorporated in and forming a part of the specification embodies several aspects of the present disclosure and, together with the description, serves to explain the principles of the disclosure. In the drawings:
[0016] FIG. 1 is a schematic diagram of an example of a beverage brewing apparatus;
[0017] FIG. 2 is a graph comparing flow rate and volumetric variation measured for a single beverage brewing apparatus;
[0018] FIG. 3 is a graph illustrating the pulses of a flow meter over a set period of time for a single beverage brewing apparatus;
[0019] FIG. 4 is a graph comparing flow rate and calibration variation measured for a single beverage brewing apparatus;
[0020] FIG. 5 is a graph comparing pulse rate and calibration variation measured for a single beverage brewing apparatus
[0021] FIG. 6 is a graph comparing flow rate and pulse rate based on the measured data of a single beverage brewing apparatus;
[0022] FIG. 7 is a graph representing a volume of fluid delivered by a flow meter having fixed logic and a flow meter having advanced calibration logic compared to a target volume; and
[0023] FIG. 8 is a graph comparing pulse rate to the volume variance for a plurality of beverage brewing apparatuses having varying operational parameters.
[0024] The detailed description explains embodiments of the disclosure, together with advantages and features, by way of example with reference to the drawings.
DETAILED DESCRIPTION
[0025] With reference now to FIG. 1 , a schematic diagram of an example of a basic automatic beverage brewing apparatus 20 , such as a coffee maker for example, is illustrated in more detail. The apparatus includes a housing 22 , a reservoir 24 , a heating mechanism 26 , a shower head 28 , and a brew basket 30 . The reservoir 24 , heating mechanism 26 , showerhead 28 , and brew basket 30 are arranged sequentially in fluid communication. Upon activation of the apparatus 20 , water or another fluid stored within the reservoir 30 , is provided to a heating mechanism 26 . After being heated to a desired temperature, the water is provided to the shower head 28 . The shower head is aligned with and disposed vertically above the brew basket. The water is configured to flow through one or more holes formed in the shower head onto coffee grounds or another flavorant contained within the brew basket. The fluid containing a portion of the flavorant, is provided to a container 31 via an outlet formed near the bottom of the brew basket.
[0026] As illustrated in FIG. 1 , a flow meter 32 may be arranged within a conduit extending between the water reservoir 24 and the heating mechanism 26 . As shown, the water reservoir 24 may be vertically aligned with the flow meter 32 such that water is fed to the system 20 , and more specifically to the flow meter 32 , by gravity. The flow meter 32 is configured to monitor an amount of water passing there through, which is generally indicative of the amount of water provided to the shower head 28 . Various types of flow meters are within the scope of the disclosure. For example, the flow meter 32 may be a rotatable paddle wheel where each rotation generates a signal indicating that a known amount of water has passed through the flow meter 92 . Further detail on this type of beverage brewing apparatus 20 is disclosed in U.S. patent application Ser. No. 14/568,471 filed on Dec. 12, 2014 and U.S. patent application Ser. No. 14/812,731 filed on Jul. 29, 2015, the contents of both of which are incorporated herein by reference. However, it should be understood that the beverage brewing apparatus 20 described herein is intended as an example only, and any other apparatus including a flow meter is within the scope of the invention.
[0027] With reference now to FIGS. 2-8 , a software algorithm for dynamically calibrating the flow meter 32 based on the operational parameters of the beverage brewing system 20 , also referred to herein as “advanced calibration logic”, is described in more detail. The brewing apparatus 20 is configured to provide a known volume of fluid when operated in a first mode. To generate an equation to be applied to operation of the flow meter 32 as advanced calibration logic, the relationship between pulse rate and the calibration variance of the flow meter 32 must be identified.
[0028] By measuring the actual volume of fluid provided and by monitoring one or more operational parameters of the system 20 , a relationship between operation of the flow meter 32 and one or more parameters of the system 20 may be determined. For example, as shown in Table 1 illustrated below, the voltage provided to the flow meter 32 and the time required to provide the desired volume of fluid are measured.
[0000]
TABLE 1
Recorded Measurements from Test Unit 1
Volume
vs.
Effective
Flow
Voltage
Delivered
Target
Time (s)
Rate
128
1267
−1.1%
305
4.15
128
1259
−1.7%
303
4.16
120
1294
1.0%
340
3.81
120
1291
0.8%
337
3.83
112
1310
2.3%
382
3.43
112
1323
3.3%
386
3.43
104
1351
5.5%
447
3.02
104
1348
5.2%
451
2.99
[0029] In the illustrated, non-limiting embodiment, the programmed volume of fluid to be provided was 1281 mL. As shown in the table above, the difference between the programmed volume and the measured volume was between −1.7% and 5.5% for each of the various test runs. Through this experimentation, it has been determined that the accuracy of the flow meter 32 fluctuates with the flow rate when the voltage applied to the system 20 is varied. A graph comparing the flow rate (mL/s) and Volume Variation of the data of Table 1 is illustrated in FIG. 2 .
[0030] During operation, the system 20 is only configured to observe pulses generated by the flow meter 32 and has no knowledge of flow rate. FIG. 3 indicates the recorded pulse rates on a moving average basis, or more specifically, the number of pulses recorded in a set time period. Although a time period of 2 seconds was used in the illustrated, non-limiting embodiment, any length of time sufficient to provide an accurate representation of the data with a minimized delay is acceptable. Using this pulse information, the average flow rate can be tracked and converted into a calibration scaling factor. An example of the data recorded for a 50 pulse section of the graph of FIG. 3 is shown in Table 2 below.
[0000]
TABLE 2
Time Array of recorded pulses
Array
Pulse
Element
Time
0
8801
1
8966
2
9086
3
9225
4
9329
5
9444
6
9542
7
9642
8
9744
9
9851
10
9946
11
10053
12
10160
13
10284
14
10391
15
10501
16
10604
17
10705
18
10800
19
10904
20
11001
21
11109
22
11209
23
11321
24
11427
25
5252
26
5335
27
5428
28
5514
29
5611
30
5703
31
5805
32
5901
33
6008
34
6111
35
6226
36
6338
37
6463
38
6584
39
6720
40
6852
41
7008
42
7164
43
7362
44
7581
45
7864
46
8115
47
8337
48
8513
49
8665
[0031] By analyzing this data relative to voltage and temperature ranges, two graphs, shown in FIGS. 4 and 5 , were generated to identify the relationship between flow rate and calibration variance ( FIG. 4 ), as well as pulse rate and calibration variance ( FIG. 5 ). The graph of pulse rate vs. calibration variance is configured to indicate the variation in the calibration coefficient based on how fast the flow meter 32 is rotating.
[0032] The relationship presented in FIG. 5 directly correlates a signal sent from the flow meter 32 and received by a controller of the brewing system 20 with a calibration variation. As a result, the calibration coefficient can be used to determine a total volume delivered by the flow meter 32 with each pulse. In this embodiment, for every pulse fewer recorded per 2-second averaging window, the calibration would increase by 2.64% as noted by the linear regression through the data set. In this embodiment, the nominal calibration coefficient, corresponding to a volume of water passing through the flow meter, was specified to be 0.656 milliliters of fluid per pulse under nominal conditions. If a pulse were to exist whereby the average number of pulses recorded in a 2-second window was 10.0, the scaling factor would thus be calculated as:
[0000] Scaling Factor=−0.0264*(10.0)+1.3751=1.111
[0000] This pulse, therefore, would have a delivery volume of 0.656 milliliters*1.111=0.7288 milliliters, which is then added to the total volume delivered. This scaling factor is applied to every pulse observed by the flow meter 32 until the total volume delivered has reached a prescribed target volume, in this embodiment 1281 mL.
[0033] This scaling factor can be applied to a recorded data set to more accurately predict the volume of fluid delivered by a flow meter 32 . For example, the graph of FIG. 7 compares the volume of fluid delivered by a flow meter 32 using the fixed calibration logic, and the volume of fluid delivered by a flow meter 32 using the scaling factor of the advanced calibration logic relative to a target volume. As is clearly illustrated, the flow meter 32 using the advanced calibration logic is substantially more accurate relative to the target volume.
[0034] Because both of the graphs in FIGS. 4 and 5 compare calibration variance, a relationship between the flow rate and the average pulse rate may be established. A graph illustrating the relationship between the average flow rate and the average pulse rate is illustrated in FIG. 6 . This relationship enables an average pulse rate to be approximated for test runs on where only volume and time were recorded.
[0035] The data illustrated in Tables 1 and 2 and FIGS. 2-7 is representative of a single beverage brewing apparatus 20 . Although each unit of a mass produced beverage brewing apparatus 20 is formed substantially identically, differences in performance may occur due to variances in manufacturing, assembly, or usage conditions. To create a universal calibration coefficient applicable to all of the units of a mass produced beverage brewing apparatus 20 , similar experimentation is performed using a plurality of units of the beverage brewing apparatus 20 to create an approximation of the average pulse rates based on average flow rates thereof, as shown in FIG. 6 .
[0036] By applying similar transformations to the data collected from a plurality of units, for example 14 units, it was determined that although a spread in performance exists, most of the units followed a predictable trend illustrated in FIG. 8 . FIG. 8 , which compares average pulse rate to volumetric variance, clearly shows that in the absence of advanced calibration logic, the volume of water delivered via a flow meter 32 may drastically increase as the power to the system varies. It is also observed that a nominal calibration coefficient is centered about 13.4 average pulses, which corresponds to room temperature water being brewed using 120V of power. However, because the voltage range provided across the United States extends from between 107V to 128V and because most brewing apparatuses 20 instruct an operator to use cold water, it is desirable to set the neutral point of operation at averaged conditions assuming a power supply of 117V and a cold water temperature of about 3-5° C. Under these conditions, the average pulse count is approximately 10.2 pulses per 2 seconds. By adjusting the equation of the linear regression line of FIG. 8 to account for this shift in the average conditions, the resultant dynamic flow meter calibration scaling value is:
[0000] Scaling Value=−0.012305* n pulses +1.25508
[0037] Application of this scaling value to the flow meter calibration coefficient allows the volume of fluid measured by the flow meter 32 to adjust dynamically during operation of the apparatus 20 to such that a more accurate amount of water is consistently provided for brewing a beverage.
[0038] All references, including publications, patent applications, and patents cited herein are hereby incorporated by reference to the same extent as if each reference were individually and specifically indicated to be incorporated by reference and were set forth in its entirety herein.
[0039] The use of the terms “a” and “an” and “the” and similar referents in the context of describing the disclosure (especially in the context of the following claims) is to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The terms “comprising,” “having,” “including,” and “containing” are to be construed as open-ended terms (i.e., meaning “including, but not limited to,”) unless otherwise noted. Recitation of ranges of values herein are merely intended to serve as a shorthand method of referring individually to each separate value falling within the range, unless otherwise indicated herein, and each separate value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein, is intended merely to better illuminate the disclosure and does not pose a limitation on the scope of the disclosure unless otherwise claimed. No language in the specification should be construed as indicating any non-claimed element as essential to the practice of the disclosure.
[0040] Exemplary embodiments of this disclosure are described herein, including the best mode known to the inventors for carrying out the disclosure. Variations of those embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the disclosure to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.
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A beverage brewing apparatus is provided including a reservoir, a brew basket configured to container a flavorant for preparing a brewed beverage, and a heating mechanism fluidly coupled to the reservoir and the brew basket. A flow meter is configured to measure a volume of fluid supplied from the reservoir to the brew bask. The flow meter is configured to calibrate dynamically in response to at least one operating parameter of the beverage brewing apparatus.
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FIELD
[0001] The present disclosure relates to a gearbox for a gas turbine engine.
BACKGROUND
[0002] A typical gas turbine engine for an aircraft may include an accessory drive gearbox. The gearbox is rotationally coupled to at least one spool of the engine by a tower shaft. The gearbox may be coupled to an engine core and enclosed by a core nacelle surrounding the engine core. A compact gearbox configuration may be desirable to fit within the space between the core nacelle and engine core. Reducing inventory of spare parts and the need for multiple dissimilar components is also desirable.
SUMMARY
[0003] A system and method for coupling accessories to a gearbox of a turbine engine are described herein. In one exemplary embodiment, a first housing that includes a first auxiliary gear drive on a first portion thereof, a second housing that includes a second auxiliary gear drive on a second portion thereof, and a third housing that includes a third auxiliary gear drive on a third portion thereof. The housings are interconnected so that the first portion of the first housing, the second portion of the second housing and the third portion of the third housing form a substantially triangular polyhedron shape, with the second portion of the second housing disposed between the first portion of the first housing and the third portion of the third housing. The gear drives project outwardly in mutually divergent directions.
[0004] In a further embodiment of any of the above, the first faces of the first and second housing portions are provided respectively by removable first and second covers.
[0005] In a further embodiment of any of the above, a first set of bevel gears interconnects the first and third gear sets. A second set of bevel gears interconnects the second and third gear sets.
[0006] In a further embodiment of any of the above, accessory drive components are secured to the accessory drive component mounts.
[0007] In a further embodiment of any of the above, each of the first faces of the first and second housing portions includes accessory drive component mounts.
[0008] In another exemplary embodiment, a gas turbine engine includes an engine static structure housing a compressor section, a combustor section and a turbine section. A spool supports at least a portion of each of the compressor and turbine sections for rotation about an axis. A gearbox is supported by the engine static structure and is coupled to the spool by a tower shaft. A gas turbine engine assembly comprising, a gearbox including a first housing that includes a first auxiliary gear drive on a first portion thereof, a second housing that includes a second auxiliary gear drive on a second portion thereof, and a third housing that includes a third auxiliary gear drive on a third portion thereof, the housings being interconnected so that the first portion of the first housing, the second portion of the second housing and the third portion of the third housing form a substantially triangular polyhedron shape, with the second portion of the second housing disposed between the first portion of the first housing and the third portion of the third housing. The first auxiliary gear drive, the second auxiliary gear drive and the third auxiliary gear drive project outwardly in mutually divergent directions.
[0009] In a further embodiment of any of the above, gears of the first, second and third auxiliary drives and/or gear sets each include an axis. The gear axes of the first gear set are perpendicular to a first plane. The gear axes of the second gear set are perpendicular to a second plane. The gear axes of the third gear set are perpendicular to a third plane. The first and second planes are non-parallel to one another. The first, second and third planes are transverse to one another. The gear axes of the first and second gear sets are arranged circumferentially with respect to the axis.
[0010] In a further embodiment of any of the above, the intermediate housing portion includes first and second faces opposite one another. The input shaft extends through the first face of the intermediate housing portion and is coupled to the third gear set.
[0011] In a further embodiment of any of the above, the second face of the intermediate housing portion includes a tower shaft cover removably secured to the intermediate housing portion over an opening sized to receive the tower shaft.
[0012] In a further embodiment of any of the above, the first and second faces of each of the first and second housing portions are parallel to one another.
[0013] In a further embodiment of any of the above, the second faces are about 90° apart, and the intermediate housing portion is about 120° apart from each of the first and second housing portions. The forgoing features and elements may be combined in various combinations without exclusivity, unless expressly indicated herein otherwise. These features and elements as well as the operation of the disclosed embodiments will become more apparent in light of the following description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The subject matter of the present disclosure is particularly pointed out and distinctly claimed in the concluding portion of the specification. A more complete understanding of the present disclosure, however, may best be obtained by referring to the detailed description and claims when considered in connection with the drawing figures, wherein like numerals denote like elements.
[0015] FIG. 1A is a cross-sectional view of a gas turbine engine, in accordance with various embodiments;
[0016] FIG. 1B is a cross-sectional view of a gas turbine engine and diversified gearbox, in accordance with various embodiments;
[0017] FIG. 2 is a perspective view of a gearbox, in accordance with various embodiments;
[0018] FIG. 3 is a view of the gears of a gearbox, in accordance with various embodiments;
[0019] FIG. 4 is a view of gears and bearing of a gearbox, in accordance with various embodiments;
[0020] FIG. 5 is a view of the bevel gearsets of a gearbox, in accordance with various embodiments; and
[0021] FIG. 6 is a view of mounting surface angle options to accommodate components, in accordance with various embodiments.
DETAILED DESCRIPTION
[0022] The detailed description of exemplary embodiments herein makes reference to the accompanying drawings, which show exemplary embodiments by way of illustration. While these exemplary embodiments are described in sufficient detail to enable those skilled in the art to practice the inventions, it should be understood that other embodiments may be realized and that logical, chemical and mechanical changes may be made without departing from the spirit and scope of the inventions. Thus, the detailed description herein is presented for purposes of illustration only and not of limitation. For example, the steps recited in any of the method or process descriptions may be executed in any order and are not necessarily limited to the order presented. Furthermore, any reference to singular includes plural embodiments, and any reference to more than one component or step may include a singular embodiment or step. Also, any reference to attached, fixed, connected or the like may include permanent, removable, temporary, partial, full and/or any other possible attachment option. Additionally, any reference to without contact (or similar phrases) may also include reduced contact or minimal contact.
[0023] Different cross-hatching and/or surface shading may be used throughout the figures to denote different parts but not necessarily to denote the same or different materials.
[0024] FIG. 1A schematically illustrates an example gas turbine engine 20 that includes a fan section 22 , a compressor section 24 , a combustor section 26 and a turbine section 28 . Alternative engines might include an augmenter section (not shown) among other systems or features. The fan section 22 drives air along a bypass flow path B while the compressor section 24 draws air in along a core flow path C where air is compressed and communicated to a combustor section 26 . In the combustor section 26 , air is mixed with fuel and ignited to generate a high pressure exhaust gas stream that expands through the turbine section 28 where energy is extracted and utilized to drive the fan section 22 and the compressor section 24 .
[0025] Although the disclosed non-limiting embodiment depicts a turbofan gas turbine engine, it should be understood that the concepts described herein are not limited to use with turbofans as the teachings may be applied to other types of turbine engines; for example a turbine engine including a three-spool architecture in which three spools concentrically rotate about a common axis and where a low spool enables a low pressure turbine to drive a fan via a gearbox, an intermediate spool that enables an intermediate pressure turbine to drive a first compressor of the compressor section, and a high spool that enables a high pressure turbine to drive a high pressure compressor of the compressor section.
[0026] The example gas turbine engine 20 generally includes a low speed spool 30 and a high speed spool 32 mounted for rotation about an engine central longitudinal axis X relative to an engine static structure 36 via various bearing systems 38 . It should be understood that various bearing systems 38 at various locations may alternatively or additionally be provided.
[0027] The low speed spool 30 generally includes an inner shaft 40 that connects a fan 42 and a low pressure (or first) compressor 44 section to a low pressure (or first) turbine 46 section. The inner shaft 40 drives the fan 42 through a speed change device, such as a geared architecture 48 , to drive the fan 42 at a lower speed than the low speed spool 30 . The high speed spool 32 includes an outer shaft 50 that interconnects a high pressure (or second) compressor 52 section and a high pressure (or second) turbine section 54 . The inner shaft 40 and the outer shaft 50 are concentric and rotate via the various bearing systems 38 about the engine central longitudinal axis X.
[0028] A combustor 56 is arranged between the high pressure compressor 52 and the high pressure turbine 54 . In one example, the high pressure turbine 54 includes at least two stages to provide a double stage high pressure turbine 54 . In another example, the high pressure turbine 54 includes only a single stage. As used herein, a “high pressure” compressor or turbine experiences a higher pressure than a corresponding “low pressure” compressor or turbine.
[0029] The example low pressure turbine 46 has a pressure ratio that is greater than about 5. The pressure ratio of the example low pressure turbine 46 is measured prior to an inlet of the low pressure turbine 46 as related to the pressure measured at the outlet of the low pressure turbine 46 prior to an exhaust nozzle.
[0030] A mid-turbine frame 57 of the engine static structure 36 is arranged generally between the high pressure turbine 54 and the low pressure turbine 46 . The mid-turbine frame 57 further supports various bearing systems 38 in the turbine section 28 as well as setting airflow entering the low pressure turbine 46 .
[0031] The core airflow C is compressed by the low pressure compressor 44 then by the high pressure compressor 52 mixed with fuel and ignited in the combustor 56 to produce high speed exhaust gases that are then expanded through the high pressure turbine 54 and low pressure turbine 46 . The mid-turbine frame 57 includes vanes 59 , which are in the core airflow path and function as an inlet guide vane for the low pressure turbine 46 . Utilizing the vane 59 of the mid-turbine frame 57 as the inlet guide vane for low pressure turbine 46 decreases the length of the low pressure turbine 46 without increasing the axial length of the mid-turbine frame 57 . Reducing or eliminating the number of vanes in the low pressure turbine 46 shortens the axial length of the turbine section 28 . Thus, the compactness of the gas turbine engine 20 is increased and a higher power density is achieved.
[0032] The disclosed gas turbine engine 20 in one example is a high-bypass geared aircraft engine. In a further example, the gas turbine engine 20 includes a bypass ratio greater than about six (6), with an example embodiment being greater than about ten (10). The example geared architecture 48 is an epicyclical gear train, such as a planetary gear system, star gear system or other known gear system, with a gear reduction ratio of greater than about 2.3.
[0033] In one disclosed embodiment, the gas turbine engine 20 includes a bypass ratio greater than about ten (10:1) and the fan diameter is significantly larger than an outer diameter of the low pressure compressor 44 . It should be understood, however, that the above parameters are only exemplary of one embodiment of a gas turbine engine including a geared architecture and that the present disclosure is applicable to other gas turbine engines.
[0034] With continuing reference to FIG. 1B , a gearbox 62 coupled to a gas turbine engine 20 is illustrated. A core nacelle is arranged about the engine static structure 36 and encloses the gearbox 62 .
[0035] As illustrated in FIG. 2 , the gearbox 62 is operatively coupled to the high spool by a tower shaft. For example, the tower shaft is rotationally driven by a high spool via a gear set, which is provided by beveled gears. The tower shaft is connected to an input shaft 80 that is supported by the gearbox 62 . The input shaft 80 provides the rotational coupling to various accessory drive components 84 , 86 , 88 , 90 , 92 , and 94 . Gearbox 62 assists with external line connection and maintenance due to components being mounted on the axial surface. Stated another way, gearbox 62 assists with external line connection and maintenance due to components being mounted parallel with the engine axis. Gearbox 62 adds flexibility to a gas turbine engine assembly. Mounting surfaces are angled in various positions to fit the components in the package envelope.
[0036] The gearbox 62 is provided by a generally a triangular polyhedron shaped structure housing 68 having a first housing portion 70 and second housing portion 72 interconnected to one another by an intermediate housing portion 74 . The intermediate housing portion 74 supports the input shaft 80 . The first housing portion 70 includes a first face 76 A. The second housing portion 72 includes a first face 76 B. The intermediate housing portion 74 includes a first face 76 C. The first faces 76 A-C are adjacent to the engine static structure 36 , with brief reference to FIG. 1A . The first face 76 C of intermediate housing portion 74 forms a triangle bounded on two sides by an edge 625 , 635 of the first face of the first and second housing portions (with brief reference to FIG. 6 ).
[0037] Instead of mounting the accessory drive components such that their rotational axes are in the same direction as the core engine axis X, with brief reference to FIG. 1A , the accessory drive components are mounted on both of the first faces 76 A, 76 B, on the first and second housing portions 70 , 72 , as desired. That is, the axes of the accessory drive components 84 , 86 , 88 , 90 , 92 , and 94 are arranged circumferentially relative to the engine static structure 36 (with brief reference to FIG. 1A ). The gearbox 62 comprises a plurality of independent gear trains with a triangle shaped intermediate housing portion 74 to give more space for long components. The gearbox 62 can be adjusted in any direction by changing the shaft angle of bevel gearsets 116 and 118 , rotate the mounting surfaces around input shaft 80 or moving the first set of first and second idler gears 122 and 124 , also known a spur gears, forward or aft to allow the long component fit in given space, with brief reference to FIG. 3 ).
[0038] As illustrated in FIG. 2 , a variable frequency generator (VFG) 88 , air turbine starter 90 , and a lubrication pump 84 are mounted to the first face 76 A. A hydraulic pump 86 , a fuel pump 92 , and a permanent magnet alternator (PMA) 94 are mounted to the first face 76 B.
[0039] An integrated drive generator (IDG), and/or a deoiler is optionally mounted to at least one of first face 76 A or first face 76 B. In this manner, the axial length of the gearbox 62 and its arrangement of accessory drive components 84 , 86 , 88 , 90 , 92 , 94 are reduced compared to axially oriented accessory drive components. As a result, the gearbox 62 and accessory drive components 84 , 86 , 88 , 90 , 92 , 94 are positioned easily along the length of the engine static structure 36 to more desirable locations where more space and/or cooler temperatures are provided.
[0040] The mounting locations 84 M, 86 M, 88 M, 90 M, 92 M, 94 M for the accessory drive components 84 , 86 , 88 , 90 , 92 , 94 are shown in more detail as 84 M, 86 M, 88 M, 90 M, 92 M, 94 M in FIG. 3 . Like numerals are used to indicate an association amongst components. The first faces 76 A, 76 B of the first housing portion 70 and second housing portion 72 are provided by removable a first cover 310 and a second cover 320 that selectively provide access to an interior of the generally a triangular polyhedron shaped housing 68 within which the gear train is mounted.
[0041] The covers are removable to provide access to any gear 130 , which are mounted to the shafts 126 , which are supported by bearings 128 relative to the housing 68 , as shown in FIG. 4 . In this manner, the bearings 128 and gears 130 are easily serviced.
[0042] With reference to FIG. 3 , the first, second and intermediate housing portions 70 , 72 , 74 respectively house first, second and third gear sets 110 , 112 , 114 . The first gear set 110 is operatively connected to the third gear set 114 by a first bevel gear set 116 . The second gear set 112 is operatively coupled to the third gear set 114 by the second bevel gear set 118 , with reference to FIG. 5 . The input shaft 80 rotationally drives an input gear 120 which rotationally drives the first and second gear sets 110 , 112 via first and second idler gears 122 , 124 . The first gear set 110 includes gears 86 G, 92 G, 94 G, that respectively rotationally drive the hydraulic pump 86 , a fuel pump 92 , a permanent magnet alternator (PMA) 94 . The second gear set 112 includes second gears 84 G, 88 G, 90 G, 88 G that respectively drive the back-up variable frequency generator (VFG) 88 , air turbine starter 90 , and the lubrication pump 84 .
[0043] As can be appreciated by FIG. 3 , the gears of the first gear set 110 are parallel with one another relative to a plane P 1 . The gears of the second gear set 112 are parallel with one another with respect to a second plane P 2 . First face 76 A intersects with first face 76 B along common edge 81 . The gears of the third gear set 114 are parallel with one another with respect to a third plane P 3 . The planes P 1 -P 3 are independent and not parallel relative to one another.
[0044] As illustrated in FIG. 6 , first face 76 A or first face 76 B are angled at desired orientations to accommodate accessory drive components 84 , 86 , 88 , 90 , 92 , 94 , such as the distance measured from the first face 76 A or first face 76 B of accessory drive components 84 , 86 , 88 , 90 , 92 , 94 . Narrowing dimensions of first face of 76 C of the intermediate housing portion 74 of gearbox 62 assists with creating space in location A and location B for further component extension from first face 76 A or first face 76 B.
[0045] Accordingly the mounting surfaces of gearbox 62 can be adjusted in any direction by changing the shaft angle of bevel gearsets and rotating the mounting surfaces around the input shaft in kind. Also, the mounting surfaces of gearbox 62 can be adjusted by moving the first set of spur gears forward or aft to allow a long component to fit in given space.
[0046] Benefits, other advantages, and solutions to problems have been described herein with regard to specific embodiments. The scope of the disclosure, however, is provided in the appended claims.
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A gas turbine engine assembly comprising, a gearbox including a first housing that includes a first auxiliary gear drive on a first portion thereof, a second housing that includes a second auxiliary gear drive on a second portion thereof, and a third housing that includes a third auxiliary gear drive on a third portion thereof, the housings being interconnected so that the first portion of the first housing, the second portion of the second housing and the third portion of the third housing form a substantially triangular polyhedron shape, with the second portion of the second housing disposed between the first portion of the first housing and the third portion of the third housing. The first auxiliary gear drive, the second auxiliary gear drive and the third auxiliary gear drive project outwardly in mutually divergent directions.
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This application claims the benefit of U.S. provisional application Ser. No. 60/040,358 filed Mar. 12, 1997.
FIELD OF THE INVENTION
The present invention is in the field of handling and transportation of spent nuclear fuel and other hazardous materials. In particular, the present invention is a system for modular handling and transportation primarily of single or multiple spent nuclear fuel (SNF) assemblies to an interim storage facility, transfer point, or final federal disposal site.
BACKGROUND OF THE INVENTION
Methods and machines for transportation and transfer of SNF and other radioactive materials are well known in the art. Nuclear reactors and storage sites for SNF and other radioactive materials have been in operation for decades and, as a consequence of their operation, generate the need to dispose of SNF and other radioactive by-products. The latter may include contaminated primary equipment and primary piping that is damaged or obsolete. Various government agencies, such as the Department of Energy, have developed guidelines for the safe handling of SNF and other nuclear by-products with personnel safety as a primary concern. Secondary concerns addressed by regulation relate to spill avoidance and containment which protects against long term environmental contamination and accompanying risks to human and animal health.
Increasingly strict regulations, in conjunction with the increasing demand for nuclear power and products, provide the impetus for improvements in the safe handling and transportation of radioactive materials. Any operation involving the handling of SNF or other radioactive materials may involve special procedures because of the threat of leakage of radioactive materials. SNF, though depleted for fuel purposes, emits high amounts of radiation known to be damaging to living organisms including humans. To handle SNF safely, personnel must be protected from high levels of radiation by using appropriate containment vessels around SNF. To better provide for safe handling of nuclear materials, a variety of SNF handling containers using suitable shielding materials has evolved to package SNF for transport and transfer. The disadvantage of prior art methods include the lack of standardized container sizes and scalable means for handling both small and large SNF loads. Prior art methods of transporting SNF and other by-products of nuclear industry include loading SNF into either shielded casks or into canisters. Such canisters may then be placed into a shielded overpack.
A cask may be described as a "stand alone" SNF container having integral shielding, fuel basket and containment features. The disadvantage of cask-based handling systems is that the casks including their shielding must be handled as a unit or in systems designed for handling multiple casks. Such systems usually involve assembling and disassembling cask handling units into larger and smaller units as they progress through their distribution and disposal route. Such assembly or disassembly is time consuming and laborious, requiring special equipment.
A canister may be described as an unshielded SNF container forming a component of a fuel storage and a fuel transportation system. A canister, once loaded with SNF, may be stored within a shielded container or overpack forming the chief component of a larger storage and transportation system. The size and capacity of both cask- and canister-based systems may vary. Systems having one or two SNF assemblies may weigh approximately 20 tons and are suitable for truck transport. Systems with over 50 SNF assemblies may weigh over 100 tons and require heavy-mode or heavy-haul transport. Cranes are typically used in such systems to place casks or canisters, already placed within overpacks, onto a truck trailer, rail car or heavy-haul transporter. The disadvantage of typical prior art cask and canister systems is the non-uniform size of the casks and canisters and the inability to easily transfer casks and canisters from a transport means of one scale to a transport means of another scale without disassembly or the use of heavy equipment.
While competitive forces driving the SNF disposal industry make taking advantage of the "economy of scale" that higher capacity systems offer attractive, many plants and facilities lack the capability to handle larger-scale SNF transport systems. Smaller plants may, on the other hand often have a smaller budget for facility upgrades and must look to small, truck transportable systems to ship SNF to its final destination. Lack of space, lack of crane capacity, fuel pool floor loading limits and other technical limitations may restrict the use of large scale SNF transport systems for some facilities. Some nuclear power plants and other SNF storage facilities lack on-site access to rail or barge transport, and thus require heavy-haul of large cask or canister systems to the nearest rail spur or port. Heavy-haul transportation over public roads may be slow and may tie up traffic creating hazardous driving conditions. Moreover, public transportation infrastructure often requires strengthening of bridges and other costly upgrades to accommodate heavy-haul loads. Heavy-haul loads, especially with SNF payloads, may require special permits and escorting, and may not be permitted at all in some regions.
Once a cask or canister system reaches an exchange site, transfer to a new transport means may be required. Such a transfer, from a heavy-haul truck transport to a rail car or barge, for example, may often involve providing temporary crane and handling services in remote locations. This may increase the overall expense of an SNF transport evolution, expose workers and the public to increased risks associated with handling accidents, and create unnecessary delays. Furthermore, federal requirements may necessitate the transfer of large casks from rail back to heavy-haul truck for transport over large distances to federal facilities.
Accordingly, an alternate system and method of transfer and transportation of SNF using standard fuel handling methods would be welcome in the art. Such system and method for SNF transport could be employed without the use of cranes and heavy-haul equipment. An SNF transport system that would easily accommodate intermodal transfer of multiple canisters between standard transport means such as truck, rail, barge, and the like. Such a system would further allow standardization of SNF transportation equipment and allow truck sized components to be handled by nearly all SNF storage facilities.
SUMMARY OF THE INVENTION
The Intermodal Modular Spent Nuclear Fuel Transportation System of the present invention overcomes the deficiencies of prior art handling methods. The system of the present invention uses conventional truck, rail, barge or ship equipment to transport nuclear materials including SNF in standardized modules thus maximizing the interchangeability of transportation components, while minimizing overall impact and requirements for upgrades to the public transportation infrastructure. The system of the present invention does not require crane or heavy equipment to handle or transfer SNF containers. Such heavy equipment, however, may be used in the assembly of overpack bundles. The system of the present invention allows for configuration of transportation components to optimize the ratio of truck to rail standard module containers to best match the required throughput for specific shipping campaigns.
The system of the present invention includes a plurality of conventional trucks, each with a single overpack mounted to a cradle on the truck platform. The overpack thus forms the basic module of the present invention. SNF canisters may be transferred from the single truck-mounted overpack, using a winch or other movement device, to and from an empty overpack in an overpack bundle disposed within a cradle assembly further disposed on the rail car or barge. An overpack bundle comprises a plurality of overpacks clamped together. The empty overpack in the overpack bundle may be placed into position for receiving an SNF canister by axial rotation of the overpack bundle to align with the truck-mounted overpack.
To receive an SNF canister from a truck-mounted overpack, the cradle assembly may be rotated horizontally right or left to allow truck docking from a direction perpendicular to the normal orientation of the rail car. The truck-mounted overpack and the corresponding empty rail car overpack may be "docked" and an SNF canister may be transferred from the truck-mounted overpack to a corresponding overpack in the rail- or barge-mounted overpack bundle. Actual transfer may be accomplished using a pulling or pushing device or other movement device such as a winch or like means. The process may be reversed at an intermodal transfer point to load truck-mounted overpacks with SNF canisters from the corresponding overpack of the rail or barge overpack bundle using a pushing or pulling means such as a winch. Standard module exchange may occur without removing the cradle assembly and overpack bundle from the rail car or requiring the use of a crane.
The system of the present invention may further facilitate the transfer of multiple SNF canisters to the overpack bundle using indexing or rotation of the overpack bundle. The overpack bundle may be indexed axially using a chain or gear drive to allow positioning of the next receiving overpack opening to match the truck-mounted overpack opening.
The overpack bundle of the present invention is formed by coupling together a plurality of overpacks using stockade clamps. At least two clamps, at least one of which is adapted to accommodate bundle rotation are used to secure overpacks into a bundle and to provide a supporting surface and means to which a drive may be engaged. The overpack bundle is disposed upon a cradle assembly and secured with tiebands. The cradle assembly is provided with rollers that are displaced into an operative position in which the overpack bundle may be raised and supported while facilitating axial rotation and may further have a horizontal turntable. The overpack bundle is indexed or rotated, as described, about a longitudinal axis to allow one of the empty overpacks to dock with the truck-mounted overpack. The turntable may further be rotated back into line with the rail car or barge axis after overpack bundle loading is complete.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation view of the overpack bundle of the present invention on a rail car.
FIG. 2 is a plan view of the overpack bundle of the present invention on a rail car.
FIG. 3 is an end elevation view of the overpack bundle of the present invention on a rail car.
FIG. 4 is a cross-sectional view of the stockade clamp of the present invention.
FIG. 4A is a cross sectional perspective taken at line A--A 400 in FIG. 4.
FIG. 4B is a cross sectional perspective taken at line B--B 401 in FIG. 4.
FIG. 5 is a cross-sectional view of the geared stockade clamp of the present invention.
FIG. 5A is a cross sectional perspective taken at line A--A 500 in FIG. 5.
FIG. 5B is a cross sectional perspective taken at line B--B 501 in FIG. 5.
FIG. 6 is a perspective view of the cradle assembly of the present invention.
FIG. 6A is a detailed cross sectional view of the roller assembly of the present invention disposed within the cradle assembly shown in FIG. 6.
FIG. 7 is a perspective view of the cradle assembly with an exploded view of the stockade clamps and geared stockade clamp of the present invention.
FIG. 8 is an elevation view during the assembly of module containers and stockade clamps of the present invention.
FIG. 9 is a cross-sectional view of the overpack bundle of the present invention disposed on a rail car.
FIG. 10 is a detailed view of the tiebands and cradle assembly of the present invention.
FIG. 10A is a view of the tiebands and cradle assembly of the present invention taken along line AA in FIG. 10.
FIG. 10B is a view of the tiebands and cradle assembly of the present invention taken along line BB in FIG. 10.
FIG. 10C is a view of the tiebands and cradle assembly of the present invention taken along line CC in FIG. 10.
FIG. 11 is a plan view showing the overpack bundle of the present invention mounted on a rail car and rotated on turntable into docking position.
FIG. 12 is a plan view showing the overpack bundle docking with a truck-mounted overpack of the present invention.
FIG. 13 is an elevation view of the transfer of a SNF canister from a truck-mounted overpack into the overpack bundle of the present invention.
FIG. 14 is an elevation view of the transfer of a SNF canister from the overpack bundle into the truck-mounted overpack of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
A portion of the Intermodal Modular Spent Nuclear Fuel Transportation System of the present invention as disposed on a transportation means which may include, in the preferred embodiment, rail car 103 is best shown in FIG. 1 ready for transporting nuclear material. The transportation means of the present invention could further include a barge or other form of heavy haul means as previously described. The present invention includes overpack 110--a special container adapted to contain spent nuclear fuel or other nuclear or hazardous material (shown in FIG. 13 as SNF canister 1300.) Overpack 110 is capable of being carried on a standard highway vehicle such as a tractor trailer truck. Large numbers of overpacks 110 may be built to a standard design and are interchangeable between deployment in single truck-mounted configurations and heavy-haul bundles. Overpack 110 thus forms the basic module of the invention. FIGS. 12 through 14 show overpack 110 mounted on a standard tractor trailer truck 1200.
A plurality of overpacks 110 are assembled into overpack bundle 100 mounted on rail car 103 which is capable of being rotated about a longitudinal axis so that each overpack 110 can be loaded and unloaded with SNF canisters 1300 and the like. To facilitate loading and unloading, the entire assembly may be rotated in a horizontal plane about a central vertical axis so that loading can take place between one overpack 110 in overpack bundle 100 and a single overpack 110 mounted, for example, on truck 1200 approaching from the side as shown in FIGS. 12 through 14.
Overpack bundle 100 of the present invention comprises four overpacks 110 and is best shown in FIGS. 1, 2 and 3 as being aligned with the longitudinal axis of rail car 103. Overpack bundle 100 sits in cradle assembly 301 upon individual cradle sections 301A, 301B and 301C curved in such a shape to accept the generally cylindrical cross section of bundle 100. Impact limiters 104 are placed at each end of bundle 100 and are used in conjunction with impact limiter supports 106 to secure bundle 100 from longitudinal displacement. Bundle 100 is further secured to cradle sections 301A, 301B, and 301C using tiebands 105. Tiebands 105 comprise solid or partially flexible metal straps extending over bundle 100 accommodating bundle 100's generally cylindrical cross section and attaching to cradle sections 301A, 301B, and 301C using bolts 302.
Overpacks 110 are formed into overpack bundle 100 by means of a series of stockade clamps 402 (shown in FIG. 4) which provide secure clamping and corresponding structural definition to overpack bundle 100. Stockade clamps 402 are distributed at points along bundle 100 and lie in planes perpendicular to the longitudinal axis of bundle 100. Stockade clamps 402 encircle overpacks 110 to form overpack bundle 100. Stockade clamps 402 are shown in detail in FIG. 4 and also shown in FIGS. 7 and 8. Stockade clamps 402 each comprise three sections 402A, 402B, and 402C which are stacked together and bolted at vertical brackets 403A and horizontal brackets 403B as shown in views A--A and B--B of FIGS. 4A and 4B respectively. Openings 410 shown in FIGS. 4, 4A and 4B accommodate overpacks 110. Stockade clamps 402 sections 402A, 402B, and 402C bolt together securely clamping overpacks 110 rigidly in place and provide structural support for overpack bundle 100.
While openings 410 are shown as cylindrical in shape and four in number, more or fewer openings of various shapes are possible provided that the load limitation of the heavy mode transport is not exceeded and other size and weight considerations associated with carrying more than four overpacks are taken into account. To provide structural support, more than one stockade clamp 402 must be used and, in the preferred embodiment, two stockade clamps 402 are used in conjunction with a geared stockade clamp 502 as shown in detail in FIG. 5.
Geared stockade clamp 502 operates identically to stockade clamps 402 for securing overpacks 110. Geared stockade clamp 502 comprises three sections 502A, 502B, and 502C which are stacked together and bolted at vertical brackets 503A and horizontal brackets 503B as shown in views A--A and B--B of FIGS. 5A and 5B respectively. Openings 410 shown in FIGS. 5, 5A and 5B are sized to accommodate overpacks 110. Geared stockade clamp 502, unlike stockade clamps 402, is further provided with gear teeth 504 or alternatively sprocket teeth to engage a chain, toothed belt or drive gear connected to a drive such as drive 900 shown in FIG. 9 and described hereinafter. Such a configuration of geared stockade clamp 502 and drive 900 allows for axial rotation of overpack bundle 100.
Referring now to FIG. 6 of the drawings, cradle sections 301A, 301B, and 301C are shown in more detail highlighting additional elements. Roller assemblies 600 and open section 610 greatly facilitate axial rotation of overpack bundle 100 by providing a lifting and rolling function in the case of roller assemblies 600 and by accommodating operative elements of drive 900 described hereinafter in the case of open section 610. Roller assemblies 600, during transport, are normally recessed within cradle sections 301A and 301C. Noting the alignment of cradle sections 301A and 301C with stockade clamps 402 as also shown in FIG. 7, roller assemblies 600 may be brought into engagement with the smooth surfaces of stockade clamps 402 of overpack bundle 100 to facilitate axial rotation. FIG. 6A of the drawings shows roller assemblies 600 in position for engaging and lifting smooth surfaced stockade clamps 402 (not shown in FIG. 6A) by way of a series of individual rollers 601 placed at regular intervals along the curved surface 605 of roller assembly 600. Load bearing brackets 603 placed at each end of roller assembly 600 provide contact surfaces for jacks 602, which may be hydraulic or mechanical jacks, capable of lifting and supporting overpack bundle 100 slightly off of supporting cradle sections 301A, 301B, and 301C, allowing indexed rotation of overpack bundle 100 by providing a low friction surface upon which overpack bundle 100, by way of stockade clamps 402, may freely roll.
An exploded view of two stockade clamps 402 and geared stockade clamp 502 is shown in FIG. 7. FIG. 7 illustrates the three dimensional relationship not only between individual sections of stockade clamps 402 and geared stockade clamp 502, but individual cradle sections 301A, 301B, and 301C of cradle assembly 301. Stockade clamps 402 are shown in alignment with cradle sections 301A and 301C for providing maximum load support of overpack bundle 100 and for providing a smooth surface for rollers 601, not shown in FIG. 7, to engage and support overpack bundle 100 in lifting relation. Geared stockade clamp 502 is shown in FIG. 7 as being in alignment with cradle section 301B. Open section 610, not shown in FIG. 7, sits beneath geared stockade clamp 502 and allows the operative means of drive 900 to engage teeth 504 from below. The exploded view provided in FIG. 7 further illustrates the relation of elements for the purpose of assembling overpack bundle 100.
Overpack bundle 100 is assembled in sections starting from the bottom. Assembly may be performed with base sections 402A and 502A of stockade clamps 402 and geared stockade clamp 502 respectively resting upon cradle assembly 301 as it rests on turntable 102 and rail car 103 as partially illustrated in FIG. 7 but best shown in FIGS. 8 and 9. An overpack 110, which may be empty or full during assembly, is placed into one of two openings 410 of stockade clamp base sections 402A and 502A (obstructed in this view) during the construction of overpack bundle 100 using crane 801 which may be any type of conventional crane. A second empty overpack 110 is placed in the second of two openings 410 to complete the first layer in overpack bundle 100. Next, stockade clamp middle sections 402B and 502B are placed on the top of the two overpacks 110 already in place and secured to stockade clamp base sections 402A and 502A using bolts which may be secured at vertical and horizontal brackets 403A, 503A and 403B, and 503B respectively as shown in FIGS. 4 and 5. In similar manner, two additional overpacks 110 are lifted into the two remaining openings 410 present on the upper portion of stockade clamp middle sections 402B and 502B.
When empty overpacks 110 are in place, stockade clamp top sections 402C and 502C are lifted into place and secured to the top of stockade clamp middle sections 402B and 502B accordingly using bolts at the second set of vertical and horizontal brackets 403A, 503A and 403B, and 503B respectively.
As an alternative to assembly of overpack bundle 100 upon intermodal transport means such as rail car 103, crane 801 may be used to move overpack bundle 100 in its entirety between heavy-haul means such as from rail car 103 to a barge or heavy-haul ground transport.
During construction of overpack bundle 100 as described, geared stockade clamp 502 is placed in the center of overpack bundle 100 for the purpose of engaging a drive. Teeth 504 engage a chain, a belt or a gear drive to rotate overpack bundle 100 about its longitudinal axis. In the preferred embodiment, a drive such as chain drive 900 using drive motors 901 is used to index overpack bundle 100 between positions accommodating the loading of empty overpacks 110 and is best shown in FIG. 9. Chain 903 may be positioned within open section 610 (FIG. 6) of cradle section 301B during assembly in preparation for placement of geared stockade clamp base section 502A. Once top section 502C of geared stockade clamp 502 is installed, chain 903 is wrapped around geared stockade clamp 502 and the ends of chain 903 are linked together. Chain drive 900, as previously described, may now be used to rotationally index overpack bundle 100 between positions accommodating the loading of SNF canister 1300 from a truck-mounted overpack as is hereinafter described and illustrated in FIG. 13.
Referring again to FIG. 9, chain drive 900 engages geared stockade clamp 502 around a substantial portion of its circumference requiring clearance within cradle section 301B necessitating that the construction of cradle section 301B include open section 610 (FIG. 6) if drive means is to be incorporated therein. It is possible however, in an alternative embodiment, to locate the drive means separately from a cradle section allowing cradle section to be of conventional construction. It is further possible in an alternative embodiment for the drive means to be incorporated in a manner which does not necessitate an open top construction, but rather requires a partially open top or an opening on the side of a cradle section.
Just as roller assemblies 600 and supporting mechanisms are recessed within cradle sections 301A and 301C, chain drive 900 and its mechanisms including motors 901 are disposed within cradle section 301B.
Tiebands 105 are further shown with particularity in FIG. 10. To secure overpack bundle 100 upon cradle assembly 301, tiebands 105 are bolted in place to cradle sections 301A, 301B, and 301C. FIG. 10A shows the top of cradle 301. FIGS. 10B and 10C show side and top views of tiebands 105 respectively and show flange 302A welded to tiebands 105. FIG. 10B shows the side of cradle 301 including bolts 302, flanges 302A and 302B, and tiebands 105. Flanges 302B are welded to cradle sections 301A, 301B, and 301C. Bolts 302 connect flanges 302A and 302B to secure overpack bundle 100 to cradle 301. Bolts 302 are tightened or loosened which in turn increases or reduces the tension on tiebands 105 depending on whether indexing is required of overpack bundle 100. Prior to indexing however, overpack bundle 100 may be rotated 90 degrees or more or less on turntable 102 to accommodate loading of a single SNF canister 1300 from a overpack 110 mounted to truck 1200 on cradle 1202 as is shown in FIGS. 11-14. Truck 1200 may approach overpack bundle 100 from a direction in longitudinal alignment therewith when bundle 100 is rotated 90 degrees as described. Rotating bundle 100 in such a manner provides a more convenient loading angle.
To transfer SNF canister 1300 back and forth between overpack 110 resting in truck-mounted cradle 1202 and one of the empty overpacks 110 of overpack bundle 100 within the system of the present invention, overpack bundle 100 must be properly oriented to conduct the transfer operation. The transfer operation is carried out on the preferred embodiment of the present invention as mounted on rail car 103. The preferred embodiment of the present invention incorporated as a barge mounted system may operate in a similar manner using a pier as a perpendicular transfer point.
At the intermodal transfer site, rail car 103 is chocked and jacked using rail car jacks 300 as shown in FIGS. 3, 13 and 14. Impact limiters 104 and impact limiter supports 106 for restraining overpack bundle 100 from longitudinal movement are retracted and impact limiter 104 on the receiving end of overpack bundle 100 is removed completely to accommodate loading as best shown in FIGS. 11-14. Turntable 102 mounted on rail car 103, supporting overpack bundle 100 may be rotated by use of a gear drive, hydraulic drive, or by pushing or pulling means. FIGS. 11 and 12 show turntable 102 rotated 90°. Once turntable 102 has been rotated to the 90° loading position, tiebands 105 may be loosened, as described, and roller assemblies 600, disposed within cradle sections 301A and 301C, may be raised using jacks 602. Overpack bundle 100 is thereby supported by rollers 601 allowing and facilitating axial rotation as previously described. Finally, chain drive 900, or like drive means, may be tensioned or engaged for facilitating axial indexing of overpack bundle 100 to position overpacks 110 for loading or unloading to or from truck 1200 with a truck-mounted overpack 110 as further illustrated in FIG. 12.
Truck 1200 with overpack 110 mounted thereto and containing an SNF canister 1300 is moved into position such that when turntable 102 is rotated 90° or more or less, overpack bundle 100 is in alignment with overpack 110 as mounted on truck 1200. Indexing is achieved when an overpack 110 within overpack bundle 100 is rotated into alignment with overpack 110 on truck 1200 for transferring an SNF canister 1300. Indexing overpack bundle 100 may include rotating an overpack 110 from any relative upper position on overpack bundle 100 to a relative position at the bottom of overpack bundle 100. Truck-mounted overpack 110 may be aligned and docked with the indexed bundled overpack. Proper docking requires that the center of overpack 110 be in longitudinal alignment with the center of overpack 110 of overpack bundle 100 positioned for transfer of SNF canister 1300. SNF canister 1300 may be transferred from overpack 110 into the indexed overpack 110 using a conventional load transfer or movement device 1302 as further shown in FIG. 13. Movement device 1302 may include, for instance, a winch, a hydraulic system, a ram, a grapple, and the like, but is shown as a cable winch with a hook end 1302A which engages SNF canister 1300 at a corresponding eye 1302B mounted thereto.
After completing the transfer of SNF canister 1300 and while empty overpacks 110 are available in overpack bundle 100, empty truck-mounted overpack 110 may be undocked and overpack bundle 100 indexed to bring the next empty overpack 110 into position for docking with the next truck-mounted overpack 110. Indexing and loading may proceed in like manner until the remaining empty overpacks 110 within overpack bundle 100 are filled. When all overpacks 110 in overpack bundle 100 are loaded with SNF canisters 1300, roller assemblies 600 may be lowered into cradle sections 301A and 301C bringing overpack bundle 100 into supporting relation to cradle 301A, 301B, and 301C. Tiebands 105 are tightened and turntable 102 is rotated back into longitudinal alignment with rail car 103. Impact limiters 104 are replaced and impact limiter supports 106 restored into position.
At the destination for SNF canister 1300 transfer, the loading process may be reversed and overpack bundle 100 unloaded by moving SNF canisters into truck-mounted overpack 110 as shown in FIGS. 13 and 14. FIG. 14 shows SNF canister 1300 being transferred from overpack bundle 100 into truck-mounted overpack 110 using movement device 1302 comprising a cable and hook assembly for applying a pulling force from the opposite direction.
In an alternative embodiment, the system of the present invention may be easily adapted to handle other radioactive material. Such material may include high and low level radioactive material generated during the decommissioning of contaminated sites, non-fuel assembly hardware, consolidated SNF assemblies, failed or broken fuel rods, and vitrified radioactive waste. The system of the present invention may bundle units other than overpacks 110. Other units may include SNF casks, liquid transport tanks, gas transport tanks, and the like. Similarly, stockade clamps 402, and geared stockade clamp 502 for accommodating cylindrical overpacks, may be adapted to bundle non-circular shapes such as rectangular and elliptical standard modules.
In yet another embodiment, the system of the present invention may be further adapted for general purposes to handle any material susceptible of being placed in a container designed to fit into overpacks 110 and equivalent configurations. Such material may include non-radioactive liquid commodities such as gasoline or liquid chemicals and may further include non-radioactive solid commodities such as grain, solid chemicals, and the like. Since the general purpose embodiment of the present invention is primarily for commodity transport, shielded overpacks of the kind required for handling nuclear material are generally not required. Thinner walled overpacks instead may be used. In some cases where canisters are particularly well suited for exposure to environmental elements, canisters may be transferred directly into openings 410 within clamping assemblies 401 and 501 without the need for overpacks. Alternatively, overpack bundle 100 may be assembled using pre-packed commodity canisters, the assembly operation being as previously described.
To fully exploit the improved material handling capabilities of overpack bundle 100, general purpose overpacks, containers, and trailer systems adapted for container handling are used. Tractor trailers carrying, for example, gasoline in a conventional fixed tank may instead be adapted to carry gasoline in a transferrable canister. In the general purpose embodiment, such a canister is secured to the trailer within a trailer mounted overpack and is transferred to and from overpack bundle 100 in a manner similar to the preferred embodiment.
From the foregoing detailed description, it will be evident that there are a number of changes, adaptations and modifications of the present invention which come within the province of those persons having ordinary skill in the art to which the aforementioned invention pertains. However, it is intended that all such variations not departing from the spirit of the invention be considered as within the scope thereof as limited solely by the appended claims.
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The Intermodal Modular Spent Nuclear Fuel Transportation System uses standardized truck, rail, barge or ship mounted equipment to transport nuclear materials including Spent Nuclear Fuel (SNF) in standardized overpacks maximizing interchangeability of transportation components. One or more standard truck transportable SNF canisters or standard overpacks are transported in shielded, truck-mounted overpacks. SNF canisters are transferred, using a winch or other movement device, to empty positions within large rail or barge transportable overpack bundles constructed using a plurality of overpacks. An overpack bundle is supported and raised by a cradle assembly and further may be rotated horizontally right or left to allow truck docking from a direction perpendicular to the normal orientation of the rail car. The overpack bundle is axially indexed for positioning empty overpacks for loading. Transfer of standard overpack may be accomplished using a pulling or pushing device or other movement device such as a winch. The overpack bundle is disposed upon a cradle assembly and secured with tiebands. The cradle assembly is provided with rollers displaced into operative position. The overpack bundle may be raised and supported while facilitating axial rotation.
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TECHNICAL FIELD
The present invention relates to an apparatus for reducing the formation of nitrogen oxides. More precisely, it relates to an apparatus for reducing the formation of nitrogen oxides from turbocharged engines and from systems employing exhaust gas recirculation.
BACKGROUND OF THE INVENTION
There are apparatus' for reducing nitrogen oxides (NOx) from exhaust gases, but these apparatus' have normally been limited to the use of water injection systems for reducing NOx emission from the exhaust gases of combustion engines. Water injection systems in reciprocating engines have been used for increasing power and internal cooling, but not directly for reducing the formation of NOx.
Exhaust gas recirculation (EGR) has been used as a NOx reduction technique in reciprocating engines, but its use has been limited in diesel engines which are turbocharged and aftercooled, because normal engine aftercoolers are typically small finned core heat exchangers. The small air spaces in these heat exchangers are quickly fouled by soot which all diesel engines emit, even if only for startup. Accordingly, there is a need for an aftercooler apparatus that would solve the traditional aftercooler fouling problem seen with EGR systems while also cooling the intake air and reducing the formation of NOx emission levels.
Further, the presently used NOx reducing devices remove gaseous or particulate matter from the exhaust stream of an engine or apparatus through the use of chemical reagents, activated carbon filter elements or exhaust gas conditioners. There is a need for a NOx reducing apparatus that reduces the formation of NOx in the engine by treating the intake air to the engine, thereby also affecting the combustion process and eliminating the need to remove the sediment formation from NOx reducing after treatment type devices due to the concentration of soot or other such contaminants.
In order to overcome the above-mentioned defects in the previously known methods and apparatus' for reducing the NOx emissions from turbocharged engines, there is a need for an apparatus for reducing NOx emissions from turbocharged engines that acts on the intake air of the engine, not the exhaust gases, and that reduces the formation of NOx rather than removing it from the exhaust stream of the engine. There is also a need for an apparatus for reducing NOx emissions from turbocharged engines that does not require the removal of concentrated pollutants from the treatment device and which allows for the removal of traditional engine aftercooler devices thereby reducing air flow restriction and increasing fuel economy. There is also a need for an apparatus for reducing NOx emissions that uses water as a coolant without requiring the cooling water to be treated for the removal of dissolved solids in the water prior to using the water as a coolant. The apparatus of the present invention meeting these requirements is described in more detail below.
SUMMARY OF THE INVENTION
In accordance with the present invention, the disadvantages of the prior methods and apparatus' for reducing NOx emissions from the exhaust of engines has been overcome. The apparatus of the present invention is environmentally safe, increases fuel economy, eliminates the requirement of removing concentrated pollutants produced from combustion and lowers exhaust temperature which leads to increased engine life.
According to the present invention, the apparatus consists of an aftercooler device that is connected to an engine turbocharger and to a reciprocating engine. Turbocharged air from the turbocharger is directed into the aftercooler through an inlet tube into the aftercooler's primary saturation chamber. The incoming air is initially mixed with and cooled by the water located at the bottom of the primary saturation chamber before being divided and directed toward and through a diffusion screen. The air exiting the diffusion screen enters a secondary saturation chamber where intense bubbling and foaming increases the air-water contact area that further cools the air and results in an air-water mixture approaching the temperature and moisture level of saturation.
The cooler and saturated air is then moved through a tangential outlet into a primary drying chamber where a majority of the moisture is removed from the air through the use of centrifugal force. The air is then directed toward an outlet tube that forces the air to make an abrupt 180 degree turn thereby assisting in removing any unevaporated water not separated from the air stream. The now cooler moist air is directed toward the engine intake manifold, whereby the moisture in the air stream acts to reduce the NOx formation during the combustion process. The exhaust gas from the engine is collected in the exhaust manifold and directed toward the turbine wheel in the turbocharger, which uses the energy in the exhaust stream to drive the turbocharger's compressor.
Accordingly, it is the primary object of the present invention to provide an apparatus the reduces the formation of NOx emissions from turbocharged engines rather than removing NOx emissions from the exhaust stream of the engines.
It is a further object of the present invention to provide an apparatus for reducing NOx emissions from turbocharged engines that does not require the removal of concentrated pollutants from the treatment device and which allows for the removal of traditional engine aftercooler devices thereby reducing air flow restriction and increasing fuel economy.
It is another object of the present invention to provide an apparatus for reducing NOx emissions from turbocharged engines that acts on the intake air of the engines, not the exhaust gases, and that reduces the formation of NOx emissions rather than removing these emissions from the exhaust stream of the engines.
It is a further object of the present invention to provide an apparatus for reducing the NOx emissions from engines that uses water as a coolant without requiring the cooling water to be treated for the removal of dissolved solids in the water prior to using the water as a coolant. Other objects and advantages of this invention will become apparent from the following description wherein is set forth, by way of illustration and example, certain embodiments of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a turbocharged engine system using the apparatus.
FIG. 2 is an elevational right side view of the turbocharged engine system depicted in FIG. 1.
FIG. 3 is an elevational front view of the turbocharged engine system depicted in FIG. 1.
FIG. 4 is an elevational left side view of the turbocharged engine system depicted in FIG. 1.
FIG. 5 is a perspective view of the apparatus shown in FIG. 1.
FIG. 6 is a longitudinal sectional view of the apparatus taken along lines 6--6 of FIG. 5.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, a typical embodiment of the invention is shown in FIGS. 1-6. Before the present invention is described, however, it is to be understood that this invention is not limited to a particular or specific description. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting, as the scope of the present invention will be limited only by the appended claims. Further, unless defined otherwise, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Referring to FIGS. 1-4, a reciprocating engine 1 is shown connected to the engine turbocharger 3 through the engine's exhaust manifold 4. The engine 1 produces high temperature exhaust gas 5. The turbocharger 3 has an exhaust pipe 7 that allows for a lower temperature exhaust gas 5a to leave the turbocharger 3. The turbocharger 3 also has a compressor 8 that compresses filtered air 6 having an ambient temperature. The filtered air 6 is drawn into the compressor 8 through an inlet tube 9 and is then discharged as compressed, heated air 10. The compressed, heated air 10 is directed through a discharge tube 11 to a NOx reducing aftercooler 12.
The aftercooler 12 humidifies and cools the incoming compressed heated air 10 by direct water contact. The now moist air is directed as an air stream 13 to the engine 1 through an engine intake manifold 15 by an air tube 16. Inside the engine 1 the moisture in the air stream 13 acts to reduce the formation of NOx emissions during the combustion process in the engine 1. The exhaust gas 5 from the engine 1 is collected in the exhaust manifold 4 and is directed to the turbine wheel 20 of the turbocharger 3. The turbocharger 3 uses the energy in the exhaust gas 5 to drive the turbine wheel 20, which results in the exhaust gas 5a having a lower temperature. The turbocharger 3 then discharges the lower temperature exhaust gas 5a out into the atmosphere through the exhaust pipe 7.
Through the use of the aftercooler 12, which treats the filtered air 6 that is compressed and directed to the aftercooler 12 and which becomes the intake air (the air stream 13) of the engine 1, the formation of NOx emissions is reduced. The aftercooler 12 thereby provides for a more efficient method of reducing NOx emissions by reducing the formation of NOx during the combustion process versus attempting to remove these emissions from the exhaust gases 5 after being formed in the combustion process in an engine.
Referring now to FIGS. 1, 5 and 6, the aftercooler 12 is shown in more detail. The aftercooler 12 consists of a two-part pressure vessel 26 having a top half 27 and a bottom half 28. The discharge tube 11 of the turbocharger 3 is connected to the aftercooler's inlet air tube 25. The inlet air tube 25 is located at the lower end 29 of the bottom half 28 of the aftercooler 12. The vessel 26 is also shown to have three chambers: a primary air saturation chamber 30, a secondary air saturation chamber 35 and a drying chamber 40. The primary air saturation chamber 30 and the secondary air chamber 35 are located in the bottom half 28 of the vessel 26. The drying chamber 40 is located in the top half 27 of the vessel 26.
The secondary air saturation chamber 35 has a closed end cylinder 35a that is located immediately above the primary air saturation chamber 30 and is held in place by fasteners. At the bottom of the closed end cylinder 35a is a diffusion screen 36. The closed end cylinder 35a is positioned above the primary air chamber 30 such that the diffusion screen 36 is directly above the entry way 45 of the inlet tube 25.
In operation, the compressed, heated air 10 enters the vessel 26 through the inlet air tube 25 into the primary air saturation chamber 30. The primary air saturation chamber 30 has a layer of water 50 located in the lower end 29 of the bottom half 28. The water 50 with the incoming compressed, heated air 10 causes a tremendous air-water turbulence which leads to some of the water 50 to evaporate thereby causing the compressed, heated air 10 to cool to form semi-cooled compressed air 51. The diffusion screen 36 while allowing the semi-cooled compressed air 51 to enter into the secondary air saturation chamber 35 divides the semi-cooled compressed air 51 into separate flows of air where intense bubbling and foaming increases the air-water contact. The additional air-water contact further cools the semi-cooled compressed air 51 to form an air-water mixture 52 that approaches the temperature and moisture level of saturation.
Located at the top end 53 of the closed end cylinder 35a is a tangential outlet tube 55 that allows the air-water mixture 52 to exit the secondary air saturation chamber 35 and to enter the drying chamber 40. The tangential outlet tube 55 forces the air-water mixture 52 to make a 90 degree turn before entering the drying chamber 40. The 90 degree turn causes the air-water mixture 52 to circulate along the interior walls of the drying chamber 40. Due to the resulting centrifugal force most of the mist 52a in the air-water mixture 52 is separated from the air-water mixture 52, thereby forming moist compressed air 56. The mist 52a is allowed to drain back into the primary saturation chamber 29 through the use of return water passages 57.
As shown in FIGS. 1, 5 and 6, the moist compressed air 56 proceeds further up into the drying chamber 40 until it makes an abrupt 180 degree turn as it enters the outlet air tube 60 which directs the moist compressed air 56 out of the aftercooler 12, through the air tube 16 and into the engine intake manifold 15. The last reversal created by the abrupt 180 degree turn works to ensure that any unevaporated water not previously separated in the primary drying chamber 40 will be separated from the moist compressed air 56. As the moist compressed air 56 is flowing through the air tube 16, the moist compressed air 56 passes a temperature sensor 65 that provides air temperature data to a process control computer 70. The computer 70 is electrically connected to an injection water solenoid valve 75 located in a water inlet port 76 that provides water to the primary air saturation chamber 29. The computer 70 is programmed to cycle the injection water solenoid valve 75 based on the air temperature data provided by the temperature sensor 65. The computer 70 also is programmed to activate an alarm if the air temperature data of the moist compressed air 56 is too high or falls too low, thereby indicating a malfunction of the aftercooler 12 which could potentially damage the engine 1.
The water inlet port 76 is also shown to have a water pressure regulator 80 that has a gauge. The water pressure regulator 80 is modulated to maintain the desired pressure in the make-up of the water 50 in the primary saturation chamber 29. The desired quality of the water 50 is further maintained by the use of water bleed down ports 81. The water bleed down ports 81 are located on the exterior wall of the bottom half of the vessel and allow a portion of the mist 52a draining from the drying chamber 40 to flow out of the vessel through the water bleed down ports 81. The desired make-up of the water 50 is important because any dissolved solids in the water 50 become concentrated as the evaporation process takes place. Thus, the amount of solids in the water 50 is regulated by the water bleed down ports 81. The rate of the flow through the water bleed down ports 81 is in turn regulated by the size of the hose 82 that is connected to the water bleed down ports 81 and the location of the bleed down ports 81 along the exterior wall of the bottom half of the vessel 26. Note, however, that the water inlet port 76 which provides the water 50 to the primary air saturation chamber 29 does not have to have a treatment system to first treat the incoming water, nor does the incoming water have to be pretreated.
Thus, the aftercooler 12 can function as a NOx reducing aftercooler using water 50 as a coolant with water 50 having high levels of dissolved solids. The quantity of the water 50 required for the aftercooler 12 to function properly is approximately equivalent to 20 to 25 percent of the volume of water required if after-treatment NOx devices were used. With the present invention, the use of the water bleed down ports 81, along with the computer 70, work to provide and maintain the desired quality of the make-up of the water 50 to provide the moist compressed air 55 for the engine 1. The resulting use of the aftercooler 12 provides that a much less water volume level is required and consumed for the aftercooler 12 to operate and aid in the reduction in the formation of NOx emissions.
Additionally, the aftercooler 12 can be used with industrial waste waters that contain specific volatiles in limited concentrations. The volatiles in the industrial waste waters will be destroyed during the combustion process after the waste waters have been used to form the moist compressed air 56 for the engine 1. Examples of such waste waters include water contaminated with small quantities of gasoline or diesel fuel.
Further, the aftercooler 12 can be used to concentrate and recover various products from industrial waste waters or low concentration industrial product streams that contain commercially valuable substances in concentration too low to otherwise be valuable. The aftercooler 12 can operate to concentrate these substances to a level where further recovery is economically viable. Examples include water contaminated by small quantities of glycol or antifreeze.
The aftercooler 12 can also be used in conjunction with exhaust gas recirculation systems to further reduce the formation of NOx emissions during a combustion process. In this application, a small amount of combustion gas is intentionally mixed with the incoming air stream 6 to provide a more non-reactive mass in the combustion mixture and thereby further reduce the formation of NOx emissions.
SUMMARY
The aftercooler 12 receives compressed, heated air 10 from a turbocharger 3 that is connected to a reciprocating engine 1. The aftercooler 12 consists of a two-part pressure vessel 26, with the top half 27 of the vessel 26 containing the drying chamber 40 and the bottom half 28 containing the primary air saturation chamber 30 and the secondary air saturation chamber 35. The compressed, heated air 10 first enters the aftercooler 12 through the inlet air tube 25 and into the primary air saturation chamber 30. The primary air saturation chamber 30 has a layer of water 50 that with the incoming compressed, heated air 10 causes an air-water turbulence to occur which leads to some of the water 50 being evaporated, thereby causing the air 10 to cool and form a semi-cooled compressed air 51. A diffusion screen 36 is located above the primary air saturation chamber 30 and allows the semi-cooled compressed air 51 to exit the primary air saturation chamber 30 and to enter the secondary air saturation chamber 35, where bubbling and foaming increases the air-water contact. This additional air-water contact further cools the semi-cooled compressed air 51 and forms an air-water mixture 52 that approaches the temperature and moisture level of saturation.
The air-water mixture 52 exits the secondary air saturation chamber 35 through a tangential outlet tube 55, which directs the air-water mixture 52 to enter the drying chamber 40. The tangential outlet tube 55 forces the air-water mixture 52 to make a 90 degree turn before entering the drying chamber 40. The 90 degree turn causes the air-water mixture 52 from the tube to circulate along the interior walls of the drying chamber 40, which results in centrifugal force acting to separate the mist 52a from the air-water mixture 52, thereby forming moist compressed air 56. The separated mist 52a is allowed to drain back into the primary saturation chamber 29 through the use of water return passages 57.
The moist compressed air 56 circulates further up into the drying chamber 40 until is makes an abrupt 180 degree turn into an outlet air tube 60 which directs the moist compressed air 56 out of the aftercooler 12 through the air tube 16 and into the engine air intake manifold 15. The last reversal created by the abrupt 180 degree helps to separate any unevaporated water from the moist compressed air 56. As the moist compressed air 56 enters the engine intake manifold 15, it is directed inside the engine 1 where the moisture in the moist compressed air 56 acts to reduce the NOx formation during the combustion process in the engine 1. The exhaust gas 5 from the engine 1 is collected in the exhaust manifold 4 and directed to the compressor 8 of the turbocharger 3, which uses the energy in the exhaust gas 5 to drive the turbocharger 3.
It is to be understood that while certain forms of this invention have been illustrated and described, the invention is not limited thereto, except insofar as such limitations are included in the following claims.
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An aftercooler apparatus that is connected to a turbocharger and to a reciprocating engine has a primary and a secondary saturation chamber, and a drying chamber. Turbocharged air from the turbocharger is directed into the primary saturation chamber. The incoming air is initially mixed with and cooled by water located at the bottom of the primary saturation chamber before being directed through a diffusion screen. The air exiting the diffusion screen enters the secondary saturation chamber where intense bubbling and foaming increases the air-water contact area to further cool the air and form an air-water mixture approaching the temperature and moisture level of saturation. The air-water mixture is then directed into the drying chamber where a majority of the moisture is removed from the air through the use of centrifugal force. The now cooler moist air is directed toward the engine intake manifold, whereby the moisture in the air stream acts to reduce the NOx formation during the combustion process. The aftercooler apparatus acts to reduce the formation of NOx emissions from turbocharged engines rather than attempting to remove the NOx emissions from the exhaust stream of the engines. The aftercooler apparatus may also be used to beneficially recycle industrial waste waters.
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FIELD OF THE INVENTION
[0001] The present invention relates to a biosafety cabinet (BSC); more particularly, relates to forming an air-isolator at an opening of a door to isolate air flows inside and outside the BSC, to prevent circulations in the BSC, and to prevent contamination leakage from the BSC.
DESCRIPTION OF THE RELATED ARTS
[0002] In many microbiological experiments or procedures, biological dangers may do harm to operators. BSC is used to protect germs in the cabinet and to prevent contamination inside from leaking out.
[0003] Although BSC is used to protect germs in the cabinet and to protect the operator, events keep on happening that operators died because of contamination. It shows that BSC still has some problem. In an actual operation, there are two types of problems: (1) not obtaining the most proper design: They include insufficient suction amount, improper suction slot position, improper air supplier position, uneven flow rate at front opening, bad opening shape design, etc.; and (2) not operating in a best state: They include that the contamination is too much, the opening is too wide opened, that the suction amount is not well adjusted following an actual situation, etc.
[0004] According to NSF/ANSI 49, 2002, which is a newly revised standard for a level II BSC, the BSCs can be divided into four categories: A1, A2, B1 and B2.
[0005] Clark and Mullan, Rake, Kennedy, Kruse, etc. test BSCs for capabilities in exhausting contamination and found that the level II BSC can not resist a sudden change in indoor air pressure. Hence, the capability in exhausting contamination for a level II BSC has to be improved.
[0006] In the B2 BSC, waste gases are totally exhausted without recycling; all gases are flowed through HEPA filter; and the gases are exhausted to the exhausting system of a building. The BSC has a HEPA filter on top to supply air by an air blower. Thus, outer air is not allowed to enter the cabinet directly; and environments inside and outside the cabinet are separated. Then the air is exhausted by an air-suction device at a rate of 0.57 cubic meters per second for obtaining a negative pressure in the cabinet. And, if air supply is not enough, a sash may be opened to supply air into the BSC from outside. Yet, in such a situation, the contamination in the BSC may leak out at the opening by the interference of the outside flow and/or the action of the BSC door. Therefore, traditional BSC is weak in defending interferences of side flow and door operation. Hence, the prior art does not fulfill all users' requests on actual use.
SUMMARY OF THE INVENTION
[0007] The main purpose of the present invention is to prevent contamination leakage from the BSC and to prevent circulations in the BSC.
[0008] To achieve the above purpose, the present invention is an air curtain-isolated BSC, comprising a main body, a door, an air blower, a suction box, a gas sucker, a plurality of cross flow fans and a high efficiency particulate air (HEPA) filter, where the main body has a space to contain a harmful gas to be exhausted and has an open space at a side; the door is movably assembled to the main body at the side to control an opening and has an air-pushing veil; the air blower is connected to an air inlet on top of the main body to supply fresh air; the suction box is set beneath the main body and has a suction slot at an edge of the main body corresponding to the air-pushing veil of the door; the gas sucker is set at an exit of the suction box for exhausting the harmful gas; the HEPA filter is set on top of the main body to supply air by the air blower; and air flows inside and outside the BSC is isolated to prevent operators from damages owing to leakage of the contamination in the BSC, and to prevent contamination outside of the BSC from entering into the BSC to pollute a product in the BSC. Accordingly, a novel air curtain-isolated BSC is obtained.
BRIEF DESCRIPTIONS OF THE DRAWINGS
[0009] The present invention will be better understood from the following detailed description of the preferred embodiment according to the present invention, taken in conjunction with the accompanying drawings, in which
[0010] FIG. 1 is the perspective view showing the preferred embodiment according to the present invention;
[0011] FIG. 2 is the side view showing the preferred embodiment;
[0012] FIG. 3 is the view showing the preferred embodiment with the coordinated devices;
[0013] FIG. 4 is the view showing the straight curtain;
[0014] FIG. 5 is the view showing the slightly concave curtain;
[0015] FIG. 6 is the view showing the severely concave curtain; and
[0016] FIG. 7A to FIG. 7C are the views showing the changes of the oscillating curtain at different times.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0017] The following description(s) of the preferred embodiment(s) is/are provided to understand the features and the structures of the present invention.
[0018] Please refer to FIG. 1 to FIG. 3 , which are a perspective and a side views showing a preferred embodiment according to the present invention; and a view showing the preferred embodiment with coordinated devices. As shown in the figures, the present invention is an air curtain-isolated biosafety cabinet (BSC), comprising a main body 11 , a door 12 , an air blower 13 , a suction box 14 , a gas sucker 15 , a plurality of cross flow fans 20 and a high efficiency particulate air (HEPA) filter 16 , where air flows inside and outside the BSC are isolated with no air circulation and dissipation and thus contamination in the cabinet is well prevented from leakage.
[0019] The main body 11 has a space to contain a harmful gas to be exhausted; and has an open space at a side.
[0020] The door 12 is movably assembled to the main body 11 at a side. The door 12 has a handle 121 to move the door for controlling an opening 125 . A plurality of cross flow fans 20 is set on the door 12 and the door 12 is a telescopic sliding door to change opening size of the door 12 . The door blows air by setting a plurality of cross flow fans controlled by a cross-flow fan controller 2 . Air is blown from upper side of the door 12 to a section of honeycombs 123 . And then the air is continuously blown through a stabilizing passage 124 to dissipate turbulence energy to reach an opening 125 of the door 12 .
[0021] Concerning supplying a down flow of air, the air blower 13 is controlled by an inverter 17 a and is connected with the air inlet 111 on the top of the HEPA filter 16 to supply fresh air.
[0022] The suction box 14 is set beneath the main body 11 ; and has a suction slot 141 located at an edge of the main body 11 corresponding to the air-pushing veil 122 of the door 12 .
[0023] The gas sucker 15 is set at an exit of the suction box 14 to suck the harmful gas. Another inverter 17 b is used to change a rotation rate of the gas sucker 15 to control an average blowing rate of the air blower 13 and an average sectional sucking rate of the suction slot 141 . A Venturi flow meter 18 is set between an exit of the gas sucker 15 and an exit of the suction box 14 to measure an air-blowing rate; and obtains a pressure difference between them with a coordination of a pressure transducer 19 .
[0024] The HEPA filter 16 is deposed on top of the main body 11 to supply air in an average rate through the air blower 13 . Thus, with the above structure, a novel air curtain-isolated BSC is obtained.
[0025] The present invention has the following characteristics: The door 12 is movably assembled at a side of the main body 11 and has an air-pushing veil 122 . The inverter 17 a is used to control the air blower 13 and the air blower 13 is connected to the air inlet 111 on the HEPA filter 16 through a flexible pipe. A plurality of cross flow fans 20 is set on the door 12 ; and the door is a telescopic sliding door to change a position of mouth for blowing air. The cross flow fans 20 is controlled by a cross-flow fan controller 2 to provide a steady air flow to flow from the upper side of the door 12 and to flow through a section of honeycombs 123 . Then, the air is flowed through a stabilizing passage 124 to dissipate turbulence energy to reach the opening of the door 12 . The suction box 14 is set beneath the main body 11 and the suction slot 141 is located at an edge of the main body 11 corresponding to the air-pushing veil 122 of the door 12 , where a push-pull air-isolator is thus obtained. The flow fields of the BSC are examined through a flow visualization and are effectively controlled to prevent contamination in the cabinet from leakage; and the position of the suction slot 141 can be changed to suck the contamination more effectively. Through the HEPA filter 16 on the main body 11 , fresh air flow is supplied to meet a physical mechanism between air suction and air supply. Accordingly, the air curtain-isolated BSC obtains the physical mechanism between air suction and air supply; the air-isolator formed by the local air suction near the contamination source prevents the contamination from leakage; and, thus, energy is saved and contamination is prevented from leakage with practicality, convenience and safety.
[0026] Please further refer to FIG. 4 to FIG. 7C , which are views showing a straight curtain, a slightly concave curtain and a severely concave curtain; and views showing the changes of the oscillating curtain at different times. As shown in the figures, push-pull air-isolators are divided into four type, comprising a straight curtain 71 , a slightly concave curtain 72 , a severely concave curtain and an oscillating curtain 74 .
[0027] On using the present invention, flow fields in the main body 11 are described as follows:
[0028] (a) Slightly concave curtain 72 : When an air-blowing velocity, an air-supplying velocity and an air-sucking velocity are adjusted to obtain a proper ratio, an air-isolator formed by the air from the door 12 is slightly concave inward the BSC. When the flow is close to the suction slot 141 , the air flow is pulled down to be prevented from flowing outside or inside the BSC.
[0029] (b) Straight curtain 71 : When the air-sucking velocity is smaller than the above one and thus is weak, the air isolator formed by the air from the door 12 is straight and not concave with no circulation formed in the cabinet.
[0030] (c) Severely concave curtain 73 : When the air-sucking velocity is big, the air-isolator is moved inwardly and is severely concave; and, thus, obvious circulations are formed in the BSC.
[0031] (d) Oscillating curtain 74 : Obvious circulations are generated inside and outside the BSC with the air-isolator swinging in and out of the BSC at different times.
[0032] With the above descriptions concerning the four types of flow fields, it is suggested to adjust push-pull velocities of air to obtain a slightly concave curtain 72 for operations in the BSC.
[0033] To sum up, the present invention is an air curtain-isolated BSC, where an air-isolator is formed at an opening of a door for isolating air flows inside and outside the BSC to prevent operators from damages owing to contamination leakage from the BSC, and to prevent contamination outside of the BSC from entering into the BSC to pollute a product in the BSC.
[0034] The preferred embodiment herein disclosed is not intended to unnecessarily limit the scope of the invention. Therefore, simple modifications or variations belonging to the equivalent of the scope of the claims and the instructions disclosed herein for a patent are all within the scope of the present invention.
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A biological safety cabinet (BSC) has an air curtain to isolate air inside and outside the BSC. A most preferable slight concave curtain of air can be obtained. With the curtain, neither contamination in the BSC leaks out nor outside contamination enters the BSC. Furthermore, no circulation is formed in the BSC by blowing the air curtain. Thus, the operator using the BSC and the product in the BSC are both well protected.
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BACKGROUND OF THE INVENTION
The present invention relates to the information arts. In finds particular application in relational database systems that distribute data across a plurality of computers, servers, or other platforms, and will be described with particular reference thereto. However, the invention also finds application in many other systems including distributed information systems, in information backup systems, and the like.
Relational database systems are widely used in business, government, and other organizations to record, store, process, share, and otherwise manipulate information. Because such organizations are commonly regional, national, or global in scope, the relational database is preferably accessible from regionally, nationally, or globally distributed computers, terminals, or other devices across local area networks, Internet links, wireless links, and other communication pathways. For example, worldwide offices of a corporation preferably access a single corporate database or selected portions thereof.
A problem arises in that accessing a single database by a large number of remote computer systems creates substantial communication and data processing bottlenecks that limits database speed. To overcome such bottlenecks, a distributed database system is used, in which database information is shared or distributed among a plurality of database servers that are distributed across the communication network.
A distributed database system typically includes a central database and various remote databases that are synchronized with the central database using various techniques. The remote databases can contain substantially the entire central database contents, or selected portions thereof. Moreover, transactions can be generated at the central database server or at one of the remote servers. In a commercial enterprise, for example, remote database servers at sales offices receive and generate purchase order transactions that propagate by data distribution to the central database server and in some cases to other database servers. Similarly, remote servers at billing centers generate sales invoice transactions that propagate through the distributed database system, and so forth. The central database server provides a repository for all database contents, and its contents are preferably highly robust against server failures.
To provide for recovery in the event that the central database fails, the central database can include primary and secondary database instances. The secondary database instance mirrors the primary database instance and acts as a hot backup providing failover recovery in the event of a primary database failure. Mirroring is maintained by shipping logical log files of the primary database instance to the secondary instance as they are being copied to disk or other non-volatile storage on the primary instance. The secondary instance remains in recovery mode as it is receiving and processing the shipped logical log files. Since all log records are processed at the secondary instance, the secondary instance provides a mirror image backup of the primary database instance, except for recent transactions that may not have been copied to the secondary instance yet. The primary and secondary database instances are in some cases configured such that a transaction commit is not completed at the primary until the log of that transaction is shipped to the secondary instance. Such a central database is robust against primary database failure and provides a fail-safe solution for high availability. However, it is limited in functionality, supporting only a single or limited number of synchronized secondary instances, which must be substantially compatible. For example, the primary log records should be interpretable by the secondary server without introducing substantial translation processing overhead.
Remote databases which store some or all information contained in the central database are typically maintained by synchronous or asynchronous data replication. In synchronous replication, a transaction updates data on each target remote database before completing the transaction. Synchronous replication provides a high degree of reliability and substantially reduced latency. However, synchronous replication introduces substantial delays into data processing, because the replication occurs as part of the user transaction. This increases the cost of the transaction, and can make the transaction too expensive. Moreover, a problem at a single database can result in an overall system failure. Hence, synchronous replication is usually not preferred except for certain financial transactions and other types of transactions which require a very high degree of robustness against database failure.
Asynchronous replication is preferred for most data distribution applications. In asynchronous replication, transaction logs of the various database servers are monitored for new transactions. When a new transaction is identified, a replicator rebuilds the transaction from the log record and distributes it to other database instances, each of which apply and commit the transaction at that instance. Such replicators have a high degree of functionality, and readily support multiple targets, bi-directional transmission of replicated data, replication to dissimilar machine types, and the like. However, asynchronous replicators have a substantial latency between database updates, sometimes up to a few hours for full update propagation across the distributed database system, which can lead to database inconsistencies in the event of a failure of the central database server. Hence, asynchronous replicators are generally not considered to be fail-safe solutions for high data availability.
Therefore, there remains a need in the art for a method and apparatus for fail-safe data replication in a distributed database system, which provides for reliable fail-safe recovery and retains the high degree of functionality of asynchronous replication. Such a method and/or apparatus should be robust against a failure at a critical node within the replication domain, and should ensure the integrity of transaction replications to other servers within the replication domain in the face of such a critical node failure.
The present invention contemplates an improved method and apparatus which overcomes these limitations and others.
SUMMARY OF THE INVENTION
In accordance with one aspect, a database apparatus includes a critical database server having a primary server supporting a primary database instance and a secondary server supporting a secondary database instance that mirrors the primary database instance. The secondary server generates an acknowledgment signal indicating that a selected critical database transaction is mirrored at the secondary database instance. A plurality of other servers each support a database. A data replicator communicates with the critical database server and the other servers to replicate the selected critical database transaction on at least one of said plurality of other servers responsive to the acknowledgment signal.
In accordance with another aspect, a method is provided for integrating a high availability replication system that produces at least one mirror of a critical database node, with a data distribution replication system that selectively replicates data at least from the critical database node to one or more remote databases. In the data distribution replication system, an object at the critical database node targeted for replication is identified. In the high availability replication system, objects including the identified object are replicated at the mirror and a mirror acknowledgment indicative of completion of replication of the identified object at the mirror is generated. In the data distribution replication system, the identified object is replicated responsive to the mirror acknowledgment.
In accordance with another aspect, a method is provided for coordinating data replication to distributed database servers with a hot-backup instance of a database. Database transactions are backed up at the hot-backup instance. A backup indicator is maintained that identifies database transactions backed up at the hot-backup source. Data replication of a database transaction is delayed until the backup indicator identifies the database transaction as having been backed up at the hot-backup source.
In accordance with yet another aspect, an article of manufacture includes a program storage medium readable by a computer and embodying one or more instructions executable by the computer to perform process operations for executing a command to perform a database operation on a relational database connected to the computer. A transaction performed in the relational database is identified. The identified transaction is replicated responsive to an indication that the identified transaction has been backed up at the relational database.
In accordance with still yet another aspect, an apparatus for supporting a distributed relational database includes primary and secondary servers. The primary server supports a primary database instance that includes a primary database instance log file. The secondary server supports a secondary database instance that includes a secondary instance log file. A plurality of other servers each support a database instance. A highly available data replication component communicates with the primary and secondary servers to transfer primary database instance log file entries from the primary server to the secondary server. The secondary server produces an acknowledgment indicating that the transferred log file entries have been received. A logical data replication component communicates with the primary server and the other servers to identify a log record in the primary database instance log file, construct a replication transaction corresponding to the identified log record, and, responsive to the highly available data replication component indicating that the identified log record has been received at the secondary server, cause one or more of the other servers to perform the replication transaction.
One advantage resides in avoiding data inconsistencies among remote servers in the event of a failure of the central database primary server.
Another advantage resides providing asynchronous replication functionality that is robust with respect to primary database failure.
Yet another advantage resides in providing for fail-safe recovery via a high availability replication system, while retaining the broad functionality of data distribution by asynchronous replication.
Still further advantages and benefits will become apparent to those of ordinary skill in the art upon reading and understanding the following detailed description.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may take form in various components and arrangements of components, and in various process operations and arrangements of process operations. The drawings are only for the purposes of illustrating preferred embodiments and are not to be construed as limiting the invention.
FIG. 1 is a block diagram showing a distributed relational database system including a central database server with a primary database server and a hot-backup secondary database server, a highly available data replication component for maintaining the hot-backup secondary database, and a logical data replication component for selectively distributing data amongst remote servers and the central database.
FIG. 2 is a block diagram showing the distributed relational database system of FIG. 1 after the primary server of the central database server has failed and failover recovery control has passed to the secondary database server.
FIG. 3 is a flowchart showing a preferred method for synchronizing logical data replication with highly available data replication.
FIG. 4 is a block diagram showing a preferred embodiment of the highly available data replication component that includes communication of a synchronizing acknowledgment signal to a send queue of the logical data replication component.
FIG. 5 is a flowchart showing a modification of the process of FIG. 3 for providing robust synchronization of logical data replication with highly available data replication in a case where the logical data replicator sends a replication transaction to the primary server.
FIG. 6 is a block diagram showing another distributed relational database system, which has a tree topology with three critical nodes, each critical node having a highly available data replication pair including a primary database server and a hot-backup secondary database server, and a logical data replication component for selectively distributing data amongst servers of the tree topology.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
With reference to FIG. 1 , a distributed relational database system 10 of a spokes-and-hub topology includes a central database server 12 and a plurality of remote database servers 14 , 16 , 18 . The central database server 12 includes a primary server 20 and a secondary server 22 that mirrors the primary server 20 . The mirroring is provided by a highly available data replication (HDR) component 26 that transfers log records of the central database primary server 20 to the secondary server 22 . The log records are applied and logged at the secondary server 22 . In this manner, the secondary server 22 is maintained as a mirror image of the primary server 20 , except for a set of most recent primary server transactions which may not yet have been transferred by the highly available data replication component 26 .
Although the primary and secondary server components 20 , 22 of the central database 12 are shown together in FIG. 1 , the combination is a logical combination, and is not in general a physical combination. That is, the primary and secondary server components 20 , 22 can be spatially remote from one another and in operative communication via a communication network, which may also include the remote servers 14 , 16 , 18 . The servers 20 , 22 are preferably logically compatible. For example, the log files of the primary server 20 are preferably readily interpretable by the secondary server 22 without computationally intensive translation processing.
The distributed database 10 is of the spokes-and-hub topology, in which there is one critical node, namely the central database server 12 , which serves as the hub. The plurality of remote database servers 14 , 16 , 18 are spokes that connect at the hub. The central database server 12 is a critical node because a failure of that server results in service interruption for a number of other servers, such as the remote database servers 14 , 16 , 18 . Rather than a spokes-and-hub topology, other topologies can be employed, such as a tree topology, in which there is more than one critical node. In topologies which include more than one critical node, each critical node is preferably supplied with its own highly available data replication (HDR) hot backup.
Data distribution by asynchronous replication amongst the primary server 12 and the remote servers 14 , 16 , 18 of the database system 10 is performed by an asynchronous logical data replication component 30 . The data replication component 30 produces computation threads that monitor transaction logs of the primary server 20 of the central database 12 and of the remote servers 14 , 16 , 18 to identify recent transactions. Advantageously, such log monitoring does not significantly slow operation of the servers 12 , 14 , 16 , 18 . When a recently logged transaction is identified, the data replication component 30 constructs one or more replication transactions that effect replication of the logged transaction.
Because replication transactions are generated by the data replication component 30 , the replication transaction can be different in form but equivalent in function to the original transaction. This allows the central database server 12 and the various remote database servers 14 , 16 , 18 to be dissimilar, for example with respect to operating system, computer type, and the like. Replication to multiple targets, bi-directional transmission of replicated data, replication to dissimilar machine types, and the like are readily supported by the data replication component 30 . Data replication can also be selective. That is, only certain data on the central database 12 or the remote servers 14 , 16 , 18 can be replicated to selected remote servers 14 , 16 , 18 . For example, if remote servers 14 , 16 , 18 are Eastern, Midwestern, and Western regional servers, then data is suitably regionally filtered and selectively distributed to the appropriate regional remote server 14 , 16 , 18 by the data replication component 30 .
In FIG. 1 , an exemplary row insertion “R- 1 ” transaction 32 is performed at the primary server 20 of the central database 12 . Although an exemplary row insertion transaction is described herein for purposes of illustrating a preferred embodiment, substantially any type of relational database transaction can be similarly processed. The row insertion transaction 32 is logged at the primary database, identified by the data replication component 30 , and a replication transaction 32 ′ is generated. However, the replication transaction 32 ′ is not immediately sent to the remote servers 14 , 16 , 18 . Rather, the data replication component 30 initially waits for an indication that the transaction 32 has been backed up at the secondary server 22 of the central database 12 before sending it to the remote servers 14 , 16 , 18 .
Specifically, in the embodiment of FIG. 1 the highly available data replication component 26 transfers recent log records of the primary server 20 , including a log record of the row insertion transaction 32 , to the secondary server 22 . At the secondary server 22 , the transferred log records are applied and logged, including a row insertion transaction 32 ″ that mirrors the row insertion transaction 32 which was performed at the primary server 20 . The secondary server 22 generates an acknowledgment indicating that the row insertion transaction 32 ″ is applied and logged.
In response to this acknowledgment, the highly available data replication component 26 produces a mirror acknowledgment 34 indicating that the transaction 32 of the primary server 20 is mirrored at the secondary server 22 . Responsive to the mirror acknowledgment 34 , the data replication component 30 begins sending the replication transaction 32 ′ to the remote servers 14 , 16 , 18 .
With continuing reference to FIG. 1 and with further reference to FIG. 2 , a significant advantage of delaying transmission of the replication transaction 32 ′ to the remote servers 14 , 16 , 18 until receipt of the mirror acknowledgment 34 is described. In FIG. 2 , the primary server 20 of the central database 12 is shown by its absence in FIG. 2 as having failed after the transaction 32 ′ has been transmitted to the remote server 14 , but before the transaction 32 ′ has been transmitted to the remote servers 16 , 18 . Because the data replication component 30 delayed sending the transaction 32 ′ until after receipt of the mirror acknowledgment 34 , it is assured that the transaction 32 is mirrored at the secondary server 22 by the mirror transaction 32 ″ before the replication transaction is distributed. Moreover, the replication transaction 32 ′ remains queued for sending at the data replication component 30 , which continues to forward the replication transaction 32 ′ to the remaining remote servers 16 , 18 so that all remote servers 14 , 16 , 18 scheduled for receipt of the replication transaction 32 ′ actually receive the transaction. As a result, there are no data inconsistencies between the central database server 12 and the remote servers 14 , 16 , 18 .
In contrast, in a conventional arrangement in which there are no delays, replication transactions are transmitted as soon as they are reconstructed. As a result, none, some, or all of the remote servers may or may not receive the replication transaction in the event of a failure of the central database primary server. Furthermore, the transaction being replicated may or may not have been copied to the secondary server prior to failover. Thus, data inconsistencies may result between the remote servers, and between remote servers and the central database server, in the event of a failure of the central database primary server.
In addition to the highly available data replication component 26 providing the synchronizing mirror acknowledgment 34 , to ensure data consistency in the event of a failover recovery, the data replicator 30 preferably generates transaction replication threads that communicate only with the primary server 20 , and not with the secondary server 22 . In its preferred form, this is accomplished during replication thread generation by checking whether a server of the replication thread is acting as a secondary server of a highly available data replication component. If it is, then the thread is canceled or a suitable error indicator generated. Preferably, the distributed database 10 is configured so that the central server 12 appears as a single logical entity to the data replicator 30 .
With continuing reference to FIG. 1 and with further reference to FIG. 3 , the preferred data replication method 40 executed by the relational database system 10 is described. A transaction 42 occurs on the primary server 20 of the central database 12 . The data replicator 30 monitors, or snoops 44 , the log files of the primary server 20 and identifies a log record corresponding to the transaction 42 . The data replicator 30 reconstructs 46 the transaction 42 based on the identified transaction log record to generate a replication transaction that is placed in a send queue 48 . However, the replication transaction is not immediately sent.
The highly available data replication component 26 also processes the transaction 42 , by shipping 52 log files including a log of the transaction 42 to the secondary server 22 . The transaction logs are applied and logged 54 at the secondary server 22 , and the secondary sever 22 transmits 56 an acknowledgment 60 to the primary server 20 .
Responsive to the acknowledgment 60 , a transmit gate 62 transmits the corresponding replication transaction in the send queue 48 to the remote servers 14 , 16 , 18 . Each remote server receives, applies, and logs the replication transaction, and generates a replication acknowledgment 64 . Responsive to the replication acknowledgment 64 , the data replicator 30 clears 66 the corresponding replication transaction from the send queue 48 .
With reference to FIG. 4 , the preferred configuration of the highly available data replication component 26 is described. The component 26 generates a gating signal for synchronizing the data replicator 30 with the highly available data replication component 26 . The primary server 20 maintains a primary server log file 70 . Recent transactions are stored in a primary server log buffer 72 . The contents of the log buffer 72 are from time to time flushed and written to the primary server log file 70 which is stored on a magnetic disk or other non-volatile storage.
As log records are transferred from the primary server log buffer 72 to the primary server log file 70 , the buffered log records are also copied to a primary-side buffer 74 of the highly available data replication component 26 . From time to time, the contents of the primary side-buffer 74 are transmitted to the secondary server 22 and temporarily stored in a secondary-side buffer 80 of the highly available data replication component 26 . A secondary server-side apply component 82 applies the logged transactions to the mirror database on the secondary server 22 and logs the applied transactions in a secondary server log file 84 which is stored on a magnetic disk or other non-volatile storage. After the transactions are applied and logged at the secondary server 22 , an acknowledgment is transmitted to the primary server 20 and a control structure 86 of the highly available data replication component 26 is updated with a most recent log position of the primary server log file 70 to be backed up at the secondary server 22 .
An example of operation of the primary server log buffer 72 is illustrated in FIG. 4 . The state of the buffer reflected in that FIGURE shows that the most recent log records 10 – 13 are stored. Prior log records 6 – 9 have been flushed from the primary server log buffer 72 , written to the primary server log file 70 , and copied to the primary-side buffer 74 of the highly available data replication (HDR) component 26 . The log records 6 – 9 are transferred to the secondary-side buffer 80 of the highly available data replication component 26 , applied at the secondary server 22 and logged in the secondary server log file 84 .
An acknowledgment is transmitted back to the primary server 20 , and the control structure 86 of the highly available data replication component 26 is updated to indicate that the most recently acknowledged back up is the log position 9 of the primary server 20 . This indication is communicated to the send queue 48 of the data replicator 30 as a gating signal to commence transmission of corresponding queued replication transactions up to and including the primary log position 9 to target servers.
With reference again to FIGS. 1 and 3 , a problem can arise if the transaction 42 is a replication transaction supplied to the central server 12 by the data replicator 30 . If the method 40 of FIG. 3 operates in unmodified form on a replication transaction applied to the primary server 20 , the replication acknowledgment 64 is sent immediately after the replication transaction is applied and logged at the primary server 20 , and the clear operation 66 clears the send queue 48 of the replication transaction. If the primary server 20 fails after the send queue 48 is cleared but before the highly available data replication component 26 copies the transaction to the secondary server 22 , then the transaction never reaches the secondary server 22 , and a data inconsistency can result.
With returning reference to FIGS. 1 and 3 , and with further reference to FIG. 5 , a modification to the method 40 of FIG. 3 is preferably included when the transaction 42 is a replication transaction supplied to the central server 12 by the data replicator 30 . The data replication is applied and logged 90 at the primary server 20 . However, rather than sending the data replication acknowledgment 64 without delay as shown in FIG. 3 , the replication acknowledgment is instead stored 92 in a posted data replication acknowledgment list 94 . The posted acknowledgment is associated with the current log position of the primary server log, and is referred to herein as a posted log position.
The posted log position is processed by a designated post monitor computation thread 100 of the data replicator 30 . The post monitor computation thread 100 is selectively executed as new posted log positions are added to the posted data replication acknowledgment list 94 . The thread 100 is also executed at regular intervals, preferably about once every second. The most recent primary log position backed up by the highly available data replication component 26 is retrieved 102 , for example by reading the control structure 86 shown in FIG. 4 , and is compared 104 with the posted log position stored in the posted data replication acknowledgment list 94 . If the most recently backed up primary log position is more recent than the posted log position, then a send control 106 sends the replication acknowledgment 64 to the queue clear operation 66 of the method 40 .
If, however, the posted log position is more recent than the most recently backed up primary log position, this could indicate that the highly available data replication component 26 has stalled or otherwise malfunctioned, and is not mirroring recent transactions. The post monitor computation thread 100 preferably verifies that the highly available data replication component 26 is functioning properly by creating 110 a dummy transaction that is applied at the primary server 20 , and forcing a flushing 112 of the primary log buffer 72 . The post monitor computation thread 100 then checks 114 whether the backup log is advancing, for example by monitoring the control structure 86 shown in FIG. 4 . If it appears that the current log position at the primary server 20 is advancing but the highly available data replication component 26 is stalled, then a suitable alert is posted 116 .
The processing modification shown in FIG. 5 is also applicable to synchronization during advancement of the replay position. Since the replay position can be advanced as a result of spooling the in-memory replicated transaction stored in the primary log buffer 72 to disk, it should be assured that the logs of the transaction that copied the in-memory transaction to disk have been successfully shipped to the secondary server 22 . Otherwise, the transaction could be lost in the event of a fail-over recovery such as that illustrated in FIG. 2 .
In the embodiment described above with reference to FIGS. 1–5 , the distributed database system 10 includes the highly available data replication component 26 that transfers log records of the central database primary server 20 to the secondary server 22 , and also includes the logical data replicator 30 . However, those skilled in the art can readily adapt the described embodiment for synchronizing other or additional types of logical data replicators with other or additional highly available data replication components.
For example, a highly available data replication component communicating with a corresponding secondary server (components not shown) can be included in one or more of the remote servers 14 , 16 , 18 of the database system 10 to provide a hot backup for that remote server. In such an arrangement, the highly available data replication component associated with the remote server suitably provides an acknowledgment signal to the data replicator 30 , and the data replicator 30 suitably delays sending replication transactions originating at the mirrored remote server until the corresponding acknowledgment signal is sent. The data replicator 30 does not communicate directly with the secondary of the remote server, and preferably the remote server and its secondary server appear as a single logical unit to the data replicator 30 .
With reference to FIG. 6 , another distributed database system 120 has a tree topology. Unlike the spokes-and-hub topology of the distributed database system 10 , the topology of the distributed database system 120 has more than one critical node. Specifically, the exemplary distributed database system 120 has three critical server nodes 122 , 124 , 126 , along with end-user server nodes 130 , 132 , 134 , 136 . To ensure high availability in the event of a failure of a critical node, each critical server node 122 , 124 , 126 preferably includes a highly available data replication (HDR) pair.
Thus, the critical server node 122 includes a primary server 140 and a secondary server 142 that is maintained as a hot backup by an HDR component 144 . The HDR component 144 is preferably substantially similar to the highly available data replication component 26 described previously with reference to the relational database system 10 . In particular, the HDR component 144 includes a mirror acknowledgment pathway 146 from the secondary server 142 to the primary server 140 which indicates that a transaction or other critical object has been applied or backed up at the secondary server 142 . Similarly, the critical server node 124 includes primary and secondary servers 150 , 152 , with the secondary server 152 maintained as a hot backup by an HDR component 154 that includes a mirror acknowledgment pathway 156 . The critical server node 126 includes primary and secondary servers 160 , 162 , with the secondary server 162 maintained as a hot backup by an HDR component 164 that includes a mirror acknowledgment pathway 166 .
Data replication links 170 between nodes provide selected asynchronous data replication. Similarly to the HDR/logical data replication arrangement of the distributed database system 10 , a logical data replication of a transaction or other critical object sourced at one of the critical nodes 122 , 124 , 126 is queued until the corresponding mirror acknowledgment pathway 146 , 156 , 166 returns an acknowledgment verifying that the transaction or other critical object has been applied at the secondary server 142 , 152 , 162 . Once the mirror acknowledgment is received, the asynchronous data replication link 170 processes the transaction or other critical object to replicate the transaction or other critical object at selected servers.
Moreover, the data replication links 170 communicate with the critical nodes 122 , 124 , 126 as single logical entities, preferably by communication with the primary server 140 , 150 , 160 of each respective critical node 122 , 124 , 126 . The data replication links 170 preferably do not communicate with the secondary servers 142 , 152 , 162 as logical entities distinct from the respective critical nodes 122 , 124 , 126 .
In the tree topology employed in the distributed database system 120 , replication traffic may traverse critical nodes during transfer from a source to a destination. For example, if a transaction applied at the server 130 is to be replicated at the server 134 , the corresponding transaction replication traverses the critical server node 124 , the critical server node 122 , and the critical server node 126 en route to the final destination server 134 . At each intermediate critical node 124 , 122 , 126 , the transaction is a critical object which is backed up at the corresponding secondary server 152 , 142 , 162 . At each intermediate critical node 124 , 122 , 126 , the logical replication via one of the logical replication links 170 to the next node in the transmission chain is queued until acknowledgment of the backup at that intermediate node is received.
The tree topology of the distributed database system 120 is exemplary only. Additional branches, critical nodes, and end-user servers are readily included. One or more of the critical nodes can also be used for end-user access. Other topologies that include multiple critical nodes can be similarly configured to ensure high data availability at each critical node. Generally, to provide robust failover for any critical node that includes highly available data replication (HDR), each critical object applied to that critical node is applied on the secondary server of the HDR pair before the critical object is processed by the logical data replication system.
In the exemplary embodiments of FIGS. 1–6 the nodes referred to as critical nodes, namely the nodes 12 , 122 , 124 , 126 , are those nodes that provide the hub or branch interconnections of the distributed database network. Failure of one of these interconnection nodes impacts more than just the failed node, and so HDR backup protection is typically desirable for such interconnection nodes. However, in general a critical node includes any node which the user views as sufficiently important or critical to justify providing HDR protection for that node. Hence, a particularly important end-node (such as one or more of the end-nodes 14 , 16 , 18 , 130 , 132 , 134 , 136 ) is optionally included as a critical node and provided with HDR protection. Similarly, although in the preferred embodiments each interconnection node is provided with HDR protection, HDR protection is optionally omitted from one or more interconnection nodes at the user's discretion.
The invention has been described with reference to the preferred embodiments. Obviously, modifications and alterations will occur to others upon reading and understanding the preceding detailed description. It is intended that the invention be construed as including all such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
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In a database apparatus ( 10 ), a critical database server ( 12 ) includes a primary server ( 20 ) supporting a primary database instance and a secondary server ( 22 ) supporting a secondary database instance that mirrors the primary database instance. The secondary server ( 22 ) generates an acknowledgment signal ( 60 ) indicating that a selected critical database transaction ( 42 ) is mirrored at the secondary database instance. A plurality of other servers ( 14, 16, 18 ) each support a database. A data replicator ( 30 ) communicates with the critical database server ( 12 ) and the other servers ( 14, 16, 18 ) to replicate the selected critical database transaction ( 42 ) on at least one of said plurality of other servers ( 14, 16, 18 ) responsive to the acknowledgment signal ( 60 ).
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The disclosed invention pertains to heat extractors in general and more particularly to those having controlled means of supplying air to the combustion chamber.
2. Description of the Prior Art
Numerous devices exist in the prior art for extracting heat from a firebox. All are aimed at recovering heat that would otherwise be lost by passage up the chimney.
Many consist of grate-like structures upon which material is burned and air is circulated by convection. Others run tubes through the coals and burning material and blow air through the tubes. Both such devices risk the danger of burn out with the result that noxious gases can escape into the room.
Still others are built after the manner of the circulating fireplace wherein an air path is constructed behind the brick lining of the fireplace and air is circulated therein, picking heat up from the warm bricks.
SUMMARY OF THE INVENTION
The invention is directed to improvements in recovering otherwise wasted heat from the combustion chamber of a stove or fireplace.
A principal object of the invention is to provide a means of circulating room air through a heat extractor which also supplies air to the combustion chamber in a controlled manner.
A further object of the invention is to provide a means of supplying air to the combustion chamber from a source outside the room in which the heater is located.
Throughout the following description the further objects and advantages of the invention will become apparent to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the extractor showing it installed in a stove. The stove is shown in phantom.
FIG. 2 is a perspective view of a portion of the heat extractor showing an alternative construction of the means of controlling and supplying air to the combustion chamber.
FIG. 3 shows a manual device for controlling the combustion chamber air supply.
FIG. 4 is a sectional view taken along line 4--4 of FIG. 1.
FIG. 5 shows an alternative construction to that shown in FIG. 4.
FIG. 6 shows a perspective view of an alternative construction for a combustion chamber air supply wherein the air is brought in from outside the room where the heater is located. The figure is partially broken away to more clearly reveal the details.
FIG. 7 is a plan view taken through section 7--7 of the air intake port shown in FIG. 8. The view is broken away to more clearly show the details.
FIG. 8 is a side elevational view of the stove and the air supply system shown in FIG. 6. The heat extractor is also shown.
DETAILED DESCRIPTION
Referring now to the drawings, a stove is shown having a body 1. Within the body 1 is a combustion chamber 3. The stove rests on a plurality of legs 5 and has a pipe outlet 7 at the top of body 1. The combustion chamber 3 has a floor 9, sides 11, back wall 13 and top 15. The front or mouth of the combustion chamber defines an opening through which fuel is inserted into the stove. The opening is closed off by structural elements to be described later.
A heat extraction unit is contained within the combustion chamber 3. The extraction unit is comprised of an air intake manifold 17, a lower air passageway 19 and an upper air passageway 21 which terminates in an air exit port 23 which is covered by a screen 25. The extractor is so shaped that it lies against the sidewall 11 and back wall 13 of combustion chamber 3. Both manifold 17 and exit port 23 are located outside body 1 of the stove. The intake manifold is operatively connected to an air circulating fan 27. The fan 27 is equipped with a control switch 29, a thermostat 31 and is connected to a source of electrical power by cord 33.
A combustion chamber air supply tube 35 is connected to the lower air passageway 19. Tube 35 is preferably of flexible steel construction operatively connected to a manifold 37 which has a plurality of air ducts 39 branching therefrom.
In one construction the manifold 37 lies on the floor 9 and has a horn-like throat 41 into which protrudes tube 35. The diameter of manifold 37 increases with distance from throat 41, as shown in FIG. 1. However, tube 35 is not directly connected to throat 41 and air from within the combustion chamber may be drawn into manifold 37 as well as being blown in through tube 35. This construction is analagous to a jet pipe. FIG. 4 illustrates the arrangement of the parts.
In the construction shown in FIG. 5 the tube 35 is connected to manifold 37 to form a venturi.
In the construction of FIG. 2 tube 35 is connected to a housing 43 having a blade-like valve 45 contained therein. The valve 45 is positioned by automatic control 47 which is attached to air temperature sensor 49 located in upper air passageway 21. Manifold 37 is operatively connected to housing 43.
In FIG. 3 tube 35 is connected to housing 43 as is manifold 37. However, the valve 45 within the housing 43 is manually positioned by handle 48.
On the front of the combustion chamber 3 is mounted a set of glass doors 50 and spacers (not shown) which, when closed, seal off the opening of the combustion chamber from the room where the stove is located.
In an alternate construction as shown in FIGS. 6, 7 and 8 an external air supply duct is interposed between the opening of combustion chamber 3 and doors 50. The duct brings air from a source outside the room in which the stove is contained. The duct is comprised of a tubular conduit, shown as having a rectangular cross section 51, and having an air intake port 53 in one end. The mouth of port 53 is covered with screen 55. At its other end conduit 51 joins a rectangular manifold 57 containing a series of air exit ports 59. These air exit ports are located in several places on the inner periphery of the rectangular manifold 57. The inside surface 61 of manifold 57 mates with the opening of combustion chamber 3 and doors 49 mounted to the outside surface 63 of manifold 57. Air ducts 39 may be optionally fitted to an air exit port 55 near the combustion chamber floor to direct air into fuel burning in chamber 3. Air conduit 51 has a large hole 65 cut in its underside 67. This hole is closed with a rectangular plate 69 upon which is mounted intake port 53. Because plate 69 is rectangular, it can be positioned so that intake port 53 will fall at several different locations to that it will miss an interfering floor joist 70 under the room containing the stove. An upwardly protruding lip surrounds the opening of air intake port 53 and defines a spark guard 71.
OPERATION
The operation of the invention is as follows. A fire is built within combustion chamber 3 and the doors 49 are closed, sealing the opening of chamber 3 from the room. Fan 27 is turned on with switch 29. Air is pulled into intake manifold 17 and forced through lower air passageway 19 where it picks up heat as it moves into upper air passageway 21 to be further heated before passing out into the room via air exit port 23. Depending on the volume of air circulated through passageways 19 and 21, air may be raised to temperatures as high as 500° or more.
As air is blown into passage 19 by fan 27 to be heated, some of it is forced into air supply tube 35 and is routed via manifold 37 and ducts 39 to the burning fuel.
In the construction as shown in FIGS. 1 and 4 air is blown from tube 35 into throat 41 and manifold 37 where the air is fed to the burning material via ducts 39. This action will draw air into manifold 37 from the combustion chamber 3. This combustion chamber air contains carbon monoxide which mixes with the fresh air from tube 35 and is chemically altered, thus materially reducing pollution in the flue gases.
In the construction of FIG. 5 the venturi configuration formed by joining tube 35 to manifold 37 as shown increases the air speed but lowers its pressure so that the air fed to the burning fuel does not materially disturb the hot ashes within combustion chamber 3. This arrangement of tube 35 and manifold 37 to form a venturi makes up a forced draft which branches off air passage 19 and assures that an adequate supply of air will always be available within the chamber 3.
In the construction of FIG. 2 air entering manifold 37 is controlled by the position of butterfly valve 45 which is positioned from full open to completely closed by the automatic control 47. Control 47 senses the air temperature in upper passage 21 through sensor 49. Control 47 can be optionally set to shut off air to combustion chamber 3 at any required temperature. Thus, the air supply to the fire can be shut off and the fire will die down. This will result in cooler air in passage 21. The sensor 49 will detect the cooling and the automatic control 47 will open valve 45 to admit air. The fire will then burn more intensely. This will raise the air temperature in passage 21 until sensor 49 again determines that the air has reached the predetermined temperature. Control 47 will then respond and close off air via valve 45.
In the construction of FIG. 3 the valve 45 is manually postioned with handle 48 and must be repositioned if more or less air to the combustion chamber 3 is desired.
In the alternate construction shown in FIGS. 6, 7 and 8, the means for circulating room air and heating it is as described above through passages 19 and 21 except that air is supplied to the combustion chamber and burning fuel as follows. The natural draft of the stove draws outside air through intake port 53 into conduit 51. The conduit 51 lies on the floor of the room and passes under the body 1 of the stove. Intake port 53 protrudes through the floor to draw air from a source other than the room where the stove is located. Rectangular plate 69 which carries port 53 may be positioned in several orientations to avoid floor joists 70. Spark guard 71 surrounds the upper end of port 53 and prevents hot sparks from escaping out of the conduit 51.
The incoming air passes into manifold 57 and through multiple air exit ports 59 into combustion chamber 3. Ducts 39 direct the air into the burning fuel. This structure supplies air from a source outside the room which contains the stove.
Having described the preferred embodiment of our invention and its operation in detail, it will be apparent to those skilled in the art that many modifications could be made without departing from the true spirit and scope of the invention. We claim all such modifications as fall within the scope of the appended claims.
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A heat extractor for stoves or other type heaters is disclosed. The extractor is mounted in the firebox. The extractor takes air from the room and circulates it through a closed air path in the firebox where it is heated to a high temperature and returned to the room. Air from the extractor is also supplied to the combustion chamber in a controlled manner so that the rate of fuel burning is affected. Alternative methods of supplying and controlling air to the combustion chamber are disclosed.
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CROSS-REFERENCE TO RELATED APPLICATION
This is a continuation in part of application Ser. No. 777,471 filed Sept 18, 1985, abandoned.
BACKGROUND OF THE INVENTION
This invention relates to substituted bridged-diazabicycloalkyl quinolone carboxylic acids and acid derivatives thereof, antibacterial compositions containing said compounds, and a method of using said compounds.
Since the introduction of nalidixic acid, 1,4-dihydro-1-ethyl-4-oxo-7-methyl-1,8-naphthyridine-3carboxyl acid, in 1963, a considerable number of patents and scientific papers have been published on compounds having a related structure.
For instance, Australian Patent No. 107300 discloses compounds of the formula ##STR2## wherein X may be CF or CH, R may be lower alkyl and Z may be a heterocyclic group such as 1-pyrrolidinyl or a spiro group such as 2,7-diazaspiro[4,4]non-2-yl.
Japanese Patent No. 056219 discloses norfloxacin, 1-ethyl-6-fluoro-1,4-dihydro-7-piperazino-4-oxo-quinoline-3-carboxylic acid, European patent publication 78362 discloses ciprofloxacin, 1-cyclopropyl-1,4-dihydro-4-oxo-6-fluoro-7-piperazinoquinoline-3-carboxylic acid, and European patent publication 47005 discloses similar piperazinoquinolines wherein a third ring connects the positions 1 and 8 of the quinolone group. Diazabicycloalkane hydroquinoline and benzoxazine carboxylic acids are disclosed in Japanese Patent Publications 59219293, 59204194, 59204195, 59137481, 60023381 and 60023382.
The above references all disclose antibacterial activity for their compounds.
SUMMARY OF THE INVENTION
In accordance with the invention, antibacterial compounds are provided having the formula I: ##STR3## or a pharmaceutically acceptable acid addition salt thereof, wherein R 1 is hydrogen, a pharmaceutically acceptable cation, or (C 1 -C 6 )alkyl;
A is CH, CF, CCl or N;
Y is (C 1 -C 3 )alkyl, (C 1 -C 3 )haloalkyl, cyclopropyl, vinyl, methoxy, N-methylamino, p-fluorophenyl, p-hydroxyphenyl or p-aminophenyl; or
A is carbon and is taken together with Y and the carbon and nitrogen to which A and Y are attached to form a five or six membered ring which may contain O, and which may have attached thereto R' which is methyl or methylene; and
R 2 is a bridged-diazabicycloalkyl substituent selected from the group consisting of ##STR4## wherein n is 1, 2 or 3;
m is 1 or 2;
p is 0 or 1; and
Q is hydrogen, (C 1 -C 3 )alkyl, (C 1 -C 6 )alkyl-carbonyl or (C 1 -C 6 )alkoxy carbamoyl.
The compounds of the invention include tricyclic compounds wherein A is carbon and A and Y are taken together with the carbon and nitrogen to which they are respectively attached to form a five or six membered ring which may contain oxygen. The oxygen may be present at any available position in the ring but is preferably attached to A. The tricyclic compounds of formula I wherein R' is methylene preferably have the methylene group on the carbon attached to the quinoline nitrogen atom. Preferably, compounds (I) wherein A and Y are taken together have the formula: ##STR5## wherein X is CH 2 or O, q is 0 or 1 and Z is CH 2 , CH(CH 3 ) or C═CH 2 .
Preferred compounds of the invention are those of formula I wherein R 1 is hydrogen or a pharmaceutically acceptable cation such as sodium or potassium.
Other preferred compounds (I) are those wherein Y is ethyl.
Specific preferred compounds are as follows:
1-ethyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid,
1-ethyl-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2.]non-4-yl)-4-oxo-3-quinoline carboxylic acid,
1-vinyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid,
1-vinyl-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2.]non-4-oxo-3-quinoline carboxylic acid,
10-(1,4-diazabicyclo[3.2.2]non-4-yl)-9-fluoro-3-methyl-7-oxo-2,3-dihydro(7H)-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid,
1-cyclopropyl-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid,
1-(2-fluoroethyl)-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid,
1-cyclopropyl-6-fluoro-1,4-dihydro-7-(2,5-diazabicyclo[2.2.1]hept-2-yl)-4-oxo-3-quinoline carboxylic acid,
1-cyclopropyl-6-fluoro-1,4-dihydro-6-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid,
1-ethyl-6,8-difluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid,
1-(4-fluorophenyl)-6-fluoro-1,4-dihydro-7-(1,4diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid,
1-methylamino-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid,
1-(2-fluoroethyl)-6,8-difluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid, and
1-ethyl-6-fluoro-1,4-dihydro-7-(2,5-diazabicyclo[2.2.1]hept-2-yl)-4-oxo-3-quinoline carboxylic acid.
In one embodiment, the compounds of the invention have the following formula: ##STR6## or a pharmaceutically acceptable acid addtion salt thereof, wherein R 3 is hydrogen, a pharmaceutically acceptable cation, or (C 1 -C 6 )alkyl;
A is CH, CF, CCl or N;
Y 1 is methoxy, N-methylamino, p-fluorophenyl, p-hydroxyphenyl or p-aminophenyl; or
A is carbon and is taken together with Y and the carbon and nitrogen to which A and Y are attached to form a six membered ring which may contain oxygen, and which may have attached thereto R' which is methyl or methylene, and
R 4 is a bridged-diazabicycloalkyl substituent selected from the group consisting of ##STR7## wherein m is 1 of 2;
n is 2 or 3; and
Q is hydrogen, (C 1 -C 3 )alkyl, (C 1 -C 6 )alkoxy-carbonyl or (C 1 -C 6 )alkyl-carbamoyl.
Preferred compounds within this embodiment have the formula IA wherein R 3 is hydrogen, A is CH, CF, or N, and Y 1 is methoxy, N-methylamino, p-fluorophenyl, p-hydroxyphenyl or p-amininophenyl.
Other preferred compounds have the formula ##STR8## wherein X 1 is CH 2 or O, and Z 1 is CH 2 , or C═CH 2 .
The above two preferred classes of compounds may have a group R 4 which is selected from 8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl; 1,4-diazabicyclo[3.2.2]non-4-yl; 9-methyl-3,9-diazabicyclo[4.2.1]non-3-yl; 3,9-diazabicyclo[4.2.1]non-3-yl; 2,5-diazabicyclo[2.2.1]hept-2-yl; 9-methyl-3-,9-diazabicyclo[3.3.1]-non-3-yl; 2,5-diazabicyclo[2.2.1]hept-2-yl; 5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl; 1,4-diazabicyclo[3.3.1]non-4-yl; 5-methyl-2,5-diazabicyclo[2.2.2]oct-2-yl; and 2,5-diazabicyclo[2.2.2]oct-2-yl.
Specific preferred compounds are 1-methoxy-6-fluoro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-methoxy-6-fluoro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-1,4-dihydro-4-oxo-3-quinolone carboxylic acid, 1-methoxy-6-fluoro-7-(2,5-diazabicyclo[2.2.1]hept-2-yl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-methoxy-6-fluoro-7-(5-methyl-2,5-diazabicyclo[2.2.1]-hept-2-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-methoxy-6-fluoro-7-(1,4-diazabicyclo[3.3.1]-non-4-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-methoxy-6-fluoro-7-(5-methyl-2,5-diazabicyclo[2.2.2]oct-2-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-methoxy-6-fluoro-7-(2,5-diazabicyclo[2.2.2]oct-2-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-(p-fluorophenyl)-6-fluoro-7-(1,4-diazabicyclo[3.3.2]non-4-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-(p-fluorophenyl)-6-fluoro-7-(5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-(p-fluorophenyl)-6-fluoro-7-(1,4-diazabicyclo[3.3.1]non-4-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-(p-fluorophenyl)-6-fluoro-7-(5-methyl-2,-5-diazabicyclo[2.2.2]oct-2-yl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-(p-fluorophenyl)-6-fluoro-7-(2,5-diazabicyclo[2.2.2]oct-2-yl)1,4-dihydro-4-oxo-3-quinoline carobyxlic acid, 1-methylamino-6-fluoro-7(1,4-diazabiyclo[3.2.2]non-4-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1-methylamino-6-fluoro-7(5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl)-1,4-di-hydro-4-oxo-3-quinoline carboxylic acid, 1-methylamino-6-fluoro-7-(1,4-diazabicyclo[3.3.1]non-4-yl)-1-1,4-dihydro- 4-oxo-3-quinoline carboxylic acid, 1-methylamino-6-fluoro-6-(5-methyl-2,5-diazabicyclo[2.2.2]oct-2-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid, 1 -methylamino-6-fluoro-7-(2,5diazabicyclo[2,2,2]oct-2-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid.
In another embodiment, the compounds of the invention have the formula: ##STR9## or a pharmaceutically acceptable acid addition salt thereof, wherein R 5 is hydrogen, a pharmaceutically acceptable cation, or (C 1 -C 6 )alkyl; A is CH, CF, CCl or N; Y 2 is (C 1 -C 3 )alkyl, (C 1 -C 3 )haloalkyl, cyclopropyl or vinyl; or A is carbon and is taken together with Y 2 and the carbon and nitrogen to which A and Y 2 are attached to form a six-membered ring which may contain oxygen and which may have attached thereto R' which is methyl or methylene; and R 6 is a bridged-diazabicycloalkyl substituent selected from the group consisting of 1,4-diazabicyclo[3.2.2]non-4-yl, 1,4-diazabicyclo[3.3.1]non-4-yl, 1,4-diazabicyclo[4.2.2]dec-4-yl, ##STR10## wherein Q is hydrogen, (C 1 -C 3 )alkyl, (C 1 -C 6 )alkylcarbonyl or (C 1 -C 6 -)alkylcarbamoyl. In a specific embodiment, R 5 is hydrogen. Specific compounds of formula IB are 1-ethyl-6-fluoro-1,4-dihydro-7-(1,4diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline-carboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7-(1,4diazabicyclo[3.3.1]non-4-yl)-4-oxo-3-quinoline-carboxylic acid, 1-ethyl-6,8-difluoro-1,4-dihydro-7(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline-carboxylic acid, 1-vinyl-6-fluoro-1,4-dihydro-7(1,4-diazabicyclo[3.3.1.]non-4-yl)-4-oxo-3-quinoline-carboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(9-methyl-3,9-diazabicyclo[4.2.1]non-3-yl)-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid, and 10-(1,4diazabicyclo[3.2.2]non-4-yl)-9-fluoro-3-methyl-7-oxo-2,3-dihydro-(7H)-pyrido[1,2,3-de]-1,4-benzoxazine-6-carboxylic acid.
In yet another embodiment, the compounds of the invention have the following formula: ##STR11## or a pharmaceutically acceptable acid addition salt thereof, wherein R 7 is hydrogen, a pharmaceutically acceptable cation, or (C 1 -C 6 )alkyl; Y 3 is (C 1 -C 3 )alkyl or cyclopropyl; and R 8 is 3,8-diazabicyclo[3.2.1]oct-3-yl, 8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl, (1S,4S)-2,5-diazabicyclo[2.2.1]hept-2-yl, (1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl, 2,5-diazabicyclo[2.2.2]oct-2-yl, or 5-methyl-2,5diazabicyclo[2.2.2]oct-2-yl. In more specific embodiments, R 7 is hydrogen and/or Y 3 is ethyl or cyclopropyl. Preferred compounds are 1-ethyl-6-fluoro-1,4-dihydro-7-[(1S,4S)-5-methyl-2,5-diazabicyclo[2.2.1]hept-2-yl]-4-oxo-3-quinoline carboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7-(5-methyl-2,5diazabicyclo[2.2.2]oct-2-yl)-4-oxo-3-quinoline carboxylic acid, 1-ethyl-6-fluoro-1,4-dihydro-7-(3,8-diazabicyclo[ 3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7-[(1S,4S)-2,5-diazabicyclo[2.2.1]hept-2-yl]-4-oxo-3-quinoline carboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7-[(1S,4S)-5-methyl-2,5-diazabicyclo-[2.2.1]hept-2-yl]-4-oxo-3-quinoline carboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(2,5-diazabicyclo[2.2.2]oct-2-yl)-4-oxo-3-quinoline carboxylic acid, 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(5-methyl-2,5-diazabicyclo[2.2.2]oct-2-yl)-4-oxo-3-quinoline carboxylic acid, and 1-cyclopropyl-6-fluoro-1,4-dihydro-7-(3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid.
The compounds of the invention may have chiral centers in view of the bridged structures resulting in formation of stereoisomers. Compounds (I) wherein R 2 is c have a chiral center at the carbon atom in the bridge alpha to the nitrogen atom. Compounds (I) wherein R 2 is d have a chiral center at the carbon atom which is alpha to the nitrogen atom linking R 2 to the quinolone group. These steroisomers may be designated with reference to R and S rotation in accordance with standard nomenclature. The comounds of the invention include racemic mixtures and optical isomers.
The invention includes pharmaceutical compositions comprising a pharmaceutically acceptable carrier or diluent and a compound of the formulae I, IA, IB or IC in an antibacterially effective amount. The pharmaceutical compositions preferably contain the above specific, preferred, and specific preferred compounds.
The invention yet further provides a method of treating an animal, including a human being, having a bacterial disease which comprises administering to the animal an antibacterially effective amount of a compound of the formula I, IA, IB or IC or a pharmaceutical composition as defined above.
DETAILED DESCRIPTION OF THE INVENTION
The compounds (I) of the invention may be prepared by reacting a compound of the formula II: ##STR12## with a compound of the formula R 2 H or derivatives thereof wherein R 1 , R 2 , A, and Y are as defined above in connection with formula I, and Hal is halogen such as fluoro, chloro or bromo
The reaction may be performed with or without a solvent, preferably at elevated temperature, and for a time sufficient to substantially complete the reaction The reaction is preferably carried out in the presence of an acid acceptor such as an inorganic or organic base, e.g. an alkali metal or alkaline earth metal carbonate or bicarbonate or a tertiary amine such as triethylamine, pyridine or picoline.
The solvents for this reaction are solvents which are non-reactive under the reaction conditions such as acetonitrile, tetrahydrofuran, ethanol, chloroform, dimethylsulfoxide (DMSO), dimethylformamide, pyridine, water, or mixtures thereof.
The reaction temperature usually ranges from about 20° C. to about 150° C.
The starting materials of formula II are known in the art, e.g. as disclosed in Australian Patent 107300, and U.S. Pat. Nos. 4,382,892 and 4,416,884.
The starting materials of formula R 2 H have the following more specific formulae ##STR13## wherein Q, m, n and p are as defined above.
The compounds of formulas III to VII are either known or may be made by methods analogous to those described in the prior art from known starting materials.
Compound (III) wherein m and n are each one and Q is methyl is prepared according to Reaction Scheme I from glutaric acid. First, dibromoglutarate diethylester is formed by treatment of glutaric acid with thionyl chloride, removal of excess reagent, treatment with bromine and quenching with excess ethanol in accordance with the method described in Org. Syn., Coll. Vol. III, 623 (1955). The dibromodiester is reacted with anhydrous methylamine in a sealed autoclave at 90° C. in toluene to give aminoester 3 in accordance with U.S. Pat. No. 3,947,445. Monobenzamide 4 (Ph is phenyl) is obtained by reaction with benzylamine in refluxing xylenes. Cyclization to imide 5 is by heating to 200°-210° C. for about 48 hours. The 7-benzyl derivative of compound III wherein m and n are each one is obtained on reduction with sodium bis(2-methoxyethoxy)aluminum hydride (Red-Al). Catalytic debenzylation with palladium on carbon in acidic methanol affords the desired product
Compound (I) wherein R 2 is derived from compound (III) wherein n and m are one and Q is hydrogen may be obtained by the sequence described in Reaction Scheme II starting with the dibromodiester 2 of Scheme I.
The diester 2 is reacted with benzylamine (3 equivalents) in refluxing toluene to give N-benzyl-2,4-dicarboethoxy azetidine 7. After catalytic removal of the benzyl group, e.g. with 10% Pd-carbon (Pd/C) catalyst to 8, benzamide 9 is formed on reaction with about one equivalent of benzylamine and cyclized to imide 10 by heating to about 200°-210° C. for about 48 hours. After reduction with Red-Al to compound 11, reaction with ethylchloroformate provides carbamate 12 which is debenzylated by catalytic hydrogenation with 10% Pd-C to 13. Intermediate 13 is reacted with compound (II) wherein R 1 is hydrogen and A and Y are as defined above in connection with compounds of formula I. The reaction product is hydrolyzed under standard conditions in aqueous acid or base to remove the ethoxycarbonyl group and provide compound (I) wherein R 2 is 3,7-diazabicyclo[3.1.1]-heptyl (III wherein n═m═1 and Q═H).
The compounds (I) wherein R 2 is derived from formula IV wherein n and m are 1 and Q is hydrogen or methyl may be prepared by reacting compound 11 of Scheme II in a standard displacement reaction with compound (II) wherein R 1 is hydrogen and A and Y are as defined before in connection with compound (I). The formed product is debenzylated by catalytic hydrogenation with e.g. 10% Pd-C to give compound (I) wherein R 3 is 3,7-diazabicyclo[3.1.1]heptyl. Reaction with formaldehyde and formic acid provides the corresponding compound (I) wherein Q is methyl. ##STR14## compound (II) wherein R 1 is hydrogen and A and Y are as defined before in connection with compound (I). The formed product is debenzylated by catalytic hydrogenation with e.g. 10% Pd-C to give compound (I) wherein R 3 is 3,7-diazabicyclo[3.1.1]heptyl. Reaction with formaldehyde and formic acid provides the corresponding compound (I) wherein Q is methyl.
Compounds (III) and (IV) wherein n is 2 and m is 1 are described in U.K. Patent No. 937,183.
Compounds (III) wherein n is 3 and m is 1 are described in J. Amer. Chem. Soc., 75, 975 (1953).
Compound (III) wherein n is 1, m is 2 and Q is methyl,1,8-methyl-3,8-diazabicyclo[4.1.1]octane, may be prepared by the method of Reaction Scheme III by starting with commercially available pimelic acid diethylester 15. The ester 15 is treated with lithium diisopropylamine in tetrahydrofuran to give the dianion which is quenched with about 2 equivalents of phenylselenium chloride. The formed diselenide is oxidized with metachloroperbenzoic acid and heated to form the dienoate 16. A double Michael addition of monoethylamine results in azetidine 17. Ketone 18 is formed by Dieckmann cyclization of 17 with potassium t-butoxide in toluene at reflux temperature. Oxime 19 is formed on reaction with hydroxylamine in aqueous sodium bicarbonate and rearranged with hot sulfuric acid to lactam 20. The desired compound 21 forms on reduction with lithium aluminum hydride (LiAlH 4 ).
Compound (I) wherein R 2 is derived from compound (III) wherein n is 1, m is 2 and Q is hydrogen is formed on reacting benzylamine rather than monomethylamine with compound 16 in Scheme III. Proceeding as in Scheme III, 8-benzyl-3,8-diazabicyclo[4.1.1]octane is formed which is coupled with compound (II) and then debenzylated by catalytic hydrogenation, as before.
Compound (IV) wherein n is 1, m is 2 and Q is methyl, 3-methyl-3,8-diazabicyclo[4.1.1]octane, is prepared as in Scheme III reacting 16 with benzylamine instead of monomethylamine and reacting N-benzyl substituted lactam 20 with methyliodide in the presence of sodium hydride and dimethylformamide before reduction of the lactam with lithium aluminum hydride Debenzylation by catalytic hydrogenation provides the desired compound.
Compound (I) wherein R 2 is derived from compound (IV) wherein n is 1, m is 2 and Q is hydrogen is prepared by reacting lactam 20 which is N-benzyl substituted as described above with lithium aluminum hydride in tetrahydrofuran (THF). The secondary amino group in the compound is reacted with ethylchloroformate in an inert solvent with pyridine to provide carbamate 22 ##STR15## On standard debenzylation, the formed secondary amine is reacted with compound (II) and the resulting intermediate hydrolyzed in aqueous acid or base to give the final product of formula I wherein R 2 is derived from compound (IV).
Compound (III) wherein m and n are 2 and Q is methyl is prepared from commercially available tropinone 23 as outlined in Reaction Scheme IV. Tropinone is reacted with hydroxylamine in sodium bicarbonate to form the corresponding oxime which is rearranged with hot sulfuric acid to lactam 24 and reduced with LiAlH 4 in THF at reflux temperature to form 25. ##STR16##
Reaction Scheme V shows the preparation of a derivative of compound (III) wherein m and n are each 2. The known compound 26, 2,6-cycloheptadienone, J. Org. Chem., 44, 4285 (1979), is reacted with benzylamine to form the bridged bicyclic ketone 27. The standard Beckmann rearrangement via the oxime in hot sulfuric acid results in lactam 28 which is reduced with LiAlH 4 in THF to 9-benzyl-3,9-diazabicyclo[4.2.1]nonane 29. On reaction with compound (II) and debenzylation as described above, compound (I) is formed wherein R 2 is derived from compound (III) wherein m and n are each 2 and Q is hydrogen.
Compound (IV) wherein m and n are each 2 and Q is methyl may be prepared as shown in Reaction Scheme VI. Lactam 28 of Scheme V is methylated with methyl iodide and sodium hydride in DMF to form N-methyl lactam 30 which is reduced with LiAlH 4 in THF at reflux temperature and debenzylated as described above to form 3-methyl-3,9-diazabicyclo[4.2.1]nonane.
As described above in connection with Reaction Scheme II, compound 29 (analogous to compound 11) may be reacted with ethylchloroformate to the corresponding carbamate, the benzyl group removed by catalytic hydrogenation and the resulting compound reacted with compound (II). Compound (I) may be formed on hydrolysis, wherein R 2 is derived from compound (III) wherein m and n are each 2 and Q is hydrogen.
Compounds (III) and (IV) wherein m is 2, n is 3 and Q is hydrogen or methyl may be prepared as outlined in Schemes IV, V and VI and the above disclosure using as the starting material cyclooctadienone as described in J. Org. Chem., 44, 4285 (1979). ##STR17##
Compounds (V) wherein n is 1 and Q is hydrogen may be made as described in U.S. Pat. No. 3,947,445 and J. Org. Chem., 31, 1059 (1966). Compounds (I) wherein R 3 is derived from compound (V) wherein n is 1 and Q is methyl may be prepared by standard methylation with formic acid and paraformaldehyde (Eschweiler-Clark) of corresponding compounds (I) wherein Q is hydrogen.
Methods for preparing compounds (V) wherein n is 2 and Q is hydrogen or methyl are described in Heterocyclic Chem., 11, 449 (1974). The same methods may be used for preparing compounds (V) wherein n is 3 replacing adipic acid by pimelic acid as the starting material.
Compound (VI) wherein n is 1 and p is 0, 1,3-diazabicyclo[2.1.1]hexane, may be prepared from 1-benzhydryl-3-amino-azetidine 32, described in Chem. Pharm. Bull., 22, 1490 (1974), as shown in reaction Scheme VII. Diamine 33 is formed on catalytic hydrogenation e.g. with Pd on C (10%) of 32. The 1,3-bridge forms with 30% aqueous formaldehyde according to the general procedures disclosed in Aust. J. Chem., 20, 1643 (1967).
Compound (VI) wherein n and p are each one may be prepared from the known compound pyrazyl methanol 34 in Reaction Scheme VIII. Pyrazine 34 is catalytically reduced with e.g. PtO 2 catalyst to 2-(2-hydroxymethyl)piperazine 35, as described in U.S. Pat. 3,281,423. Ring closure to compound VI is accomplished by chlorination with thionyl chloride and heating with aqueous sodium hydroxide.
Compound (VI) wherein n is 2 and p is 0 (1,3-diazabicyclo[2.2.1]heptane) may be prepared from commercially available N-benzylpyrrolidone 37 by reductive animation with benzylamine and sodium borohydride to 1,3-dibenzyl-3-aminopyrrolidine 38, as outlined in Reaction Scheme IX. The pyrrolidine is debenzylated by catalytic hydrogenation, as described before, and ring closure of 39 is effected with aqueous formaldehyde to compound (VI). ##STR18##
Compound (VI) wherein n is 2 and p is 1, 1,4-diazabicyclo[3.2.1]octane is described in U.S. Pat. No. 3,954,766.
Compound (VI) wherein n is 3 and p is 0, 1,3-diazabicyclo[3.2.1]octane may be prepared from commercially available N-benzylpiperidone by the same method as shown in Reaction Scheme IX.
Compound (VI) wherein n is 3 and p is 1, 1,4-diazabicyclo[3.3.1]nonane, is prepared from known compound nipecotic acid ethyl ester 40. The secondary amine is alkylated with bromoacetic acid ethylester to 41. The diethylester is treated with potassium t-butoxide in toluene to give ketone 42 which is converted to oxime 43 as described before by treatment with hydroxylamine in aqueous sodium bicarbonate. The oxime is rearranged in hot sulfuric acid to lactam 44. Reduction with LiAlH 4 leads to compound VI wherein n is 3 and p is 1.
Compound (VII) wherein n is 1, 1,3-diazabicyclo[2.2.2]octane, may be prepared from commercially available 4-amino-N-benzylpiperidine 45 as outlined in Reaction Scheme XI. The benzyl group is removed by catalytic hydrogenation e.g. with Pd/C (10%) to give 4-aminopiperidine 46. The carbon bridge is formed on treatment with aqueous formaldehyde to VII.
Compound (VII) wherein n is 2,1,4-diazabicyclo[3.2.2]nonane, is described in Org. Syn., Coll. Vol. V, 989 (1973) and Zh. Org. Khim., 1 (7), 1336 (1965). ##STR19##
Compound (VII) wherein n is 3,1,5-diazabicyclo[4.2.2]decane, may be prepared from commercially available 4-amino-N-benzylpiperidine 45, see Reaction Scheme XII. Aminobromide 46 is formed on reductive amination of 45 with 3-bromopropionaldehyde and sodium borohydride. On heating, the quaternary ammonium bromide 48 is formed By conventional debenzylation as described before, the desired compound (VII) is formed
Compounds (I) wherein Q is (C 1 -C 3 )alkyl may be prepared by substituting the required alkylamine for methylamine or the required aldehyde for formaldehyde in the above described reactions.
Compounds (I) wherein Q is (C 1 -C 6 )alkyl-carbonyl of the formula ##STR20## or (C 1 -C 6 )alkylcarbamoyl of the formula ##STR21## may function as prodrugs. These compounds are prepared by reacting compounds (III) to (VII) wherein Q is hydrogen with (C 1 -C 6 )alkyl chlorforomates or (C 1 -C 6 )alkylisocyanates in an inert solvent at about 0° to 100° C.
The pharmaceutically acceptable acid addition salts of compounds (I) are prepared in a conventional manner by treating a solution or suspension of the free base (I) with about one chemical equivalent of a pharmaceutically acceptable acid. Conventional concentration and recrystallization techniques are employed in isolating the salts. Illustrative of suitable acids are acetic, lactic, succinic, maleic, tartaric, citric, gluconic, ascorbic, benzoic, methanesulfonic, cinnamic, fumaric, phosphonic, hydrochloric, hydrobromic, hydroiodic, sulfamic, and sulfonic acid.
The pharmaceutically acceptable cationic salts of compounds (I) may be prepared by conventional methods from the corresponding acids, e.g. by reaction with about one equimolar amount of a base. These cationic salts do not increase the toxicity of the compound toward animal organisms. Examples of suitable cationic salts are those of alkali metals such as sodium or potassium, alkaline earth metals such as magnesium or calcium, and ammonium or organic amines such as diethanol amine or N-methylglucamine.
The novel compounds of formula I and the pharmaceutically acceptable acid addition salts thereof are useful in the treatment of bacterial infections of broad spectrum, particularly the treatment of grampositive bacterial strains.
The compounds of the invention may be administered alone, but will generally be administered in admixture with a pharmaceutical carrier selected with regard to the intended route of administration and standard pharmaceutical practice. For example, they can be administered orally or in the form of tablets containing such excipients as starch or lactose, or in capsules either alone or in admixture with excipients, or in the form of elixirs or suspensions containing flavoring or coloring agents. In the case of animals, they are advantageously contained in an animal feed or drinking water in a concentration of 5-5000 ppm, preferably 25-500 ppm. They can be injected parenterally, for example, intramuscularly, intravenously or subcutaneously. For parenteral administration, they are best used in the form of a sterile aqueous solution which can contain other solutes, for example, enough salt or glucose to make the solution isotonic. In the case of animals, compounds can be administered intramuscularly or subcutaneously at dosage levels of about 0.1-50 mg/kg/day, advantageously 0.2-10 mg/kg/day given in a single daily dose or up to 3 divided doses.
The invention also provides pharmaceutical compositions comprising an antibacterially effective amount of a compound of the formula (I) together with a pharmaceutically acceptable diluent or carrier.
The compounds of the invention can be administered to humans for the treatment of bacterial diseases by either the oral or parenteral routes, and may be administered orally at dosage levels of about 0.1 to 500 mg/kg/day, advantageously 0.5-50 mg/kg/day given in a single dose or up to 3 divided doses. For intramuscular or intravenous administration, dosage levels are abut 0.1-200 mg/kg/day, advantageously 0.5-50 mg/kg/day. While intramuscularly administration may be a single dose or up to 3 divided doses, intravenous administration can include a continuous drip. Variations will necessarily occur depending on the weight and condition of the subject being treated and the particular route of administration chosen as will be known to those skilled in the art.
The antibacterial activity of the compounds of the invention is shown by testing according to the Steer's replicator technique which is a standard in vitro bacterial testing method described by E. Steers et al., Antibiotics and Chemotherapy, 9, 307 (1959).
The following examples illustrate the invention.
EXAMPLE 1
1-Ethyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinolinecarboxylic acid
(Y=ethyl; R 1 =H; A=CH; R 2 =a; n=2; m=1; Q=methyl)
A stirred suspension of 1-ethyl-6,7-difluoro-4-oxo-1,4-dihydro-3-quinolinecarboxylic acid (3.0 g, 11.9 mmol) and 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride (4.5 g, 22.7 mmol) in 15 ml of dry pyridine under N 2 was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (7.0 g, 4.6 mmol). The mixture was heated to 80° C. for three hours. A solution resulted which was cooled to room temperature and poured into 50 ml of water. The aqueous solution was washed five times with 100 ml of chloroform. The combined organic layer was dried over Na 2 SO 4 , filtered and concentrated in vacuo. The resulting solid was washed with diethyl ether, dissolved in water at pH=1 with 1N hydrochloric acid and washed with chloroform. The aqueous layer was neutralized with saturated aqueous sodium bicarbonate and the product was extracted with chloroform (5×100 ml). The chloroform layer was dried over Na 2 SO 4 , filtered and concentrated to about 25 ml of chloroform. The pure product was precipitated as a white solid with 75 ml of diethyl ether. The solid was collected by suction filtration and washed with diethyl ether to afford 2.77 g (65% yield) of the title compound, m.p. 244°-245° C.
EXAMPLE 2
1-Ethyl-6,8-difluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinolinecarboxylic acid
(Y=ethyl; R 1 =H; A=CF; R 2 =a; Q=methyl; n=2; m=1)
The title compound was prepared according to example 1 by reacting 1-ethyl-6,7,8-trifluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid with 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride, m.p. 215°-219° C.
EXAMPLE 3
1-Fluoroethyl-6,8-difluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinolinecarboxyic acid
(Y=fluoroethyl; R 1 =H; A=CF; R 2 =a; n=2; m=1; Q=CH 3 )
The title compound was prepared according to example 1 by reacting 1-fluoroethyl-6,7,8-trifluoro-oxo-1,4-dihydroquinoline-3-carboxylic acid with 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride, m.p. 216°-219° C.
EXAMPLE 4
1-Methyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinolinecarboxylic acid
Y=CH 3 ; R 1 =H; A=CH; R 2 =a; n=2; m=1; Q=CH 3 )
The title compound (68% yield) was prepared according to example 1 by reacting 1-methyl-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid with 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride, m.p. 251°-252° C.
EXAMPLE 5
1-Vinyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinolinecarboxylic acid
(Y=vinyl; R 1 =H; A=CH; R 2 =a; Q=methyl; n=2; m=1; Q=CH 3 )
The title compound (276 mg, 66% yield) was prepared according to example 1 by reacting 1-vinyl-6,7-difluoro-4-oxo-1,4-dihydroqunoline-3-carboxylic acid (296 mg, 1.18 mmol) with 8-methyl-3,8-diazabicyclo[3.2.1.]octane dihydrochloride (471 mg, 2.36 mmol), m.p. 225°-232° C. with decomposition.
EXAMPLE 6
1-p-Fluorophenyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl) -4-oxo-3-quinolinecarboxylic acid
(Y=p-fluorophenyl; R 1 =H; A=CH; R 2 =a; n=2; m=1; Q=CH 3 )
A stirred suspension of 1-p-fluorophenyl-6,7-difluoro-4-oxo-1,4-dihydro-3-quinolinecarboxylic acid (319 mg, 1.0 mmol) and 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride (400 mg, 2.02 mmol) in 8 ml of dry pyridine under N 2 treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (609 mg, 4.00 mmol). The mixture was heated to 80° C. for three hours, cooled to room temperature and poured into 25 ml of water. The aqueous layer was extracted five times with 75 ml of chloroform. The chloroform layer was dried over Na 2 SO 4 , filtered and concentrated in vacuo. The resulting solid was washed several times with diethyl ether and treated with lN HCl until the pH was 1. The water-insoluble hydrochloride salt was filtered and air dried. Recrystallization from acetonitrile gave 150 mg (35% yield) of a white solid, m.p. 319°-320 (with decomposition).
EXAMPLE 8
1-Ethyl-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinolinecarboxylic acid
(Y=ethyl; R 1 =H; A=CH; R 2 =e; n=2)
A stirred suspension of 1-ethyl-6,7-difluoro-4-oxo-1,4-dihydro-3-quinolinecarboxylic acid (76 mg, 0.302 mmol) and 1,4-diazabicyclo[3.2.2]nonane (95 mg, 0.754 mmol) in 3 ml of dry pyridine under N 2 was heated to 90° C. for 18 hours. The mixture was cooled to room temperature and diluted with 50 ml of water. The aqueous solution was extracted two times with 50 ml of chloroform. The combined organic layers were then washed twice with water, dried over Na 2 SO 4 , filtered and concentrated in vacuo. The solid was triturated several times with diethylether and filtered to give (27 mg, 25% yield) of a pale yellow solid, m.p. 223°-225° C.
EXAMPLE 8
1-Ethyl-6-fluoro-1,4-dihydro-7-(9-methyl3,9-diazabicyclo[4.2.1]non-3-yl)-4-oxo-3-quinolinecarboxylic acid
(Y=ethyl; R 1 =H; A=CH; R 2 =a; n=m=2; Q=CH 3 )
A suspension of 1-ethyl-6,7-difluoro-1,4-dihydro-oxo-3-quinolinecarboxylic acid (578 mg, 2.28 mmol) in 20 ml of dry pyridine under N 2 was treated with 9-methyl-3,9-diazabicyclo[4.2.1]nonane (800 mg, 5.71 mmol). The mixture was heated to 90° C. for three hours, cooled to room temperature and poured into 200 ml of water. The aqueous solution was extracted three times with 100 ml of chloroform. The combined chloroform extracts were washed twice with 150 ml of 1N hydrochloric acid. The aqueous extracts were washed once with 300 ml of chloroform and then the pH was adjusted to 6.8 with 6N NaOH. The aqueous solution was extracted three times with 200 ml of chloroform. The final chloroform extracts were dried over Na 2 SO 4 , filtered and concentrated to give a pale yellow solid. This material was washed with diethylether and ethylacetate in a volume ratio of 1:1 to give 453 mg (53% yield) of a pale yellow solid, m.p. 187°-188° C.
EXAMPLE 9
1-Ethyl-6,8-difluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinolinecarboxylic acid
(Y=ethyl; R 1 =H; A=CF; R 2 =d; n=2; p=1; Q=H)
A. 3-oxo-1,4-diazabicyclo[3.2.2]nonane
Quinuclidone HCl (200 g, 1.24 moles) was dissolved in concentrated sulfuric acid (500 ml) and chilled to 0°-5° C. in a very large ice-water bath. NaN 3 (200 g, 3.07 moles) was added in small portions over 2 hours. The resulting mixture was stirred at 0° C. for 4 hours. The reaction mixture was then slowly and carefully diluted with 1 liter of water and slowly quenched with a solution of sodium hydroxide (900 g, 22.5 moles) in 1.5 liters of water. After the quench, the pH of the reaction mixture was approximately 13.5. The resulting sodium sulfate was filtered and then washed with 2 liters of chloroform. The aqueous supernatant was extracted with three times 2 l of chloroform. The combined extracts were dried with magnesium sulfate and concentrated to give 94.9 g of a solid residue. This residue was chromatographed (2.0 kg SiO 2 ; 9:1 chloroform:methanol) to give 13.59 g of the title compound as white crystals, m.p. 210°-211° C., yield 7.8%.
In addition 42.9 g of a byproduct identified as 2-(3,4-dehydropiperidin-1-yl)acetamide was isolated as white plates, m.p. 121°-122° C., yield 24.7%.
B. 1,4-diazabicyclo[3.2.2]nonane
Lithium aluminum hydride (2.0 g, 51.4 mmoles) was slurried in 250 ml of dry tetrahydrofuran and 3-oxo-1,4-diazabicyclo[3.2.2]nonane (3.6 g, 25.7 mmoles) was added carefully as a solid in one portion at room temperature. The resulting mixture was then heated to a gentle reflux for 20 hours. The reaction was cooled to room tempeature and quenched by slow addition of 2.5 ml water. The salts were filtered and washed several times with diethyl ether totaling 1.0 1. These washings and the supernatant were combined, dried over magnesium sulfate and concentrated to give 2.09 g (64.5%) of the title compound as a pale yellow oil.
NMR ( 13 C; 63 MHz, CDCl 3 ): 59.11, 47.97, 46.67, 43.67, 29.43.
C. 6,7,8-Trifluoro-1-ethyl-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid (271 mg, 1.0 mmol) was dissolved in 5 ml of dry pyridine and heated to 90° C. 1,4-Diazabicyclo[3.2.2]nonane (315 mg, 2.5 mmoles) in 1 ml of dry pyridine was added and the resulting mixture was heated at 90° C. for 2.5 hours. The solution was then cooled to 10° C. resulting in the formation of a precipitate which was filtered and washed several times with ethyl acetate and dried under vacuum to afford 103 mg (27%) of the title compound as a cream colored solid with m.p. 261°-263° C.
EXAMPLE 10
1-(2-Fluoroethyl)-6-fluoro-1,4-dihydro-7(1,4-diazabicyclo[3.2.2]-non-4-yl)-4-oxo-3-quinolinecarboxylic acid.
(Y=2-fluoroethyl; R 1 =H; A=CH; R 2 =d; n=2; p=1; Q=H)
The title compound was prepared in 50.1% yield according to example 9 by reacting 6,7-difluoro-1-(2-fluoroethyl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 1,4-diazabicyclo[3.2.2]nonane, m.p. 256°-258° C.
EXAMPLE 11
1-Vinyl-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]-non-4-yl)-4-oxo-3-quinolinecarboxylic acid.
(Y=vinyl; R 1 =H; A=CH; R 2 =d; n=2; p=1; Q=H)
The title compound was prepared in 49.6% yield according to example 9 by reacting 6,7-difluoro-1-vinyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 1,4-diazabicyclo[3.2.2]nonane, m.p. 255°-257° C.
EXAMPLE 12
1-(4-Fluorophenyl)-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinolinecarboxylic acid.
(Y=4-fluorophenyl; R 1 =H; A=CH; R 2 =d; n=2; p=1; Q=H)
The title compound was prepared in 68% yield according to example 9 by reacting 6,7-difluoro-1(4-fluorophenyl)-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid with 1,4-diazabicyclo[3.2.2]nonane, m.p. 320° C.
NMR: (CDCl 3 and DMSOd 6 , 250 MHz): 8.60 (1H, s); 7.98 (1H, d, J=13 Hz); 7.54 (2H, m); 7.41 (2H, m); 6.28 (1H, d, J=7Hz); 3.89 (1H, m); 3.26 (2H, t); 2.9-3.15 (6H, m); 1.95-2.10 (2H, m); 1.75-1.90 (2H, m).
EXAMPLE 13
1-Methylamino-6-fluoro-1,4-dihydro-7-(1,4-diazabicyclo-[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid
(Y=methylamino; R 1 =H; A=CH; R 2 =d; n=2; p=1; Q=H)
The title compound was prepared in 73% yield according to example 9 by reacting 6,7-difluoro-1-methylamino-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 1,4-diazabicyclo[3.2.2]nonane, m.p. 245°-247° C.
EXAMPLE 14
10-(1,4-Diazabicyclo[3.2.2]non-4-yl)-9-fluoro-3-methyl-7-oxo-2,3-dihydro-(7H)-pyrido(1,2,3-de)-1,4-benzoxazine-6-carboxylic acid
(A--Y=CH--O--CH 2 --C(CH 3 )H; R 1 =H; R 2 =d; n=2; p=1; Q=H)
9,10-Difluoro-3-methyl-7-oxo-2,3-dihydro-(7H)-pyrido-(1,2,3-de)-1,4-benzoxazine-6-carboxylic acid (281 mg, 1.0 mmol) was dissolved in 5 ml DMSO and heated to 120° C. 1,4-Diazabicyclo[3.2.2]nonane (315 mg, 2.5 mmoles) in 1 ml dry pyridine was added and the resulting mixture was heated at 120° C. for 4.5 hours. The solution was then cooled to room temperature and poured in 250 ml water. The aqueous mixture was extracted 3 times with 250 ml chloroform. The combined chloroform extracts were further extracted 3 times with 1.0 N HCl (250 ml). The aqueous acidic extracts were combined and neutralized to a pH of 7.0 with 6N NaOH, and then extracted 3 times with 250 ml chloroform. The combined chloroform extracts were dried over sodium sulfate and stripped of solvent to give asolid residue that was slurried in ethyl acetate, filtered, washed with ethyl acetate, and dried to give the title compound (55 mg, 14% yield) as a pale yellow solid, m.p. 230°-232° C.
EXAMPLE 15
1-Vinyl-6-fluoro-7-(9-methyl-3,9diazabicyclo[4.2.1]non-3-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid
(Y=vinyl; R 1 =H; A=CH; R 2 =a; m=n=2; Q=CH 3 )
A. 9-Methyl-4-oxo-3,9-diazabicyclo[4.2.1]nonane
Tropinone (5.0 g, 35.97 mmoles) was dissolved in a mixture of concentrated sulfuric acid (20 ml) and chloroform (50 ml) and chilled to 0°-5° C. in an efficient ice-water bath. NaN3 (5.8 g, 89.9 mmoles) was added in small portions over 15 minutes. The resulting mixture was stirred at 0° C. for 1 hour. After this time the reaction mixture was diluted carefully with 50 ml water and sufficient solid K 2 CO 3 was added to raise the pH of the mixture to 9.5. Then 250 ml chloroform was added and the entire mixture was filtered. The layers were separated and the aqueous layer was extracted with an additional 250 ml of chloroform. The combined chloroform extracts were dried over magnesium sulfate and concentrated to give a solid residue that was recrystallized from diethyl ether to give 3.36 g (60.6%) of the title compound A as colorless needles, m.p. 78°-80° C.
B. 7-Methyl-3,9-diazabicyclo[4.2.1]nonane
Lithium aluminum hydride (1.56 g, 40 mmoles) was slurried in 75 ml dry tetrahydrofuran and 9-methyl-4-oxo-3,9-diazabicyclo[4.2.1]nonane (3.36 g, 21.8 mmoles) dissolved in 20 ml tetrahydrofuran was added dropwise at room temperature. The resulting mixture was heated to gentle reflux for 28 hours, then cooled to room temperature and carefully quenched by the slow additions of 3 ml water. 500 ml of diethyl ether was added and the mixture was filtered of solids, dried over magnesium sulfate, and concentrated to give 2.45 g (80.3%) of the title compound B as a colorless oil.
NMR (250 MHz, DMSOd 6 ): 4.0-4.2 (2H, m); 3.45-3.6 (2H, m); 3.2-3.35 (2H, m); 2.84 (3H, s); 1.9-2.5 (6H, m).
C. The title comound was prepared in 44.7% yield according to example 8 by reacting 6,7-difluoro-1-vinyl-1,4-dihydro-4-oxo-3-quinoline-carboxylic acid with 9-methyl-3,9-diazabicyclo[4.2.1]nonane, m.p. 214°-215° C.
EXAMPLE 16
1-Methyl-6-fluoro-7-(9-methyl-3,9-diazabicyclo[4.2.1]non-3-yl)-1,4-dihydro -4-oxo-3-quinoline carboxylic acid
(Y=methyl; R 1 =H; A=CH; R 2 =a; m=n=2; Q=CH 3 )
The title compound was prepared in 8.5% yield according to example 8 by reacting 6,7-difluoro-1-methyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 9-methyl-3,9-diazabicyclo[4.2.1]nonane, m.p. 220°-222° C.
EXAMPLE 17
1-(2-Fluoroethyl)-6-fluoro-1,4-dihydro-7(9-methyl-3,9-diazabicyclo[4.2.1]non-3-yl)-4-oxo-3-quinoline carboxylic acid
(Y=2-fluoroethyl; R 1 =H; A=CH; R 2 =a; m=n=2; Q=CH 3 )
The title compound was prepared in 13% yield according to Example 8 by reacting 6,7-difluoro-1(2-fluoroethyl)-1,4-dihydro-4-oxo-3-quinolinecarboxylic acid with 9-methyl-3,9-diazabicyclo[4.2.1]nonane, m.p. 202°-203° C.
EXAMPLE 18
1-(2-Fluoroethyl)-6,8-difluoro-1,4-dihydro-7-(1,4-diazabicyclo[3.2.2]non-4-yl)-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=2-fluoroethyl; A=CF, R 2 =d; n=2; p=1)
The title compound was prepared in 13.3% yield according to example 9 by reacting 6,7,8-trifluoro-1-(2-fluoroethyl)-1,4-dihydro-4-oxo-3-quinoline carboyxlic acid with 1,4-diazabicyclo[3,2,2]nonane, m.p. 238-239° C.
EXAMPLE 19
1-Cyclopropyl-6-fluoro-7-(1,4-diazabicyclo[3.2.2]-non-4-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid
R 1 =H; Y=cyclopropyl; A=CH; R 2 =d; n=2; p=1)
The title compound was prepared in 68.4% yield according to example 9 by reacting 6,7-difluoro-1-cyclopropyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 1,4-diazabicyclo[3,2,2]nonane, m.p. 296°-297° C.
EXAMPLE 20
1-Ethyl-6-fluoro-7-(9-benzyl-3,9-diazabicyclo[4.2.1]non-3-yl)1,4-dihydro-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=ethyl; A=CH; R 2 =a; m=n=2; Q=benzyl)
A. The title compound was prepared according to example 8 in 63% yield by reacting 6,7-difluoro-1-ethyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 9-benzyl-3,9-diazabicyclo[4,2,1]nonane, m.p. 218°-220° C.
1-Ethyl-6-fluoro-7-(3,9-diazabicyclo[4.2.1]non-3-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=ethyl; A=CH; R 2 =a; m=n=2; Q=H)
B. 7-(9-benzyl-3,9-diazabicyclo[4,2,1]non-3-yl)--fluoro-1-ethyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid (963 mg, 2.15 mmoles) was dissolved in 125 ml of methanol that was previously saturated with HCl. To this solution was added 1.25 g of 10% Pd/C and the mixture was treated with an atmosphere of 45 psi hydrogen on a Parr hydrogenation apparatus at 60° C. for 4.5 hours. The mixture was then cooled to room temperature and filtered of catalyst through a celite pad. The filtrate was stripped to dryness, taken up in water (50 ml) and the pH was adjusted to 7.0 with saturated sodium bicarbonate. This aqueous layer was extracted with three times 200 ml chloroform which was dried over sodium sulfate and evaporated to give a solid residue. This residue was taken up in a small amount of chloroform and ether from which crystallized an off-white material that was filtered and dried to give 149 mg (19.3%) of the title compound, m.p. 147°-150° C.
EXAMPLE 21
1-Ethyl-6-fluoro-7-(3-methyl-3,9-diazabicyclo[4.2.1]non-9-yl)-1,4-dihydro-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=ethyl; A=CH; R 2 =b; n=2; Q=CH 3 )
The title compound was prepared in low (5%) yield according to example 1 by reacting 6,7-difluoro-1-ethyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid with 3-methyl-3,9-diazabicyclo[4.2.1]nonane, m.p.=234°-236° C.
EXAMPLE 22
1-Ethyl-6-fluoro-1,4-dihydro-7-(9-methyl-3,9-diazabicyclo[3.3.1]non-3-yl)-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=ethyl; A=CH; R 2 =a; m=1; n=3; Q=CH 3 )
The title compound (172 mg, 47% yield) was prepared according to example 1 by reacting 1-ethyl-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxyic acid (250 mg, 0.99 mmol) with 9-methyl-3,9-diazabicyclo[3.3.1]nonane (526 mg, 2.47 mmole) dihydrochloride, m.p. 180°-182° C.
EXAMPLE 23
10-(8-Methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-9-fluoro-3-methyl-7-oxo-2,3-dihydro-(7H)-pyrido-(1,2,3-de)-1,4-benzoxazine-6-carboxylic acid
(R 1 =H; A--Y=C--O--CH 2 --C(CH 3 )H; R 2 =a; m=1; n=2; Q=methyl)
9,10-Difluoro-3-methyl-7-oxo-2,3-dihydro-(7H)pyrido(1,2,3-de)-1,4-benzoxazine-6-carboxylic acid (425 mg, 1.51 mmol), 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride (425 mg, 2.14 mmol) and 1,8diazabicyclo[5.4.0]undec-7-ene (672 mg, 4.41 mmol) were dissolved in 8.0 ml of dry DMSO. The reaction mixture was heated to 80° C. for 29 hours, cooled to room temperature and poured into 100 ml of water. The product was then extracted with chloroform, dried over sodium sulfate, filtered and evaporated to a small volume.
Ether was then added to precipitate beige crystals which were purified by acid-base treatment to give 125 mg (21% yield) of a cream colored solid, m.p. 248°-252° C.
EXAMPLE 24
1-(2-Fluoroethyl)-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=2-fluoroethyl; A=CH; R 2 =a; m=1; n=2; Q=methyl)
The title compound (288 mg, 52% yield) was prepared according to example 1 by reacting 1-ethyl-6,7-difluoro-4-oxo-1,4-dihydroquinoline-3-carboxylic acid (363 mg, 1.34 mmol) with 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride (400 mg, 2.0 mmol) in 1,8-diazabicyclo[5.4.0]undec-7-ene (610 mg, 4.01 mmol) and pyridine (4.0 ml) at 80° C. for 3 hours, m.p. 270°-273° C. (HCl salt).
EXAMPLE 25
1-Ethyl-6-fluoro-1,4-dihydro-7-{(1S,4S) 5-benzyl-2,5-diazabicyclo[2.2.1]hept-2-yl)}4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=ethyl; A=CH; R 2 =c; n=1; Q=benzyl)
A. The title compound (70 mg, 33% yield) was prepared according to example 1 by reacting 1-ethyl-6,7-difluoro-4-oxo-1,4-dihydro-3-quinoline caboxylic acid (126 mg, 0.5 mmol) with (1S, 4S) 5-benzyl-2,5-diazabicyclo[2.2.1]heptane dihydroiodide (444 mg, 1.0 mmol) in 1,8-diazabicyclo[4.5.0]undec-7-ene (305 mg, 2.0 mmol) in pyridine (5 ml) at 80° C. for 2 hours, m.p. 208°-209° C.
1-Ethyl-6-fluoro-1,4-dihydro-7-{(1S,4S) 2,5-diazabicyclo[2.2.1]hept-2-yl)}-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=ethyl; A=CH; R 2 =c; n=1; Q=H)
B. A stirred suspension of 1-ethyl-6,7-difluoro-4-oxo-1,4-dihydro-3-quinoline carboxylic acid (506 mg, 2.0 mmol) and (1S:4S)-2,5-diazabicyclo[2.2.1]heptane dihydrochloride (680 mg, 4.0 mmol) in 20 ml of dry pyridine was treated with 1,8-diazabicyclo[5.4.0]-undec-7-ene(1.2 g, 8.0 mmol). The mixture was heated to 80° C. for 3 hours, cooled to room temperature and poured into water. The aqueous phase was extracted with chloroform (3 times 50 ml). The product precipitated from the aqueous layer on standing and was collected by suction filtration, air dried, and recrystallized from hot acetonitrile to give (90 mg, 14% yield) of an off-white solid, m.p. 283°-285° C.
EXAMPLE 26
1-Cyclopropyl-6-fluoro-1,4-dihydro-7-{(1S:4S) 2,5-diazabicyclo[2.2.1]hept-2-yl)}-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=cyclopropyl; A=CH; R 2 =c; n=1; Q=H)
The title compound (167 mg, 63%) was prepared by reacting 6,7-difluoro-1-cyclopropyl-1,4-dihydro-4-oxo-3-quinoline carboxylic acid (207 mg, 0.78 mmol) with (1S:4S)2,5-diazabicyclo[2.2.1]heptane dihydrochloride (249 mg, 1.46 mmol) in 1,8-diazabicyclo[5.4.0]undec-7-ene (450 mg, 2.96 mmol) and pyridine (3 ml) at 80° C. for 2 hours, m.p. 301°-302° C. w/decomp (recrystallized from chloroform:methanol, 1:1 (v/v)).
EXAMPLE 27
1-Cyclopropyl-6-fluoro-1,4-dihydro-7-(8-methyl-3,8-diazabicyclo[3.2.1]oct-3-yl)-4-oxo-3-quinoline carboxylic acid
(R 1 =H; Y=cyclopropyl; A=CH; R 2 =a; m=1; n=2; Q=methyl)
A stirred suspension of 6,7-difluoro-1-cyclopropyl-4-oxo-1,4-dihydro-3-quinoline carboxylic acid (1.5 g, 5.66 mmol) and 8-methyl-3,8-diazabicyclo[3.2.1]octane dihydrochloride (1.45 g, 7.32 mmol) in 10.0 ml of pyridine was treated with 1,8-diazabicyclo[5.4.0]undec-7-ene (2.26 g, 14.9 mmol). The reaction mixture was heated to 80° C. for 4 hours, cooled to room temperature and poured into 250 ml of chloroform. The chloroform layer was washed with water (twice 200 ml), dried over sodium sulfate, filtered and concentrated in vacuo. The crude off white solid was dissolved in 1N hydrochloride with warming and this solution was washed with chloroform/methanol (9:1 v/v). The aqueous solution as then basified with saturated aqueous sodium bicarbonate and extracted with chloroform (three times 200 ml). The chloroform layer was dried with sodium sulfate, filtered, concentrated in vacuo, and washed with diethyl ether to give 1.80 g (86% yield) of an off white solid, m.p. 278°-279° C. with decomposition.
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Antibacterial compounds have the formula ##STR1## wherein R 1 is hydrogen, a pharmaceutically acceptable cation, or alkyl; A is CH, CF, CCl or N; Y is alkyl, haloalkyl, cyclopropyl, vinyl, methoxy, N-methylamino, p-fluorophenyl, p-hydroxyphenyl or p-aminophenyl; or A is carbon and is taken together with Y and the carbon and nitrogen to which A and Y are attached to form a five to seven membered ring which is optionally substituted; and R 2 is a bridged-diazabicycloalkyl group.
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BACKGROUND OF THE INVENTION
The present invention relates to a process for producing a flux for brazing, and more particularly to a process for producing a flux for brazing for use in fabricating automotive condensers, radiators, evaporators, heaters and other aluminum heat exchangers.
The percentages as used herein and in the appended claims are by weight, and the term "aluminum" is used herein as including alloys thereof.
In brazing aluminum materials, fluxes are used for removing oxide coatings from the surfaces to be joined together. While chloride fluxes have heretofore been used for this purpose, they leave residues which cause corrosion to aluminum after brazing and which must therefore be removed by washing. Nevertheless, depending on the construction of the brazed article, such residues are not always removable completely.
To overcome the above problem, U.S. Pat. No. 3,951,328 proposes a flux in the form of a mixture of potassium fluoaluminate complexes essentially free of unreacted KF and having a composition corresponding to an AlF 3 /KF ratio between about 65:35 and about 45:55. The "potassium fluoaluminate complexes" refers to complexes of the type formed by fusion of AlF 3 and KF, such complexes having the formulas K 3 AlF 6 and KAlF 4 . The complexes are formed by the fusion of AlF 3 and KF to render the flux free from unreacted KF. When containing unreacted KF, the flux is hydroscopic and is unsuitable for use in the form of an aqueous slurry, since slurrying of the flux in water would result in solution of KF and consequent possibility of disproportionation of the flux on drying and melting point variability.
However, resorting to the step of fusing KF and AlF 3 in forming the complexes entails an increase in the production cost of the flux and is unfavorable in view of production efficiency.
SUMMARY OF THE INVENTION
The present invention has overcome the foregoing problems and provides a process for producing a flux for brazing which comprises preparing 31.5% to 56.2% of KF and 68.5% to 43.8% of at least one of Υ-AlF 3 and β-AlF 3 , reacting the KF with the AlF 3 in water, and drying the reaction product. A flux free from unreacted KF can be obtained efficiently by this process without resorting to any fusion step.
The AlF 3 to be used in the process of the invention must be Υ-AlF 3 , β-AlF 3 or a mixture of Υ-AlF 3 and β-AlF 3 . α-AlF 3 , if reacted with KF, fails to undergo an exothermic reaction, permitting the resulting flux to contain unreacted KF.
The amounts of the reactants should be 31.5% to 56.2% of KF, and 68.5% to 43.8% of at least one of Υ-AlF 3 and β-AlF 3 because if the amounts are outside these ranges, the liquidus temperature exceeds 600° C., with the likelihood that the flux will not melt fully during brazing, possibly failing to effect satisfactory brazing. Solders generally used for brazing aluminum are about 600° C. in melting point. In the above ranges, it is more preferably to use 38.9% to 46.8% of KF, and 61.1% to 53.2% of at least one of Υ-AlF 3 and β-AlF 3 . Most preferably, about 45.8% of KF, and about 54.2% of at least one of Υ-AlF 3 and β-AlF 3 are used.
Finely divided KF and at least one of finely divided Υ-AlF 3 and finely divided β-AlF 3 are prepared. First, the KF is dissolved in water to obtain a KF aqueous solution. Since KF has a high solubility in water (about 97%), the KF to be dissolved can be in the form of a block instead of the finely divided KF.
The finely divided AlF 3 is then placed into the KF aqueous solution, preferably in small portions while stirring the solution so as to uniformly disperse the finely divided AlF 3 . The finely divided AlF 3 to be used is about 150 mesh (about 100 μm) in means particle size as is usually the case with commercial products for industrial use, although this particle size is not limitative. After the AlF 3 has been placed into the KF aqueous solution, the mixture is further continuously stirred for 10 to 20 minutes when required. The stirring is discontinued upon the KF and AlF 3 starting to undergo an exothermic reaction. When it takes an excessively long period of time to initiate the exothermic reaction, it is recommended to preheat the KF aqueous solution to about 50° C. Both KF and AlF 3 may be placed into water and then stirred.
The exothermic reaction proceeds at 120° to 130° C. With the progress of the exothermic reaction, the water evaporates off almost completely. The reaction product is dried in the atmosphere at a temperature of 100° to 550° C. to give a flux.
When the flux obtained is to be used for brazing, it is desirable to suspend the flux in water or like liquid and uniformly apply the suspension to the two pieces of aluminum material to be joined together with a brazing solder interposed therebetween. The flux may be applied by any method such as immersion, spraying or brush coating, but immersion is most desirable. The solder is melted for brazing by heating the assembly in a nonoxidizing atmosphere such as an inert gas atmosphere at a temperature lower than the melting point of the aluminum material but higher than the melting point of the flux.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Example 1
Finely divided KF (5.5 kg) having a purity of 99.8% and 6.5 kg of finely divided Υ-AlF 3 having a purity of at least 90% for industrial use were prepared. First, 6 liters of water was added to the KF to obtain a KF aqueous solution.
The Υ-AlF 3 was then placed in small portions in the KF aqueous solution while stirring the solution. When the stirring was continued for 10 minutes further after the whole amount of Υ-AlF 3 was placed in, an exothermic reaction started, whereupon the stirring was discontinued. The water evaporated off almost completely with the progress of the exothermic reaction.
The reaction product was dried in the atmosphere at 200° C. for 300 minutes, giving a flux. When the composition of the flux was analyzed, the flux was found to contain Υ-AlF 3 , K 3 AlF 6 and a small amount of K 2 AlF 5 but no KF.
Example 2
Finely divided KF (5.0 kg) having a purity of at least 97% for industrial use and 7.0 kg of finely divided Υ-AlF 3 having a purity of at least 90% for industrial use were prepared. First, 6 liters of water was added to the KF to obtain a KF aqueous solution.
The Υ-AlF 3 was then placed in small portions into the KF aqueous solution while stirring the solution. When the stirring was continued for 10 minutes further after the whole amount of Υ-AlF 3 was placed in, an exothermic reaction started, whereupon the stirring was discontinued. The water evaporated off almost completely with the progress of the exothermic reaction.
The reaction product was dried in the atmosphere at 200° C. for 300 minutes, giving a flux. When analyzed, the flux was found to contain Υ-AlF 3 , KAlF 4 , K 3 AlF 6 and K 2 AlF 5 -H 2 O but no KF.
Example 3
A flux was prepared in the same manner as in Example 2 with the exception of using β-AlF 3 having a purity of at least 90.0% for industrial use in place of the Υ-AlF 3 . When analyzed, the flux was found to contain β-AlF 3 , KAlF 4 , K 3 AlF 6 and a small amount of K 2 AlF 5 -H 2 O but no KF.
Example 4
A flux was obtained in the same manner as in Example 2 with the exception of preparing 50.0 kg of finely divided KF having a purity of 99.3%, and 30.0 kg of Υ-AlF 3 and 4.0 kg of β-AlF 3 both finely divided and having a purity of at least 90.0% for industrial use. When analyzed, the flux was found to contain Υ-AlF 3 , β-AlF 3 , KAlF 4 , K 3 AlF 6 and a small amount of K 2 AlF 5 -H 2 O but no KF.
Comparative Example
Finely divided KF (5.5 kg) having a purity of at least 97.0% for industrial use and 6.3 kg of finely divided α-AlF 3 having a purity of at least 90.0% for industrial use were prepared. First, 6 liters of water was added to the KF to obtain a KF aqueous solution. The α-AlF 3 was then placed in small portions into the KF aqueous solution while stirring the solution. Although the mixture was continuously stirred after the whole amount of α-AlF 3 was placed in, no exothermic reaction occurred.
The reaction product was dried in the atmosphere at 200° C. for 300 minutes to give a flux. When analyzed, the flux was found to contain α-AlF 3 , K 3 AlF 6 and further large quantities of unreacted KF and KF-2H 2 O.
The fluxes obtained in Examples 1 to 4 were tested for brazing properties by the following method, using aluminum panels of A1050, and brazing sheets each comprising a base of A3003 and a brazing solder of A4045 cladding one surface of the base. Water was added to each of the fluxes of Examples 1 to 4 to prepare a suspension having a concentration of 8%. The aluminum panel and the brazing sheet to be joined together were immersed in the suspension, then withdrawn and dried.
The panel and sheet were then fitted together and heated at 610° C. for 5 minutes for brazing in an oven adjusted to a dew point of -40° C. with N 2 gas.
Each of the brazed assemblies thus obtained was then checked for the brazed state to find that the fillet formed was satisfactory to give an excellent brazed joint.
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A flux for brazing is prepared from 31.5% to 56.2% of KF and 68.5% to 43.8% of at least one of Υ-AlF 3 and finely divided β-AlF 3 . The KF is dissolved in water, and the AlF 3 is then placed into the resulting KF aqueous solution to react the KF with the AlF 3 . The reaction product is dried.
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BACKGROUND OF THE INVENTION
This invention relates to a damper device and, especially to a buffering assembly used in a hinge structure of a lid or cover, such as a stool lid of a toilet stool of Western style or a cover of a personal computer of wrap-top type which is opened upwards and closed downwards.
Such manually operated lid or cover which is hinged about a horizontal axis can be opened lightly if the frictional resistance between an axle and a bearing of the hinge structure is small. However, if it is released from a hand when it is closed, it freely runs down against a body to cause not only an unpleasant strike sound but also a possible damage of the device due to shock. However, if the frictional resistance is increased for preventing these problems, unnecessary resistance acts at the time of opening and the hand must be used to the last at the time of closing. In order to avoid such troubles, it has been proposed, as described, for example, in the Japanese utility model opening gazette No. H2-6594, to use a buffering fluid such as grease for braking the lid therewith when it is closed. However, such a device as using a fluid is complicated in structure and, moreover, it conceives such problems in that it is troublesome to handle the fluid in the manufacturing process and it may leak out in the future. With this structure, moreover, a long time is needed for closure when only the gravity regards, since a uniform braking torque acts throughout the closing operation.
Accordingly, an object of this invention is to provide a novel and improved damper device using no buffering fluid, in which the braking effect does not appear at the time of opening but appears only at the time of closing.
Another object of this invention is to provide an improved damper device for a hinge structure in which the braking effect at the time of closing is raised especially at the last step to prevent collision of the lid.
A further object of this invention is to provide an improved damper device in which the braking effect is raised especially within a specific range in the way of closing, so that the lid can be stood still at any position within the range.
SUMMARY OF THE INVENTION
According to a feature of this invention, the damper device, which is generally used in a hinge structure including two hinge members pivoted about an axis, comprises two principal members to be fixed to the hinge members, respectively which have mutually facing surfaces, respectively, and are coaxially combined with each other to enable relative rotation, and at least one idle member disposed between the facing surfaces, and at least one of the principal members and idle member includes an elastic material. At least a portion of one of the facing surfaces has a first depression and a second depression shallower than the first depression, which are formed therein in circumferentially adjoining and partly overlapping relation and the idle member lies in one of these depressions. The idle member moves from the first depression to the second depression with friction when one of the principal members is rotated forward with respect to the other, while it moves from the second depression to the first depression when it is rotated backward. Accordingly, the forward rotation is effected lightly and easily due to reduced friction or resistance, while the backward rotation tends to be braked due to raised friction or resistance.
According to another feature of this invention, the other facing surface having no depression is raised at a portion thereof which the idle member passes in the abovementioned backward rotation thereby increasing the braking effect within that portion.
These and other features and operation of this invention will be described in more detail below in connection with some preferred embodiments thereof with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is an exploded perspective view of an embodiment of the damper device according to this invention;
FIGS. 2 to 7 are cross-sectional views of the embodiment of FIG. 1 illustrative of the operation thereof;
FIGS. 8 and 9 are cross-sectional views showing variations of the embodiment of FIG. 1;
FIGS. 10 to 12 are exploded perspective views showing other variations of the embodiment of FIG. 1; and
FIG. 13 is an exploded perspective view of another embodiment of the damper device of this invention.
Throughout the drawings, same reference numerals are given to structural components which correspond in function.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1 the damper device of this invention comprises a cylindrical inner body 8 having an axle 5 which is integrated therewith to be fixed to a lid of a toilet stool (not shown), for example, and a cylindrical cup-like outer body 7 having an end wall 6 to be fixed to a body (not shown) of the toilet stool, for example, and a pair of round rod-like idle members 9a and 9b disposed between both bodies 7 and 8. The inner body 8 is loosely inserted in the outer body 7 and one end of its axle 5 is rotatably supported in a central hole 10 of the outer body 7. The outer body 7 has another end wall 17 having a central hole 18 and the end wall 17 is fit in and fixed to the opening of the outer body 7 after the inner body 8 is inserted in the cup member 7. Then, the other end of the axle 5 of the inner body 8 is inserted and rotatably supported in the central hole 18 of the end wall 17. Accordingly, the inner body 8 is freely rotatable within the outer body 7 and a gap which is less than the diameter of the idle members 9a and 9b is kept therebetween. In the outer wall of the inner body 8, two pairs of longitudinal grooves 19a, 19b and 20a, 20b are formed adjoiningly at axially symmetric positions. The first grooves 19a and 19b are a little deeper than the second grooves 20a and 20b and both grooves are partly connected as shown to form a low barrier therebetween. In this embodiment, both bodies 7 and 8 are formed of hard plastic and the idle members 9a and 9b formed of elastic rubber. The idle members 9a and 9b lie always in one of the first and second grooves and can roll and elastically get over the barrier between the first and second grooves to move from one to the other since they are in contact with both members 7 and 8.
As is shown more clearly in FIG. 2, the inner wall of the outer body 7 is depressed symmetrically across central angles of about 112 degrees each to form rolling surfaces 11a and 11b having first steps 13a and 13b and second steps 14a and 14b, respectively, at both ends thereof. Thus, a pair of mesas 12a and 12b are formed between the rolling surfaces 11a and 11b. A pair of shallow detent grooves 15a and 15b are formed adjacent to the first steps 13a and 13b at one each of the rolling surfaces 11a and 11b and a pair of portions 16a and 16b adjoining the other ends thereof and corresponding to central angles of about 30 degrees each are a little raised from the remainder of the rolling surfaces or ascended toward the mesas.
In the drawing, when the inner body 8 is rotated counterclockwise with respect to the outer body 7, the idle members 9a and 9b roll or slip on the rolling surfaces 11a and 11b while being held in the first grooves 19a and 19b, respectively. Thereafter, they collide against the first steps 13a and 13b and enter the detent grooves 15a and 15b to come to a stop. There are a pair of central angles of about 18 degrees each between the first and second grooves 19a, 19b and 20a, 20b formed in the inner body 8; and the stool lid (not shown) is fixed to the inner body 8 along a radius 21 thereof corresponding to the second groove 20a. On the other hand, the outer body 7 is fixed to the toilet stool body (not shown) so that its diameter 22 nearly corresponding to the second steps 14a and 14b lies in a horizontal plane. Accordingly, the stool lid forms an angle of about 130 degrees with respect to the horizontal plane 22 when it is fully opened.
Next, when the inner body 8 is rotated clockwise from the state of FIG. 2 to close the stool lid (not shown), the idle members 9a and 9b roll within the detent grooves 15a and 15b and move from the first grooves 19a and 19b to the second grooves 20a and 20b while being elastically compressed, as shown in FIG. 3. If the inner body 8 is further rotated the idle members 9a and 9b leave the detent grooves 15a and 15b as shown in FIG. 4 and roll or slip on the rolling surfaces 11a and 11b in some compressed state. At last the idle members 9a and 9b pass the raised or ascended portions 16a and 16b while being slightly compressed as shown in FIG. 5 and then collide against the second steps 14a and 14b to come to a stop as shown in FIG. 6. When the stool lid (as shown schematically with a phantom line 21) is closed therefore, it is subjected to some braking torque which increases at the last step. Accordingly, the stool lid should not collide against the stool body if it is released from a hand.
Then, if the inner body 8 is rotated counterclockwise when the stool lid is opened, the idle members 9a and 9b roll between both bodies 7 and 8 and move from the second grooves 20a and 20b to the deeper first grooves 19a and 19b to expand elastically. If the rotation is continued, the idle members 9a and 9b pass the raised or ascended portions 16a and 16b as being released from compression as shown in FIG. 7 and go through the rolling surfaces 11a and 11b to return to the full open state of FIG. 2. Accordingly, the stool lid con be lightly opened since the frictional resistance disappears almost.
While the open lid angle (130 degrees in the drawing) cannot exceed 180 degrees in the design of the above embodiment, FIG. 8 shows a design variation which enables it. In this variation, the width of the second grooves 20a and 20b of the inner body 8 is much greater than the width of the first grooves 19a and 19b and the idle members 9a and 9b can move on the surface of the inner body 8 across a central angle of about 108 degrees instead of 18 degrees in FIG. 2. Accordingly, the angle of rotation of the inner body 8 is increased by the difference therebetween and the open lid angle becomes 220 degrees. This variation is advantageous for use in lid and door, such as those used in office automation equipments, which need a large open angle.
When the lid or door (schematically shown with a phantom line 21) is closed from its full open state of FIG. 8 in which the idle members 9a and 9b lie in the detent grooves 15a and 15b of the outer body 7 and the first grooves 19a and 19b of the inner body 8, if the inner body 8 is rotated clockwise, the idle members 9a and 9b first get over the second grooves 20a and 20b and compressed, and then roll or slip to the other ends thereof (position of the phantom line 21) with rotation of the inner body 8. Thereafter, they roll or slip on the rolling surfaces 11a and 11b and pass the raised or ascended portions 16a and 16b to reach the closed position (of the phantom line 22) as same as in the embodiment of FIG. 1. Therefore, the rotation is braked similarly at the time of closing. Next, when the lid is opened the idle members 9a and 9b roll as being compressed between the rolling surfaces 11a and 11b and the wide second groove 20a and 20b brake the rotation at first, while they are released from compression to provide easy light rotation as above-mentioned to the last after they enter the first grooves 19a and 19b.
Although the width of the second grooves 20a and 20b is increased in the variation of FIG. 8, it is understood that a similar effect is obtainable by widening the first grooves 19a and 19b or both grooves. Such selection may be made in accordance with use of the device.
While, in the above embodiment, the first and second grooves 19a, 19b and 20a, 20b are formed in the inner body 8 and the raised or ascended portions 16a and 16b are formed on the outer body 7, the same effect is obtainable even if the grooves are formed in the outer body and the raised or ascended portions are formed on the inner body. Moreover, while the idle members 9a and 9b are formed of rubber in the above embodiment, a similar effect is expectable even if the inner or outer body is made of rubber. FIG. 9 shows another variation in which the grooves are formed in the outer body and part of the inner body is made of rubber.
In the drawing, the inner body 8 is composed of a core portion 27 and a shell portion 28 and the core and shell portions 27 and 28 are made of hard plastic and elastic rubber, respectively. Part of the cylindrical surface of the shell portion 28 is depressed symmetrically to form a pair of rolling surfaces 11a and 11b corresponding to central angles of about 135 degrees each. A pair of first steps 13a and 13b are formed at one each of the rolling surfaces 11a and 11b and second steps 14a and 14b are formed at the other end. A device lid is fixed to the core portion 27 of the inner body 8 along a radius 21 corresponding to the second step 14a. A pair of raised or ascended portions 16a and 16b are formed on the rolling surfaces 11a and 11b in correspondence to central angles of about 60 degrees each from the first steps 13a and 13b. The idle members 9a and 9b are made of hard plastic and lie in two pairs of grooves 19a, 19b and 20a, 20b formed symmetrically in the inner wall of the outer body 7. The outer body 7 is fixed to the device body so that its diameter 22 passing the first grooves 19a and 19b lies horizontally.
When the inner body 8 is rotated in clockwise direction as arrowed for closing the device lid 21, the hard idle members 9a and 9b move first to the shallower second grooves 20a and 20b as shown and partially sink in the relatively soft shell portion 28 of the inner body 8. With rotation of the inner body 8, the idle members 9a and 9b roll, as they are, over the raised portions 16a and 16b of the shell portion 28 across a central angle of about 60 degrees. Accordingly, there is a large resistance for this time and the lid 21 can hold still, without external assistance, at any position. After the idle members 9a and 9b pass the raised portions 16a and 16b, their sinking in the shell portion 28 is reduced and the frictional resistance is also reduced to enable smooth closing of the lid 21. When the lid is opened, the idle members 9a and 9b move to the deeper first grooves 19a and 19b as aforementioned. Therefore, the frictional resistance is further reduced and it becomes much easier and lighter to open the lid. This variation may be utilized effectively, for example, in a wrap-top type personal computer having a liquid crystal display board attached to its lid. In this case, the lid may be rotated in closing direction by a suitable angle and stood still at a position where the display on the board can be observed most clearly, after it is once fully opened. In this case, moreover, if it is arranged that the second steps 14a and 14b of the inner body 8 are slightly deformed elastically by the idle members 9a and 9b and the lid is latched when the lid is fully closed, the lid is elastically opened a little when the latch is released, and it becomes easy to catch it with fingers.
While, in the above embodiment, a pair of idle members 9a and 9b are disposed at both ends of a diameter, a single idle member may be used. However, it is recommendable to use two or more idle members circumferentially at equal intervals in order to avoid eccentric load and assure smooth rotation. FIG. 10 shows an example in which four idle members are disposed at intervals of 90 degrees. In this example, outer and inner bodies 7 and 8 are halved normally to their axes, both halves are joined together with 90 degree rotation and a pair of idle members 9a and 9b are disposed in each half.
FIG. 11 shows a variation of FIG. 1 in which the idle members 9a and 9b are divided into plural pieces (two pieces in the drawing) each. The idle members 9a and 9b may be subjected to undesirable distortion when they are made or rubber and considerably long. This variation is effective to avoid such trouble. Moreover, this variation can delicately modify a braking mode by giving mutually different diameters to the respective idle members.
FIG. 12 shows a further variation of the variation of FIG. 11, in which the divided idle members 9a and 9b are substituted with a series of balls. In this example, the grooves are provided with partitions 25 in order to prevent irregular longitudinal distribution of the balls. The balls may be substituted with other kind of bodies of revolution such as ellipsoids of revolution.
While, in the above-mentioned embodiment, the facing surfaces of the outer and inner bodies 7 and 8 are cylindrical, it is obvious that a similar effect is obtainable even if they are conical. While the facing surfaces will be two planes normal to the axis if the vertical angle of the conical surface is 180 degrees, such structure is also within the technical range of this invention. An embodiment thereof is shown in FIG. 13.
In the drawing, the damper device includes two outer discs 7A and 7B corresponding to the outer body 7 of the embodiment of FIG. 1 and an inner disc 8 corresponding to the inner body 8 thereof. These members are assembled by passing a rotational shaft 5 fixed to the inner disc 8 through central holes 10A and 10B of the outer discs 7A and 7B and fitting a cylindrical shell 30 on the outer discs 7A and 7B and, in this state, the inner disc 8 is rotatable with respect to the outer discs 7A and 7B. As shown, a mesa 12A, a raised portion 16A and a rolling surface 11A respectively corresponding to the mesas 12a and 12b, raised portions 16a and 16b and rolling surfaces 11a and 11b of FIG. 2 are formed on the inner surface of one outer disc 7A and, though not shown in the drawing, similar mesa 12B, raised portion 16B and rolling surface 11B are formed on the inner surface of the other outer disc 7B. A pair of depressions 19B and 20B corresponding to the grooves 19a , 20a and 19b, 20b of the embodiment of FIG. 1 are formed in one surface of the inner disc 8 and, though not shown in the drawing, similar depressions 19A and 20A are formed in the other surface of the inner disc 8. At the time of assembling, balls 9A and 9B corresponding to the idle members 9a and 9b of the embodiment of FIG. 1 are put in these depressions. While any one of the inner and outer discs and idle members is made of an elastic material also in this case, its selection depends upon use and usage of the device. The operation of this embodiment will not be described further since it will be obvious from the operation of the embodiment of FIG. 1. However, it is understood that an angle of rotation almost close to 360 degrees is obtained in this embodiment by reducing the width of the mesa 12A.
The above embodiments are provided for illustrative purpose only and do not mean any limitation of the invention. It should be obvious to those skilled in the art that various modifications and changes can be made on these embodiments without leaving the spirit and scope of the invention as defined in the appended claims.
For example, the sizes and angles used in the above description can be selected arbitrarily in accordance with the use of the device. Although a ridge which separates the first and second grooves is shown therebetween in the drawings, the less the interval of the grooves, the lower the ridge and, at last, the two grooves may become a single groove having a simple slanting bottom. In other words, it should be noted that presence of the ridge is not included in the limiting conditions of the invention. Although the first and second grooves are shown as parallel to the axis of the device, they need not be parallel but may be slanting with respect to a generator of the cylinder as a tooth of a helical gear. If so, such an effect as similar to the helical gear, that is, smoother rotation will be obtained. The idle member need not always contact with the facing rolling surface. A necessary condition of this invention is that the idle member is urged against the facing surface to move from the first groove to the second groove or vice versa in a part of the relative rotation (e.g., at the beginning or end thereof), and it may not contact with the facing surface in the other part, especially, in the process of opening the lid. The hard plastic material may be substituted with any other hard material such as metal and the elastic rubber may be substituted also with any other elastic material such as synthetic resin having elasticity.
Although, in the above description, the outer body 7 is fixed to a main body of the device for use and the inner body 8 is fixed to its lid, its converse is also possible. A plurality of such damper devices may be connected in series for use. For example, when a plurality of hinge structures are disposed on a single axis as in the case of stool lid and stool seat of a toilet stool, the damper may be provided with a single outer body fixed to the stool body and two inner bodies respectively fixed to the lid and seat and having their own idle members. Moreover, the inventive damper device may be used not only in a hinge structure having a horizontal axis as above-mentioned, but also in those having vertical and slanting axes. In other words, it may be used in a hinge structure for an entrance door.
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A buffering device used in a hinge structure of a lid or cover, such as stool lid of a toilet stool of Western style, which is pivoted on a horizontal axis and generally opened upwards by hand and closed downwards by gravity, comprising two members such as of coaxial cylinder type having mutually facing surfaces, respectively, and being combined coaxially to enable relative rotation, and at least one idle member disposed within a gap between the facing surfaces to roll with the relative rotation, and including no buffering fluid, in which the torque for closure is made large as compared with the torque for opening, so that the lid can be opened lightly when it is opened by hand, while it is automatically braked for preventing it from colliding against the stool body to produce an undesirable strike sound when it is naturally closed by gravity.
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This Application claim benefit to Provisional Application No. 60/127,328 filed Apr. 1, 1999 which claims benefit to No. 60/128,478 filed Apr. 9, 1999.
The invention described and claimed herein was made in part under a grant from the National Institutes of Health. The U.S. Government has certain rights in the invention.
FIELD OF THE INVENTION
The present invention relates to novel analogs of the hormone 1α,25 dihydroxy vitamin D 3 . Such analog materials exhibit a pharmacologically desirable combination of high antiproliferative and high transcriptional activity in vitro along with no or low calcemic activity in vivo.
BACKGROUND OF THE INVENTION
Because of its extraordinarily high potency in regulating diverse biochemical events vital to good health in humans, 1α,25-dihydroxy vitamin D 3 , also known as calcitriol or 1,25D 3 , has stimulated the worldwide interest of medical researchers, molecular biologists, pharmacologists, medicinal and organic chemists, and researchers in the area of products for personal care and cancer prevention and/or treatment. This Material corresponds to the structure set forth in Formula I.
Numerous references can be cited as showing prior work with respect to vitamin D 3 analogues, calcitriol or the like. See, for example:
Vitamin D. Chemical, Biochemical and Clinical Update, Proceedings of the Sixth Workshop on Vitamin D, Merano, Italy, March 1985; Norman, A. W., Schaefer, K., Grigoleit, H. G., Herrath, D. V. Eds.; W. de Gruyter; New York, 1985; Brommage, R., DeLucca, H. F., Endocrine Rev. (1985) 6:491; Dickson, I., Nature (1987) 325:18; Cancela, L., Theofon, G., Norman, A. W., in Hormones and Their Actions. Part I; Cooke, B. A., King, R. J. B., Van der Molen, H. J. Eds.; Elsevier, Holland, 1988; Tsoukas, D. C., Provvedini, D. M., Manolagas, S. C., Science, (Washington, D.C.) (1984) 224:1438; Provvedini, D. M., Tsoukas, C. D., Deftoe, L. J., Manolagas, S. C., Science (Washington, D.C.) (1983) 221:1181; Vitamin D. Chemical Biochemical, and Clinical Endocrinology of Calcium Metabolism, Proceedings of the Fifth Workshop on Vitamin D, Williamsburg, Va., February 1982, Norman, A. W., Schaefer, K., Herrath, D. V., Grigoleit, H. G., Eds., W. de Gruyter, New York, 1982, pp. 901-940; Calverley, M. J. in Vitamin D: Molecular, Cellular, and Clinical Endocrinology, Norman, A. W., Ed., de Gruyter; Berlin, 1988, p. 51; Calverley, M. J., Tetrahedron ( 1987) 43:4609. Vitamin D, A Pluripotent Steroid Hormone: Structural Studies, Molecular Endocrinology and Clinical Applications, ed. Norman, Boullion and Thomasset, 1994, Walter de Gruyter, New York. Calverley and Binderup, Bioorganic & Medicinal Chemistry Letters (1993) 3:1845. U.S. Pat. Nos. 5,274,142; 5,389,622; 5,403,832 and 5,830,885 also describe and claim vitamin D 3 analogs. The entire contents of each reference and patent cited above and elsewhere in the present application are hereby incorporated by reference.
A major chemical challenge has been to design and synthesize analogs of 1α,25-dihydroxy vitamin D 3 that retain potent antiproliferative and pro-differentiating activities but that lack hypercalcemic activity. Some synthetic analogs exhibiting such selective physiological activities, like 1α, 25-dihydroxy-16-ene-23-yne-26,27-hexafluorocholecalciferol developed by Hoffman-La Roche, have been shown to possess very desirable pharmacological properties. Only a few 24-fluoro and 24,24-difluoro analogs of 1,25D 3 , having natural A-ring substituents and stereochemistry, have been synthesized. They have been shown, however, to be disappointingly similar to 1,25D 3 in terms of calcemic activity. Although their binding affinity to the vitamin D receptor (VDR) is similar to that of calcitriol, such materials do have longer plasma half-lives.
Given the foregoing, it is clear that there is a continuing need to identify additional synthetic analogs of the hormone 1α,25-dihydroxy vitamin D 3 , which analogs selectively exhibit desirable pharmacological activities but do not exhibit hypercalcemic activity. Accordingly, it is an object of the present invention to provide novel 1,25D 3 analogs which are useful for a wide variety of beneficial medicinal and/or personal care product uses but which do not exhibit undesirably high levels of calcemic activity in vivo.
SUMMARY OF THE INVENTION
The present invention relates to novel sulfur-containing, and optionally fluorinated, unsaturated and/or oxa-containing analogs of 1α,25-dihydroxy vitamin D 3 . Such analogs have the diastereoisomeric structural formulas set forth as Formulas II, III, IV, V, VI, VII, VIII, IX and X.
In Formulae II-X and other compounds of the invention, the hydroxyl substituents at Position 1 and at position 3 on the A-ring can be such that the analogs are either in the (−), i.e. (1α, 3β) or the (+), i.e. (1β, 3α) , diastereomeric configuration. The C—O bonds at these positions are occasionally indicated by wavy lines in structural formulae hereinbelow to indicate that alternative configurations are intended. Compounds with substituents in the (1α, 3β) diastereomeric configuration are preferred according to the invention.
The present invention also includes materials which are similar to the compounds of Formulae II-X but which have 23-oxa-25-sulfone, 20-epi-22-oxasulfone; 16-ene-alkenyl sulfone; 16-ene-alkynyl sulfone; and 22E, 24E diene sulfone units. Compounds represented by Formulae XIV-XVII and XIX are among the preferred compounds of the invention:
Compounds of the invention can be represented by the general formulae XI-XIII and XVIII
wherein X is H 2 or F 2 and R is a branched or straight chain lower alkyl (1-6 carbons), an unsubstituted phenyl group or a phenyl group substituted with a lower alkyl or alkoxy group. Compounds wherein R is methyl, t-butyl, phenyl, and methoxyphenyl are especially preferred.
wherein X is H 2 or F 2 and R is a branched or straight chain lower alkyl (1-6 carbons), an unsubstituted phenyl group or a phenyl group substituted with a lower alkyl or alkoxy group. Compounds wherein R is methyl, t-butyl, phenyl, and methoxyphenyl are especially preferred.
wherein n is 1 or 2, and R is a branched or straight chain lower alkyl (1-6 carbons), an unsubstituted phenyl group or a phenyl group substituted with a lower alkyl or alkoxy group. Compounds wherein R is methyl, t-butyl, phenyl, and methoxyphenyl are especially preferred.
wherein R is a branched or straight chain lower alkyl (1-6 carbons), an unsubstituted phenyl group or a phenyl group substituted with a lower alkyl or alkoxy group. Compounds wherein R is methyl, t-butyl, phenyl, and methoxyphenyl are especially preferred.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 : Dose response effects of vitamin D 3 analogs on keratinocyte proliferation. N 0 represents the number of cells at zero hours and N 1 represents the number of cells at 96 hours. KRC 22E, 24Ediene 26SO2-1=compound 23a; KRC 22E, 24Ediene 26SO2-2=compound 23b; KRC-20epi 22oxa 26 PMP-1=compound 15a; KRC-20epi 22oxa 26 PMP-2=compound 15b.
FIG. 2 : Effect of 22E, 24E diene sulfone vitamin D 3 analog on calcium levels in rat urine. Values shown for control, calcitriol and diene sulfone analog groups, each containing three animals.
FIG. 3 : Effect of 22E, 24E diene sulfone vitamin D 3 analog on weight gain. Weight gain of rats, days 0-7 of treatment is shown for control, calcitriol and diene sulfone analog groups, each containing three animals.
DETAILED DESCRIPTION OF THE INVENTION
In preparing the calcitrol analogs corresponding to Formulas II-VIII, several considerations are taken into account in order to arrive at the desired combination of substitutents which will diminish calcemic activity yet also provide potently pro-differentiating side chains. Position 24 on the side chain is typically the site of side chain metabolic oxygenation. Therefore, it is believed that replacing C—H by stronger C—F bonds at this position should increase lifetime of such an analog in vivo. Further, the atomic size of a fluorine substituent closely matches that of a hydrogen atom, thereby causing no steric hindrance to receptor binding. Further, it is postulated that the presence of two fluorine atoms should increase the lipophilicity of the analog relative to its non-fluorinated counterpart, thereby enhancing rates of absorption and transport in vivo. Further, presence of a t-butylsulfone group at position 24 or 25 is expected to simulate the polar environment in that region characteristic of the natural polar 25-OH group. Finally, a 16-ene carbon-carbon double bond often potentiates antiproliferative activity.
Taking these considerations into account, the sulfur-containing, and optionally fluorine-containing, unsaturated and oxa-containing analogs of the present invention can be prepared via multi-step organic synthesis reaction procedures as set forth hereinafter in Schemes 1, 2, 3, 4, 5, 6, 7, 8 and 9. Steps in the reaction process as depicted in the schemes are described in the examples following each scheme.
Unless otherwise noted, in all of the examples, reactions are run in flame-dried round-bottomed flasks under an atmosphere of ultra high purity (UHP) argon. Diethyl ether (ether) and tetrahydrofuran (THF) are distilled from sodium benzophenone ketyl prior to use. Methylene chloride (CH 2 Cl 2 ) is distilled from calcium hydride prior to use. All other compounds are purchased from Aldrich Chemical Company and used without further purification. Analytical thin-layer chromatography (TLC) is conducted with Silica Gel 60 F 254 plates (250 μm thickness, Merck). Column chromatography is performed using short path silica gel (particle size<230 mesh), flash silica gel (particle size 400-230 mesh), or Florisil® (200 mesh). Yields are not optimized. Purity of products is judged to be >95% based on their chromatographic homogeneity. High performance liquid chromatography (HPLC) is carried out with a Rainin HPLX system equipped with two 25 mL/min preparative pump heads using Rainin Dynamax 10 mm×250 mm (semi-preparative) columns packed with 60 Å silica gel (8 μm pore size), either as bare silica or as C-18-bonded silica. Melting points are measured using a Mel-Temp metal-block apparatus and are uncorrected. Nuclear magnetic resonance (NMR) spectra are obtained either on a Varian XL-400 spectrometer, operating at 400 MHz for 1 H and 100 MHz for 13 C or on a Varian XL-500 spectrometer, operating at 500 MHz for 1 H and 125 MHz for 13 C. Chemical shifts are reported in parts per million (ppm, δ) downfield from tetramethylsilane. Infrared (IR) spectra are obtained using a Perkin-Elmer 1600 FT-IR spectrometer. Resonances are reported in wavenumbers (cm −1 ). Low and high resolution mass spectra (LRMS and HRMS) are obtained with electronic or chemical ionization (EI or Cl) either (1) at Johns Hopkins University on a VG Instruments 70-S spectrometer run at 70 eV for EI and run with ammonia (NH 3 ) as a carrier gas for CI, or (2) at the University of Illinois at Champaign-Urbana on a Finnigan-MAT CH5, a Finnigan-MAT 731, or a VG Instruments 70-VSE spectrometer run at 70 eV for EI and run with methane (CH 4 ) for CI.
Preparation of the Formula II materials is set forth in Scheme 1 as follows.
Synthesis of the iodide derivative 5 of the C,D-ring is carried out from the calcitriol starting material 1 through intermediates 2, 3, and 4 in conventional manner. These steps in the synthesis are described in greater detail in our publication, Journal of Organic Chemistry, 1997, Vol. 62, pp. 3299-3314.
Preparation of the various intermediates 6, 7, 8, 9, and 10 and the Formula II compounds is described in Examples 1 through 5 hereinafter.
EXAMPLE 1
TES protected C,D-ring Sulfone (+)-6
A solution of methyl tert-butyl sulfone (594 mg, 4.40 mmol) and 20 ml of THF was cooled to −78° C., and then 3.1 mL (4.40 mmol, 1.4 M solution in hexane) of n-BuLi was added dropwise to the solution. After 15 minutes, 1.3 mL of HMPA was added and the solution was stirred for another 15 minutes. A precooled (−78° C.) solution of iodide 5 (381 mg, 0.87 mmol) in 20 mL of THF was added slowly via cannula. The reaction mixture was then warmed up to room temperature. The reaction was quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then purified by column chromatography (25% EtOAc/hexanes) to give 336 mg (87%) of the desired sulfone (+)-6 as a colorless oil: [α] 25 D +45.9° (c 3.3, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ4.02 (d, J=1.6 Hz, 1H), 3.01-2.90 (m, 1H), 2.85-2.73 (m, 1H), 2.07-1.75 (m, 4H), 1.71-1.50 (m, 4H), 1.41 (s, 9H), 1.40-1.18 (m, 5H), 1.16-1.00 (m, 2H), 0.96-0.89 (m, 15H), 0.54 (q, J=8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ69.46, 59.15 56.56, 53.20, 43.30, 42.44, 40.92, 34.99, 34.76, 27.41, 26.33, 23.76, 23.12, 18.56, 17.85, 13.74, 7.14, 5.12; IR (neat, cm −1 ) 2943, 2872, 1461, 1302, 1284, 1114, 1014; HRMS m/z (M + ) calcd 444.3093 for C 24 H 48 O 3 SSi, found 480.3098.
EXAMPLE 2
Difluorinated C,D-ring Sulfone (+)-8
To a solution of the TES protected C,D-ring sulfone (+)-6 (265 mg, 0.60 mmol) in THF (6.0 mL) was added 0.85 mL of n-BuLi (1.4 M solution in hexane, 1.19 mmol) at −78° C. After being stirred for 30 minutes, a precooled solution of NFSI (N-fluorobenzenesulfonimide, bought directly from Aldrich, 226 mg, 0.72 mmol) in 5.0 mL of THF was added slowly to the reaction mixture, and then it was warmed up to room temperature. The reaction was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo, and then purified by column chromatography (25% EtOAc/hexanes) to give a mixture of mono and di-fluorinated sulfones.
The mixture (280 mg) was dissolved in 6.0 mL of THF and the solution was cooled to −78° C. To the solution was added 1.1 mL of n-BuLi (1.4 M solution in hexane, 1.54 mmol) and the reaction mixture was stirred for 30 minutes. A precooled solution of NFSI (386 mg, 1.22 mmol) in 5.0 mL of THF was then added slowly via cannula. The reaction mixture was warmed up to room temperature, quenched with water, extracted with EtOAc, washed with brine and concentrated. Purification by column chromatography (25% EtOAc/hexanes) gave 230 mg (80%) of the desired difluoronated C,D-ring sulfone (+)-8 as a colorless oil: [α] 25 D +40.7° (c 2.1, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ4.02 (d, J=2.8 Hz, 1H), 2.45 (ddd, J=35.6, 13.6, 8.8 Hz, 1H), 2.05-1.75 (m, 5H), 1.70-1.54 (m, 3H), 1.52 (s, 9H), 1.44-1.13 (m, 6H), 1.08 (d, J=6.0 Hz, 3H), 0.95 (s, 3H), 0.94 (t, J=8.0 Hz, 9H), 0.55 (q, J=8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ130.37 (t, J=289.3 Hz), 69.49, 63.29, 56.97, 53.32, 42.58, 40.89, 35.21 (t, J=18.3 Hz), 34.72, 30.76, 27.75, 24.48, 23.09, 20.55, 17.83, 13.56, 7.17, 5.14; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−94.82 (dd, J=218.1, 35.0 Hz), −97.41 (dd, J=218.3, 30.6 Hz); IR (neat, cm −1 ) 2950, 2876, 1459, 1322, 1165, 1134, 1083, 1018; HRMS m/z (M + ) calcd 480.2905 for C 24 H 46 F 2 O 3 SiS, found 480.2900.
EXAMPLE 3
Deprotected Difluoronated C,D-ring Alcohol (+)-9
A solution of silyl ether (+)-8 (226 mg, 0.47 mmol) in THF (5.0 mL) and 1.2 mL of 1.0 M solution of tetra-n-butylammonium fluoride (TBAF) in THF was stirred overnight at room temperature. The mixture was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by column chromatography (25% EtOAc/hexanes) to give 147 mg (85%) of the desired alcohol as a white solid: mp 105-106° C.; [α] 25 D +34.7° (c 1.7, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ4.07 (d, J=2.4 Hz, 1H), 2.45 (ddd, J=35.4, 13.6, 9.2 Hz, 1H), 2.05-1.74 (m, 6H), 1.64-1.12 (m, 18H), 1.09 (d, J=6.0 Hz, 3H), 0.97 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ130.27 (t, J=289.3 Hz), 69.42, 63.32, 56.77, 52.82, 42.29, 40.51, 35.16 (t, J=18.5 Hz), 33.68, 30.76, 27.63, 24.47, 22.61, 20.44 (d, J=2.8 Hz), 17.57, 13.53; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−94.82 (dd, J=218.1, 35.0 Hz), −97.43 (dd, J=218.1, 32.0 Hz); IR (neat, cm −1 ) 3564, 2939, 2869, 1317, 1133; HRMS m/z (M + ) calcd 366.2040 for C 18 H 32 F 2 O 3 S, found 366.2047; Anal. Calcd for C 18 H 32 F 2 O 3 S: C, 58.98; H, 8.74. Found: C, 58.45; H, 8.76.
EXAMPLE 4
C,D-ring Ketone (+)-10
To a solution of the C,D-ring alcohol (+)-9 (74 mg, 0.20 mmol) in CH 2 Cl 2 (5.0 mL) were added 150 mg of oven-dried celite and pyridinium dichromate (PDC, 152 mg, 0.40 mmol) at room temperature. The reaction mixture was stirred overnight and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by column chromatography (25% EtOAc/hexanes) to give 67 mg (91%) of the desired C,D-ring ketone (+)-10 as a colorless solid: mp 106-107° C.; [α] 25 D +15.7° (c 3.5, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ2.51-2.33 (m, 2H), 2.30-2.14 (m, 2H), 2.12-2.04 (m, 1H), 2.04-1.80 (m, 5H), 1.72 (m, 1H), 1.64-1.42 (m, 12H), 1.33 (m, 1H), 1.12 (d, J=6.0 Hz, 3H), 0.65 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ211.56, 129.93 (t, J=289.4 Hz), 63.31, 61.99, 56.63, 49.90, 40.98, 38.95, 35.20 (t, J=18.5 Hz), 30.79, 27.75, 24.35, 24.02, 20.54 (d, J=2.6 Hz), 19.14, 12.49; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−94.87 (ddd, J=219.0, 33.6, 5.6 Hz), −97.46 (ddd, J=219.0, 30.5, 8.5 Hz); IR (neat, cm −1 ) 3013, 1708, 1314, 1208; HRMS m/z (M + ) calcd 364.1884 for C 18 H 30 F 2 O 3 S, found 364.1884; Anal. Calcd for C 18 H 30 F 2 O 3 S: C, 59.31; H, 8.24. Found: C, 59.42; H, 8.27.
EXAMPLE 5
Analogs Formula II
A solution of 102 mg (0.18 mmol) of racemic phosphine oxide (A-ring) in 2.0 mL of anhydrous THF was cooled to −78° C. and treated with 94 μL (0.15 mmol, 1.6 M solution in THF) of phenyllithium under argon atmosphere. The mixture turned reddish orange and was stirred for 30 min at −78° C. To the solution was added dropwise a solution of 45 mg (0.12 mmol) of the C,D-ring ketone (+)-10 (dried azeotropically three times with benzene and held under vacuum for at least 24 h prior to use) in 1.0 mL of anhydrous THF. The reaction kept going on at −78° C. until the reddish orange color faded to yellow (about 4 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then purified by column chromatography (97% hexanes/ether) to afford 59 mg (66%) of the coupled product as a colorless oil.
The coupled product (59 mg, 0.081 mmol) was dissolved in 3.0 mL of anhydrous THF, and to this solution were added TBAF (0.32 mL, 0.32 mmol, 1.0 M solution in THF) and 46 μL (0.32 mmol, 4 equiv) of Et 3 N. The reaction was run in darkness overnight, then quenched with water and extracted with EtOAc. The organic portions were washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by silica gel chromatography (90% EtOAc/hexanes) to give 32 mg (79%) of a mixture of two diastereomers as a white solid. One portion (6 mg) of the diastereomers was separated by reverse phase HPLC (C-18 semipreparative column, 52% MeCN/H 2 O, 3.0 mL/min) to afford 5.7 mg (19%) of Formula II-1 (1α, 3β, t R 100.8 min) as a foaming solid and 4.1 mg (14%) of Formula II-2 (1β, 3α, t R 95.8 min) as a colorless oil. Formula II-1: [α] 25 D +17.4° (c 0.6, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.37 (d, J=11.2 Hz, 1H), 6.01 (d,J=11.6 Hz, 1H), 5.33 (s, 1H), 4.99 (s, 1H), 4.44 (m, 1H), 4.23 (m, 1H), 2.83 (dd, J=12.4, 3.6 Hz, 1H), 2.66-2.38 (m, 2H), 2.31 (dd, J=13.4, 6.6 Hz, 1H), 2.10-1.20 (m, 24H), 1.12 (d, J=6.0 Hz, 3H), 0.59 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ147.78, 142.73, 133.42, 130.24 (t, J=288.0 Hz), 125.04, 117.56, 112.10, 71.03, 67.06, 63.36, 56.70, 56.55, 46.17, 45.46, 43.02, 40.57, 35.13, 31.43, 29.17, 27.96, 24.48, 23.67, 22.40, 20.76, 12.09; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−94.87 (dd, J=217.7, 37.2 Hz), −97.39 (dd, J=219.0, 28.0 Hz); UV (EtOH) λ max 263 nm (ε 12,225); IR (neat, cm −1 ) 3695, 3601, 2931, 2872, 1596, 1467, 1308, 1132, 1043; HRMS m/z (M + ) calcd 500.2772 for C 27 H 42 F 2 O 4 S, found 500.2774. Formula II-2: [α] 25 D +8.50° (c 0.4, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.38 (d, J=11.2 Hz, 1H), 6.01 (d, J=11.2 Hz, 1H), 5.32 (s, 1H), 5.00 (s, 1H) 4.45 (m, 1H), 4.22 (m, 1H), 2.83 (dd, J=12.8, 4.4 Hz, 1H), 2.62 (dd, J=12.8, 4.7 Hz, 1H), 2.46 (m, 1H), 2.29 (dd, J=13.4, 7.4 Hz, 1H), 2.20-1.20 (m, 24H), 1.12 (d, J=6.0 Hz, 3H), 0.59 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ147.41, 142.76, 133.29, 130.24 (t, J=289.3 Hz), 125.05, 117.55, 112.91, 71.58, 67.00, 63.36, 56.70, 56.52 46.17, 45.69, 42.97, 40.55, 35.32 (t, J=17.8 Hz), 31.43, 29.14, 27.94, 24.47, 23.65, 22.42, 20.74, 12.09; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) −94.81 (dd, J=220.7, 29.7 Hz), −97.38 (dd, J=215.8, 26.7 Hz); UV (EtOH) λ max 263 nm (ε 12,200); IR (neat, cm −1 ) 3695, 3613, 2919, 1596, 1308, 1126, 1043. HRMS m/z (M + ) calcd 500.2772 for C 27 H 42 F 2 O 4 S, found 500.2784.
Preparation of the Formula III materials is set forth in Scheme 2 as follows:
Synthesis of the iodide derivative 14 of the C,D-ring is carried out from the sulfonate starting material 4 and proceeds through intermediates 11, 12, and 13 as set forth in Scheme 2. These steps in the synthesis are described in greater detail in the following experimental sections.
Preparation of the various intermediates 15, 16, and 17 and the Formula III compounds is described in Examples 6 through 9 hereinafter.
EXAMPLE 6
TES Protected 25-phenyl C,D-ring Sulfone (+)-15
To a solution of methyl phenyl sulfone (181 mg, 1.16 mmol) and THF (10 mL) was added 0.83 mL (1.16 mmol) of a 1.4 M solution of n-BuLi in hexane at −78° C. After 15 minutes, 0.3 mL of HMPA was added and the solution was stirred for another 15 minutes at −78° C. A precooled (−78° C.) solution of iodide 14 (105 mg, 0.23 mmol) in 3.0 mL of THF was added slowly via cannula. The reaction mixture was then warmed up to room temperature. The reaction was quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , and concentrated to give a crude product that was purified by column chromatography (25% EtOAc/hexanes) to give 105 mg (95%) of the desired sulfone (+)-15 as a colorless oil: [α] 25 D +44.10° (c 1.3, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.94-7.86 (m, 2H), 7.70-7.52 (m, 3H), 4.00 (d, J=2.4 Hz, 1H), 3.03 (m, 2H), 1.93-1.46 (m, 7H), 1.44-1.22 (m, 5H), 1.22-0.96 (m, 5H), 0.92 (t, J=8.0 Hz, 9H), 0.85 (s, 3H), 0.83 (d, J=6.4 Hz, 3H), 0.53 (q, J=7.9 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ139.43, 133.74, 129.39, 128.15, 69.45, 56.88, 56.51, 53.14, 42.27, 40.85, 35.10, 34.72, 34.54, 27.43, 23.07, 19.45, 18.47, 17.79, 13.64, 7.10, 5.07; IR (neat, cm −1 ) 2949, 2875, 1447, 1307, 1149, 1087, 1025; HRMS m/z (M + ) calcd 478.2937 for C 27 H 46 O 3 SiS, found 478.2932.
EXAMPLE 7
Deprotected 25-phenyl C,D-ring Sulfone (+)-16
A flame-dried 5 mL flask was charged with 105 mg (0.22 mmol) of the silyl ether (+)-15, 2.0 mL of anhydrous THF and 0.55 mL (0.55 mmol) of a 1.0 M solution of TBAF in THF. The resulting reaction mixture was stirred overnight at room temperature, and then it was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by chromatography (20% EtOAc/hexanes) to give 79.mg (99%) of the desired alcohol (+)-16 as a colorless oil: [α] 25 D +31.80° (c 3.0, CHCl 3 ); 1 H NMR(400 MHz, CDCl 3 ) δ7.92-7.84 (m, 2H), 7.63 (t, J=7.4 Hz, 1H), 7.58-7.50 (m, 2H), 4.02 (d, J=2.4 Hz, 1H), 3.02 (m, 2H), 1.92 (d, J=13.2 Hz, 1H), 1.85-1.67 (m, 4H), 1.62-0.94 (m, 12H), 0.86 (s, 3H), 0.82 (d, J=6.8 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ139.32, 133.75, 129.38, 128.10, 69.27, 56.78, 56.31, 52.62, 41.95, 40.42, 35.05, 34.42, 33.65, 27.25, 22.55, 19.39, 18.35, 17.51,13.61; IR (neat, cm −1 ) 3539, 2937, 2872, 1446, 1305,1147,1086; HRMS m/z (M + ) calcd 364.2072 for C 21 H 32 O 3 S, found 364.2069.
EXAMPLE 8
C,D-ring Ketone (+)-17
To a solution of the C,D-ring alcohol (+)-16 (68 mg, 0.19 mmol) in CH 2 Cl 2 (5.0 mL) were added 140 mg of oven-dried celite and pyridinium dichromate (PDC, 140 mg, 0.38 mmol) at room temperature. The reaction mixture was stirred overnight and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by silica gel chromatography (50% EtOAc/hexanes) to give 62 mg (92%) of the desired C,D-ring ketone (+)-17 as a colorless oil: [α] 25 D +10.8° (c 3.4, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.94-7.82 (m, 2H), 7.63 (t, J=7.4 Hz, 1H), 7.58-7.48 (m, 2H), 3.02 (m, 2H), 2.39 (dd, J=11.6, 7.2 Hz, 1H), 2.30-2.10 (m, 2H), 2.10-1.26 (m, 12H), 1.26-1.02 (m, 2H), 0.89 (d, J=6.4 Hz, 3H), 0.57 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ211.97, 139.34, 133.80, 129.41, 128.07, 61.91, 56.67, 56.28, 49.93, 41.01, 38.96, 35.30, 34.41, 27.56, 24.10, 19.33, 19.11, 18.53, 12.56; IR (neat, cm 31 1 ) 2943, 2872, 1708, 1443, 1378, 1302, 1143, 1079; HRMS m/z (M + ) calcd 362.1916 for C 21 H 30 O 3 S, found 362.1910.
EXAMPLE 9
Analogs Formula III
Racemic phosphine oxide (A-ring, 102 mg, 0.18 mmol) was dissolved in 2.0 mL of anhydrous THF and cooled to −78° C. under argon atmosphere. To this solution was added 94 μL (0.15 mmol) of phenyllithium (1.8 M solution in THF) dropwise. The mixture turned deep reddish orange and persisted. After stirring at −78° C. for 30 minutes, a precooled (−78° C.) solution of C,D-ring ketone (+)-1 7 (44 mg, 0.12 mmol) dissolved in 1.0 mL of anhydrous THF was added dropwise via cannula. The reaction kept going on until the reddish orange color faded to yellow (about 4 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was allowed to warm to room temperature, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , filtered, concentrated in vacuo, and then purified by column chromatography (20% EtOAc/hexanes) to afford 47 mg (54%) of the coupled product as a colorless oil.
The coupled product (47 mg, 0.065 mmol) was dissolved in 3.0 mL of anhydrous THF with 38 μL of Et 3 N, and to this solution was added 0.26 mL (0.26 mmol) of TBAF (1.0 M solution in THF) at room temperature. The reaction was run in darkness overnight, then extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by column chromatography (90% EtOAc/Hexanes) to give 29 mg (90%) of a mixture of two diastereomers as a colorless oil. One portion (20 mg) of the diastereomers was separated by reverse phase HPLC (C-18 semipreparative column, 51% MeCN/H 2 O, 3.0 mL/min) to afford 9.1 mg (22%) of Formula III-1 (1α, 3β, t R 66.4 min) and 2.6 mg (6%) of Formula III-2 (1β, 3α, t R 63.7 min) as colorless oils. Formula III-1: [α] 25 D +23.0° (c 1.0, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.96-7.88(m, 2H), 7.66 (t, J=7.4 Hz, 1H), 7.62-7.54 (m, 2H), 6.36 (d, J=11.2 Hz, 1H), 6.00 (d, J=11.2 Hz, 1H), 5.32 (s, 1H), 4.99 (s, 1H), 4.42 (m, 1H), 4.22 (m, 1H), 3.04 (m, 2H), 2.81 (dd, J=12.0, 3.6 Hz, 1H), 2.59 (dd, J=13.2, 3.2 Hz, 1H), 2.31 (dd, J=13.4, 6.6 Hz, 1H), 2.08-1.04 (m, 18H), 0.88 (d, J=6.4 Hz, 3H), 0.51 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ147.80, 143.11, 139.48, 133.84, 133.20, 129.48, 128.23, 125.13, 117.32, 112.02, 71.03, 67.05, 56.92, 56.44, 56.33, 46.07, 45.45, 43.04, 40.60, 36.02, 34.70, 29.22, 27.81, 23.73, 22.41, 19.55, 18.74,12.19; UV (EtOH) λ max 264 nm (ε 15,100); IR (neat cm −1 ) 3683, 3601, 2931, 2861, 1596, 1443, 1378, 1302, 1149, 1079, 1043; HRMS m/z (M + ) calcd 498.2804 for C 30 H 42 O 4 S, found 498.2818. Formula III-2: [α] 25 D −2.7° (c 0.3, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.98-7.88 (m, 2H), 7.66 (t, J=7.6 Hz, 1H), 7.62-7.54 (m, 2H), 6.38 (d, J=11.6 Hz, 1H), 5.99 (d, J=11.6 Hz, 1H), 5.31 (s, 1H), 4.99 (s, 1H), 4.44 (m, 1H), 4.21 (m, 1H), 3.05 (m, 2H), 2.82 (d, J=13.2 Hz, 1H), 2.61 (dd, J=13.2, 3.6 Hz, 1H), 2.29 (dd, J=13.0, 7.4 Hz, 1H), 2.20-1.06 (m, 18H), 0.89 (d, J=6.8 Hz, 3H), 0.51 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ147.48, 143.16, 139.49, 133.85, 133.09, 129.49, 128.24, 125.14, 117.33, 112.76, 71.55, 67.02, 56.92, 56.44, 56.33, 46.08, 45.67, 43.02, 40.59, 36.02, 34.71, 29.20, 27.81, 23.71, 22.44, 19.56, 18.75, 12:19; UV (EtOH) λ max 263 nm (ε 13,600); IR (neat, cm −1 ) 3695, 3613, 2966, 1596, 1449, 1384, 1249, 1043; HRMS m/z (M + ) calcd 498.2804 for C 30 H 42 O 4 S, found 498.2814.
Preparation of the Formula IV materials is set forth in Scheme 3 as follows:
Synthesis of the iodide derivative 24 of the C,D-ring is carried out from the 17-ene starting material 18 and proceeds through intermediates 19, 20, 21, 22, and 23 as set forth in Scheme 3. These steps in the synthesis are described in greater detail in J. Med. Chem. 1999, Vol. 41, pp. 3008-3014.
Preparation of the various intermediates 25, 26, and 27 and the Formula IV compounds are described in Examples 10 through 13 hereinafter.
EXAMPLE 10
TES Protected C,D-ring Sulfone (+)-25
A solution of methyl t-butyl sulfone (118 mg, 0.87 mmol) and THF (3.0 mL) was cooled to −78° C. and treated dropwise under argon with 0.61 mL (0.85 mmol) of a 1.4 M solution of n-BuLi in hexane. The solution was stirred for 15 minutes at −78° C. To the solution was added 0.3 mL of HMPA and then the solution was stirred for another 15 minutes. A precooled (−78° C.) solution of iodide 24 (78 mg, 0.17 mmol) in 2.0 mL of THF was added slowly via cannula. The reaction mixture was then warmed up to room temperature. The reaction was quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then purified by column chromatography (20% EtOAc/hexanes) to give 73 mg (92%) of the desired sulfone (+)-25 as a colorless oil: [α] 25 D +18.5° (c 7.3, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.26 (s, 1H), 4.10 (d, J=2.0 Hz, 1H), 2.87 (t, J=7.8 Hz, 2H), 2.24 (t, J=13.2 Hz, 1H), 2.07 (m, 1H), 1.94-1.76 (m, 4H), 1.72-1.56 (m, 4H), 1.55-1.28 (m, 13H), 0.99 (s, J=5.2 Hz, 3H), 0.93 (t, J=7.8 Hz, 9H), 0.54 (q, J=7.9 Hz, 6H); 13 C NMR (100 MHz CDCl 3 ) δ159.41, 120.15, 68.85, 58.73, 54.99, 46.61, 45.68, 35.71, 35.64, 34.83, 31.55, 30.68, 23.39, 22.16, 18.87, 18.77, 17.98, 6.88, 4.84; IR (neat, cm −1 ) 2943, 2872, 1455, 1284, 1108, 1079, 1026; HRMS m/z (M + ) calcd 456.3093 for C 25 H 48 O 3 SSi, found 456.3090.
EXAMPLE 11
Deprotected C,D-ring Sulfone (+)-26
To a solution of silyl ether (+)-25 (83 mg, 0.18 mmol) in THF (3.0 mL) was added 0.45 mL (0.45 mmol) of a 1.0 M solution of TBAF in THF, and then it was stirred overnight at room temperature. The reaction mixture was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by chromatography (20% EtOAc/hexanes) to give 61 mg (99%) of the desired alcohol (+)-26 as a colorless oil: [α] 25 D +4.2° (c 1.5, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.30 (d, J=1.2 Hz, 1H), 4.15 (s, 1H), 2.87 (t, J=8.0 Hz, 2H), 2.25 (t, J=13.4 Hz, 1H), 2.07 (m, 1H), 2.00-1.45 (m, 12H), 1.38 (s, 9H), 0.99 (d, J=6.8 Hz, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ159.23, 120.26, 68.94, 58.75, 54.31, 46.28, 45.62, 35.56, 35.38, 33.75, 31.57, 30.15, 23.38, 22.06, 18.88, 18.37, 17.71; IR (neat, cm −1 ) 3519, 2919, 1461, 1367, 1284, 1108; HRMS m/z (M + ) calcd 342.2229 for C 19 H 34 O 3 S, found 342.2235.
EXAMPLE 12
C,D-ring Ketone (+)-27
To a solution of the C,D-ring alcohol (+)-26 (60 mg, 0.18 mmol) in CH 2 Cl 2 (5.0 mL) were added 130 mg of oven-dried celite and pyridinium dichromate (PDC, 132 mg, 0.35 mmol) at room temperature. The reaction mixture was stirred overnight and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by column chromatography (50% EtOAc/hexanes) to give 56 mg (94/%) of the desired C,D-ring ketone (+)-27 as a colorless oil: [α] 25 D +14.7° (c 5.2, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.27 (t, J=1.4 Hz, 1H), 2.86 (t, J=7.8 Hz, 2H), 2.81 (m, 1H), 2.40 (ddt, J=15.8, 10.6, 1.4 Hz, 1H), 2.29-2.19 (m, 2H), 2.17-1.90 (m, 4H), 1.90-1.58 (m, 5H), 1.56-1.40 (m, 1H), 1.36 (s, 9H), 1.04 (d, J=6.8 Hz, 3H), 0.77 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ210.72, 157.10, 120.67, 62.92, 58.73, 53.64, 45.37, 40.35, 35.40, 34.24, 32.64, 26.95, 23.86, 23.31, 21.47, 18.79, 17.24; IR (neat, cm −1 ) 2954, 1713, 1455,1367, 1284, 1108; HRMS m/z (M + ) calcd 340.2072 for C 19 H 32 O 3 S, found 340.2073.
EXAMPLE 13
Analogs Formula IV
A solution of 108 mg (0.19 mmol) of racemic phosphine oxide (A-ring) in 2.0 mL of anhydrous THF was cooled to −78° C. and treated with 107 μL (0.16 mmol, 1.5 M solution in THF) of phenyllithium under argon atmosphere. The mixture turned reddish orange and was stirred for 30 min at −78° C. To the solution was added dropwise a solution of 40 mg (0.12 mmol) of the C,D-ring ketone (+)-27 in 1.0 mL of anhydrous THF. The reaction kept going on until the reddish orange color faded to yellow (about 5 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then purified by column chromatography (20% EtOAc/hexanes) to afford 37 mg (45%) of the coupled product as a colorless oil.
The coupled product (37 mg, 0.053 mmol) was dissolved in 3.0 mL of anhydrous THF, and to this solution were added 0.21 mL (0.21 mmol) of a 1.0 M solution of TBAF in THF and 29 μL (0.21 mmol) of triethylamine. The reaction was run in darkness overnight, then extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by silica gel chromatography (90% EtOAc/hexanes) to give 19 mg (76%) of a mixture of two diastereomers as a colorless oil. The diastereomers were separated by reverse phase HPLC (C-18 semipreparative column, 49% MeCN/H 2 O, 3.0 mL/min) to afford 6.3 mg (11%) of Formula IV-1 (1α, 3β, t R 47.9 min) and 4.1 mg (7%) of Formula IV-2 (1β, 3α, t R 43.2 min) as colorless oils. Formula IV-1: [α] 25 D +6.7° (c 0.6, EtOH); 1 H NMR (400 MHz, CDCl 3 ) δ6.37 (d, J=11.2 Hz, 1H), 6.11 (d, J=10.4 Hz, 1H), 5.34 (s, 2H), 5.01 (s, 1H), 4.45 (m, 1H), 4.24 (m, 1H), 3.00-2.75 (m, 3H), 2.60 (d, J=12.8 Hz, 1H), 2.40-1.50 (m, 16H), 1.40 (s, 9H), 1.05 (d, J=6.8 Hz, 3H), 0.69 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.85, 147.62, 142.31, 133.09, 124.83, 120.84, 116.91, 111.64, 70.63, 66.86, 58.81, 58.31, 50.04, 45.62, 45.14, 42.82, 35.53, 35.28, 32.65, 29.39, 28.74, 23.57, 23.46, 21.59, 18.73, 16.98; UV EtOH) λ max 263 nm (ε 12,000); IR (neat, cm −1 ) 3425, 2919, 1284, 1108, 1049; HRMS m/z(M + ) calcd 476.2960 for C 28 H 44 O 4 S, found 476.2952. Formula IV-2: [α] 25 D −8.9° (c 0.5, EtOH); 1 H NMR (400 MHz, CDCl 3 ) δ6.39 (d, J=11.2 Hz, 1H), 6.09 (d, J=10.6 Hz, 1H), 5.32 (s, 2H), 5.01 (d, J=1.6 Hz, 1H), 4.45 (m, 1H), 4.22 (m, 1H), 2.94-2.76 (m, 3H), 2.62 (m, 1H), 2.42-1.46 (m, 16H), 1.41 (s, 9H), 1.05 (d, J=6.8 Hz, 3H), 0.68 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.84, 147.02, 142.40, 132.88, 124.89, 120.83, 116.91, 113.00, 71.55, 66.74, 58.82, 58.30, 50.06, 45.63, 45.53, 42.73, 35.54, 35.26, 32:65, 29.43, 28.73, 23.56, 23.47, 21.61, 18.72, 16.99; UV EtOH) λ max 264 nm (ε 13,200); IR (neat, cm −1 ) 3401, 2919, 1455, 1284, 1108, 1049; HRMS m/z (M + ) calcd 476.2960 for C 28 H 44 O 4 S, found 476.2955.
Preparation of the Formula V materials is set forth in Scheme 4 as follows:
Scheme 4 begins with the same iodide derivative 24 and the next intermediate 25 as set forth in Scheme 3. Preparation of the various intermediates 28, 29, and 30 and the Formula V compounds is described in Examples 14 through 17 hereinafter.
EXAMPLE 14
Difluorinated C,D-ring Sulfone (+)-28
To a solution of the TES protected C,D-ring sulfone (+)-25 (56 mg, 0.12 mmol) in THF (3.0 ml) was added 0.18 mL (0.29 mmol) of a 1.6 M solution of n-BuLi in hexane at −78° C. After being stirred for 30 minutes, a precooled (−78° C.) solution of NFSI (N-fluorobenzenesulfonimide, 77 mg, 0.24 mmol) in 1.0 mL of THF was added slowly to the reaction mixture, and then it was warmed up to room temperature. The reaction was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, and concentrated in vacuo. Purification by column chromatography (20% EtOAc/hexanes) gave a mixture of mono and di-fluorinated sulfones.
The mixture (58 mg) was dissolved in THF (3.0 ml) and the solution was cooled to −78° C. To the solution was added 0.18 mL of n-BuLi (1.6 M solution in hexane, 0.29 mmol) and the reaction mixture was stirred for 30 minutes at −78° C. A precooled (−78° C.) solution of NFSI (96 mg, 0.30 mmol) in 1.0 mL of THF was then added slowly via cannula. The reaction mixture was warmed up to room temperature, quenched with water, extracted with EtOAc, washed with brine and concentrated. Purification by column chromatography (20% EtOAc/hexanes) gave 35 mg (58%) of the desired difluoronated C,D-ring sulfone (+)-28 as a colorless oil: [α] 25 D +16.7° (c 3.5, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.30 (d, J=1.2 Hz, 1H), 4.11 (d, J=2.0 Hz, 1H), 2.45-2.02 (m, 4H), 1.94-1.58 (m, 9H), 1.56-1.20 (m, 10H), 1.02 (d, J=6.8 Hz, 3H), 1.00 (s, 3H), 0.95 (t, J=8.0 Hz, 9H), 0.56 (q, J=7.9 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ158.80, 129.63 (t, J=287.9 Hz), 120.94, 69.08, 63.30, 55.28, 46.81, 35.92, 35.10, 31.65, 30.99, 29.02 (t, J=19.3 Hz), 27.00, 24.36, 22.49, 18.91, 18.25, 7.17, 5.11; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−97.76 (t, J=16.9 Hz); IR (neat, cm −1 ) 2955, 2933, 2876, 1458, 1324, 1136, 1082, 1029; HRMS m/z (M + ) calcd 492.2905 for C 25 H 46 F 2 O 3 SSi, found 492.2907.
EXAMPLE 15
Deprotected Difluoronated C,D-ring Alcohol (+)-29
A solution of silyl ether (+)-28 (89 mg, 0.18 mmol) in THF (2.0 mL) and 0.45 mL of 1.0 M solution of TBAF in THF was stirred overnight at room temperature. The mixture was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by column chromatography (20% EtOAc/hexanes) to give 45 mg (66%) of the desired alcohol as a colorless oil: [α] 25 D +3.4° (c 3.8, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.34 (t, J=1.4 Hz, 1H), 4.16 (s, 1H), 2.34-1.36 (m, 23H), 1.03 (d, J=6.8 Hz, 3H), 1.02 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.62, 129.52 (t, J=287.7 Hz), 121.04, 69.19, 63.29, 54.57, 46.47, 35.57, 33.96, 31.63, 30.42, 28.96 (t, J=19.8 Hz), 26.93, 24.32, 22.37, 18.50, 17.96; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−97.83 (m); IR (neat, cm −1 ) 3568, 2930, 2870, 1458, 1320, 1134; HRMS m/z (M + ) calcd 378.2040 for C 19 H 32 F 2 O 3 S, found 378.2047.
EXAMPLE 16
C,D-ring Ketone (+)-30
A flame-dried 5 mL flask was charged with 40 mg (0.11 mmol) of the C,D-ring alcohol (+)-29, 3.0 mL of anhydrous THF, 100 mg of oven-dried celite and 100 mg (0.27 mmol) of PDC. The reaction mixture was stirred overnight at room temperature and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by column chromatography (20% EtOAc/hexanes) to give 31 mg (78%) of the desired C,D-ring ketone (+)-30 as a colorless oil: [α] 25 D +12.9° (c 3.4, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.33 (d, J=1.2 Hz, 1H), 2.83 (dd, J=10.4, 6.4 Hz, 1H), 2.45 (dd, J=15.6, 10.8 Hz, 1H), 2.36-1.56 (m, 12H), 1.50(s, 9H), 1.09 (d, J=6.8 Hz, 3H), 0.80 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ210.87,156.51, 129.38 (t, J=287.8 Hz), 121.68, 63.36, 63.23, 53.83, 40.63, 34.50, 32.64, 28.85 (t, J=19.6 Hz), 27.31, 26.90, 24.31, 24.14, 21.70, 17.47; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−97.79 (m); IR (neat, cm −1 ) 2939, 2873, 1718, 1458, 1377, 1320, 1130; HRMS m/z (M + ) calcd 376.1884 for C 19 H 30 F 2 O 3 S, found 376.1889.
EXAMPLE 17
Analogs Formula V
Racemic phosphine oxide (A-ring, 89 mg, 0.15 mmol) was dissolved in 2.0 mL of anhydrous THF and cooled to −78° C. under argon atmosphere. To this solution was added 100 μL (0.16 mmol) of phenyllithium (1.6 M solution in THF) dropwise. The mixture turned deep reddish orange and persisted. After stirring at −78° C. for 30 minutes, a precooled (−78° C.) solution of C,D-ring ketone (+)-30 (30 mg, 0.080 mmol) dissolved in 1.0 mL of anhydrous THF was added dropwise via cannula. The reaction kept going on until the reddish orange color faded to yellow (about 4 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was allowed to warm to room temperature, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , filtered, concentrated in vacuo, and then purified by column chromatography (10% EtOAc/hexanes) to afford 50 mg (84%) of the coupled product as a colorless oil.
The coupled product (50 mg, 0.067 mmol) was dissolved in 3.0 mL of anhydrous THF with 37 μL of Et 3 N, and to this solution was added 0.27 mL (0.27 mmol) of TBAF (1.0 M solution in THF) at room temperature. The reaction was run in darkness overnight, then extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by column chromatography (90% EtOAc/Hexanes) to give 33 mg (96%) of a mixture of two diastereomers as a colorless oil. The diastereomers were separated by reverse phase HPLC (C-18 semipreparative column, 52% MeCN/H 2 O, 3.0 mL/min) to afford 16.6 mg (41%) of Formula V-1 (1α, 3β, t R 145.3 min) as a foaming solid and 7.0 mg (17%) of Formula V-2 (1β, 3α, t R 129.2 min) as a colorless oil. Formula V-1: [α] 25 D +0.1° (c 1.7, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.36 (d, J=11.2 Hz, 1H), 6.10 (d, J=11.2 Hz, 1H), 5.40-5.30 (m, 2H), 5.00 (s, 1H), 4.43 (dd J=8.0, 4.4 Hz, 1H), 4.23 (m, 1H), 2.81 (dd, J=12.0, 4.0 Hz, 1H), 2.59 (dd, J=13.2, 2.8 Hz, 1H), 2.43-2.13 (m, 5H), 2.09-1.96 (m, 2H), 1.95-1.63 (m, 9H), 1.51 (s, 9H), 1.07 (d, J=6.8 Hz, 3H), 0.68 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.19, 147.85, 142.36, 133.43, 129.60 (t, J=287.7 Hz), 124.99, 121.67, 117.21, 111.88, 70.82, 67.07, 63.34, 58.52, 50.18, 45.35, 43.02, 35.42, 32.58, 29.65, 28.94, 28.70 (t, J=19.6 Hz), 26.81, 24.36, 23.77, 21.79, 17.05; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−97.86 (m); UV (EtOH) λ max 263 nm (ε 16,100); IR (neat, cm −1 ) 3601, 2931, 2837, 1455, 1314, 1126, 1043; HRMS m/z (M + ) calcd 512.2772 for C 28 H 42 F 2 O 4 S, found 512.2781. Formula V-2: [β] 25 D −24.1° (c 0.7, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.39 (d, J=11.2 Hz, 1H), 6.10 (d, J=11.2 Hz, 1H), 5.35 (t, J=1.2 Hz, 1H), 5.32 (s, 1H), 5.01 (d, J=2.0 Hz, 1H), 4.44 (dd, J=6.0, 4.0 Hz, 1H), 4.22 (m, 1H), 2.82 (dd, J=11.8, 4.2 Hz, 1H), 2.62 (dd, J=13.2, 4.0 Hz, 1H), 2.42-2.12 (m, 5H), 2.10-1.96 (m, 2H), 1.95-1.55 (m, 9H), 1.52 (s, 9H), 1.07 (d, J=6.8 Hz, 3H), 0.68 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.20, 147.22, 142.49, 133.18, 129.62 (t, J=288.0 Hz), 125.09, 121.66, 117.20, 113.29, 71.80, 66.96, 63.35, 58.53, 50.20, 45.78, 42.94, 35.40, 32.58, 29.70, 28.94, 28.69 (t, J=19.1 Hz), 26.82, 24.38, 23.77, 21.81, 17.07; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−97.88 (m); UV (EtOH) λ max 263 nm(ε 15,000); IR (neat, cm −1 ) 3683, 3601, 2931, 1314, 1132, 1043; HRMS m/z (M + ) calcd 512.2772 for C 28 H 42 F 2 O 4 S, found 512.2776.
Preparation of the Formula VI materials is set forth in Scheme 5 as follows:
Scheme 5 begins with the same iodide derivative 24 as set forth in Schemes 3 and 4. Preparation of the various intermediates 31, 32 and 33 and the Formula VI compound is described in Examples 18 through 21 hereinafter.
EXAMPLE 18
TES Protected 16-ene25-phenyl C,D-ring Sulfone (+)-31
A solution of methyl phenyl sulfone (147 mg, 0.95 mmol) and THE (3.0 mL) was cooled to −78° C., and then 0.60 mL (0.96 mmol, 1.6 M solution in hexane) of n-BuLi was added dropwise to the solution. After 15 minutes, 0.2 mL of HMPA was added and the solution was stirred for another 15 minutes. A precooled (−78° C.) solution of iodide 24 (85 mg, 0.19 mmol) in 1.0 mL of THF was added slowly via cannula. The reaction mixture was then warmed up to room temperature. The reaction was quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then purified by column chromatography (20% EtOAc/hexanes) to give 79 mg (88%) of the desired sulfone (+)-31 as a colorless oil: [α] 25 D +14.7° (c 7.8, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.92-7.84 (m, 2H), 7.63 (t, J=7.4 Hz, 1H), 7.54 (t, J=7.6 Hz, 2H), 5.15 (t, J=1.2 Hz, 1H), 4.08 (d, J=2.0 Hz, 1H), 3.04 (m, 2H), 2.15 (t, J=13.0 Hz, 1H), 2.01-1.76 (m, 3H), 1.73-1.22 (m, 10H), 0.95 (t, J=8.0 Hz, 9H), 0.92 (d, J=6.8 Hz, 3H), 0.87 (s, 3H), 0.55 (q, J=8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ159.31, 139.19, 133.71, 129.32, 128.25, 120.35, 69.03, 56.58, 55.15, 46.72, 35.82, 35.06, 35.02, 31.52, 30.82, 22.50, 21.25, 18.86, 18.16, 7.14, 5.07; IR (neat, cm −1 ) 2953, 2874, 1447, 1319, 1306, 1148, 1082, 1028; HRMS m/z (M + ) calcd 476.2780 for C 27 H 44 O 3 SSi, found 476.2787.
EXAMPLE 19
Deprotected 25-phenyl C,D-ring Sulfone (O)-32
A solution of silyl ether (+)-31 (78 mg, 0.16 mmol) in THF (2.0 mL) and 0.41 mL of 1.0 M solution of TBAF in THF was stirred overnight at room temperature. The mixture was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by column chromatography (20% EtOAc/hexanes) to give 55 mg (93%) of the desired alcohol ()-32 as a colorless oil: [α] 25 D −0.8° (c 5.8, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.92-7.84 (m, 2H), 7.63 (t, J=7.4 Hz, 1H), 7.58-7.50 (m, 2H), 5.20 (t, J=1.4 Hz, 1H), 4.13 (d, J=2.4 Hz, 1H), 3.04 (m, 2H), 2.18 (t, J=13.2 Hz, 1H), 2.02-1.18 (m, 13H), 0.93 (d, J=6.8 Hz, 3H), 0.92 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ159.20, 139.21, 133.78, 129.37, 128.20, 120.51, 69.12, 56.54, 54.49, 46.43, 35.52, 35.04, 33.98, 31.60, 30.32, 22.34, 21.20, 18.49, 17.89; IR (neat, cm −1 ) 3535, 2926, 2864, 1447, 1305, 1147, 1086; HRMS m/z (M + ) calcd 362.1916 for C 21 H 30 O 3 S, found 362.1913.
EXAMPLE 20
C,D-ring Ketone (+)-33
To a solution of the C,D-ring alcohol (+)-32 (55 mg, 0.15 mmol) in CH 2 Cl 2 (3.0 mL) were added 114 mg of oven-dried celite and pyridinium dichromate (PDC, 114 mg, 0.30 mmol) at room temperature. The reaction mixture was stirred overnight and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by column chromatography (50% EtOAc/hexanes) to afford 52 mg (95%) of the desired C,D-ring ketone (+)-33 as a colorless oil: [α] 25 D +11.2° (c 5.1, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.88-7.82 (m, 2H), 7.63 (t, J=7.4 Hz, 1H), 7.53 (t, J=7.6 Hz, 2H), 5.18 (t, J=1.4 Hz, 1H), 3.03 (t, J=7.8 Hz, 2H), 2.77 (dd, J=10.8, 6.4 Hz, 1H), 2.38-2.20 (m, 3H), 2.12-1.36 (m, 10H), 0.98 (d, J=6.8 Hz, 3H), 0.67 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ210.93, 157.03, 139.13, 133.83, 129.38, 128.13, 120.91, 63.10, 56.37, 53.80, 40.58, 34.87, 34.40, 32.58, 27.14, 24.07, 21.80, 21.05, 17.32; IR (neat, cm −1 ) 2943, 2861, 1708, 1443, 1302, 1143, 1085; HRMS m/z (M + ) calcd 360.1759 for C 21 H 28 O 3 S, found 360.1758.
EXAMPLE 21
Analogs Formula VI
A solution of 89 mg (0.15 mmol) of recemic phosphine oxide (A-ring) in 2.0 mL of anhydrous THF was cooled to −78° C. and treated with 100 μL (0.15 mmol, 1.5 M solution in THF) of phenyllithium under argon atmosphere. The mixture turned reddish orange and was stirred for 30 min at −78° C. To the solution was added dropwise a solution of 52 mg (0.14 mmol) of the C,D-ring ketone (+)-33 in 1.0 mL of anhydrous THF. The reaction kept going on until the reddish orange color faded to yellow (about 4 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then purified by column chromatography (20% EtOAc/hexanes) to afford 76 mg (73%) of the coupled product as a colorless oil.
The coupled product (76 mg, 0.10 mmol) was dissolved in 3.0 mL of anhydrous THF, and to this solution were added TBAF (0.41 mL, 0.41 mmol, 1.0 M solution in THF) and 59 μL of Et 3 N. The reaction was run in darkness overnight, then quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by column chromatography (90% EtOAc/hexanes) to give 52 mg (96%) of a mixture of two diastereomers as a colorless oil. The diastereomers were separated by reverse phase HPLC (C-18 semipreparative column, 50% MeCN1H 2 O, 3.0 mL/min) to afford 19.1 mg (28%) of Formula VI-1 (1α, 3β, t R 59.3 min) and 12.7 mg (18%) of Formula VI-2 (1β, 3α, t R 53.6 min) as colorless oils. Formula VI-1: [α] 25 D −1.6° (c 1.9, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.94-7.86 (m, 2H), 7.65 (t, J=7.4 Hz, 1H), 7.60-7.52 (m, 2H), 6.35 (d, J=11.2 Hz, 1H), 6.08 (d, J=11.2 Hz, 1H), 5.35 (d, J=1.6 Hz, 2H), 5.01 (s, 1H), 4.44 (dd, J=8.0, 4.0 Hz, 1H), 4.23 (m, 1H), 3.05 (t, J=8.0 Hz, 2H), 2.79 (dd, J=12.4, 4.4 Hz, 1H), 2.59 (dd, J=13.2, 2.8 Hz, 1H), 2.40-2.26 (m, 2H), 2.20-2.00 (m, 3H), 2.00-1.84 (m, 2H), 1.84-1.20 (m, 9H), 0.98 (d, J=6.8 Hz, 3H), 0.58 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.80, 147.93, 142.36, 139.30, 133.81, 133.43, 129.41, 128.26, 124.98, 121.14, 117.16, 111.71, 70.76, 67.07, 58.47, 56.57, 50.16, 45.31, 43.08, 35.41, 34.98, 32.66, 29.55, 28.92, 23.74, 21.79, 21.02, 17.08; UV (EtOH) λ max 264 nm (ε 12,400); IR (neat, cm −1 )3613, 2919, 2837, 1443, 1302, 1143, 1043; HRMS m/z (M + ) calcd 496.2647 for C 30 H 40 O 4 S, found 496.2635. Formula VI-2: [α] 25 D −22.8° (c 1.3, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ7.94-7.86 (m, 2H), 7.65 (t, J=7.4 Hz, 1H), 7.60-7.52 (m, 2H), 6.38 (d, J=11.2 Hz, 1H), 6.07 (d, J=11.2 Hz, 1H), 5.33 (s, 1H), 5.23 (d, J=1.2 Hz, 1H), 5.01 (d, J=1.6 Hz, 1H), 4.46 (dd, J=5.6, 4.0 Hz, 1H), 4.22 (m, 1H), 3.05 (t, J=8.0 Hz, 2H), 2.80 (dd, J=11.6, 4.0 Hz, 1H), 2.62 (dd, J=13.0, 3.8 Hz, 1H), 2.36-2.24 (m, 2H), 2.20-1.86 (m, 5H), 1.84-1.20 (m, 9H), 0.98 (d, J=6.8 Hz, 3H), 0.58 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.83, 147.30, 142.48, 139.34, 133.81, 133.19, 129.42, 128.26, 125.07, 121.13, 117.15, 113.11, 71.75, 66.92, 58.48, 56.59, 50.18, 45.72, 42.99, 35.40, 35.00, 32.67, 29.59, 28.91, 23.72, 21.79, 21.01, 17.11; UV (EtOH) λ max 264 nm (ε 16,400); IR (neat, cm −1 ) 3601, 2919, 2849, 1443, 1302, 1143, 1085, 1043; HRMS m/z (M + ) calcd 496.2647 for C 30 H 40 O 4 S, found 496.2650.
Preparation of the Formula VII materials is described in Scheme 6 as follows:
Scheme 6 begins with the same protected aldehyde derivative 22 as set forth in Scheme 3 above. Preparation of the various intermediates 34-E, 34-Z, 35-E, and 36-E, and the Formula VII compounds is described in Examples 22 through 25 hereinafter.
EXAMPLE 22
TES Protected C,D-ring Sulfone (+)-34-E
A solution of 5.0 mL of THF and 0.53 mL of n-BuLi (1.5 M solution in THF, 0.80 mmol) was cooled to −78° C. , and then 0.11 mL (0.80 mmol) of diisopropylamine was added dropwise to the solution. After 15 minutes, monofluorinated methyl tert-butyl sulfone (58.4 mg, 0.38 mmol) was added via cannula and the resulted reaction mixture was stirred for another 15 minutes. Diethyl chlorophosphate (52 μL, 0.36 mmol) was added and the reaction was stirred at −78° C. for one hour. A precooled (−78° C.) solution of TES protected aldehyde 22 (75.0 mg, 0.22 mmol) in 1.0 mL of ill was added slowly via cannula. The reaction mixture was then warmed up to room temperature. The reaction was quenched with water, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo, and then the mixture (75 mg, 71%) was separated by column chromatography (2% Et2O/hexanes) to give 45 mg of the desired E isomer and 30 mg of the Z isomer as colorless oils. (+)-34-E: [α] 25 D +28.2° (c 2.8, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.05 (dt, J=32.8, 7.6 Hz, 1H), 5.31 (t, J=1.6 Hz, 1H), 4.11 (d, J=2.4 Hz, 1H), 2.54-2.18 (m, 4H), 1.98-1.20 (m, 17H), 1.06 (d, J=6.8 Hz, 3H), 1.00 (s, 3H), 0.94 (t, J=8.0 Hz, 9H), 0.56 (q, J=8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ158.62, 151.81 (d, J=294.8 Hz), 122.33 (d, J=6.4 Hz), 121.38, 69.02, 59.73, 55.19, 46.95, 35.98, 35.01, 31.41, 31.33, 30.96, 23.47, 22.16, 19.05, 18.22, 7.15, 5.10; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−119.77 (d, J=33.5 Hz); IR (neat, cm −1 ) 2954, 2931, 2860, 1666, 1455, 1320, 1132, 1026; HRMS m/z (M + ) pending.
EXAMPLE 23
Deprotected C,D-ring Alcohol (+)-35E
A solution of silyl ether (+)-34-E (73.5 mg, 0.16 mmol) and TBAF (0.39 mL, 1.0 M solution in THF, 0.39 mmol) in 2.0 mL of THF was stirred for 4 hours at room temperature. The mixture was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by column chromatography (50% EtOAc/hexanes) to give 30 mg (54%) of the desired alcohol as a colorless oil: [α] 25 D +6.8° (c 1.9, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.05 (dt, J=33.2, 7.8 Hz, 1H), 5.36 (t, J=1.6 Hz, 1H), 4.17 (d, J=2.0 Hz, 1H), 2.55-2.20 (m, 4H), 2.06-1.30 (m, 17H), 1.06 (d, J=6.8 Hz, 3H), 1.03 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.45, 151.92 (d, J=295.2 Hz), 122.07 (d, J=6.3 Hz), 121.51, 69.14, 59.72, 54.52, 46.63, 35.64, 34.03, 31.34, 31.32, 30.45, 23.48, 22.14, 18.64, 17.93; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−119.62 (d, J=33.5 Hz); IR (neat, cm −1 ) 3542, 2919, 2872, 1666, 1455, 1137, 1114; HRMS m/z (M + ) pending.
EXAMPLE 24
C,D-ring ketone (+)-36-E
A flame-dried 5 mL flask was charged with 30.0 mg (0.084 mmol) of the C,D-ring alcohol (+)-35-E, 3.0 mL of anhydrous CH 2 Cl 2 , 70 mg of oven-dried celite and 63.0 mg (0.17 mmol) of PDC. The reaction mixture was stirred overnight at room temperature and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by column chromatography (50% EtOAc/hexanes) to give 24.0 mg (78%) of the desired C,D-ring ketone (+)-36-E as a colorless oil: [α] 25 D +26.0° (c 2.4, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.03 (dt, J=32.8, 7.6 Hz, 1H), 5.35 (t, J=1.2 Hz, 1H), 2.85 (dd, J=10.8, 6.6 Hz, 1H), 2.60-2.20 (m, 6H), 2.18-1.60 (m, 5H), 1.38 (s, 9H), 1.13 (d, J=6.4 Hz, 3H), 0.80 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ210.70, 156.35, 152.31 (d, J=295.7 Hz), 121.95, 121.38 (d, J=6.4 Hz), 63.15, 59.74, 53.90, 40.60, 34.56, 32.24, 31.25, 27.34, 24.12, 23.47, 21.62, 17.54; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−119.06 (d, J=33.1 Hz); IR (neat, cm 31 1 ) 2943, 1713, 1666, 1455, 1314, 1120, 1038; HRMS m/z (M + ) pending.
EXAMPLE 25
Analogs Formula VII
Racemic phosphine oxide (A-ring, 48.9 mg, 0.084 mmol) was dissolved in 2.0 mL of anhydrous THF and cooled to −78° C. under argon atmosphere. To this solution was added 65 μL (0.08 mmol) of phenyllithium (1.2 M solution in THF) dropwise. The mixture turned deep reddish orange and persisted. After stirring at −78° C. for 30 minutes, a precooled (−78° C.) solution of C,D-ring ketone (+)-36-E (24.2 mg, 0.068 mmol) dissolved in 1.0 mL of anhydrous THF was added dropwise via cannula. The reaction kept going on until the reddish orange color faded to yellow (about 4 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was allowed to warm to room temperature, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , filtered, concentrated in vacuo, and then purified by column chromatography (8% EtOAc/hexanes) to afford 33 mg (67%) of the coupled product as a colorless oil.
The coupled product (31 mg, 0.043 mmol) was dissolved in 2.0 mL of anhydrous ethanol, and then 0.34 mL of HF (49% solution in water) was added and the resulted reaction mixture was stirred for 1 hour at room temperature. The reaction was quenched with diluted NaHCO 3 solution and extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by column chromatography (80% EtOAc/Hexanes) to give 17.0 mg (80%) of a mixture of two diastereomers as a colorless oil. The diastereomers were separated by reverse phase HPLC (C-18 semipreparative column, 52% MeCN/H 2 O, 3.0 mL/min) to afford 5.7 mg (17%) of Formula VII-1 (1α, 3β, t R 77.3 min) as a foaming solid and 4.2 mg (12%) of Formula VII-2 (1β, 3α, t R 70.4 min) as a colorless oil. Formula VII-1: [α] 25 D +3.2° (c 0.57, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.36(d, J=11.2 Hz, 1H), 6.10 (d, J=10.8 Hz, 1H), 6.05 (dt, J=33.2, 7.6 Hz, 1H), 5.37 (s, 1H), 5.34 (t, J=1.6 Hz, 1H), 5.00 (s, 1H), 4.44 (dd, J=7.8, 4.2 Hz, 1H), 4.24 (m, 1H), 2.82 (dd, J=12.2, 4.6 Hz, 1H), 2.60 (d, J=13.6 Hz, 1H), 2.54-1.18 (m, 23H), 1.10 (d, J=6.4 Hz, 3H), 0.69 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.03, 152.01 (d, J=295.3 Hz), 147.86, 142.11, 133.56, 124.97, 122.12, 121.88 (d, J=6.3 Hz), 117.36, 111.90, 70.89, 67.07, 59.73, 58.51, 50.20, 45.37, 43.08, 35.46, 32.30, 31.26, 29.66, 28.90, 23.72, 23.50, 21.52, 17.21; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−119.50 (d, J=33.1 Hz); UV (EtOH) λ max 263 nm (ε 14,700); IR (CHCl 3 , cm −1 ) 3707, 3601, 2919, 1654, 1455, 1314, 1220, 1038; HRMS m/z (M + ) pending. Formula VII-2: [β] 25 D −16.7° (c 0.42, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.38 (d, J=11.6 Hz, 1H), 6.09 (d, J=10.4 Hz, 1H), 6.05 (dt, J=33.6, 7.6 Hz, 1H), 5.37 (s, 1H), 5.33 (s, 1H), 5.01 (d, J=1.6 Hz, 1H), 4.46 (m, 1H) 4.22 (m, 1H), 2.82 (dd, J=12.0, 4.4 Hz, 1H), 2.62 (dd, J=13.2, 3.6 Hz, 1H), 2.56-1.20 (m, 23H), 1.10 (d, J=6.8 Hz, 3H), 0.69 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.03, 152.01 (d, J=295.7 Hz), 147.34, 142.20, 133.38, 125.02, 122.12, 121.89 (d, J=5.9 Hz), 117.36, 113.03, 71.65, 67.00, 59.73, 58.51, 50.22, 45.71, 43.01, 35.45, 32.32, 31.27, 29.70, 28.89, 23.71, 23.51, 21.54, 17.23; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−119.51 (d, J=32.0 Hz); UV (EtOH) λ max 263 nm (ε 14,900); IR (CHCl 3 , cm −1 ) 3601, 2919, 2849, 1655, 1455, 1314, 1214, 1038; HRMS m/z (M + ) pending.
Preparation of the Formula VIII materials is described in Scheme 7 as follows:
Scheme 7 begins with the same iodide derivative 24 as set forth in Schemes 3, 4, and 5. Preparation of the various intermediates, 37, 38, 39, 40, and 41, and the Formula VIII compounds is described in Examples 26 through 29 hereinafter.
EXAMPLE 26
Difluorinated C,D-ring Sulfone (+)-39
To a solution of the TES protected C,D-ring sulfone (+)-38 (64 mg, 0.15 mmol) in THF (3.0 mL) was added 0.29 mL (0.58 mmol) of a 2.0 M solution of n-BuLi in pentane at −78° C. Afer being stirred for 30 minutes, a precooled (−78° C.) solution of NFSI (N-fluorobenzenesulfonimide, 127 mg, 0.41 mmol) in 1.0 mL of THF was added slowly to the reaction mixture, and then it was warmed up to room temperature. The reaction was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, and concentrated in vacuo. Purification by column chromatography (20% EtOAc/hexanes) gave a mixture of mono and di-fluorinated sulfones.
The mixture was dissolved in THF (3.0 mL) and the solution was cooled to −78° C. To the solution was added 0.29 mL of n-BuLi (2.0 M solution in pentane, 0.58 mmol) and the reaction mixture was stirred for 30 minutes at −78° C. A precooled (−78° C.) solution of NFSI (127 mg, 0.41 mmol) in 1.0 mL of THF was then added slowly via cannula. The reaction mixture was warned up to room temperature, quenched with water, extracted with EtOAc, washed with brine and concentrated. Purification by column chromatography (20% EtOAc/hexanes) gave 55 mg (80%) of the desired difluoronated C,D-ring sulfone (+)-39 as a colorless oil: [α] 25 D +21.9° (c 5.5, CHCl 3 ); 1 H NMR (400 M , CDCl 3 ) δ5.37 (s, 1H), 4.12 (s, 1H), 2.68-2.18 (m, 4H), 1.96-1.30 (m, 17H), 1.12 (d, J=5.6 Hz, 3H), 1.04 (s, 3H), 0.94 (t, J=7.8 Hz, 9H), 0.56 (q, J=8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ158.94, 129.52 (t, J=289.2 Hz), 121.67, 69.04, 63.31, 55.13, 47.36, 35.94, 35.05, 31.00, 25.44, 24.44, 23.91, 22.89, 19.01, 18.22, 7.13, 5.11; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−96.24 (ddd, J=219.2, 31.9, 6.6 Hz), −97.83 (ddd, J=219.6, 29.9, 5.5 Hz); IR (neat, cm −1 ) 2934, 2876, 1458, 1320, 1134, 1029; HRMS m/z (M + ) pending.
EXAMPLE 27
Deprotected Difluoronated C,D-ring Alcohol (+)-40
A solution of silyl ether (+)-39 (55 mg, 0.11 mmol) in THF (2.0 mL) and 0.29 mL (0.29 mmol) of 1.0 M solution of TBAF in THF was stirred overnight at room temperature. The mixture was quenched with water and extracted with EtOAc. The combined organic portions were washed with brine, dried, concentrated in vacuo and then purified by column chromatography (20% EtOAc/hexanes) to give 27 mg (66%) of the desired alcohol as a colorless oil: [α] 25 D +9.3° (c 2.7, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.41 (d, J=1.2 Hz, 1H), 4.17 (d, J=2.4 Hz, 1H), 2.72-2.20 (m, 4H), 2.06-1.32 (m, 17H), 1.13 (d, J=6.0 Hz, 3H), 1.06 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.70, 129.45 (t, J=289.7 Hz), 121.75, 69.17, 63.38, 54.45, 47.01, 35.96 (t, J=18.6 Hz), 35.60, 34.00, 30.46, 25.44, 24.42, 22.89, 18.57, 17.94; 19 F NMR (376 ZT7, CDCl 3 , CFCl 3 as internal) δ−96.22 (ddd, J=219.6, 32.4, 8.0 Hz), δ−97.76 (ddd, J=219.6, 29.7, 6.8 Hz); IR (neat, cm −1 ) 3566, 3448, 2931, 2860, 1455, 1314, 1126; HRMS m/z (M + ) pending.
EXAMPLE 28
C,D-ring ketone (+)-41
A flame-dried 5 mL flask was charged with 27 mg (0.074 mmol) of the C,D-ring alcohol (+)-40, 3.0 mL of anhydrous THF, 100 mg of oven-dried celite and 69 mg (0.19 mmol) of PDC. The reaction mixture was stirred overnight at room temperature and then passed through a 2 cm pad of flash silica gel and washed with EtOAc. The filtrate was concentrated and purified by column chromatography (20% EtOAc/hexanes) to give 24 mg (89%) of the desired C,D-ring ketone (+)-41 as a colorless oil: [α] 25 D +17.5° (c 2.5, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ5.41 (s, 1H), 2.84 (dd, J=10.4, 6.4 Hz, 1H), 2.74-2.22 (m, 6H), 2.16-1.74 (m, 5H), 1.51 (s, 9H), 1.19 (d, J=6.4 Hz, 3H), 0.84 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ210.76, 156.38, 129.20 (t, J=289.9 Hz), 122.29, 63.47, 63.12, 54.14, 40.62, 36.03 (t, J=18.5 Hz), 34.54, 27.36, 26.48 (t, J=2.7 Hz), 24.41 (t, J=2.6 Hz), 24.11, 22.56, 17.50; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−96.20 (ddd, J=219.8, 28.9, 9.2 Hz), δ−97.49 (ddd, J=219.8, 28.9, 10.3 Hz); IR (neat, cm −1 ) 2943, 1713, 1314, 1132; HRMS m/z (M + ) pending.
EXAMPLE 29
Analogs Formula VIII
Racemic phosphine oxide (A-ring, 43.4 mg, 0.075 mmol) was dissolved in 1.0 mL of anhydrous THF and cooled to −78° C. under argon atmosphere. To this solution was added 58 μL (0.070 mmol) of phenyllithium (1.2 M solution in THF) dropwise. The mixture turned deep reddish orange and persisted. After stirring at −78° C. for 30 minutes, a precooled (−78° C.) solution of C,D-ring ketone (+)-41 (24.8 mg, 0.068 mmol) dissolved in 1.0 mL of anhydrous THF was added dropwise via cannula. The reaction kept going on until the reddish orange color faded to yellow (about 4 hours). The reaction was quenched by adding 3.0 mL of a 1:1 mixture of 2 N sodium potassium tartrate and 2 N K 2 CO 3 solution. The reaction mixture was allowed to warm to room temperature, extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , filtered, concentrated in vacuo, and then purified by column chromatography (10% EtOAc/hexanes) to afford 37.2 mg (75%) of the coupled product as a colorless oil.
The coupled product (37.2 mg, 0.051 mmol) was dissolved in 3.0 mL of anhydrous THF with 29 μL of Et 3 N, and to this solution was added 0.20 mL (0.20 mmol) of TBAF (1.0 M solution in THF) at room temperature. The reaction was run in darkness overnight, then extracted with EtOAc, washed with brine, dried over anhydrous MgSO 4 , concentrated in vacuo and then purified by column chromatography (90% EtOAc/Hexanes) to give 18.6 mg (73%) of a mixture of two diastereomers as a colorless oil. The diastereomers were separated by reverse phase HPLC (C-18 semipreparative column, 52% MeCN/H 2 O, 3.0 mL/min) to afford 7.4 mg (22%) of Formula VIII-1 (1α, 3β, t R 90.7 min) as a foaming solid and 4.3 mg (13%) of Formula VIII-2 (1β, 3α, t R 84.3 min) as a colorless oil. Formula VIII-1: [β] 25 D +2.1° (c 0.7, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.37 (d, J=11.6 Hz, 1H), 6.10 (d, J=11.2 Hz, 1H), 5.42 (s, 1H), 5.33 (s, 1H), 5.00 (s, 1H), 4.44 (dd, J=7.2, 4.0 Hz, 1H), 4.24 (m, 1H), 2.82 (dd, J=11.8, 4.2 Hz, 1H), 2.74-2.50 (m, 3H), 2.44-2.16 (m, 5H), 2.10-1.48 (m, 16H), 1.17 (d, J=6.8 Hz, 3H), 0.72 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.32, 147.83, 142.25, 133.45, 129.44 (t, J=290.0 Hz), 125.03, 122.26, 117.30, 111.92, 70.91, 67.08, 63.40, 58.42, 50.50, 45.39, 43.05, 35.98 (t, J=18.6 Hz), 35.44, 29.67, 28.90, 26.49, 24.45, 23.71, 22.42, 17.14; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−96.17 (ddd, J=218.6, 32.0, 8.1 Hz), δ−97.64 (ddd, J=219.8, 29.7, 8.5 Hz); UV EtOH) λ max 263 nm (ε 16,900); IR (CHCl 3 , cm −1 ) 3601, 2931, 2849, 1649, 1602, 1455, 1314, 1132, 1043; HRMS m/z (M + ) pending. Formula VIII-2: [α] 25 D −19.3° (c 0.4, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.38 (d, J=11.2 Hz, 1H), 6.09 (d, J=11.2 Hz, 1H), 5.42 (s, 1H), 5.32 (s, 1H), 5.01 (d, J=1.2 Hz, 1H), 4.45 (m, 1H), 4.22 (m, 1H), 2.82 (dd, J=12.0, 4.4 Hz, 1H), 2.74-2.50 (m, 3H) 2.44-2.16 (m, 5H), 2.10-1.48 (m, 16H), 1.17 (d, J=6.8 Hz, 3H), 0.72 (s, 31); 13 C NMR (100 MHz, CDCl 3 ) δ158.34, 147.32, 142.32, 133.26, 129.45 (t, J=294.7 Hz), 125.07, 122.26, 117.29, 113.07, 71.70, 66.99, 63.40, 58.41, 50.51, 45.73, 42.98, 35.99 (t, J=18.6 Hz), 35.43, 29.70, 28.89, 26.49, 24.46, 23.71, 22.42, 17.14; 19 F NMR (376 MHz, CDCl 3 , CFCl 3 as internal) δ−96.17 (dd, J=222.0, 28.4 Hz), δ−97.69 (dd, J=219.6, 28.9 Hz); UV (EtOH) λ max 262 nm (ε 14,000); IR (CHCl 3 , cm −1 ) 3601, 2931, 2849, 1455, 1314, 1132, 1038; HRMS m/z (M + ) pending.
Preparation of the Formula IX materials is described in Scheme 8 as follows:
Scheme 8 begins with the same aldehyde derivative as set forth in Schemes 3 and 6. Preparation of the various intermediates, 42, 43E, 44E, and 45E, and the Formula IX compounds is described in Examples 30 through 34 hereinafter.
EXAMPLE 30
16-Ene-23-Hydroxy-25-Sulfones 42
To a solution of methyl t-butylsulfone (103 mg, 0.76 mmol) in 10 mL of THF was added 0.52 mL of n-BuLi (1.60 M, 0.83 mmol) dropwise at −78° C. After 1 h at −78° C., a solution of aldehyde (+)-22 (45 mg, 0.13 mmol) in 10 mL of THF was added dropwise at −78° C. After 2 h at −78° C., the reaction mixture was quenched with saturated ammonium chloride solution (20 mL) and extracted with EtOAc (50 mL×3). The combined organic portions were washed with brine (30 mL), dried over MgSO 4 and concentrated. The crude product was purified by flash column chromatography (33% EtOAc/hexanes) to give 45 mg (76%) of diastereomeric alcohols 42 as colorless oils: 1 H NMR (400 MHz, CDCl 3 ) δ5.33 and 5.27 (two s, 1H), 4.48 and 4.38 (two s, 1H), 4.12 (s, 1H), 3.47 and 3.37 (two s, 1H), 3.09-2.94 (m, 2H), 2.41 (m, 1H), 2.26 (m, 1H), 1.91-1.41 (m, 13H), 1.42 and 1.41 (two s, 9H), 1.04 (m, 6H), 0.95 and 0.94 (t, J=8.0 Hz, 9H), 0.56 and 0.55 (q, J=8.0 Hz, 6H); IR (neat, cm −1 ) 3523, 2932, 1290, 1114; HRMS m/z (M + ) calcd 472.3043 for C 25 H 48 O 4 SSi, found 472.3037.
EXAMPLE 31
16,23-Diene-25-Sulfone (+)-43E
To a solution of alcohols 42 (42 mg, 0.089 mmol) in 10 mL of dry CH 2 Cl 2 was added 0.20 mL of triethylamine and methanesulfonyl chloride (0.050 mL, 0.65 mmol) at 0° C. The mixture was stirred for 1 h at 0° C. The solution was concentrated in vacuo. The residue was diluted with brine (20 mL) and extracted with EtOAc (30 mL×3). The combined organic portions were dried over MgSO 4 and concentrated. The crude mesylates were used for the next step without further purification.
To a solution of the mesylates in 7 mL of dry benzene was added 1,8-diazabicyclo[5.4.0]undec-7-ene (0.050 mL, 0.33 mmol). The solution was gently refluxed for 15 min and then allowed to cool to room temperature. The reaction mixture was diluted with brine (20 mL) and extracted with EtOAc (30 mL×3). The combined organic portions were dried over MgSO 4 and concentrated. The crude product was purified by flash chromatography (33% EtOAc/hexanes) to give 38 mg (94%) of the unsaturated sulfone (+)-43E as a colorless oil: [α] 25 D +20.0 (c 1.4, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.81 (dt, J=14.8, 7.6 Hz, 1H), 6.23 (d, J=15.2 Hz, 1H), 5.29 (s, 1H), 4.11 (s, 1H), 2.51 (m, 1H), 2.41-2.02 (m, 3H), 1.91 (m, 2H), 1.73-1.37 (m, 10H), 1.04 (d, J=6.4 Hz, 3H), 1.01 (s, 3H), 0.94 (t, J=8.0 Hz, 9H), 0.56 (q, J=8.0 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ158.38, 150.43, 124.31, 121.34, 68.75, 58.17, 54.95, 46.75, 38.76, 35.78, 34.74, 30.91, 30.70, 23.23, 21.83, 18.84, 17.96, 6.88, 4.83; IR (neat, cm −1 ) 2932, 1294, 1115; HRMS m/z pending.
EXAMPLE 32
16,23-Diene-8-Hydroxy-25-Sulfone (+)-44E
To a solution of the sulfone (+)-43E (24 mg, 0.053 mmol) in 10 mL of acetonitrile was added hydrofluoric acid (2% in H 2 O, 0.10 mL, 0.10 mmol) at 0° C. After 2 h at 0° C., the reaction mixture was quenched with saturated NaHCO 3 solution (20 mL) and extracted with EtOAc (30 mL×3). The combined organic layers were washed with brine (30 mL), dried over MgSO 4 and concentrated. The crude product was purified by flash chromatography (50% EtOAc/hexanes) to give 17 mg (94%) of the alcohol (+)-44E as a colorless oil: [α] 25 D +5.9 (c 2.9, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.82 (dt, J=15.2, 7.6 Hz, 1H), 6.25 (dt, J=15.2, 1.6 Hz, 1H), 5.35 (s, 1H), 4.18 (s, 1H), 2.54-2.22 (m, 4H), 2.02-1.52 (m, 14H), 1.35 (s, 9H), 1.06 (d, J=8.0 Hz, 3H), 1.05 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ158.30, 150.22, 124.45, 121.45, 68.89, 58.19, 54.31, 46.46, 38.72, 35.47, 33.79, 30.99, 30.22, 23.28, 21.84, 18.46, 17.70; IR (neat, cm −1 ) 3526, 2927, 1290, 1120; HRMS m/z (M+NH 4 + ) calcd 358.2416 for C 19 H 32 O 3 S, found 358.2408.
EXAMPLE 33
16,23-Diene-8-Keto-25-Sulfone (+)-45E
To a solution of the alcohol (+)-44E (28 mg, 0.083 mmol) in 10 mL of dry CH 2 Cl 2 was added 57 mg of oven dried celite and pyridinium dichlomate (57 mg, 0.15 mmol) at rt. After 16 h, the reaction mixture was filtered through a flash silica gel pad, and then eluted with EtOAc. The filtrate was concentrated and purified by flash chromatography (50% EtOAc/hexanes) to give 25 mg (89%) of the ketone (+)-45E as a colorless oil: [α] 25 D +22.2 (c 2.0, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.78 (dt, J=15.2, 7.6 Hz, 1H), 6.25 (d, J=15.2 Hz, 1H), 5.33 (s, 1H), 2.85 (m, 1H), 2.55-2.27 (m, 6H), 2.15-1.74 (m, 7H), 1.33 (s 9H), 1.11 (d, J=6.4 Hz, 3H), 0.81 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ210.43, 156.21, 149.49, 124.89, 121.80, 62.89, 58.19, 53.69, 40.34, 38.56, 34.35, 27.09, 23.86, 23.25, 21.35, 17.32; IR (neat, cm −1 ) 2935, 1715, 1289, 1113; HRMS m/z (M+NH 4 + ) calcd 356.2259 for C 19 H 30 O 3 S, found 356.2266.
EXAMPLE 34
16,23-Diene-25-Sulfone Analogs (−)-Formula IX-1 and (−)-Formula IX-2
To a solution of racemic phosphine oxide (±)-A (60 mg, 0.10 mmol) in 1 mL of anhydrous THF was treated dropwise with phenyllithium (1.22 M in cyclohexane-ether, 0.082 mL, 0.10 mmol) at −78° C. The resulting reddish orange solution was stirred at −78° C. for 30 min and then a solution of the ketone (+)-45E (24 mg, 0.071 mmol) in 1 mL of anhydrous THF was added dropwise. The reaction mixture was stirred until reddish color tuned to pale yellow, and then quenched with 3 ml of a 1:1 mixture of 2 N sodium potassium tartrate solution and 2 N K 2 CO 3 solution. The aqueous layer was extracted with EtOAc (50 mL×3). The combined organic portions were washed with brine (50 mL), dried over MgSO 4 , and concentrated. The residue was purified by preparative TLC (EtOAc) to give 44 mg (88%) of the coupled product as a colorless oil.
To a solution of the coupled product (44 mg, 0.062 mmol) in 2 mL of anhydrous ethanol was added hydrofluoric acid (49% in H 2 O, 0.50 mL, 12.3 mmol). The solution was stirred at rt for 2 h in dark. The reaction mixture was quenched with NaHCO 3 solution (20 mL) and the aqueous layer was extracted with EtOAc (30 mL×3). The combined organic portions were washed with brine (20 mL), dried over MgSO 4 , and concentrated. The residue was purified by preparative TLC (EtOAc) to give 27 mg (91%) of diastereomeric diols Formula IX as colorless oils . The diastereomers were separated by reverse phase HPLC (C-18 semi preparative column, 52% MeCN/48% H 2 O, 3 mL/min) to give 12 mg (36%) of (−)-Formula IX-1 (1α,3β, t R 30.2 min) and 9 mg (27%) of(−)-Formula IX-2 (1β,3α, t R 27.1 min) as colorless oils. (−)-Formula IX-1: [α] 25 D −2.5 (c 1.1, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.81 (dt, J=15.2, 7.4 Hz, 1H), 6.36 (d, J=11.2 Hz, 1H), 6.24 (d, J=15.2 Hz, 1H), 6.10 (d, J=11.6 Hz, 1H), 5.34 (two s, 2H), 5.00 (s, 1H), 4.44 (m, 1H), 4.24 (m, 1H), 2.88 (dd, J=12.4, 4.2 Hz, 1H), 2.61-2.48 (m, 3H), 2.38-2.14 (m, 7H), 2.06-1.51 (m, 18H), 1.34 (s, 9H), 1.09 (d, J=6.4 Hz, 3H), 0.70 (s, 3H); 13 C NMR (100 MHz, CDCl 3 ) δ157.86, 150.15, 147.63, 141.81, 133.37, 124.70, 124.50, 122.98, 117.14, 111.64, 70.62, 66.83, 58.28, 58.21, 50.02, 45.12, 42.84, 38.64, 35.29, 32.00, 29.43, 28.67, 23.49, 23.29, 21.29, 17.03; IR (neat, cm −1 ) 3606, 2931, 1291, 1113; UV (EtOH) λ max 263 nm (ε 11,793); HRMS m/z pending. (−)-Formula IX-2: [α] 25 D −10.9 (C 0.8, CHCl 3 ); 1 H NMR (400 MHz, CDCl 3 ) δ6.81 (dt, J=15.2, 7.6 Hz, 1H), 6.38 (d, J=11.6 Hz, 1H), 6.24 (d, J=15.2 Hz, 1H), 6.09 (d, J=11.2 Hz, 1H), 5.35 and 5.33 (two s, 2H), 5.01 (s, 1H), 4.46 (m, 1H), 4.23 (m, 1H), 2.83 (dd, J=12.8, 4.0 Hz, 1H) 2.46-2.48 (m, 3H), 2.34-2.15 (m, 7H), 2.05-1.52 (m, 20H), 1.35 (s, 9H), 1.09 (d, J=6.4 Hz, 3H), 0.69 (s, 3H) ); 13 C NMR (100 MHz, CDCl 3 ) δ157.86, 150.15, 147.09, 141.91, 133.18, 124.76, 124.52, 121.98, 117.14, 112.82, 71.42, 66.74, 58.28, 58.22, 50.03, 45.47, 42.78, 38.64, 35.28, 32.01, 29.47, 28.66, 23.48, 23.30, 21.32, 17.05; R (neat, cm −1 ) 3606, 2931, 1291, 1112; UV (EtOH) λ max 263 nm (ε 11,572); .HRMS m/z pending.
Preparation of the Formula X materials is described in Scheme 9 as follows:
Scheme 9 begins with a ketone derivative 46, the preparation of which is described in Posner et al; J. Org. Chem. Vol. 62. 1997 at pp. 3299-3314 and also uses t-butyl, 3-hydroxypropyl sulfone 49 as a reagent. Preparation of the various intermediates 47, 48, 50, 51 and 52 and the Formula X compounds is described in Examples 35 through 40 hereinafter.
EXAMPLE 35
Hydroxy Ketone 47
To a solution of (triethylsilyloxy)ketone (+)-46 (78 mg, 0.225 mmol) in 5 mL of THF at 0° C. was added 338 μL (0.338 mmol, 1.0 M in THF) of tetrabutylammonium fluoride dropwise via syringe. The reaction mixture was brought to rt and stirred for 5 h, after which the solvent was evaporated. The crude mixture was purified by column chromatography (20% EtOAc/hexanes) to give 48 mg of the desired hydroxy ketone 47 in quantitative yield: 1 H NMR (CDCl 3 ) δ4.07 (m, 1H), 2.45 (t, J=8.8 , 1H), 2.05 (s, 3H), 0.82 (s, 3H); 13 C NMR (CDCl 3 ) δ209.4, 68.5, 64.1, 52.6, 43.3, 39.4, 33.3, 31.4, 22.5, 21.6, 17.3, 15.1; [α] 25 D , IR, HRMS pending.
EXAMPLE 36
Acetoxy Ketone 48
To a solution of hydoxy ketone 47 (48 mg, 0.245 mmol) in 2.2 mL of CH 2 Cl 2 at 0° C. was added DMAP (1 mg, 0.03 mmol), pyridine (44 μL, 0.539 mmol), and Ac 2 O (46 μL, 0.489 mmol) sequentially and the resulting solution stirred for 5 h while warming to rt. Following concentration, the reaction mixture was passed through flash silica gel (10% EtOAc/hexanes) to afford acetoxy ketone 48 as a pale yellow oil (55 mg, 94%): 1 H NMR (CDCl 3 ) δ5.08 (m, 1H), 2.42 (t, J=8.8 Hz, 1H), 2.02 (s, 3H), 1.94 (s, 3H), 0.73 (s, 3H); 13 C NMR (CDCl 3 ) δ208.7, 170.4, 70.3, 63.6, 51.2, 43.1, 38.8, 31.3, 30.1, 22.5, 21.4, 21.0, 17.6, 14.5; [α] 25 D , IR, HRMS pending
EXAMPLE 37
t-Butyl 3-(Trimethylsilyloxy)-propyl Sulfone 50
To a solution of t-Butyl 3-hydroxypropyl sulfone 1 49 (1.01 g, 5.60 mmol) in 25 mL of CH 2 Cl 2 was added Et 3 N (1.17 mL, 8.40 mmol) and then TMSCI (0.78 mL, 6.16 mL). The resulting solution was stirred for 1 h, cooled to 0° C., and quenched with saturated NaHCO 3 (5 mL). After warming, the reaction mixture was diluted with H 2 O (10 mL), extracted with CH 2 Cl 2 (3×15 mL), dried over Na 2 SO 4 , filtered, and concentrated to a red oil. Rapid column chromatography (25% EtOAc/hexanes) afforded the desired product 50 as a clear, colorless oil (0.75 g, 53% from 2-methyl-2-propanethiol 1 ): 1H NMR (CDCl 3 ) δ3.71 (t, J=5.8 Hz, 2H), 3.00 (t, J=7.8 Hz, 2H), 2.07 (m, 2H), 1.4 (s, 9H), 0.09 (s, 9H); 13 C NMR (CDCl 3 ) δ60.7, 58.8, 42.5, 23.8, 23.3, −0.63; IR (neat, cm −1 ) 2959, 2906, 2875, 1301-1249, 1113; HRMS submitted
EXAMPLE 38
Acetoxy Sulfone 51
To a solution of ketone 48 (24 mg, 0.101 mmol) in 1 mL of CH 2 Cl 2 at −78° C. was added 35 mg (0.138 mmol) of (trimethylsilyl)ether 50 in 0.350 mL of CH 2 Cl 2 . To this solution was added TMSOTf (0.019 mL, 0.105 mmol) via syringe and the resulting solution stirred at −78° C. for 1 h. Et 3 SiH (0.017 mL, 0.105 mmol) was added via syringe and the reaction mixture brought to rt. After 4 h, the reaction was ceased by the addition of a saturated NaHCO 3 solution (1 mL). This mixture was diluted with H 2 O (10 mL), extracted with CH 2 Cl 2 (3×), dried over MgSO 4 , filtered, concentrated, and passed through flash silica gel (25% EtOAc/hexanes) to afford the acetoxy sulfone 51 as a clear, colorless oil (21.0 mg, 52%): 1 H NMR (CDCl 3 ) δ5.14 (m, 1H), 3.69 (dt, J=9.2, 6.0 Hz, 1H), 3.35 (dt, J=9.2, 6.0 Hz, 1H), 3.30 (m, 1H), 3.04 (t, J=7.8 Hz, 2H), 2.13 (m, 2H), 2.03 (s, 3H), 1.83 (m, 1H), 1.41 (s, 9H), 1.05 (d, J=6.0 Hz, 3H), 0.88 (s, 3H); 13 C NMR (CDCl 3 ) δ170.8, 77.7, 71.1, 65.8, 58.8, 56.6, 50.9, 43.2, 41.8, 40.0, 30.6, 24.7, 23.4, 22.8, 21.7, 21.4, 18.1, 17.8, 13.7; [α] D 25 , IR, HRMS pending
EXAMPLE 39
C,D-Ring Ketone 52
To a solution of acetoxy sulfone 51 (18 mg, 0.045 mmol) in 2 mL of EtOH was added 10 M NaOH (aq) (1 mL) dropwise. After stirring for 3 h, the reaction mixture was cooled to 0° C., diluted with Et 2 O (1 mL), neutralized with 10% HCl (aq) (1 mL), extracted with EtOAc (3×5 mL), the combined organics washed with brine, dried over MgSO 4 , filtered, and concentrated to afford the crude alcohol (16 mg). This alcohol (16 mg) was then dissolved in 4 mL CH 2 Cl 2 , and to this solution was added celite (25 mg) and PDC (25 mg, 0.067 mmol). After stirring for 12 h, the suspension was passed through a short plug of celite and rinsed with CH 2 Cl 2 . The filtrate was then concentrated and passed through a short plug of flash silica gel (35% EtOAc/hexanes) to give the desired ketone 52 (16 mg) as a white solid in quantitative yield. 1 H NMR (CDCl 3 ) δ3.69 (dt, J=9.2, 6.0 Hz, 1H), 3.36 (dt, J=9.2, 6.0 Hz, 1H), 3.29 (m, 1H), 3.01 (dt, J=7.7, 3.0 Hz, 2H), 2.45 (dd, J=11.2, 7.2 Hz, 1H), 1.41 (s, 9H) 1.08 (d, J=6.0 Hz, 3H), 0.64 (s, 3H); 13 C NMR (CDCl 3 ) δ211.8, 77.5, 65.9, 61.4, 58.9, 56.7, 49.8, 42.9, 41.1, 39.0, 25.0, 24.1, 23.4, 21.7, 19.3, 18.2, 13.1; mp, [α] D D , IR, HRMS pending
EXAMPLE 40
20-Epi-22-oxa-26-sulfone Formulas X-1 and X-2
Racemic phosphine oxide (±)-A (51 mg, 0.087 mmol) was dissolved in 1 mL of THF and cooled to −78° C. under argon. To this solution was added 51 μL (0.086 mmol 1.69 M in cyclohexane/Et 2 O) of PhLi dropwise via syringe. The deep orange solution was stirred for 30 min, at which time a cold solution of C,D-ring ketone 52 (31 mg, 0.082 mmol) in 0.7 mL of THF was added dropwise via cannula. The resulting solution was stirred at −78° C. in the dark for approximately 4 h and then quenched with 3 mL of a 2:1 (v:v) mixture of 2 N sodium potassium tartrate and 2 N potassium carbonate. Upon warming to rt, the reaction mixture was extracted with EtOAc (3×20 mL), dried over MgSO 4 , filtered, concentrated and purified by silica gel column chromatography (20% EtOAc/1% NEt 3 /hexanes) to afford 43 mg (72% based on 52) of the coupled product as a yellow oil. This oil was immediately dissolved in 10 mL of THF with 20 μL of NEt 3 . To this solution was added 178 μL (0.178 mmol, 1.0 M in THF) of tetrabutylammonium fluoride dropwise via syringe. The reaction mixture was stirred for 16 h in the dark, after which the solvent was evaporated and the crude mixture purified by column chromatography (1% NEt 3 /EtOAc) to give 21 mg (71%) of a mixture of two diastereomers Formula X-1 and Formula X-2. This diastereomeric mixture was purified by reversed-phase HPLC (C-18 semipreparative column, 40% MeCN/H 2 O, 3 mL/min) giving Formula X-1 (1α, 3β, t R 70.7 min) and Formula X-2 (1β, 3α, t R 66.6 min): Formula X-1 (1α, 3β): 1 H NMR (CDCl 3 ) δ6.38 (d, J=11.2 Hz, 1H), 6.00 (d, J=11.2 Hz, 1H), 5.32 (m, 1H), 4.99 (m, 1H), 4.46-4.40 (m, 1H), 4.26-4.19 (m, 1H), 3.70 (dt, J=9.2, 6.0 Hz, 1H), 3.34 (dt, J=9.2, 6.0 Hz, 1H), 3.29 (m, 1H), 3.03 (m, 2H), 2.83 (dd, J=13.2, 4.4 Hz, 1H), 2.60 (dd, J=13.2, 3.6 Hz, 1H), 2.29 (dd, J=13.4, 6.4 Hz, 1H), 1.41(s, 9H) 1.08 (d, J=5.6 Hz, 3H), 0.55 (s, 3H); 13 C NMR, UV, [α] 25 D −50.8 (c 4.4, CHCl 3 ); Formula X-2 (1β, 3α): 1 H NMR (CDCl 3 ) δ6.39 (d, J=11.6 Hz, 1H), 5.99 (d, J=11.2 Hz, 1H), 5.31 (m, 1H), 5.00 (m, 1H), 4.47-4.41 (m, 1H), 4.26-4.19 (m, 1H), 3.71 (dt, J=9.2, 6.0 Hz, 1H), 3.35 (dt, J=9.2, 6.0 Hz, 1H), 3.29 (m, 1H), 3.04 (m, 2H), 2.83 (dd, J=13.2, 4.0 Hz, 1H), 2.61 (dd, J=13.2, 4.0 Hz, 1H), 2.30 (dd, J=13.0, 7.6 Hz, 1H), 1.41 (s, 9H) 1.08 (d, J=5.6 Hz, 3H), 0.55 (s, 3H); 13 C NMR, UV, [α] 25 D −36.2 (c 3.0, CHCl 3 ).
Via synthesis procedures similar to those set forth in the examples herein, it is possible to prepare related 23-oxa-25-sulfones and 20-epi-22-oxa-sulfones. Such compounds have the generic structures shown in Formulas XI and XII as follows:
Via conventional organic synthesis procedures starting from materials described herein, it is also possible to prepare related 16-ene-alkenylsulfones and 16-ene-alkynylsulfones. Such compounds have the generic structure shown in Formula XIII as follows:
EXAMPLE 41
4-[(Methoxy)phenyl]-3-tosyloxypropyl Sulfide 10
To a solution of NaOH (0.572 g, 14.3 mmol) in EtOH (12 mL) at 0° C. was added dropwise via syringe 4-methoxythiophenol (1.75 mL, 14.3 mmol) over 2 min. The resulting solution was warmed to rt and stirred for 30 min. Upon dropwise addition of 3-chloro-1-propanol (1.19 mL, 14.3 mmol), the reaction mixture was heated to reflux and stirred overnight. The resulting suspension was filtered to remove NaCl, which was rinsed thoroughly with CH 2 Cl 2 . The filtrate was neutralized with 1 M HCl (12 mL), diluted with H 2 O (20 mL), extracted with CH 2 Cl 2 (3×20 mL), washed with H 2 O, dried over Na 2 SO 4 , filtered, and concentrated to a pale yellow oil which solidified on standing.
A portion of this pale yellow solid (613 mg, 2.66 mmol) was dissolved in CH 2 Cl 2 (17 mL) and cooled to 0° C. To this solution was added DMAP (390 mg, 3.19 mmol) and TsCl (558 mg, 2.93 mmol), and the resulting solution was allowed to stir with gradual warming to rt overnight. The reaction mixture was quenched with 10% HCl (aq) (5 mL), partitioned between CH 2 Cl 2 and H 2 O, extracted with CH 2 Cl 2 (3×20 mL), dried over Na 2 SO 4 , filtered, concentrated, and purified by column chromatography (30-50% EtOAc/hexanes) to give the desired tosylate (448 mg, 44%) as a clear oil: 1 H NMR (CDCl 3 ) δ7.77 (dt, J=8.4, 1.6 Hz, 2H), 7.34 (m, 2H), 7.27 (dt, J=9.0, 2.2 Hz, 2H), 6.82 (dt, J=9.0, 2.2 Hz, 2H), 4.13 (t, J=6.0 Hz, 2H), 3.78 (s, 3H), 2.80 (t, J=7.0 Hz, 2H), 2.44 (s, 3H), 1.86 (m, 2H); 13 C NMR (CDCl 3 ) δ159.10, 144.77, 133.58, 132.82, 129.81, 127.81, 125.15, 114.57, 68.61, 55.26, 31.62, 28.35, 21.59; IR (neat) 3063, 2957, 2834, 1594, 1571, 1494, 1462, 1441, 1359, 1284, 1244, 1187, 1174, 1096, 1030; HRMS: calcd for C 17 H 20 O 4 S 2 352.0803, found 352.0804.
EXAMPLE 42
R-Alcohol (+)-12.
To a stirred solution of (t-butyldimethylsilyloxy)ketone (+)-11 1 (803 mg, 2.59 mmol) in THF (50 mL) at −78° C. was added lithium tri-tert-butoxyaluminohydride (7.76 mL, 1.0 M in THF) dropwise via syringe. The reaction mixture was brought to rt slowly overnight. The reaction was quenched with a saturated aqueous NH 4 Cl solution (15 mL) and the resulting mixture was extracted with EtOAc (3×25 mL), dried with brine and MgSO 4 , filtered, and concentrated. The crude mixture was purified on short path silica gel (5-10% EtOAc/hexanes) to give 658 mg (81%) of the desired R-alcohol (+)-12 and 113 mg (14%) of the S-alcohol, both having spectroscopic and physical characteristics analogous to those reported previously. 2
EXAMPLE 43
8β-[(t-Butyldimethylsilyl)oxy]-20-epi-22-oxa-26-p-methoxyphenyl Sulfone (+)-13
Potassium hydride (63 mg of a 35 wt. % dispersion in mineral oil—approximately 22 mg, 0.54 mmol dry weight) was rinsed and dried according to methods described by Brown. 3 To a suspension of the resulting dry KH in THF (1.0 mL) was added a solution of alcohol (+)-12 (50 mg, 0.16 mmol) in THF (2.2 mL) dropwise via syringe. The resulting yellow solution was stirred for 1 h. Then tosylate 10 (123 mg, 0.32 mmol) in THF (0.88 mL) was added via syringe. After 3 h, the reaction was cautiously diluted with EtOAc and H 2 O, and extracted with EtOAc (3×15 mL). The combined organic phases were dried over MgSO 4 , filtered, concentrated and purified on flash silica gel (2-5% EtOAc/hexanes) to afford 50 mg (63%) of the desired ether (+)-13 with 11 mg (22%) of recovered alcohol (+)-12: [α] D 25 +1.63 (c 3.0, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.34 (dt, J=9.0, 2.2 Hz, 2H), 6.83 (dt, J=9.0, 2.2 Hz, 2H), 4.00 (m, 1H), 3.79 (s, 3H), 3.62 (dt, J=9.0, 6.0 Hz, 1H), 3.31-3.22 (m, 2H), 2.91 (t, J=7.2 Hz, 2H), 2.02 (dt, J=12.4, 2.8 Hz, 1H), 1.85-1.05 (m, 13H), 1.04 (d, J=6.0, 3H), 0.93 (s, 3H), 0.89 (s, 9H), 0.01 (s, 3H), 0.01 (s, 3H); 13 C NMR (CDCl 3 ) δ158.75, 133.02 126.53, 114.47, 77.71, 69.29, 66.24, 57.08, 55.29, 52.61, 42.00, 40.56, 34.59, 32.94, 29.92, 25.80, 24.95, 23.20, 18.22, 18.01, 17.63, 14.46, −4.79, −5.19; IR (neat) 3002, 2949, 2928, 2855, 1593, 1494, 1471, 1462, 1454, 1284, 1245, 1168, 1104, 1078, 1034, 1019; HRMS: calcd for C 28 H 48 O 3 SSi 492.3093, found 492.3093.
EXAMPLE 44
C,D-Ring Ketone (−)-14
Oxone® (20% aqueous solution: 68 mg, 0.11 mmol in 275 μL H 2 o) was added dropwise to a stirred solution of ether (+)-13 in MeOH (1.0 mL). The resulting solution was stirred for 2 d, with additional oxone® solution being added to consume starting material. Upon dilution with H 2 O and extraction with CHCl 3 , the combined organics were dried, filtered and concentrated to give a crude mixture of sulfones (C8-OTBS : C8-OH), which was immediately dissolved in THF (3.5 mL) and treated with TBAF (400 μL, 1.0 M in THF). The resulting solution was stirred at reflux for 2 d, with additional TBAF solution being added to consume starting material. The reaction mixture was cooled to rt, diluted with EtOAc and H 2 O (10 mL each), extracted with EtOAc (3×10 mL), dried, filtered, and concentrated to give crude hydroxy sulfone which was carried forward.
To crude hydroxy sulfone in CH 2 C 2 (8 mL) was added celite (57 mg) and PDC (57 mg, 0.15 mmol) and the resulting brown suspension was stirred overnight. Upon filtration through celite®, the reaction mixture was concentrated and passed through a short pad of flash silica gel (40% EtOAc/hexanes) to afford the desired C,D-ring ketone (−)-14 as a pale yellow oil (37 mg, 90% from (+)-13): [α] 25 D − 40.8 (c 3.0, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.80 (dt, J=9.2, 2.2 Hz, 2H), 7.00 (dt, J=9.2, 2.2 Hz, 2H), 3.86 (s, 3H), 3.54 (dt, J=9.2, 6.2 Hz, 1H), 3.28-3.06 (m, 5H), 2.45-2.38 (dd, J=11.2, 7.6 Hz, 1H), 2.28-1.07 (m, 12H), 1.01 (d, J=6.0, 3H), 0.57 (s, 3H); 13 C NMR (CDCl 3 ) δ211.76, 163.64, 130.52, 130.09, 114.37, 77.41, 65.38, 61.31, 56.59, 55.63, 53.97, 49.68, 41.01, 38.85, 24.91, 24.03, 23.92, 19.25, 18.09, 12.98; IR (neat) 2961, 2874, 1708, 1595, 1578, 1498, 1317, 1298, 1260, 1226, 1140, 1108, 1089, 1023; HRMS: calcd for C 22 H 32 O 5 S 408.1970, found 408.1976.
EXAMPLE 45
20-Epi-22-oxa-26-p-methoxyphenyl Sulfone Analogs 15a and 15b
Racemic phosphine oxide (±)-8 (78 mg, 0.13 mmol) was dissolved in 1.3 mL of THF and cooled to −78° C. under argon. To this solution was added 88 μL (0.13 mmol, 1.5 M in cyclohexane/Et 2 O) of PhLi dropwise via syringe. The deep orange solution was stirred for 30 min, at which time a cold (−78° C.) solution of C,D-ring ketone (−)-14 (36 mg, 0.087 mmol) in 1.2 mL of THF was added dropwise via cannula. The resulting solution was stirred in the dark at −78° C. for approximately 3 h, and for an additional 1 h at −60° C. The reaction mixture was quenched with 3 mL of a 2:1 (v:v) mixture of 2 N sodium potassium tartrate and 2 N potassium carbonate. Upon warming to rt, the reaction mixture was diluted with H 2 O, extracted with EtOAc (4×20 mL), dried over MgSO 4 , filtered, concentrated and purified by silica gel column chromatography (20% EtOAc/hexanes-<0.1% NEt 3 ) to afford 40 mg (64% based on (−)-14) of the coupled product as a yellow oil.
This oil was immediately dissolved in THF (10 mL) with 10 μL of NEt 3 . To this solution was added 170 μL (0.17 mmol, 1.0 M in THF) of tetrabutylammonium fluoride dropwise via syringe. The reaction mixture was stirred for 16 h in the dark, after which the solvent was evaporated and the crude mixture purified by column chromatography (1% NEt 3 /EtOAc) to give 27 mg (90%) of a mixture of two diastereomers 15a and 15b. This diastereomeric mixture was purified by reversed-phase HPLC (C-18 semipreparative column, 43% MeCN/H 2 O, 3 mL/min) giving 15a (27%, t R 93.8 min) and 15b (15%, t R 88.9 min): 15a (1α, 3β): [α] D 25 −44.6 (c 2.5, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.81 (dt, J=8.8, 2.0 Hz, 2H), 7.01 (dt, J=8.8, 2.0 Hz, 2H), 6.37 (d, J=11 Hz, 1H), 5.98 (d,, J=11 Hz, 1H), 5.31 (m, 1H), 4.98 (m, 1H), 4.45-4.38 (m, 1H), 4.26-4.19 (m, 1H), 3.54 (dt, J=9.2, 6.2 Hz, 1H), 3.28-3.06 (m, 5H), 2.85-2.76 (dd, J=12.2, 3.0 Hz, 1H), 2.63-2.54 (dd, J=12.2, 3.0 Hz, 1H), 2.34-2.26 (dd, J=13.3, 6.8 Hz, 1H), 2.06-1.04 (m, 19H), 1.01 (d, J=6.0, 3H), 0.49 (s, 3H); 13 C NMR (CDCl 3 ) δ163.65, 147.61, 142.86, 132.98, 130.63, 130.17, 124.88, 117.02, 114.40, 111.73, 78.19, 70.77, 66.80, 65.45, 56.66, 55.75, 55.67, 54.12, 45.71, 45.21, 42.84, 40.34, 29.06, 25.04, 24.01, 23.49, 22.40, 18.22, 12.63; IR (neat) 3706-3115 (br), 3019, 2945, 2872, 1644, 1595, 1578, 1497, 1443, 1413, 1372, 1317, 1296, 1261, 1219, 1165, 1139, 1109, 1088, 1057, 1027; UV (MeOH) λ max 240 (ε20,102), 264 nm (ε13,165); HRMS: calcd for C 31 H 44 O 6 S 544.2859, found 544.2857. 15b (1β, 3α): [α] D 25 −43.0 (c 4.1, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.81 (dt, J=8.8, 2.0 Hz, 2H), 7.01 (dt, J=8.8, 2.0 Hz, 2H), 6.38 (d, J=11.2 Hz, 1H), 5.98 (d, J=11.2 Hz, 1H), 5.30 (m, 1H), 4.99 (m, 1H), 4.46-4.40 (m, 1H), 4.26-4.18 (m, 1H), 3.55 (dt, J=9.2, 6.2 Hz, 1H), 3.28-3.06 (m, 5H), 2.85-2.76 (dd, J=12.2, 3.0 Hz, 1H), 2.63-2.54 (dd, J=12.2, 3.0 Hz, 1H), 2.34-2.26 (dd, J=13.3, 6.8 Hz, 1H), 2.06-1.04 (m, 19H), 1.01 (d, J=6.0, 3H), 0.49 (s, 3H); 13 C NMR (CDCl 3 ) δ163.65, 147.29, 142.93, 132.82, 130.65, 130.18, 124.91, 117.01, 114.41, 112.45, 78.19, 71.29, 66.78, 65.46, 56.66, 55.75, 55.67, 54.12, 45.72, 45.44, 42.82, 40.33, 29.03, 25.04, 24.01, 23.48, 22.43, 18.22, 12.65; IR (neat) 3686-3076 (br), 2947, 2926, 2871, 1595, 1578, 1498, 1458, 1438, 1372, 1317, 1296, 1260, 1220, 3.: 1139, 1109, 1089, 1053, 1025; UV (MeOH) λ max 240 (ε17,201), 261 nm (ε10,346); HRMS: calcd for C 31 H 44 O 6 S 544.2859, found 544.2857.
EXAMPLE 46
20-Epi-22-oxa-25-difluoro-26-tert-butyl Sulfone Analogs 25a and 25b
20-Epi-22-oxa-25-difluoro-26-tert-butyl Sulfone Analogs 25a and 25b
Racemic phosphine oxide (±)-8 (70 mg, 0.12 mmol) was dissolved in 1.2 ML of THF and cooled to −78° C. under argon. To this solution was added 80 μL of n-BuLi (0.12 mmol, 1.53 M in hexanes) dropwise via syringe. The deep red solution was stirred for 1 h, at which time a cold (−78° C.) solution of C,D-ring ketone (−)-24 (24 mg, 0.061 mmol) in 1.0 mL of THF was added dropwise via cannula. The resulting solution was stirred at −78° C. in the dark for approximately 3 h, then slowly warmed to 40° C. over 2 h. The reaction mixture was quenched with H 2 O (1 mL), warmed to rt, extracted with Et 2 O (3×10 mL), washed with brine, dried over MgSO 4 , filtered, concentrated and purified by silica gel column chromatography (5-40% EtOAc/hexanes) to afford 43 mg of the coupled product as a clear oil.
This oil was immediately dissolved in 3.0 mL of EtOH. To this solution was added 100 μL of an aqueous HF solution (49% wt) dropwise via syringe. The reaction mixture was stirred for 4 h in the dark, which, after general aqueous workup and column chromatography (75% EtOAc/hexanes), yielded 30 mg [93% from (−)-24] of a mixture of diastereomers 25a and 25b. This diastereomeric mixture was purified by reversed-phase HPLC (C-18 semipreparative column, 49% MeCN/H 2 O, 3 ml/min) giving 10 mg (31%) of 25a (1α, 3β, t R 111 min) and 3.0 mg (9%) of 25b (1β, 3α, t R 105 min): 25a (1α, 3β): 1 H NMR (CDCl 3 ) δ6.38 (d, J=11 Hz, 1H), 5.99 (d, J=11 Hz, 1H), 5.32 (m, 1H), 4.99 (m, 1H), 4.45-4.39 (m, 1H), 4.264.17 (m, 1H), 3.84 (m, 1H), 3.51 (m, 1H), 3.31 (m, 1H), 2.82 (dd, J=16, 4.3 Hz, 1H 1H), 2.60 (m, 3H), 2.31 (dd, J=18, 8.8 Hz, 1H), 1.52 (s, 9H) 1.09 (d, J=5.6 Hz, 3H), 0.54 (s, 3H); 13 C NMR (CDCl 3 ) δ147.62, 143.12, 132.82, 124.98, 116.94, 111.71, 78.56, 70.80, 66.83, 60.05, 56.58, 55.82, 45.76, 45.23, 42.84, 40.17, 31.47, 29.12, 25.09, 24.14, 23.52, 22.42, 18.12, 12.53; HRMS: calcd for C 2 H 44 F 2 O 5 S 530.2878, found 530.2877; 25b (1β, 3α): 1 H NMR (CDCl 3 ) δ6.40 (d, J=12 Hz, 1H), 5.98 (d, J=12 Hz, 1H), 5.31 (m, 1H), 5.00 (m, 1H), 4.44 (m, 1H), 4.23 (m, 1H), 3.85 (m, 1H), 3.52 (m, 1H), 3.31 (m, 1H), 2.82 (dd, J=16, 4.3 Hz, 1H 1H), 2.59 (m, 3H), 2.29 (dd, J=18, 8.8 Hz, 1H), 1.52 (s, 9H) 1.09 (d, J=6.0 Hz, 3H), 0.54 (s, 3H); 13 C NMR (CDCl 3 ) δ147.28, 143.18, 132.68, 125.00, 116.94, 112.49, 78.57, 71.35, 66.80, 60.06, 56.58, 55.82, 45.78, 45.48, 42.82, 40.16, 31.48, 29.10, 25.09, 24.14, 23.52, 22.45, 18.13, 12.55; HRMS: calcd for C 28 H 44 F 2 O 5 S 530.2878, found 530.2877; 19 F NMR, UV, [α] D 25 , IR pending.
Through the use of similar methods, 27-t-butyl sulfone and 26-methyl sulfone analogs can be synthesized as shown in Schemes 11 and 12.
1 Fernandez, B.; Perez, J. A. M.; Granja, J. R.; Castedo, L.; Mourino, A. J. Org. Chem. 1992, 57, 3173-3178.
2 Posner, G. H.; White, Dolan, P.; Kensler, T. W.; Yukihiro, S.; Guggino, S. E. Biorg. Med. Chem. Let. 1994, 4, 2919-2924.
3 Brown, C. A. J. Org. Chem. 1974, 39, 3913-3918.
EXAMPLE 47
22E, 24E-diene sulfones can be synthesized by the method shown in Scheme 13. Analogous compounds in which the t-butyl group is replaced by an alternate lower alkyl group or by an unsubstituted phenyl or a phenyl substituted with a lower alkyl or alkoxy can be made with modifications which will be evident to persons of skill in the art.
E-3-Bromo-l-propenyl 1-butyl sulfone 16
To a solution of NaOH (2.40 g, 60.0 mmol) in ethanol (50 μL) at 50° C. was added dropwise via syringe 2-methyl-2-propanethiol (6.76 mL, 60 mmol) over 2 min. The resulting solution was stirred for 30 min while cooling to n. Upon dropwise addition of allylbromide (5.19 mL, 60 mmol), the reaction mixture was heated to reflux and stirred overnight. The resulting suspension was filtered to remove NaBr, which was rinsed thoroughly with Et 2 O. The filtrate was neutralized with 1 M HCl (50 mL), diluted with H 2 O (100 mL), extracted with Et 2 O (3×25 mL), washed with H 2 O, dried over Na 2 SO 4 , filtered, and concentrated to a pale yellow oil by removing EtOH and Et 2 O via slow distillation.
This pale yellow oil (7.81 g theor.) was dissolved in 215 mL of MeOH and cooled to 0° C. To this solution was added a 26% oxone solution (55.3 g, 90.0 mmol in 150 mL H 2 O) dropwise via addition funnel. The resulting suspension was allowed to stir with gradual warming to rt overnight. The reaction mixture was diluted with 150 mL H 2 O, extracted with CHCl 3 (3×75 mL), washed with H 2 O and brine (150 mL each), dried over Na 2 SO 4 , filtered, and concentrated to give essentially pure allyl i-butyl sulfone as a clear oil.
A portion of this sulfone (1.00 g, 6.16 mmol) was dissolved in CCl 4 (40 mL), treated with bromine (0.317 mL, 6.16 mmol) for 3 h, and concentrated to give the desired dibromide (1.46 g, 74%) as a pale orange solid (mp 75-80° C.) from cold Et 2 O/hexanes, clean enough for the following transformation.
The dibromide was dissolved in THF (50 mL), cooled to 0° C., and treated with Et 3 N (0.945 mL, 6.78 mmol) overnight, while gradually warming to rt. The reaction mixture was neutralized with dilute HCl, diluted with H 2 O, extracted with Et 2 O (3×25 mL), dried over Na 2 SO 4 , filtered, concentrated, and purified by column chromatography (10-20% Et 2 O/pentane) to give 16 (385 mg, 26% two steps) as white crystals: mp 60-62° C.; 1 H NMR (CDCl 3 ) δ7.00 (dt, J=15, 6.8 Hz, 1H), 6.55 (dt, J=15, 1.2 Hz, 1H), 4.07 (dd, J=6.8, 1.2 Hz, 2H), 1.38 (s, 9H); 13 C NMR (CDCl 3 ) δ143.82, 127.63, 58.94, 27.36, 23.23; IR (neat) 3068, 3053, 2976, 1636, 1305, 1275, 1109, 982; Anal. Calcd for C 7 H 13 BrO 2 S: C, 34.86; H, 5.43. Found: C, 34.98; H, 5.32.
Di-n-butylphosphonate 17
A stirred solution of tri-n-butyl phosphite (5 mL) and sulfone 16 (370 mg, 1.53 mmol) was heated to 130° C. for 12 h, cooled to rt, concentrated and purified on silica gel (75% EtOAc/hexanes) to give 519 mg (95%) of 16 as a clear oil: 1 H NMR (CDCl 3 ) δ7.00 (dt, J=15, 8.0 Hz, 1H), 6.38 (ddt, J=15, 4.6, 1.2 Hz, 1H), 4.03-3.92 (m, 4H), 2.76 (ddd, J=25, 8.0, 1.2 Hz), 1.62-1.53 (m, 4H), 1.38-1.30 (m, 4H); 1.29 (6H), 0.85 (t, J=7.2 Hz, 6H); 13 C NMR (CDCl 3 ) δ140.23 (d, J=11Hz), 128.24 (d, J=14 Hz), 66.18 (d, J=6.8 Hz), 58.69, 32.47 (d, J=6.1 Hz), 29.97 (d, J=140 Hz), 27.36, 23.18, 13.52; IR (neat) 2961, 2935, 2874, 1633, 1477, 1464, 1289, 1246, 1114, 1024, 983; Anal. Calcd for C 15 H 31 O 5 PS: C, 50.83; H, 8.82; S, 9.05. Found: C, 50.64; H, 8.65; S, 8.91.
8β-[(Triethylsilyl)oxy]-22E,24E-diene 26-tert-Butyl Sulfone (+)-21
A solution of lithium tert-butoxide (1.0 M in THF, 0.491 mL, 0.491 mmol) was added via syringe to a cold (−78° C.) solution of phosphonate 17 (175 mg, 0.493 mmol) in THF (1.0 mL). The mixture was warmed slightly to effect solution, then returned to −78° C. The resulting yellow solution was delivered via cannula to a stirred solution of aldehyde (+)-20 (64.0 mg, 0.197 mmol) in THF (1.5 mL) at rt. After 10 min. the solvent was removed and the residual brown oil was flash chromatographed (8% EtOAc/hexanes) to give 86 mg of (+)-21 (93%) as a moist solid: [α] D 25 +77.9 (c 4.0, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.11 (m, 1H), 6.14 (t, J=15 Hz, 1H), 6.09 (m, 2H), 4.02 (m, 1H), 2.27-2.17 (m, 1H), 1.96-1.89 (m, 1H), 1.89-1.74 (qt, J=13, 3.8 Hz, 1H), 1.35 (s, 9H), 1.04 (d, J=6.8 Hz, 3H), 0.93 (t, J=8.0 Hz, 9H), 0.93 (s, 3H), 0.54 (q, J=8.0 Hz, 6H); 13 C NMR (CDCl 3 ) δ153.66, 147.16, 123.71, 120.43, 69.20, 58.55, 55.83, 52.87, 42.38, 40.61, 40.10, 34.52, 27.39, 23.32, 22.94, 19.35, 17.62, 13.75, 6.90, 4.88; IR (neat) 2950, 2935, 2873, 1638, 1458, 1300, 31134, 1018, 1004; HRMS: calcd for C 26 H 48 O 3 SSi: 468.3093, found 468.3094.
C,D-Ring Ketone (+)-22
An aqueous solution of HF (0.500 mL, 10% wt) was added dropwise to a stirred solution of (+)-21 in H 2 O:THF (1.00 mL H 2 O: few drops of THF to effect solution) and the resulting solution stirred at rt for 2 d (two additional 0.500 mL portions of 10% HF (aq) were added over this period to consume starting material). The reaction mixture was then carefully neutralized (sat. NaHCO 3 ), diluted with H 2 O, and extracted with CH 2 Cl 2 (3×10 mL). The combined organics were dried (Na 2 SO 4 ), filtered and concentrated to give the desired hydroxy sulfide as a white solid.
To crude hydroxy sulfide in CH 2 Cl 2 (3 mL) was added 4-methymorpholine N-oxide (NMO, 58.0 mg, 0.492 mmol) and powdered molecular sieves (4A), followed by tetrapropylammonium perruthenate (TPAP, 4.30 mg, 0.0123 mmol). After stirring for 15 min, the reaction mixture was filtered, concentrated and passed through a short pad of flash silica gel (20% EtOAc/hexanes) to afford the desired keto sulfone (+)-22 as a white foam (79 mg, quantitative from (+)-21): 1 H NMR (CDCl 3 ) 8 7.08 (dd, J=15, 10 Hz 1H), 6.15 (t, J=15 Hz, 1H), 6.08 (m, 2H), 2.43 (m, 1H), 2.29-2.15 (m, 3H), 1.32 (s, 9H), 1.08 (d, J 6.4 Hz, 3H), 0.63(s, 3H); 13 C NMR (CDCl 3 ) δ211.39, 152.05, 146.59, 124.38, 121.21, 61.62, 58.57, 55.62, 49.85, 40.86, 40.12, 38.71, 27.46, 23.94, 23.30, 19.61, 19.06, 12.72; IR (neat) 2955, 2934, 2872, 1708, 1638, 1587, 1461, 1296, 1278, 11 11, 1001, 824; HRMS: calcd for C 2 O 32 O 3 S: 352.2072, found 352.2066.
22E,24EDiene26-tert-butyl Sulfone Analogs 23a and 23b
Racemic phosphine oxide (±)-8 (78.0 mg, 0.134 mmol) was dissolved in 1.34 mL of THF and cooled to −78° C. under argon. To this solution was added 97.0 μL of PhLi (0.134 mmol, 1.38 M in cyclohexane/Et 2 O) dropwise via syringe. The deep orange solution was stirred for 30 min, at which time a cold solution of C,D-ring ketone (+)-22 (31.0 mg, 0.0880 mmol) in 1.00 mL of THF was added dropwise via cannula. The resulting solution was stirred in the dark at −78° C. for approximately 4 h, then slowly warmed to −40° C. over 2 h. The reaction mixture was quenched with 3 ml of a 2:1 (v:v) mixture of 2 N sodium potassium tartrate and 2 N potassium carbonate. Upon warming to rt, the reaction mixture was diluted with H 2 O, extracted with EtOAc (4×20 mL), dried over MgSO 4 , filtered, concentrated and purified by silica gel column chromatography (10-50% EtOAc/hexanes-<0.1 % Et 3 N) to afford 33 mg (90% based on (+)-22) of the coupled product as a yellow oil.
This oil was immediately dissolved in 1.50 mL of EtOH, cooled to 0° C., and treated with HF (0.100 mL, 49% aqueous). This solution was slowly warmed to rt and treated with additional HF (0.100 mL) to complete the deprotection. After aqueous work-up the resulting white film was flash chromatographed (1% NEt/EtOAc) to afford 17.3 mg (77% for deprotection) of a mixture of diastereomers 23a and 23b. This diastereomeric mixture was purified by reversed-phase HPLC (C-8 semipreparative column, 46% MeCN/H 2 O, 3 mL/min) giving 8.8 mg of 23a (20%, t R 15 min) and 2.1 mg of 23b (5%, t R 111 min). 23a (1α, 3β): [α] D 25 +97 (c 7.5, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.12 (m, 1H), 6.37 (d, J=11 Hz, 1H), 6.16 (t, J=15 Hz, 1H), 6.11 (m, 2H), 6.01 (d, J=11 Hz, 1H), 5.32 (m, 1H), 4.99 (m, 1H), 4.4-64.40 (m, 1H), 4.264.19 (m, 1H), 2.83 (dd, J=12, 3.7 Hz, 1H), 2.59 (dd, J=14, 3.2 Hz, 1H), 1.36 (s, 9H), 1.09 (d, J=6.8 Hz, 3H), 0.57 (s, 3H); 13 C NMR (CDCl 3 ) δ153.13, 147.58, 146.98, 142.43, 133.24, 124.78, 124.00, 120.74, 117.30, 111.83, 70.80, 66.81, 58.60, 56.09, 55.63, 46.06, 45.23, 42.83, 40.69, 40.26, 28.97, 27.45, 23.45, 23.35, 22.24, 19.69, 12.29; IR (neat) 3598-3148 (br), 3013, 2935, 2870, 1637, 1588, 1457, 1295, 1108; HRMS: calcd for C 29 H 44 O 4 S 488.2960, found 488.2950. 23b (1β, 3α): [α] D 25 +32 (c 1.0, CHCl 3 ); 1 H NMR (CDCl 3 ) δ7.12 (m, 1H), 6.38 (d, J=11 Hz, 1H), 6.16 (t, J=15 Hz, 1H), 6.11 (m, 2H), 6.01 (d, J=11 Hz, 1H), 5.32 (m, 1H), 4.99 (m, 11H), 4.474.40 (m, 1H), 4.26-4.18 (m, 1H), 2.84 (dd, J=12, 3.8 Hz, 1H), 2.61 (dd, J=14, 3.2 Hz, 1H), 1.36 (s, 9H), 1.09 (d, J=6.8 Hz, 3H), 0.57 (s, 3H); 13 C NMR (CDCl 3 ) δ153.13, 147.27, 147.01, 142.52, 133.10, 124.82, 124.01, 120.76, 117.30, 112.56, 71.32, 66.75, 58.61, 56.10, 55.64, 46.07, 45.45, 42.83, 40.70, 40.25, 29.00, 27.44, 23.45, 23.38, 22.28, 19.71, 12.32; IR (neat) 3568-3087 (br), 3016, 2954, 2928, 2872, 1637, 1588, 1457, 1295, 1109; HRMS: calcd for C 29 H 44 O 4 S 488.2960, found 488.2944. UV pending.
EXAMPLE 48
Assay of Pharmacological Activities
The compounds of the invention have been compared with calcitriol for biological activity.
The compounds were tested for growth inhibition of murine keratinocyte cells (cell line PE) and for the inhibition of TPA-induced ornithine decarboxylase (ODC) activity as described in U.S. Pat. No. 5,830,885.
The cell line PE was derived from a papilloma induced in female SENCAR mice by a standard skin initiation/promotion protocol ( Carcinogenesis, 7:949-958 (1986), the entire contents of which are hereby incorporated by reference) and was chosen for its particular sensitivity to the induction of ornithine decarboxylase (ODC) activity by the extensively characterized tumor promoter TPA. The PE cell line culture medium used in the tests consisted of Eagle's minimal essential medium without calcium chloride supplemented with 8% chelexed fetal calf serum and 1% antibiotic-antimycotic and the addition of CaCl 2 to 0.05 mM Ca ++ .
The results are shown in FIG. 1, and indicate that the compounds of the invention inhibit cell proliferation, compounds 23a and 15a being nearly as effective as calcitriol.
The compounds were also tested for their effect on calcium excretion and weight gain in rats according to the methods described in Posner et al., J. Med. Chem. 41:3008-3014 (1998). The results are shown in FIGS. 2 and 3, and demonstrate that the compounds of the invention do not inhibit weight gain nor stimulate calcium secretion in contrast to calcitriol.
Thus, compounds according to the invention exhibit the antiproliferative effects of vitamin D 3 without the associated effects on calcium excretion and weight gain exerted by vitamin D 3 . Accordingly, they should prove valuable as therapeutic agents in diseases where excessive cell proliferation and/or failure of cells to differentiate may occur, including but not limited to psoriasis and cancer. External or internal administration of the compounds of the invention can be made in accord with the condition to be treated using methods known to those of ordinary skill in the medical and veterinary arts, with appropriate dosages determined by routine experimentation.
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Novel sulfur-containing analogs of 1α,25-dihydroxy vitamin D 3 are provided. These analogs are synthesized in a convergent manner by joining A-ring and C,D ring fragments. Each analog with 1α,3β-substituent stereochemistry shows a pharmacologically desirable combination of high antiproliferative and high transcriptional activities in vitro and also low calcemic activity in vivo.
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RELATED APPLICATIONS
The present application is a continuation-in-part of U.S. patent application Ser. No. 08/140,319, filed on Oct. 22, 1993 now abandoned, and entitled "POLYMERIZATION METHOD FOR WHOLLY AROMATIC POLYESTERS".
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates in general to an interfacial polymerization method for preparing a non-halogenated aromatic polyesters, and more particularly to improvements in a polymerization time for a bisphenol polyarylate with along an interfacial polymerization method and a phase-transfer catalyst.
2. Description of the Prior Art
As well known to the art, aromatic polyesters produced from a mixture of terephthalic acids and/or functional derivatives thereof and isophthalic acid and/or functional derivatives thereof, and a bisphenol have many superior properties, for example, mechanical properties such as tensile strength, elongation, flexural strength, bend recovery, impact strength, physical properties such as high thermal distortion temperature, good dimensional stability, and a high heat decomposition temperature, excellent electrical properties such as inherent resistivity, dielectric breakdown strength and arc resistance. Due to these superior properties, aromatic polyesters are known to be useful in a wide range of fields as various molded articles, films, fibers and coating materials produced by injection molding, extrusion molding, press molding, and other molding techniques.
Generally, these aromatic polyesters can be prepared, for example, using an interfacial polymerization method which comprises adding an aromatic dicarboxylic acid chloride dissolved in a water-immiscible organic solvent to an alkaline aqueous solution of a bisphenol as described in J. Polym., Sci., 40, 399(1959) to W. M. Eareckson, or Japanese Patent Publication Nos. Sho. 38-3589 and 40-1959, a solution polymerization method which comprises heating a bisphenol and an aromatic dicarboxylic acid chloride in an organic solvent as described in Ind. Eng. Chem., 51, 147(1959) to A. Conix and Japanese Patent Publication No. Sho. 37-5599, or a melt polymerization method which comprises heating a polyester of an aromatic dicarboxylic acid and a bisphenol as described in Japanese Patent Publication Nos. Sho. 38-15247 and 43-28119.
It has been known that the melt and the solution polymerization method have various problems. For example, when an aromatic polyester is produced by the solution polymerization method or the melt polymerization method, a high temperature or a reduced pressure is required. In addition, the aromatic polyesters produced by the two aforementioned methods often show low molecular weights and are frequently discolored. Accordingly, the interfacial polymerization method has taken the lead recently in producing the aromatic polyesters.
According to the literature, the reagents used in the interfacial polymerization are classified into two: first, dispersing agents such as surfactants which are capable of stabilizing the reaction system, as described in detail in J. Polym. Sci., 40, 339(1959) to W. M. Eareckson and J. Macromol. Sci. Chem., A13, 875(1979) to E. Z. Casassa, D. Y. Chao and M. Henson; second, phase-transfer catalysts such as quaternary ammonium salts which are capable of activating the transfer of reactants from an aqueous layer into an organic layer, as indicated in detail in J. Macrotool, Sci. Chem., A15, 683(1981) to P. W. Morgan. For example, the latter is added to a alkaline aqueous solution containing hisphenols to activate the transfer rate of bisphenolates produced therein into an organic layer.
In accordance with other literatures, it is more effective to use a phase-transfer catalyst which has higher lypophilicity. For example, as described in J. Polym. Sci.: Part A, Vol 26, 2039(1988) to Y. D. Lee and H. B. TSAI, tetrabutyl ammonium chloride (hereinafter "TBAC"), tfiethylbutyl ammonium chloride (hereinafter "TEBAC"), and tetraethyl ammonium chloride (hereinafter "TEAC") are effective in the interfacial polymerization and because the lypophilicity of a catalyst is proportional to the number of carbon atoms contained therein, TBAC is the most effective among those. Of course, TEBAC is more effective than TEAC.
In the prior art, the quaternary ammonium salt as phase-transfer catalysts are added into an aqueous solution to produce aromatic polyesters. For example, an alkaline aqueous solution of a bisphenol containing benzyltrimethyl ammonium chloride (hereinafter "BTMAC") is used in U.S. Pat. No. 4,229,332.
However, when BTMAC is added into the aqueous layer, the concentration of bisphenolate in the organic layer is increased slowly and this increasing phenomenon proceeds continuously in even case that 60 minutes elapses. In the event of some other catalysts, the transfer rate of bisphenolate from an aqueous layer to an organic layer is relatively high, but an equilibrium state is not reached even though 60 minutes elapses. Thus, such interfacial polymerization method requires a long reaction time.
On the other hand, to make certain halogenated aromatic polyesters, an organic solution of an acid chloride containing TEBAC is used in U.S. Pat. No. 4,066,623. The authors said that their invention, which is the inverse interfacial polymerization i.e. adding the aqueous phase to the organic phase, could reduce the mount of low molecular weight fraction which accompanies the formation of these polyesters when prepared by standard interfacial polymerization techniques.
However, when this inverse interfacial polymerization is applied in polymerization method for non-halogenated aromatic polyesters, the resulting polymers were obtained in low product yield with low solution viscosity.
SUMMARY OF THE INVENTION
For solving the aforementioned problems, the present inventors have recognized that there exists a need for a polymerization method for preparing a non-halogenated aromatic polyesters, capable of reducing a reaction time, simultaneously obtaining high reaction yield and high enough solution viscosity.
Therefore, it is an object of the present invention to provide an interfacial polymerization method for bisphenol polyarylates, improved in a reaction rate, a reaction yield and a solution viscosity in an economical aspect.
In one aspect of the presently claimed invention there is provided a method for preparing a non-halogenated aromatic polyesters having a repeating unit of the following general formula (I) ##STR1##
wherein X is selected from the group consisting of an alkylene group containing 1 to 4 carbon atoms; or alkylidene group containing 1 to 4 carbon atoms;
and n is an integer of not less than 100, by the standard interfacial polymerization of a non-halogenated bisphenol and mixture of isophthaloyl chloride and terephthaloyl chloride.
I. Adding the organic phase to the aqueous phase over a period of time of from 1% to 10% of the total polymerization time.
II. Providing an organic phase comprising
a. an organic solvent,
b. phthaloyl chloride mixture, and
c. a catalytic amount of tetrabutyl ammonium bromide(TBAB) as the phase-transfer catalyst
III. Providing an aqueous phase comprising
a. demineralized water
b. an alkali salt of said non-halogenated bisphenol, and
c. a molecular weight-controlling agent having the general formula (II) ##STR2##
Wherein R 1 , R 2 , R 3 , R 4 , and R 5 are the same or different and represent the group consisting of a hydrogen, a halogen and an alkyl group consisting 1 to 4 carbon atoms.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken with reference to the accompanying drawings, in which:
FIG. 1 is a graph illustrating the effect of phase-transfer catalysts on the transfer rate of bisphenolate from an aqueous layer to an organic layer when they are added into the aqueous layer; and
FIG. 2 is a graph illustrating the effect of phase-transfer catalysts on the transfer rate of bisphenolate from an aqueous layer to an organic layer when they are added into the organic layer.
DETAILED DESCRIPTION OF THE INVENTION
A phase-transfer catalyst used in an interfacial polymerization for aromatic polyesters has great influence on the reaction time, so that it is necessary to carefully select the catalyst and the usage thereof most suitable to the method.
To select a most suitable catalyst and a usage thereof, there is determined a transfer rate of bisphenolate from an aqueous layer to an organic layer in producing an aromatic polyester. For this reason, we have chosen several catalysts which are tetrabutyl ammonium bromide (hereinafter "TBAB"), tetrabutyl ammonium chloride (hereinafter "TBAC"), tetrabutyl ammonium fluoride (hereinafter "TBAF"), benzyltrimethyl ammonium chloride (hereinafter "BTMAC"), benzyltriethyl ammonium bromide (hereinafter "BTEAB), and benzyltriethyl ammonium chloride (hereinafter "BTEAC"). In practice, the concentration of phenylene group transferred into the organic layer per unit time is measured using an UV spectroscope at 240 nm in both cases of addition of the catalyst into an aqueous layer and addition of the catalyst into an organic layer. In both cases, the cell of an UV spectroscope is half filled with an organic solution and the remained half volume is then filled with an aqueous solution so carefully as not to shake the organic layer. The concentration variation of bisphenolate in the organic layer is measured by analyzing the concentration of phenyl groups in the same layer. FIG. 1 illustrates the phase-transfer rate of bisphenolates by various catalysts when they are added into an aqueous layer. On the other hand, FIG. 2 illustrates the rate when they added into an organic layer. As shown in FIG. 1, surprisingly the phase-transfer rate in case of addition of BTEAC and BTMAC is similiar to that in case of none. In addition, BTEAC, BTEAB and BTMAC let the concentration of the bisphenolate increase so slowly that it does not reach a satisfactory level even when 60 minutes elapses. In cases of TBAB and BTMAB, though the concentrations show a little faster increments, they never reach equilibrium states after 60 minutes. In the meantime, when the catalysts are added into an organic layer, as illustrated in FIG. 2, each of BTEAC, BTEAB, BTMAC and BTMAB has a little faster than none, but may be not said to be worth while catalysts. However, the addition of TBAB allows the concentration to be increased remarkably and an equilibrium to be reached within 30 minutes.
Therefore, when aromatic polyesters are produced by an interfacial polymerization method, the addition of a phase-transfer catalyst into an aqueous layer requires a longer reaction time. It is apparent that the lypophilicity of a catalyst has influence on the phase-transfer rate, as described in the aforementioned J. Polym. Sci.. In addition, the ionization degree of a catalyst has a function that affects the reaction rate. For example, when the phase-transfer catalysts exist in an aqueous layer, the ammonium bromide group catalysts are much more effective than the ammonium chloride group ones. In the meanwhile, when added into an organic layer, TBAB brings about greater effects than any other catalyst does. Consequently, when TBAB is added into an organic layer, the fastest phase-transfer rate of bisphenolate is resulted.
In accordance with the present invention, non-halogenated aromatic polyesters are produced by a novel method which comprises adding TBAB into an organic solution which contains dicarboxylic acid chlorides, and then adding the resulting organic solution to an alkaline aqueous solution which contains bisphenols. Along with the polymerization method, aromatic polyesters having desired physical properties may be obtained in a high yield within a short time.
In an interfacial polymerization method for non-halogenated aromatic polyesters, bisphenols are dissolved in an alkaline aqueous solution to form alkaline salts of bisphenol. Suitable alkaline salts include sodium hydroxide and potassium hydroxide. The alkaline salts formed in the aqueous solution are easily transferred into a layer of the organic solution by the catalyst. The amount of the tetrabutyl ammonium bromide as the phase-transfer catalyst is preferably on the order of 0.01 to 1.0% by mole referred to the bisphenol used.
With regard to solvents used in the present invention, solvents suitable to the interfacial polymerization method include chlorine-containing hydrocarbon compounds and chlorine-containing aromatic compounds which are immiscible with water. For example, these include methylene chloride, tetrachloroethane, benzene, chlorobenzene, nitrobenzene, ethyl ether, isopropyl ether and the like, and exclude solvents that have acid groups, hydroxy groups, or amine groups.
The amount of the monomers in the alkaline aqueous solution is preferably on the order of 5 to 20% by weight, and more preferably not more than 15% by weight in order to progress the interfacial polymerization reaction adequately. The amount of the monomers in the organic solution is preferably on the order of 9 to 20% by weight. For the satisfactory phase separation of the alkaline aqueous layer from the organic layer, the ratio of water to the organic solvent is preferably in a range of 1 to 1.3. In addition, it is advantageous to adjust the equivalent ratio of the alcohol and the acid to 1. That is, the mole ratio of the reactants (for example, bisphenol A:isophthalic acid chloride:terephthalic acid chloride) is preferably on the order of 1:0.8:0.2 to 1:0.2:0.8.
The addition rate of organic phase to aqueous phase is preferably on the order of 1% to 10% of the total polymerization time. For example, if too short the addition rate is, the reaction temperature can't be easily controlled because it is exothermic reaction. On the other hand, if too long the addition rate is, the molecular weight distribution of the resulting polymers is too broad.
Condensation is effected at temperature which may vary from about 15° C. and to about 40° C.
In order to produce the non-halogenated aromatic polyester having a desired inherent viscosity (ηinh), phenols having one hydroxyl group may be used as a molecular weight-controlling agents. Suitable molecular weight-controlling agent include para-cumyl phenol, ortho-phenyl phenol, para-phenyl phenol, meta-cresol, beta-naphthol, para-tertiary butyl phenol and the like. The amount of the molecular weight-controlling agent is preferably on the order of 0.5 to 5.0% by mole referred to the bisphenol used. This agent is dissolved in an alkaline aqueous solution having a pH value of not less than 11.
In order to insure good physical properties for the aromatic polyester used in the present invention, they should have an inherent viscosity number (ηinh), defined by the following equation; of about 0.3 to about 1.0 preferably 0.4 to 0.8. ##EQU1##
wherein t 1 is the falling time (in seconds) of a solution of the polyester in a capillary tube of viscometer;
t 2 is the falling time(in seconds) of the solvent; and
C is the concentration (in g/dl) of the polyester in the solution. The inherent viscosity, as used herein, is determined in a mixture of phenol and 1,1,2,2-tetrachloroethane (weight ratio; 6:4) at 25° C. with the concentration of the polyester being 1 g/dl.
In accordance with the present invention, the non-halogenated aromatic polyester has a repeating unit of the following general formula (I): ##STR3##
wherein X is selected from a group consisting of an alkylene group containing 1 to 4 carbon atoms or alkylidene group containing 1 to 4 carbon atoms.
The present invention is produced by adding an organic phase containing an organic solvent, a terephthalic acid chloride and a isophthalic acid chloride with mole ratio therebetween being a range of 8:2 to 2:8 and a catalytic amount of TBAB as a phase-transfer catalyst to an aqueous solution containing demineralized water, a bisphenol of the following formula (II): ##STR4##
wherein X is selected from a group consisting of an alkylene group containing 1 to 4 carbon atoms or an alkylidene group containing 1 to 4 carbon atoms;
and, an alkaline salt in amounts sufficient to dissolve the hisphenol used, and a molecular weight-controlling agent having the following formula (II): ##STR5##
wherein R 1 , R 2 , R 3 , R 4 , and R 5 , may be the same or different, and represent the group consisting of a hydrogen atom, a halogen atom, and an alkyl group containing 1 to 4 carbon atoms, and stirring them.
The following examples and comparative examples are merely intended to illustrate the present invention in further detail and should not by no means be considered to be limitative of the scope of the invention.
EXAMPLE 1
Preparation of Aqueous Phase
71.45 g of bisphenol-A, 25.42 g of sodium hydroxide, and 1.41 g of para-tertiary butylphenol with 410 ml of demineralized water were charged into the three-neck flask equipped with a mechanical stirrer, a thermometer and a condensor.
Preparation of Organic Phase
Each 31.82 g of terephthalic acid chloride and isophthalic acid chloride were dissolved in 425 ml of methylene chloride in combination with 0.151 g of TBAB as a phase-transfer catalyst.
Standard Interfacial Polymerization
The organic solution is then placed in a dropping funnel and added in 1 minute to the aqueous solution under conditions of agitation. After stirring for 0.5 hour with keeping a reaction temperature at 30° C., the reaction was then stopped, and the aqueous solution layer was removed from the reaction vessel. The remained methylene chloride layer was subjected to the treatment of removing by-products with an alkaline and an acidic aqueous solutions. Thereafter, the organic layer was washed with distilled water in several times, diluted into about 10% by weight and treated to precipitation in methanol. The precipitate was dried for at least 24 hours at 100° C. to give 112.2 g of polyester.
The inherent viscosity of the polymer was measured and the result (ρinh) is given as shown in Table 1 together with the yield therefor.
EXAMPLE 2
A polymerization was carried out in a manner similar to Example 1 except that the reaction time was 1 hour instead of 0.5 hour. 110.61 g of polyester was yielded.
The inherent viscosity of the polymer was measured and the result (ρinh) is given as shown in Table 1 together with the yield therefor.
EXAMPLE 3
A polymerization was carried out in a manner similar to Example 1 except that the reaction time was 2 hours instead of 0.5 hour. 110.61 g of polyester was yielded.
The inherent viscosity of the polymer was measured and the result (ρinh) is given as shown in Table 1 together with the yield therefor.
EXAMPLE 4
A polymerization was carried out in a manner similar to Example 2 except that 0.108 g of BTMAB instead of TBAB was used as a phase-transfer catalyst. 111.4 g of polyester was yielded.
The inherent viscosity of the polymer was measured and the result (ρinh) is given as shown in Table 1 together with the yield therefor.
EXAMPLE 5
A polymerization was carried out in a manner similar to Example 2 except that 0.087 g of BTMAC instead of TBAB was used as a phase-transfer catalyst. 112.0 g of polyester was yielded.
The inherent viscosity of the polymer was measured and the result (ρinh) is given as shown in Table 1 together with the yield therefor.
EXAMPLE 6
A polymerization was carried out in a manner similar to Example 2 except that 0.087 g of BTEAB instead of TBAB was used as a phase-transfer catalyst. 112.2 g of polyester was yielded.
The inherent viscosity of the polymer was measured and the result (ρ inh) is given as shown in Table 1 together with the yield therefor.
EXAMPLE 7
A polymerization was carried out in a manner similar to Example 2 except that 0.107 g of BTEAC instead of TBAB was used as a phase-transfer catalyst. 111.6 g of polyester was yielded.
The inherent viscosity of the polymer was measured and the result (ρinh) is given as shown in Table 1 together with the yield therefor.
COMPARATIVE EXAMPLE 1 TO 7
A polymerization was carried out in a manner similar to Examples aforementioned except that the phase-transfer catalysts were added into the aqueous solutions instead of the organic solutions.
The inherent viscosities of the polymers were measured and the results (ρinh) are given as shown in Table 1 together with the yields therefor.
COMPARATIVE EXAMPLE 8
A polymerization was carried out in a manner similar to example 1 aforementioned except that the order of addition was inverted, that is, by adding the aqueous phase to the organic phase.
The results are given as shown in table 1.
TABLE 1______________________________________Example Layer.sup.b) Reaction ηinh.sup.c) YieldNo. PTC.sup.a) of PTC Time (hr) (dl/g) (%)______________________________________1 TBAB Organic 0.5 0.53 98.82 TBAB Organic 1.0 0.54 97.43 TBAB Organic 2.0 0.54 97.44 BTMAB Organic 1.0 0.38 98.15 BTMAC Organic 1.0 0.45 98.66 BTEAB Organic 1.0 0.43 98.87 BTEAC Organic 1.0 0.44 98.2C. 1 TBAB Aqueous 0.5 0.55 96.3C. 2 TBAB Aqueous 1.0 0.55 97.6C. 3 TBAB Aqueous 2.0 0.51 99.2C. 4 BTMAB Aqueous 1.0 0.23 95.2C. 5 BTMAC Aqueous 1.0 0.24 95.1C. 6 BTEAB Aqueous 1.0 0.45 96.6C. 7 BTEAC Aqueous 1.0 0.40 98.1C. 8 TBAB Organic 0.5 0.30 89.4______________________________________ .sup.a) Phasetransfer catalyst .sup.b) Layer into which the phasetransfer catalyst was added. .sup.c) Inherent Viscosity in phenol/1,1,2,2tetrachloroethane (6/4 weight ratio, at 25° C., 1 g/dl.)
EVALUATION TEST 1
Each 4.7X10-4 mol of phase-transfer catalyst (e.g. TBAB: 0.151 g, BTMAB: 0.108 g, BTMAC: 0.087 g, BTEAB: 0.087 g, BTEAC:0.107 g) was added into a solution consisting of 400 ml of distilled water, 71.45 g (0.31 mol) of bisphenol A and 24.8 g (0.62 mol) of sodium hydroxide. The resultant alkaline aqueous solution was poured into a cell of an infrared spectroscope, the half volume of which had been filled with methylene chloride, so carefully as not to shake the organic layer. The concentration of phenylene group transferred into the organic layer per unit time was measured at 240 nm. The transfer rate of bisphenolate from the aqueous layer to the organic layer was determined by analyzing the concentration variation of phenylene groups per time.
EVALUATION TEST 2
Each 4.7X10-4 mol of phase-transfer catalyst (e.g. TBAB: 0.151 g, BTMAB: 0.108 g, BTMAC: 0.087 g, BTEAB: 0.087 g, BTEAC:0.107 g) was added into 400 ml of methylene chloride. This organic solution was placed in a cell of an UV spectroscope. A solution consisting of 400 ml of distilled water, 71.45 g (0.31 mol) of bisphenol A and 24.8 g (0.62 mol) of sodium hydroxide was then poured into the cell so carefully that the organic layer may be not shaken. The concentration of phenylene group transferred into the organic layer per unit time was measured at 240 nm. The transfer rate of bisphenolate from the aqueous layer to the organic layer was determined by analyzing the concentration variation of phenylene groups per time.
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The present invention relates to a polymerization method for preparing non-halogenated aromatic polyesters by a standard interfacial polymerization except the addition of a phase-transfer catalyst to the organic phase. More specifically, the present invention offers a method for substantially reducing the polymerization time and improving the reaction yield, by introducing a specific phase transfer catalyst, tetrabutyl ammonium bromide, to the organic phase.
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BACKGROUND OF THE INVENTION
This invention relates to novel pyrazino[2',3'-3,4]pyrido[1,2-a]-indole derivatives, to therapeutically acceptable acid addition salts thereof, to processes for their preparation, to methods of using the derivatives and to pharmaceutical compositions of the derivatives. These derivatives are useful for treating hypertension in a mammal.
SUMMARY OF THE INVENTION
The compounds of this invention are represented by formula I ##STR1## in which R 1 is hydrogen, halogen, lower alkyl, lower alkoxy or trifluoromethyl; R 2 is hydrogen or lower alkyl having one to three carbon atoms; and R 3 and R 4 each is hydrogen, lower alkenyl, lower alkynyl, cyclo(lower)alkyl, lower alkanoyl, hydroxy(lower)alkyl, lower alkoxycarbonyl(lower)alkyl, phenyl(lower)alkyl or phenoxy(lower)alkyl; or a therapeutically acceptable acid addition salt thereof.
The above compounds of formula I include the trans and cis compounds of formula Ia and Ib, respectively ##STR2## in which R 1 , R 2 , R 3 and R 4 are as defined herein.
A preferred group of compounds of this invention is represented by formula I in which R 1 is hydrogen or bromo; R 2 is methyl; R 3 and R 4 each independently is hydrogen, lower alkyl, lower alkynyl, lower alkanoyl, hydroxy(lower)alkyl, lower alkoxycarbonyl(lower)alkyl, or phenoxy(lower)alkyl; or a therapeutically acceptable acid addition salt thereof.
Another preferred group of compounds of this invention is represented by formula Ia in which R 1 is hydrogen or bromo; R 2 is methyl; R 3 is hydrogen, lower alkyl, lower alkanoyl, hydroxy(lower)alkyl or lower alkoxycarbonyl(lower)alkyl; and R 4 is hydrogen, lower alkyl, lower alkynyl, hydroxy(lower)alkyl or lower alkoxycarbonyl(lower)alkyl; or a therapeutically acceptable acid addition salt thereof.
A most preferred group of compounds of this invention is represented by formula Ia in which R 1 is hydrogen; R 2 is methyl; R 3 is hydrogen, lower alkyl or hydroxy(lower)alkyl; and R 4 is hydrogen, lower alkyl, lower alkynyl or hydroxy(lower)alkyl; or a therapeutically acceptable acid addition salt thereof.
The compounds of formula I or a therapeutically acceptable acid addition salt thereof can be prepared by selecting a process from the group of:
(a) cyclizing a compound of formula II ##STR3## in which R 1 and R 2 are as defined herein, and R 5 is lower alkyl to obtain the corresponding compound of formula Ib in which R 1 and R 2 are as defined herein, and R 3 and R 4 are the same lower alkyl;
(b) hydrogenating a compound of formula III ##STR4## in which R 1 and R 2 are as defined herein to obtain the corresponding compound of formula Ib in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen;
(c) condensing a compound of formula IV ##STR5## in which R 1 and R 2 are as defined herein and X is bromo or chloro with ethylenediamine and reducing the resulting intermediate to obtain the corresponding compound of formula Ia in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen;
(d) subjecting a compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen to alkylation, acylation and/or reduction in optional order and to the extent required to obtain the corresponding compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and R 4 each is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, cyclo(lower)alkyl, lower alkanoyl, hydroxy(lower)alkyl, lower alkoxycarbonyl(lower)alkyl, phenyl(lower)alkyl or phenoxy(lower)alkyl; and
(e) reacting a compound of formula I in which R 1 , R 2 , R 3 and R 4 are as defined herein with a therapeutically acceptable acid to obtain the corresponding compound of formula I as the salt with the therapeutically acceptable acid.
A pharmaceutical composition is provided by combining the compound of formula I, or a therapeutically acceptable acid addition salt thereof, and a pharmaceutically acceptable carrier.
The compounds of this invention can be used to treat hypertension in a hypertensive mammal by administering to the mammal an effective antihypertensive amount of a compound of formula I or a therapeutically acceptable acid addition salt thereof optionally with a second antihypertensive agent.
DETAILED DESCRIPTION OF THE INVENTION
The term "lower alkyl" as used herein means straight and branched chain alkyl radicals containing from one to six carbon atoms, preferably one to four carbon atoms, and includes methyl, ethyl, propyl, 1-methylethyl, butyl, 1,1-dimethylethyl, pentyl and the like, unless stated otherwise.
The term "halo" as used herein means halo radicals and includes fluoro, chloro, bromo and iodo, unless stated otherwise.
The term "lower alkoxy" as used herein means straight chain alkoxy radicals containing from one to six carbon atoms and branched chain alkoxy radicals containing three to six carbon atoms and includes methoxy, ethoxy, 1-methylethoxy, butoxy, hexoxy and the like.
The term "lower alkanoyl" as used herein means straight chain 1-oxoalkyl radicals containing from two to six carbon atoms and branched chain 1-oxoalkyl radicals containing four to six carbon atoms and includes acetyl, 1-oxopropyl, 2-methyl-1-oxopropyl, 1-oxohexyl and the like.
The term "lower alkenyl" as used herein means straight chain alkenyl radicals containing from two to six carbon atoms and branched chain alkenyl radicals containing three to six carbon atoms and includes ethenyl, 2-methyl-2-propenyl, 4-hexenyl and the like.
The term "lower alkynyl" as used herein means straight chain alkynyl radicals containing from two to six carbon atoms and branched chain alkynyl radicals containing four to six carbon atoms and includes ethynyl, 2-propynyl, 1-methyl-2-propynyl, 3-hexynyl and the like.
The term "cyclo(lower)alkyl" as used herein means saturated cyclic hydrocarbon radicals containing from four to six carbon atoms and includes cyclobutyl, cyclopentyl and cyclohexyl.
The term "complex borohydride" as used herein means the metal borohydrides and includes, for example, sodium borohydride, sodium cyanoborohydride, potassium borohydride, lithium borohydride and zinc borohydride.
The term "complex metal hydride" as used herein means metal hydride reducing agents and includes, for example, lithium aluminum hydride, lithium aluminum hydride-aluminum chloride, diisobutylaluminum hydride, and sodium bis-(2-methoxyethoxy)aluminum hydride.
The term "lower alkanol" as used herein means both straight and branched chain alkanols containing from one to four carbon atoms and includes methanol, ethanol, 1-methylethanol, butanol and the like.
The term "organic proton acceptor" as used herein means to organic bases or amines, for instance, triethylamine, pyridine, N-ethylmorpholine, 1,5-diazabicyclo[4.3.0]non-5-ene and the like.
The term "inorganic proton acceptor" as used herein means the inorganic bases, preferably the alkali methyl hydroxides, carbonates and bicarbonates, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and the like.
The term "proton acceptor" as used herein means a proton acceptor selected from an organic proton acceptor and inorganic proton acceptor, as defined hereinabove.
The compounds of this invention are capable of forming acid addition salts with therapeutically acceptable acids. The acid addition salts are prepared by reacting the base form of the appropriate compound of formula I with one or more equivalents, preferably with an excess, of the appropriate acid in an organic solvent, for example, diethyl ether or an ethanoldiethyl ether mixture.
These salts, when administered to a mammal, possess the same pharmacologic activities as the corresponding bases. For many purposes it is preferable to administer the salts rather than the basic compounds. Suitable acids to form these salts include the common mineral acids, e.g. hydrohalic, sulfuric or phosphoric acid; the organic acids, e.g. maleic, citric or tartaric acid; and acids which are sparingly soluble in body fluids and which impart slow-release properties to their respective salts, e.g. pamoic or tannic acid or carboxymethyl cellulose. The addition salts thus obtained are the functional equivalent of the parent base compound in respect to their therapeutic use. Hence, these addition salts are included within the scope of this invention and are limited only by the requirement that the acids employed in forming the salts be therapeutically acceptable.
The antihypertensive effect of the compounds of formula I or a therapeutically acceptable acid addition salt thereof is demonstrated in standard pharmacological tests, for example, in tests conducted in the spontaneously hypertensive rat (SHR). The latter test method is as follows: Male rats, Okamoto-Aoki Strain, ranging in weight between 250-400 g were anesthetized with diethyl ether. Their left femoral arteries and veins were cannulated with polyethylene tubing of the appropriate size. Each animal was then enfolded in a rubber mesh jacket which was secured with 4 towel clamps. The animal was suspended via the towel clamps from a bar and allowed to recover from the anesthesia. The femorial arterial cannula was connected to a Stratham pressure transducer (Model P23, Gould Stratham Instruments, Hato Rey, Porto Rico), which in turn was attached to a polygraph for recording the mean arterial blood pressure and pulse rate. The pulse rate was considered to be the heart rate. The test compound was administered by gastric gavage in a volume of 5 ml/kg. Heart rate and blood pressure were noted at 5, 10, 15, 30, 45 and 60 minutes and hourly thereafter for a period of at least 4 hours after drug administration.
Using this method, the following representative compounds of formula I are effective for reducing the blood pressure (BP) in the spontaneously hypertensive rat (the amount of test compound and the reduction in BP are indicated in the parenthesis):
(4a,12a-cis)-1,4-diethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole dihydrochloride (described in Example 5, at a dose of 25 mg/kg of body weight caused a 20% decrease in mean BP at 1 hour), (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]-pyrido[1,2-a]indole maleate (described in Example 11, at a dose of 10 mg/kg of body weight caused a 19% decrease in BP at 4 hours), (4a,12a-trans)-7-bromo-1,4-diethyl-5-methyl-1,2,3,4,4a-11,12,12a-octahydropyrazino[2',3'-3,4]-pyrido[1,2-a]indole hydrochloride (described in Example 12, at a dose of 10 mg/kg of body weight caused a 15% decrease in BP at 4 hours), (4a,12-a-trans)-1-(2-propynyl)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4)pyrido[1,2-a]indole dihydrochloride (described in Example 13, at a dose of 10 mg/kg of body weight caused a 14% decrease in BP at 4 hours), (4a,12a-trans)-1,4,5-trimethyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole maleate (described in Example 14, at a dose of 10 mg/kg of body weight caused a 23% decrease in BP at 4 hours), (4a,12a-trans)-5-methyl-1,2,3,4,4a-11,12,12a-octahydropyrazino[2', 3'--3,4]pyrido[1,2-a]indole-1,4-diethanol dihydrochloride (described in Example 15, at a dose of 10 mg/kg of body weight caused a 34% decrease in BP at 1 hour), (4a,12a-trans)-1-ethyl-5-methyl-4-propyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole hydrobromide (described in Example 17, at a dose of 10 mg/kg of body weight caused a 42% decrease in BP at 4 hours), (4a,12a-trans)-4-butyl-1-ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole dihydrochloride (described in Example 17, at a dose of 10 mg/kg of body weight caused a 36% decrease in BP at 4 hours), and (4a,12a-trans)-4-ethyl-5-methyl-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole dihydrobromide (described in Example 17, at a dose of 10 mg/kg caused a 43% decrease in BP at 4 hours).
The compounds of formula I of this invention are used alone or in combination with pharmacologically acceptable carriers, the proportion of which is determined by the solubility and chemical nature of the compound, chosen route of administration and standard biological practice. For example, they are administered orally in the form of suspensions or solutions or they may be injected parenterally. For parenteral administration they can be used in the form of a sterile solution containing other solutes, for example, enough saline or glucose to make the solution isotonic.
The tablet compositions contain the active ingredient in admixture with non-toxic pharmaceutical excipients known to be suitable in the manufacture of tablets. Suitable pharmaceutical excipients are, for example, starch, milk sugar, certain types of clay and so forth. The tablets can be uncoated or they can be coated by known techniques so as to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period.
The aqueous suspensions of the compounds of formula I contain the active ingredient in admixture with one or more non-toxic pharmaceutical excipients known to be suitable in the manufacture of aqueous suspensions. Suitable excipients are, for example, methylcellulose, sodium alginate, gum acacia, lecithin and so forth. The aqueous suspensions can also contain one or more preservatives, one or more coloring agents, one or more flavoring agents and one or more sweetening agents.
Non-aqueous suspensions can be formulated by suspending the active ingredient in a vegetable oil, for example, arachis oil, olive oil, sesame oil, or coconut oil, or in mineral oil, for example liquid paraffin, and the suspension may contain a thickening agent, for example beeswax, hard paraffin or cetyl alcohol. These compositions can also contain a sweetening agent, flavoring agent and antioxidant.
The dosage of the compounds of formula I as antihypertensive agents will vary with the form of administration and the particular compound chosen. Furthermore, it will vary with the particular host as well as the age, weight and condition of the host under treatment as well as with the nature and extent of the symptoms. Generally, treatment is initiated with small dosages substantially less than the optimum dose of the compound. Thereafter, the dosage is increased by small increments until the optimum effect under the circumstances is reached. In general, the compounds of this invention are most desirably administered at a concentration level that will generally afford effective results without causing any harmful or deleterious side effects. For example, the effective antihypertensive amount of the compounds for oral administration can usually range from about 0.05 to 100 mg per kilogram body weight per day in single or divided doses although as aforementioned variations will occur. However, a dosage level that is in the range of from about 0.1 to 50 mg per kilogram body weight per day in single or divided doses is employed most desirably for oral administration in order to achieve effective results.
The compounds of formula I also can be used to produce beneficial effects in the treatment of hypertension, peripheral and cerebral vascular diseases and related disorders when combined with a second therapeutic agent comprising a therapeutically effective amount of a diuretic and/or antihypertensive agent commonly used in antihypertensive therapy. Such diuretic and/or antihypertensive therapeutic agents include, for example, the thiazide diuretics for instance, chlorothiazide or hydrochlorothiazide; mineralocorticoid antagonizing diuretic agents, e.g., spironolactone; and other diuretics such as triameterene and furosemide. Examples of still other suitable antihypertensive agents are prazosine, hydralazine and centrally active antihypertensive agents such as methyldopa, clonidine, and reserpine; as well as the β-adrenergic blocking agents, for instance, propranolol. The compound of formula I can be administered sequentially or simultaneously with the antihypertensive and/or diuretic agent. Preferred antihypertensive and/or diuretic therapeutic agents are the antihypertensive agents such as the thiazides, mineralocorticoid antagonizing diuretic agents and the β-adrenergic blocking agents. A combination of the foregoing antihypertensive agents are well known in the art; for instance, "Physician Desk Reference", 33 ed., Medical Economics Co., Oradell, N.J., U.S.A., 1979. For example, propanolol is administered daily to humans in a range of 80 to 640 mg, usually in the form of unit doses of 10, 20, 40 or 80 mg. When used in combination, the compound of formula I is administered as described previously.
The compounds of formula I are prepared in the following manner.
Reaction scheme 1 illustrates a method for preparing some of the compounds of formula Ib ##STR6##
With reference to reaction scheme 1, bromobutyrolactone is condensed with an ethylenediamine derivative of formula IV in which R 5 is benzyl or lower alkyl to obtain the corresponding piperazine of formula V in which R 5 is as defined herein. Preferred conditions for the condensation involve reacting together about equivalent amounts of bromobutyrolactone and the compound of formula IV in the presence of an equivalent amount of a proton acceptor, preferably triethylamine, in an inert organic solvent, preferably tetrahydrofuran, at about 60° to 70° C. for about 15 to 30 hours.
Reaction of the piperazine of formula V in which R 5 is as defined herein with about 10 to 25 molar equivalents of thionyl chloride or bromide gives the corresponding piperazine of formula VI in which R 5 is as defined herein and X is bromo or chloro. A suitable solvent is methylene chloride and the reaction is conducted at about 0° to 20° C. for about 15 minutes to two hours.
Condensation of the piperazine of formula VI in which R 5 and X are as defined herein with a dihydroindole of formula VII in which R 1 and R 2 are as defined herein gives the corresponding compound of formula VIII in which R 1 , R 2 and R 5 are as defined herein. A useful method of preparing the dihydroindoles of formula VII from the corresponding indole is described by A. Smith and J. H. P. Utley, Chem. Commun., 427 (1965). Preferably about 1.5 molar equivalents of the piperazine of formula VI is used with respect to the dihydroindole of formula VII. For the inert solvent in the condensation, toluene is preferred. The condensation is usually conducted at about 100° to 120° C. for about 15 to 30 hours.
In order to form the indole ring system, the compound of formula VIII in which R 1 , R 2 and R 5 are as defined herein is oxidized with a mixture of manganese dioxide and palladium on charcoal to obtain the corresponding compound of formula II in which R 1 , R 2 and R 5 are as defined herein. Preferably about equal parts by weight of manganese dioxide and about one tenth part by weight of 5 percent palladium on charcoal is used. The oxidation is maintained at about 125° to 150° C. for about 15 to 30 hours in an inert organic solvent, preferably xylene.
Cyclodehydration of the compound of formula II in which R 1 and R 2 are as defined herein and R 5 is lower alkyl with phosphorus oxychloride followed by reduction of the resulting intermediate gives the corresponding compound of formula Ib in which R 1 and R 2 are as defined herein, and R 3 and R 4 are the same lower alkyl. In the cyclodehydration, an excess of phosphorus oxychloride is used or usually phosphorus oxychloride also acts as the solvent for the cyclodehydration. The cyclodehydration is conducted at about 90° to 110° C. for about two to ten hours. The intermediate obtained from the cyclodehydration is immediately reduced with an excess of sodium in a lower alkanol, preferably ethanol, at about 15° to 25° C. for about 15 minutes to one hour.
Similarly, cyclodehydration of the compound of formula II in which R 1 and R 2 are as defined herein and R 5 is benzyl followed by reduction of the resulting intermediate gives the corresponding compound of formula III in which R 1 and R 2 are as defined herein.
Hydrogenation of the compound of formula III in which R 1 and R 2 are as defined herein, preferably in the presence of palladium on carbon in a lower alkanol, affords the corresponding compound of formula Ib in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen.
Reaction scheme 2 illustrates a method for preparing some of the compounds of formula Ia. ##STR7##
With reference to reaction scheme 2, an indole of formula IX in which R 1 and R 2 are as defined herein, is condensed with butyrolactone to obtain the corresponding acid of formula X in which R 1 and R 2 are as defined herein. In this condensation, the indole of formula IX is first reacted with about one molar equivalent of sodium hydride at about 100° C. to generate the anion of the compound of formula IX. A solution of the anion in an inert organic solvent, preferably dimethylformamide, is mixed with about two molar equivalents of butyrolactone. The resulting solution is maintained at about 130° to 160° C. for about five to ten hours, and the corresponding acid of formula X is isolated.
Dehydrative cyclization of the acid of formula X in which R 1 and R 2 are as defined herein gives the corresponding tricyclic ketone of formula XI in which R 1 and R 2 are as defined herein. Preferred conditions for the cyclization involve reacting the acid of formula X with an excess of a dehydrating agent, preferably polyphosphoric acid, which can also act as the solvent, at about 80° to 120° C. for about 30 minutes to 5 hours.
A number of methods can be used to convert the tricyclic ketone of formula XI in which R 1 and R 2 are as defined herein to the halo compound of formula IV in which R 1 and R 2 are as defined herein and X is bromo or chloro. Examples of such methods include use of bromine or chlorine in various inert organic solvents, for example, diethyl ether, chloroform, methylene chloride and acetic acid, at various temperatures (i.e. -78° to 20° C.); N-bromosuccinimide or N-chlorosuccinimide in an inert organic solvent at 0° to 30° C.; dioxane dibromide; pyridinium hydrobromide perbromide; trimethylphenylammonium tribromide; and a mixture of trimethylphenylammonium tribromide and hydrogen bromide. For the subsequent condensation, the compounds of formula IV in which R 1 and R 2 are as defined herein an X is bromo are preferred. The preferred method of preparing the latter compounds of formula IV in which X is bromo involves reacting, in the dark, the compound of formula XI with about one molar equivalent of trimethylphenylammonium tribromide in an inert organic solvent, preferably methylene chloride, at about 10° to 30° C. for about 20 to 40 hours.
Condensation of the compound of formula IV in which R 1 , R 2 and X are as defined herein with ethylenediamine and followed by reduction of the resulting intermediate gives the corresponding compound of formula Ia in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen. In the condensation, about two to ten molar equivalents of ethylenediamine are required and an inert organic solvent, preferably dioxane, is used to dissolve the reactants. The condensation reaction is maintained at about 15° to 30° C. for about 15 to 30 hours. Preferably without isolating the condensation product, the condensation reaction mixture is treated with a complex borohydride reducing agent, preferably sodium borohydride, in order to reduce the product of the condensation. For the reduction, usually the condensation reaction mixture is diluted with a lower alkanol, preferably methanol, and a small amount of water, and the reduction reaction is maintained at about 10° to 30° C. for about one to five hours.
If desired, the compound of formula I (includes compounds of formulae Ia and Ib) in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen can be reacted with a lower alkyl, lower alkenyl, lower alkynyl, cyclo(lower)alkyl, lower alkanoyl, lower alkoxycarbonyl(lower)alkyl, phenyl(lower)alkyl or phenoxy(lower)alkyl halide wherein the halide is selected from bromo, chloro or iodo in the presence of a proton acceptor to obtain the corresponding compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and R 4 each is hydrogen, lower alkyl, lower alkenyl, lower alkynyl, cyclo(lower)alkyl, lower alkanoyl, lower alkoxycarbonyl(lower)alkyl, phenyl(lower)alkyl or phenoxy(lower)alkyl. Preferred proton acceptors include potassium carbonate and triethylamine, and preferred solvents are benzene, acetonitrile, dimethylformamide and methylene chloride. The amount of halide alkylating agent can vary from about 1.1 to 1.5 molar equivalents if monosubstitution is desired and from about three to ten molar equivalents if disubstitution is desired. The reaction conditions can also vary; usually a temperature of about 10° to 50° C. for about one to ten hours will produce monosubstitution and a temperature of about 20° to 120° C. for about 6 to 72 hours will give disubstitution. A monosubstituted compound of formula I, i.e. R 3 or R 4 is hydrogen, can then be substituted in the above manner to obtain the corresponding compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and R 4 are different and are selected from lower alkyl, lower alkenyl, lower alkynyl, cyclo(lower)alkyl, lower alkanoyl, lower alkoxycarbonyl(lower)alkyl, phenyl(lower)alkyl and phenoxy(lower)alkyl.
A preferred method for preparing the compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and R 4 are methyl involves reacting the hydrochloride salt of the corresponding compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and R 4 are hydrogen with aqueous formaldehyde at about 10° to 30° C. for about one to ten hours. The resulting intermediate is then reduced by treating the reaction mixture with the reducing agent, sodium cyanoborohydride, at about 10° to 30° C. for about 15 to 30 hours.
Usually, the above alkylation type reactions will preferentially first take place at one of the secondary nitrogen positions, for example, in the compound of formula Ia, the secondary nitrogen at position 1 of the ring system is the more reactive. If it is desired that the alkylation type reaction take place at the less reactive secondary nitrogen, the more reactive nitrogen can be blocked by an easily removable blocking group. Such a blocking group is introduced by reaction with about one molar equivalent of benzoyl chloride. After the desired alkylation type reaction is conducted at the other secondary position, the benzoyl blocking group is removed under alkaline hydrolysis.
If desired, the compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and/or R 4 is lower alkoxycarbonyl(lower)alkyl can be reduced with a complex metal hydride reducing agent to obtain the corresponding compound of formula I in which R 1 and R 2 are as defined herein, and R 3 and/or R 4 is hydroxy(lower)alkyl. For the reduction, about four to six molar equivalents of lithium aluminum hydride, as the preferred complex metal hydride reducing agent, is used and the reduction is conducted in an inert organic solvent, preferably diethyl ether. The reduction is maintained at about 30° to 50° C. for about 10 to 20 hours.
If desired, some of the trans compounds of formula Ia can be isomerized to the corresponding cis compounds of formula Ib. Most of the trans compounds of formula Ia in which R 3 and R 4 are not hydrogen can be isomerized under acidic conditions, for example, in the presence of hydrogen chloride at 20° to 120° C., to obtain the corresponding cis compound of formula Ib. In some instances, base-catalyzed trans to cis isomerizations can occur. For example, treatment of the compound of formula Ia in which R 1 is 7-bromo, R 2 is methyl, and R 3 and R 4 are ethyl with a solution of sodium methoxide in hexamethylphosphoramide at 150° to 200° C. for 10 to 30 hours afforded the corresponding cis compound of formula Ib in which R 1 is 7-bromo, R 2 is methyl, and R 3 and R 4 are ethyl.
The following examples illustrate further this invention.
EXAMPLE 1
3-(2-Hydroxyethyl)-1,4-dimethyl-2-piperazinone (V, R 5 =Me)
The mixture of sym. dimethylethylenediamine (1 eq, 53 g), bromobutyrolactone (1 eq, 100 g) and triethylamine (1 eq, 120 ml) in 1000 mL of tetrahydrofuran was refluxed overnight. The crude precipitate was filtered and thoroughly washed with diethyl ether. The ether was evaporated and the residue was purified by elution through a silica gel column using 2% (v/v) methanol in chloroform to obtain the title compound. A small sample was converted into a picrate and crystallized from methanol to obtain the picrate salt of the title compound: mp 157°-159° C.; IR (KBr) 3220, 1650, 1565 and 1330 cm -1 ; UV max (MeOH) 353 nm (ε 18090); and NMR (DMSO-d 6 ) δ 2.1 (m, 2H), 2.9 and 2.93 (singlets, 6H), 3.5 (m, 6H), 3.95 (m, 1H), and 8.55 (s, 2H).
In the same manner but replacing sym. dimethylethylenediamine with an equivalent amount of sym. diethylethylenediamine, the following compound of formula V was obtained, 1,4-diethyl-3-(2-hydroxyethyl)-2-piperazinone picrate: mp 127°-129° C. (crystallized from methanol-diethyl ether); IR (mineral oil) 3290, 1640, 1565 and 1315 cm -1 ; UV max (MeOH) 354 nm (ε 15675); and NMR (DMSO-d 6 ) δ 1.05 and 1.25 (triplets, J=7.5 Hz, 6H), 2.04 (q, J=5.5 Hz, 2H), 3.05-3.75 (m, 10H), 3.95 (t, J=5.5 Hz, 1H), and 8.55 (s, 2H).
EXAMPLE 2
3-(2-Chloroethyl)-1,4-dimethyl-2-piperazinone (VI: R 5 =Me and X=Cl)
Thionyl chloride (1.5 mL) was added dropwise to an ice cooled methylene chloride (5 mL) solution of 3-(2-hydroxyethyl)-1,4-dimethyl-2-piperazinone (0.40 g, described in Example 1). The reaction mixture was stirred for 30 min and poured on an ice solution of 10% sodium bicarbonate. The mixture was extracted with methylene chloride, and the organic extract was dried and evaporated to give the title compound: IR (CHCl 3 ) 1635 cm -1 ; and NMR (CDCl 3 ) δ 2.35 (s, 3H) and 2.90 (s, 3H).
In the same manner, but replacing 3-(2-hydroxyethyl)-1,4-dimethyl-2-piperazinone with an equivalent amount of 1,4-diethyl-3-(2-hydroxyethyl)-2-piperazinone (described in Example 1), the following compound of formula VI was obtained, 3-(2-chloroethyl)-1,4-diethyl-2-piperazinone: IR (CHCl 3 ) 1635 cm -1 ; and NMR (CDCl 3 ) δ 1.1 (t, 6H) and 3.65 (t, 2H).
EXAMPLE 3
1,4-Dimethyl-3-[2-(2,3-dihydro-3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone (VIII: R 1 =H, and R 2 and R 5 =Me)
2,3-Dihydro-3-methylindole (3.99 g, 1 eq, described by A. Smith and J. H. P. Utley, Chem. Commun., 1965, 427) and 3-(2-chloroethyl)-1,4-dimethyl-2-piperazinone (5.7 g, 1 eq, described in Example 2) were combined in toluene (100 mL) and refluxed overnight. The cold mixture was poured into an ice solution of 10% sodium bicarbonate and the product was extracted with methylene chloride. Evaporation of the extract gave 9 g of crude product. The crude product was passed through a silica gel column using 3% (v/v) methanol in chloroform to give the title compound (6 g): IR (CHCl 3 ) 1640 cm -1 ; UV max (MeOH) 296 nm (ε 2300) and 257 (5900); and NMR (CDCl 3 ) ε 1.25 (d, 3H), 2.35 (s, 3H), 2.8 (s, 3H) and 6.35-7.1 (m, 4H).
In the same manner, but replacing 3-(2-chloroethyl)-1,4-dimethyl-2-piperazinone with an equivalent amount of 3-(2-chloroethyl)-1,4-diethyl-2-piperazinone (described in Example 2), the following compound of formula VIII was obtained, 1,4-diethyl-3-[2-(2,3-dihydro-3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone: IR (CHCl 3 ) 1635 cm -1 ; UV max (MeOH) 298 nm (ε 2800) and 251 (9500); and NMR (CDCl 3 ) δ 1.1 (m, 6H), 1.25 (d, 3H) and 6.4-7.15 (m, 4H).
EXAMPLE 4
1,4-Dimethyl-3-[2-(3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone (II: R 1 =H, R 2 and R 5 =Me)
A suspension of 1,4-dimethyl-3-[2-(2,3-dihydro-3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone (3.5 g, described in Example 3), manganese dioxide (3.5 g) and 5% palladium on charcoal (0.35 g) in xylene (200 mL) was refluxed overnight. The hot suspension was filtered and the filtrate was evaporated to dryness giving 3 g of the title compound. The title compound was converted into the maleate salt and crystallized from methanol-diethyl ether: mp 130°-134° C.; IR (mineral oil) 2370, 1950 and 1665 cm -1 ; UV max (MeOH) 290 nm (ε 5625) and 225 (36100); NMR (DMSO-d 6 ) δ 2.2 (s, 3H), 2.5 (s, 3H), 2.8 (s, 3H), 6.15 (s, 2H) and 7.2 (m, 4H); and Anal. Calcd for C 17 H 23 N 3 O.C 4 H 4 O 4 : C, 62.83% H, 6.78% N, 10.47% and Found: C, 62.41% H, 6.75% N, 10.29%.
In the same manner, but replacing 1,4-dimethyl-3-[2-(2,3-dihydro-3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone with an equivalent amount of 1,4-diethyl-3-[2-(2,3-dihydro-3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone (described in Example 3), the following compound of formula II was obtained, 1,4-diethyl-3-[2-(3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone: IR (CHCl 3 ) 1640 cm -1 ; UV max (MeOH) 290 nm (ε 5800), 258 (5400), 251 (5500) and 226 (26400); and NMR (CDCl 3 ) δ 1.1 (m, 6H), 2.3 (s, 3H), 4.15 (m, 2H), 6.88 (s, 1H), and 7.05-7.6 (m, 4H).
EXAMPLE 5
(4a,12a-cis)-1,4,5-Trimethyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indol (Ib: R 1 =H, and R 2 , R 3 and R 4 =Me)
A solution of 1,4-dimethyl-3-[2-(3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone (2.5 g, described in Example 4) in phosphorous oxychloride (10 mL) was refluxed for 3.5 hr. Benzene (50 mL) was added to the mixture and the mixture was evaporated under vacuum. The residue was dissolved in absolute ethanol and 1.5 g of sodium metal was added in small portions under nitrogen. Water was added to the sodium free ethanolic solution and the solution was extracted with diethyl ether. Evaporation of the extract gave 2.5 g of crude product. Chromatography on silica gel using 5% (v/v) methanol in chloroform yielded 0.7 g of the title compound. The title compound was converted to the dihydrochloride salt of the title compound and crystallized from acetonitrile: mp 210°-212° C.; IR (mineral oil) 2430; UV max (MeOH) 282 nm (ε 6710), 276 (7210) and 225 (31790); NMR (DMSO-d 6 ) δ 2.35 (s, 3H), 2.65 (s, 3H), 3.0 (s, 3H), 5.2 (br, s, 1H), 7.3 (m, 4H) and 7.93 (s, 1H); and Anal. Calcd for C 15 H 23 N 3 .HCl: C, 59.29% H, 7.90% N, 12.20% and Found: C, 59.39% H, 8.07% N, 12.14%.
In the same manner, but replacing 1,4-dimethyl-3-[2-(3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone with an equivalent amount of 1,4-diethyl-3-[2;l -(3-methyl-1H-indol-1-yl)ethyl]-2-piperazinone (described in Example 4), the following compound of formula Ib was obtained, (4a,12a-cis)-1,4-diethyl-5-pyrido[1,2-a]indole as the dihydrochloride salt; mp 283°-240° C. (crystallized from methanol-diethyl ether); IR (mineral oil) 2350 cm -1 ; UV max (MeOH) 284 nm (ε 7900), 277 (8325) and 228 (38430); NMR (DMSO-d 6 ) δ 1.25 (m, 6H), 2.35 (brs, 3H), 5.25 (br s, 1H) and 7.3 (m, 4H); and Anal. Calcd for C 19 H 27 N 3 .2HCl: C, 61.61% H, 7.89% N, 11.35% and Found: C, 60.89% H, 8.19% N, 10.92%.
EXAMPLE 6
3-Methyl-1H-indole-1-butanoic Acid (X: R 1 =H and R 2 =Me)
3-Methylindole (13.1 g; 1 eq) and sodium hydride (5 g of 50% suspension-1 eq) were melted together in a 3-neck round bottom flask immersed in 100° C. oil bath until evolution of hydrogen gas ceased. The mixture was cooled down and dissolved in 250 mL of dry dimethylformamide. Butyrolactone (17.2 g-2 eq) was added and the solution was refluxed for 7 hr and poured on ice. The mixture was extracted with diethyl ether, and the acid was liberated with 10% hydrochloric acid solution. The mixture was extracted with diethyl ether. Evaporation of the extract gave a residue which was chromatographed on silica gel using 10% (v/v) ethyl acetate in benzene. Evaporation of the appropriate eluates gave 5.5 g of the title compound, mp 82°-84° C.
EXAMPLE 7
10-Methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (XI: R 1 =H and R 2 =Me)
3-Methyl-1H-indole-1-butanoic acid (5 g, described in Example 6) was suspended in polyphosphoric acid and the mixture was heated at 100° C. for 1 hr, cooled, and poured on ice. The mixture was extracted with diethyl ether. The extract was washed with 10% aqueous sodium bicarbonate, evaporated (4.4 g of crude product) and chromatographed through silica gel using 5% methanol in chloroform (v/v).
The appropriate eluates were evaporated to give the title compound: mp 87°-89° C.; IR (CHCl 3 ) 1648 cm -1 ; UV max (MeOH) 316 nm (ε21611) and 241 (26009); NMR (CDCl 3 ) δ 2.2 (m, 2H), 2.5 (m, 2H), 2.58 (s, 3H), 4.0 (t, 2H), 7.1 (m, 3H) and 7.4 (m, 1H); and Anal. Calcd for C 13 H 13 NO: C, 78.36% H, 6.58% N,, 7.03% and Found: C, 78.16% H, 6.84% N, 7.07%.
EXAMPLE 8
2-Bromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (XI: R 1 =2-Br and R 2 =Me)
Aged N-bromosuccinimide (1 g) was added in small portions to a solution of 10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (described in Example 7, 1.0 g), in methylene chloride (50 mL). The mixture was stirred at room temperature for 30 min, washed successively with water, 5% aqueous sodium bicarbonate, and water again. After drying (MgSO 4 and filtration), the solvent was evaporated, and the residue was crystallized from diethyl ether, mp 142°-144° C; yield 1.25 g; NMR (CDCl 3 ) δ 2.34 (m, 2H), 2.57 (s, 3H), 2.68 (m, 2H), 4.11 (t, J=5.5 Hz, 2H), 7.10 (d, J 34 =8.5 Hz, 1H), 7.37 (dd, J 34 =8.5 Hz, J 13 =2 Hz, 1H) and 7.75 (d, J 13 =2 Hz, 1H).
EXAMPLE 9
8-Bromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (IV: R 1 =H, R 2 =Me and X=Br)
The reaction was performed in the dark (the flask wrapped in a tin-foil), and with the provision for maintaining a nitrogen atmosphere. To a solution of 10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (described in Example 7, 49.75 g) in methylene chloride (250 mL) was added a solution of trimethylphenylammonium tribromide (94 g) in methylene chloride (1200 mL) as fast as possible (over 2 min); the inside temperature was maintained at 10° C. The reaction mixture was stirred at room temperature for 30 hr, evaporated in vacuo, and the solid residue was partitioned between water (600 mL) and benzene-diethyl ether 1:1 (800 mL, v/v). The separated organic layer was dried (MgSO 4 ), filtered, and the filtrate was evaporated. The crude product was dissolved in chloroform (55 mL), and diethyl ether (600 mL) was added at once, whereby a voluminous, dark-green material precipitated. It was quickly removed by filtration (without suction), and the filtrate was chilled to 0° C. The crystals which formed were collected by filtration; 38 g, mp 126°-128° C. This material was recrystallized from chloroform-diethyl ether (1:8, v/v) to give 35 g of the title compound, mp 131°-133° C.; IR (CHCl 3 ) 1665-1660, and 1535 cm -1 ; UV max (MeOH) 246 and 327 nm, (ε16000) and (18200) respectively; NMR (CDCl 3 ) δ 2.67 (br s, 3H), overlapping with 2.65 (m, 2H), 4.29 (dd, J 1 =7.5 Hz, J 2 =4.5 Hz, 2H), 4.67 (t, J=4 Hz, 1H), 7.25-7.7 (m, 4H); Anal. Calcd for C 13 H 12 BrNO: C, 56.12% H, 4.35% N, 5.03% and Found: C, 56.20% H, 4.32% N, 5.05%.
EXAMPLE 10
2,8-Dibromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (IV: R 1 =2-Br, R 2 =Me and X=Br)
Aged N-bromosuccinimide (4.89 g, 27.5 mmol) was added in small portions (over 15 min) to a solution of 2-bromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (described in Example 8, 5.0 g) in methylene chloride (100 mL) and stirring at room temperature was continued for 30 min. This crude mixture was then protected against light, and a solution of bromine (2 ML) in methylene chloride (200 mL) was added very slowly from a dropping funnel. The reaction mixture was washed successively with cold water, 5% sodium bicarbonate, and water again. After drying (MgSO 4 ) and filtration, the solvent was evaporated, and the title compound was crystallized from chloroform, mp 156° C.; yield 6.6 g; Anal. Calcd for C 13 H 11 Br 2 NO: C, 43.72% H, 3.10% N, 3.92% and Found: C, 43.35% H, 3.00% N, 3.99%.
EXAMPLE 11
(4a,12a-trans)-5-Methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3' -3,4]-pyrido[1,2-a]indole (I: R 1 , R 3 and R 4 =H and R 2 =Me)
A solution of ethylenediamine (11 mL, 9.9 g, 165 mmol) in dioxane (11 mL) was added at once to a solution of 8-bromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (described in Example 9, 8.34 g, 30 mmol) in the same solvent (75 mL) while the inside temperature was maintained at 15° C. and nitrogen was being introduced in the reaction apparatus. The mixture was stirred at room temperature for 18 hr, cooled in an ice-water bath, and diluted with methanol (75 mL). Water (1 mL) was added, and upon cooling and stirring, sodium borohydride (3.1 g, 82 mmol, pulverized) was slowly added in portions. After the borohydride addition was complete, stirring was continued for 2 hr, the mixture was poured (upon cooling) into 10% hydrochloric acid (90 mL), and the pH of the resultant solution was adjusted to 2. The solution was washed with diethyl ether (150 mL), and the aqueous solution was basified (pH 10-11) with 50% sodium hydroxide upon strong cooling. The product was extracted with benzene-diethyl ether (2:1 v/v, 2 X 350 mL). The combined extracts were dried (MgSO 4 ), filtered, and evaporated to give 5.5 g of the title compound (mp 190°-192° C.). The title compound was crystallized from hot acetonitrile: mp 196°-197° C.; IR (CHCl 3 ) 3340 and 3290 cm -1 ; NMR (CDCl 3 ) δ 1.67 (s, 2H), 1.90 (m, 2H), 2.44 (s, 3H), 2.98 (m, 4H), 2.5-2.9 and 3.15-4.4 (m), 7.10 (m, 3H) and 7.42 (m, 1H); Anal. Calcd for C 15 H 19 N 3 ; C, 74.65% H, 7.94% N, 17.41% and Found: C, 74.37% H, 7.85% N, 17.22%.
A methanolic solution of the title compound (1.7 g) was treated with a methanolic solution of maleic acid (1.4 g); isopropanol was added until the mixture became opalescent. On standing at room temperature for 18 hr, the salt crystallized. The salt was recrystallized from methanoldiethyl ether to give the maleate salt of the title compound; mp 229°-231° C.; Anal. Calcd for C 15 H 19 N 3 .C 4 H 4 O: C, 63.85% H, 6.48% N, 11.76% and Found: C, 63.50% H, 6.41% N, 11.69%.
In the same manner but replacing 8-bromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one with an equivalent amount of 2,8-dibromo-10-methyl-6,7,8,9-tetrahydropyrido[1,2-a]indol-9-one (described in Example 10), the following compound of formula Ia was obtained; (4a,12a-trans)-7-bromo-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole; mp 185° C. (crystallized from acetonitrile-methanol); NMR (CDCl 3 ) δ 1.66 (br s, 2H), 2.35 (s, 3H), 6.95 (d, J 89 =8 Hz, 1H), 7.14 (dd, J 89 =8 Hz, J 68 =1 Hz, 1H) and 7.54 (br s, 1H); Anal. Calcd for C 15 H 18 BrN 3 : C, 56.25% H, 5.66% N, 13.12% and Found: C, 56.04% H, 5.60% N, 13.07%.
The latter compound was dissolved in methanol and a solution of hydrogen chloride in diethyl ether was added. The precipitate was recrystallized from acetonitrile to obtain the hydrochloride salt of the latter compound: mp 382° C.; IR (mineral oil) 3350 and 2700 cm -1 ; UV max (MeOH) 233, 286, and 293, (ε37700), (6960) resp.; NMR (DMSO-d 6 ) δ 2.42 (s, 3H), 4.34 (d, J=11 Hz, 1H), 7.25 (br s, 2H) and 7.67 (s, 1H); Anal. Calcd for C 15 H 18 BrN 3 .HCl: C, 45.82% H, 5.13% N, 10.69% and Found: C, 45.59% H, 4.99% N, 10.87%.
EXAMPLE 12
(4a,12a-trans)-1,4-Diethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indol (Ia: R 1 =H, R 2 =Me and R 3 and R 4 =Et)
A mixture of (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (described in Example 11), dimethylformamide (DMF, 225 mL), ethyl iodide (10 g, 64 mmol), and K 2 CO 3 (8.83 g, 64 mmol) was stirred at room temperature overnight, then heated at 70° C. for 4 hr, cooled, and poured into 200 mL of water. Crude product was extracted with diethyl ether (3 X 150 mL), and the combined extracts were washed with water, dried (MgSO 4 ), filtered, and evaporated. The residue was applied on a column of silica gel; and elution with methylene chloridemethanol (20:1, v/v) afforded 3.5 g of the title compound: NMR (CDCl 3 ) δ 1.04 and 1.10 (J=7.5 Hz, 6H), 1.3-2.1 (m, 2H), 2.43 (s, 3H), 2.55 (m, 4H), 3.15 (overlapping quartets, J=7.5 Hz, 4H), 3.55-4.4 (m, 4H), 7.1 (m, 3H), 7.45 (m, 1H).
The title compound (6 g) was dissolved in methanol (80 mL) and a methanolic solution of hydrogen bromide (0.0574 g of HBr/mL, 30 mL =1.6 g) was added. The hydrobromide salt of the title compound crystallized out, it was collected by filtration and recrystallized from methanol-acetonitrile 15:85 (v/v) yield 5.76 g; mp 237°-238° C.; IR (mineral oil) 2600 cm -1 ; UV max (MeOH) 229 and 286 nm, (ε38510) and (8020) resp.; NMR (DMSO-d 6 ) δ 1.03 and 1.29 (t, J=7.5 Hz, 6H), 2.32 (s, 3H), 4.74 (d, J=11Hz, 1H); and Anal. Calcd for C 19 H 27 N 3 .HBr: C, 60.31% H, 7.46% N, 11.10% and Found: C, 60.41% H, 7.50% N, 11.45%.
In the same manner but replacing ethyl iodide with an equivalent amount of propyl iodide the following compound of formula I was obtained, (4a,12a-trans)-5-methyl-1,4-dipropyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole: NMR (CDCl 3 ) δ 0.81 and 0.93 (t, J=7.5 Hz, 6H), multiplets centered at 1.54 (4H), 2.42 (s, 3H); and the corresponding hydrobromide salt (crystallized from methanol): mp 246°-248° C.; IR (mineral oil) 2550 cm -1 ; UV max (MeOH) 285 nm (ε8070); NMR (DMSO-d 6 ) δ 0.80 and 0.97 (t, J=7 Hz), 4.76 (d, J=10 Hz, 1H), 6.75-7.55 (m, 4H); and Anal. Calcd for C 21 H 31 N 3 .HBr: C, 62.06% H, 7.93% H, 10.34% and Found: C, 62.11% H, 8.11% N, 10.33%.
Similarly, use of ethyl bromoacetate gave (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole-1,4-diacetic acid diethyl ester; NMR (CDCl 3 ) δ 1.20 and 1.27 (two triplets, J=7.5 Hz, 6H), 2.35 (s, 3H), 3.47 (br s, 4H); and the corresponding hydrochloride salt (crystallized from methylene chloride-diethyl ether): mp 183°-184° C.; IR (mineral oil) 2400, 1745, and 1740 cm -1 ; UV max (MeOH) 229 and 286 nm (ε=7470) and (7890) resp.; (DMSO-d 6 ) δ 1.15 and 1.28 (t, J=7.5 Hz, 6H), 2.05 (s, 3H), 2.27 (br s, 4H), 4.06 and 4.23 (quartets, J=7.5 Hz, 4H), 5.00 (d, J=10 Hz, 1H); and Anal. Calcd for C 23 H 31 N 3 O 4 .HCl: C, 61.38% H, 7.17% N, 9.34% and Found: C, 60.96% H, 7.16% N, 9.30%.
Similarly, condensation of ethyl iodide with (4a,12a-trans)-7-bromo-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido]1,2-a]indole gave (4a,12a-trans)-7-bromo-1,4-diethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole: mp 130° C. (crystallized from diethyl ether); and NMR (CDCl 3 ) δ 1.02 and 1.07 (overlapping triplets, 6H), 2.35 (br s, 3H), 6.96 (d, J 89 =8.5 Hz, 1H), 7.14 (dd, J 89 =8.5 Hz, J 68 =1 Hz, 1H), 7.55 (d, J 68 =1 Hz, 1H); and the corresponding hydrochloride salt (crystallized from acetonitrile): mp 290°-291° C.; IR (mineral oil) 3400, and 2400 cm -1 ; UV max (MeOH) 233, 288, and 294 nm (ε=35550), (6650) and (6900) resp.; NMR (DMSO-d 6 ) δ 1.02 and 1.29 (t, J=7.5 Hz, 6H), 2.31 (s, 3H), 4.96 (d, J=10 Hz, 1H), 7.20 (m, 2H), 7.57 (d, J=Hz, 1H), 11.5 (br, exchangeable, 1H); and Anal. Calcd for C 19 H 26 BrN 3 .HCl: C, 55.27% H, 6.59% N, 10.18% and Found: C, 55.39% H, 6.52% N, 10.26%.
EXAMPLE 13
(4a,12a-trans)-1-Ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (Ia: R 1 and R 3 =H, R 2 =Me and R 4 =Et)
To a solution of (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (4.82 g, 20 mmol, described in Example 11) in DMF (200 mL) was added anhydrous K 2 CO 3 (3.45 g, 25 mmol), and ethyl iodide (3.9 g, 25 mmol). The mixture was stirred at room temperature for 3 hr, and evaporated. The residue was partitioned between water and chloroform, and the organic phase was separated, dried (MgSO 4 ), filtered and evaporated. The residue was chromatographed on silica gel (200 g) using chloroform-methanol (99:1, v/v) to give 3.6 g of the title compound: NMR (CDCl 3 ) δ 1.06 (t, J=7.5 Hz, 3H), 1.83 (br s, 1H), 2.42 (s, 3H), 4.25 (dd, 1H).
The title compound was reacted with hydrogen bromide to obtain the dihydrobromide salt of the title compound: mp 237°-238° C. (crystallized from methanol-diethyl ether); UV max (MeOH) 285 nm (ε7,400), 277 (7,700), 236 (34,700); and Anal. Calcd for C 17 H 23 N 3 .2HBr: C, 47.34% H, 5.84% N, 9.74% and Found: C, 47.13% H, 6.01% N, 9.82%.
In the same manner, but replacing ethyl iodide with an equivalent amount of 2-iodopropane, the following compound of formula Ia was obtained, (4a,12a-trans)-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole: mp 125°-126° C. (crystallized from acetonitrile); NMR (CDCl 3 ) δ 0.92 and 1.17 (doublets, 6H), 2.46 (br s, 3H), 1.80 (s, 1H); and the dihydrochloride salt thereof: mp 239°-241° C. (crystallized from methanol); IR (mineral oil) 3500, 3420 and 2500 cm -1 ; UV max (MeOH) 285, 278, and 226 nm (ε7660), (7550), and (37200) resp.; NMR (DMSO-d 6 ) δ 1.20 and 1.41 (doublets, J=7 Hz, 6H), 2.47 (br s, 3H), 5.33 (d, J=10 Hz, 1H), 6.9-7.6 (m, 4H); and Anal. Calcd for C 18 H 25 N 3 .2HCl: C, 60.67% H, 7.63% N, 11.78% and Found: C, 59.40% H, 7.55% N, 11.49%.
Similarly, replacement of ethyl iodide by 3-bromopropyne gave (4a,12a-trans)-5-methyl-1-(2-propynyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole: NMR (CDCl 3 ) δ 2.51 (s, 3H), 2.84 and 2.91 (doublets, 1H+2H); and the dihydrochloride salt thereof: mp 220°-221° C. (crystallized from methanol-diethyl ether); IR (mineral oil) 3300, 3200, 2660, 2320, and 2120 cm -1 ; UV max (MeOH) 227, 277, and 285 nm (ε34600), (7160), and (7020) resp.; NMR (DMSO-d 6 ) δ 2.47 (s, 3H), 4.88 (d, J=11 Hz, 1H), 5.45 (br, 3H), 6.95-7.6 (m, 4H); Anal. Calcd for C 18 H 21 N 3 .2HCl: C, 62.36% H, 6.58% N, 11.93% and Found: C, 60.87% H, 6.82% N, 11.86%.
Similarly, replacement of ethyl iodide by 2-(phenoxy)ethyl bromide gave (4a,12a-trans)-5-methyl-1-[2-(phenoxy)ethyl]-1,2,3,4,4a,11,12,12a-octahydropyrazo[2',3'-3,4]pyrido[1,2-a]indole: NMR (CDCl 3 ) δ 1.72 (s, 1H), 2.41 (s, 3H), 4.00 (m, 5H), 6.65-7.60 (m, 9H); and the maleate salt thereof: mp 177°-178° C. (crystallized from methanol-diethyl ether); IR (mineral oil) 3300, 2500, 1700, and 1585 cm -1 ; UV max (MeOH) 224, 272, and 276 nm (ε50190), (9030), and (9500) resp.; NMR (DMSO-d 6 ) δ 2.38 (s, 3H), 5.97 (s, 2H), 6.75-7.55 (m, 9H); and Anal. Calcd for C 23 H 27 N 3 O.C 4 H 4 O 4 :C, 67.90% H, 6.54% N, 8.80% and Found: C, 67.59% H, 6.50% N, 8.70%.
Similarly, replacement of ethyl iodide by ethyl bromoacetate gave (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole-1-acetic acid ethyl ester: NMR (CDCl 3 ) δ 1.26 (t, 3H), 2.47 (s, 3H), 3.47 (s, 2H), 4.19 (q, 2H), 7.12 (m, 3H) and 7.48 (m, 1H); and the maleate salt thereof: mp 203°-204° C. (crystallized from ethanol); and Anal. Calcd for C 19 H 25 N 3 O 2 .C 4 H 4 O 4 : C, 62.29% H, 6.59% N, 9.48% and Found: C, 61.97% H, 6.66% N, 9.34%.
Similarly, reaction of 2-iodopropane with (4a,12a-trans)-7-bromo-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole gave (4a,12a-trans)-7-bromo-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydroprazino[2',3'-3,4]pyrido[1,2-a]indole: mp 138° C. (crystallized from diethyl ether); NMR CDCl 3 ) δ 0.93 and 1.18 (doublets, J=7 Hz, 6H), and 7.59 (d, 1H); and Anal. Calcd for C 18 H 24 BrN 3 : C, 59.66% H, 6.68% N, 11.60% and Found: C, 59.49% H, 6.64% N, 11.58%.
EXAMPLE 14
(4a,12a-trans)-1,4,5-Trimethyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (Ia: R 1 =H, and R 2 , R 3 and R 4 =Me)
To a solution of (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (5.5 g, described in Example 11) in methanol (150 mL) was added a diethy ether solution saturated with HCl (20 mL), and the mixture was evaporated. The residue was dissolved in 37% aqueous formaldehyde and stirred at room temperature for 2 hr. Upon cooling, the reaction mixture was treated dropwise with a solution of sodium cyanoborohydride (7.6 g) in methanol (400 mL). Molecular sieves (16.5 g) were added, and stirring was continued overnight. After filtration, methanol was evaporated, and the residue was partitioned between 5% ammonium hydroxide and chloroform. The organic layer was separated, evaporated, and the oily product (6.1 g) was chromatographed on silica gel. Elution with AcOEt-hexane-Et 3 N (60: 35:5, v/v) afforded the title compound (4.2 g) as an oil: NMR (CDCl 3 ) δ 2.32 (s, 3H), 2.38 (s, 3H), and 2.42 (s, 3H).
The corresponding monomaleate salt of the title compound was crystallized from methanol: mp 178°-180° C.; IR (CHCl 3 ) 2400, 1900, 1700, 1570, and 1345 cm -1 ; UV max (MeOH) 226, 279, and 285 nm (ε42710), (7790), and (8170) resp.; NMR (CDCl 3 ) δ 2.35 (br s, 6H), 2.89 (s, 3H), 2.05-4.45 (m, 9H), 4.70 (d, J=10 Hz, 1H), 6.22 (s, 3H), 7.12 (m, 3H), 7.49 (m, 1H); and Anal. Calcd for C 17 H 23 N 3 .C 4 H 4 O 4 : C, 65.43% H, 7.06% N, 10.90% and Found: C, 65.59% H, 6.99%N, 10.82%.
EXAMPLE 15
(4a,12a-trans)-5-Methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole-1,4-diethanol (Ia: R 1 =H, R 2 =Me, and R 3 and R 4 =CH 2 CH 2 OH)
(4a,12a-trans)-5-Methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]-pyrido[1,2-a]indole-1,4-diacetic acid diethyl ester (2.07 g, described in Example 12) was dissolved in anhydrous diethyl ether (50 mL); the solution was filtered and added dropwise to a stirred suspension of LiAlH 4 (0.835 g) in diethyl ether (30 mL) over 5 min. The reaction mixture was refluxed for 14 hr, cooled and decomposed (under nitrogen) by a successive addition of water (4.17 mL), 15% sodium hydroxide (4.17 mL), and water (4.17 mL) again. The resultant slurry was stirred for 60 min, filtered, and the filtrate was dried (MgSO 4 ) and evaporated. The filter cake was extracted with chloroform, the extracts were filtered, and combined with the material obtained from the ethereal phase. There was obtained 1.05 g (64%) of the title compound.
The corresponding dihydrochloride was prepared in a chloroform solution by addition of a solution of HCl in diethyl ether, and evaporation to dryness. The residual solids were crystallized from ethanol-diethyl ether and recrystallized from methanol-diethyl ether, mp 202° C.; IR (mineral oil) 3200 and 2600 cm -1 ; UV max (MeOH) 227 and 286 nm (ε39230) and (8010) resp.; NMR (DMSO-d 6 ) δ 2.38 (s, 3H), 5.16 (d, J=11 Hz, 1H), 5.13 and 5.25 (broad singlets 4H), 6.9-7.6 (m, 4H); and Anal. Calcd for C 19 H 27 N 3 O 2 .2HCl: C, 56.71% H, 7.26% N, 10.44% and Found: C, 56.67% H, 7.51% N, 10.27%.
EXAMPLE 16
(4a,12a-trans)-4-Acetyl-1-ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (Ia: R 1 =H, R.sup. 2 =Me, R 3 =COCH 3 , and R 4 =Et)
(4a,12a-trans)-1-Ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (1.0 g, described in Example 13) in 60 ml of methylene chloride was added to 6 ml of 10% solution of sodium hydroxide, followed by dropwise addition of 0.8 ml of acetyl chloride. The mixture was stirred at room temperature for 1 hr, poured on ice and extracted with methylene chloride. Evaporation of the solvent gave 2.2 g of crude product. Chromatography on neutral alumina (chloroform) gave 1.15 g of the title compound. The basic product was converted to the hydrobromide salt and crystallized from methanol-diethyl ether: mp 230°-231° C.; IR (mineral oil) 2600, 1660 cm -1 ; UV max (MeOH) 285 nm (ε 7750); 229 (37300); Anal. Calcd for C 19 H 26 BrN 3 O: C, 58.16% H, 6.68% N, 10.71% and Found: C, 57.71% H, 6.70% N, 10.80%; and NMR (DMSO-d 6 ) ε 1.29 (t, 3H), 2.10 (br s, 6H), 5.20 (m, 1H).
EXAMPLE 17
(4a,12a-trans)-1-Ethyl-5-methyl-4-propyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3' -3,4]pyrido[1,2-a]indole (Ia: R 1 =H, R 2 =Me, R 3 =Pr and R 4 =Et)
A mixture of (4a,12a-trans)-1-ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole (7 g, 26.2 mmol, described in Example 13), DMF (200 mL), K 2 CO 3 (14.4 g, 104 mmol), and 1-iodopropane (17.6 g, 10.4 mL, 104 mmol) was stirred at room temperature for 48 hr. After adding K 2 CO 3 (4g) and 1-iodopropane (5 ml), stirring was continued at 90° C. for 4 hr. The latter operation was repeated. The cold reaction mixture was poured into 200 mL of water, and extracted with diethyl ether (3 X 70 mL). The combined extracts were washed with water, dried (MgSO 4 ), filtered, and evaporated. The residual oil (4.5 g) was chromatographed on silica gel; elution with a mixture of hexane-AcOEt-Et 3 N (6:3:1, v/v) afforded 3.8 g of the title compound: NMR (CDCl 3 ) δ 0.82 (t, J=7.5 Hz, 3H), 1.10 (t, J=7.5 Hz, 3H), 2.41 (s, 3H).
The title compound was dissolved in methanol and converted to the corresponding hydrobromide salt: mp 252°-254° C. (crystallized from methanol); IR (mineral oil) 2600 cm -1 ; UV max (MeOH) 229 and 286 nm, (ε 39200) and (7960) resp.; NMR (DMSO-d 6 ) ε 0.8 (t, J=7.5 Hz, 3H), 1.29 (t, J=7.5 Hz, 3H), 2.32 (s, 3H), 4.79 (d, J=10 Hz, 1H); and Anal. Calcd for C 20 H 29 N 3 .HBr: C, 61.22% H, 7.44% N, 10.70% and Found: C, 61.20% H, 7.74% N, 10.87%.
Similarly, but replacing 1-iodopropane with 1-iodobutane, the following compound of formula Ia was obtained, (4a,12a-trans)-4-butyl-1-1-ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole and the corresponding dihydrochloride salt thereof; mp 221°-222° C. (crystallized from acetonitrile-diethyl ether); IR (mineral oil) 3300 and 2400 cm -1 ; UV max (MeOH) 227 and 285 nm (ε 34980) and (6770) resp.; NMR (DMSO-d 6 ) ε 0.83 (t, J=6 Hz, 3H), 1.32 (t, J=7 Hz, 3H), 2.40 (s, 3H), 5.19 (d, J=10 Hz, 1H), 6.85-7.55 (m, 4H); and Anal. Calcd for C 21 H 31 N 3 .2HCl: C, 63.30% H, 8.35% N, 10.55% and Found: C, 62.64% H, 8.12% N, 10.43%.
Similarly, but replacing 1-iodopropane with ethyl bromoacetate, the following compound of formula Ia was obtained, (4a,12a-trans)-1-ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2',3'-3,4]pyrido[1,2-a]indole-4-acetic acid ethyl ester: NMR (CDCl 3 ) ε 1.10 and 1.21 (t, J=7.5 Hz, 6H), 2.36 (s, 3H), 3.44 (s, 2H), and 4.12 (q, J=7.5 Hz, 2H), and the corresponding hydrochloride salt thereof: mp 260°-261° C. (crystallized from ethanol); IR (mineral oil) 2460, and 1735 cm -1 ; UV max (MeOH) 229 and 286 nm (ε 33750) and (8075) resp.; NMR (DMSO-d 6 ) ε 1.15 and 129 (t, J=7 Hz, 6H), 2.26 (s, 3H), 4.05 (q, J=7 Hz, 2H), 4.97 (d, J=11 Hz, 1H), 6.8-7.5 (m, 4H); and Anal. Calcd for C 21 H 29 N 3 O 2 .HCl: C, 64.35% H, 7.71% N, 10.72% and Found: C, 64.19% H, 7.69% N, 10.71%.
Similarly, condensation of ethyl bromide with (4a,12a-trans)-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (described in Example 13) gave (4a,12a-trans)-4-ethyl-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole: NMR (CDCl 3 ) ε 0.96 and 1.22 (doublets, J=7 Hz), 1.04 (t, J=7.5 Hz) and 2.41 (s, 3H); and the dihydrobromide salt thereof: mp 229°-230° C. (crystallized from methanol); IR (mineral oil) 3540, 3450, 2600 cm -1 ; UV max (MeOH) 285 nm (ε 7855); NMR (DMSO-d 6 ) ε 1.1 (t, J=7 Hz), 1.28 and 1.4 (doublets, J=7 Hz), 2.37 (s, 3H), 5.23 (d, J=10 Hz, 1H), 6.85-7.55 (m, 4H); and Anal. Calcd for C 20 H 29 N 3 .2HBr: C, 50.75% H, 6.60% N, 8.79% and Found: C, 50.57% H, 6.51% N, 8.86%.
Similarly, condensation of 1-iodopropane with (4a,12a-trans)-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (described in Example 13) gave (4a,12a-trans)-5-methyl-1-(1-methylethyl)-4-propyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole: NMR (DCDl 3 ) ε 0.8 (t, 3H), 0.96 and 1.16 (doublets, 6H) and 2.4 (s, 3H); the hydrobromide salt thereof: mp 255°-256° C. (crystallized from methanol): IR (mineral oil) 2500 cm -1 ; UV max (MeOH) 228 and 285 nm, (δ3900) and (8040) resp.; NMR (DMSO-d 6 ) ε 0.77 (t, J=7.5 Hz, 3H), 1.24 and 1.35 (doublets, J=7 Hz, 6H), 2.30 (s, 3H), 4.92 (d, J=10 Hz, 1H), 6.8-7.45 (m, 4H); and Anal. Calcd for C 21 H 31 N 3 .HBr: C, 62.05% H, 7.93% N, 10.34% and Found: C, 61.71% H, 7.81% N, 10.23%.
Similarly, condensation of ethyl iodide with (4a,12a-trans)-5-methyl-1,2,3,4,4a,11,12,12a-octahydro-1-(2-phenoxyethyl)-pyrazino[2', 3'-3,4]pyrido[1,2-a]indole (described in Example 13) gave (4a,12a-trans)-4-ethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydro-1-(2-phenoxyethyl)-pyrazino[2', 3'-3,4]pyrido[1,2-a]indole; and the dihydrochloride salt thereof: mp 230°-231° C. (crystallized from methanol-diethyl ether); IR (mineral oil) 2440 cm -1 ; UV max (MeOH) 224, 276, and 285 nm (ε 41900), (8740), and (8320) resp.; NMR (DMSO-d 6 ) ε 1.13 (t, J=6.5 Hz, 3H), 2.41 (s, 3H), multiplets centered at 2.2, 2.8, 3.65, and 4.35 (15H), 5.3 (d, J=9 Hz, 1H), 6.7-7.55 (m, 9H); and Anal. Calcd for C 25 H 31 N 3 O.2HCl: C, 64.92 % H, 7.19% N, 9.06% and found: C, 64.92% H, 7.13% N, 9.02%.
Similarly, condensation of ethyl bromide with (4a,12a-trans)-7-bromo-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (described in Example 13) gave (4a,12a-trans)-7-bromo-4-ethyl-5-methyl-1-(1-methylethyl)-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole: mp 125° C. (crystallized from diethyl ether); NMR (CDCl 3 ) ε 0.95 and 1.16 (doublets, J=7 Hz, 6H), 1.03 (t, 3H), and 7.58 (d, 1H); and Anal. Calcd for C 20 H 28 BrN 3 : C, 61.53% H, 7.23% N, 10.77% and Found: C, 61.47% H, 7.20% N, 10.77%; and the corresponding dihydrochloride salt thereof: mp 228° C. (crystallized from methanol-isopropanol).
EXAMPLE 18
(4a,12a-cis)-5-Methyl-1-[2-(phenoxy)ethyl]-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (Ib: R 1 and R 3 =H, R 2 =Me and R 4 =CH 2 CH 2 OC 6 H 5 )
In the initial attemps to form the maleate and dimethansulfonate salts of (4a,12a-trans)-5-methyl-1-[2-(phenoxy)ethyl]-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (2.1 g, described in Example 13), the latter compound was repeatedly liberated by partitioning between CH 2 Cl 2 and 10% aq. NaOH. Attempts to crystallize the salts involved heating in methanol, acetonitrile, and in the case of dimethanesulfonate, heating in aqueous methanol. Finally, the TLC (silica gel, CHCl 3 -hexane-MeOH 60:37:3, v/v) analysis of the recovered base showed two spots: the starting trans-product with R f 0.7, and the title cis-product with R f 0.55. The mixture was chromatographed, and the title compound (1.4 g) was separated, and converted to the dihydrochloride salt: mp 230°-232° C. (crystallized from methanol-acetonitrile 1:1, v/v); IR (mineral oil) 3630, 3440, 2700, and 2280 cm -1 ; UV max (MeOH) 224, 272, and 276 nm (ε 42900), (9080), and (9430) resp.; NMR (DMSO-d 6 ) ε 2.35 (s, 3H), 5.30 (br s, 1H), 6.8-7.65 (m, 9H); and Anal. Calcd for C.sub. 23 H 27 N 3 0.2HCl: C, 63.59% H, 6.73% N, 9.67% and Found: C, 62.63% H, 6.77% N, 9.36%.
EXAMPLE 19
(4a,12a-cis)-7-Bromo-1,4-diethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (Ib, R 1 =7-Br, R 2 =Me, and R 3 and R 4 =Et)
A mixture of (4a,12a-trans)-7-bromo-1,4-diethyl-5-methyl-1,2,3,4,4a,11,12,12a-octahydropyrazino[2', 3'-3,4]pyrido[1,2-a]indole (0.3 g, described in Example 12), sodium methoxide (0.3 g), and hexamethylphosphoramide (10 mL) was heated at 190° C. for 24 hr. After cooling, the resulting solution was poured into water, and extracted with diethyl ether. The combined extracts were washed with water, dried (MgSO 4 ), filtered and evaporated. The residual oil was purified chromatographically on a column of silica gel. Elution with methanol-chloroform (1:9, v/v) afforded 0.21 g of the title compound: mp 125° C.; NMR (CDCl 3 ) δ 0.89 and 1.10 (triplets, J=7.5 Hz, 6H), and 2.20 (s, 3H). The corresponding hydrochloride salt (mp 246° C.) was crystallized from acetonitrile or methanol; NMR (DMSO-d 6 ) δ 5.05 (br, s, 1H).
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Herein is disclosed pyrazino[2',3'-3,4]pyrido[1,2-a]indole derivatives, therapeutically acceptable acid addition salts thereof, processes for their preparation, methods of using the derivatives and pharmaceutical compositions. The derivatives are useful for treating hypertension in a mammal.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a reactive ion etching method applied in the process of manufacturing a semiconductor, and more particularly, to a method of etching an object mass containing an interposed thin insulation layer prepared from silicon dioxide, silicon nitride or the like.
2. Description of the Prior Art
As a semiconductor integrated circuit increases in density, the patterned size of its gate material and wiring material is reduced to less than 1 micron. For the formation of such an extremely fine pattern, reactive ion etching is now considered indispensable as an art of effectively etching exactly the true patterned size of, for example, a resist mask. This reactive ion etching allows for anisotropic etching. The fundamental principle of said reactive ion etching (illustrated in FIG. 1) is described below. High frequency power is impressed in a decompressed condition between a pair of flat parallel electrode plates which are set opposite each other (namely, the upper electrode plate 1, for example, is grounded, and high frequency power is impressed on the lower electrode plate 2, which is parallel to said upper electrode plate 2, from a high frequency power source 3 through an impedance matching device 4 and blocking capacitor 5). At this time, discharge takes place between both electrode plates 1, 2, giving rise to the distribution of D.C. potential between said electrode plates 1, 2. As a result, a noticeable D.C. potential difference (cathode drop voltage V dc ) arises particularly in the vicinity of the lower electrode plate 2 which has been impressed with high frequency power. Referring to the above-mentioned D.C. potential distribution, V p denotes plasma potential. Positive voltage is impressed on the plasma side, while negative voltage is impressed on the lower electrode plate. The above-mentioned cathode drop voltage V dc arises from the fact that after the start of the discharge, a larger amount of electrons than positive ions is carried into the lower electrode plate 2, and consequently, the electrons are stored in said lower electrode plate 2. The magnitude of said cathode drop voltage V dc is determined by the difference between the mobilities of ions and electrons and the area ratio between cathode and anode. When, therefore discharge takes place in a reactive gas atmosphere mainly consisting of a halogen, the positive ions of the halogen are accelerated by the cathode drop voltage V dc in a D.C. field and are carried into the lower electrode plate 2 impressed with high frequency power or into an object to be etched placed on said lower electrode plate 2. Further description may now be made with reference to FIG. 2. Ions 8 of a reactive gas are not carried into that portion of the object of etching 6 in which the mask material 7 is mounted, namely, that portion thereof which is concealed by said mask material 7. Therefore, anisotropic etching true to the patterned size of a mask is effected.
In connection with the above-mentioned reactive ion etching process, reference is made to three conductive layers mounted on a semiconductor substrate with a thin insulation layer interposed therebetween. In this case, it sometimes happens that in the breakdown voltage test after etching, the damage to said insulation layer is detected.
Particularly in the case of, for example, an LSI element, high integration results in a decrease in the minimum width of said element, and further causes the thickness of an oxide gate membrane to be reduced to, for example, 400 Å at 64 KDRAM, or 250 Å at 256 KDRAM. When the aforementioned plasma etching was applied to a polycrystalline silicon layer, a refractory metal layer, or layer consisting of refractory metal silicide which was deposited on such an extremely thin oxide layer, then the underlying oxide layer was noticeably reduced in its breakdown voltage, thus failing to fully function as an insulation layer. In this connection, experimental data is set forth in FIG. 3A on the frequency of the damage to the oxide insulation layer. In comparison, FIG. 3B indicates experimental data on the frequency of the damage to the oxide insulation layer when the aforementioned polycrystalline silicon layer, the refractory metal layer, or the layer consisting of refractory metal silicide deposited on the extremely thin gate oxide layer was subjected to a chemical dry-etching process giving rise to no accumulation of electrical charge. Etching was applied to a phosphorus-doped polysilicon layer deposited on a silicon wafer with a gate oxide having a thickness of 400 Å. FIGS. 3A and 3B indicate the relationship between the gate breakdown voltage (a breakdown electrical field as converted per 1 cm of thickness) and the number of damaged samples. The above-mentioned data clearly show that the reactive ion etching process damages the gate insulation layers on a larger number of samples in a region of lower voltage than the chemical dry etching process.
SUMMARY OF THE INVENTION
This invention has been accomplished in view of the above-mentioned circumstances, and is intended to provide a reactive ion etching method which can effect the anisotropic etching of an object without damaging the thin insulation layer included in said object of etching.
To attain the above-mentioned object, this invention provides a reactive ion etching method which comprises the steps of mounting an object of etching comprising 3-ply structure consisting of a conductive layer formed on a semiconductor substrate with a thin insulating layer interposed therebetween, and impressing high frequency power between a pair of mutually facing electrodes in an atmosphere of reactive gas to etch said object. After the etching and immediately before stopping the impressing of said high frequency power, gradual reduction is effected in the cathode drop voltage, arising in the proximity of that electrode to which said high frequency power is supplied. Upon stopping the supply of high frequency power, voltage impressed on the insulation layer included in the object of etching by the reverse flow of an electrical charge accumulated in the lower electrode; is made to fall below the breakdown voltage of said insulation layer. Thereafter, the impression of said high frequency power is stopped.
The present inventors searched for the cause of the damage to an insulation layer occurring during one reactive etching, and discovered that when the impression of high frequency power was stopped after one completion of etching, an electrical charge accumulated in the lower electrode 2 made a reverse flow, as previously described, and converged toward both sides of the insulation layer included in the object of etching. When said concentration grow noticeably, the insulation layer was damaged. For instance when etching was carried out by supplying a high frequency power of 500 watts and said supply was stopped without taking any precautionary measure, a peak value of voltage temporarily impressed on the insulation layer substantially corresponded to the cathode drop voltage V dc (approximately 225 V as determined from FIG. 4), a sufficiently high enough level to damage the insulation layer.
The present inventors further noticed that the magnitude of the cathode drop voltage V dc depended on the level of the high frequency power, the pressure of reactive atmospheric gas, and the ratio between the areas of the anode and cathode of an etching apparatus. The inventors succeeded in preventing the deterioration of the breakdown voltage of the underlying insulation layer by the steps of controlling the abovementioned factors immediately before stopping the impression of the high frequency power, gradually reducing the cathode drop voltage V dc below a prescribed level, and finally stopping the impression of the high frequency power. FIG. 4 indicates the relationship between the cathode drop voltage V dc and high frequency power and proves that said cathode drop voltage V dc is directly proportional to the high frequency power. FIG. 5 shows the relationship between the level of the cathode drop voltage V dc and the pressure of the reactive atmospheric gas and proves that said cathode drop voltage V dc is inversely proportional to the pressure of the reactive atmospheric gas. FIG. 5 shows a curve determined when a composite gas, consisting of 20 SCCM of Cl 2 and 6 SCCM of H 2 , was introduced and an RF power of 500 W (0.3 W/cm 2 ) was applied.
Description may now be made of the relationship between the ratio which the area of the anode bears to that of the cathode and the cathode drop voltage V dc . Let it be assumed that A a denotes the area of the anode, A c represents the area of the cathode, and V a shows the level of reduced voltage on the anode. Then the following equation results: ##EQU1## where: α=2 to 4
V a =a difference between the potentials of the plasma and anode and, when the anode is grounded, a value equal to a plasma potential V p (that is, V a =V p )
In the ordinary RIE, the equation A a >>A c is established. V dc generally has a large value. When, however, the ratio between the areas of A c and A a is so reduced as to approach 1, when V dc can fall to the proximity of V p . V p stands at 20 to 30 volts under ordinary conditions. The concrete process of decreasing the ratio of A a /A c should advisably be carried out by the steps of reducing the interelectrode distance and reducing the area of the wall of the plasma etching device (which acts as an anode when grounded).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates the fundamental principle of the reactive ion etching method;
FIG. 2 is a cross sectional view of an object of etching subjected to anisotropic etching;
FIGS. 3A and 3B, respectively, graphically show the experimental data on the damage to an insulation layer, included in an object of etching, when subjected to the reactive ion etching and chemical dry etching;
FIG. 4 is a curve diagram showing the relationship between the level of the cathode drop voltage occurring in the proximity of the lower electrode of FIG. 1 and the magnitude of high frequency power;
FIG. 5 graphically indicates the relationship between the cathode drop voltage V dc and the pressure of the reactive atmospheric gas;
FIG. 6 is a cross sectional view of a plasma etching apparatus used in the reactive ion etching method embodying this invention;
FIG. 7 is a cross sectional view of an object of etching used in the subject reactive ion etching method; and
FIGS. 8 and 9, respectively, graphically show the relationship between the frequency of the damage to an insulation layer and the level of a breakdown electrical field.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A description may now be made with reference to the accompanying drawings of a reactive ion etching method embodying this invention.
FIG. 6 is a cross sectional view of a plasma etching apparatus used in the reactive ion etching method embodying this invention. Reference numeral 10 is a stainless steel vacuum vessel. Provided in parallel in the vacuum vessel 10 are an upper plate electrode 11 and a lower plate electrode 12 which constitute part of the wall of said vacuum vessel 10. The plate electrodes 11, 12 are insulated from the vacuum vessel 10 by the corresponding Teflon rings 13, 14. An object of etching 30 is mounted on the lower plate electrode 12. The plate electrodes 11, 12 are respectively cooled by water running through cooling pipes 15, 16 penetrating said plate electrodes 11, 12. Reactive gas is taken into the vacuum vessel 10 through an inlet 17 formed in the center of the upper plate electrode 11. The vacuum vessel 10 is evacuated by, for example, a rotary pump (not shown) through an exhaust pipe 18 provided below the vacuum vessel 10. An output from the RF power source 19 is supplied to the upper plate electrode 11 or lower plate electrode 12 through the corresponding, matching apparatuses 21, 22 by means of a changeover switch 20. The vacuum vessel 10 is always grounded. The plate electrode 11 or 12, which is not impressed with high frequency power, is grounded by one corresponding changeover switch 23 or 24.
FIG. 7 is a cross sectional view of an object of etching 30 etched by the method of this invention and involving the application of the aforementioned plasma etching apparatus. Said object of etching 30 is a mass constructed by growing an oxide layer 32 having a thickness of 400 Å on a 4-inch P type single crystal silicon substrate 31 by a thermal oxidation process, and further depositing a polycrystalline silicon layer 33 with a thickness of 4000 Å on said thermally oxidized layer 32. Said polycrystalline silicon layer 33 is doped with diffused phosphorus. A resist layer 34 having a prescribed pattern is formed on the surface of said doped polycrystalline silicon layer 33. In this case, it is possible to apply an insulation layer, for example, a thermally grown silicon nitride layer, in place of said thermally oxidized layer 32. The polycrystalline silicon layer 33 is marked with a resist layer 34 to expose a region of etching. The etching region may be formed not only in a polycrystalline silicon layer, but also an amorphous silicon layer, a refractory metal layer, a metal silicide compound layer, a laminate consisting of said polycrystalline silicon layer and refractory metal layer, or a laminate formed of said polycrystalline silicon layer and silicide compound layer.
When work is applied to the polycrystalline silicon layer 33 deposited on the thin insulation layer 32, and thereafter an insulation layer (for example, a CVD SiO 2 layer) superposed over said polycrystalline silicon layer 33 is subjected to reactive ion etching, or reactive ion etching is applied to a conductive layer of, for example, aluminum alloy mounted on said insulation layer, the reactive ion etching method of this invention can be applied.
The application of the subject reactive ion etching by the aforementioned apparatus is carried out by the following steps. First, the vacuum vessel 10 is evacuated by an evacuation pump through the exhaust pipe 18 to maintain the degree of vacuum in the vacuum vessel 10 at a prescribed level (for example, 0.08 Torr). A reactive gas (in the case of this invention, a gaseous mixture of Cl 2 and H 2 ) is taken into the vacuum vessel 10. High frequency power of, for example, 500 watts is impressed on the lower electrode 12 from a high frequency power source 19 through impedance matching devices 21, 22. As a result, discharge arises between the upper and lower electrodes 11, 12, giving rise to the aforementioned distribution of D.C. potential in the area defined between both electrodes 11, 12. Cathode drop voltage V dc is applied particularly in the proximity of the lower electrode 12. The positive ions of the reactive gaseous mixture are accelerated and perpendicularly brought into the surface of a wafer mounted on the lower electrode 12. As a result, the phosphorus-doped polysilicon layer (gate material) formed on the wafer is anisotropically etched.
Further according to the reactive ion etching method of this invention, the high frequency power is gradually decreased to about 50 watts immediately before the impression of the high frequency voltage is stopped after the completion of etching. This enables the total voltage stored in a capacitor surrounding the gate insulation layer to drop to a lower level than the breakdown voltage of the gate insulation layer (when the gate insulation layer has a thickness of 400 Å, its breakdown voltage ranges between 30 and 40 volts). If, thereafter, the impression of the high frequency voltage is stopped, it is possible to prevent transitory, excessively high voltage from being impressed on the gate insulation layer, thereby substantially eliminating the damage of said gate insulation layer. The cathode drop voltage V dc arising when the high frequency power is reduced to 50 watts, as described above, substantially stands at 25 volts as seen from FIG. 4. FIG. 8 shows the experimental data on the frequency of the damage to the insulation layer which arises from stopping the impression of high frequency power. A comparison between said experimental data and the data of FIG. 3A, obtained from the conventional reactive ion etching method, clearly proves that the reactive ion etching method of this invention ensures a noticeable decrease in the frequency of damage to the insulation layer occurring in a small breakdown electrical field.
A description may now be made of another example of this invention in which the cathode drop voltage V dc was made to drop by varying the pressure of a reactive atmospheric gas. First, an object of etching 30 was set at the prescribed spot on the surface of the lower electrode 12 as shown in FIG. 6. Etching was applied to an object of etching 30, formed of a polycrystalline silicon layer 33, under the following conditions. A gaseous mixture consisting of 20 SCCM of Cl 2 and 6 SCCM of H 2 was taken into the vacuum vessel 10 in such a manner that the pressure of the interior of said vacuum vessel 10 stood at 0.07 Torr. The radio frequency power source 19 supplied a power of 13.56 Hz 0.3 w/cm 2 to the lower electrode 12. Under the above-mentioned condition, etching was carried out with a resist layer used as a mask. The cathode drop voltage V dc reached 300 volts, and anisotropic etching was applied to the polycrystalline silicon layer 33. The flow rate of the reactive gas was increased 5 seconds before the radio frequency power source 19 ceased to supply power, thereby increasing the pressure of the interior of the vacuum vessel 10 to 0.2 Torr. At this time, the cathode drop voltage dropped to a lower level than 100 volts. After this condition was maintained for several seconds, the radio frequency power source 19 stopped operation, thereby bringing the subject etching to an end. In this case, the process of elevating the pressure of the interior of the vacuum vessel 10 may be carried out not only by increasing the flow rate of the reactive etching gas, but also by introducing other gas into the vacuum vessel 10 or by throttling the valve of the evacuation system.
After being subjected to the reactive ion etching, the object body 30 was washed with a solution containing sulfuric acid to remove the resist layer 34. Thereafter, determination was made of the distribution of the breakdown electrical field of the thermally oxidized layer 32; the results being set forth by a numeral I given in FIG. 9. This FIG. 9 shows that the breakdown electrical field of the thermally oxidized layer 32 indicated a voltage of 10 MV/cm, substantially equal to its intrinsic breakdown voltage. Now let it be assumed that the electrode of the polycrystalline silicon layer 33 has an area of 10 mm 2 , and that when a given level of voltage is impressed on said electrode, a current of 1 μA flows through said electrode. As used herein, the breakdown electrical field is defined to have a voltage represented by a value arrived at by dividing said current of 1 μA by the thickness of the thermally oxidized layer 32 (assumed to be 400 Å). Following is the reason why the breakdown electric field of the thermally oxidized layer 32 has such a high value. When the pressure of the interior of the vacuum was raised immediately before the radio frequency power source 19 ceased to be operated, the cathode drop voltage V dc was reduced. Therefore, an electrical charge accumulated in a block condenser (not shown), interposed between the matching device 21 and the lower electrode 12, was gradually discharged. Thereafter the radio frequency power source 19 stopped operation. As a result, it is supposed that a highly intensive electrical field was prevented from being applied to the front and back planes of the thermally oxidized layer 32 as a transitory current.
To effect comparison with the reactive ion etching method of this invention, a plasma etching apparatus and object of etching 30 with having the same type as described above were provided. Said object of etching 30 was etched under the same conditions as applied in the etching method of the invention. In the case of this control, however, the pressure of the interior of the vacuum vessel 10 was not increased. But etching was brought to an end when the radio frequency power source 19 ceased to be operated. Thereafter, the resist layer 34 was removed by a solution containing sulfuric acid. A voltage determination was made of the yield electrical field produced in the case of the above-mentioned control; the results being set forth in FIG. 9, II. This FIG. 9, II clearly shows that the breakdown electrical field produced in the case of the above-mentioned control had a lower voltage than 1 MV/cm, disclosing that the breakdown electric field was noticeably deteriorated as compared with that which is realized in the reactive ion etching of this invention.
As mentioned above, the subject reactive ion etching method offers the advantage that an object body can be subjected to anisotropic etching without destroying a thin insulation layer included in said object body.
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A reactive ion etching method utilizing high frequency voltage wherein cathode drop voltage developed in the vicinity of an electrode disposed for impressing a high frequency power is gradually reduced immediately before stopping the impression of high frequency power at the end of ion etching process, thereby reducing the voltage impressed on an insulation layer within a semiconductor wafer below the breakdown voltage of the insulation layer.
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BACKGROUND OF THE INVENTION
(1) Field of the Invention
This invention relates to table type miniature bowling games that provide for a bowling experience in a self-contained table apparatus.
(2) Description of Prior Art
Prior art devices of this type have been directed to a variety of bowling simulation games in which miniature bowling lanes are used with appropriate scaled down balls and pins to re-create the bowling experience, see for example U.S. Pat. Nos. 3,857,562, 5,096,192, 5,655,768, 6,319,144 and Patent Publication US 2002/0163130 A1.
In U.S. Pat. No. 3,857,562 a miniature bowling game apparatus is disclosed wherein a table top lane, pin setter and ball launcher are used to simulate regulation bowling.
U.S. Pat. No. 5,096,192 discloses a miniature bowling game having a game table with a lane, a pin setting device on one end and a ball guide and release device on the lane's remaining end. This device also includes a ball return extending below the lane surface.
A bowling toy is shown in U.S. Pat. No. 5,655,768 in which a unique ball launching and pin setting apparatus are disclosed. The ball is driven by a spinning engagement wheel. The pin setting apparatus is loaded with pins and then pivoted down into place on one end of the playing surface for pin placement.
In U.S. Pat. No. 6,319,144 a billiard bowling game is disclosed using scale down bowling lanes, balls and pins. It is directed to an automated pin setting device that cleans the lane and resets the pins for the next player similar to that found in regulation bowling alleys.
Patent Publication 2002/0163130 A1 discloses a shell and chance game that utilizes a preset arrangement of receivers at one end within a ball and ball launcher to propel a ball towards the receivers for hopeful engagement there within.
SUMMARY OF THE INVENTION
The present invention defines a self-contained scale down bowling experience utilizing miniature bowling balls and pins for use on a table lane configuration. An adjustable ball director and launcher allows handicapped individuals and the elderly to aim and roll the ball towards the pins using only arm and hand motion by gripping and pushing a drive cue. A ball containment shoe bracket within the lane area stabilizes and aligns the ball on the lane.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view with portions broken away of a bowling game of the invention;
FIG. 2 is a top plan view thereof;
FIG. 3 is an enlarged partial top plan view of a ball aiming and launching device of the invention; and
FIG. 4 is an enlarged sectional view on lines 4 — 4 of FIG. 3 .
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIGS. 1 and 2 of the drawings, a bowling game 10 of the invention can be seen having a main support table 11 defining a game lane 12 with upstanding elongated side rails 13 and 14 . Pairs of folding support legs 15 and 16 extend from the underside 17 of the table 11 as is typically known within the art.
The game lane 12 and table 11 has an end rail 18 which in combination with the side rails 13 and 14 define the length and width of the game lane 12 . A ball aiming and launching device 20 is removably positioned on one end 21 of the game lane 12 having a main body member 22 . A guide rail 23 extends transversely across the game lane 12 in spaced parallel relation to said end rail 18 which together form guide tracks 24 for the main body member 22 . A pair of guide channels 25 and 26 are formed on the undersides of the main body member 22 and are registerable with the hereinbefore described end and guide rails 18 and 23 respectively as shown in dotted lines in FIG. 3 and solid lines in FIG. 4 of the drawings.
The alignment and launching device 20 of the game has a pair of guide bores at 27 and 28 extending transversely therethrough which through which a slidably positioned corresponding ball cue 29 can be selectively positioned therein. Ball engagement shoes 30 A and 30 B are secured to a front surface 20 A of the launching device 20 extending into the game lane 12 . The ball shoes 30 A and 30 B are identical having a back plate 31 with spaced opposing side plates 32 extending at right angles therefrom.
The ball cue 29 is extended selectively through the guide bores 27 and 28 in the main body member 22 and define hand grip portion 33 thereon as best seen in FIG. 3 of the drawings.
A pair of viewing slots S are formed in the top surface of the alignment and launching device 20 extending inwardly from the front surface 20 A and align with the respective guide bores 27 and 28 so as to allow for viewing the end of the cue 29 for striking a scaled down bowling ball 41 .
It will be evident from the above description that the alignment and launching device 20 of the game can be slidably repositioned transversely along the length of the respective end and guide rails 18 and 23 by an attached handle H which will allow for full lane positioning of one or more of the other ball shoes 30 A and 30 B and engageable ball cue 29 as described.
The game lane 12 is further defined by a pair of parallel spaced recessed gutter surfaces 34 and 35 which extend longitudinally the length of the game lane 12 spaced inwardly from the respective side rails 13 and 14 forming ball gutters 36 and 37 thereon emulating a real bowling alley (not shown).
A pin placement area 38 in the game lane 12 is an oppositely disposed longitudinal relation to said alignment and launching device 20 of the game adjacent the end of the game lane 12 . A plurality of scaled down bowling pin representations 39 are “set” thereon, again to simulate a real bowling experience. Each of the pins 39 have a multi-sided flat side surfaces 39 A with a reduced diameter base 39 B for lane engagement. This prevents the pins 39 from rolling excessively about the game lane 12 after they are struck during play. A pin repository and launching device storage case 40 is removably attached below the end 19 of the game lane surface 12 and acts as a pin repository during use which will be described in greater detail hereinafter.
In use, the scaled down bowling ball 41 of the game, shown in broken lines in FIGS. 3 and 4 of the drawings, is positioned within either of the respective ball shoes 30 A or 30 B. Ball placement depends on where the alignment and launch device 20 of the game has been positioned by the player, (not shown) along the guide rails 18 and 23 to line up for the next “roll” of the bowling ball 41 . The hand grip portion 33 of the cue 29 is then grasped by the player to strike the bowling ball 41 positioned within the respective ball shoe as down the game lane 12 towards the pins 39 within the pin placement area 38 as hereinbefore described.
The ball gutters 36 and 37 on either side of the game lane 12 are used to retrieve the bowling ball 41 back to the alignment and launching device 20 of the game for reuse. Alternately, just as in real bowling an errant ball “roll” will deposit the bowling ball 41 into the respective gutters 36 and 37 , although by use of the alignment and launching device 20 of the game there is less likelihood of doing so.
The storage case 40 is divided up into multiple receiving areas 42 , 43 , and 44 for the respective pins 39 , ball 41 , cues 29 and alignment and launching device 20 .
It will be evident that due to the relative height of the game table 11 , it allows individuals in wheelchairs to easily play the game. Also by directing the bowling ball 41 by use of the cue 29 and ball shoes 30 A and 30 B diminished physical ability will not prevent the participation by potential users in the game.
It will thus be seen that a new and novel bowling ball game has been illustrated and described and it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the spirit of the invention.
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A bowling game table having a game lane surface with oppositely disposed ball return gutters, multiple ball engagement shoes are movably positioned transversely at one end thereof with a plurality of pins set up at the other end thereof. An independent playing cue selectively registerable through and aligned with said ball engagement shoes. Selective ball positioning on the game lane within said ball engagement shoes before launch towards the pins by engagement with said cue.
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[0001] This Application is a division of U.S. patent application Ser. No. 11/184,695 filed on Jul. 19, 2005, which is a division of U.S. patent application Ser. No. 10/604,164 filed on Jun. 28, 2003, now U.S. Pat. No. 6,951,775.
FIELD OF THE INVENTION
[0002] The present invention relates to the field of semiconductor processing; more specifically, it relates to a method of forming a solder interconnect structure on a thin wafer.
BACKGROUND OF THE INVENTION
[0003] Increasing density of semiconductor devices has allowed semiconductor chips to decrease in area. Along with the decrease in chip area, has come a need to make the semiconductor chips thinner. Current methods of thinning semiconductor wafers often lead to damage of the semiconductor chips.
SUMMARY OF THE INVENTION
[0004] A first aspect of the present invention is a method of forming a semiconductor interconnect comprising, in the order recited: (a) providing a semiconductor wafer; (b) forming bonding pads in a terminal wiring level on the frontside of the wafer; (c) reducing the thickness of the wafer; (d) forming solder bumps on the bonding pads; and (e) dicing the wafer into bumped semiconductor chips.
[0005] A second aspect of the present invention is a method of forming a semiconductor interconnect comprising, in the order recited: (a) providing a semiconductor wafer; (b) forming bonding pads in a terminal wiring level on the frontside of the wafer; (c) reducing the thickness of the wafer to produce a reduced thickness wafer; (d) providing an evaporation fixture comprising a bottom ring, a shim, an evaporation mask and a top ring; (e) placing the shim into the bottom ring; (f) placing the reduced thickness wafer on the shim; (g) placing on and aligning the mask to the reduced thickness wafer; (h) placing said top ring over said mask and temporarily fastening said top ring to said bottom ring; (i) evaporating solder bumps on the bonding pads through the mask; (j) removing the reduced thickness wafer from the fixture; and (k) dicing the reduced thickness wafer into bumped semiconductor chips.
[0006] A third aspect of the present invention is A fixture for holding wafer and an evaporative mask comprising: a bottom ring having a inner periphery and an outer periphery, the bottom ring having a raised inner lip formed along the inner periphery and a raised outer lip formed along the outer periphery, the height of the inner lip above a surface of the bottom ring being greater than a height of the outer lip above the surface of the bottom ring; a shim having a inner and an outer periphery, the outer periphery of the shim fitting inside and in proximity to the outer lip of the bottom ring, a bottom surface of the shim proximate to the inner periphery of the shim contacting an upper surface of the inner lip of the bottom ring; a top ring having an inner periphery and an outer periphery, the top ring having a lower raised lip formed along the inner periphery of the bottom ring and extending below a bottom surface of the top ring; and the bottom ring and the top ring adapted to press a bottom surface of the wafer against an upper surface of the shim and to press a top surface of the wafer against a bottom surface of the mask and to press a top surface of the mask proximate to the periphery of the mask against a lower surface of the lower raised lip of the top ring.
BRIEF DESCRIPTION OF DRAWINGS
[0007] The features of the invention are set forth in the appended claims. The invention itself, however, will be best understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
[0008] FIGS. 1A through 1F are partial cross-sectional views of the fabrication of a semiconductor wafer according to the present invention;
[0009] FIG. 2 is a cross-sectional view through an interconnect structure formed by the present invention;
[0010] FIG. 3A is a top view of a base portion of a wafer to mask alignment fixture for forming interconnects according to the present invention;
[0011] FIG. 3B is a cross-section view through line 3 B- 3 B of FIG. 3A ;
[0012] FIG. 4 is a top view of an evaporative mask portion of the wafer to mask alignment fixture for forming interconnects according to the present invention;
[0013] FIG. 5A is a top view of a top portion of the wafer to mask alignment fixture for forming interconnects according to the present invention;
[0014] FIG. 5B is a cross-section view through line 5 B- 5 B of FIG. 5A ;
[0015] FIG. 6A is a top view of a shim portion of a wafer to mask alignment fixture for forming interconnects according to the present invention;
[0016] FIG. 6B is a cross-section view through line 6 B- 6 B of FIG. 6A ;
[0017] FIG. 7 is a partial cross-section view through the assembled wafer to mask alignment fixture for forming interconnects according to the present invention; and
[0018] FIG. 8 is a partial cross-section view through the assembled wafer to mask alignment fixture for forming interconnects illustrating dimensional relationships between the component parts of the wafer to mask alignment fixture according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0019] For the purposes of the present invention, the terms substrate and wafer may be used interchangeably.
[0020] FIGS. 1A through 1F are partial cross-sectional views of the fabrication of a semiconductor wafer according to the present invention. In FIG. 1A , a substrate 100 such as a semiconductor bulk silicon substrate or a semiconductor silicon-on-insulator (SOI) substrate has a thickness T 1 . Formed in/on substrate 100 is a multiplicity of active Field effect transistors (FETs) 105 . FETs 105 include gate electrodes 115 formed over gate dielectric formed 116 and between spacers 117 on a top surface 110 of substrate 100 and source/drains 118 formed in the substrate. FETs 105 are exemplary of devices and structures normally found in semiconductor circuits of semiconductor chips and many other structures and devices such as capacitors, resistors, inductors, bipolar transistors and diffused and dielectric isolation. FETs 105 are wired into circuits in a first wiring level 120 A, a second wiring level 120 B, a third wiring level 120 C and a terminal wiring level 120 D. First wiring level contains contacts 125 interconnecting FETs 105 to conductors 125 B in second wiring layer 120 B. Conductors 125 B are in turn connected to conductors 125 C in third wiring level 120 C. Conductors 125 C are in turn connected to terminal conductors 125 D in terminal wiring level 120 D. Terminal conductors 125 D include a multiplicity of bonding pads 130 . Bonding pads 130 are exposed on surface 135 of terminal wiring layer 120 D. First wiring level 120 A, second wiring level 120 B, third wiring level 120 C and terminal wiring level 120 D are exemplary of wiring levels found in semiconductor chips and more or less wiring levels fabricated by any number of methods well known in the art such as subetch, liftoff, damascene and dual damascene may be used. Substrate 100 has a backside surface 140 .
[0021] In FIG. 1B , wafer 100 A is reduced from thickness T 1 (see FIG. 1A ) to a new thickness T 2 (where T 1 >T 2 ) by any number of wafer thinning techniques well known in the art. In a first example, backside surface 140 (see FIG. 1A ) is ground down to a new backside surface 145 by grinding the backside surface with a rotating diamond grindstone. In a second example, backside surface 140 (see FIG. 1A ) is etched down to new backside surface 145 by etching the backside surface with a mixture of hydrofluoric and nitric acids while rotating the wafer. In a third example, backside surface 140 (see FIG. 1A ) is lapped down to new backside surface 145 by introducing a slurry containing abrasive particles between the backside of the wafer and a rotating wheel. In a fourth example, backside surface 140 (see FIG. 1A ) is chemical-mechanical-polished (CMP) down to new backside surface 145 by introducing a slurry containing abrasive particles mixed with a silicon etchant solution between the backside of the wafer and a rotating wheel.
[0022] In one example of thinning, a 200 mm diameter wafer having an initial thickness T 1 of about 650 to 780 microns is thinned to a new thickness T 2 of about 150 to 450 microns. The present invention may be practiced using any diameter wafer including 100 mm, 125 mm and 300 mm wafer of any initial thickness T 1 , reducing the wafer to any final thickness T 2 as required by the use of the finished chip.
[0023] In FIG. 1C an evaporative mask 150 having openings 155 is placed on top surface 135 (or very close to top surface 135 ) of terminal wiring level 120 D. Openings 155 are aligned to bonding pads 130 . Openings 155 have inner knife-edges 160 . Evaporative mask 150 is typical of the type of mask used to fabricate controlled collapse chip connection (C 4 ) interconnect structures. C 4 interconnect structures are also known as solder bump interconnections. In one example, mask 150 is made from molybdenum.
[0024] In FIG. 1D , a pad limiting metallurgy (PLM) 165 is evaporated through opening 155 onto bonding pads 130 . PLM 165 is discussed more fully infra in reference to FIG. 2 . PLM is also known as ball limiting metallurgy (BLM).
[0025] In FIG. 1E , mask 150 is not moved and a solder bump 170 is evaporated through opening 155 onto PLM 165 . Solder bump 170 has the shape of a truncated cone.
[0026] In FIG. 1F , mask 150 (see FIG. 1E ) is removed and a reflow anneal is performed in order to reshape solder bumps 170 into semi-spherical solder bumps (also known as solder balls or C 4 balls) 170 A. Solder bumps 170 A are discussed more fully infra in reference to FIG. 2 .
[0027] FIG. 2 is a cross-sectional view through an interconnect structure formed by the present invention. In FIG. 2 , terminal wiring level 120 D includes bonding pad 125 D embedded in a dielectric layer 175 . In one example, bonding pad 125 D is aluminum, copper or alloys thereof. Formed on top of dielectric layer 175 is an optional capping layer 180 . In one example, capping layer 180 is silicon nitride. Formed on top of capping layer 180 is an optional passivation layer 185 . In one example, passivation layer 185 is silicon dioxide, silicon nitride, silicon oxynitride or combinations thereof. Formed on top of passivation layer 185 is an optional dielectric layer 190 . In one example, dielectric layer 190 is polyimide. An optional via 195 is provided through capping layer 180 , passivation layer 185 and dielectric layer 190 exposing bonding pad 125 D in terminal wiring level 120 D. Via 195 may be formed by any number of well known plasma etch techniques. PLM 165 is formed over dielectric layer 190 , sidewalls of via 195 and exposed portions of terminal wiring level 120 D. In one example, PLM 165 is titanium nitride, copper, gold, titanium-tungsten, chrome, chrome-copper or combinations thereof. A typical combination is gold over copper over chrome. Another typical combination is copper over chrome copper over titanium-tungsten. PLM 165 is in electrical contact with bonding pad 130 . C 4 ball 170 A is formed on and in electrical contact with PLM 165 . Examples of C 4 ball 170 A compositions include but are not limited to 95% lead and 5% tin, 97% lead and 3% tin, 100% lead, other lead alloys, 100% tin and tin alloys. In one example, the reflow anneal mentioned supra is performed at a temperature of between about 350° C. and 380° C. in a reducing atmosphere such as hydrogen or forming gas. Thinned substrate 100 A (see FIG. 1F ) may now be diced into individual thin chips.
[0028] The evaporation process for forming PLMs 165 and solder bumps 170 (see FIG. 1E ) is performed by placing the semiconductor substrate in wafer to mask alignment fixture that allows alignment of mask 150 to thinned substrate 100 A (see FIG. 1E ). The evaporation process includes loading multiple wafer to mask alignment fixtures (with wafers and masks and in the case of the present invention, shims) into spaces in a dome of a multi-source evaporator and each material of PLM and then the solder pad are evaporated onto contacts pads on the wafer through holes in a mask. Such a wafer to mask alignment fixture is illustrated in FIGS. 3A, 3B , 4 , 5 A, 5 B, 6 A and 6 B and described infra.
[0029] FIG. 3A is a top view of a base portion of a wafer to mask alignment fixture for forming interconnects according to the present invention and FIG. 3B is a cross-section view through line 3 B- 3 B of FIG. 3A . In FIGS. 3A and 3B , a bottom ring 200 includes an outer lip 205 and an inner lip 210 joined by an integral plate portion 215 . Inner lip 210 defines the extent of an opening 220 centered in bottom ring 200 . Plate portion 215 includes a multiplicity of openings 225 and a multiplicity of retaining post holes 227 . Opening 220 provides access for a wafer handling fixture (not shown) and openings 225 are for thermal expansion and heat retention control. Bottom ring 200 has a diameter D 1 and opening 220 has a diameter D 2 . The inside distance between opposite points on outer lip 205 is D 3 . Outer lip 205 has a height H 1 measured from a top surface 230 of plate portion 215 and inner lip 210 has a height H 2 measured from the top surface of the plate portion. The difference in height between outer lip 205 and inner lip 210 is H 3 where H 3 =H 2 −H 1 and H 2 is greater than H 1 . In one example, for an standard un-thinned 200 mm diameter wafer about 650 microns thick, H 2 is about 0.080 inches and H 1 is about 0.073 inches, making H 3 about 0.007 inches. H 1 and H 2 will vary based on wafer diameters and standard un-thinned wafer thickness.
[0030] FIG. 4 is a top view of an evaporative mask portion of the wafer to mask alignment fixture for forming interconnects according to the present invention. In FIG. 4 , mask 250 includes a multiplicity of openings 255 arranged in groups 260 . Each group 260 corresponds to a chip on a wafer that will be placed under mask 250 as illustrated in FIG. 7 and described infra. Mask 250 has a diameter of D 1 , the same as the diameter of bottom ring 200 illustrated in FIG. 3A and described supra. Mask 250 includes a multiplicity of retaining post holes 262 .
[0031] FIG. 5A is a top view of a top portion of the wafer to mask alignment fixture for forming interconnects according to the present invention and FIG. 5B is a cross-section view through line 5 B- 5 B of FIG. 5A . In FIGS. 5A and 5B , top ring 270 has a lower lip 275 protruding from a bottom surface 280 of the top ring. Lower ring 275 protrudes a distance H 4 . In one example, for a standard 200 mm diameter wafer having a thickness of about 650 microns, H 4 is about 0.002 inches. Top ring 270 includes an opening 280 centered within ring 270 . Top ring 270 has a diameter of D 1 , the same as the diameter of bottom ring 200 illustrated in FIG. 3A and described supra. Top ring 270 includes a multiplicity of retaining posts 282 .
[0032] FIG. 6A is a top view of a shim portion of a wafer to mask alignment fixture for forming interconnects according to the present invention and FIG. 6B is a cross-section view through line 6 B- 6 B of FIG. 6A . In FIGS. 6A and 6B a shim 290 has an opening 295 centered within the shim. Shim 290 has a diameter D 3 A where D 3 A is just slightly smaller than D 3 , the inside distance between opposite points on outer lip 205 (see FIG. 3A ). D 3 is greater than the diameter of the wafer being held in the fixture. Opening 295 has a diameter D 2 the same as the diameter of opening 220 of bottom ring 200 illustrated in FIG. 3A and described supra. Shim 290 has a thickness T 3 . Shim 290 includes a multiplicity of retaining post notches 297 in a perimeter 298 of the shim.
[0033] FIG. 7 is a partial cross-section view through the assembled wafer to mask alignment fixture for forming interconnects according to the present invention. In FIG. 7 , only half of the assembled fixture 300 (about centerline 305 ) is illustrated. To load/assemble fixture 300 , shim 290 is placed in bottom ring 200 (contacting inner lip 210 ), thinned substrate 100 A is placed on shim 290 , mask 250 is placed on thinned substrate 100 A and top ring 270 is placed on mask 250 . Mask 250 is pressed between top ring 270 and outer lip 205 of bottom ring 200 and lower lip 275 of the top ring presses on mask 250 . The only portion of bottom ring 200 contacted by shim 290 is inner lip 210 . Clips (not shown) hold assembled fixture 300 together. Also, alignment pins and alignment holes in bottom and top rings 200 and 270 and alignment holes in mask 250 and shim 290 are present but not illustrated in FIG. 7 . The combination of the difference in heights between outer and inner lips 205 and 210 of bottom ring 200 and the height of lower lip 275 of top ring 270 deflects (or bows) shim 290 , substrate 100 A and mask 250 into very shallow but semi-spherical shapes by pressing the peripheries of mask 250 and substrate 100 A towards bottom ring 200 . The degree of deflection of substrate 100 A is D 4 measured along the top surface of substrate 100 A. The bow imparted to substrate 100 A prevents or reduces such problems associated with evaporation through an knife edge opening in a mask such as sputter haze, PLM flaring and solder pad haloing.
[0034] Retaining post 282 passes through retaining post hole 262 in mask 250 , retaining post notches 297 in shim 290 and retaining post hole 227 in bottom ring 200 . A spring clip 310 engages retaining post 305 and temporarily fastens assembled fixture 300 together.
[0035] FIG. 8 is a partial cross-section view through the assembled wafer to mask alignment fixture for forming interconnects illustrating dimensional relationships between the component parts of the wafer to mask alignment fixture according to the present invention. The dimensions H 1 , H 2 of outer and inner lips 205 and 210 of bottom ring 200 and the dimension H 4 of lower lip 275 of top ring 270 (see FIG. 5A ) are experimentally determined for each combination of wafer diameter and standard un-thinned wafer thickness. Note it is possible that one wafer manufacturer may produce standard 200 mm diameter wafers that are 780 microns thick, while another manufacturer may produce standard 200 mm diameter wafers that are 640 microns thick. Either two sets of fixtures having different values of H 1 , H 2 and H 4 are required, or 640 micron thick wafers are treated as “thin” wafers compared to the 780 micron thick wafers and a single fixture is designed for 780 micron thick wafers. There are two methods of determining the thickness T 3 for shim 290 . The first method is to use the formula T 3 (shim thickness) equals T 1 (un-thinned or standard wafer thickness that fixture is designed for) minus T 2 (thinned wafer thickness). For example, assume a fixture designed for a 200 mm diameter 640 micron thick having values of 0.073 for H 1 , 0.080 for H 2 and 0.002 for H 4 . If the wafer has been thinned to 250 microns, then T 3 will be 390 microns (640−250=390) even if the original thickness of the wafer was greater than 640 microns. If the fixture had been designed for a 780 micron thick wafer than shim 290 , in the present example, would be 530 microns (720−250=530) thick.
[0036] The second method is to experimentally determine for a given thinned wafer thickness (T 2 ) a shim thickness (T 3 ) that yields the same wafer deflection (D 4 ) (see FIG. 7 ) as the un-thinned standard wafer (of thickness T 1 ) that the fixture was designed for. For example assume a fixture designed for a 200 mm diameter 640 micron thick having values of 0.073 for H 1 , 0.080 for H 2 and 0.002 for H 4 . If the wafer has been thinned to 250 microns, then T 3 will be selected from an experimentally determined table of shim thickness (T 3 ) versus thinned wafer thickness (T 2 ) versus wafer deflection (D 4 ) to give the same wafer deflection (D 4 ) with a shim in place as a 640 micron thick wafer even if the original thickness of the wafer was not equal to 640 microns.
[0037] The description of the embodiments of the present invention is given above for the understanding of the present invention. It will be understood that the invention is not limited to the particular embodiments described herein, but is capable of various modifications, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, it is intended that the following claims cover all such modifications and changes as fall within the true spirit and scope of the invention.
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A method of forming a semiconductor interconnect including, in the order recited: (a) providing a semiconductor wafer; (b) forming bonding pads in a terminal wiring level on the frontside of the wafer; (c) reducing the thickness of the wafer; (d) forming solder bumps on the bonding pads; and (e) dicing the wafer into bumped semiconductor chips.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of priority of German Patent Application No. 102007045141.7, filed Sep. 20, 2007. The entire text of the priority application is incorporated herein by reference in its entirety.
FIELD OF THE DISCLOSURE
[0002] The disclosure relates to a plasma processing plant of the type using a processing chamber into which bottles to be processed can be fed, and a supply unit for a process gas.
BACKGROUND
[0003] The preservability of drinks in PET bottles is reduced to an undesirably short period of time by the limited gas tightness of the bottle wall. This applies especially to the storage of carbonated drinks. Hence, various attempts have already been made for improving the gas tightness of the bottle wall by plasma coating, e.g. by applying a gas barrier layer of SiO 2 .
[0004] Such a method is known e.g. from US 2005/0233077 A1 in the case of which up to two PET bottles are arranged in a common processing chamber and evacuated through a respective contact pressure valve and a common line. For this purpose, the bottles are first positioned on the contact pressure valves, the processing chamber being connected to the interior of the bottles in the open condition of the valve. The valve is closed by pressing the bottle thereagainst and the processing chamber is thus sealed against the interior of the bottles. The evacuation of the bottles and of the processing chamber as well as the supply of process gas are controlled through separate valves in the lines.
[0005] U.S. Pat. No. 6,328,805 B1 additionally discloses a plasma processing plant in the case of which the processing chamber and the interior of the bottle are evacuated in common. A valve, which can be used for adjusting the differential pressure, is provided between the processing chamber and an area connected to the bottle interior. The control of the process gas supply is executed via a separate valve. The processing chamber can only accommodate one bottle at a time and is opened between the respective coating processes. The pressure difference adjusted with the aid of the valve thus ceases to exist.
[0006] EP 1 391 535 B1 additionally discloses a contact pressure valve which seals the interior of a bottle to be evacuated against the exterior of said bottle, when the bottle opening is pressed against said valve.
SUMMARY OF THE DISCLOSURE
[0007] It is the aspect of the present disclosure to provide a simplified device for coating continuously fed PET bottles, in particular a plasma processing plant with simplified gas guidance and a smaller number of control mechanisms. More particularly, in one aspect, the disclosure concerns a plasma processing plant of the type using a processing chamber into which bottles to be processed can be fed, a vacuum chamber, a valve which is connected to the vacuum chamber and which, in its open condition, connects the interior of the bottle via an evacuation channel to the vacuum chamber and seals the interior of the bottle agains the processing chamber in a gastight fashion, and further comprising a supply unit for a process gas.
[0008] According to another aspect of the present disclosure, the vacuum chamber is arranged inside the processing chamber so that a plurality of PET bottles can be evacuated successively in a common processing chamber. In view of the fact that the vacuum chamber and the processing chamber are sealed against one another in a gastight fashion throughout the whole coating process, a constant differential pressure can be maintained between said chambers. Since the valve is opened in response to the pressure which the bottle opening applies to the inlet area of the valve, the valve can be opened automatically, e.g. along a guiding rail, and the use of a separate triggering mechanisms can thus be dispensed with.
[0009] Another advantageous embodiment is so conceived that, in the open condition of the valve, the supply unit for a process gas is connected to the interior of the bottle via a supply channel of the valve, whereas, in the closed condition of the valve, the supply channel is interrupted. The use of an additional control mechanism for guiding the process gas can thus be dispensed with.
[0010] A particularly advantageous embodiment is so conceived that, in the closed condition of the valve, the supply unit for the process gas is connected to a discharge channel of the valve. In this case, an additional complicated control of the process gas flow for each individual valve can be dispensed with, when a large number of valves is integrated in a carrousel-type unit.
[0011] According to another embodiment, the discharge channel of the valve is connected to the vacuum chamber. In this case, additional outgoing lines can be dispensed with.
[0012] Another advantageous embodiment is so conceived that a pressure difference continuously exists between the processing chamber and the vacuum chamber. The sequence of evacuation steps can thus be executed and supervised more easily.
[0013] Another particularly advantageous embodiment is so conceived that the vacuum chamber is supported such that it is rotatable relative to the processing chamber. This allows the processing chamber to be designed as a carrousel-type unit in the case of which the bottles are fed continuously and coated at individual stations.
[0014] According to a particularly advantageous embodiment of the present invention, the pressure generated in the interior of the bottle is 10-50 mbar lower than the pressure prevailing in the processing chamber. This creates optimum conditions for igniting the plasma in the bottle interior and for avoiding an ignition of the plasma in the outer area of the bottle as well as a deformation of the bottle caused by an excessively high pressure difference.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] In the following, the present disclosure will be explained in more detail on the basis of an embodiment shown in the drawing, in which:
[0016] FIG. 1 shows a plasma processing plant in a schematic sectional view;
[0017] FIG. 2 shows a valve of the plasma processing plant in a closed condition in a schematic sectional view;
[0018] FIG. 3 shows a valve of the plasma processing plant in an open condition in a schematic sectional view.
DETAILED DESCRIPTION
[0019] FIG. 1 shows a plasma processing plant 1 with a processing chamber 2 for the bottles 3 to be processed, the processing chamber 2 being configured as a carrousel-type unit. A sub-stantially rotation-symmetric vacuum chamber rotates in the interior of the processing chamber 2 about the axis 4 ′. The processing chamber 2 and the vacuum chamber 4 are evacuated so that a predetermined pressure difference between the two chambers 2 and 4 will continuously exist.
[0020] The valves 5 , only two of which are exemplarily shown in FIG. 1 , are arranged in an annular configuration in the circumferential peripheral region of the vacuum chamber 4 . On the upper side of the vacuum chamber 4 , a supply unit 8 for a process gas 9 is arranged above each valve 5 . FIG. 1 shows, on the left, a bottle 3 positioned below the valve 5 and, on the right, a bottle 3 pressed against the valve 5 . An annular or U-shaped electrode 14 extends below the bottles 3 to be processed; said electrode 14 consists preferably of copper, but it can be provided with a coating or jacket consisting e.g. of plastic material. The shape of the electrode 14 is explicitly not limited to a U-shape. The bottles are held by conventional technical means, preferably a holding clip, and they are pressed against the valve. This process can be carried out by a guiding rail or by other means, e.g. by means of electric or pneumatic drives.
[0021] FIG. 2 shows the valve 5 in a closed condition as well as the adjoining areas of the vacuum chamber 4 and of the supply unit 8 for the process gas 9 . The valve 5 is shown schematically in a tripartite form comprising an essentially cylindrical valve body 15 and a plunger 16 which is movable within said valve body 15 and within which the tube 17 , which can be implemented e.g. as a tubular microwave transmitter or as a tubular electrode, is secured in position. For the sake of clarity, the representation of additional sealing components has been dispensed with. The bias of the pressure spring 18 presses the plunger 16 in the direction of the inlet opening 11 against a stop, which is not shown. Hence, the valve 5 is closed at its normal position.
[0022] The lower end face of the plunger 16 defines the inlet area 11 of the valve 5 comprising the evacuation opening 19 and the evacuation channel 7 a . In the closed condition of the valve 5 , the evacuation channel 7 a ends at the wall of the valve body 15 . Hence, the closed valve 5 seals the processing chamber 2 against the vacuum chamber 4 in a gastight fashion.
[0023] The inner wall of the tube 17 defines the supply channel 12 a for the process gas 9 . Since also the upper end of the supply channel 12 a ends at the wall of the valve body 15 in the closed condition of the valve 5 , the supply channel 12 a does not communicate with the supply unit 8 for the process gas 9 when the valve 5 is closed.
[0024] The upper area of the valve body 15 has an inlet opening 21 for the process gas 9 , which communicates with the supply unit 8 and which is connected to the outlet opening 22 via the supply channel 12 b and the discharge channel 13 . In the present embodiment, the outlet opening 22 leads directly into the vacuum chamber 4 so that the process gas 9 will be conducted into said vacuum chamber 4 in the closed condition of the valve 5 . Alternatively, the outlet opening 22 may, however, also be connected to a separate discharge means for the process gas 9 , which is not shown.
[0025] Due to this guidance of the process gas flow, a complicated control of the process gas flow for each individual valve can be dispensed with, when a large number of valves is integrated in a carrousel-type unit. It is, however, also imaginable to interrupt the supply of gas by mechanical, electrical or pneumatic shut-off devices which are coupled to the position of the valve.
[0026] FIG. 3 shows the valve 5 with a bottle 3 connected thereto and in an open condition. Other than in the case of FIG. 2 , the plunger 16 is pressed upwards against the force of the pressure spring 18 by the pressure with which the bottle opening 10 is pressed against the inlet area 11 . This has the effect that a connection will be established between the evacuation channel 7 a in the plunger 16 and the evacuation channel 7 b and the outlet opening 23 in the wall of the valve body 15 . It follows that, in the open condition of the valve, pressure compensation will take place between the vacuum chamber 4 and the interior 6 of the bottle 3 .
[0027] The inlet area 11 of the valve 5 is provided with a suitable sealing element, e.g. a flexible sealing ring, which seals the interior 6 of the bottle 3 against the processing chamber 2 in a gastight fashion.
[0028] Simultaneously, the supply channel 12 a is connected to the inlet opening 21 via the supply channel 12 b and the connection between the supply channel 12 b and the discharge channel 13 is interrupted. The process gas 9 is consequently conducted through the tube 17 and the outlet opening 20 into the interior 6 of the bottle 3 and an ingress of process gas 9 into the processing chamber 2 is prevented by the sealing contact between the bottle opening 10 and the inlet area 11 .
[0029] In addition, the plunger 16 can be configured as a rotatably supported component which allows the bottle 3 to rotate during the process.
[0030] When the bottle 3 is lowered, the valve closes automatically due to the bias of the pressure spring 18 , so that the connection between the channel sections 7 a and 7 b as well as 12 a and 12 b will be interrupted as long as the bottle opening 10 is still in gastight contact with the inlet area 11 . An ingress of process gas 9 into the processing chamber 2 and a pressure compensation between said processing chamber 2 and the vacuum chamber 4 will be prevented in this way. Simultaneously, excessive process gas will be conducted into the vacuum chamber 4 .
[0031] In the following, the mode of operation of the embodiment of a plasma processing plant according to the present invention, which is shown in the drawing, will be explained:
[0032] The bottles 3 to be processed are continuously fed through a pressure lock into the processing chamber 2 that has been evacuated to a predetermined degree and are entrained by holding devices, which are coupled in a suitable fashion to the rotating vacuum chamber 4 , so that each bottle 3 will be positioned below a valve 5 . The bottles 3 are advanced along a guiding rail and are thus pressed against the inlet areas 11 of the valves 5 with their bottle openings 10 , whereby said valves 5 will be opened.
[0033] The individual bottles 3 , which are connected to the open valves 5 , communicate through the evacuation channels 7 a and 7 b with the common vacuum chamber 4 and are evacuated down to a predetermined pressure for a predetermined period of time.
[0034] With simultaneous sealing of the bottle opening 10 , this leads to the generation of a pressure difference between the interior 6 of the bottle 3 and the processing chamber 2 so that, outside the bottle 3 , a plasma cannot ignite, since the external pressure is either too low or too high, whereas the pressure in the interior of the bottle 3 is ideal for a plasma process.
[0035] During evacuation of the bottle 3 , the process gas 9 for the plasma processing is conducted through the supply channel 12 a , 12 b into the bottle 3 . A pressure of approx. 0.1 mbar should prevail in the bottle 3 under a gas load of approx. 50 sccm of process gas 9 (under European standard conditions).
[0036] Since a continuously maintained pressure difference exists between the processing chamber 2 and the vacuum chamber 4 , conditions suitable for igniting the plasma are obtained in all the bottles 3 after an approximately constant period of time after the expiration of which the respective bottle 3 is coated by igniting the plasma.
[0037] In the present embodiment, only the inner wall of the bottle 3 is to be processed by a plasma process. The pressure outside the bottle 3 should be a pressure at which plasma can no longer ignite. Such a suitable pressure is e.g. a relative overpressure of approx. 10 mbar in comparison with the pressure in the interior 6 of the bottle 3 . The relative overpressure must, however, not be excessively high, so that a PET disposable bottle cannot be compressed, i.e. it should be smaller than approx. 40-50 mbar in comparison with the internal pressure.
[0038] Depending on the pressure difference between the processing chamber 2 ad the vacuum chamber 4 , it can, however, also be achieved that the plasma ignites only outside, but not inside the bottle 3 .
[0039] When the bottles 3 have been coated, they are lowered along a descending guiding rail and discharged through a pressure lock.
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A plasma processing plant for plastic bottles, having a vacuum chamber arranged inside the processing chamber and when a respective bottle opening is pressed against a valve, the valve will open and establish a connection between the interior of the bottle and the vacuum chamber, and the chambers are continuously sealed against one another in a gastight fashion. With such approach, the gas can be conducted more easily and the number of control mechanisms can be reduced.
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CROSS REFERENCE TO RELATED APPLICATIONS
This is a Divisional of Application Ser. No. 09/576,761 filed May 24, 2000, now pending, the disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
The invention relates to a twisting nozzle used as a processing aid in the manufacture of multi-filament yarn. More particularly, the invention concerns a system that includes processes and equipment for improving the uniformity of yarn finish application on the individual filaments of rapidly advancing yarn by utilizing a pneumatic false twister.
BACKGROUND AND SUMMARY OF THE INVENTION
A conventional method disclosed in U.S. 3,201,931 separates yarns having continuous fibers in order to bulk the yarn by feeding the yarn into a jet of air, so that the yarn is supported by the jet of air and the individual filaments are separated from each other. The separated individual fibers are thus passed through a turbulent area where intermingling and texturing occurs. The bulked yarn is then passed through a dye bath.
A process of twisting of filaments into a cohesive single yarn entity is disclosed in U.S. 3,534,453, where the resultant yarn bundle is textured via pneumatic means and atomized dye stuffs are introduced via the sonic or subsonic fluid flows before the yarn bundle is completely closed by the twisting action of the flow currents. The thread enters the interior of a nozzle and a stream of pressurized air enters a ‘heart-shaped’ “bulb” or annulus through a duct. The position of the duct relative to the nozzle axis produces the familiar effect of the required amount of twisting, fixing, and untwisting. A “true twist” of the yarn bundle is a result of this process, and the manifestation of false twist “S” or “Z” patterns in individual discrete filaments in the resultant processed yarns is due to either direct contact with the chamber wall or the interactions of subsonic and sonic pneumatic flows within the nozzle chamber on the plurality of fibers.
A method for opening and applying finishes to multifilament tows is disclosed in U.S. 3,226,773, in which a compressed air stream is used for spreading and separating the filaments of a tow bundle and for carrying the particles, droplets, or mist of the finish composition to be applied to the filaments. In actual practice, the oscillation of the advancing tow bundle within the nozzle chamber creates momentary flow disturbances in the plenum chamber and supply metering orifice that alter the concentrations of entrained atomized finish particles. Sufficient filament displacement occurs within the advancing tow bundle for it to be described as “fleecy,” intermingling and interlacing thereby occuring.
The invention relates to a finish application system that uses several variations of air nozzles that are somewhat similar to conventional interlacers/interminglers, but have completely different functions. Conventional interlacers/interminglers operate at relatively high pressures (up to 4 bars) and are designed to provide additional cohesion to the filament yarn by creating so-called nodes or loose knots. The conventional devices are designed to work at very low tensions and are not suitable for finish application.
The invention relates to the application of yarn finishes, such as those containing lubricants and/or other additives, to the advancing filaments within the converged yarn bundle in state-of-the-art high speed extrusion processes for yarns formed of man-made and/or natural polymeric materials. These processes have reached speed ranges of as much as 3000-8000 meters per minute, where the extrusion tension levels and the residence times on the conventional wetted type applicator surfaces preclude a high degree of uniform and consistent capillary action on the individual filaments within the yarn bundle. This can be attributed to several causes: the entrained boundary layer of cooling air flow that each filament brings to the applicator; the residual retraction forces associated with filament tension that are still remaining in the filaments within the advancing yarn bundle due to the drawing process; the apparent viscosity phenomena associated with the high speed contact of the filaments within the advancing yarn bundle with the pool of yarn finish containing lubricants, and/or other additives on the wetted applicator surface; and, due to the applicator's ability to renew the pool of finish under the yarn bundle contact zone.
In order to reduce these and other conventional problems associated with uniformity of finish application, it is an object of the present invention to dissipate the entrained boundary of air, steam, inert gas, or other types of cooling or heating fluids that inhibit the uptake of the yarn finish containing lubricants or other additives on the advancing yarn bundle prior to the entrance of the yarn bundle into a nozzle device.
It is an additional object of the present invention to disturb the linear interfilament cohesion within the advancing fiber bundle that inhibits the attachment of yarn finish through capillary action without also creating noticable sinusoidal and/or nodal mixing patterns (known as “intermingling” or “interlacing” patterns) in the advancing yarn fiber bundle that could inhibit downstream processing techniques.
It is a further object of the present invention to introduce yarn finish containing lubricants, or other additives, into an applicator chamber that provides for low pressure contact of the individual filaments with the wetted surfaces of the applicator chamber and with the atomized fluid volume within the nozzle chamber.
It is another object of the present invention to provide a low pressure nozzle chamber that dampens pressure and volumetric irregularities in the introduction of the yarn finish into the applicator chamber.
Yet another object of the present invention is to immediately close the opened filaments of the advancing fiber bundle containing the yarn finish immediately after passing the nozzle, in order to aid in the prevention of the previously applied finish being stripped off by the reattachment of the boundary layer air, after the yarn passes through the nozzle.
Still another object of the present invention is to provide a type of air bearing yarn filament support medium within the applicator chamber, to inhibit the escalation of tension in the advancing yarn line normally associated with direct fiber filament contact with the application surface.
An additional object of the present invention is to introduce more surfaces of the advancing filament bundle cross sections to the wetted surfaces of the applicator and to the atomized finish particles within the nozzle chamber.
Another object of the present invention is to allow the applicator to renew with finish the application surfaces of the applicator, in order to facilitate the uniform and consistent presentation of the finishes to the advancing yarn line.
Another object of the present invention is to reduce the friction and the friction buildup of the yarn within the nozzle chambers, so that the moving yarn may be opened or closed under high tension, allowing the nozzle to act as an air bearing.
Different air pressures can be used to operate the pneumatic false twister. Low pressure (up to 2 bars) air nozzles can be used for the application of yarn finish processing aid components. The Advanced Finish Nozzle (AFN) of the present invention contains compressed air delivery orifices that are used to effect the false twisting and untwisting of the yarn within the nozzle. When air pressure is applied to the AFN, the yarn filaments remain twisted together, and when no air pressure is applied to the AFN the yarn remains untwisted. The AFN is capable of opening and closing of multi-filament yarn at high tensions (up to 1.0 gram per denier) by the application of a “S/Z” semi-twist, or false twist, to the moving yarn. The AFN is also designed to apply finish onto the moving yarn while “open” inside of the nozzle. The nozzle can be used immediately after a conventional application of a liquid finish to the multifilament yarn, or can contain additional orifices that are used to spray the finish onto the yarn while the yarn has been opened by the nozzle and before the yarn closes into its normal state. This action allows for extremely uniform finish application especially in situations where some additional amount of finish has to be applied on already spun and drawn (or even heat set) yarns.
The nozzle is designed so that an air bearing curtain (e.g., helix) is provided surrounding the advancing threadline to cause an orbital dislocation, thereby separating and opening the yarn bundle. A convergence of the thread can occur within or just after passing the nozzle.
The AFN does not use the atomizing of particles of finish for reasons of system complexity and overall variability of finish concentrations. The AFN requires the delivery of a metered stream of yarn finish directly into the yarn processing chamber and thereby improves over conventional systems such as the abovementioned 3,226,773.
The manifestation of the “S” or “Z” twist patterns in the filaments of the advancing yarn bundle in the AFN is the result of individual filaments within the advancing yarn bundle accepting rotational torque and radial bundle displacement from the helical discharge path of the perimeter air currents within the nozzle chamber. The algebraic sum of this twist is zero when measured over a certain length of the yarn bundle.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention, together with further objects and advantages thereof may be understood by reference to the following description, taken in conjunction with the accompanying drawings.
FIG. 1 shows a top view of an AFN nozzle assembly according to the present invention.
FIG. 2 is a side view of the AFN nozzle assembly shown in FIG. 1 .
FIGS. 3A and 3B are a side and bottom view, respectively, of an AFN nozzle assembly having tube fittings for supplying of compressed air or other fluid medium and yarn finish lubricant.
FIG. 4 is a schematic view of a preferred rig used for finish application according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The AFN can apply finish onto the moving yarn while the yarn is “open” inside of the nozzle. AFN opening and closing performance is related to parameters of speed, tension, and pressure.
Experimental testing was performed where the goals of the testing program were to confirm opening-closing action of the AFN nozzle design, characterize friction build-up at the nozzle, and to evaluate the effect of the nozzle on finish level and finish uniformity. Testing was done using 126-denier 34 filament polyester finish-free POY partially oriented) yarn loaded on a high-speed Fiber-to-Metal (F/M) friction meter and run at 100, 250, 500, and 1000 m/min. The AFN, and optionally a ceramic finish application guide, was installed between the load cells of the friction meter and connected to a regulated air supply, which provided up to two bars of pressure. Images of the nozzle action were taken using a high-speed (1000 frames/sec.) camera. The photographs confirmed the opening/closing action of the AFN and allowed for evaluation of the opening frequency and action of the nozzle. An average opening frequency was established as 345+106 Hz for all experimental conditions (i.e., speed, tension, pressure). The opening/closing action of the AFN has a generally multifrequency character rather than a single frequency one. Testing that combines black and white yarns will better illustrate the AFN action.
The importance of friction build-up on the applicator guides must be emphasized. In many modem man-made fiber processes, friction build-up on stationary surfaces limits production speeds. For example, at speeds above 4000 mn/min., fiber producers are forced to use special low friction ceramic to minimize the friction drag over the applicator guides. The current industry standard is the special “rough” ceramic guide produced by Kyocera and others. The new AFN design is intended to be used either with or without a standard ceramic finish application guide. The AFN is intended to be used either as a stand-alone finish applicator nozzle, or as a complementary device to enhance the finish uniformity of a standard applicator nozzle placed either before or after the AFN nozzle. In either case, the AFN is designed to generate friction build-up comparable with existing low friction ceramic applicator guides.
To investigate friction build-up on the AFN nozzle, a coefficient of friction was measured at a wide range of speeds and pretensions, and then compared with a coefficient of friction measured for a low friction ceramic guide, which is considered an industry standard for a low friction surface. The same 126/34 finish-free polyester yarn was used for this test. Results of the friction testing are summarized in Table 1. Investigated variables were tension (T 1 , grains), pressure (P, bars), and yarn speed (V, m/min.). The results illustrate that although the prototype was actually made from highly polished stainless steel, which has an inherently higher coefficient of friction compared to ceramic, the nozzle produced less friction build-up.
TABLE 1
Friction Build-up
T 1
P
Yarn Speed V, m/min
Guide Setup
(grams)
(Bar)
100
250
500
1000
AFN Alone
12
1
0.097
0.126
0.169
0.211
1.5
0.094
0.134
0.167
0.211
2
0.097
0.125
0.163
0.212
18
1
0.073
0.092
0.144
0.183
1.5
0.066
0.090
0.117
0.180
2
0.072
0.089
0.119
0.183
24
1
0.059
0.073
0.093
0.142
1.5
0.058
0.071
0.090
0.144
2
0.053
0.074
0.095
0.149
Ceramic
12
1
0.105
0.135
0.173
0.258*
Guide
1.5
0.102
0.133
0.182
0.200
+ AFN
2
0.101
0.132
0.182
0.207
18
1
0.072
0.090
0.118
0.186
1.5
0.073
0.090
0.112
0.192
2
0.070
0.101
0.133
0.188
24
1
0.059
0.069
0.092
0.146
1.5
0.061
0.074
0.099
0.146
2
0.060
0.082
0.106
0.150
Ceramic
12
N/A
0.085
0.109
0.142
0.213
Guide
18
0.063
0.083
0.097
0.176
Alone
24
0.051
0.066
0.082
0.124
*Yarn starts to break at these conditions.
Data presented in Table 1 indicates that the coefficient of friction on both the ceramic finish application guide and the AFN significantly increases with the yarn speed. Increase in the input yarn tension leads to a lower coefficient of friction, which is in excellent agreement with existing friction theory. At the same time, the effect of operation pressure is negligibly small, and may be easily omitted from further consideration. This actually means that the AFN is quite adaptable and may be operated in a reasonably wide range of pressures. Interestingly enough, the coefficient of friction measured for the combination of the AFN and ceramic finish applicator guide is actually lower than the sum of the individual coefficients of friction. This result actually confirms the wiping action of the AFN, which apparently leads to a lowering of a contact area between the ceramic application guide and moving yarn. To summarize the friction experiments: the AFN showed approximately 14% higher friction than the low friction ceramic guide; the combination of the AFN and ceramic applicator guide showed a 17% higher coefficient of friction compared to the low friction ceramic applicator guide alone.
Thorough comparison of friction surfaces involves 3-dimensional plots of yarn speed v. input tension v. coefficient of friction, for each of the AFN, ceramic guide, and the combination of AFN+ceramic guide. The comparison reveals one very important detail of the AFN's performance. For the ceramic applicator guide, the higher the speed the higher the friction, and such an increase is virtually linearly proportional to the yarn speed. At the same time, the AFN exhibits a slowing of friction build-up with increased speed, and this effect is also pronounced for the combination of the AFN and ceramic applicator guide. This means that at yarn speeds exceeding 1000 m/min., friction build-up for the AFN will be smaller compared to the ceramic applicator guide alone.
Next, finish application and finish uniformity evaluations are summarized. The AFN allows for the direct injection and application of the yarn finish directly into the yarn processing chamber and not into the compressed air stream as the injection of finish lubricants into the compressed air stream creates back pressure in the finish lines, which can lead to periodic blockages of the finish flow and corresponding sputtering of the finish flow when the pressure is again equalized by the positive pump feed. This problem is solved by the addition of separate finish delivery orifices in the low pressure zone inside the nozzle and by using the same pressure or a slight higher pressure to actuate the finish supply. The feasibility of using the AFN as a stand-alone finish applicator guide, and its ability to improve uniformity of finish distribution on the applied yarns were evaluated. To accomplish this task, finish neat and from 10% emulsion was applied onto 126/34 finish-free polyester yarn. Application speed was set at 200 m/min. and target FOY (finish on yarn) level was 1%. The schematic of the application rig is shown in FIG. 4 . Operating air pressure for the AFN was set at 2 bar for all experiments. Lurol PT-128 was used as the finish and, in order to characterize finish uniformity, a fluorescent tracer was added at 0.1% w/w to the oil base. After conditioning, the applied yarns were examined by high-resolution dynamic fluorometry to characterize finish uniformity. Dynamic fluorometry tests were run at 5.4 m/min. and 30 Hz acquisition frequency. At these test conditions resolution is 3 mm for the length of the yarn. This test yields an absolute mean and a percent CV (coefficient of variation, which is equal to standard deviation divided by the mean). The absolute mean is a direct measure of the finish level on the yarn, while the %CV is a quantitative characteristic of finish uniformity. The lower the %CV, the better the uniformity of finish distribution along the yarn. Actual finish levels (FOY) were determined by cold solvent extraction with an isopropanol/hexane mixture. The %FOY was determined using the isopropanol/hexane cold solvent method. Generated results are summarized in Table 2. Data in Table 2 shows that the AFN indeed improves uniformity of finish distribution in both cases of neat and emulsion application. It also provides finish levels closer to the theoretical ones compared to the regular ceramic applicator guide.
TABLE 2
Effect of AFN on Finish Uniformity and Finish Level
Sample
Setup
Appli-
Absolute
%
%
LD.
Applicator
Air Supply
cation
Mean
CV
FOY
A
Ceramic
None
Neat
1.26
55.4
0.80
Applicator
B
Ceramic
AFN (2 bars)
1.35
49.5
0.85
Applicator
C
AFN
AFN (2 bars)
1.68
48.2
0.99
D
Ceramic
None
Emulsion
0.97
60.6
0.79
Applicator
E
Ceramic
AEN
1.09
32.9
0.84
Applicator
(2 bars)
F
AFN
AFN (2 bars)
1.13
33.2
0.92
As mentioned above, the most drastic effect of the AFN action can be seen in the improvement of finish uniformity. Finish uniformity was improved more then 12% in the case of neat application and almost twice in the case of emulsion. Even addition of the AFN after the ceramic applicator guide noticeably improved finish uniformity. This effect is explained by the wiping action of the twisted yarn across the ceramic applicator guide.
The new AFN design is intended to be used either with or without a ceramic applicator guide or other type of finish applicator upstream of the AFN. A twisting and wiping motion of the yarn across the guide is caused by the twisting action of the AFN. When the nozzle is installed after such a conventional ceramic applicator guide, the wiping action is beneficial for enhancing the uniformity of finish distribution and preventing a dripping of finish from the applicator guide.
The thorough testing of the Advanced Finish Nozzle (AFN) thus confirms the revolutionary nature of this device in the field of spin finish application technology. The most advantageous features of the AFN are the opening/closing action of the filament bundle, wiping effect over the ceramic guide (where used) leading to enhanced finish uniformity, and ability for extremely (approximately twice as effective in enhancing the finish uniformity when compared to regular applicator guides) uniform finish application.
The AFN is intended to be used either as a stand alone finish applicator nozzle, or as a complementary device to enhance finish uniformity.
An embodiment of the invention as illustrated in FIGS. 1 and 2 is now described. The yarn enters the AFN 1 as a fiber bundle. The fiber bundle can be placed in the AFN 1 during setup by temporarily loosening a tension on the fiber bundle and slipping the fiber bundle into the AFN via fiber bundle entry slot 2 . A loosening of the tension on the fiber bundle may not be required where the yarn material is flexible or where the tension is not great. A tensioning of the fiber bundle may then be adjusted after placement in the AFN 1 is completed. The fiber bundle passes in a lengthwise direction through the AFN by entering the fiber bundle entry 3 , passing through a fiber processing chamber 5 , and then exiting through a fiber bundle exit 4 . The AFN can be positioned so that, when properly tensioned, the fiber bundle's passage through the AFN is approximately centered with respect to fiber bundle entry 3 , fiber processing chamber 5 , and fiber bundle exit 4 , so that the fiber bundle does not rub against the corresponding surfaces of the passage.
The fiber bundle entry slot 2 , as shown in FIG. 2, is constructed so that its end view cross section is rounded, allowing the fiber bundle to be easily inserted laterally into the AFN. This fiber bundle entry slot 2 divides a lengthwise half of the AFN laterally and then turns 90° and connects to the fiber processing chamber 5 . The edges of the corresponding surfaces throughout the fiber bundle entry slot 2 are each rounded in order to prevent damage to the yarn and provide smoother insertion of the fiber bundle into the AFN. The fiber bundle entry 3 and the fiber bundle exit 4 each have a funnel shape that opens out from the fiber processing chamber 5 . This fennel shape can be optimized for both a desired internal pressure within the fiber processing chamber 5 as well as a control of the boundary layer air.
An air supply tube fitting 20 , shown in FIG. 3A, connects an external pressurized air supply to the AFN. A compressed air plenum 6 delivers the pressurized air from the air supply tube fitting 20 to a pair of compressed air delivery orifices 7 , 8 positioned parallel to each other along a centered diameter line of the compressed air plenum 6 , the centered diameter line of the compressed air plenum 6 being parallel to and laterally offset from the advancing yarn fiber bundle. The compressed air delivery orifices 7 , 8 , as shown in FIG. 2, are also vertically offset from the fiber bundle.
A finish supply tube fitting 21 connects an external source of the finish to the fiber lubricant reservoir 9 , which is positioned with its longitudinal axis at approximately a 45° angle with respect to the longitudinal axis of the compressed air plenum 6 . Two fiber lubricant delivery orifices 10 , 11 are positioned at the distal ends of parallel shafts that extend from the fiber lubricant reservoir 9 into the fiber processing chamber 5 . The pair of lubricant delivery orifices 10 , 11 are located immediately adjacent each other with a slight space inbetween, the pair of lubricant delivery orifices 10 , 11 being centered inbetween the pair of compressed air delivery orifices 7 , 8 . This relative placement of the air and finish orifices allows the AFN to apply the finish to the fiber bundle in its “open” state, and then immediately close the opened filaments of the advancing fiber bundle so that the applied finishes are not stripped off by the reattachment of the boundary layer air. Nozzle jet configuration will vary in accordance with optimizing the various parameters (e.g., yarn speed, air pressure, finish flow rate, temperature, etc.) for each combination of finish type and fiber type/coarseness, in order to facilitate the uniform and consistent presentation of the finishes to the advancing yarn. A highly accurate gear metering pump (not shown) is the preferred source of the metered finish supply.
The present invention is not limited regarding the type of multifilament, monofilament and bonded multifilament yarn, but is applicable to all hosiery, textile, techical and industrial yarns on which finish is now applied. Even so there is a practical upper limit to textile yarn size, since the present invention is not applicable to tows. The yarn when a multifilament yarn (including bonded yarn) will have a denier of from about 10 to 6,000 denier with a denier of about 0.1 to 1,000 per filament. Monofilament yarn will often have a denier of about 1.0 to 2,000.
The yarns useable in the practice of the present invention cover the entire spectrum of man-made and natural textile yarns. For example, the textile yarn can be formed of nylon 6 ; nylon 6 . 6 ; polyester (PET, PTT, PBT, etc.); acrylic polymer; polyethylene, polypropylene; can be bi-component (ex.: PE/PP, PET/PE, PET/PP, etc.); can be an elastomeric yarn (including spandex); glass; carbon yarn; cellulosic yarn and so-called advanced yarn types such as Kevlar, Spectra, etc.
Similarly, yarn finish now applied-or developed in the future will be usable in the practice of the present invention. Yarn finishes are now applied from neat oil, oil/water and water/oil emulsions, suspensions and solutions, all within the scope of the present invention.
As is well known, the basic function of the fiber finish is to modify frictional and antistatic properties of especially man-made fibers and yarns by the modification of surface properties of the base polymer material. Three major purposes of applying spin finish in the process of man-made fiber production are as follows:
Provide controlled Fiber-to-Metal (Fiber-to-Ceramic, or any other point of contact) friction and lubrication;
Provide necessary Fiber-to-Fiber friction and/or cohesion to maintain yarn integrity during processing; and
Provide required production against build-up of static electricity by the rapid dissipation of generated charges.
In addition to these major purposes, spin finish also may affect fiber and yarn hydrophilicity and hydrophobicity by making fiber or yarn water absorbent or water repellent depending on end-use requirements.
Spin finishes are usually comprised from lubricants, antistats, emulsifiers, and special additives.
Examples of Lubricants:
Mineral oils, vegetable oils, animal oils, fatty acid esters, Polyethers, ethylene oxide/propylene oxide copolymers, castor oil, glyceryl esters, silicones.
Examples of Emulsifiers:
Fatty acid amine soaps, fatty acid metal soaps, alcohol ether ethoxylates, ethoxylated alkylphenols, ethoxylated glycerides, ethoxylated sorbitol esters.
Examples of Antistats:
Quaternary amines (“Quats”), phosphate esters, aliphatic alcohol phosphates and their potassium salts, polyoxyethylene aliphatic alcohol phosphates and their potassium salts.
Although not described herein, the AFN system can also be applied to the manufacture of spandex and other types of elastomeric yarns to increase the finish uniformity and consistency. Such a use would be readily adaptable by one skilled in the art using the system as described above.
Variations of the invention will be apparent to the skilled artisan.
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A process for improving the uniformity of yarn finish application on the individual filaments of a rapidly advancing synthetic continuous monofilament, bonded multi-filament, multi-filament hosiery, textile, technical and industrial yarns includes imparting a pneumatic false twist to the advancing yarn having a wet finish thereon while the yarn is under a tension allowing the rapid opening and closing of the multi-filament yarn but preventing texturing or coherency from increasing by commingling of the yarn filaments in the false twister. A nozzle has a reduced friction and can either be used as a stand-alone air bearing or to apply finish within the nozzle. A plurality of finish delivery orifices open into the chamber in a low pressure zone inside the nozzle, and wherein the exact same or slightly greater pressure that is used for the compressed air supplied to the air delivery orifices is used to actuate the finish supplied to the plurality of the finish delivery orifices. The process and apparatus can also be used with monofilament textile yarn and bonded textile yarn.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to systems and methods for providing a hydraulic drilling sub assembly for use in the excavation, mining and drilling fields. Specifically, the present invention relates to a drilling sub assembly incorporating a hydraulically driven turbine that directly drives a drill bit without the use of gears or other mechanical means to limit the rate of rotation for the drill bit.
2. Background and Related Art
As the world becomes increasingly populated and developed, greater demands are made on the world's supply of natural resources. For example, as technology becomes increasingly accessible and affordable to third-world countries, demands for ground water, natural gas, and petroleum also increase. As a result, greater efforts have been required to recover these natural resources to meet the growing demands of the world's population. To address these challenges, the service industry must develop new technology while improving existing products to provide economical solutions to efficiently tap deep reservoirs of natural resources.
Hydraulic drilling is the process of using turbines to rotate a drill bit. As a drilling fluid is passed over the turbine, the turbine is rotated thereby causing the drill bit to rotate. Typically, a drilling fluid is delivered to the turbine via a string of drill pipes extending from the surface to the turbine. There are many types of drilling fluids including air, air and water, air and polymer, water, water-based mud, oil based mud, and synthetic-based fluid. On a drilling rig, drilling fluid (sometimes referred to as mud) is pumped from mud pits through the drill string where it sprays out of nozzles on the drill bit, cleaning and cooling the drill bit in the process. The mud then carries the crushed or cut rock up the annular space between the drill string and the sides of the hole being drilled. These cuttings are then driven up through the surface case where they emerge back at the surface.
The rate of rotation for the drill bit is commonly controlled by incorporating reducer gears between the turbine and the drill bit. In this way, one can select the speed of the bit by selecting an appropriate gear ratio for a given application. However, several difficulties exist with this method of speed control.
For example, reducer gears are commonly exposed to sediments and other debris found in the drilling fluid. Debris within the drilling fluid can become lodged within the reducer gears causing jams and other malfunctions that must be cleared. The process of clearing these jams are time consuming, expensive and potentially damaging to the drilling equipment. Furthermore, in the event that the drill bit becomes jammed while cutting the rock, the inclusion of reducer gears prevents the drill bit from spinning freely in a direction opposite to the jam. Accordingly, the process of undoing the jam results in downtime and may result in damage to the drill bit and other components of the drilling string.
Thus, while techniques currently exist for hydraulic drilling applications, challenges still exist with such techniques. Accordingly, it would be an improvement in the art to augment or even replace current techniques with other techniques.
BRIEF SUMMARY OF THE INVENTION
The present invention relates to systems and methods for providing a hydraulic drilling sub assembly for use in the excavation, mining and drilling fields. Specifically, the present invention relates to a drilling sub assembly incorporating a hydraulically driven turbine that directly drives a drill bit without the use of gears or other mechanical means to limit the rate of rotation for the drill bit.
In some implementations of the present invention, a drilling sub assembly is provided as a means for converting an upstream drilling fluid into a rotational force that directly drives a drill bit. Thus, in some implementations the drilling sub assembly is interposedly coupled between a string of drill pipes and a drill bit.
The drilling sub assembly generally includes an upper component, a mid component and a lower component, each component having an internal space through which a drilling fluid is capable of flowing. The upper component includes a body casing having an internal lumen for housing a baffle and a turbine unit. The baffle includes a fluid channel through which drilling fluid is directed and applied directly to the turbine unit. The position of the baffle is maintained within the internal lumen such that the baffle is prevented from rotating within the internal lumen. However, a bearing is interposed between the baffle and the turbine unit such that the turbine unit is permitted to rotate relative to the baffle. Thus, as the drilling fluid leaves the baffle and contacts the turbine unit, the turbine unit rotates freely relative to the fixed position of the baffle and body casing.
The mid component includes a bearing housing having a plurality of bearing surfaces for supporting various bearing units. The bearing housing is threadedly coupled to the body casing such that a first bearing unit is interposedly positioned between the bearing housing and the turbine unit.
The lower component includes a mandrel having a base from which extends a shaft. The shaft is extends through the bearing housing and is threadedly coupled to the turbine unit. A second bearing unit is interposedly positioned between the base portion of the mandrel and the bearing housing. The interposing second bearing unit thereby permits the mandrel to rotate freely relative to the fixed position of the bearing housing. Thus, as the drilling fluid rotates the turbine unit, the direct coupling between the turbine unit and the mandrel causing the mandrel to rotate at the same rate as the turbine unit.
A free end of the body casing includes a set of threads for threadedly coupling the drilling sub assembly to an upstream drill pipe. Furthermore, a free end of the mandrel includes a set of threads for threadedly coupling a drill bit. Thus, as the drilling fluid flows through the baffle and over the turbine unit, the turbine unit and coupled mandrel rotate thereby rotating the coupled drill bit relative to the fixed positions of the drill pip, the body casing, the baffle and the bearing housing.
BRIEF DESCRIPTION OF THE DRAWINGS
In order that the manner in which the above-recited and other features and advantages of the invention are obtained will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. These drawings depict only typical embodiments of the invention and are not therefore to be considered to limit the scope of the invention.
FIG. 1 is a perspective view of a drilling rig assembly incorporating a drilling sub assembly in accordance with a representative embodiment of the present invention.
FIG. 2 is a cross-section view of a drilling sub assembly in accordance with a representative embodiment of the present invention.
FIG. 3 is a cross-section view of body casing in accordance with a representative embodiment of the present invention.
FIG. 4A is a perspective view of a baffle in accordance with a representative embodiment of the present invention.
FIG. 4B is a cross-section view of a baffle in accordance with a representative embodiment of the present invention.
FIG. 5A is a perspective view of a turbine unit in accordance with a representative embodiment of the present invention.
FIG. 5B is a partial cross-section view of a turbine unit in accordance with a representative embodiment of the present invention.
FIG. 5C is a cross-section view of a turbine unit in accordance with a representative embodiment of the present invention.
FIG. 6 is a cross-section view of a turbine unit threadedly coupled to a mandrel and a first bearing unit in accordance with a representative embodiment of the present invention.
FIG. 7 is a cross-section view of a mandrel in accordance with a representative embodiment of the present invention.
FIG. 8 is a cross-section view of a partially assembled drilling sub assembly in accordance with a representative embodiment of the present invention.
FIG. 9 is a cross-section view of a bearing housing in accordance with a representative embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The presently preferred embodiments of the present invention will be best understood by reference to the drawings, wherein like reference numbers indicate identical or functionally similar elements. It will be readily understood that the components of the present invention, as generally described and illustrated in the figures herein, could be arranged and designed in a wide variety of different configurations. Thus, the following more detailed description, as represented in the figures, is not intended to limit the scope of the invention as claimed, but is merely representative of presently preferred embodiments of the invention.
Referring now to FIG. 1 , an implementation of a drilling sub assembly 10 is shown as interposedly coupled between a drill pipe 12 and a drill bit 14 . The drill pipe 12 generally includes an elongate tubular member having an internal lumen for transferring a drilling fluid from the surface to the drill bit 14 . The drill bit 14 generally includes a drill bit or another known cutting surface configured to cut a borehole 16 . In some embodiments, the drill bit 14 further includes a fluid outlet whereby drilling fluid is released through the drill bit 14 to assist in removing debris from the borehole 16 . The debris are removed to the surface via the interstitial space 18 between the drill pipe 12 and the borehole 16 , as is known in the art.
In general, the drilling sub assembly 10 is provided as a means for converting the flow of drilling fluid into a rotational force at the drill bit 14 . Specifically, the drilling sub assembly 10 utilizes a turbine unit to convert the linear flow of drilling fluid into a rotational force needed to rotate the drill bit 14 .
Some embodiments of the drilling sub assembly 10 comprise a modular unit having a plurality of interconnected sections. Each section is configured to work compatibly with the remaining sections to achieve desired working conditions for the drill bit 14 . For example, in some embodiments the drilling sub assembly 10 includes an upper component 20 , a mid component 30 and a lower component 40 . The upper component 20 generally comprises a body casing having a first end 22 for threadedly coupling the drill pipe 12 . The upper component 20 further comprises a second end 24 for threadedly coupling the mid component 30 or bearing housing of the drilling sub 10 .
The bearing housing 30 houses various bearing units to permit free rotation of the lower component 40 or mandrel relative to the stationary drill pipe 12 , body casing 20 and bearing housing 30 . The mandrel 40 comprises a threaded end 42 for coupling the drill bit 14 . Thus, the various components 20 , 30 and 40 of the drilling sub assembly 10 are configured to achieve gearless rotation of the drill bit 14 , as further described below.
Referring now to FIG. 2 , a cross-section view of the drilling sub assembly 10 is shown, as isolated from the drill pipe and the drill bit. The upper component 20 or body casing generally comprises an elongate tubular member having an internal lumen 26 , as shown in FIGS. 2 and 3 . The internal lumen 26 is generally configured to include various diameters to receive internal components of the sub assembly 10 . For example, in some embodiments the internal lumen 26 houses a baffle 50 adjacent to the first end 22 opening. The baffle 50 generally comprises a plug having a fluid channel 52 for directing and focusing a drilling fluid to selectively interact with downstream internal components. The position of the baffle 50 within the internal lumen 26 is generally maintained via a set screw 100 . Set screw 100 not only maintains the vertical position of baffle 50 , but also prevents baffle 50 from rotating relative to the body casing 20 . In some embodiments, a plurality of set screws 100 is provided to maintain the position of baffle 50 . In other embodiment, an o-ring 110 or other means for sealing is further interposed between the baffle 50 and the internal lumen 26 to prevent drilling fluid from bypassing the baffle 50 .
Baffle 50 comprises a first end 54 and a second end 56 , as shown in FIGS. 2 , 4 A and 4 B. The first end 54 comprises an upper chamber 70 for receiving an upstream drilling fluid. The upper chamber 70 is generally cylindrical having a bottom surface 74 that is slanted or oblique relative to the vertical walls 76 of the chamber 70 . The upper chamber 70 further includes a plurality of windows 78 in fluid communication with fluid channel 52 . Fluid channel 52 generally comprises a groove on the external surface of baffle 50 , wherein the inner surface 28 of the internal lumen 26 combines with the groove to complete the fluid channel 52 . Thus, the out diameter of baffle 50 is selected to minimize any tolerance between the baffle 50 and the inner surface 28 of the body casing 20 .
In some embodiments, fluid channel 52 comprises a first portion 60 and a second portion 62 , as shown in FIG. 4A . First portion 60 is generally vertically oriented. However, second portion 62 is generally angled thereby redirecting the flow of the drilling fluid. The combined features of first and second portion 60 and 62 thereby provide means for directing the drilling fluid to selectively interact with a downstream internal component. In some embodiments, first portion 60 is angled to be aligned with second portion 62 . In other embodiments, second portion 62 is aligned vertically with first portion 60 . Still further, in other embodiments baffle 50 comprises more than two fluid channels 52 .
The slanted configuration of bottom surface 74 naturally provides the upper chamber 70 with varying depths. The portion of the upper chamber 70 having the greatest depth experiences aberrant currents as the drilling fluid flows down the slanted surface into the vertical interior wall 80 . In particular, drilling fluid within this portion of the upper chamber 70 experiences eddies that churn and otherwise mix the drilling fluid.
In some embodiments, unwanted debris within the drilling fluid gravitate to this portion of the upper chamber 70 where they are subjected to aberrant currents that reduce the size and/or trap the unwanted debris. Eventually, the unwanted debris is sufficiently reduced in size and thereby released from the aberrant current and permitted to exit the upper chamber 70 via the window 78 . In some embodiments, the dimensions of window 78 are selected to prevent passage of unwanted debris having a size sufficient to harm or jam downstream internal components. Accordingly, the combined features of the slanted bottom surface 74 and the plurality of windows 78 prevents jams and other malfunctions due to debris in the drilling fluid.
The second end 56 of baffle 50 comprises a lower chamber 72 for rotatably receiving a downstream internal component. In particular, lower chamber 72 comprises a recess for compatibly receiving a first end 92 of a turbine unit 90 , as shown in FIGS. 2 and 5 A- 5 C.
Turbine unit 90 generally comprises a cylindrical body having an outer sleeve 96 and an internal lumen 98 . A plurality of blades 120 is set within the internal lumen 98 whereby a drilling fluid is permitted to pass over the blades 120 and through the internal lumen 98 . The turbine unit 90 is positioned within the recess of the lower chamber 72 of the baffle 50 such that an outlet 64 of the fluid channel 52 (see FIG. 4A ) guides the drilling fluid to directly contact the plurality of blades 120 . Thus, in some embodiments the second portion 62 of the fluid channel 52 is positioned at an angle 66 to achieve a desired contact between the drilling fluid and the plurality of blades 120 . For example, in some embodiments angle 66 is selected to be 90° to the plurality of blades 120 . In other embodiments, angle 66 is selected to be less than or greater than 90° to the plurality of blades 120 .
A second end 94 of the turbine unit 90 comprises a threaded opening 114 through which the drilling fluid exits the internal lumen 98 . As the drilling fluid passes over the blades 120 , the turbine unit 90 is activated resulting in rotation of unit 90 .
The first end 92 of the turbine unit 90 further includes a bearing surface 102 for supporting a bearing unit 112 , such as a sealed bearing. A complimentary bearing surface 122 is located in lower chamber 72 of baffle 50 . Thus, bearing unit 112 permits free rotation of turbine unit 90 relative to the stationary positions of baffle 50 and body casing 20 .
Referring now to FIGS. 6 , 7 and 8 , threaded opening 114 of turbine unit 90 is further configured to threadedly receive a shaft portion 132 of mandrel 40 . Mandrel 40 generally comprises a tubular member having a first end 140 , a second end 142 and a fluid pathway 150 extending therebetween. First end 140 comprises an elongate shaft having a set of external threads 144 to threadedly couple threaded opening 114 of turbine unit 90 . Once coupled, fluid pathway 150 and internal lumen 98 are in fluid communication. In some embodiments, an o-ring 110 or other sealing means is interposed between mandrel 40 and turbine unit 90 to contain the flow of drilling fluid to within the internal pathways 26 , 70 , 78 , 52 , 98 and 150 of the assembly 10 .
Second end 142 comprises a stepped base having a set of internal threads 146 to threadedly couple a drill bit 14 . The stepped configuration provides various horizontal surfaces which act to support various components of the assembly 10 , discussed in detail below.
With reference to FIGS. 6 and 8 , the outer diameter of shaft portion 132 is selected to receive a first bearing unit 160 . Bearing unit 160 is provided to permit free rotation of turbine unit 90 and mandrel 40 relative to the stationary positions of body casing 20 (not shown) and bearing housing 30 . Thus, in some embodiments the second end 94 of turbine unit 90 comprises a generally horizontal bearing surface 104 to receive and support bearing unit 160 .
Bearing unit 160 may include any combination of bearings, spacers, sealing means, grommets, o-rings, and the like as known and commonly used in the art. In some embodiments, bearing unit 160 comprises a combination of various units including thrust bearings 162 , spacers 164 , and sealed bearings 170 . In other embodiments, bearing unit 160 further comprises a spacer 174 having a plurality of recesses to receive various o-rings, such as a Teflon® o-ring 176 and a rubber o-ring 178 . Thus, the combination of various units provides a bearing unit 160 configured to allow turbine unit 90 and mandrel 40 to freely rotate within the drilling sub assembly 10 .
Referring now to FIGS. 6-9 , bearing housing 30 generally comprises a tubular member having an inner diameter 32 configured to rotatably receive shaft 132 of mandrel 40 . A first end 34 of bearing housing 30 comprises a set of threads for threadedly coupling the second end 24 of body casing 20 . The inner lumen of bearing housing 30 further includes an upper bearing surface 176 and a lower bearing surface 178 configured to support both the first bearing unit 160 and a second bearing unit 180 , respectively. In some embodiments, the second bearing unit 180 comprises a combination of various bearing units, similar to those described in connection with the first bearing unit 160 , above. The second bearing unit 180 is seated over shaft 132 of mandrel 40 such that the second bearing unit 180 is interposed between bearing surface 136 of mandrel 40 and lower bearing surface 178 of bearing housing 30 .
The first and second bearing units 160 and 180 are selectively set to a desired thrust load by threadedly coupling, to a desired torque, the turbine unit 90 and the mandrel 40 . One of skill in the art will appreciate that variations in the size, type and configuration of the bearing units will necessarily alter the required thrust load. In some embodiments, the desired thrust load of the bearing units is maintained by locking the threaded relationship between the turbine unit 90 and the mandrel 40 via a thread-lock material. In other embodiments, the threaded relationship between the turbine unit 90 and the mandrel 40 is maintained via a tack weld or a set screw (not shown).
The bearing unit 112 interposed between the turbine unit 90 and baffle 50 is set to a desired thrust load by threadedly coupling, to a desired torque, the bearing housing 30 and the body casing 20 . Thus, the first and second bearing units 160 and 180 , and bearing unit 112 are capable of being independently adjusted to desired thrust loads, as may be required by the individual bearing unit configurations.
In some embodiments, bearing housing 30 further comprises a valve 36 . Valve 36 is generally provided as a means for accessing the first and second bearing units 160 and 180 following assembly of the drilling sub device 10 . In some embodiments, valve 36 comprises a grease port whereby a lubricant is injected into the bearing housing 30 via valve 36 . Thus, valve 36 provides a means whereby the first and second bearing units 160 and 180 are capable of being repacked with a lubricant following use of the assembly 10 . In some embodiments, bearing housing 30 further comprises a second valve (not shown) to permit exchange of spent lubricant within the housing 30 during the process of injecting new lubricant via valve 36 .
Referring generally to the various Figures discussed above, of particular interest to the present invention is the lack of gears or other means for controlling the direction and/or speed of turbine unit 90 . In some embodiments of the present invention, the rate of rotation for the turbine unit 90 is directly proportional to the flow rate of drilling fluid through the drilling sub assembly 10 . Thus, the speed of the turbine unit 90 may be variably adjusted by increasing or decreasing the flow rate of the drilling fluid. In some embodiments, the flow rate of the drilling fluid is controlled by adjusting a pump or flow regulator associated with the drilling fluid. In other embodiments, the flow rate of the drilling fluid is adjusted by modifying the features of baffle 50 .
For example, in some embodiments baffle 50 is modified to include an increased number of windows 78 and fluid channels 52 , thereby increasing the flow rate of the drilling fluid through the drilling sub assembly 10 . In other embodiments, baffle 50 is modified to include fewer windows 78 and fluid channels 52 , thereby decreasing the flow rate of the drilling fluid through the drilling sub assembly 10 . In some embodiments, the dimensions of fluid channels 52 are modified to increase or decrease the flow rate of the drilling fluid through the baffle 50 . Finally, in some embodiments fluid channel 52 is tapered to accelerate the flow rate of the drilling fluid as it exits baffle 50 .
The absence of gears within the present invention eliminates the possibility of damage to the drilling sub assembly 10 in the event of an internal or external jam. For example, should the turbine unit 90 jam due to the presence of debris within the drilling fluid, the turbine unit 90 would simply cease to rotate. The drilling fluid would continue to bypass the turbine unit 90 until either the debris was dislodged by the drilling fluid, or the jam was physically removed. Similarly, in the event of the drill bit 14 becoming jammed, the turbine unit 90 , the mandrel 40 and the drill bit 14 would simply cease rotating. Accordingly, an operator would back the drill bit 14 away from the jam thereby permitting the turbine unit 90 , the mandrel 40 and the drill bit 14 to recover their rotation. The operator would then resume the drilling operation.
The drilling sub assembly 10 of the present invention is generally assembled by first positioning baffle 50 within body casing 20 . In some embodiments, o-ring 110 is first within internal lumen 26 so as to be interposed between baffle 50 and the abutting surface of the body casing 20 . Once in place, baffle 50 is secured via set screw 100 thereby preventing further movement or rotation of baffle 50 .
Prior to coupling the body casing 20 to the bearing housing 30 , the turbine unit 90 , the bearing housing 30 , the bearing units 160 and 180 , and the mandrel 40 are preassembled, as shown in FIG. 8 . In particular, the second bearing unit 180 is first placed on bearing surface 136 of the mandrel 40 . Mandrel 40 and bearing unit 180 are then inserted into bearing unit 30 such that bearing unit 180 is seated against lower bearing surface 178 . First bearing unit 160 is then placed over shaft 132 of mandrel 40 such that bearing unit 160 is seated against upper bearing surface 176 . Mandrel 40 is then threadedly coupled to turbine unit 90 , such that o-ring 110 is interposed between threaded opening 114 and first end 140 of mandrel 40 . The mandrel 40 and turbine unit 90 are threadedly coupled to a desired torque so as to achieve a desired thrust load for the first and second bearing units 160 and 180 .
The final step in assembly is to threadedly couple the bearing housing 30 to the body casing 20 . Bearing unit 112 is first positioned on the first end 92 of turbine unit 90 . Turbine unit 90 is then inserted into the internal lumen 26 of the body casing 20 . Bearing housing 30 is then threadedly coupled to body casing 20 until bearing unit 112 is seated in within lower chamber 72 of baffle 50 . Bearing housing 30 and body casing 20 are threadedly coupled to a desired torque so as to achieve a desired thrust load for bearing unit 112 .
The present invention may be embodied in other specific forms without departing from its structures, methods, or other essential characteristics as broadly described herein and claimed hereinafter. Thus, the described embodiments are to be considered in all respects only as illustrative, and not restrictive. The scope of the invention is, therefore, indicated by the appended claims, rather than by the foregoing description. All changes that come within the meaning and range of equivalency of the claims are to be embraced within their scope.
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A drilling sub assembly adapted to be coupled between a drill bit of a drilling rig and a drill pipe, the drilling sub assembling including a turbine unit directly coupled to the drill bit via a mandrel, such that passage of a drilling fluid through the drilling sub assembly rotates the turbine unit which in turn directly rotates the drill bit coupled thereto. The present invention further relates to a baffle for controlling and reducing debris present within a drilling fluid used in combination with the drilling sub assembly.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The invention generally relates to baseball and, more particularly, to a statistical method for evaluating the performance of a relief pitcher.
[0003] 2. Description of the Prior Art
[0004] Baseball thrives, and in large measure survives, by its ability to evaluate, differentiate and classify its product—namely, its players and teams. This is true for hitters, for pitchers, and, to a lesser extent, for position players in the field.
[0005] Who had the best season at the plate? Generally speaking, the batting average tells us.
[0006] Who had the most productive season? Perhaps it's the slugging percentage or the Runs Batted In (RBI) that tells us. Or is it the statistic that indicates which player crossed home plate the most times (Runs Scored)? Or perhaps the statistic that states who had the best on-base average, or the most walks, or the most hits.
[0007] Measuring pitching performance has also been one of the most common subjects of statistics, and can be found in newspapers from the 1800s. Which pitcher won how many games? The won/loss columns tell us. This is the most widely used measure of a pitcher's worth. Which pitcher struck out the most batters? Which pitcher yielded the fewest walks? Which pitcher allowed the fewest hits? Which pitcher allowed the fewest batters to cross home plate due to his mistakes (the Earned Run Average, or “ERA”)? This is the second most widely used measure of a pitcher's worth, after the total amount of “wins.” Which pitcher had the most “saves,” so to speak, out of the bullpen? A “save” is credited to a relief (or “substitute”) pitcher when the pitcher who starts the game is removed from the game while his team is in the lead; the relief pitcher holds the opposite team in check so that his team remains ahead and goes on to win the game. (It has been said that the “blown save” is baseball's most “deflating moment, and its most haunting,” The New York Times, Mar. 31, 2002, Sect. 8a, p. 3.)
[0008] The following is a more specific definition of a “save” in pitching: A pitcher can earn a save by completing all three of the following terms:
[0009] (1) Finishes the game won by his team;
[0010] (2) Does not receive the win;
[0011] (3) Meets one of the following three items:
[0012] (a) Enters the game with a lead of no more than three runs and pitches at least one inning;
[0013] (b) Enters the game with the tying run either on base, at bat or on deck; and/or
[0014] (c) Pitches effectively for at least three innings.
[0015] The number of “saves” has been used for years as a measure of the value of a relief pitcher. Baseball is not immune to society's rush into specialization. Just as a general practitioner M.D. recommends a patient to a specialist, and an attorney might specialize in maritime law, baseball is becoming more and more specialized as to how it uses its players. Very few “complete”—nine-(or more)-inning games—are pitched by the starting pitchers. A manager will use a “pitch count” to determine how far his ace (the starting pitcher) can go. There are middle-inning (fifth-seventh inning) relief pitchers, and there are “closers,” who finish pitching the game.
[0016] Relief pitching has become an art and a specialty. However, the statistics related to relief pitching has not kept pace.
[0017] Assume the following situation. Several relief pitchers have come into a different number of games and have “inherited” a different number of base runners. However, all of these relief pitchers end the season with similar numbers of saves. Because the actual games each pitcher entered can be widely disparate, a fixed number of saves—say, 15 —might not have the same value for each pitcher. It's possible that reliever no. 1 pitched in twice as many games as reliever no. 2 . Clearly, in such a case, “15 saves” would not mean that they are of equal value. And what of the situations in which each of these pitchers allowed runs or scores and did not “save” the game (“blown saves”)?
[0018] Most of the baseball statistics we know are readily computed and reflect simple performance parameters. The common and not-so-common items used to measure pitching performance in the major leagues today include “Adjusted Pitching Runs” (“APR” or “PR/A”). This is an advanced pitching statistic used to measure the number of runs that a pitcher prevents from being scored compared to the League's average pitcher in a neutral park in the same amount of innings. This is similar to the “ERA” (“Earned Run Average”) and acts as a quantitative counterpart.
[0019] The abovementioned ERA is simply computed by the following formula:
ERA = R × 9 I
[0020] where R=the number of earned runs and I=total no. of innings pitched.
[0021] The ERA is one of the oldest pitching statistics and is one of the most commonly used and understood statistics in the major leagues. Virtually every fan knows what it means, but many often forget the formula used to compute the pitcher's ERA.
[0022] The Earned Run Average Plus (“ERA+” or “RA”) is computed by dividing the league ERA by the ERA of a pitcher. This statistic uses a league-normalized ERA in the calculation and is intended to measure how well the pitcher prevented runs from being scoring relative to pitchers in the rest of the league. It is similar to the Hitters' PRO statistic.
[0023] Another commonly used statistic is the “Walks and Hits per Innings Pitched” (“WHIP”), which is computed as follows:
WHIP = H + W I
[0024] where H=number of hits, W=number of walks, and I=total number of innings pitched. There is a popular statistic that is probably used and frequently discussed in certain leagues. It was developed to measure the approximate number of walks and hits a pitcher allows in each inning he pitches, and then to compare the value received to other pitchers to formulate a pitcher's index.
[0025] The winning percentage is another common statistic in baseball and is also quite easy to understand and easy to compute. The primary purpose of this statistic is to gauge the percentage of a pitcher's games that are won.
[0026] In some instances, certain statistics become very sophisticated and more difficult to compute. Thus, for example, “Game Score” is computed as follows:
GAMESCORE = 50 + 3 I - 2 ( H + R + E ) - W + S + 2 I ′
[0027] where I=the number of innings pitched;
[0028] H=number of hits;
[0029] R=number of runs;
[0030] E=number of errors;
[0031] W=number of walks;
[0032] S=number of strikeouts; and
[0033] I′=the number of each full inning completed beyond the fourth inning.
[0034] This advanced pitching statistic is used to measure how dominant a pitcher's performance is in each game he pitches. This statistic rewards dominance (strikes and lack of hits) while penalizing for walks.
[0035] As it clear from the above, the number of statistics that are followed by baseball enthusiasts is rather large. Some of these statistics are, of course, more important than others to either the fans or the ball clubs.
[0036] While some of the aforementioned pitching statistics reflect a pitcher's general performance, only some of the statistics reflect the additional pressures and expectations of pitchers during critical phases of the game, when the pitchers are under particular stress. As noted, the “Game Score” is a function of full innings completed beyond the fourth inning and, therefore, reflects the performance of the pitcher toward the second half of the game. Most of the pitching statistics do not, however, reflect other parameters that are particularly stressful to pitchers and that good pitchers must overcome, including the number of outs, the number of inherited runners and the specific bases where each inherited runner is located when the relief pitcher comes on. As suggested, the number of outs, the number of inherited runners and the specific bases on which they are located, as well as the specific inning in which the pitcher comes in can, separately and in combination, be particularly stressful to a pitcher. The ability of a pitcher to overcome such stressful conditions and provide a win has never been quantified.
SUMMARY OF THE INVENTION
[0037] Accordingly, it is an object of the invention to provide a method of evaluating the performance of a relief pitcher in the final innings of a baseball game that provides an accurate measure of a pitcher's performance and value of the pitcher under stressful and/or critical conditions.
[0038] It is another object of the invention to provide a method, as in the previous object, that factors in parameters such as the number of the inning in which the relief pitcher is called in, the number of inherited runners, and the bases which they occupy, and the number of outs during the inning in which the relief pitcher is called in.
[0039] It is still another object of the invention to provide a method as in the previous objects which computes a “Save Run Average” (“SRA”) that is directly proportional to the total number of runs scored by inherited players and inversely proportional to the total number of batters faced by the pitcher in the innings in which he pitches.
[0040] It is yet another object of the invention to provide a method of the type under discussion which is simple to compute and yet provides a sophisticated and more refined method of evaluating and comparing the performances of relief pitchers by considering the number of runs scored by inherited players and the number of batters faced during the final innings, but which can be refined by also factoring in the specific innings in which the runs by the inherited runners are scored, as well as the number of outs when the relief pitcher is introduced into the game.
[0041] In order to achieve the above objects, as well as others that will become more apparent hereinafter, a method of evaluating the performance of a relief pitcher in the final innings of a baseball game in which the pitcher inherits at least one player on base comprises the steps of establishing the number of runs R scored by such inherited players and establishing the number of batters B faced by the pitcher in such innings. The Save-Run Average (SRA), in accordance with the present invention, is evaluated by calculating it as follows:
SRA = k ( R B )
[0042] where k=a predetermined constant selected to scale the SRA to a desired range of magnitudes; R=the number of runs scored by inherited players; and B=the number of batters faced by the pitcher in these innings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0043] With the above and additional objects and advantages in view, as will hereinafter appear, this invention comprises the devices, combinations and arrangements of parts hereinafter described by way of example and illustrated in the accompanying drawings of preferred embodiments in which:
[0044] [0044]FIGS. 1A, 1B and 1 C are three sections of the same spreadsheet that illustrates one computation of an SRA on the basis of certain game condition when the relief pitcher is called in; and
[0045] [0045]FIGS. 2A, 2B and 2 C are similar to FIGS. 1A, 1B and 1 C, but illustrating a second spreadsheet showing different game conditions and the resulting computation of a different SRA for the pitcher.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0046] The attached FIGS. 1A, 1B and 1 C and 2 A, 2 B and 2 C are two spreadsheets illustrating examples of computations of Save-Run Averages (SRAs) in accordance with the present invention for two different game conditions. This SRA functions to more clearly define the value and performance of a relief pitcher. As things are now, a relief pitcher who comes into a game with his team ahead will, in circumstances previously described, receive a “save” (provided, of course, that the team stays ahead). But if several relief pitchers each have achieved the same number of saves, will each have the same value as a relief pitcher?
[0047] The current use of baseball statistics does not provide an accurate tool by which to measure the value of a relief pitcher. Fortunately, using the SRA statistic we can now more clearly define relief pitcher superiority.
[0048] For purposes of this invention, the SRA is an average that is directly proportional to the number of runs scored by players on base inherited by a relief pitcher, and inversely proportional to the number of batters faced in the final innings of the game. Therefore, in its most fundamental or basic aspect, the SRA can be represented as follows:
SRA = k ( R B )
[0049] where k is a predetermined constant selected to scale the SRA to a selected range of magnitudes, and may be equal to “1”. However, as suggested, the SRA can be significantly refined to more fully reflect the value or performance of a relief pitcher in the final innings of the game. For purposes of discussing such refinements, the following definitions will be used:
[0050] (1) The Inning Factors—Preferably, these factors exist for the seventh, eighth, and ninth innings only. Through the sixth inning there is little pressure for a relief pitcher, as the game has a substantial amount of time left. As the game enters the seventh inning, the pressure mounts for the relief pitcher to hold the opposite team back. The “Inning Factor” variable “k i ” is increased as the game progresses through the seventh, eighth, and ninth innings, as the pressure increases and as the amount of time to correct a miscue decreases for a team. In short, the SRA reflects a greater penalty for failure as the game progresses.
[0051] (2) The Out Factor—the more outs there are when a relief pitcher enters the game, the more the reliever is penalized for a miscue. For example, if in the eighth inning with a player on first base the pitcher allows a runner to score with one out he is penalized by a factor of 0.48; if he allows the runner to score with two outs the penalty “out factor” 0.6. These factors are used because there is more pressure on the relief pitcher when he is pitching to a batter with, for example, two outs in the ninth inning than to a batter with no outs, so he is penalized more in these circumstances.
[0052] (3) The Base Factor—It takes a greater miscue to allow a runner to score from first base than it does to allow one to score from third base. Thus, the pitcher is penalized to a greater extent if the player on first scores under the same conditions as in a situation in which the player on third scores.
[0053] Turning now to specific examples of computations of SRAs in accordance with the more refined formula in accordance with the invention, and first referring to FIGS. 1A, 1B and 1 C, it should be noted that the tables or spreadsheets show cumulative data for a pitcher over a number of games and not just one game. The data may be calculated over a season or over a lifetime of games for a pitcher.
[0054] In the initial column, the inning is indicated in which the relief pitcher enters. This can, of course, be in any inning, but, as noted above, the SRA only takes into account the seventh, eighth and ninth-plus innings. Because a game can include extra innings, and should the game go into such extra innings, the same variables, factors and constants as used for the ninth inning are preferably also used for any succeeding inning(s).
[0055] The second column provides an “Inning Factor.” It will be noted that the Inning Factor increases from Inning 7 to Inning 8 to Inning 9 . The Inning Factor is designated as “k i ”.
[0056] The third column in FIG. 1A lists a factor reflecting “0” or “no outs” during Innings 7 , 8 and 9 , when a pitcher might be called in. The “Zero Out Factor” is represented by “k 00 ”, this factor increasing throughout the three final innings of the game. Thus, if a pitcher enters the seventh inning with no outs, he is penalized less than if he enters the eighth inning with no outs. He is penalized even more, then, if he enters the ninth inning with no outs, and allows inherited runners to score.
[0057] The fifth, seventh and ninth columns list factors k 1 , k 2 and k 3 . These factors represent parameters that are associated with inherited runners on first base, second base and third base, respectively. It will be noted that the factors k 1 , k 2 and k 3 decrease as the position of the inherited runner moves up from first to second to third base. Therefore, if an inherited runner on first base scores, the pitcher will be penalized more severely than if he enters the game with an inherited runner on third base, and that runner scores.
[0058] The fourth, sixth and eighth columns set forth the inherited runners on respective bases that may be found when the relief pitcher enters the game. With the aforementioned data entered into the respective columns, a first component, “V 0 ,” is computed as follows:
V 0 = ( R 1 k 1 + R 1 k 1 k i ) ( 1 + k 00 ) + ( R 2 k 2 + R 2 k 2 k i ) ( 1 + k 00 ) + ( R 3 k 3 + R 3 k 3 k i ) ( 1 + k 00 ) .
[0059] The value V 0 is computed for each inning during which inherited runners are on base when a relief pitcher enters the game. In the example given, V 0 =3.12, on the basis of an inherited runner on second base in the eighth inning, and V 0 =5.27, in connection with the inherited runner on first base during the ninth inning. In both case, the V 0 values are added for a total value of V 0 =8.39.
[0060] Similar computations are performed using the next seven columns, in which the factors k 1 , k 2 and k 3 are the same. The only difference from the first set of columns is that in the first column in this set (FIG. 1B), there is “one out” when the pitcher enters the game. For this reason, the first factor k 10 differs from the values of column 3 in FIG. 1A. Thus, it will be noted that k 10 , for the same inning, will increase when there is one out, as opposed to no outs. Therefore, the pitcher is being more severely penalized if he enters the game with one out and an inherited runner scores than he would be if he had entered the game with no outs and that same runner scored. Again, using the same expression (2) above, values of V 1 are computed for each inning as follows:
V 1 = ( R 1 k 1 + R 1 k 1 k i ) ( 1 + k 10 ) + ( R 2 k 2 + R 2 k 2 k i ) ( 1 + k 10 ) + ( R 3 k 3 + R 3 k 3 k i ) ( 1 + k 10 ) .
[0061] In this case, the total of the V 1 values is zero since no runs have been scored from any base with only one out.
[0062] Finally, referring to FIG. 1C, similar computations are performed for the last seven columns in which the constants are the same with the exception that the first column for k 20 is increased even further than the corresponding factors or values k 00 and k 10 . For the same reasons mentioned previously, this is to penalize the pitcher more severely in the event that an inherited runner scores when there are two outs when the relief pitcher comes into the game. Again, using the same expression (2), the values V 2 are computed for each inning as follows:
V 2 = ( R 1 k 1 + R 1 k 1 k i ) ( 1 + k 20 ) + ( R 2 k 2 + R 2 k 2 k i ) ( 1 + k 20 ) + ( R 3 k 3 + R 3 k 3 k i ) ( 1 + k 20 ) .
[0063] In the example shown in FIG. 1C, the total of V 2 is equal to 9.93 on the basis of two runs in the seventh and ninth innings with players on first base.
[0064] It will be noted that each of the quantities V 0 , V 1 and V 2 (equations 2, 3 and 4) reflects the number of runs scored, with each run R modified or weighted by the factor multipliers.
[0065] The SRA can now been computed as follows, using formula (1) and using k=5 and B=27:
SRA = 5 ( V 0 + V 1 + V 2 ) B
[0066] In the example illustrated, where the pitcher faced 27 batters,
SRA= 5(8.39+0+9.93)÷27
SRA= 3.39.
[0067] The constant “5” is not critical for purposes of the present invention and is merely a scaling factor that can be selected to scale the general resulting computation to a number that is manageable, easy to remember or otherwise convenient. The SRA may also be scaled to a number that is generally consistent with other baseball averages, as both fans and clubs may be most more familiar and more comfortable with them.
[0068] Referring to FIGS. 2A, 2B and 2 C, the same factors are utilized. However, here there is one inherited runner on second base in the eighth inning with no outs, two inherited runners with one out on second and third bases in the seventh and ninth innings and two inherited runners on first base in the seventh and ninth inning, with two outs. Here, with the total number of batters faced in relief also being equal to 27, the SRA is computed as 3.03, using the identical formula or computation.
[0069] The distinctions between the SRA and ERA become immediately evident. Thus, for example, in a nine-inning game, with three outs per inning, there are a total of 27 outs. In the ideal game, therefore, there are 27 batters out in one game. The ERA, as noted above, is equal to the number of runs divided by the number of batters, itself divided by 27 (the number of outs). Therefore, in the ideal game, the number of runs is equal to zero, and the ERA is equal to zero. However, if the number of runs is equal to 1, the ERA is equal to 1. If the pitcher faces 54 batters, the ERA is equal to 0.5. Stated otherwise, the ERA is a reflection of the number of runners who have scored for every 27 outs. However, this is without regard to the number of inherited runners, the number of innings in which the runs were scored, the bases on which the inherited runners were on, etc. However, the SRA provides more information about the real performance of the relief pitcher. Thus, the greater the number of inherited runners that score, the higher the SRA. The SRA also increases if such runs are scored in later innings, or from lower bases.
[0070] It will be evident, therefore, that the SRA provides a more accurate and more complete picture of the capabilities or performance of a relief pitcher in the circumstances described. By using the formula for the SRA, in its broader or more refined form, a numerical value can be placed on what the relief pitcher has saved. In other words, “a save is not a save is not a save.” All saves are not equal. The SRA in accordance with the present invention makes the necessary adjustment to reflect this and serves as a valuable tool and criterion for analysis when comparing relief pitchers in the final innings of a baseball game.
[0071] While this invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that variations and modifications will be effected within the spirit and scope of the invention as described herein and as defined in the appended claims. Thus, for example, formulas (2)-(4) can be modified to add, delete or give different weights to any of the factors that serve as multipliers for the runs R 1 , R 2 and/or R 3 . The “out” factors k 00 , k 10 and k 20 may be discounted or made equal to zero. While this simplifies the computation, it eliminates the statistic's ability to vary the weight to runs scored when there are different numbers of outs at the time that the relief pitcher is called in. It should also be clear that each of the factors (e.g., k i ) can be adjusted to penalize a pitcher more or less as conditions vary. The factors can be incrementally increased or decreased, or can be inverted and adjusted as a divisor instead of a multiplier in the equations (e.g., (R 1 k 1 ÷k i ) instead of (R 1 k 1 X k i ) as in equation (2)). Additional factors not currently reflected in the equations for the SRA might also be added —such as, for example, whether the game is a night game, poor weather conditions (e.g., rain)—all of which may make it easier or more difficult for a pitcher to perform well.
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A method of evaluating the performance of a relief pitcher in the late innings of a baseball game factors through data as to when a pitcher inherits at least one player on base. The following steps of the method are disclosed: first, establishing the number of runs R scored by such inherited players; second, establishing the number of batters B faced in such innings; and, finally, evaluating the save-run average “SRA” according to the formula:
SRA = k ( R B ) ,
where k is a predetermined constant selected to scale the SRA to a desired magnitude.
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CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/515,973, filed on Aug. 7, 2011, entitled “MAC Type Auto Detection Method”, the contents of which are incorporated herein in their entirety.
BACKGROUND
With rapidly growing of user's needs for accessing digital contents everywhere, various communication technologies have been developed for transmission of the digital contents. These communication technologies may be developed for different environments, different transmission speeds and/or different user requirements. In addition, several medium access control (MAC) protocols are established based on different communication standards, which define different communication methods based on heterogeneous mediums. For example, IEEE 1901 communication standard is used for power line (PLC), IEEE 802.11 communication standard is used for wireless communication (i.e. WiFi), IEEE 802.3 communication standard is used for Ethernet, and Multimedia over Coax Alliance (MoCA) communication standard is used for coaxial cables, and so on.
As a result, a MAC abstraction sub-layer is developed for convergence of these various media. Please refer to FIG. 1 , which is a schematic diagram of an exemplary communication device 10 in a data plane. The communication device 10 may be a mobile phone, laptop, tablet computer, electronic book, modem, or portable computer system, and uses various media for communication. In FIG. 1 , the MAC abstraction sub-layer is arranged between an upper layer and a plurality of MAC types of a MAC layer corresponding to a plurality of communication standards. The upper layer can be a network layer, a transport layer, an application layer or any layer responsible for processing the signalings and the packets received from the MAC abstraction sub-layer, and signalings and packets to be transmitted via the MAC abstraction sub-layer. The plurality of MAC types of the MAC layer may include Ethernet, WiFi, PLC and MoCA complied with to the IEEE 802.3 communication standard, IEEE 802.11 communication standard, IEEE 1901 communication standard and MoCA communication standard, respectively.
However, with current MAC abstraction sub-layer architecture, the MAC abstraction sub-layer is incapable to know what the underlying MAC type (e.g. Ethernet, WiFi, PLC or MoCA) of the MAC layer is. Thus, the MAC abstraction sub-layer cannot well control the MAC layer of the communication device. For example, the MAC abstraction sub-layer may configure improper parameters to the MAC layer due to uncertain underlying MAC type of the MAC layer, causing an invalid configuration or system error in the communication device.
SUMMARY
The present invention therefore provides a method of medium access control type detection, to solve the abovementioned problems.
The present invention discloses a method of medium access control (MAC) type detection for a communication device compatible of a plurality of media each conformed to a communication standard in a network system. The method comprises generating a library, wherein the library includes at least a character for each medium, configuring a MAC layer of the communication device according to the library, and determining the existence of a medium according to the configuration result.
These and other objectives of the present invention will no doubt become obvious to those of ordinary skill in the art after reading the following detailed description of the preferred embodiment that is illustrated in the various figures and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a communication device according to the prior art.
FIG. 2 is a schematic diagram of an exemplary communication device according to the present invention.
FIG. 3 is a flowchart of a MAC type detection process according to the present invention.
FIG. 4 is a schematic diagram of a library according to an example of the present invention.
FIG. 5 is a schematic diagram of a MAC type auto detection process according to FIG. 4 .
FIG. 6 is a schematic diagram of a MAC type auto detection process according to an example of the present invention.
DETAILED DESCRIPTION
Please refer to FIG. 2 , which is a schematic diagram of an exemplary communication device 20 according to the present invention. The communication device 20 can be a device shown in FIG. 1 . The communication device 20 may include a processor 200 such as a microprocessor or an Application Specific Integrated Circuit (ASIC), a storage unit 210 and a communication interfacing unit 220 . The storage unit 210 may be any data storage device that can store a program code 214 , accessed by the processor 200 . Examples of the storage unit 210 include but are not limited to a subscriber identity module (SIM), read-only memory (ROM), flash memory, random-access memory (RAM), CD-ROM/DVD-ROM, magnetic tape, hard disk, and optical data storage device. The communication interfacing unit 220 is preferably a transceiver and can exchange signals with a unified terminal device or the network according to processing results of the processor 200 .
Note that, the main idea of the present invention is to provide a method of detecting the underlying MAC type in the MAC abstraction sub-layer. Please refer to FIG. 3 , which is a flowchart of a MAC type detection process 30 according to an example of the present invention. The MAC type detection process 30 is utilized in the MAC abstraction sub-layer shown in FIG. 1 . The MAC type detection process 30 may be compiled into the program code 214 of FIG. 2 and includes the following steps:
Step 300 : Start.
Step 302 : Generate a library including at least a character for each medium.
Step 304 : Configure a MAC layer of the communication device according to the library.
Step 306 : Determine the existence of a medium according to the configuration result.
Step 308 : End.
According to the MAC type detection process 30 , a feature library includes at least a character dedicated for a medium (or hereafter called MAC type) is generated and stored in the MAC abstraction sub-layer. The MAC abstraction sub-layer configures the underlying MAC layer with a parameter generated according to a character of a MAC type in the feature library, and then determines whether the MAC type of the MAC layer exists according to the configuration result. For example, if the configuration with the parameter is successful, the MAC abstraction sub-layer determines that the corresponding MAC type exists, whereas if the configuration with the parameter fails, the MAC abstraction sub-layer determines that the MAC type does not exist.
In detail, the feature library is generated by extracting a unique character of each medium based on a specification of the communication standard (IEEE 1901, IEEE 802.11, IEEE 802.3, and MoCA). For example, Service Set Identifier (SSID) only exists in WiFi, so SSID can be included in the feature library. Or, NPW only exists in PLC, so NPW can be included in the feature library. Further, please refer to FIG. 4 , which is a schematic diagram of a library according to an example of the present invention. In FIG. 4 , the library can be extended from 4 MAC types (e.g. Ethernet, WiFi, PLC, and MoCA) to N MAC types, and can be extended from 1 character (e.g. Speed/duplex, SSID, NPW, Password) for each MAC type to M characters for each MAC type.
Please refer to FIG. 5 , which illustrates a MAC type auto detection process 50 based on the library of FIG. 4 . In FIG. 4 , there are a number of N MAC types and a number of M characters of each MAC type. In FIG. 5 , “i” is used as a MAC type index, where i=1, 2, . . . N representing different MAC types, such as WiFi, Ethernet, PLC, and MoCA, and “j” is used as character index, where j=1, 2, . . . M representing different characters for each MAC type, such as Speed/duplex, SSID, password and NPW. The MAC abstraction sub-layer firstly generates a first parameter according to a first character (i.e. j=1, representing character of Speed/duplex) of a first MAC type (i.e. i=1, representing MAC type of Ethernet), and then configures the first parameter to the underlying MAC layer (step 504 ). After that, the MAC abstraction sub-layer reads the parameter value from the underlying MAC layer to check if the configuration with the first parameter is successful (step 506 ). If the configuration with the first parameter is successful, the MAC abstraction sub-layer records that the first MAC type exists (step 508 ). On the other hand, if the configuration with the first parameter is not successful, the MAC abstraction sub-layer generates a second parameter according to a second character (i.e. j=2) of the first MAC type (i.e. i=1, representing MAC type of Ethernet), and then configures the second parameter to the underlying MAC layer (back to step 504 ). Note that, if all parameters generated according to characters (i.e. j=1−M) of the first MAC type (i.e. i=1) fail for configuration, the MAC abstraction sub-layer determines that the first MAC type does not exist. In addition, the MAC abstraction sub-layer generates parameters according to characters (i.e. j=1−M) of a second MAC type (i=2, representing MAC type of WiFi), and configures the parameters to the underlying MAC layer one by one. After configuring one parameter associated to one character of the second MAC type to the MAC layer, the MAC abstraction sub-layer reads the parameter value from the underlying MAC layer to check if the configuration is successful. If the configuration is successful, the MAC abstraction sub-layer records that the second MAC type exists. On the other hand, if the configuration is not successful, the MAC abstraction sub-layer configures another parameter associated to another character of the second MAC type, and performs the abovementioned steps until all characters of all MAC types in the library are applied. With the concept of the MAC type auto detection process 50 , MAC abstraction sub-layer knows which MAC type is underlying, and thereby can well control the MAC layer of the communication device 20 .
Moreover, take another example based on the above description. Please refer to FIG. 6 , which is a schematic diagram of a MAC type auto detection process according to an example of the present invention. Assure that a library includes 4 MAC types, such as Ethernet, WiFi, PLC and MoCA, and 1 character for each MAC type, such as speed/duplex, SSID, NPW and password. The MAC abstraction sub-layer generates a parameter according to the speed/duplex setting=100 M/Full duplex, for Ethernet, and configures this parameter to the underlying MAC layer. The MAC abstraction sub-layer gets this parameter value from the underlying MAC layer to check if the configuration is successful. If the configuration is successful, the MAC abstraction sub-layer records Ethernet is underlying. However, if the configuration is not successful, the MAC abstraction sub-layer determines that Ethernet is not underlying. In addition, the MAC abstraction sub-layer generate another parameter according to the SSID=xxxx, for WiFi, and configures it to the underlying MAC layer. The MAC abstraction sub-layer gets this parameter value from the underlying MAC layer to check if the configuration is successful. If the configuration is successful, the MAC abstraction sub-layer records WiFi is underlying, whereas if the configuration is not successful, the MAC abstraction sub-layer determines that WiFi is not underlying. Moreover, the MAC abstraction sub-layer generate another parameter according to the NPW=YYY, for PLC, and configures it to the underlying MAC layer. The MAC abstraction sub-layer gets this parameter value from the underlying MAC layer to check if the configuration is successful. If the configuration is successful, the MAC abstraction sub-layer records PLC is underlying. Similarly, if the configuration is not successful, the MAC abstraction sub-layer determines that PLC is not underlying and further generates another parameter according to the password=zzz, for MoCA, and configures it to the underlying MAC layer, and so on
Please note that, those skilled in the art may realize the MAC type detection process by means of software, hardware or their combinations. More specifically, the abovementioned steps of the processes including suggested steps can be realized by means that could be a hardware, a firmware known as a combination of a hardware device and computer instructions and data that reside as read-only software on the hardware device, or an electronic system. Examples of hardware can include analog, digital and mixed circuits known as microcircuit, microchip, or silicon chip. Examples of the electronic system can include a system on chip (SOC), system in package (SiP), a computer on module (COM), and the communication device 20 .
To sum up, the present invention provides a method of auto detecting the underlying MAC type in the MAC abstraction sub-layer. By knowing the underlying MAC type of the MAC layer, the MAC abstraction sub-layer can well control the MAC layer control of the communication device, and thereby configures proper parameters to the MAC layer of the communication device.
Those skilled in the art will readily observe that numerous modifications and alterations of the device and method may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.
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A method of medium access control (MAC) type detection for a communication device compatible of a plurality of media each conformed to a communication standard in a network system is disclosed. The method comprises generating a library, wherein the library includes at least a character for each medium, configuring a MAC layer of the communication device according to the library, and determining the existence of a medium according to the configuration result.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a Division of U.S. application Ser. No. 13/135,996 filed Jul. 19, 2011. Said application Ser. No. 13/135,996 is a Continuation-In-Part of application Ser. No. 12/579,900 filed Oct. 15, 2009 and claims the priority date for subject matter common therewith. Said application Ser. No. 12/579,900 claims the priority date of Provisional Application No. 61/242,251 filed Sep. 14, 2009.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present invention relates to a system and method for landing/positioning a device at a known depth within a pipe string suspended within a wellbore without the use of e-line, wireline, slickline or similar tether lowered from the surface. The present invention is preferably utilized to position a downhole tool such as, for example, a jet cutter, a shaped charge, a perforating gun, an explosive charge, a perforating gun or well logging sensor in a tubing string for purposes of pipe cutting, pipe perforation, formation perforation, pipe recovery, well plugging, well logging or similar exercises. In one embodiment, the invention relates to placement of explosive charges or a jet cutter within a short section of easily and confidently severed pipe that may be inserted at numerous locations in a pipe string at numerous predetermined locations for separating an upper portion of a pipe string from a lower portion at a precisely predetermined location. In another embodiment, the invention relates to a well logging method that requires no surface linkage during the survey.
SUMMARY OF THE INVENTION
[0003] The present invention system provides a series of internally profiled seating subs which are distributed within a pipe string to form a plurality of spaced apart pipe bore apertures immovably disposed along the pipe string length. Each seating sub aperture is characterized by a cross-sectional profile of varying shape with an aperture of a predetermined diameter formed therein. The internally profiled seating subs are arranged so that the aperture diameters decrease in regressive increments as the pipe string extends deeper in a well bore. Utilized in conjunction with these internally profiled seating subs is a sealing plug of an external diameter selected to sealingly engage a specific one of said profiled seating subs. The select diameter sealing plug is configured to be secured to the exterior of a down hole tool assembly that includes a service tool such as a firing head, shaped charge cutter, perforating gun or stand alone well logging instrument to permit the tool assembly to be landed on a seating aperture at a desired depth. The known distance from the seating aperture to precisely where the service tool functions in the pipe string is critical to the ability to predict what service tool is best suited to achieving the desired result.
[0004] More specifically, an invention intent is to install these seating subs at strategically determined points along the length of a pipe string such as a drill string, drill pipe, drill collars, tubing, tubulars or casing in a sequence that progresses from the largest diameter aperture restriction to the smallest diameter aperture restriction. An independent device carrying a plug profile of predetermined diametric dimension, when dropped freely or pumped from the surface through the pipe string, will pass through the pipe string until the device strikes a seating aperture beyond which it cannot pass; e.g. a seating aperture diameter that is smaller than the outer diameter of the plug. A metal-to-metal (or other) seal will enable fluid pressure to be applied to the to the pipe string bore above the seal for various purposes such as, for example, triggering an explosive tool firing head and/or opening a by-pass valve and or revealing the location of a logging tool. The type of device utilized in the system can be any service tool utilized in downhole applications.
[0005] Although not intended to be limited for use with any particular device, the system is particularly useful in pipe recovery operations that may use service tools such as a jet cutter, severing tool, torch cutter or chemical cutter. Other uses for the invention may also include specific placement of perforating guns and well logging sensors.
[0006] An additional embodiment of the invention combines a restriction or internally profiled seating sub as described above with a specially designed cutaway sub. The combination of seating sub and cutaway sub may be integrated with a pipe string at numerous, spaced, but carefully measured locations along the pipe string length and especially above or along the drill string weight collars. The cutaway sub includes a sacrificial section having a reduced external diameter (reduced wall thickness), relative the upper and lower coupling portions of the sub. Utilizing an aperture profile positioned above the section of reduced pipe wall annulus that is to be severed, the appropriate severing tool (such as a jet cutter or shaped charge explosive) may be accurately and confidently located to effect a clean cut. Significantly, once the cut is made and the upper section of drill string is withdrawn, the severed end of the reduced pipe wall annulus remaining with the lower end of the drill string is easily accessed by conventional “fishing” technology because the severed end is not excessively flared. This reduced wall annulus section of pipe also facilitates perforating operations previously made very difficult if not impossible by the thickness of the drill collar. The tensile strength of a particular cutaway sub is designed to be sufficient to support the pipe string below the particular sub. This may be a variable value since those cutaway subs near the lower end of a pipe string support less pipe weight below them than those cutaway subs near the surface or top of a pipe string which must support the weight of the entire string below.
[0007] A sleeve or bushing may be installed over the reduced wall annulus section of the severing sub to ensure that the buckling and torsional strength threshold of the sub is maintained.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] The advantages and further features of the invention will be readily appreciated by those of ordinary skill in the art as the same becomes better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings in which like reference characters designate like or similar elements throughout.
[0009] FIG. 1A illustrates a section of pipe string having two sub units of the invention inserted between a upper pipe section and a lower pipe section.
[0010] FIG. 1B is a sectioned view of FIG. 1A showing a drop assembly within the pipe string in pipe cutting position.
[0011] FIG. 1C is a sectioned view of FIG. 1A showing the discharge of a jet cutting tool against a reduced wall annulus section of the sacrificial mandrel.
[0012] FIG. 1D is a sectioned view of the severed pipe section of FIG. 1C showing withdrawal of the upper pipe section from the severed lower pipe section.
[0013] FIG. 1E is a sectioned view of the severed pipe stub remaining below the cut of FIG. 1C .
[0014] FIG. 1F is a full profile view of the severed stub remainder of the pipe section.
[0015] FIG. 2 portrays the cross-section of a pipe string with a series of seating apertures disposed therein to form decreasing restrictions along the length of the pipe string.
[0016] FIG. 3 illustrates the invention drop assembly.
[0017] FIG. 3A is an enlarged, partially sectioned view of the drop assembly along the top section A of FIG. 3 .
[0018] FIG. 3B is an enlarged, partially sectioned view of the drop assembly along the mid-section B of FIG. 3 .
[0019] FIG. 3C is an enlarged, partially sectioned view of the drop assembly along the bottom section C of FIG. 3 .
[0020] FIG. 4 is an enlarged sectioned view of the present invention firing head.
[0021] FIG. 5 is an exploded view of a preferred cutaway sub embodiment.
[0022] FIG. 5A-A is a cross-section view of the seating sub at cutting plane A-A of FIG. 5
[0023] FIG. 6 is a sectioned view of the preferred cutaway sub embodiment.
[0024] FIG. 7 is an exploded view of an alternative cutaway sub embodiment.
[0025] FIG. 8 is a sectioned view of the FIG. 7 cutaway sub embodiment.
[0026] FIG. 9 is a sectioned view of an alternative sacrificial mandrel embodiment.
[0027] FIG. 10 is a sectioned view of a second alternative cutaway sub embodiment.
[0028] FIG. 11 is a sectioned view of an alternative invention application.
[0029] FIG. 12 is a partially sectioned view of a well logging application of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0030] As used herein, the terms “up” and “down”, “upper” and “lower”, “above” and “below” and other like terms indicating relative positions above or below a given point of element are used in the description to more clearly describe some embodiments of the invention. However, when applied to equipment and methods for use in wells that are deviated or horizontal, such terms may refer to a left to right, right to left or other relationship as appropriate. Moreover, in the specification and appended claims, the terms “pipe”, “tube”, “tubular”, “casing”, “liner” and/or other tubular goods are to be interpreted and defined generically to mean any and all of such elements without limitation of industry usage.
[0031] The basic sequence of the present invention, as practiced, for example, upon a drill string cutting operation, is represented by the six view, A-F of FIG. 1 . The FIG. 1A view shows an assembly of the basic invention components in a downhole pipe string between an upper section 10 and a lower section 16 . An expanded description of each of these constituent components will follow hereafter.
[0032] The FIG. 1A illustration is usually most relevant to that heavyweight section of drill pipe at the bottom end of a drill string having joints of pipe with extremely thick wall annuli. To the well driller's art, these pipe joints with exceptionally thick walls are known as “drill collars”. The invention seating sub 12 and cutaway sub 14 may be positioned at the upper end of the collar section or at any intermediate point or at numerous points below the upper end. However, those of ordinary skill will understand that the principles described herein with respect to drill collars are applicable to any form or application of pipe or tube.
[0033] Referring to the sectioned view of FIG. 1B , an independent drop assembly 22 is released at the surface to be driven by pump pressure or to descend in free-fall along the pipe bore to terminate upon a plug seating aperture 24 in the seating sub 12 . A drop assembly extension 26 , usually extending below the seating aperture 24 is shown to support a jet cutting pyrotechnic tool such as a thermite or shaped charge explosive 28 . The extension 26 length is selected to place the jet cutter 28 within the pipe bore opposite a thin wall section 30 of a sacrificial mandrel 20 portion of the cutaway sub 14 .
[0034] FIG. 1B illustrates the drop assembly 22 as firmly resting upon seating aperture 24 . Fluid pressure within the upper pipe string bore is increased to open a firing head valve disposed within the drop assembly 22 . Opening the firing head valve initiates the jet cutter 28 ignition sequence to discharge a high temperature cutting jet along cutting plane 29 against the thin wall section 30 of the sacrificial mandrel 20 as represented by FIG. 1C .
[0035] With the thin wall section 30 of the sacrificial mandrel 20 severed, FIG. 1D shows the seating sub 12 and torque sleeve portions of the upper pipe string 10 as free to separate from the sacrificial mandrel stub 32 which remains fixed to the well bottom. FIG. 1E shows the sacrificial mandrel stub 32 portion of the cutaway sub 14 in section as remaining with the well bottom pending further, independent action of recovery or well abandonment. FIG. 1F shows the mandrel stub 32 in full profile.
[0036] Seating Sub
[0037] While FIG. 1 illustrates the invention in one particular application and embodiment, FIG. 2 illustrates a greater and more generic application wherein a series of seating subs 12 are distributed along the length of the supported pipe string. The seating subs 12 a, 12 b, 12 c, and 12 d are internally profiled by plug seating apertures 24 of graduated diameter “D” forming restrictions in the interior diameter of the subs. The subs, positioned at measured locations in a pipe string 10 extending from the surface 11 into a well bore 19 , are arranged so that the largest diameter profile or restriction is nearest to the surface, with ever decreasing (in diameter) profiles, such that the deepest/lowest sub in the string has the smallest diameter profile or restriction. For example, in FIG. 2 , seating aperture 24 a of sub 12 a , nearest the surface 11 , has the largest diameter D a restriction, while aperture 24 d of sub 12 d, deepest in wellbore 19 , has the smallest diameter D d restriction. The consecutive diameters D a , D b , D c , and D d decrease with depth along wellbore 19 . In any event, the seating apertures 24 are disposed to engage the sealing plug 34 (shown in FIG. 3 ) of the drop assembly 22 .
[0038] In one preferred embodiment, the seating subs 12 are only approximately two feet long and can be readily threaded or inserted into a pipe string during make-up. In one embodiment of the invention, up to five seating subs 12 are provided and arranged so that the effective restriction diameter between consecutive subs decreases from the first sub (nearest the surface) to the last sub (deepest in the wellbore) in the pipe string. In other embodiments of the invention, at least fifty seating subs 12 may be provided and arranged so that the effective restriction diameter between consecutive subs decreases from the first sub (nearest the surface) to the last sub (deepest in the wellbore) in the pipe string. In the course of such pipe string make-up, records will be made of the number of standard pipe joints or drill collars between each seating sub 12 . Hence, the distance from the top end of the pipe string to each seating aperture is a measured value. Of course, the number of seating subs and restrictions will depend on the length of the overall pipe string and the diameter of the pipe in which restriction are formed.
[0039] While the seating aperture 24 may take any shape, in the preferred embodiment, the apertures are formed of a lip or flange symmetrically disposed around the interior 42 of a seating sub 12 , thereby forming an immovable opening that is axially fixed and aligned relative to the internal bore of the seating sub. Preferably, this seating aperture is formed with a continuous, fluid sealing face 44 . However, those skilled in the art will appreciate that for certain applications that do not require a fluid tight seal, the seating aperture 24 need not extend fully around the interior of the seating sub 12 so long as a resulting aperture is formed to function as a restriction, thereby creating a seat on which an object can land. Nor does the aperture need to be symmetrical or axially aligned relative to the pipe sub, so long as the overall system comprises apertures of varying size arranged in consecutive order as described herein. For example, the seating aperture 24 may take the form of one or more tabs, fingers or projections extending into the bore of a pipe sub so as to form a “restriction” therein.
[0040] In one preferred embodiment, the seating aperture 24 has an upper sealing surface 44 and lower surface 46 . The upper surface 44 is contoured so as to engage an object provided with a similarly contoured profile, thereby permitting a seal to be formed between the object and the sealing surface when the object is seated on the upper surface 44 . In the example of FIG. 2 , upper surface 44 is curved to form a concave profile and disposed to receive an object with a correspondingly rounded or tapered shape (such as is shown on drop assembly 22 of FIG. 3 ). Once an object is seated, a seal is formed between the object and the sealing surface 44 as pressure is applied to the object by the fluid column above the object or otherwise by downwardly pumped fluid to the extent the object is disposed to pass fluid therethrough. In one example, if the object is connected to a explosive device, pressure from the surface applied to the upper end of the explosive device not only maintains the seal as described but may also be utilized to activate the explosive charge below the seal.
[0041] Drop Assembly
[0042] The drop assembly 22 illustrated by FIG. 3 is a preferred configuration for a tool, device or object that may be conveyed in a pipe string and externally shaped for landing on and engaging the seating aperture 24 . One intent of the invention is to provide a universal tool body adapted to receive a specifically sized sealing plug element 34 secured to the exterior of the tool body. A variety of standard downhole devices or service tools attached to the tool body, usually below the sealing plug, provide flexibility in the system for use with whatever tool and for whatever purpose is desired. Thus, in one embodiment of the invention, sealing plug 34 may be integrally formed as part of the device with which it is utilized, while in another embodiment of the invention, sealing plug 34 may be secured to the exterior of such device as an independent attachment
[0043] The basic elements of the drop assembly 22 are shown by the enlarged sections of FIGS. 3A , 3 B, and 3 C which correspond to segments A, B and C of FIG. 3 . With respect to FIG. 3A , a fishing head 50 may be provided at the upper end of the assembly 22 for independent tool descent or removal from the pipe string when desired. The anticipated normal use of the drop assembly 22 is a free release of the assembly at the surface 11 into the pipe string bore for pumped displacement or free-fall until the sealing plug 34 engages the seating aperture 24 . To control the rate of assembly descent, one or more units of swab cups 52 are provided to restrict the flow rate of standing bore fluid past the assembly as it descends. If pumped down the pipe bore, the swab cups 52 provide a ring seal between the assembly 22 and the pipe bore wall to increase the operational area of the upper pressurized fluid upon the assembly 22 . Additional to the swab cups 52 are one or more resilient centralizers 54 to keep the assembly aligned with the pipe string axis during the descent. Although there are many pipe centralizer configurations. the present embodiment provides three spring blades 56 secured to a carrier tube 58 . Apertures 59 in the carrier tube wall allow pressure equalization between the carrier tube interior and the surrounding pipe string bore.
[0044] FIGS. 3B and 3C collectively illustrate the drop assembly firing head 60 which is also shown in enlarged section by FIG. 4 . Central to the firing head 60 is a release valve mechanism comprising a differential area piston 62 that is initially held against an annular ledge as a bottom seat 64 in a bore sleeve by shear pins 65 . The piston 62 upper diameter 67 is greater than the diameter 68 below the fluid port 66 . Displacement of the piston 62 from an initial, port 66 closing position may only occur in an upward direction into a blind bore 70 by pressure differentially shearing pins 65 . Accordingly, the piston 62 is positively caged from accidental or shock release as it descends along the pipe string bore.
[0045] The sleeve 63 is threaded onto a tube extension 70 below the swab cup 52 . Tube extension 70 includes a blind bore 71 of substantially the same inside diameter as the large diameter 67 of the piston 62 .
[0046] A reduced diameter pintle 72 projects from the lower face of piston 62 into the bore 74 of a fluid transfer tube 73 . the upper end of the transfer tube is perforated by a plurality of biased angle apertures 75 . Each of the apertures 75 contains a latching ball 76 which has substantially the same diameter as the annulus thickness that is the differential between the pintle 72 radius and radius of the counterbore 77 in the bore sleeve 63 .
[0047] For the preferred embodiment, the transfer tube 73 extends through an axial bore 77 in the sealing plug 34 into a release sleeve 78 . A fluid flow annulus is provided between the outer perimeter of the transfer tube 73 and the inside wall of the sealing plug bore 77 .
[0048] At the release sleeve end of the transfer tube 73 , the transfer tube 73 is given an enlarged outside diameter 79 for a sliding, O-ring seal fit within a release sleeve bore restriction 122 between annular chambers 123 and 124 . The lower chamber 124 is ported by apertures 126 into the surrounding pipe string annulus
[0049] A firing pin housing tube 128 is threaded into the release sleeve 78 ( FIG. 4 ). The upper end of firing pin 130 is seated within the lower end of the transfer tube bore 74 with an O-ring fluid seal. The lower distal end 131 of the transfer tube engages a perimeter shoulder on the pin 130 to limit penetration of the pin 130 into the transfer tube bore 74 . The outside perimeter of the transfer tube 74 lower end is given and O-ring fluid seal fit within the housing tube bore. The up end 137 ( FIG. 3C ) of a linking tube 138 between a tool coupling 134 and the lower end of the housing tube 128 provides a travel limit shoulder for the transfer tube 73 and hence, the firing pin 130 . For the purpose of a pyrotechnic tool such as a jet or shaped charge tubing cutter, a percussion activated explosive initiator 135 will be secured in the tool coupling 134 . The stroke of the transfer tube 73 along the housing tube bore 132 is designed to bring the firing pin 130 striker point 139 into physical contact with the percussive initiator 135 .
[0050] In most applications, plug 34 engagement of a predetermined seating aperture 24 will isolate the pipe string bore into an upper fluid pressure zone above the seating aperture 24 and a lower pressure zone below the seating aperture 24 . The pressure in the upper zone at the seating aperture 24 is determined by the fluid head standing above the seating aperture 24 and any externally applied pump pressure. Pressure in the pipe string bore below the seating aperture 24 is usually determined by multiple factors such as the standing fluid head in the wellbore annulus, the presence of well packers, and the in situ bottom hole well pressure.
[0051] To trigger the firing pin against the explosive initiator 135 , fluid pressure in the upstream pipe bore is raised by pump pressure to exceed that of below the seating aperture by a sufficient differential to shear the pins 65 . Upper pipe bore fluid pressure enters the drop assembly through ports 66 to bear against the differential area piston 62 . Due to the dimensional difference between the large diameter 67 end of the piston and smaller diameter end 68 , a net shear force on the piston 62 is borne by the shear pins 65 . When the pins 65 fail under this differential area force, the piston 62 is driven upward into the blind bore 71 of extension tube 70 . When the piston 62 enters the blind bore 71 , the pintle 72 is extracted from the upper bore end of transfer tube 73 . Resultantly, the latching balls 76 are released into the bore 74 of transfer tube 73 .
[0052] When the differential area piston 62 shifts upward into the blind bore 71 , pressurized fluid in the upper pipe string bore also enters the inner chamber of the bore sleeve 63 to bear against the transfer tube 73 cross-section. The force of such cross-sectionally applied fluid pressure drives the transfer tube 73 downward along the sealing plug bore 77 and firing pin striker point 139 against the explosive initiator 135 . Simultaneously, the enlarged diameter section 79 of the transfer tube 73 is shifted downwardly from sealing contact with the release sleeve bore restriction 122 . The latter shift permits fluid flow from the upper pipe string segment to pass through the port 66 into the flow annulus between the transfer tube 73 and sealing plug bore 77 and out the release sleeve aperture 126 thereby bypassing the pipe string bore seal at the plug seating aperture 24 .
[0053] This fluid by-pass opening between ports 66 and 126 allows the drop assembly and any attached tool to be withdrawn from the pipe string by a wireline connected to the drop assembly fishing neck 50 . As the drop assembly 22 is lifted, the by-pass opening allows fluid in the pipe string bore to drain past the drop assembly into the pipe string bore below the drop assembly.
[0054] Cutaway Sub
[0055] The foregoing description has been of a system for precisely placing a specialty tool along the length of a pipe string bore. Among the numerous downhole operations receiving advantage from such positioning accuracy is that of pipe cutting. There are occasions when it is advantageous to sever a pipe string downhole and withdraw the upstring portion. The severed lower portion of the pipe string may be either abandoned in place or, as the usual case, recovered by one of numerous “fishing” techniques. When the objective is to sever a drill pipe, care is taken to place the cutting tool at a point along the pipe length between the pipe coupling joints. Pipe coupling joints normally have a considerably greater wall thickness than the nominal wall of the pipe. The thinner wall thickness of the nominal pipe wall is more easily severed with a ‘clean’ cut face without flash, burrs or flare which may interfere with extraction of either the severed, uphole string or of the downhole string.
[0056] Drill collars, however, are a special case wherein the outside diameter of a pipe joint is the same as the coupling diameter along the entire joint length. The functional purpose of such a configuration is for ballast weight at the bottom end of the drill string. Moreover, when a pipe string becomes ‘stuck” in a borehole in progress, it is frequently due to bore wall sloughing into the bore annulus around the drill collars. Hence arises the occasional necessity to sever the drill collar string mid-length. It is for this task, that the combination of the seating sub 12 as described above with a cutaway sub 14 is particularly useful. With respect to FIG. 1 , for example, the seating sub 12 and cutaway sub 14 are positioned between upper and lower drill collars 10 and 16 , respectively. Depending on the length of the drill collar assembly there may be a plurality of seating sub and cutaway sub combinations distributed along the drill collar segment of the pipe string.
[0057] Turning to the exploded view of FIG. 5 and cross-sectional views of FIGS. 5A-A and 6 , one preferred embodiment of a cutaway sub 14 is shown to include a sacrificial mandrel 20 having male threaded end-pins 140 at both ends. Axially adjacent the end-pins are stepped bosses 142 and 144 . between the two stepped bosses 142 and 144 is a relatively thin wall tube section 30 having an outside diameter that is substantially less than the nominal drill pipe or collar diameter. The upper (smaller) stepped portion 146 of boss 142 adjacent the threads 140 is formed with chordal wrench flats corresponding to the wrench flats 149 in the torque sleeve collar 147 shown by FIG. 5A-A . The number of wrench flats 149 is shown on the inside perimeter of the sleeve collar 147 are only a representative example. Those of ordinary skill will understand the collar 147 and boss step 146 may be given as many flats as required to transfer the forces necessary for rotatively driving the drill string below the seating sub 12 .
[0058] The greater outside diameter section of stepped boss 142 is dimensioned to receive the inside diameter of torque sleeve 18 with a slip-fit overlay.
[0059] The smaller, outside diameter section 150 of lower boss 144 also is preferably given a value corresponding to a slip fit overlay of the torque sleeve 18 . The larger diameter section 152 of the lower boss 144 may be essentially the same diameter as the drill collars 10 or 16 . The shoulder 153 between the two sections is cut with an undulating profile such as the lug socket profile 154 for meshing with a corresponding lug socket profile 156 in the end of torque sleeve 18 .
[0060] It will be understood that the rotary torque transfer function accomplished by the meshed wrench flats 149 in the torque sleeve collar 147 and the mandrel boss 146 may also be served by a multiplicity of meshing splines. In either case, the sleeve 18 is assembled with the mandrel 20 by an axially sliding fit to mesh the sleeve lug profiles 156 with the corresponding profiles 154 in the mandrel boss 144 . Simultaneously, the wrench flats 149 mesh with corresponding flats on the mandrel boss 142 . When the mandrel threads 140 are meshed with corresponding threads in the seating sub 12 , the torque sleeve 18 is firmly secured against the upper mandrel boss shoulder 146 and the dominance of all torsional stress transferred by the seating sub 12 to the sacrificial mandrel 20 is carried by the torque sleeve. 18 .
[0061] As previously described, numerous sub-sets of seating subs 12 and cutaway subs 14 may be distributed along the pipe string additional to those among the drill collars. When an occasion arises to sever the pipe string at a specific point, the drop assembly 22 is equipped with the sealing plug 34 corresponding to the assigned seating aperture 24 that is most proximate above the point of desired string separation. The pipe cutting tool, also secured to the drop assembly, is positioned below the sealing plug 34 at the same, precisely known distance as is the center of the thinwall section If sacrificial mandrel 20 below the seating aperture 24 . Hence, when the drop assembly 22 settles upon the seating aperture 24 , it is known with confidence, that cutting tool is correctly positioned relative to the sacrificial mandrel 20 .
[0062] It is also known, with confidence, that the drop assembly 22 has, in fact, settled against the designated seating aperture 24 by the fluid pressure rise within the pipe string bore against a surface pump supply. As the drop assembly descends the pipe string. The pipe bore pressure remains at circulation pressure. When the sealing plug 34 settles against the seating aperture 24 , circulation is terminated and bore pressure abruptly rises against the firing head 60 . This pressure rise will continue until the shear pin 65 rupture pressure is achieved to shift the differential area piston 62 upwardly off the bottom seat 64 and release the latching balls 76 . When the latching balls fall into the transfer tube bore 74 , the transfer tube 73 shifts downwardly to open the upstream fluid port 66 to flow communication with downstream fluid flow port 126 . When flow communication is established between fluid ports 66 and 126 , the bore pressure abruptly drops to the circulation pressure. Consequently, when the pipe string pressure abruptly spikes and then falls, it may be known that the drop assembly 22 has settled on the seating aperture 24 , the firing head has opened, the firing pin as fallen and the pipe cutter 28 or perforating gun has discharged.
[0063] In the usual course of operations, after discharge of the cutter 28 , the upper pipe string is withdrawn from the wellbore along with the seating sub 12 , the torque sleeve 18 and the upper portion of the sacrificial mandrel 20 including the upper boss 142 . Of the original cutaway sub 14 , only the lower boss 144 and lower pipe string remain in the wellbore subject to abandonment or further retrieval operations.
[0064] An alternative embodiment 80 of the cutaway sub with increased buckling strength is represented by FIGS. 7 and 8 as having a reduced wall thickness tube 81 between stepped bosses 84 and 85 . The upper end of the reduced wall tube 81 is terminated by an interior portion of the upper stepped boss 84 . The lower end of the tube 81 is terminated by the interior portion of the lower stepped boss 85 . Both interior boss portions are of greater outside diameter than the reduced wall tube 81 . At an axial set-back in opposite directions are an intermediate pair of stepped bosses 86 and 87 having a greater OD than the interior bosses 84 and 85 . The abutment transition between the interior and intermediate bosses is profiled with lug detents 92 . Meshing with the lug detents 92 are the lug projections 91 at opposite distal ends of a split sleeve 90 . There may be a plurality of such meshing lug projection 91 and detents 92 .
[0065] The internal bore 101 of torque sleeve 100 is sized to pass freely but closely with a slip fit over the intermediate bosses 86 and 87 . Lug 102 on the lower end of sleeve 100 are sized and configured to mesh with the lug detents 94 in the lower pin collar 88 . Referring to FIG. 8 , an inside abutment face 104 of end collar 103 is positioned at the distal end of sleeve bore 101 to engage a mating abutment face on the intermediate stepped boss 86 as the sleeve lugs 102 mesh with the collar detents 94 . Internal wrench flats on the upper stepped boss 96 as described for FIG. 5A-A are sized and configured to mesh with mating wrench flats (not shown) on the interior perimeter of the sleeve 100 end collar 103 .
[0066] A seating sub 106 may be constructed with tapered box threads 107 and 108 at opposite ends. When the tapered threads 82 and 108 are in full engagement, the inside abutment faces of the sleeve collar 104 and intermediate boss 86 are in compressed juxtaposition.
[0067] Those of skill in the art will appreciate the operative consequence of the FIGS. 7 and 8 assembly as not only stiffening the cutaway sub 80 but is also capable of transferring drive torque across the cutaway sub 80 through both inner and outer sleeves as well as the thinwall tube 81 . However, when the thinwall tube 81 is severed, the upper pipe string maintains firm assembly with the sleeve 100 and upper stepped boss elements of the sub 80 for withdrawal from the borehole. When the sleeve 100 is withdrawn. The split sleeve 90 halves have no radial confinement and merely fall away form the severed lower portion of the sub.
[0068] In some cases, even the release of the split sleeve halves 90 as borehole debris is intolerable or extremely expensive for a follow-up fishing trip to remove the resulting debris. Responsive to those applications. A third embodiment of the invention as represented by FIGS. 9 and 10 is suggested wherein the inner step 84 of the upper boss is grooved with a perimeter encircling channel 114 . The substantially cylindrical surfaces of both inner steps 84 and 85 may be cut with wrench flats 110 and 112 .
[0069] A further modification of the FIGS. 9 and 10 embodiment may include lug and detent engagements of the split sleeve 119 at the lower end as suggested for the FIGS. 7 and 8 embodiment. In either case, whether by lug and detent or by wrench flats, drive torque is transferred from the top seating sub 106 to the lower pin 83 through the additional structure of inner split sleeve 81 and torque sleeve 100 .
[0070] Those skilled in the art will appreciate that the system described herein provides certainty as to the depth of a tool in a pipe string. Once a drop assembly has landed on a seating aperture 24 and the pipe string pressure is raised against the shear pins 65 to be abruptly released, the drop assembly is known to be on the designated seating aperture and the exact position of a tool attached to the drop assembly relative to the seating aperture is also known.
[0071] FIGS. 11 and 12 illustrate an alternative embodiment of a drop assembly configured for placement of a non-explosive tool such as a battery powered well logging sensor for detecting certain geologic characteristics of the earth where penetrated by the wellbore. Distinctively, the transfer tube 73 element of the drop assembly needs no firing pin. Consequently, the distal end of the transfer tube 73 is closed with an end plug 157 . The firing head 60 becomes a one-time pressure actuated release valve. The housing tube 128 becomes an extension to which a battery pack 164 , a data recorder 162 and well logging sensor 160 are attached. The seating aperture 24 is positioned within the seating sub 12 to allow at least the sensor 160 end to extend beyond the open end 25 of the seating sub.
[0072] When a free falling drop assembly, for example, carries sensitive instrumentation such as well logging sensors, it may be prudent to finish the internal bore of the seating sub 12 for an extended distance above the seating aperture 24 to more closely interact with the swab cups 52 to slow the drop assembly descent before engaging the seating aperture 24 .
[0073] The total length of the pipe string, including the distal end 25 of the seating sub 12 and the position of the sensor 160 relative to the seating aperture 24 will be known. When pump pressure shears the pins 65 and a pump pressure spike is suddenly released, it is known, with confidence, exactly where the sensor 160 is located within the wellbore 19 . If the data recorder 162 operates continuously, the well may be logged continuously from the known position as the supporting pipe string is withdrawn with the logging tool attached. It will be recalled that the firing head by-pass valve is open therefore permitting standing pipe bore fluid above the seating aperture 24 to by-pass the seal and equalize the fluid pressure as the pipe string rises.
[0074] An additional benefit of the system is that a symmetrically disposed seating aperture within a pipe bore allows tools positioned with the system to be centralized in a pipe string resulting in substantially improved performance of the explosives relating to the pipe recovery system.
[0075] While the system of the invention is best utilized in the context of a vertical wellbore, those skilled in the art will understand that the invention may also be utilized in other elongated tubing sections where a fluid is pumped through the tube and an operation at a precise distance into the tube is required, including without limitation, horizontal wellbores, sewer lines, pipe lines and the like.
[0076] Likewise, while the system preferably eliminates the need for e-line, wireline, slickline or similar vehicles as a method for placement of a device, the system may still be utilized in conjunction with such vehicles to control the travel of such devices through the pipe string.
[0077] Although the invention disclosed herein has been describe in terms of specified and presently preferred embodiments which are set forth in detail, it should be understood that this is by illustration only and that the invention is not necessarily limited thereto. Alternative embodiments and operating techniques will become apparent to those of ordinary skill in the art in view of the present disclosure. Accordingly, modification of the invention are contemplated which may be made without departing from the spirit of the claimed invention.
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A string of drill pipe, for example, is assembled with a severing sub in anticipation of a possible need to cut the string at some point in the operation. The severing sub includes a thin wall tube that links opposite end tool joint bosses. The tin wall tube is easily cut by a shaped charge cutter. Rotary drive torque is transmitted between the sub tool join bosses by a concentric external torque tube having a torque transmitting assembly at each boss. The torque tube connection to the upper boss has an inseparable circumferential shoulder engagement with the boss. The lower boss engagement of the torque tube is axially separable. When the thin wall tube is cut, the upper boss and torque tube is withdrawn from the well with the upper pipe string.
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BRIEF SUMMARY OF THE INVENTION
A flow controller primarily for breathing gas analysis transmits the breathing gas from a source through an inlet to a branched circuit for flow to a vacuum device. The flow is both through a first branch and a parallel second branch. A gas analyzer is connected to the first branch near the inlet. Connected to the second branch is a pressure transducer controlling a variable leak of pressure adjusting air or other gas into the second branch at a predetermined location spaced downstream from the inlet. Molecules of air or other gas from the leak are prevented from flowing upstream in the first branch toward the inlet by a conduit between the predetermined location and the inlet, the conduit being formed to have a Peclet number of at least 4 and preferably of 6 or more.
PRIOR ART
The applicants are currently unaware of any prior art pertinent to the present disclosure.
BRIEF DESCRIPTION OF THE DRAWING
The FIGURE is a diagram, with some portions broken away and some portions in cross-section, showing a flow controller pursuant to the invention.
DETAILED DESCRIPTION
It is often desirable to monitor the gases; e.g. oxygen, utilized by patients being assisted in breathing when hospitalized or when being tested. These gases are sometimes referred to herein as "a gas". The monitoring is preferably during inhalation and exhalation in order to determine the components or constituencies of the involved gas. It is helpful to maintain a rigorous test procedure with an appropriate, accurate analyzer arranged so that variations in the breathing gas are not disruptive of the monitoring process, and arranged in such a way as to afford uniform or nearly uniform test conditions.
In order to provide such a test or controlled environment, there is disclosed, as an example, a breathing tube 6. This is connected at one end to the patient in any known way, such as by a face mask, and has a connection at the other end in accordance with standard practice. The gas flows through the breathing tube 6 in opposite directions at different times during the patient's breathing cycle, as indicated by the arrow 7.
To sample such gas or gases, there is provided a tube 8 intersecting the tube 6 at an appropriate point and preferably having a control valve 9 therein so that the flow area can be varied. The tube 8 leads through a connector 11 into a conduit 12 forming part of one circuit branch. A connector 13 opening at a first predetermined point into the conduit 12 is joined to a gas analyzer 14 of any appropriate sort. The analyzer in turn extends through connectors 16 to a tube 17 forming part of another circuit branch paralleling the conduit 12. The branches, including the conduit 12, and the tube 17, provide duplex paths for conjoint gas flow. The tube 17 is joined by a tube 18 to a block 19 open to a source 21 of vacuum or subatmospheric pressure, preferably any well-known vacuum pump, conveniently a two-stage pump. The conduit 12 at a second predetermined point connects through a tee 22 and a regulating valve 23 to a coupling 24. In turn, the coupling 24 joins to the block 19 and so is also in communication with the vacuum source 21. The end of the conduit 12, the tee 22, the valve 23, the coupling 24 and the block 19 afford a first circuit, branch, flow path or duct to the vacuum source. The conduit 12, the connector 13, the gas analyzer 14, the connectors 16, the tubes 17 and 18 and the block 19 afford a separate, second circuit, branch, flow path or duct to the vacuum source 21.
Also communicating with the block 19 and subject to the influence of the associated circuit branches is a pressure transducer 26 joined to the block through a pipe 27. The transducer 26 is effective to afford an electrical signal in a conductor 28, the signal corresponding to the pressure effective upon the transducer 26. The signal in the conductor 28 goes through a servo mechanism 29 effective to control a valve 31, preferably magnetically operated. The valve 31 is interposed between an inlet tube 32 open to the atmosphere and extending through a bacteria filter 33 to the inlet of the valve 31. The outlet 34 from the valve 31 is connected to the tee 22. Since the valve 31 is controlled by a signal from the transducer 26 through the conductor 28 and the servo circuit 29 and through a lead 36, the position of the valve 31 and flow from the atmosphere into the tee 22 and beyond is under the control of the pressure transducer 26.
Also engaging the conduit 12, preferably near the connector 13 of the gas analyzer, is a pressure transducer or gauge 41 indicating the instantaneous pressure within the tube 12.
Pursuant to the invention, the construction of the conduit 12 is of a special nature. The length and internal dimensions of the conduit 12 are such that the Peclet number for the conduit 12 is preferably about 6 or more and is greater than about 4. The Peclet number is a dimensionless number expressing the relationship of the magnitude of gas mass transport through the tube 12 by bulk flow due to gas velocity and by gas diffusivity. It is expressed as:
Peclet number=(VL/D) wherein
V=gas flow in cm/sec
L=characteristic flow path length in cm
D=mass diffusivity in cm 2 /sec
In early work on the present device, it was noted that nitrogen used as a pressure compensating or make-up gas and entering through the inlet 32 into the tee 22 was diffusing upstream against the downstream-flowing breathing gas (oxygen), and so was contaminating the breathing gas in-flow into the gas analyzer 14. This caused misleading readings. A study of gas diffusion, and especially of mass diffusivity, ensued. An estimate of gas diffusivity can be made from the relationship: ##EQU1## wherein T=temperature (T°K.) in degrees Kelvin
M=molecular weight
P=pressure in atmospheres
ρ AB =interaction distance between molecules in Ångstroms
Ω D ,AB =a dimensionless relationship between temperature and the intramolecular field
Using empirical information given in the reference Bird, Stewart and Lightfoot, "Transport Phenomena" (John Wiley & Sons, 1960), the values ρ AB and Ω D .sbsb.AB can be determined for oxygen and nitrogen. If T=298° K. and P=1 Torr or 1/760 atmosphere, it is determined that D AB =165 cm 2 /sec.
With this evaluation, a representative distance (L) axially of the conduit 12 approximately between the center of the connector 13 and the center of the fitting or tee 22 is about 13 cm. The diameter of the conduit 12 in one instance is preselected as 0.375 inches. The flow rate is 5 ml/min at standard temperature and pressure. The pressure is 0.1 Torr, V is 89 cm/sec, the Peclet number is about 6.0, and there is then no upstream flow of contaminating gas.
The Peclet number can be chosen at any desired value, depending upon a corresponding relationship of the involved factors. In practice, if some contamination is tolerable, the Peclet number may be as low as about 4 or 5, but the value 6 has been found to be acceptable for no contamination under the disclosed circumstances. While the proportions and relationships can be arranged to result in even higher Peclet numbers; say, 10, there is no particular benefit so far as contamination is concerned above the value around 6. When the above-noted relationships are observed, there is produced an acceptable operation of the structure.
With the tube 6 connected and arranged as a natural or induced breathing line for an individual and with the valve 23 set at a selected value to afford the desired degree of resistance, and with the circuitry energized and the vacuum pump 21 operating, there is gas flow from the restricting valve 9 to the vacuum source 21 as well as a corresponding pressure drop. There is flow from the breathing tube 6 through the connector 13 and through the gas analyzer 14 because the analyzer is also connected through the tubes 17 and 18 and the block 19 to the vacuum source 21.
There is continuous flow into the gas analyzer so that the analyzer can afford an instantaneous, current indication of the breathing gas flowing into and through it. The pressure of the diverted gas is indicated by the monitor gauge 41. The pressure and the flow in the tube 6 may tend to vary substantially. This partly depends upon the connections thereto; that is, whether a patient alone is connected to the breathing tube, or whether a breathing device is also used.
The general gas flow is through the conduit 12 from left to right in the FIGURE and to the vacuum source. The rate of flow is regulated in part by the position and restriction of the variable valve 23. Flows from the branch containing the tube 12 and from the branch containing the conduit 17 and tube 18 merge within the block 19 and that pressure is communicated through the tube 27 to the pressure transducer 26. Variations therein furnish signals through the conductor 28 and the servo conduit 29 and the conductor 36 to the valve 31. This valve correspondingly opens and closes, at least partially, to vary the in-flow of atmospheric air (or other supplied gas) through the leak 32, the filter 33, and through the valve 31 into the tee 22.
The atmospheric in-flow is preferably such in amount that the pressure in the conduit 12, for example, is maintained as nearly as possible at a constant value. Some of this inflowing air passes through the valve 23 to the vacuum source 21. Some of this air tends to move by diffusion upstream or from the tee 22 toward the connector 13; that is, contrary to or opposite to the direction of flow of the incoming gas from the breathing tube 6. The conduit 12 under many circumstances and unless specially arranged is subject to gas flows simultaneously in two directions. One of the flows, due to pressure drop, is in a direction from the left in the FIGURE; say, from the connector 11, for example, toward the tee 22. The other flow is molecular diffusion flow toward the left in the FIGURE from the tee 22 toward the connector 11. The pressure drop flow and the molecular diffusion flow under some circumstances are acceptable, but under other circumstances they are highly deleterious in that atmospheric air, for example, flows into the gas analyzer and contaminates the breathing gas sample furnished to the gas analyzer from the tube 6, so obscuring or precluding accurate results.
Especially to prohibit or control such contamination by upstream molecular flow, the dimensions or configurations of the conduit 12 are carefully limited to afford a Peclet number as above described. Under the described circumstances, the molecular air diffusion upstream from the tee 22 toward the connector 11 is not greater than the downstream flow of breathing gas from the connector 11 toward the tee 22. Gas arriving at the tee 22 from the inlet tube 32 does not diffuse upstream through the conduit 12 and so cannot enter through the fitting 13 into the analyzer 14 and contaminate the breathing gas being tested and so cannot affect the results of the gas analyzer 14.
Thus, with this arrangement it is possible despite variations in velocity and pressure by the breathing gas from the breathing tube 6 to afford a remarkably accurate gas analysis in the analyzer 14 by maintaining appropriate pressure in and flow through the conduit 12 and without permitting contamination by other gas let in to adjust or maintain the internal pressure within the conduit 12.
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A flow controller primarily for breathing gas analysis has a gas flow circuit leading from a breathing air inlet to a gas analyzer and to a vacuum source. Another gas is bled into the circuit between the breathing air inlet and a point upstream of the vacuum source. Such other gas is precluded from flowing upstream in the circuit toward the gas analyzer by making the intervening flow path or conduit of suitable dimensions to have a Peclet number at least equal to 4 and preferably greater than 4 and about 6.
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This application is based on my U.S. Provisional Patent Application Ser. No. 60/196126 filed Apr. 11, 2000.
This invention relates to an anchoring device adapted to enable securing and transporting of articles on a vehicle surface such as the bed of a pick-up truck, by means of tie downs with hooks at their ends. It further relates to a method of producing such devices.
BACKGROUND OF THE INVENTION
Well before the introduction of the very popular small pick-up truck in the United States, owners and truck manufacturers alike recognized the need to protect the truck bed from scratching and dents caused by bouncing and sliding of loads which could abrade the bed surfaces and sides. This damaged not only the truck bed, but also the objects being transported. Paint scratches would render the bed surface susceptible to corrosion and rusting, particularly if the truck was left out in wet weather. This disadvantage was successfully combated with the mass introduction of the plastic bed liner, a vacuum-molded unibody construction that effectively covered the truck bed and the vertical walls surrounding the bed. The hinged tail gate was covered by a flat panel of the same material, making the two separate pieces fully enclose all but the top of the vehicle load-carrying area.
Although the liners were flexible and somewhat yielding when unsupported, they were required to have sufficient strength and rigidity when in place on the truck bed. This was easily accomplished by making at least the floor or bottom wall of corrugated ribs of approximately one-half inch in width and height, usually extending lengthwise of the bed. The ribs could readily withstand the weight of a cargo load and also that of a few men standing in the truck. The ribs were spaced parallel to one another on about one-and-one quarter inch centers across the width and for most of the length of the liner. Generally, they were longitudinal relative to the truck, but some rib designs are diagonal. To prevent sand, dirt and water from passing through the liner floor or walls to the bed of the truck, there were no openings through the liner, the floor being essentially liquid impervious. Sand and dirt were of concern because of their abrasiveness, since sand risked wearing the bed paint if sand grains would be pressed against the paint whenever a person stood or walked on the corrugated floor during loading and unloading. While many popular trucks have liners made to specifically and relatively tightly fit their bed shapes, some are still prone to rain leakage around the edges whether or not they have overhanging edges intended to protect against that risk. Obviously, if the walls or floor bottom of a liner permitted passage of dirt and liquid through the liner, the protection sought in purchasing the liner in the first instance is nullified.
Particularly to enable ease of sliding heavy objects around on the floor of the liner, the top edges or peaks of the ribs were coplanar. The common plastic material used was one that inherently had reduced friction characteristics, ideal for sliding large sheets of plywood, wallboard, etc. around. For this purpose, the rib tops of the liner had to provide an essentially flat surface, i.e., there were to be no projections above the rib tops. Projections or protrusions would inhibit article sliding when needed during loading and unloading. They would tend also to damage things such as wallboard and were a potential tripping point for a person working in the truck bed. They also made use of a flat shovel difficult when unloading sand, dirt or gravel.
While the reduced friction is advantageous for loading and unloading, it is disadvantageous for those times when reduced friction is anathema to the objective sought, such, for example, as avoiding shifting, sliding and rolling of an unstable article while the vehicle is moving. There is a need for a truck bed liner that retains the reduced friction capability for those times when it is needed, but prevents sliding of objects or loads resting on the bottom wall of the liner whenever the intention is to hold them against shifting. Load shifting can be dangerous to truck occupants as well as to others on the road. It risks causing of an accident, as well as causing damage to the vehicle. If something like a toolbox or length of pipe is merely laid freely on an existing standard liner floor, a sharp turn or swerve of the vehicle can cause the box to slide or the pipe to roll across the liner. A resultant noise can distract the driver, causing him or her to look over the shoulder through the rear view window, just long enough to risk having an accident.
Numerous attempts have been made in the prior art to solve the problem of load shifting by securing the load, but all have been somewhat complex, resulting in a liner floor which is difficult if not impossible to clean or sacrifices desirable attributes of existing liners. One patent, U.S. Pat. No. 5,253,918 issued Oct. 19, 1993 to Stephen R. Wood et al, shows a variety of ways for tying down articles to a bed liner. One embodiment incorporates the provision of holes in protrusions rising above the ribs of a bed liner. The protrusions effectively prevent the tops of the ribs from being used as a flat surface on which articles can be slid during loading and unloading of cargo. Those same protrusions make walking on the liner difficult without the potential for tripping. The protrusions also span three ribs crosswise, making water drainage and cleanability an additional problem due to the damming effect across the valleys between the ribs. The manner in which the protrusions are made also requires a special top surface for the vacuum form and necessitates placement of a number of vertically-standing washers on the form for each liner produced. These washers become integral parts of the liner when removed from the form. It is uncertain whether the above '918 patent teaching is capable of providing a leak proof liner surface.
There also exists the need to stabilize certain types of articles during vehicular transportation in a car trunk or on the bed of a station wagon, van or sports utility vehicle (SUV). One solution to this problem is illustrated in my U.S. Pat. No. 6,065,916 issued May 23, 2000 and entitled Portable Base for Anchoring and Transporting Unstable Articles. While quite suitable for handling dry or clean articles, the base of my '916 patent is not leak-proof and is therefore incapable of preventing liquid, dirt or sand particles from wetting or dirtying the underlying carpet or floor.
In recent years, an alternative to truck bed liners has been introduced, namely, a spray-on protective coating that permanently adheres to the inside surfaces of the bed. To date, there appears to be no known solution to preventing sliding, rolling or other shifting of cargo in such coated beds. It further appears that coated beds do not have the same reduced friction surfaces as do plastic molded bed liners, making loading and unloading of heavy or large objects a bit more difficult.
SUMMARY OF THE INVENTION
The bed liner of a pick-up truck has elongated corrugated ribs with selected ribs or portions of ribs having holes or openings extending horizontally therethrough for enabling elastic tie downs to anchor objects that are being transported, the anchoring being done in any location on the truck bed. The design is such that the holes do not pass through the liner, i.e., the inner (upper) surface of the liner does not communicate with the outer (lower) surface thereof. The strength, minimal friction, cleanability and water impermeability characteristics of the liner are retained, while adding the desirable feature of being able to selectively anchor objects of any shape and size in any location on the bed. The liner preferably may have the holes produced in the liner at the time of manufacture, or the holes may be made by the purchaser in selected locations before or after installation in the truck. The holes may, in some designs, be located in separate elements that are installed on the liner. The liner may be separate from or integral with the body structure of a truck bed. The invention is also applicable to a panel used on the floor of a car trunk or van to carry wet or dirty items such as boots, etc., adding the anchoring feature to its usefulness.
A principal object of the invention is to provide a truck bed liner which retains the desirable characteristics of a reduced-friction flat top surface and impermeability to sand, dirt and water, while adding the further features of enabling variably positioning and secure anchoring of objects to be transported.
Another object is to provide for anchoring holes to be provided in the bed liner either at the time of manufacture or afterward, integral with or separate from the liner.
Still another object of the invention is the provision of anchoring holes below the top surface of a liner, i.e., avoiding the protrusion of anchoring means extending above the top surface.
Yet another object is to provide a leak-proof truck bed article-anchoring device that may be separate from or integral with the body structure of the truck.
A further object is to provide a liner or other panel which has the characteristics of liquid impermeability, cleanability and strength, but which can have anchoring holes or openings added thereto at any time while retaining those characteristics.
Another object is to avoid having anchoring holes above a top surface of coplanar ribs and to further avoid damming of liquid or dirt from draining or being removed from between the ribs.
Still another object is to provide a novel method of producing solid material portions in a vacuum-formed corrugated panel for enabling creation of holes through the solid portions.
Other objects and advantages will become apparent from the following description, in which reference is made to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a simplified isometric view of a bed liner illustrating two different objects secured to the floor or bottom wall of the liner, as the liner would rest on the bed of a truck.
FIG. 2 is an enlarged plan view portion of the floor and/or walls of the liner of FIG. 1, illustrating a preferred form of my invention.
FIG. 3 is a cross-sectional view taken substantially along lines 3 — 3 of FIG. 2 .
FIG. 4 is a cross-sectional view taken substantially along lines 4 — 4 of FIG. 2 .
FIG. 5 is an isometric view of a variation of the rib construction in which selected ribs may be made of solid material for their full lengths.
FIG. 6 illustrates in isometric form still yet another variation of a molded liner with anchoring openings provided by a bridge spanning a pair of adjacent ribs.
FIG. 7 illustrates still another variation in which the anchoring holes are provided in parts that are separable from and secured to the liner main body.
FIG. 8 is an enlarged view of one of the separable parts of FIG. 7, showing how the part is secured to the liner body
FIG. 9 illustrates still another variation of rib which may be separable from the main body of the liner and attached thereto after molding.
FIGS. 10-12 illustrate a preferred process of producing solid material portions in a rib of a panel produced by vacuum forming.
FIG. 13 is an isometric view incorporating a portion of a vacuum form for producing a bed liner that has the good drainability and cleanability characteristics found in FIG. 14 .
FIG. 14 is a plan view of a portion of a bed liner floor produced on the vacuum form of FIG. 13 .
FIG. 15 is a simplified plan view of a panel used in car trunks and on floors of station wagons and the like for protecting carpeting from dirt and water carried on boots, shoes, etc., the panel further incorporating the anchoring feature of my invention so as to make it a multifunction article.
FIG. 16 is a simplified cross-sectional view of another embodiment of a truck bed liner which is manufactured as a permanent integral part of the vehicle bed and has anchoring means on both the bottom and side walls of the bed.
FIG. 17 is a modified version of the FIG. 16 embodiment, having only a bottom wall serving essentially as a tray that is an integral part of the vehicle.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a simplified pictorial view of one form of a separate bed liner 10 embodying my invention. The liner includes a floor or bottom wall 12 , a pair of opposed side walls 14 and a front wall 16 . A separate tail gate panel (not shown) would normally cover the open left end of the liner 10 , and would be mounted on the typical hinged tail gate. Many liner designs are provided with a rail guard or ledge 18 extending around the liner 10 for a short distance outwardly of the side and front walls to protect the upper edges of the side and front walls of the truck bed body structure and also inhibit dirt and liquids from getting between the walls of the liner and the bed. Indentations 20 are molded into the liner to cover the typical inset wheel wells of the truck.
Corrugations or ribs 22 shown in greater detail in FIG. 2 are provided on the floor 12 , and are preferably also on the side and front walls 14 and 16 . As used herein, the term corrugation is intended to include any configuration in which an air space is provided between adjacent ribs or points, etc., on opposite sides of a panel. These corrugations provide stiffening of the walls of the liner and retention of its shape. The ribs 22 provide a firm supporting surface for both individuals and cargo loads. Additionally, the ribs on the outer side outer side of the bottom wall provide an air space between the liner and the truck bed for enabling drying and drainage of moisture. A plurality of anchoring ribs 24 are interspersed between every few ribs 22 , these anchoring ribs 24 having holes 26 formed in solid material necked-down portions 28 so as not to communicate with the lower surface of the liner 10 . Obviously, if the holes 26 were made directly through the hollow ribs 22 , sand, dirt, water, mulch and various other particulate materials carried by the truck could pass through the holes, ultimately causing damage to the truck bed, particularly when moisture is also present. To avoid this possibility, and to provide a narrow opening for receipt, for example, of the hook of the typical tie down such as an elastic bungee cord, the portion 28 is preferably formed in the molded liner 10 approximately one quarter of an inch in width, and about one half inch in length and height. For use with ropes, cords or other non-elastic tie downs, the openings and the solid portions may be made larger than shown to accommodate whatever kind of tie down is used.
In the event a conventional process is employed in producing the liner, an anchoring rib 24 may be initially shaped identically to a rib 22 . After removal from the mold, a section of the rib can be heated and squeezed inwardly from its sides to form the necked-down portion 28 . A preferred method of forming the solid portion 28 is discussed in connection with FIGS. 10-12.
FIG. 1 illustrates in very simple fashion the tying down of a gas can 30 and a tool box 32 with a series of bungee cords in widely spaced sections of the liner. The gas can 30 is often full or at least partially full if being carried to a location where a gasoline driven item such as a lawn mower or chain saw is to be used. The mower or saw is also capable of being tied down separately alongside or near the gas can 30 adjacent the truck tail gate. I prefer to have about every third rib an anchoring rib 24 . If the ribs 22 are normally around 1¼ to 1½ inches center to center, the anchoring ribs 24 will be spaced between 3¾ to 4½ inches apart across the liner 10 . I also prefer that solid portions 28 and their holes 26 of anchoring ribs 24 be spaced about six inches apart along the lengths of the several anchoring ribs 24 . This, in essence, gives me an entire liner floor surface over which to locate and tie down objects of various sizes, shapes and weights. The invention is not to be limited by the amount of tie down holes used or their particular dimensions or spacing about the bottom wall or side walls of the liner 10 . If I also provide solid portions 28 and their respective holes 26 on the side and front walls 14 and 16 , I obtain still greater flexibility in how things are tied down.
The spacing of the holes 26 along an anchoring rib 24 can be modified for special circumstances. If an anchoring rib 24 ′(FIG. 5) is made solid for its full length, any spacing of holes is feasible. It is contemplated that holes 26 ′ can be drilled or punched anywhere along the rib 24 ′ by the end purchaser of the liner, according to his own needs. For example, if he always ties down objects only in one section of the liner, he needs holes 26 ′ only in that general location. Whether the liner is of the type in FIGS. 2-4, 5 or other variations yet to be described, it should be understood that the upper edges of all ribs are coplanar in order to avoid obstruction or article damage when an article is slid on those upper edges during loading and unloading, and to maintain an even, flat surface for someone who may need to stand or walk on the ribs 22 and 24 .
FIG. 6 shows an embodiment in which an anchoring bridge 34 spans adjacent ribs to form the anchoring medium. By leaving space below the bridge 34 , hosing or blowing out the liner for clearing the bed is feasible for most loads, without residue of transported material remaining dammed up between ribs on the floor 12 . This variation of my invention is not easily vacuum-formed because of the opening below the bridge 34 .
FIGS. 7 and 8 illustrate yet another variation of the invention in which separable parts 36 are captured in recesses on the inside of low ribs 38 . The ribs 38 are provided with slots through which an upright, slightly tapered portion 40 of the part 36 closely fits. Obviously, since slot creation is not possible when vacuum-forming, they must be made in a separate stage of manufacture, or the liner should be injection molded. As can be best seen in FIG. 8, the upright portion 40 is preferably notched a minute amount on opposite sides where it joins a base 42 so as to snap and be held in place in the liner once inserted there. Alternatively, the elements 36 can be heat or cement-sealed in place. If desired, instead of slots being formed in the liner to receive the upright portions 40 , removable knock-outs can be molded in the liner. The purchaser can then select where he wants his anchoring to be located and place the separable parts 36 in sections of the floor and/or side and front walls to suit his particular needs. The knock-outs would remain in place for unselected sections, retaining the impermeability of the liner. One advantage of this form of the invention is the capability of achieving the end anchoring feature at any time during the life of the liner. A disadvantage, however, is that if additional parts 36 are to be installed after the liner has already been in use in a truck, it would have to be removed to install more such parts.
FIG. 9 shows an alternative form of the invention similar in many respects to that of FIG. 5 . Here the anchoring ribs 24 ″ with holes 26 ″ are added after extrusion molding by applying rivets 43 or other fastening means. To accomplish this, selected laterally-spaced ribs 22 are left out of the liner at the time of molding, and the ribs 24 ″ are applied by the liner manufacturer or the purchaser afterward.
FIGS. 10-12 illustrate a preferred method of producing a solid material necked-down portion 28 when the liner 10 is vacuum formed. All figures are plan views for making one such portion. FIG. 10 shows a section of a vacuum form or mold 44 , FIG. 11 shows the top surface of a liner which has been formed on the mold 44 of FIG. 10, and FIG. 12 shows a half-depth cross-sectional view of the liner of FIG. 11 after laterally-directed heat and pressure have been applied thereto to produce the solid portions 28 .
The mold 44 of FIG. 10 has properly-spaced pin holes 46 through which vacuum is conventionally applied to pull down a pliable heated sheet of thermoplastic material against the top surface 48 and surrounding surfaces to create the anchoring rib 24 of FIG. 11 . As is understood in the vacuum forming art, the outer edges of a vacuum form and the sheet to be formed are sealed relative to one another to enclose the area of vacuum. The necking down occurs by spanning a thin bridging edge 50 between the two aligned top surfaces 48 . When the liner is removed from the mold, an air gap 52 spaces the opposed walls of the necked-down portion apart by a distance appearing as dimension “a” in FIG. 10 and dimension “b” in FIG. 11 . Since the necked-down portion 28 is where a hole 26 is to be drilled or punched therethrough, I solidify this area to a sealed condition as shown in FIG. 12 . This is done by applying appropriate amounts of heat and pressure in the direction of arrows 54 . The opposing walls seal as shown at the dotted line 56 . The holes 26 can be punched at the time of sealing, or can be punched or drilled later, either by the manufacturer or the end user.
FIGS. 13 and 14 respectively show a vacuum mold segment 58 and a section of a liner floor used to produce diagonal necked-down portions 60 across adjacent ribs of a liner. The advantage of the diagonal portions 60 is to enable ease of drilling the holes by obtaining a better angle and space for a power drill. FIG. 13 shows a narrow bridging edge 62 of the vacuum mold, with a slight downward dip between top surfaces 64 . The dip allows an appropriate upward flow of plastic material when the necked-down portion 60 is squeezed together under pressure according to the process described in FIGS. 10-12. A heating tool can be designed to limit the amount of upward flow until the heated plastic aligns itself with the top edges of the ribs of FIG. 14 . In this manner, the entire top surface of the ribs of FIG. 14 can kept coplanar as a flat surface, without concern of the adverse effects of bumps or protrusions. It should be noted that the diagonal relation of the portions 60 and the valley gaps 61 of the figure allows for complete water drainage and flushing or blowing dirt along the valleys between the ribs toward the tailgate. This eliminates the possibility of standing water and dirt between the ribs.
FIG. 15 shows a typical tray 66 with an upturned lip 68 that may be either a corrugation or a solid edge. Such a tray is commonly made of thin-walled plastic for containing wet and dirty objects such as boots and hiking shoes. It protects the carpeting of other floor surface of a trunk or floor of a passenger vehicle. By thickening the sheet material of the tray to about one-eight on an inch to rigidity the tray, it can also be used as an anchoring base similarly to what has been described in connection with the liner 10 . The entire lip 68 can be provided with holes at a level high enough to enable the tray to still catch and retain water dripping from whatever the tray is made to contain. Ribs corresponding to ribs 24 can be interspersed centrally with additional anchoring holes. Such ribs can be parallel, radiate outwardly from the center or selectively shaped and spaced to provide a variety of patterns. If desired, depressions can be made with surrounding lips to have standard blow-molded plastic milk cartons stabilized. The objective is to add the anchoring and leak-proof features of my invention to an already-existing product. If desired, parallel ribs exactly matching those of a truck bed liner can extend downwardly below the lip 68 and be made to interdigitate with the bed liner ribs. In essence, the tray 66 can be used to have its downwardly-depending ribs frictionally wedge into the topside ribs of a liner, maximizing surface contact and tending to stabilize the tray to the liner. With tie downs holding an article or articles in place on the tray, and with the further stability of the tray with a liner, the effect is a non-sliding tray on a liner. A tray of the type shown can be any shape and size, and be capable of portability from one vehicle to another, provided it has a large enough underside surface to avoid tipping when carrying a top-heavy article.
Additionally, tray 66 may be a permanent element on the upright back portion of the back seat of a vehicle such as an SUV, where the upright portion can be folded down horizontally with the tray 66 facing upwardly. Obviously, the article-anchoring function should be capable of being performed without liquid or debris passing through the tray.
FIG. 16 illustrates in very simple cross-sectional fashion how the liner 10 ′ can be incorporated directly into a truck bed at the time of truck manufacture, as an integral, permanent part of the truck. Vertical walls 70 may be the outside metal walls of the body structure of the vehicle, with the liner 10 ′ having a bottom wall 12 ′, side walls 14 ′ front wall 16 ′ and ledges 18 ′. The side walls 14 ′ have ribs 22 ′ and 24 ′ extending longitudinally of the truck, but they may be vertical as in the FIG. 1 embodiment. The ribs correspond to similarly-numbered ribs of the other embodiments. Although not shown, structural components would typically support the bottom wall 12 ′ to provide it with sufficient rigidity for supporting loads and individuals standing or walking on the bottom wall 12 ′.
FIG. 17 illustrates an integral liner 10 ″ which consists of a bottom wall 12 ″ attached to bottom edges of inner side walls 72 and front wall 74 of the truck bed. The wall 12 ″ is preferably formed with upturned edges so as to effectively become a shallow tray about all but the tail gate edge of the unit. If desired, various type of protruding anchoring means may be provided on the side walls for use in conjunction with the ribs 24 ″. Alternative anchoring means is feasible on the side walls because they would not obstruct loading or walking on the bottom wall. At the areas of interconnection of the liner edges with the body structure of the vehicle in both this and the FIG. 16 embodiment, appropriate fastening and sealing means are employed. Also, as in the FIG. 16 embodiment, structural components (not shown) will be provided for strengthening the liner 10 ″.
The term “liner” has been used herein in a generic sense, since it most typically involves an article-anchoring device that overlies or “lines” a horizontal surface, either as a truck bed liner or as a tray such as depicted in FIG. 15 . It should be understood, however, that the same term is also intended to include any surface which is integral with a vehicle and which is horizontal when performing its anchoring function, such as the anchoring surfaces of FIGS. 16 and 17, or the liner on an upright surface of a vehicle seat that is moved to a horizontal position when serving its primary function.
Various other changes may be made without departing from the spirit and scope of my invention.
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A tie system for the bed of a pick-up truck or an article-receiving tray has elongated coplanar corrugated ribs, with selected ribs or portions of ribs having spaced holes or openings extending horizontally therethrough for enabling hook-ended elastic tie downs to anchor objects that are being transported. Provision is made to avoid communication through the holes from one side of the system or tray to the other, thus rendering it leak-proof. The strength, minimal friction during loading, cleanability and water impermeability characteristics of the liner are retained, while adding the desirable feature of being able to selectively anchor objects of any shape and size in any location on the bed.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation application of International Patent Application No. PCT/CN2013/090091, filed Dec. 20, 2013, which itself claims the priority to Chinese Patent Application No. 201310122473.4 and 201310122497.X, both filed Apr. 9, 2013, which are hereby incorporated herein by reference in their entireties.
FIELD OF THE INVENTION
[0002] The present invention relates to the field of washing machines, and more particularly, to a music washing machine and a control method thereof.
BACKGROUND OF THE INVENTION
[0003] During a washing process of a conventional washing machine, clockwise and anticlockwise rotations of a motor generate water flows in an inner barrel, and clothes therein are washed by the water flows. In the washing process, generally a user selects a corresponding washing program of the washing machine according to information such as materials, weight, and cleanness of the clothes. The control process depends on the user, and does not have any independent determination. Therefore, a novel washing control method for a washing machine is provided, so that a user has more interactive and sensual pleasures during washing.
[0004] Meanwhile, music is everywhere in daily life, and in various fields of life, there are methods using music to control actions of devices. For example, Chinese Patent No. CN02133317.3 discloses a method of feeling music by touch, which is implemented as follows: a weak audio-frequency electric signal output when a player plays music or a weak audio-frequency electric signal obtained by a microphone is first amplified into a strong audio-frequency electric signal by using an amplifier, and the strong audio-frequency electric signal is divided into two paths: one path of signal passes through a signal delayer to a loudspeaker and is converted into a sound signal, so as to transmit into an auditory and tactile music hall from the upper portion of the hall; the other path of strong audio-frequency electric signal is input to a frequency converter, and the frequency converter is controlled to change the frequency and voltage of a power supply of a motor of a music fan, thereby controlling the rotation speed of the motor of the music fan, and making the change of the rotation speed to be the same as the change of rhythm of the sound signal output by the loudspeaker; therefore, the wind power output by the music fan has the same rhythm change with the music, and the wind power output by the music fan enters the auditory and tactile music hall directly in a short distance. In this way, people in the auditory and tactile music hall can hear and feel the rhythm of the same music simultaneously by the ears and the skin.
[0005] Therefore, it is completely feasible to convert a music signal by a converting device into a rotation-halt ratio and/or rotation speed of a motor of a washing machine, so as to implement controlling of a washing program of the washing machine by using music; therefore, during a washing process of the user, selection of a washing program is implemented together by music and a self determination of the user.
[0006] Therefore, a heretofore unaddressed need exists in the art to address the aforementioned deficiencies and inadequacies.
SUMMARY OF THE INVENTION
[0007] An objective of the present invention is to provide a music washing machine, so that the washing machine performs washing according to a music selected by a user and according to corresponding water flows, so as to achieve the effect of increasing interaction with the user. Meanwhile, the water flows during the washing process is converted into music, thereby achieving the effect of improving pleasures of the user during washing. To implement the objective of the present invention, the following technical solutions are used:
[0008] A music washing machine includes: a motor configured to generate washing water flows, where the motor is connected to a control device configured to perform mutual conversion of a rotation-halt ratio and/or rotation speed of the motor and a music feature signal, so that during a washing process of the washing machine, music output by an output device is synchronous with the rotation-halt ratio and/or rotation speed of the motor.
[0009] In one embodiment, the motor is connected to a control device configured to collect a motor rotation-halt ratio and/or rotation speed signal, the control device is provided with a converting module configured to convert the motor rotation-halt ratio and/or rotation speed signal into a corresponding music signal, and the converting module is connected to the output device configured to send the music.
[0010] In one embodiment, the motor is connected to a control device configured to control the rotation-halt ratio and/or rotation speed of the motor, the control device is provided with a storage device configured to store music, the storage device is connected to an analyzing device configured to extract, analyze and process a music feature, the analyzing device is connected to a converting device configured to convert the music signal into a rotation-halt ratio and/or rotation speed signal of the motor, and the converting device is connected to an executing device configured to control the rotation speed of the motor.
[0011] A control method of the music washing machine, where, a rotation-halt ratio and/or rotation speed of a motor of the washing machine and a music feature signal are mutually converted by a converting device of the washing machine, so that in the washing process of the washing machine, an output device sends corresponding music obtained through conversion of the rotation-halt ratio and/or rotation speed of the motor.
[0012] In one embodiment, the rotation-halt ratio and/or rotation speed of the motor of the washing machine is analyzed and processed by the control device, and then converted into a corresponding sound feature signal, and the output device sends corresponding music to the user.
[0013] In one embodiment, the rotation-halt ratio and/or rotation speed of the motor of the washing machine is extracted by the converting device to generate a corresponding electric signal, and then converted into corresponding music feature signals such as frequency, tune, and tone, and the output device outputs corresponding music to the user.
[0014] In one embodiment, the user transmits music into the control device of the washing machine, the control device extracts features of the music such as frequency, volume and tone, analyzes and processes the features, and then converts the features into a corresponding motor rotation-halt ratio and/or rotation speed signal, and the motor of the washing machine performs the washing process according to the corresponding signal.
[0015] In one embodiment, features such as frequency, tone and volume of the music at different time nodes are stored, analyzed and processed, different time nodes are matched with corresponding motor rotation-halt ratios and/or rotation speeds, and they are stored in the control device, so that the washing machine works according to the motor rotation-halt ratio and/or rotation speed matching the music during washing.
[0016] In one embodiment, the rotation-halt ratio and/or rotation speed of the motor of the washing machine is analyzed and processed by the control device, then converted into a corresponding sound feature signal, and the output device sends corresponding music to the user.
[0017] In one embodiment, the user transmits music into the control device of the washing machine, the control device extracts features of the music such as frequency, volume and tone, analyzes and processes the features, and then converts the features into a corresponding motor rotation-halt ratio and/or rotation speed signal, and the motor of the washing machine performs the washing process according to the corresponding signal.
[0018] In one embodiment, features such as frequency, tone and volume of the music at different time nodes are stored, analyzed and processed, different time nodes are matched with corresponding motor rotation speeds, and they are stored in the control device, so that the washing machine works according to the motor rotation-halt ratio and/or rotation speed matching the music during washing.
[0019] In one embodiment, the user transmits a song into the storage device of the control device, an analyzing device of the control device extracts and analyzes a feature signal of the song such as frequency, tone and volume, so as to generate a processable and convertible music feature signal, the converting device disposed on the control device converts the generated music feature signal to generate a corresponding converted rotation-halt ratio and rotation speed signal of the motor of the washing machine, and stores the signal. The control device determines, by means of a determining device, the generated motor rotation-halt ratio and rotation speed signal as a corresponding washing program, and stores music into a music library of a corresponding washing program. Therefore, when the user selects the corresponding washing program, corresponding music may be selected from the corresponding music library, so that the motor of the washing machine performs washing according to the set program, and at the same time, an audio device plays the selected music.
[0020] In one embodiment, the motor of the washing machine is connected to the control device configured to collect the motor rotation-halt ratio and/or rotation speed, the control device is connected to an analyzing and converting device configured to convert the motor rotation speed and/or rotation-halt ratio into a music signal, and the analyzing and converting device is connected to an output stereo device configured to play the converted music.
[0021] In one embodiment, the storage device stores the music selected by the user, and is connected to the analyzing and converting device configured to convert the motor rotation speed and/or rotation-halt ratio into a music signal, and the analyzing and converting device is connected, by means of the control device, respectively to the motor of the washing machine and the output stereo device, so that the music is played and the motor of the washing machine works synchronously according to the set rotation speed and rotation-halt ratio.
[0022] In one embodiment, the storage device stores the music selected by the user, and is connected to the control device, and the control device is connected to the stereo device configured to output the music. The control device is further connected to the analyzing and converting device configured to convert a music signal into a motor rotation speed and/or rotation-halt ratio, and the analyzing and converting device is connected to the motor of the washing machine, so that the music is played and the motor of the washing machine works synchronously according to the set rotation speed and rotation-halt ratio.
[0023] In one embodiment, the motor of the washing machine is connected to the control device configured to collect a motor rotation-halt ratio and/or rotation speed, the control device is connected to the analyzing and converting device configured to convert the motor rotation speed and/or rotation-halt ratio into a music signal, the analyzing and converting device is connected to the storage device configured to store the corresponding music and the motor rotation-halt ratio and/or rotation speed, and the storage device is connected to the output stereo device configured to play the converted music.
[0024] In one embodiment, methods such as mode recognition, digital signal process, artificial intelligence, and computer multimedia technologies are added, and music elements are recognized, analyzed and extracted by using computer software. The music signal of the computer is divided into two channels A and B, the music signal A is subjected to feature recognition and extraction of music elements by means of a digital audio signal processing software packet of the computer, so as to form various control signals, that is, bass, median, treble and beat; then, based on a “professional music arrangement knowledge base”, manifestation forms of “sound, light, and water flow” are selected, and by means of a computer parallel port, discrete control signals from a controller are input to a digital isolated output card to output a simulation signal, the signal is transmitted by a protection device and a driving device to execution mechanisms of the motor: the motor and a light device, so as to control changes of rotation-halt ratio and/or rotation speed of motors of various washing machines; at the same time, a response time of the music signal B lags behind that of the music signal A due to mechanical inertia of the motor and the control device, and therefore, the signal B is transmitted to the control device and a stereo system after a period of delay time, so as to ensure that changes of the water flow and the light are synchronous to and harmonious with the music.
[0025] The music arrangement method of the present invention includes the following steps: a musical composition file is selected, and the musical composition is operated by using a “play, pause, confirm, reset” menu; when the musical composition file is opened, an interface displays an actual physical waveform of the file, and an operator clicks the waveform by using a mouse while the music is playing, so as to mark segments of the musical composition, and information such as segmentation time is filled automatically to a table above the waveform file; after segmentation of a musical composition is completed, the operator modifies and adjusts the divided segments according to content of the segments of the musical composition, and the operator may add one segment, delete one segment, or adjust the time of a segment; the operator fills controls signals, such as bass, median, treble, drumbeat, rhythm, melody, program control and blank, into the table according to the divided music segments and content and feeling presented by the music; rows of the table indicate divided music segments, and in “02-09′110-00′25′160”, 02 indicates that the musical composition segment is the second segment, 09′110 indicates that the segment time of this segment is 9 seconds and 110 milliseconds, and 00′25′160 indicates that a current playing position of the music is 25 seconds and 160 milliseconds; columns of the table indicate specific control paths and numbers of the music fountain execution mechanism, and in “28-valve-phoenix tail”, it indicates that a water pattern name controlled by the 28 th path is “phoenix tail” and the control type is a “solenoid valve”; an intersection of a row and a column is a specific fountain control signal, and when table content at an intersection of the row “02-09′110-00′25′160” and the column “28-valve-phoenix tail” is “bass”, it indicates that the phoenix tail at the 28 th path of the control paths of the second segment of music is bass control, that is, when the music is played to this segment, the phoenix tail of the 28 th path starts to work when there is a bass; the operator fills the table according to the previous step, and stores the music arrangement file for future use.
[0026] The system controls and outputs the music segments one by one according to the music arrangement file of music performance, until the music ends. First, the control system needs to perform some initialization processes, and when the music is played, from the first segment, effective components of the music are extracted by means of digital audio signal processing to form control signals, and the signals are output to the execution mechanism according to the music arrangement solution specified by the music arrangement file stored in the music arrangement stage, so as to determine whether the musical composition ends or not, if not, the next segment is performed, and the digital audio signal processing is performed to the execution mechanism, the process is repeated until the musical composition ends.
[0027] In addition, to enrich the operation interface, a multimedia animation effect is added, there are various simulation pictures of water flows in actual washing machines, and in an audio control state, the water flows act along with control signals sampled in real time, so that the system is more novel and unique, and at the same time, it is conducive to music arrangement of the operator, and enriching the imagination thereof.
[0028] Another characteristic of this system lies in that, the professional music arrangement knowledge database is used to assist the operator to arrange the music, and according to the experiential knowledge and some presentation methods, when the music is soft, it is suitable to select various swing water patterns, and when the rhythm is lively, it is suitable to select water patterns such as jade pillar and beam. The computer complements the music arrangement function in advance according to the knowledge base, and the operator performs appropriate adjustment according to specific conditions, thereby increasing the difficulty in music arrangement.
[0029] In one embodiment, a frequency electric signal of the music stored in the control device of the washing machine is first amplified, by using an amplifier, into a strong audio-frequency electric signal, and the strong audio-frequency electric signal is divided into two paths: one path of signal passes through a signal delayer to an output device and is converted into a sound signal, so as to transmit to the user acoustically and tactilely; the other path of signal is input to a frequency converter, and the frequency converter is controlled to change the frequency and voltage of a power supply of a motor of the washing machine, so as to control the rotation-halt ratio and/or rotation speed of the motor, and enable the change of the rotation speed to be the same as the change of rhythm of the sound signal output by the loudspeaker, so that the water flow generated in the washing machine has the same rhythm change with the music. Therefore, a user may feel the rhythm of the music acoustically and tactilely by ears, and can also feel the change of water flows in the washing machine intuitively.
[0030] In one embodiment, when the washing machine starts a washing program, a weak audio-frequency electric signal output when a control system plays music is first amplified into a strong audio-frequency electric signal by using an amplifier, and the strong audio-frequency electric signal is divided into two paths: one path of signal passes through a signal delayer to a loudspeaker and is converted into a sound signal, so as to transmit into an auditory and tactile music hall from the upper portion of the hall; the other path of strong audio-frequency electric signal is input to a frequency converter, and the frequency converter is controlled to change the frequency and voltage of a power supply of a motor of the washing machine, so as to change the rotation-halt ratio and/or rotation speed of the motor of the washing machine, and enable the change of the rotation speed to be the same as the change of rhythm of the sound signal output by the control system, so that the water flow output by the motor of the washing machine has the same rhythm change with the music; therefore, the user may hear the music and feel the change of the water flow by ears.
[0031] In one embodiment, the user transmits a song into the storage device of the control device, the analyzing device of the control device extracts and analyzes a feature signal of the song such as frequency, tone and volume, so as to generate a processable and convertible music feature signal, the converting device disposed on the control device converts the generated music feature signal to generate a corresponding converted rotation-halt ratio and rotation speed signal of the motor of the washing machine, and stores the signal. The control device determines, by means of the determining device, the generated motor rotation-halt ratio and rotation speed signal as a corresponding washing program, and stores music into a music library of a corresponding washing program. Therefore, when the user selects the corresponding washing program, corresponding music may be selected from the corresponding music library, so that the motor of the washing machine performs washing according to the set program, and at the same time, an audio device plays the selected music.
[0032] Further, in this embodiment, when the washing machine starts a washing program, a weak audio-frequency electric signal output when a control system plays music is first amplified into a strong audio-frequency electric signal by using an amplifier, and the strong audio-frequency electric signal is divided into two paths: one path of signal passes through a signal delayer to a loudspeaker and is converted into a sound signal, so as to transmit into an auditory and tactile music hall from the upper portion of the hall; the other path of strong audio-frequency electric signal is input to a frequency converter, and the frequency converter is controlled to change the frequency and voltage of a power supply of a motor of the washing machine, so as to change the rotation-halt ratio and/or rotation speed of the motor of the washing machine, and enable the change of the rotation speed to be the same as the change of rhythm of the sound signal output by the control system, so that the water flow output by the motor of the washing machine has the same rhythm change with the music; therefore, the user may hear the music and feel the change of the water flow by ears.
[0033] By means of the above technical solutions, compared with the prior art, the present invention has the following advantages: a washing machine is made to generate water flows in different forms according to music set by a user, so as to wash clothes in the washing machine. In this way, not only the user can clearly know the conditions of the water flows in the washing machine, but also the sensitivity of the motor can be intuitively presented to the user, thereby achieving the effect of presenting the performance of the motor. More particularly, by converting the water flows of the washing machine into a form of music transmitted to the user, the washing machine can automatically generate music, thereby improving the interaction with the user, and achieving the effect of improving pleasures of the user during washing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] FIG. 1 is a structural block diagram of a washing machine generating music according to the present invention.
[0035] FIG. 2 is a structural block diagram of a preferred washing machine generating music according to the present invention.
[0036] FIG. 3 is a structural block diagram of a washing machine controlling water flows of the washing machine by music according to the present invention.
[0037] FIG. 4 is a structural block diagram of a preferred washing machine controlling water flows of the washing machine by music according to the present invention.
[0038] FIG. 5 is a flow chart of synchronizing washing machine music and a washing machine according to the present invention.
[0039] FIG. 6 is a flow chart of generating corresponding music and light in a washing machine according to the present invention.
[0040] FIG. 7 is a flow chart of generating water flows by using a preferred music control washing machine according to the present invention.
[0041] FIG. 8 is a flow chart of generating water flows by using a music control washing machine according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0042] The present invention is further described in detail through embodiments in the following.
Embodiment 1
[0043] In this embodiment, the washing machine starts a washing program, a weak audio-frequency electric signal output when a control system plays music is first amplified into a strong audio-frequency electric signal by using an amplifier, and the strong audio-frequency electric signal is divided into two paths: one path of signal passes through a signal delayer to a loudspeaker and is converted into a sound signal, so as to transmit into an auditory and tactile music hall from the upper portion of the hall; the other path of strong audio-frequency electric signal is input to a frequency converter, and the frequency converter is controlled to change the frequency and voltage of a power supply of a motor of the washing machine, so as to change the rotation-halt ratio and rotation speed of the motor of the washing machine, and enable the change of the rotation speed to be the same as the change of rhythm of the sound signal output by the control system, so that the water flow output by the motor of the washing machine has the same rhythm change with the music; therefore, a user may hear the music and feel the change of the water flow by ears.
Embodiment 2
[0044] In this embodiment, methods such as mode recognition, digital signal process, artificial intelligence, and computer multimedia technologies are added to a control device of the washing machine, and music elements are recognized, analyzed and extracted by using computer software. The music signal of the computer is divided into two channels A and B, the music signal A is subjected to feature recognition and extraction of music elements by means of a digital audio signal processing software packet of the computer, so as to form various control signals, that is, bass, median, treble and beat; then, based on a “professional music arrangement knowledge base”, manifestation forms of water flows corresponding to the rotation-halt ratio and rotation speed of the motor of the corresponding washing machine are selected, and by means of a computer parallel port, discrete control signals from a controller are input to a digital isolated output card to output a simulation signal, the signal is transmitted by a protection device and a driving device to execution mechanisms of the motor: the motor and a light device, so as to control changes of rotation-halt ratio and rotation speed of motors of various washing machines; at the same time, a response time of the music signal B lags behind that of the music signal A due to mechanical inertia of the motor and the control device, and therefore, the signal B is transmitted to the control device and a stereo system after a period of delay time, so as to ensure that changes of the water flow and the light are synchronous to and harmonious with the music.
[0045] When the washing machine is started to work after a washing program is selected, a control program invokes corresponding music according to motor rotation-halt ratios and rotation speeds at different time nodes, and transmits the music to the user by using a disposed buzzer or loudspeaker.
Embodiment 3
[0046] In this embodiment, a system sets a corresponding sound feature library according to different rotation-halt ratios and rotation speeds of a washing machine, and the sound feature library stores sounds corresponding to various different frequencies, tones and volumes. After a user selects a washing program, the washing machine starts to work, and according to invoked sounds of adjacent nodes and the selected program in a control device, a sound is retrieved from various sounds in the sound feature library corresponding to the rotation-halt ratio and rotation speed at different time nodes, and then transmitted to the user by using an output device.
Embodiment 4
[0047] In this embodiment, a control system operates a musical composition according to a musical composition file by using a “play, pause, confirm, reset” menu; the musical composition file is converted into actual sound features, for example, feature physical waveforms such as frequency, tone and tune, segments of the musical composition are marked according to the shape of the waveform while the music is playing, and information such as segmentation time is recorded; after segmentation of the musical composition is completed, the divided segments are modified and adjusted according to content of the segments of the musical composition, and one segment may be added or deleted, or the time of a segment may be adjusted; controls signals, such as bass, median, treble, drumbeat, rhythm, melody, program control and blank, are filled into a table according to the divided music segments and content and feeling presented by the music; then, motor rotation-halt ratios and rotation speeds corresponding to different time periods are set according to music features assigned at different time nodes; and they are recorded and stored for future use.
[0048] The system controls and outputs the music segments one by one according to the music arrangement file of music performance, until the music ends. First, the control system needs to perform some initialization processes, and when the music is played, from the first segment, effective components of the music are extracted by means of digital audio signal processing to form control signals, and the signals are output to the an audio device of the output device according to the music arrangement solution specified by the music arrangement file stored in the music arrangement stage. In this process, the motor of the washing machine works according to the correspondingly set rotation-halt ratio, so as to generate synchronous water flows corresponding to the music. After the first segment ends, the control device determines whether the musical composition ends or not, if not, the next segment is performed, and the digital audio signal processing is performed to the execution mechanism, the process is repeated until the musical composition ends.
[0049] When the “Symphony of Fate” is used for music arrangement, the following mapping table of rotation-halt ratios and music time nodes is generated:
[0000]
Serial
Frequency
Time
Time
Serial
No.
Time
Water Flow
(Hz)
(s)
(100 ms)
No.
Rotation
Halt
Symphony
0
0 s-3.5 s
3.0/0.5
75
3.5
35
0
30
5
of Fate
(clockwise)
1
3.5 s-8 s
4.0/0.5
75
8
80
1
40
5
(anticlockwise)
2
8 s-12.5 s
4.0/0.5
30
13
125
2
40
5
(anticlockwise)
3
12.5 s-15.5 s
1.0/0.5
40
16
155
3
10
5
4
15.5 s-17.5 s
2.0/0
50
18
175
4
20
0
(clockwise)
5
17.5 s-20.5 s
2.5/0.5
70
21
205
5
25
5
(clockwise)
6
20.5 s-25.5 s
4.0/1.0
75
26
255
6
40
10
(anticlockwise)
7
25.5 s-28 s
2.5/0
25
28
280
7
25
0
(clockwise)
8
28 s-30 s
2.0/0
30
30
300
8
20
0
(clockwise)
9
30 s-32 s
2.0/0
40
32
320
9
20
0
(clockwise)
10
32 s-34 s
2.0/0
50
34
340
10
20
0
(clockwise)
11
34 s-36 s
2.0/0
60
36
360
11
20
0
(clockwise)
12
36 s-37.5 s
1.5/0
65
38
375
12
15
0
(clockwise)
13
37.5 s-39 s
1.5/0.0
70
39
390
13
15
0
(clockwise)
14
39 s-41 s
2.0/0.0
75
41
410
14
20
0
(clockwise)
15
41 s-43.5 s
2.3/0.2
80
44
435
15
23
2
(clockwise)
16
43.5 s-45.1 s
0.8/0.8
65
45
451
16
8
8
17
45.1 s-46.2 s
0.8/0.3
55
46
462
17
8
3
18
46.2 s-48.5 s
2.0/0.3
50
49
485
18
20
3
(anticlockwise)
19
48.5 s-1:00.5 s
2.5/0.5
30
61
605
19
25
5
20
1:00.5 s-1:03 s
2.5/0
30
63
630
20
25
0
(clockwise)
21
1:03 s-1:05 s
2.0/0
45
65
650
21
20
0
(clockwise)
22
1:05 s-1:07 s
2.0/0.0
70
67
670
22
20
0
(clockwise)
23
1:07 s-1:08.5 s
1.2/0.3
70
69
685
23
12
3
(clockwise)
24
1:08.5 s-1:17 s
8.3/0.2
60
77
770
24
83
2
(anticlockwise)
25
1:17 s-1:21.7
4.5/0.2
65
82
817
25
45
2
(clockwise)
26
1:21.7-1:24.3
0.8/0.5
75
84
843
26
8
5
27
1:24.3 s-1:27.1 s
1.0/1.8
75
87
871
27
10
18
(clockwise)
Embodiment 5
[0050] In this embodiment, for the washing machine, a washing machine body may be any structure available in the market, and the washing machine body may be further provided with a converting module. Specifically, the converting module is disposed on a control device, the control device is connected to a motor configured to generate water flows, the control device is provided with a storage device connected to the converting module, and an output device is connected to the control device. The output device includes an audio device and a light device.
[0051] In this embodiment, the audio device may be configured as a buzzer, an alarm or the like disposed on the washing machine, and may also be a stereo device configured to send music and independently disposed on the washing machine, or an externally connected stereo device. The light device may be configured as a light disposed on the washing machine body and capable of changing the color, intensity and brightness, and may also be configured as a light connected to the washing machine body, disposed at the external, and capable of changing the color, intensity and brightness.
[0052] In this embodiment, the control device obtains the rotation-halt ratio and rotation speed of the current motor, and generates a rotation-halt ratio and rotation speed signal; for the control device, an analyzing module on the control device analyzes and processes the obtained rotation-halt ratio and rotation speed signal, so as to generate a convertible signal that can be converted into a music feature such as frequency, tone and volume. The convertible signal is converted by the converting module into a frequency signal, a tone signal and a volume signal. The control device invokes, according to the corresponding signal, a corresponding sound signal stored in the storage device, and the sound signal is transmitted to the user by a music output device.
[0053] Meanwhile, the control device invokes a light signal corresponding to the music feature in the storage device, and presents it to the user by generating different light colors, intensities, brightness and the like with the light device.
Embodiment 6
[0054] In this embodiment, a user transmits a song into a storage device of a control device, an analyzing device of the control device extracts and analyzes a feature signal of the song such as frequency, tone and volume, so as to generate a processable and convertible music feature signal; a converting device disposed on the control device converts the generated music feature signal to generate a corresponding converted rotation-halt ratio and rotation speed signal of the motor of the washing machine, and stores the signal. The control device determines, by means of a determining device, the generated rotation-halt ratio and rotation speed signal as a corresponding washing program, and stores music into a music library of a corresponding washing program. Therefore, when the user selects the corresponding washing program, corresponding music may be selected from the corresponding music library, so that the motor of the washing machine performs washing according to the set program, and at the same time, an audio device plays the selected music.
[0055] The embodiments and drawings are not intended to limit the production form and pattern of the present invention, and any appropriate variation or modification made by a person of ordinary skill in the art shall fall within the patent scope of the present invention.
[0056] The implementation solutions in the embodiments may be further combined or replaced, and the embodiments merely describe preferred embodiments of the present invention, which are not intended to limit the concept and scope of the present invention. Various variations and improvements made by a person skilled in the art on the technical solution of the present invention shall fall within the protection scope of the present invention.
[0057] While there has been shown several and alternate embodiments of the present invention, it is to be understood that certain changes can be made as would be known to one skilled in the art without departing from the underlying scope of the present invention as is discussed and set forth above and below including claims. Furthermore, the embodiments described above and claims set forth below are only intended to illustrate the principles of the present invention and are not intended to limit the scope of the present invention to the disclosed elements.
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A music washing machine and a control method thereof. The washing machine includes a motor for introducing a washing water flow. The motor is connected to a control device for performing mutual conversion between a rotation and stopping ratio and/or the rotation speed of the motor and a musical characteristic signal, so that the music emitted by an output device synchronizes with the rotation and stopping ratio and/or the rotation speed of the motor during working of the washing machine. By a conversion device of the washing machine, mutual conversion between the rotation and stopping ratio and/or the rotation speed of the motor of the washing machine and the musical characteristic signal is performed, so that the output device emits music corresponding to the rotation and stopping ratio and/or the rotation speed of the motor during working of the washing machine.
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CROSS-REFERENCE TO RELATED APPLICATION
This application claims priority, under 35 U.S.C. §119(e), from provisional application Ser. No. 61/680,614, filed on Aug. 7, 2012, the entire contents of which are hereby incorporated by reference.
BACKGROUND
Generally, the concepts described herein relate to a golf club (e.g., a driver, fairway wood, iron, wedge, putter, etc.). More particularly, in some embodiments, the concepts described herein relate to customizing golf club fittings. For the sake of clarity and brevity, the concepts will be described in detail below with respect to wedge-type golf clubs, but could applied to any type of golf club.
Each golfer has a different swing type and physical characteristics (e.g., golfer's height, weight, arm-length, etc.). In order to optimize a set of golf clubs (e.g., a set of irons, a set of wedges, or an entire set of golf clubs including irons, wedges, etc.) for any particular golfer, a fitting process is generally employed to determine the proper specifications for each golf club in the golfer's bag.
The golf club fitting process generally requires a golfer to swing a golf club under the supervision of a golf club fitting specialist. Based on the results, the golf club fitting specialist may suggest adjustments to various golf clubs (e.g., switching to a different shaft length, a different shaft stiffness or “flex,” etc.), or ask the golfer to try a different golf club altogether. The golfer may continue to swing the adjusted golf club, and further adjustments may be made if necessary. Through this process, the golfer may arrive at a set of custom-fit golf clubs that is deemed to be optimal for that individual.
However, such a process requires the golf club fitting specialist to carry a large number of golf club components, particularly club heads and shafts. For example, for each club head, there may be tens to hundreds of shafts needed to ensure a best fit for a golfer, since shafts come in different lengths, flexes, brands, etc. Typically, to assure that the golfer is provided the opportunity to find the best-fit club, the golfer must be provided with a large number of club heads and club shafts to be combined in various combinations during the fitting process.
With respect to wedges, assuming that the variables for golf club shafts are limited to brand, shaft length, and shaft flex or stiffness, the maximum number of shafts needed to be carried by a golf club fitting specialist to ensure a full library of customization options can generally be calculated with the following expression:
S=Σ i=1 n B·CL·SL, (1)
where S is the total number of shafts needed, n represents the number of club heads with different wedge lofts offered, B represents the number of brands offered, CL represents the number of club lengths offered, and SL represents the number of stiffness levels offered. One skilled in the art will understand that this expression may be easily reconfigured to account for additional variables, and is a mere generalization, since not every brand of shaft necessarily offers each length and stiffness.
Assuming that a manufacturer provides club heads with eight different wedge lofts (e.g., 46°, 48°, 50°, 52°, 54°, 56°, 58°, and 60°), and for each wedge loft, two different brands of shafts, with each brand providing five different club lengths at four different stiffness levels (e.g., A-flex, R-flex, S-flex, and XS-flex), the manufacturer may have to provide a fitting specialist with eight wedge heads (one for each of the eight loft angles) and approximately 320 different shafts.
One reason why such a large number of shafts is required is that each different club head may require its own set of customizable shafts. For instance, the recommended shafts for a 46° pitching wedge range from 32.775 inches to 33.775 inches (in 0.5 inch increments), while the recommended shafts for a 58° lob wedge range from 32.405 inches to 33.405 inches (in 0.5 inch increments). Therefore, otherwise similar shafts (e.g. same brand and same flex), cannot be mixed and matched between wedges of different lofts.
However, a typical golf club fitting specialist works at multiple retail fitting sites, and must transport his or her fitting equipment between each fitting site using a “fitting cart.” FIG. 1 illustrates an example of a typical “fitting cart” 100 . The fitting cart 100 includes storage space for multiple shafts 102 , multiple club heads 104 , and associated tools (not shown) for securing each head 102 to each shaft 104 . The cart 100 further typically includes wheels 106 to enhance its portability. Since storage space within the cart 100 is limited, and since the size of the cart 100 is limited by considerations of weight and portability, it is not practical for the fitting specialist to carry several hundred different shafts.
Thus, one alternative is to limit the golfer to the subset of golf shafts and club heads carried by the golf club fitting specialist. The drawback of this option is that the golf club fitting specialist has a smaller pool of customizations to offer the golfer, which inevitably requires concessions to be made during the golf club fitting process. Therefore, there is a need for a system that allows thorough fitting of wedge-type golf clubs for golfers, while reducing the number of shafts needed to be carried by the golf club fitting specialist.
SUMMARY
The present embodiments have several features, no single one of which is solely responsible for their desirable attributes. Without limiting the scope of the present embodiments as expressed by the claims that follow, their more prominent features now will be discussed briefly. After considering this discussion, and particularly after reading the section entitled “Detailed Description,” one will understand how the features of the present embodiments provide the advantages described herein.
One embodiment of this disclosure is a golf club fitting system, comprising a first club head having a first striking face, a first main body, a first hosel extending from the first main body, a first loft angle, and a first hosel length HL 1 . The system further comprises a second club head having a second striking face, a second main body, a second hosel extending from the second main body, a second loft angle greater than the first loft angle by no more than 15°, and a second hosel length HL 2 less than the first hosel length HL 1 by at least 0.340 inches.
Another embodiment is a golf club fitting system, comprising a first club head having a first striking face, a first main body, a first hosel extending from the first main body, a first loft angle, and a first hosel length HL 1 . The system further comprises a second club head having a second striking face, a second main body, a second hosel extending from the second main body, a second loft angle greater than the first loft angle by no more than 5°, and a second hosel length HL 2 less than the first hosel length HL 1 by at least 0.120 inches.
Still another embodiment is a golf club fitting system, comprising a first club head having a first striking face, a first main body, a first hosel extending from the first main body, a first loft angle LA 1 , and a first hosel length HL 1 . The system further comprises a second club head having a second striking face, a second main body, a second hosel extending from the second main body, a second loft angle LA 2 greater than the first loft angle by at least 4°, and a second hosel length HL 2 . The first and second golf club heads satisfy the following: (HL 1 −HL 2 )=R*(LA 2 −LA 1 ); and R is within the range of 0.025 inches/° to 0.035 inches/°.
A still further embodiment is a golf club fitting system, comprising a first club head having a first striking face, a first main body, a first hosel extending from the first main body, a first loft angle LA 1 , and a first hosel length HL 1 . The system further comprises a second club head having a second striking face, a second main body, a second hosel extending from the second main body, a second loft angle LA 2 greater than LA 1 angle by at least 4°, and a second hosel length HL 2 . The system further comprises a third club head having a third striking face, a third main body, a third hosel extending from the third main body, a third loft angle LA 3 greater than LA 2 by at least 4°, and a third hosel length HL 3 . The first, second and third golf club heads are configured to satisfy the following: 3.66 in−(0.03125 in/°)*LA≦HL≦3.78 in−(0.03125 in/°)*LA.
Still another embodiment is a golf club fitting system, comprising a first club head having a first loft greater than 45° and a first hosel length. HL 1 , a second club head having a second loft greater than the first loft and a second hosel length, HL 2 , less than the first hosel length and a third club head having a third loft greater than the second loft and a third hosel length, HL 3 , less than the second hosel length, wherein HL 1 =(HL 2 −x)=(HL 3 −2x).
BRIEF DESCRIPTION OF THE DRAWINGS
The present embodiments now will be discussed in detail with an emphasis on highlighting the advantageous features. These embodiments depict the novel and non-obvious golf club fitting systems and methods as shown in the accompanying drawings, which are for illustrative purposes only. These drawings include the following figures, in which like numerals indicate like parts:
FIG. 1 is a front perspective view of a typical fitting cart for containing and transporting a golf club fitting system;
FIG. 2 is a front elevation view of a golf club fitting apparatus, in accordance with embodiments of this disclosure;
FIG. 3 is a graph of hosel length versus loft angle for use in accordance with an embodiment of this disclosure; and
FIG. 4 is a graph of hosel length versus loft angle for use in accordance with another embodiment of this disclosure.
DETAILED DESCRIPTION
The proposed solution offered herein to the problem discussed above involves varying the hosel length of different clubs to enable a golf club fitting specialist to use a shaft of a particular length across different clubs, thereby reducing the total number of shafts that need to be carried by the golf club fitting specialist. And, because a golfer typically only carries a few wedges (e.g., 2 or 3 wedges) as opposed to a more substantial number of irons (e.g., 6+ iron clubs) in his or her golf bag, the below description works particularly well with wedge fitting.
FIG. 2 illustrates a golf club fitting apparatus that includes a reference club 10 comprising the components of a conventional golf club; in this specific example, a wedge. The reference club 10 has a club head 12 having a heel 14 merging into a hosel 16 having a bore 18 , into which the bottom end of a shaft 20 is removably inserted. The club head 12 has a striking face 22 and a bottom or sole 24 . A resilient grip 26 is fitted onto the upper portion of the shaft 20 . A grip cap 28 typically terminates the grip 26 and covers the top end of the shaft 20 (i.e., the end of the shaft 20 opposite the hosel 16 ).
The reference club 10 is used in conjunction with a measurement device to measure golf club dimensions for fitting a golf club to a particular golfer in accordance with this disclosure. The measurement device includes a linear measurement element 32 with a stop member 34 at one end. The linear measurement element 32 is marked in the desired measurement units (typically inches and fractions thereof; alternatively in cm and mm). In use, the reference club 10 is oriented relative to the measurement device so that, when the linear measurement element 32 is horizontal, with the stop member 34 projecting vertically upward, the heel 14 of the club head 12 and the grip 26 of the reference club 10 are resting on the linear measurement element 32 , the striking face 20 of the club head 12 is generally vertically oriented, the sole 22 of the club head 12 rests against the stop member 34 , and the longitudinal axis A of the club shaft 14 is substantially parallel to the linear measurement scale 32 . Once the reference club 10 is properly oriented relative to the measurement device, the club length CL is read from the linear measurement element 32 at a juncture 36 between the grip 24 and the grip cap 26 . Those skilled in the art will appreciate that the grip cap 26 is not included in the club length measurement CL.
The shaft length SL is a measurement of the shaft 20 from the grip/grip cap juncture 36 to the lower end of the shaft 20 (shown housed in and contacting a shaft seating surface 38 in the hosel 16 ). The bore length BL is a length of the bore 18 between the top of the hosel 16 (where the shaft 14 enters the hosel, as indicated by the phantom vertical line B) and the shaft seating surface 38 in the hosel 16 (as indicated by the phantom vertical line C). In one embodiment, the bore length BL may be measured along the shaft axis A when the shaft 14 is inserted into the bore 18 of the hosel 16 . In another embodiment, the bore length BL may be pre-measured before the shaft 14 is inserted into the hosel bore 18 .
The hosel length HL is a measurement of the distance between the stop element 34 and the shaft seating surface 38 in the hosel 16 . This measurement may be read from the linear measurement element 32 at the position of the shaft seating surface 38 in the hosel 16 (i.e, at a position coincident with the line C).
The fitting apparatus, including the reference club 10 and the measurement device of FIG. 2 , having been described, several exemplary embodiments are described below.
Embodiment 1
In one embodiment, provided is a line of eight wedge club heads of a set (e.g., a 46° PW, a 48° PW, a 50° GW, a 52° AW, a 54° SW, a 56° SW, a 58° LW and a 60° LW). By configuring the hosel length HL of each club head, a single shaft can be used interchangeably between each wedge of the set in order to achieve the desired club length CL.
With respect to a standard length, Table 1 illustrates data (in inches) for each of the eight wedge club heads, including 1) hosel length HL, 2) bore length BL, 3) shaft length SL, and 4) club length CL.
TABLE 1
SET OF WEDGES
HL
BL
SL
CL
46° PW
2.22
0.354
33.28
35.5
48° PW
2.22
0.354
33.28
35.5
50° GW
2.095
0.354
33.28
35.375
52° AW
2.095
0.354
33.28
35.375
54° SW
1.97
0.354
33.28
35.25
56° SW
1.97
0.354
33.28
35.25
58° LW
1.845
0.354
33.28
35.125
60° LW
1.845
0.354
33.28
35.125
The hosel length HL corresponds to HL of FIG. 2 , and decreases in a 0.125 in. increment for every 4° increase in loft. The bore length BL corresponds to BL of FIG. 2 , and is constant throughout the set at 0.354 in. The desired standard club length CL corresponds to CL of FIG. 2 , and also decreases in a 0.125 in. increment for every 4° increase in loft. With these above dimensions, the shaft length SL is able to be maintained at a constant 33.28 in. throughout the set. In this manner, one shaft can be removably inserted into each of the eight club heads during a fitting process. Essentially, by varying the hosel length HL from club head to club head, the shaft length SL can be kept constant to achieve the desired club length CL.
Under the prior art method of golf club fitting, there might not be a direct correlation between the hosel length HL and the club length CL. In other words, by maintaining a constant difference between CL and HL throughout the set as shown in Table 1, a constant shaft length SL may be achieved for a standard length club CL. Similar principles may be applied to extended length shaft lengths and shortened shaft lengths (e.g., ±0.5 in.)
Embodiment 2
Assumptions:
A. There are three wedge club heads that are to be fitted: (1) a 46° pitching wedge, (2) a 50° gap wedge, and (3) a 58° lob wedge).
B. Each club head can be fitted with either a Brand X shaft or a Brand Y shaft.
C. For the 46° pitching wedge club head, the standard club length CL is 35.5 in. However, the standard club length may be increased or decreased by 0.5 in. for customization purposes. Essentially, the club length CL may be represented as 35.5±0.5 in. Similarly, for the 50° gap wedge club head, the available club lengths are 35.375±0.5 in. For the 58° lob wedge club head, the available club lengths are 35.125±0.5 in.
D. For each club length, three different degrees of stiffness or “flexes” are available: (1) A-flex, (2) R-flex, and (3) S-flex.
Under this set of assumptions (which are generally abbreviated for the sake of clarity and brevity), and using the above equation (1), 54 different shafts are required to provide a full library of customizable shaft options for the three wedge club heads under a prior art fitting method. Essentially, each shaft configuration requires its own shaft.
The proposed solution aims to create a system where the number of shafts required to achieve each of the club lengths in the assumptions above is reduced to only 18. Stated differently, instead of needing S=Σ i=1 n B·CL·SL, the number of shafts required (denoted as S 2 ) can be expressed as B·CL·SL. Notably, no summation is needed for each additional wedge club head. In this, case, the total number of shafts can be reduced by ⅔, i.e., from 54 to 18. Where a large number of club heads are in the library, the reduction in the number of shafts becomes even more significant. Furthermore, the advantage becomes even more magnified where the storage space is very limited (e.g., a fitting cart or fitting display).
Different club characteristics such as (1) bore length BL, (2) hosel length HL, and (3) shaft length SL, are defined as shown in FIG. 2 . Generally, the equation for the club length CL is as follows:
CL=SL+HL, (2)
where SL is the shaft length and HL is the hosel length.
To achieve the reduction in the total number of shafts, a constant differential between club length and hosel length throughout the different wedges may be maintained. That is, CL PW −HL PW =CL GW −HL GW =CL LW −HL LW . By ensuring this relationship, the usage of one shaft for each of the standard club lengths is guaranteed. In a similar manner, the “Standard length+0.5 in.” extended shaft can be reduced to one shaft across the wedges, and the “Standard length−0.5 in.” shortened shaft can also be reduced to one shaft across the wedges. Thus, only three shafts are needed for each brand at each shaft stiffness, enabling the reduction to 18 shafts using the novel proposed method from 54 shafts using the prior art method.
Furthermore, another advantageous feature of the present invention is that no additional shafts are needed even where additional wedges are added to the library. For example, adding a 54° sand wedge does not require any additional shafts when the brands supplied, the shaft stiffness options. etc. are unchanged. With respect to Example 1, under the prior art method, each additional wedge added to the library would require another 18 shafts.
In one embodiment, with respect to a standard club length across several different wedge lofts, the standard club length may decrease by a constant length decrease increment D, proportional to an increase in loft. That is, the relationship of standard club length of a 46° pitching wedge with respect to a 50° gap wedge may be expressed as:
CL 50 =CL 46 −D, (3)
where D is the length decrease increment.
Similarly, the length decrease increment D should also be applied to the hosel lengths:
HL 50 =HL 46 −D. (4)
In one embodiment, D is set at 0.125 in. Accordingly, given a 35.5 in. standard club length for a 46° pitching wedge, the 50° gap wedge would have a 35.375 in. standard club length. This relationship holds across extended club lengths and shortened club lengths. So, given an extended club length of 36 in. for a 46° pitching wedge (35.5+0.5 in.), the 50° gap wedge would be 35.875 in. (35.375+0.5 in.).
In one or more embodiments, the 0.125 in. differential is customizable (e.g., 0.25 in., 0.5 in., etc.).
Also, in one or more embodiments, the length decrease increment D correlates to a total decrease increment D max . In one or more embodiments. D max =D×(N−1), where N is the number of wedges in the set. In Embodiment 1, D max =D×M, where M is the number of times the length decrease increment D is decremented throughout the set (M=3 in Embodiment 1). Stated differently, Embodiment 1 has a D max =0.375 in. In one or more embodiments, D max is subject to a constraint. Namely. D max cannot exceed the hosel length HL of the highest lofted wedge (e.g., a 58° SW if the 58° SW is the highest lofted wedge in the set). In other words, in this example, D max ≦HL SW .
So, with the relationships and constraints discussed above, the various hosel lengths HL can be determined for each wedge of the set, corresponding to a particular shaft length SL. Notably, CL and BL are generally given and may be set accordingly.
Embodiment 3
In one or more embodiments, the hosel length is correlated with the loft angle. As shown in the graph of FIG. 3 , as the loft angle increases, the hosel length decreases.
Furthermore, the factor or increment by which the hosel length decreases is constant when moving from a wedge of a first loft and the next two consecutive increasingly lofted wedges (e.g., moving from a 46° wedge to a 50° wedge to a 54° wedge). Indeed, this hosel length decrease increment can be represented as a rate of change R in hosel length per degree change in loft angle. For example, R may be between 0.025 in. and 0.0350 in. per degree. In this embodiment, R is 0.03125 in./degree.
The relationship between the various differently lofted wedges of a set may satisfy:
( HL 1 −HL 2 )= R *( LA 2 −LA 1 ), (5)
where HL 1 and HL 2 represent hosel lengths of the respective wedges, and LA 1 and LA 2 represent the loft angles of the respective wedges. As shown, the loft angle of each of the wedges differs from the loft angle of another wedge by at least 4°. However, other configurations are possible.
The above expression relates the hosel length and loft angles of various wedges. With any given wedge, however, a relationship between its hosel length and loft angle may also exist. For instance, in one or more embodiments, a theoretical HL 0 at zero degree loft can be extrapolated from the data of Embodiment 3 to be 3.72 in. By using this theoretical HL 0 , the expression for correlating loft angle to hosel length of a wedge of any loft angle LA may be determined as:
HL LA =3.72 in−(0.03125 in./°)* LA. (6)
In one or more embodiments. HL LA can be broadly expressed as:
3.66 in.−(0.03125 in./°)* LA≦HL LA ≦3.78 in.−(0.03125 in./°)* LA. (7)
In one or more embodiments. HL LA can be expressed according to:
3.70 in.−(0.03125 in./°)* LA≦HL LA ≦3.74 in.−(0.03125 in./°)* LA. (8)
Expressions (7) and (8) are supported by the following table (Table 2) and the graph of FIG. 4 . The loft angle LA is shown in degrees, while the hosel length HL lower boundary and upper boundary are shown in inches. As further shown in Table 2, the maximum hosel length of a set HL max is equal to the hosel length of the lowest lofted club in the golf club fitting system (in the example shown in Table 2, the club head with the 48° loft angle).
TABLE 2
Loft Angle
Hosel Length
Lower
Upper
(LA)
(HL)
boundary
boundary
48
2.22
2.16
2.28
52
2.095
2.035
2.155
56
1.97
1.91
2.03
60
1.845
1.785
1.905
While certain embodiments have been described herein, one of ordinary skill in the art will recognize that the above principles can still be applied to other correlated sets of golf clubs types or mixed golf club types. Furthermore, the construction of the wedge has been simplified for the sake of brevity and clarity and should be not construed as limiting the claims. Indeed, the above described concepts are equally applicable to golf clubs having shaft sleeves, etc.
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A system for fitting golf clubs to golfers that enables an overall club length to be varied without varying a length of a shaft. The system enables a greater number of combinations of club characteristics, such as shaft flex, brand, and length, to be contained within a club fitting cart and/or for a same number of combinations of club characteristics to be contained within a smaller cart.
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BACKGROUND OF THE INVENTION
[0001] The invention relates to a locking device for vehicles, in particular for aircraft having an actively driven drive element with an input drive shaft and an output drive shaft connected directly or indirectly to it.
[0002] Conventionally, locking devices are known which lock and/or unlock doors, aircraft doors or the like by means of a motor element, followed by a complex transmission element and redundant mechanical springs connected to it. Locking devices such as these form a security mechanism and mechanically operate appropriate safety bolts or the like in response to appropriate signals. Conventional locking devices have the disadvantage that they are very heavy, complex to manufacture and require intensive maintenance for their operation. Furthermore, in some cases, they are unreliable, which is undesirable. Furthermore, they require a large installation area which is likewise undesirable, with a very high natural weight.
[0003] The U.S. Pat. No. 6,310,455 B1 discloses a positioning and actuating drive which operates with a DC electric motor. In this case, a rotor is mounted coaxially in a stator such that it can rotate, and drives a transmission. In this case, the transmission and the motor have corresponding associated position angle sensors, motor angle sensors, which identify and determine the position exactly.
[0004] The present invention is thus based on the object of providing a locking device of the type mentioned initially, which overcomes the stated disadvantages and by means of which the reliability and the operability of the locking devices are intended to be significantly improved. A further aim is to save manufacturing costs and maintenance costs, while reducing the natural weight.
SUMMARY OF THE INVENTION
[0005] The is achieved by providing a locking device for vehicles, in particular for aircraft, having an actively driven drive element with an input drive shaft and an output drive shaft connected directly or indirectly to it, characterized in that the input drive shaft or the output drive shaft has at least one associated permanent magnet which interacts with at least one further external stationary element, in particular a permanent magnet.
[0006] The present invention, a drive element is, for example, in the form of an electric motor, but may also be of a pneumatic, hydraulic or electromechanical type. The present invention is not restricted to this.
[0007] In this case, the present invention has been found to be particularly advantageous for this purpose, in particular in order to improve the reliability, to provide a magnetically operated resetting for the output drive shaft or the input drive shaft to a rest or safe position in the event of a failure or if the drive element is switched off, which rest or safe position can be selected. The locking device is thus preferably formed from two components, with an active drive element and a passive part, which are coupled to one another. The passive part is formed from two permanent magnets, with one permanent magnet being connected to the input and/or output drive shaft, and the other permanent magnet being firmly connected to the housing. The two permanent magnets preferably engage with one another, so that, particularly in the event of failure of the drive element, the input or output drive shaft can automatically be mechanically moved to a safe position. The drive element can move the input drive shaft or the output drive shaft to different, selectable angles, which can be set precisely, up to 360° with respectto stops or hard stops which are not illustrated here. If the active drive element is deactivated, then the passive permanent magnets ensure that the shaft output or the output drive shaft is moved back to its original initial position. The two permanent magnets in the passive part are preferably in the form of a stator and rotor, with a magnetic resetting torque being produced between them. This contributes considerably to the security and reliability of the locking device in operation, in particular for aircraft doors.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] Further advantages, features and details of the invention will become evident from the following description of preferred exemplary embodiments and from the drawing, in which:
[0009] FIG. 1 shows a schematically illustrated longitudinal section through a locking device according to the invention for vehicles;
[0010] FIG. 2 shows a schematically illustrated longitudinal section through a further exemplary embodiment of a locking device as shown in FIG. 1 ; and
[0011] FIG. 3 shows a schematically illustrated longitudinal section through a further exemplary embodiment of the locking device as shown in FIG. 2 .
DETAILED DESCRIPTION
[0012] As is shown in FIG. 1 , a locking device R 1 according to the invention for vehicles, in particular for aircraft, has a housing 1 which, in the present exemplary embodiment, is subdivided by means of a partition wall 4 into a first part 2 and a second part 3 . A drive element 5 , preferably in the form of an electric motor, is connected to an input drive shaft 6 within the first part 2 of the housing 1 . The input drive shaft 6 is mounted by means of bearings 7 . In the preferred exemplary embodiment, the active part of the drive element 5 , which is preferably in the form of an electrically powered motor, is located within a cylindrical inner wall 8 of the housing 1 . However, the scope of the present invention is also intended to cover at least partially, a rotary movement of the input drive shaft 6 the active use of pneumatically or hydraulically powered motor elements.
[0013] The present invention is not restricted to this.
[0014] Following the input drive shaft 6 , a transmission element 9 is connected in the second housing part 3 to the drive element 5 , in particular to the input drive shaft 6 . The transmission element 9 is preferably in the form of an epicyclic transmission with a sun wheel and sun wheels. The output drive shaft 10 is connected to the transmission element 9 . Particularly for the locking device R 1 , the output drive shaft 10 is pivoted about an axis A to selectable specific angles in order to operate corresponding locking elements, which are not illustrated here, with a slide or the like. By way of example, if the drive element 5 fails, for example as a result of a power failure or failure of a hydraulic pump, then it is important in the case of the present invention for the output drive shaft 10 to move back to its original initial position in order to ensure a specific locking state. For this purpose, in the case of the present invention, it has been found to be particularly advantageous for an inner permanent magnet 11 to be associated with the output drive shaft 10 , and to be firmly seated on the output drive shaft 10 . A further permanent magnet 12 is firmly connected to the housing 1 within the cylindrical inner wall 8 , located axially at approximately the same height. A gap S is formed between the permanent magnet 11 and the permanent magnet 12 .
[0015] At least one permanent magnet 11 (and preferably a number of permanent magnets 11 ) is or are radially distributed and is or are permanently associated with the output drive shaft 10 , and this or these interacts or interact with at least one passive outer permanent magnet 12 on the housing 1 . By way of example, if the drive element 5 fails or is switched off, then the magnetic flux between the permanent magnets 11 and 12 rotates the output drive shaft 10 back to a selectable rest or safe position and, by way of example, secures a lock on an aircraft door or the like.
[0016] Furthermore, it is intended to be within the scope of the present invention for elements composed of metal or the like, which then interact with the permanent magnets 12 , to be arranged on the input drive shaft 6 and/or on the output drive shaft 10 instead of on the permanent magnets 11 .
[0017] This allows the reliability, in particular the operational reliability, of locking devices to be considerably improved.
[0018] In a further exemplary embodiment of the present invention, FIG. 2 shows a locking device R 2 in which the locking device R 2 is formed from components comprising a housing 1 , a drive element 5 , an input drive shaft 6 and an output drive shaft 10 . There is no transmission element 9 in this exemplary embodiment. In this case, the input drive shaft 6 and the output drive shaft 10 coincide. In the present exemplary embodiment, at least one permanent magnet 11 can be associated directly with the drive element 5 , in particular the input drive shaft 6 and the output drive 10 , and interacts with at least one radially aligned outer permanent magnet 12 , which is associated with the cylinder inner wall 8 , in the manner described above, in order, for example, to move the input drive shaft 6 and the output drive shaft 10 back to a selectable safe or initial position in the event of failure of the drive element 5 . In this case, it is also intended to be within the scope of the present invention for the permanent magnet 12 and/or 11 to be a component of the drive element 5 .
[0019] The exemplary embodiment of the present invention in FIG. 3 shows a locking device R 3 in which the permanent magnets 11 and 12 are connected upstream of or precede the drive element 5 , merely in comparison to the exemplary embodiment shown in FIG. 2 .
[0020] It is also intended to be within the scope of the present invention for at least one sensor 13 to be provided in order to identify limit positions of the input and/or output drive shafts 6 , 10 . Stop elements or the like, which are not illustrated here, can be provided in order to limit the rotary movement of the input drive shaft 6 and/or output drive shaft 10 .
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A locking device for vehicles, especially for aeroplanes, comprising an actively driven drive element provided with an input shaft and an output shaft which is directly or indirectly connected to the input shaft. According to the invention, at least one permanent magnet is associated with the input shaft or the output shaft, the magnet interacting with at least one other external fixed element, especially a permanent magnet.
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BACKGROUND OF THE INVENTION
The present invention relates to a safety system designed to eliminate fallout of liquids and as a function of the fluctuations in the flow to be flared or disposed of, to insure good combustion or good dispersion in order to shorten the flame and diminish the heat radiation and noise intensity received in the installations, during the flaring or dispersion of gases in the production, processing and transportation of hydrocarbons, especially off-shore.
Generally speaking, it is known that the evacuation of liquids, particularly in the form of drops, through the flare tip, as a result, for example, of a liquid congestion of installations upstream, or owing to rapid depressurization of volumes of liquids containing dissolved gases, constitutes a serious danger in installations for the production, processing and transportation of hydrocarbons, and in particular in fixed or floating installations situated off-shore.
As a matter of fact, as they leave the flare tip, the condensates or the oil, issuing from the gas or entrained by the latter, are ignited and fall back in flames on the installation or in the immediate proximity to it, thereby endangering the life of all personnel and the entire installation.
This danger is even greater in off-shore installations since the personnel run the risk of being trapped on the burning platform or floating supports, and furthermore the condensates or oil floating on the water can form a sheet of fire preventing any possibility of evacuation.
Moreover, in installations producing, processing and transporting hydrocarbons, of the gaseous type in particular, it is sometimes necessary, for operational or safety reasons, to vent large quantities of gas in a very short time. The combustion of fluctuating, and sometimes very substantial gas flows leads to the relegation of the flare far from the installations in order not to generate levels of temperature and noise in the latter that are intolerable for the personnel and the equipment. Unfortunately in the case of offshore locations, when the water becomes rather deep, this solution only solves the problem locally at a cost that increases rapidly with the depth of the water. When the water is very deep, the above arrangement becomes problematical and its cost prohibitive. Because this arrangement always creates a substantial interference to navigation, which is always tricky in the vicinity of the installation.
SUMMARY OF THE INVENTION
It is the object of the invention therefore, to eliminate all these drawbacks.
It therefore proposes a safety system constituted by all or part depending on the application, of a set of elements cooperating to:
Eliminate, where the case applies, the liquids entrained or condensed, in the vertical or subvertical part of the flare stack,
Pulverize in a mist at the flare tip, the liquid condensations that may be produced in the upper part of the flare stack, in the flare tip and at the vent, with allowance for the evolution during this travel, of the thermodynamic conditions to which the gas is subjected.
Improve the dispersion in the case of a vent, or shorten the flame generated by the combustion of all of the gas to be eliminated, by dividing the total jet into several parallel convergent or divergent jets, and increasing the aeration of the gases as they are vented to the atmosphere.
Put a ceiling on the heat radiation and the intensity of the noises received, regardless of fluctuations in gasflow, which can reach substantial levels.
In the case of discontinuous venting, to avoid or diminish additional flows of combustible or inert gas, proper to avoiding the entry of air through the flare tip during periods of gas flow shutdown, and thus avoid the risks associated with the correct determination thereof.
In order to achieve these results, the safety system according to the invention therefore introduces into the flow chain of the gas, between the potential source of liquid and the vent to the atmosphere, at least one chamber such as a flare-base flask, connected at its top to at least two flare stacks, or one or more chambers each connected to at least one flare stack, the said flare stacks each comprising:
A standard back-pressure device consisting, for example, of a calibrated check valve or a valve with manual, automatic or piloted operation, the level of the back-pressure exerted on the gas upstream (pressure threshold) being different for each of the flares, so that in the course of a continuous rise in pressure of the gases, a sequential, staged opening of the back-pressure devices is obtained, and thus the velocity of flow of the gases inside the flares will always be relatively high, and
A venting tip or orifice making it possible, owing to the high velocity of gas flow, to pulverize as a mist any drops of liquid remaining in the gas flux and quickly insure an intimate mixture of the gas with the ambient air in order to obtain rapid and total combustion and thereby avoid condensation and fallout of liquid drops, flaming or not, in the vicinity thereof.
It should be pointed out that the opening of the said back-pressure devices is gradually adjusted to the flow of gas to be evacuated, without thereby creating an inadmissible pressure or pressure surges in the installations upstream.
Each of these back-pressure devices can be matched, in parallel by a fast positive-opening device such as a bursting plate, for example, making it possible to put a ceiling on the upstream pressure at a pre-selected level, in the event of an accidental blockage of the standard back-pressure device. Each standard back-pressure device can also either be equipped with at least one small leak orifice so that during inoperative periods of the flaring or dispersion system, the flare will continue to be supplied with combustible or inert gas, or equipped with an auxiliary pipe serving the above function, in order to avoid entries of air through the flare tip and the troublesome consequences that could result. Depending on the characteristics of the flare tip, this small leak orifice can be of a less than a flame-choking size, thereby avoiding the installation of auxiliary devices preventing any propagation of the flame.
Moreover, if it is deemed necessary, a device with manual or automatic purge will be provided to collect drips and runoff that can accumulate above the back-pressure devices and interfere with their dependable operation. Likewise, if the formation of hydrates is to be feared, means of heating, or inhibition of formation of hydrates can be incorporated upstream, or in the back-pressure device.
Moreover, below the said back-pressure device, each flare stack can be equipped with, as a nonlimiting example, a liquid drop separator using a centrifugual or other effect, the condensates and liquids thus recovered being reinserted in the subjacent installations at a point where there would be no pressure incompability or prejudicial interferences with safety. Depending on the embodiment chosen, this separator can be equipped with an automatic or manual purge with high-level alarm indicating to the personnel the operating condition of the latter.
Level with the tip or venting orifice of each of the flares, the pulverization of the remaining liquid can be insured, for example, by a venting of the gases at a substantial initial velocity generated by one or more orifices with a thin lip, or through one or more calibrated tubes. This thin-lip orifice or calibrated tube may perhaps fulfill the motor function of a unit based on the Venturi effect, centripetal acceleration or the COANDA effect to entrain the ambient air and mix it intimately with the gas to be flared or dispersed by turbulence and accelerated diffusion.
Moreover, the latter device offers a large number of advantages, among which are:
(a) A shortening of the length of the flame by rapid combustion of the mass of gas released to the atmosphere owing to good aeration on the one hand, and on the other hand to the thinness of the lip /of the/ venting orifice (compared with the length of the flame resulting from the combustion of the entire flow of gas vented through a single pipe of circular section);
(b) A shortening of the length of the flame corresponding to the distribution of the gas flow among the various flare tips. It is recognized, as a matter of fact, that the length of a flame is a function increasing with the diameter of the flare tip when the latter is constituted by a cylindrical tube;
(c) A substantial reduction in the intensity of the noise emitted by the gas jet and the flame corresponding to the distribution of the total flow to be flared. As a matter of fact, experience shows that the total noise emitted by a plurality of jets and flames is less, under certain conditions, than the noise emitted by one of these jets alone;
(d) The venting of the gas can be done through a circular annular section with possible induction of air through the central section, the result is a substantial reduction in volume, even the elimination of the central core of gas at high temperature situated in the heart of the flame, the latter being primarily responsible for the heat radiation of a flame coming from a jet of gas of full circular section. Since this radiation is a cause of insecurity for the personnel and equipment subjected thereto if it is of high intensity, and since its calculation is always subject to caution, it appears primordial to treat the causes thereof in order to better circumvent the effects;
(e) If the gas vent lip is thin enough and the width close to or less than the flame choking distance, there will no longer be any possibility of a flareback inside the flare stack, and consequently it will no longer be necessary to insure a permanent scavenging of the flare with combustible or inert gas, in any event its output can be considerably diminished;
(f) The multiplicity of flare stacks, in the event of substantial fluctuations in flows, in normal operation, or required for reasons of safety, will make it possible to maintain a velocity of flow of the gases in the flare or flares necessary for correct operation of the equipment described above, and to insure the functions described above. Accessorily, the plurality of flare stacks may make it possible to constitute a self-supporting structure /of/ the constituent elements of the flare as well as of elements foreign to the system such as radiocommunication antennas.
Furthermore, in certain applications the flare will be equipped with means for manual or automatic ignition or extinction making it possible to start or smother the flame in various operational configurations, or for reasons of safety or otherwise.
The result, then is a system of very great safety particularly adapted to the needs of flaring or dispersion on confined installations, off shore, for example.
Embodiments of the invention will be described below by way of nonlimiting examples with reference to the attached drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a production installation equipped with a safety device assembly according to a first example of embodiment of the invention, corresponding more generally to a continuous and relatively minor flow of gas coming, for example, from an installation for separation or processing of hydrocarbons.
FIG. 2 is a schematic representation of a second installation equipped with the safety device assembly according to a second example of embodiment calling on a plurality of flare stacks, corresponding more generally to a substantial flow of gas with wide fluctuations in flow, or to intermittent flows of gas such as those which can be encountered in installations of production or transportation of gas.
FIGS. 3A, 3B, 3C, 3D, 3E, 3F are schematic representations showing details of embodiment of the back-pressure device.
FIGS. 4A, 4B, 4C are schematic representations showing simple details of embodiment of the device for separation of entrained liquids.
FIG. 4D is a schematic view along arrow F of FIG. 4A.
FIGS. 5A, 5B, 5C, 5F are schematic representations showing details of embodiment of the device for pulverization of the liquids entrained or condensed, and aeration of the gas jet with flame stabilization.
FIG. 5E is a schematic overhead view of FIG. 5C.
FIG. 5D is a fragmentary and schematic overhead view of FIG. 5F.
FIG. 6 is a schematic representation of the safety device assembly in which the lower part of the flare stack serves as a flare base flask in order to obtain a less bulky installation.
FIG. 7 is a schematic representation of the safety device assembly in which all its component elements are aligned on a generally vertical axis with direct opening of the bottom of the flare-base flask into the sea.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIG. 1, the installation comprises, first of all, either a source of entrainment of liquid hydrocarbons constituted by a separator 1 receiving the crude petroleum or the crude gas through an intake duct 2, or a source of gas constituted by a pipeline 2', or both sources simultaneously. Separator 1 is equipped in classic fashion with a circuit 3 for normal collection of oil and condensates, a circuit 4' for normal collection of gas and a gas outlet connected to a gas flow chain 4 to the tip 5 of the flare. This gas flow chain 4 includes, between separator 1 and flare tip 5, a flare-base flask 6 equipped in classic fashion with a circuit for collection of drips 7 perhaps comprising a pumping means 8 and a safety overflow tube 10 opening below the level 17 of the sea, with breather 9. Separator 1, flare-base flask 6 and safety overflow tube 10 are all three equipped with a high-level detection circuit, which, in case of an abnormally high level of liquid, shuts off the source of supply of crude or of gas to the installation. Following the direction of flow of the gas in flare stack 13, this installation comprises in succession, according to the invention, a back-pressure device 11 paralleled by a bursting plate 11', a liquid separator 12 and a flare tip 5.
If the flaring of the gas is not part of the normal operation of the installation, back-pressure device 11 is shut off, the flow of combustible or inert gas proper to avoiding the entry of air through flare tip 5 is brought either by a lateral pipe 15 or through a small orifice provided through back-pressure device 11. When gas is flared, with, perhaps, fast tripping of the flow, a first damping of the pressure surge will be produced by safety overflow tube 10 thereby serving as a damper, with simultaneous opening of back-pressure device 11 and flow of gas to the flare. A pressure rise upstream of device 11 due to an excessively slow opening, a blockage of the latter or for any other reason, will burst the diaphragm of bursting plate 11' and the flow of gas into flare 5. Any liquids entrained or condensed are trapped in separator 12 and reintroduced into the installations upstream by a pipe 14 equipped with a manual or automatic, piloted or unpiloted liquid purge device 16. The gas then reaches flare tip 5 where the liquids remaining are pulverized and together with the gas are intimately mixed with the ambient air by the effect of a high velocity of ejection and a disposition of tip 5 favoring the diffusion and mixture.
If the flaring of the gas is part of the normal operation of the installation, the back-pressure device 11 will normally be open and the safety device assembly will be in service.
Referring to FIG. 2, the installation comprises a plurality of flare stacks 12a, 12b, 12c, limited to three in the drawing for reasons of clarity only, and each of these can be equipped with the device provided in FIG. 1, in particular the back-pressure devices 11a, 11b, 11c being calibrated at substantially different opening pressures in order to maintain in each flare stack, as a function of the flow to be flared, a sufficiently high velocity in the downstream devices to enable them to operate correctly. Furthermore with a plurality of flares the length of the flame resulting from all of the gas flow will just be that corresponding substantially to the flow passing through one of the flare stacks, and not that corresponding to the entire flow to be flared, regardless of the method of calculation used to determine the length thereof. Moreover, the intensity of the jet and flame noises will be maximum with only one of the flares in operation at maximum flow, and will correspond to the flow passing through it. The successive actuation of the other flares corresponding to an increase in the flow to be flared will result in a diminution of the intensity of the noise defined above.
In a confined installation such as those encountered off shore, the fact of overcoming the length of the flame and the intensity of the noise will in itself justify the implantation of a plurality of flares as soon as the flows of gas to be flared are substantial and variable.
Finally, in a certain number of installations where high gas pressure is available for flaring, without thereby interfering with the overall safety of the installation or with the operation of the set of safety devices, the service pressure of the flare-base flask 6 can be raised to a substantial extent in view of the operation of these auxiliary devices, this leading to a substantial diminution in the corresponding volumes and weights. This advantage can be substantial in offshore installations where costs are very sensitive to weights and volumes.
The back-pressure devices 11, 11a, 11b, 11c can be embodied in different ways and installed in different manners. In the representation in FIG. 3A, the back-pressure device is constituted by a calibrated check valve 21 pierced with an orifice 22, a cock 23 permits manual and periodic verification that there is no accumulation of liquids on the valve to interferw with its working.
In the representation in FIG. 3B, orifice 32 which helps maintain the gas overlay is pierced laterally in the gas duct above the back-pressure valve 31, the liquids running off in the flare stack are trapped in a bulge in the flare stacks and purged by an automatic valve 33 operated by a level detector 34. In the representation in FIG. 3C, the overlay of combustible gas is maintained by an outside duct 41. The overlay of inert gas is maintained by an outside duct 42, equipped with a non-return check 47, the liquids running off from the top are trapped in a boot 43 and evacuated by an automatic purge valve 44. A detector of abnormally high level KLA 45 and a detector of abnromally low level LLA 46, inform the operators of a malfunction in the drip collection system.
In the representation in FIG. 3D, the back-pressure device is constituted by a valve 51 whose position is governed by a pressure regulator PC 52.
In the representation in FIG. 3E the back-pressure valve 61 is placed laterally to a boot 62 for recovery of drips equipped with a liquid purge duct 63 with a manual valve 64. A pipeline 65 equipped with a valve 66 and a non-return check 67 makes it possible to feed combustible or inert gas to the top of the flare stack during periods of shutdown.
In the representation in FIG. 3F the back-pressure valve 71 is placed on a horizontal or sub-horizontal part of the flare stack. The vertical part of the flare stack downstream terminates at the bottom in a boot 72 for collection of drips. This boot is equipped with a liquid purge duct 73 with a valve 74 operated by a sensor of the liquid level 75. Detectors of abnormally high level 77 and low level 76 inform the operators of malfunctions in the drip collection system.
The device for separation of liquids entrained can be embodied in different ways and installed in various manners. In particular, the device represented in FIGS. 4A and 4D includes a centrifugal separator 81 with a tangential input 82 of the fluid, the separated liquids being evacuated toward the bottom through a duct 83 for drip collection equipped with an automatic purge device 84 and the gases toward the top through the downstream part of flare stack 85, FIG. 4B proposes a horizontal or subhorizontal disposition in which the gas input 91 is connected to a bulge 92 in the duct, having a central core 93 connected to the outside tube by spiral vanes 94, imparting a helical movement to the fluids passing through it. The gas issuing from this device goes to the flare tip through a duct 95 while the liquids adhering to the wall are collected in a boot 96 equipped with a purge duct 97 with a valve 98 operated by a level detector 99. High level 100 and low level alarm 101 inform the operators of any malfunction in the purge system.
The device represented in FIG. 4C relates to a device similar to the one in FIG. 4B but which can be placed vertically on the flare stack in order to reduce the bulk. Furthermore entry pipe 111 is not bulged and has spiral vanes 112 which do not necessarily cover the full section of pipe 111. Chamber 113 for liquid recovery has plates pierced with holes 114 catching the liquids entrained, and vertical gutters 115 channeling them toward the bottom of the device where they will be withdrawn through a duct 116 equipped with devices as in the preceding examples.
The flare tip can be embodied in various ways which will always be installed vertically or subvertically. For example, in FIG. 5A the end of flare stack 121 has a calibrated nozzle 122 of reduced circular section to speed up the gas, opening above a horizontal circular plate 123 with vertical radial vanes 124 to guide the streams of air or wind into the convergent-divergent part of a venturi 125 whose neck 126 will be placed slightly above the upper end of nozzle 122 in order to obtain the desired effect of entrainment of air. The outer surface of venturi 125 can be provided with vertical vanes 130 to guide the streams of air or wind. The upper end of the venturi will have a perforated, circular, inner crown 127 to permit the flame to "catch." If low-pressure gas were to be eliminated, this could be embodied by a pipe 128 opening at 129 in the venturi, beyond the neck, in the negative-pressure zone of the said venturi. In FIG. 5B the flare tip can include the same devices as FIG. 5A but it differs from the latter in that the outlet nozzle for gas is replaced by a circular annular crown 132 in which the gas input is axial in direction 135 or tangential 135' to the crown 132, depending on the effect desired. Furthermore, a central core 133 can be placed in the center of the device to accentuate the venturi effect for certain applications. Vanes 134 for suspension of the central core 133 can be plane and vertical, or have a helical surface in order to be adapted to the desired guidance effect.
In FIG. 5C, the disposition of the elements constituting the flare tip is similar to those provided in FIGS. 5A and 5B, but it differs in that the upper part of the venturi is a set of petals 136 admitting air laterally through slots 137 to improve the air-gas mixture.
FIG. 5F proposes a disposition similar to the preceding, but in which the gas outlet takes place through a lip 138 tangent to the internal surface of the venturi, either in the bottom thereof or at the neck, or as represented in its divergent part, this lip being inclined to the axis of the cone so as to impart an ascending spiral movement to the gas.
For certain applications, the embodiment represented in FIG. 6 offers a simplified solution of very small bulk in which all the elements of the system are assembled in two vertical or subvertical units, one ascending 141 and the other descending 142, connected together and to the installations by the piping necessary for their operation. The vertical ascending unit has, at its base, the vertical flare-base flask 143 surmounted by a housing 144 surrounding all the required components up to the flare tip, and whose principle functions are:
to protect the elements of the system from the outside elements such as frost and ice,
to support the elements of the system,
to permit access for control and maintenance of the elements of the system up to the flare tip;
to improve the aerodynamic profile of the system in order to diminish the outside loading to be allowed for in designing this structure;
for heating, where applicable, the system as a whole by some means such as steam, heat-bearing fluid or electricity, to palliate the problems created, for example, without limitation thereto, by the accumulation of frost on the surfaces in contact with the atmosphere or deposits of gas hydrates in the equipment and piping.
The descending vertical part 142 can also be equipped with a similar housing in order to obtain similar advantages.
In addition, a further simplification will consist in embodying the flare and overflow column as a continuous pipe, perhaps variable in section, as represented in FIG. 7, in which continuous pipe 150 constitutes active parts of the system and of the protective housings of the elements of the system, from the flare tip 151 to the end of the overflow tube 152.
Finally, in all the configurations of installations of this safety system, the latter can use, for its embodiment, parts of already existing pipes, made of steel or other materials, and capable of serving other functions such as the supporting of installations. This supporting can also be embodied from other elements such as frames, whether or not required for other functions.
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Safety system designed to eliminate liquids entrained or condensed, and to limit the heat radiation and the intensity of the noises received in the flaring or dispersion of gases from the production, processing and transportation of crude hydrocarbons, and elaborated on land or offshore.
The system according to the invention involves a chamber 6 such as a flare-base flask connected to at least one flare stack which includes: a back-pressure device 11 and a tip 5 or an orifice for venting to the atmosphere, and means to pulverize into a mist any drops of liquid remaining in the gas flow, and to insure, rapidly, an intimate mixture of the gas with the ambient air.
This system can be installed on land, at sea, on any type of fixed or floating support.
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BACKGROUND OF THE INVENTION
The present invention relates to the art of securing bottles of shampoo and other similar products within easy reach of the user.
DESCRIPTION OF THE PRIOR ART
Many commercial products are available for holding shampoo and similar shaped tub and shower products in a convenient position for the user. Whether due to age or injury, many people are unable to safely bend over in a shower in order to reach bath products which commonly reside on a tub ledge. As a result, bottle racks which fit over a shower head, as well as shelving systems held in place by tension rods, have been widely used in the art to place cleaning products in easy reach of someone in shower. However, shower head racks tend to interfere with the adjustment of the shower head and are often inadvertently hit jarring the contents loose. Shelving units tend to collect moisture resulting in mildew problems. Further, both shelves and racks interfere with the cleaning of the tub/shower facility.
Thus, there is a need for an apparatus which permits the positioning of shampoo and other similar containers in a location convenient to the user but which does not interfere with the normal use of the shower and which does not create cleaning obstacles.
SUMMARY OF THE INVENTION
It is thus an object of this invention to provide a bottle hanger apparatus which can secure a bottle to a walled surface of a shower or tub.
It is a further object of this invention to provide a bottle hanger apparatus which does not interfere with the normal use or cleaning of the shower environment.
It is still a further and more particular object of this invention to provide a bottle hanger apparatus which can reversibly engage to a variety of walled surfaces.
It is still a further and more particular object of this invention to provide a bottle hanger apparatus which does not damage or mar the attachment walls.
These and other objects of the invention are provided by a bottle hanger apparatus which provides a collar which is inserted over the neck of the bottle and secured in place by the reattachment of the bottle's screw on cap. The collar has an upper surface, a lower surface and an outer rim which projects below the plane of the lower surface. An aperture traverses the center of the collar to allow placement of the collar over a bottle's neck. A separate suction mounted lip is reversibly attached to a shower wall, the lip then being used to engage the lower surface and rim of the collar thereby supporting the attached bottle.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view in partial section of the bottle hanger adapter seen in partial section.
FIG. 2 is a perspective view of the wall mounted lip.
FIG. 3 is a perspective view of the bottle hanger collar.
DETAILED DESCRIPTION
According to this invention, a novel bottle hanger is provided which can secure bottles of shampoo and similarly packaged goods to the typically hard surfaced tub/shower walled surfaces.
In reference to FIGS. 1 through 3, a bottle hanger apparatus 1 has a collar 2 and a wall mounted lip 21. Collar 2 has an upper surface 3, a lower surface 5 and a rim 7 which extends below the plain of lower surface 5. A circular aperture 9 traverses surfaces 3 and 5. Aperture 9 should be slightly larger than the neck 11 of bottle 13 so that collar 2 may be inserted over neck 11. A cap 15 has been reattached to bottle 13 securing collar 2 between bottle 13 and cap 15.
The bottle with attached collar can then engage the upper edge 23 of lip 21. Lip 21 is carried by the convex side 27 of a suction disk 25, the disk being used to reversibly anchor lip 21 to a wall or other support. Concave side 29 of disk 25 can reversibly engage common bathroom wall material such as tile, marble, fiberglass, acrylic, as well as sliding glass bathroom doors. All such surfaces provide an optimal surface for mounting suction disk 25.
Edge 23 is designed to engage the lower surface 5 of collar 2. Rim 7 prevents lip 21 from disengaging from the collar. As seen in the embodiment of FIG. 2, lip 21 has an arcuate surface which corresponds to the arcuate rim 7.
The present invention allows bottles of shampoo to be placed at any height or location within a shower or tub. This is a particular usefulness for individuals with limited mobility who may not be physically able to reach bottles stored on a tub ledge or on an elevated rack. Further, the present invention allows the user to sequentially organize bathroom products. This is advantageous of individuals with poor eyesight who, through the use of the invention, can now organize products by location.
The bottle hanger apparatus is preferably constructed of a rigid plastic, nylon or rubber material which is resistant to impacts and impervious to high moisture and temperature variations. Further, the apparatus is compact and portable making it suitable for traveling.
It is thus seen in accordance with this invention, an apparatus is provided which allows bottles of personal cleaning products to be reversibly attached to a shower wall. This arrangement allows the efficient positioning of bathroom supplies at a safe location and in a manner which does not damage walls or interfere with the cleaning of the shower. As variations will become apparent to those of skill in the art from a reading of the above description, such variations are embodied within the spirit and scope of the invention as defined by the following appended claims.
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A bottle hanger adapter having a collar defining an aperture and an outer circumferential rim for engaging a lip carried by a suction disc where the lip engages the collar and the collar rim thereby providing a means of supporting bottles carrying the collar.
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This is a continuation of U.S. application Ser. No. 13/463,736 filed May 3, 2012, now U.S. Pat. No. 8,376,540, which is a continuation of U.S. application Ser. No. 13/163,429 filed on Jun. 17, 2011, now U.S. Pat. No. 8,192,007, which is a continuation of U.S. application Ser. No. 12/609,233, now U.S. Pat. No. 7,984,982, filed Oct. 30, 2009 which is a continuation of U.S. application Ser. No. 11/797,651, filed May 4, 2007, now U.S. Pat. No. 7,631,964, which is a continuation of application Ser. No. 11/046,734, filed Feb. 1, 2005, now U.S. Pat. No. 7,229,162, which is a divisional of U.S. application Ser. No. 10/264,323, filed Oct. 4, 2002, now U.S. Pat. No. 7,070,263, which claims priority from Japanese Patent Application Nos. 2001-309106, dated Oct. 4, 2001; 2002-260048, dated Sep. 5, 2002 and 2002-291152, dated Oct. 3, 2002. The entire disclosures of the prior applications are considered part of the disclosure of the accompanying continuation application and are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This present invention relates to a liquid jet head, and a liquid jet apparatus, such as a recording head for an ink jet recording apparatus, an electrode member ejection head for an electrode forming apparatus, an organic substance jet head for a bio chip manufacture apparatus, etc., in which liquid are ejected by deformation of piezoelectric elements formed on a surface of a diaphragm formed as a part of pressure generating chambers communicating with nozzle orifices from which liquid are ejected.
2. Description of the Related Art
A typical inkjet recording head (a kind of liquid jet head) using a longitudinally oscillating piezoelectric transducer (referred to below as simply a “recording head”) has, as shown in FIG. 16 , an ink path unit 1 in which a plurality of nozzle openings 8 and a pressure generation chamber 7 are formed, and a head case 2 to which this ink path unit 1 is bonded and in which piezoelectric transducers 6 are housed.
The ink path unit 1 is a laminar construction including a nozzle plate 3 in which the nozzle openings 8 are arranged in rows orthogonally to the recording medium surface, a flow channel substrate 4 in which a pressure generation chamber 7 is disposed communicating with each of the nozzle openings 8 , and a diaphragm 5 covering the bottom opening of each pressure generation chamber 7 . An ink reservoir 9 communicating with each pressure generation chamber 7 by way of ink supply path 10 and storing the ink supplied to each pressure generation chamber 7 is formed in the flow channel substrate 4 . It should be noted that two sets of nozzle openings 8 and pressure generation chambers 7 are shown in the example in FIG. 16 .
The head case 2 is made from synthetic resin with the piezoelectric transducers 6 disposed in through-spaces 16 , which are vertically oriented as seen in the figure. The spaces 16 extend in line with the rows of nozzle openings 8 , and there are two spaces 16 corresponding to the rows of the nozzle openings 8 . The back end side of each piezoelectric transducer 6 is bonded to a fixed plate 11 affixed to the head case 2 , and the front end side of each piezoelectric transducer 6 is bonded to a pad 5 C on the bottom surface of the diaphragm 5 .
The piezoelectric transducers 6 are forced to expand and contract longitudinally by applying a drive signal generated by a drive circuit (not shown in the figure) to the transducers 6 by way of flexible printed circuit 13 . Expansion and contraction of the piezoelectric transducers 6 causes the pad 5 C of the diaphragm 5 to vibrate and thereby change the pressure inside the pressure generation chamber 7 so that ink inside the pressure generation chamber 7 is discharged from the nozzle opening 8 as an ink droplet. Also shown in FIG. 16 is the ink refilling tube 15 for refilling the ink reservoir 9 with ink from an ink cartridge (not shown in the figure).
The diaphragm 5 in this example is made from a polyphenylene sulfide (PPS) film, and a damper chamber 12 for absorbing through the diaphragm 5 pressure change in the ink reservoir 9 during ink discharge is formed in the head case 2 at an appropriate position to the ink reservoir 9 . If this damper chamber 12 is an independent space that does not communicate with the exterior, air inside the damper chamber 12 can dissolve into the ink through the diaphragm 5 made of PPS film, thereby lowering the pressure inside the damper chamber 12 , increasing the tension of the diaphragm 5 , and can thus easily make it difficult to achieve the desired damping effect. This pressure drop inside the damper chamber 12 is therefore prevented by opening an external communication path 14 passing from the inside surface of the damper chamber 12 toward and out the back side of the head case 2 so that the damper chamber 12 can communicate with the outside.
PROBLEM TO BE SOLVED
A problem with the recording head described above is that the damper chamber 12 is open to the air. When the recording head is left unused or stored for a long time, water in the ink inside the ink reservoir 9 is therefore able to pass as water vapor through the PPS film diaphragm 5 and the viscosity of ink inside the ink reservoir 9 gradually increases. The ink can even dry to the point that clogging of the flow path cannot be corrected and ink cannot be normally discharged even after a cleaning operation, for example, that forcibly vacuums ink from within the ink path when the recording head is used the next time. This tendency is particularly pronounced with pigment inks that easily increase in viscosity, and pigment inks are increasingly used in order to achieve a desired print quality.
There is therefore a strong need for an inkjet recording head whereby this increase in ink viscosity can be prevented during extended storage.
It is also desirable in achieving a means for solving this problem to minimize the number of parts and achieve high precision and quality with the simplest possible method.
The present invention is directed to solving these problems and an object of the invention is to provide an inkjet recording head and an inkjet recording apparatus capable of preventing an increase in ink viscosity inside the flow paths during long term storage.
SUMMARY OF THE INVENTION
To achieve this object in a liquid jet head having nozzle openings, a pressure generation chamber communicating with each nozzle opening, a liquid reservoir for storing liquid supplied to pressure generation chambers, a liquid path unit including the pressure generation chambers and a seal plate for covering an opening to the liquid reservoir, and a head case to which the liquid path unit is bonded, a liquid jet head according to our invention provides a damper chamber at a part corresponding to the liquid reservoir in the head case or seal plate for releasing pressure change in the liquid reservoir; a release path formed in the head case for releasing pressure in the damper chamber to the air; and a control path imparted with specific flow resistance formed in the head case and/or seal plate for restricting moisture dispersion while communicating the damper chamber with the release path.
In other words, a liquid jet head according to the present invention has a damper chamber for releasing pressure change in the liquid reservoir formed at a part corresponding to the liquid reservoir in the head case or seal plate; a release path formed in the head case for releasing pressure in the damper chamber to the air; and a control path with specific flow resistance formed in the head case and/or seal plate to restrict moisture dispersion while communicating the damper chamber with the release path.
The flow of water vapor from the liquid that passes through the seal plate is therefore restricted by the flow resistance of the control path, and undesirable dispersion of moisture from the liquid is thus suppressed.
Because the outflow of vapor to the air is restricted by the control path, evaporation of moisture from liquid in the liquid reservoir is restricted by the control path and an increase in the viscosity of liquid in the liquid reservoir is prevented even when the recording head is stored unused for a long time. Therefore, when the recording head is used again after being stored for a long time the liquid can be normally discharged after applying a normal cleaning operation, and discharge problems such as conventionally occur can be substantially eliminated.
Preferably, the control path of this liquid jet head is formed in an interfacial surface between the seal plate and head case.
The control path can be easily formed in these opposing surfaces, thus helping to improve the efficiency of recording head production.
Further, preferably the control path is formed in the seal plate.
In this case the depth of the control path is at most the thickness of the seal plate, and a high precision control path can therefore be formed using a press or other simple technique.
In another preferable embodiment the control path is formed in the head case.
In this case the control path can be formed by molding or other process at the same time the head case is manufactured, further contributing to efficient production.
Yet further preferably the seal plate of the liquid jet head has a barrier thin film and a path formation thin film in which the control path is formed.
Because the control path is formed in a thin film for forming the path, for example, the control path can be formed easily.
Further preferably in this case the barrier thin film is made from a resin thin film material, and the liquid path formation thin film is made from a metal thin film material.
Because the control path is formed in a metal thin film in this case the control path can be formed with high precision using a simple method, and the evaporation of liquid vapor can be restricted under optimal conditions.
Yet further preferably the control path is formed in the metal thin film using an etching process.
The etching process can be controlled to achieve a control path with high shape and dimensional precision, and the evaporation of liquid vapor can be restricted under optimal conditions.
Yet further preferably, the flow resistance is set to a permeability characteristic lower than the moisture permeability of the resin thin film.
The flow resistance imparted by this permeability characteristic assures reliable control and restriction of liquid vapor dispersion and evaporation as described above.
The flow resistance of the control path in the present invention is based on the following equations for vapor flow Q per unit time,
Q =( W 0− W 1)/ R
where W0 is the vapor density at the path inlet, W1 is the vapor density at the path outlet, and R is the flow resistance of the path.
R=L /( D×S )
where L is the length of the path, D is the vapor dispersion coefficient, and S is the section area of the path.
The major factors determining flow resistance are the above L and S.
Further preferably, the resin thin film is a polyphenylene sulfide film.
In this case the moisture permeability of the film itself works ideally in conjunction with the permeability characteristic of the control path, and the dispersion of moisture vapor can be optimally controlled.
Yet further preferably the liquid jet head of this invention also has a connection cavity communicating with the damper chamber formed or connected to the damper chamber, and the connection cavity is disposed to the head case and/or seal plate and communicates with the control path.
In this case alignment error in the relative positions of the control path and damper chamber when the dimensionally precise control path is connected to the damper chamber can be absorbed by the connection cavity. This absorption of alignment error also absorbs misalignment when the seal plate is bonded to the head case, and effectively improves production efficiency.
Further preferably, connection cavities disposed to each of multiple damper chambers communicate with each other.
This configuration enables multiple damper chambers to communicate through the control path with the release path by means of a simple structure. Furthermore, when the damper chambers thus communicate with the release path through multiple control paths from the connection cavities communicating with the damper chamber, communication between the multiple damper chambers and the air is maintained by the remaining good control paths when flow through part of the control paths becomes obstructed for some reason, and a worst-case increase in the liquid viscosity can also be avoided.
Yet further preferably the seal plate is bonded to the head case using adhesive, and a cavity for holding excess adhesive is formed at least in proximity to the control path.
If excessive adhesive is applied this configuration captures the excess adhesive in this cavity and prevents the adhesive from flowing into the control path. Furthermore, even if some adhesive gets into the control path the amount will be within the allowable range and normal flow through the control path can be assured.
Further preferably this cavity communicates with the control path.
With this configuration excess adhesive is captured and held in the cavity communicating with the control path. The amount of adhesive penetrating the control path can therefore be minimized and the control path can be kept clear and functional.
Further preferably, the cavity for holding excess adhesive is narrower in width than the control path and communicates with the control path.
By making the cavity for holding excess adhesive narrower than the control path, the likelihood of the control path becoming plugged with adhesive can be reduced.
Further preferably the liquid jet head discharges a pigment ink.
Pigment type inks are particularly susceptible to an increase in viscosity due to evaporation of moisture from the ink. By effectively preventing the evaporation of moisture from ink in the liquid reservoir, the present invention is therefore particularly effective as a means enabling the recording head to be used smoothly again after having been stored for a long time.
The pressure generation element of a liquid jet head according to the present invention is preferably a piezoelectric transducer.
It is therefore possible to prevent evaporation of moisture from liquid in the liquid reservoir of a recording head using a piezoelectric transducer as the pressure generation means, and enable the recording head to be used smoothly again after having been stored for a long time.
Further preferably, the pressure generation element is a longitudinal oscillation mode piezoelectric transducer.
Because resin films such as polyphenylene sulfide films that pass water vapor easily are commonly used as the seal plate in recording heads that use a longitudinal oscillation mode piezoelectric transducer, this configuration of our invention can effectively prevent evaporation of moisture from liquid in the liquid reservoir, and can therefore enable the recording head to be used smoothly again after having been stored for a long time.
Yet further preferably the piezoelectric transducer is contained in the head case and applies a pressure change to the pressure generation chamber.
This configuration helps improve production efficiency because the head case is used both to secure the piezoelectric transducer and to form the control path.
Preferably, the pressure generation element of the recording head is a heating element for heating liquid in the liquid path.
With this configuration the invention can effectively prevent evaporation of moisture from liquid in the liquid reservoir of a recording head using a heating element as the pressure generation means, and can therefore enable the recording head to be used smoothly again after having been stored for a long time.
Alternatively, the control path formed in the liquid path formation thin film is a straight release path enabling the connection cavity and release path to communicate in a straight line.
Because there are no curves in the control path with this configuration, it is difficult for adhesive to collect inside the control path.
Further preferably, a seal plate cavity is formed in the seal plate at a position appropriate to the liquid reservoir, the seal plate cavity is formed in the liquid path formation thin film, and a part of the seal plate cavity disposed in proximity to the straight release path formed in the liquid path formation thin film and opposite the straight release path is substantially parallel to the straight release path.
With this configuration the seal plate cavity and straight release path are formed by removing at least a part of the liquid path formation thin film. The rigidity of the seal plate cavity and straight release path is therefore weaker than where these parts are not formed and this part is susceptible to wrinkling.
In addition, the part of the seal plate cavity and straight release path disposed in proximity to the easily wrinkled part is even more susceptible to wrinkles.
Therefore, by forming the part of this seal plate cavity that is opposite the straight release path so that it is parallel to the straight release path, external force is applied evenly and not concentrated to one side, thereby reducing susceptibility to wrinkling.
Further preferably a bonding pad is formed in the seal plate cavity.
When the seal plate is bonded to the pressure generation chamber and liquid reservoir opening, this configuration can firmly hold the seal plate at the bonding pad, thereby reducing the likelihood of bonding defects.
Other objects and attainments together with a fuller understanding of the invention will become apparent and appreciated by referring to the following description and claims taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partially exploded oblique view of a first embodiment of an inkjet recording head according to the present invention;
FIG. 2 is a section view of the inkjet recording head shown in FIG. 1 ;
FIG. 3 is a plan view of just the head case in the inkjet recording head shown in FIG. 1 ;
FIG. 4 is a plan view showing the diaphragm affixed to the head case;
FIG. 5 is an oblique view showing the opposite side of the diaphragm;
FIG. 6 is a section view through line ( 6 )-( 6 ) in FIG. 4 ;
FIG. 7 is a section view through line ( 7 )-( 7 ) in FIG. 4 ;
FIG. 8 is a section view through line ( 8 )-( 8 ) in FIG. 3 , and shows a second embodiment of the present invention;
FIG. 9 is an oblique viewing showing a third embodiment in which the control paths are formed on the head case side;
FIG. 10 is a section view showing a variation of a configuration in which the control paths are formed on the head case side;
FIG. 11(A) is a plan view of a diaphragm according to a first variation in accordance with a fourth embodiment of the invention;
FIG. 11(B) is a plan view of a diaphragm according to a second variation in accordance with a fourth embodiment of the invention;
FIG. 12 is a plan view showing a variation of the connection between the control path and release path;
FIG. 13 is a side section view showing a control path in which a separate orifice is used;
FIG. 14 is a schematic diagram showing the main parts of a recording head according to a fifth embodiment of the invention;
FIG. 15 is a schematic view showing a variation of the fifth embodiment;
FIG. 16 is a section view of a conventional inkjet recording head; and
FIG. 17 is an illustration showing an ink-jet recording head in accordance with the present invention showing a heating element used as the transducer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention are described below with reference to the accompanying figures. It will be noted that because the embodiment described below is a preferred embodiment of the invention various technically desirable limitations are also described, but unless otherwise specifically noted the scope of the present invention shall not be limited to the embodiments described below.
Embodiment 1
FIG. 1 to FIG. 7 show an inkjet recording head (referred to below as simply a recording head) as a first embodiment of an inkjet recording head disposed to an inkjet recording apparatus according to the present invention. This recording head is basically the same as the recording head shown in FIG. 16 , and like parts are therefore identified by like reference numerals below. Furthermore, while there are two rows of nozzle openings 8 and pressure generation chambers 7 in the recording head shown in FIG. 16 , there are four such rows in the head case 2 shown in FIG. 3 . More specifically, the section through either side of the dot-dash line L in FIG. 3 corresponds to the views shown in FIG. 1 , FIG. 2 , and FIG. 16 . FIG. 3 is a top plan view of the head case 2 .
The ink path unit 1 is a laminar construction including a nozzle plate 3 to which nozzle openings 8 are disposed in rows, a flow channel substrate 4 in which rows of pressure generation chambers 7 each communicating with a corresponding nozzle opening 8 are disposed and in which is formed ink reservoirs 9 for holding ink for supply to each of the pressure generation chambers 7 through an ink supply path 10 , and a diaphragm 5 (seal plate) for covering the bottom openings of the pressure generation chambers 7 and ink reservoirs 9 . In FIG. 3 the damper chambers 12 in the middle are positioned in a mutually compatible shape, and there is a corresponding space 16 for each damper chamber 12 .
The head case 2 is injection molded from a thermosetting resin or thermoplastic resin. The piezoelectric transducers 6 are housed in the vertically through-passing spaces 16 at positions corresponding to the pressure generation chambers 7 . The spaces 16 extend in line with the rows of nozzle openings 8 and are disposed corresponding to these rows. The piezoelectric transducers 6 are longitudinal oscillation mode transducers, the back end side of which is bonded to the fixed plate 11 affixed to the head case 2 , and the front end surface is bonded to a pad 5 C on the bottom surface of the diaphragm 5 .
The diaphragm 5 in this embodiment is made of polyphenylene sulfide (PPS) film laminated with a stainless steel pad 5 C. Damper chambers 12 for absorbing pressure fluctuations inside the ink reservoirs 9 through the diaphragm 5 are formed in the head case 2 at locations appropriate to the ink reservoirs 9 .
As shown in FIG. 1 to FIG. 3 , a seal-side cavity such as diaphragm-side cavity 14 I is disposed to the diaphragm 5 at positions corresponding to the damper chambers 12 disposed to the head case 2 . As shown in FIG. 3 , these diaphragm-side cavities 14 I are substantially identical in shape to the damper chambers 12 .
The diaphragm (seal) 5 is a laminate of a thin-film barrier such as resin thin film 5 A and a thin film such as a metal thin film 5 B for forming flow channels. The resin thin film 5 A could be a polyphenylene sulfide (PPS) film. A stainless steel alloy is typically used for the metal thin film 5 B. The diaphragm-side cavities 14 I are formed in the metal thin film 5 B, and are more specifically formed in the diaphragm (seal) 5 surface facing the head case 2 .
The diaphragm 5 (seal) shall not be limited to this configuration and could be electroformed Ni or SUS, for example, or formed from dry film and resin film.
The ink used with an inkjet recording head is generally deaerated in order to prevent bubbles from forming. As a result, if the damper chamber 12 is an independent space that does not communicate with the exterior, air inside the damper chamber 12 can dissolve into the ink through the PPS film diaphragm 5 , thereby lowering the pressure inside the damper chamber 12 , increasing the tension of the diaphragm 5 , and thus easily making it difficult to achieve the desired damping effect. This pressure drop inside the damper chamber 12 is therefore prevented by enabling the damper chamber 12 to communicate with the outside through an external communication path 14 disposed to the head case 2 .
The piezoelectric transducers 6 are forced to expand and contract longitudinally by applying a drive signal generated by a drive circuit (not shown in the figure) to the piezoelectric transducers 6 by way of flexible printed circuit 13 . Expansion and contraction of the transducers 6 causes the pad 5 C of the diaphragm 5 to vibrate and change the pressure inside the pressure generation chamber 7 so that ink inside the pressure generation chamber 7 is discharged from the nozzle opening 8 as an ink droplet. Also shown in the figures are the ink refilling tubes 15 for refilling the ink reservoir 9 with ink from an ink cartridge (not shown in the figure), and ink refilling holes 20 disposed at corresponding positions to the ink refilling tubes 15 in the diaphragm 5 .
The external communication path 14 includes a control path 14 A to which flow resistance is applied to suppress ink evaporation, and release path 14 B opening the control path 14 A to the air. The control path 14 A is designed so that the path area is small and the path curves in an optimal pattern. The flow resistance of the control path 14 A itself is determined by appropriately determining the path area and the routing pattern. It should be noted that the exemplary control path 14 A shown in these figures is shaped like the numeral 7 .
As shown in FIG. 1 to FIG. 3 , the control paths 14 A are formed in the metal thin film 5 B, and are more specifically formed in the surface of diaphragm 5 facing the head case 2 using an etching process.
It should also be noted that the control paths 14 A could be formed on the head case 2 side rather than the diaphragm 5 .
The release path 14 B is formed in the head case 2 and is identical to the air hole provided by the external communication path 14 shown in FIG. 16 . That is, the release path 14 B forms a ventilation hole with a large internal diameter and passes through the head case 2 in the top to bottom direction as seen in FIG. 2 . The release path 14 B itself is not used to restrict the flow of ink vapor. Note that FIG. 4 is a plan view showing the layout with the nozzle plate 3 and flow channel substrate 4 removed for easier understanding.
As noted above the diaphragm (seal) 5 is a laminate of a resin thin film 5 A and a metal thin film 5 B. The resin is typically a PPS film and the metal is typically a stainless steel alloy, for example. The control path 14 A is formed in the metal thin film 5 B, and more specifically on the surface of the diaphragm (seal) 5 facing the head case 2 .
Various methods can be used to form the control path 14 A, but an etching process as noted above is ideal. The dimensional specifications of the control path 14 A can be optimally selected according to the specifications of the recording head, and the control path 14 A in this example is designed to a depth (that is, thickness of the thin film 5 A) of approximately 0.03 mm and a width of approximately 0.3 mm. The control path 14 A shall also not be limited to the above-described shape of the numeral 7 , and could be S-shaped, zigzag, or otherwise configured to match the vapor permeability of the diaphragm 5 . Note that in this case the sectional area of the control path 14 A is a determining factor of the path resistance.
A connection cavity 12 A is formed in the damper chamber 12 to connect and enable communication between the damper chamber 12 and control path 14 A. The connection cavity 12 A is formed as a partial extension of the space in the damper chamber 12 . More specifically, the connection cavity 12 A is formed in the head case 2 by removing a part of the inside wall of the damper chamber 12 . When seen in plan view as shown in FIG. 4 , the area of the damper chamber 12 is significantly greater than the width of the control path 14 A.
The release path 14 B is opened in the head case 2 . As will also be known from FIG. 4 , the sectional area of the release path 14 B is significantly greater than the width of the control path 14 A disposed in the diaphragm 5 . The one end 14 C of the control path 14 A overlaps and communicates with connection cavity 12 A. The other end 14 D of the control path 14 A similarly overlaps and communicates with the release path 14 B.
It should be noted that the connection cavity 12 A is disposed to the head case 2 in this embodiment because it is bonded with an adhesive applied to the head case 2 , but the connection cavity 12 A could alternatively be formed in the metal thin film 5 B of diaphragm 5 [ 3 , sic] using an etching process.
In this first embodiment of the invention water vapor from ink stored in the damper chamber 12 gradually flows through connection cavity 12 A into the control path 14 A. Because the flow resistance of the control path 14 A is high, that is, because the vapor permeability characteristic of the control path 14 A is set lower than the vapor permeability of the thin film 5 A of the diaphragm 5 , the flow of water vapor from the ink is restricted by the control path 14 A.
Because the outflow of water vapor to air is restricted by the control path 14 A as described above, evaporation of moisture from the ink in the ink reservoir 9 is restricted by the control path 14 A even when the recording head is stored for a long time, and an increase in ink viscosity in the ink reservoir 9 is thereby suppressed. When the recording head is then used again after being stored for some time, ink can be normally discharged after applying a normal cleaning operation, and discharge problems such as conventionally occur are substantially eliminated.
The control path 14 A can be formed to a precise shape and dimensions by etching the control path 14 A into the metal thin film 5 B, and this technique is therefore ideal for imparting the appropriate flow resistance to the control path 14 A. Furthermore, because the connection cavity 12 A is disposed to the damper chamber 12 , the size of the connection cavity 12 A relative to the control path 14 A enables the connection cavity 12 A to absorb alignment error when the control path 14 A and head case 2 are bonded, thus simplifying process management and precision control during manufacturing.
Embodiment 2
A second embodiment of the present invention is described with reference to FIG. 3 and FIG. 8 . In this embodiment the connection cavities 12 A of plural damper chambers 12 communicate with each other. As a result two control paths 14 A communicate with the mutually communicating connection cavities 12 A as will be clear from the double-dot dash line in FIG. 3 . The other ends of the two control paths 14 A are connected to one release path 14 B. It is also possible to use only one or to use three or more control paths 14 A.
Because connection cavities 12 A communicate with each other in this embodiment, ink vapor from two damper chambers 12 can be conducted with a simple construction. In addition, when a problem occurs with flow through one control path 14 A, deficient yet minimal flow control is sustained by the other control path 14 A. Ink viscosity can therefore be prevented from reaching a worst-case condition, and a pressure drop in the damper chambers can be suppressed.
Embodiment 3
A third embodiment of the invention is shown in FIG. 9 and FIG. 10 . In this embodiment the control paths 14 A are formed in the head case 2 . FIG. 9 shows the control path 14 A inset into the surface of the head case 2 facing the diaphragm (seal) 5 . FIG. 10 shows the control path 14 A disposed as a narrow ventilation hole in the head case 2 . Note that a connection cavity 12 A is not present in the configuration shown in FIG. 10 .
This embodiment is advantageous in terms of manufacturability because the control path 14 A can be formed at the same time the head case 2 is manufactured.
Embodiment 4
A fourth embodiment of the invention is described with reference to FIG. 11 . This embodiment has two variations, the first shown in FIG. 11(A) .
This first variation of the fourth embodiment prevents the adhesive used to bond the ink path unit 1 and head case 2 from flowing into the control path 14 A, and has cavities 17 for holding any excess adhesive. In this example there are three cavities 17 , each branching off from and communicating with control path 14 A. The control path 14 A also passes completely through and beyond the connection cavity 12 A to form an extension 17 A, and likewise passes through and beyond the release path 14 B to form another extension 17 B at the opposite end. These extensions 17 A and 17 B can also be used as storage cavities for excess adhesive.
These cavities 17 , 17 A, and 17 B can be simultaneously formed when forming the control path 14 A with an etching process.
Excess adhesive tends to collect easily in the dead-end parts of the cavities 17 , thus making it more difficult for excess adhesive to collect in the control path 14 A.
The cavities 17 can also be made narrower than the control path 14 A. This further lowers the possibility of the control path 14 A being clogged with adhesive.
Cavity 17 shown with a double-dot dash line in FIG. 11(A) is independent of the control path 14 A. It should be noted that the cavities 17 for holding excess adhesive shall not be limited to a narrow trench shape as described above, and could be a circular, square, or otherwise shaped cavity of a suitable area.
The second variation of this fourth embodiment is shown in FIG. 11(B) . In this variation the control path 14 A is a trapezoidally shaped endless path suitable for where mutually communicating connection cavities 12 A connect with the release path 14 B. A plurality of cavities 17 such as described above and shown in FIG. 11(A) are formed on the inside of this trapezoidal control path 14 A.
If too much adhesive is applied when bonding the ink path unit 1 and head case 2 together and there is excessive adhesive, the excess collects in the cavities 17 in this embodiment and adhesive is thereby prevented from flowing into the control path 14 A. Furthermore, even if some adhesive flows into the control path 14 A, interference with flow through the control path 14 A is minimized.
Various configurations can be used to connect the end of the control path 14 A with the release path 14 B. One example is a hooked end 17 C such as shown in FIG. 12 . This configuration assures dependable communication between the control path 14 A and release path 14 B even if the diaphragm 5 and release path 14 B are slightly misaligned, and thus simplifies precision control during manufacturing.
The control path 14 A is designed with a specific fine shape and sectional area determining the flow resistance, but it is alternatively possible to set the flow resistance of the control path 14 A by inserting an orifice 18 such as shown in FIG. 13 . In this case the control path 14 A is formed to a somewhat large sectional area and a separate orifice element 19 plate is then inserted from the outside.
Embodiment 5
FIG. 14 is a schematic diagram showing the major parts of a recording head according to a fifth embodiment of the invention.
The configuration of an inkjet recording head according to this embodiment is substantially the same as the inkjet recording head according to the first and second embodiments described above. Like parts are therefore identified by like reference numerals and further description thereof is omitted below where primarily the differences are described.
FIG. 14 is a schematic plan view of the head case 2 . The control path 24 A formed in the metal thin film 5 B of diaphragm 5 is a straight open channel enabling the connection cavity 12 A and release path 14 B to communicate in a straight line.
Unlike the control path 14 A of the first embodiment, this control path 24 A therefore does not have any curves. It is therefore difficult for excess adhesive to collect in the control path 14 A when the ink path unit 1 shown in FIG. 1 is bonded to the head case 2 .
A common connection cavity 12 A is also formed at the bottom part of the two middle damper chambers 12 as shown in FIG. 14 , and a straight release path 24 A enabling connection cavity 12 A and release path 14 B to communicate in a straight line is also provided.
Because the release path 24 A is thus straight, a space results in the part enclosed by the connection cavity 12 A, damper chamber 12 , and release path 14 B, unlike the configuration shown in FIG. 3 . This embodiment uses this space to provide one or more adhesive cavities 27 for holding excess adhesive. Two cavities 27 are formed in this embodiment.
When too much adhesive is applied when bonding the ink path unit 1 to the head case 2 , the excess adhesive is held in the adhesive cavities 27 in the present embodiment. This prevents the adhesive from flowing into the control path 24 A [ 14 A, sic] and minimizes any flow interference in case adhesive does enter the control path 24 A.
A diaphragm-side cavity 24 I is also disposed near the left-side control path 24 A, for example, in FIG. 14 . The part of this diaphragm-side cavity 24 I opposite the control path 24 A is substantially parallel to the control path 24 A.
More specifically, the right side surface 24 F of the control path 24 A in FIG. 14 is disposed substantially parallel to the left side surface 24 G at the bottom left end of the diaphragm-side cavity 24 I. The control path 24 A and diaphragm-side cavity 24 I are made from only the resin thin film 5 A with an etching process removing the metal thin film 5 B of the diaphragm 5 as shown in FIG. 2 .
The parts where the control path 24 A and diaphragm-side cavity 24 I are formed are therefore less rigid than the surrounding parts, and are easily wrinkled when external force is applied. Moreover, the part where the easily wrinkled control path 24 A and diaphragm-side cavity 24 I are juxtaposed wrinkles even more easily.
However, by arranging the opposing control path 24 A and right-side surface 24 F, and the left-side surface 24 G at the bottom left part of the diaphragm-side cavity 24 I in this easily wrinkled area so that they are parallel, external force is not concentrated at one part but is applied uniformly. Rigidity is thus improved and wrinkles do not occur easily.
The part where the left-side surface 24 G of the diaphragm-side cavity 24 I in FIG. 14 is formed is segmented into a substantially triangular shape by the substantially rectangular bonding pad 24 E.
More specifically, this bonding pad 24 E is left after etching metal thin film 5 B of diaphragm 5 while the ends of the bonding pad 24 E are etched away, thus forming two channels 24 H linking the substantially triangular part and the substantially trapezoidal diaphragm-side cavity 24 I.
When the diaphragm 5 is bonded to, for example, the flow channel substrate 4 having openings to the pressure generation chamber and ink reservoir, the diaphragm 5 is typically held with a tool. Because the bonding pad of the present embodiment contacts the tool or other device at this time, the diaphragm 5 can be firmly bonded with good precision to the flow channel substrate 4 .
Variation of Embodiment 5
FIG. 15 shows a variation of the fifth embodiment described above. This variation differs from the fifth embodiment shown in FIG. 14 only in the shape of the bonding pad 24 E and is otherwise the same. Like parts are therefore referenced with like reference numerals and further description thereof is therefore omitted below where primarily the differences are described.
As shown in FIG. 15 the bonding pads 34 E in the present embodiment differ from the bonding pad 24 E in FIG. 14 . More specifically, a plurality of slender individual bonding pads 34 E are provided with a channel 34 H between adjacent bonding pads 34 E and at the ends. Note that in the example shown in FIG. 15 there are four bonding pads 34 E and five channels 34 H.
The bonding pads 34 E are 0.1 mm or less wide. Making the bonding pads 34 E narrow reduces interference with ink reservoir 9 compliance after bonding with the flow channel substrate 4 .
It should be noted that while the present invention has been described with reference to a recording head using longitudinal oscillation mode piezoelectric transducers 6 , the invention shall not be so limited. For example, the invention can be applied to a recording head using a deflection mode piezoelectric transducer, or to a recording head using a heating element for heating ink inside the ink path as the pressure generation element.
An inkjet recording head and inkjet recording apparatus according to the present invention as described above thus provide a control path through which the damper chamber communicates externally rather than opening the damper chamber directly to the air. Evaporation of moisture from ink held in the ink reservoir is thus restricted by this control path and an increase in the viscosity of ink in the ink reservoir is suppressed even when the recording head is stored without being used for a long time. Therefore, when the recording head is next used after being stored for a long time, ink can be discharged normally after performing a normal cleaning operation, and discharge problems such as conventionally occur are substantially eliminated.
Moreover, because formation of the control paths is important, it is not necessary to provide any additional special parts, and the invention thus offers the further advantage of a simple configuration.
Although the present invention has been described in connection with the preferred embodiments thereof with reference to the accompanying drawings, it is to be noted that various changes and modifications will be apparent to those skilled in the art. Such changes and modifications are to be understood as included within the scope of the present invention as defined by the appended claims, unless they depart therefrom.
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A liquid jet apparatus is provided. The liquid jet apparatus includes a first damper chamber and a second damper chamber, a release path operatively associated with both the first damper chamber and the second damper chamber, and a control path connecting the first damper chamber, the second damper chamber, and the release path to each other.
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BACKGROUND OF THE INVENTION
The present invention relates to a shielded electrical connector for flat cable.
The need for shielding communications cable to prevent interference with signals carried by the cable is well recognized. Such cables are usually shielded by a braid or by foil around one or more insulated conductors; the shield is often followed by a drain wire which facilitates grounding the shield at termination points. Recently there has been an increased requirement for shielded electrical connectors to eliminate breaks in shielding continuity at cable termination and connection points. U.S. patent application Ser. No. 452,171, hereby incorporated by reference, discloses such a connector directed to terminating a braided round cable.
Flat multiconductor cable, including shielded flat multiconductor cable developed in recent years, has proven quite useful since the close control of conductor spacing facilitates mass termination. Flat cable is also useful for routing under carpets and other places where a low profile is required.
SUMMARY
The present invention is directed to a shielded connector for flat cable with two pairs of foil shielded signal conductors and a drain wire for each shield. The connector comprises a terminal housing which holds terminals for the signal wires in the cable and top and bottom shield members which fit against the terminal housing. The shield members are stamped and formed from metal and have serrated flanges which grip the foil shield where external insulation has been stripped away, and latches on either side of the flanges. The latches on the bottom member are coplanar with the flange and incorporate slots for terminating the drain wires, while the latches on the top member are perpendicular to the flange and cooperate with the bottom latches to firmly grip the cable between the flanges. The two shield members thus provide grounding for the drain wires as well as the foil shield, and further latch together to firmly grip the cable.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an exploded perspective of the connector.
FIG. 2 is a cross section of the cable.
FIGS. 3A, 3B, and 3C are perspectives showing the cable strippiing sequence.
FIGS. 4A, 4B, and 4C are perspectives showing the termination of the stripped cable in the shielded connector.
FIG. 5 is a cross section of the assembled connector.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Each connector is of identical hermaphroditic construction and comprises a terminal housing 10, a wire stuffer 18, a strain relief bushing 19, a bottom shield member 20, a top shield member 35, a bottom cover 50, and a top cover 60. The terminal housing 10 comprises a platform 10 with channels 12 profiled to receive terminals 2. Each terminal 2 has a wire receiving slot 6 in a barrel 4 and a contact tongue 8. Shorting bars 16 are received between sidewalls 14 which are bridged at one end by hood 17 and have frangible plugs 15 extending from the other end. Other details of the housing 10 and terminals 2 are as described in U.S. application Ser. No. 452,171. The cable 70 has been stripped as will be described in FIG. 2A et seq to expose signal conductors 71, foil shield 74, and drain wires 76. The external insulation 77 is received in strain relief bushing 19, which is folded onto the cable.
Referring still to FIG. 1, bottom shield member 20 is stamped and formed from a single piece of sheet metal such as brass and comprises a panel 22 with retaining holes 23 therein, a contact portion 24, and an opposed cable connecting portion 26. The cable connecting portion 26 comprises a flange 28 formed substantially perpendicular to the panel 22 and a pair of coplanar tabs 30 upstanding from edge 29 of the flange 28. Each tab 30 has a slot 31 extending toward panel 22 and a detent 32 formed on the edge thereof facing the other tab 30. Top shield member 35 likewise comprises a panel 37, a contact portion 39, and a cable connecting portion 41. The cable connecting portion 41 comprises a reverse bend 42 with a flange 43 having edge 44. Tabs 46 upstanding from panel 37 adjacent flange 43 each have an aperture 47. The tabs 46 are parallel to each other and substantially perpendicular to panel 37 and flange 43.
Bottom cover 50 has a base 51 with studs thereon which are received in holes 23 in bottom shield member 20, which is trapped between base 51 and foot 13 on housing 10. Base 51 is flanked by sidewalls 53 having recesses 54 profiled to receive blanks 54 and a rear wall 55 with a recess 56 profiled to receive bushing 19. A latch arm 57 has an integral T-bar 58 profiled for mating in T-slot 68 in latch arm 67 of top cover 60 of a like connector. The top cover 60 further comprises a base 61 flanked by sidewalls 63 having recesses 64 and a rear wall 65 with a recess 66.
FIG. 2 is a cross section of the flat cable 70 for which the preferred embodiment of shielded connector is most suited. Each pair of signal conductors 71 in polyolefin foam insulation 72 is contained in extruded PVC jacket 73 surrounded by a foil shield 74. The cigarette-wrapped shield 74 is 0.001 inch aluminum on the inside and 0.001 inch polyester on the outside, and lies against a drain wire 76 in a groove in the jacket 73. An external PVC jacket 77 extruded about the two pairs of shielded signal conductors 71 includes sloped side wings 79 for undercarpet application and V-grooves 78 to facilitate separation of the pairs from each other or the wings 79.
FIG. 3A illustrates the first step in preparing the cable 70 for termination, which is removal of the side wings 79 for a distance from the end to be terminated. Next the external insulation 77 is stripped to expose the shields 74 and the drain wires 76 are pulled through the respective foil shields 74, as shown in FIG. 3B. Next the individual signal wire insulation 72, internal jackets 73, and shields 74 are stripped as shown in FIG. 3C.
FIG. 4A et seq illustrate the assembly sequence. FIG. 3A shows the bottom shield member 50 as assembled to terminal housing 10, with the panel 22 sandwiched between the housing 10 and bottom cover 50 (FIG. 5). Cable 70 is shown with signal conductors 71 poised for termination to terminals 2 and drain wires 76 terminated in tabs 30 which flank the exposed shields 74. Wire stuffer 18, which has four plug members profiled to fit in barrels 4, is shown poised to force the conductors 71 into slots 6 in the barrels 4. The stuffer 18 is ribbed for alignment between sidewalls 14 of the housing 10.
FIG. 4B shows the stuffer 18 and the top shield member 35 in place. The contact portion 39 (FIG. 1) is fit under platform 11 which bridges sidewalls 14, and tabs 46 are fit between tabs 30. During assembly of the top shield member 35 to the terminal housing 10, the tabs 46 flex inwardly until the detents 32 on tabs 30 snap into apertures 47 in tabs 46, thus locking the shielding members 20, 35 together. The reverse bend 42 provides resilience which causes the edge 44 of flange 43 to bear against the cable shields 74. After the shield member 35 is in place, the bushing 19 is fitted to the cable 70 in recess 54 of rear wall 55. The only remaining step is placing the top cover 60 as shown in FIG. 4C. Latching is provided as described in U.S. application Ser. No. 452,171. If a right angle termination is desired, one of the blanks 15 is removed prior to assembling the housing 10 to bottom cover 50, and the cable 70 is folded on a line at 45 degrees across its axis to exit through the hole formed by a pair of recesses 54, 64. A bushing 19 is used similarly and a plug as in application Ser. No. 452,171 is used in the rear walls 55, 65.
FIG. 5 is a cross-sectional view of the assembled connector with shielded cable 70 terminated thereto. Terminals 2 are in place in terminal housing 10 and signal conductors 71 are terminated in barrels 4 of the terminals 2, while drain wires 76 are terminated in tabs 30 of bottom shield member 20. The cable shield 74 is gripped between edge 24 of flange 28 of bottom shield member 20 and edge 44 on flange 43 of top shield member 35. The edge 44 bears resiliently against the shield 74 under the spring action of reverse bend 42, thereby providing positive grounding as well as strain relief, and further provides positive placement of the cable 70 while bushing 19 is placed in covers 50, 60 to grip the external insulation 77 to provide secondary strain relief. The bottom shield is positively located by studs 52 on base 5, and retained by sandwiching between the foot 13 of housing 10 and the base 51 of bottom cover 50. The top shield member 35 is positioned by mating the tabs 46 with tabs 30, and is also held down by locating rib 62 on base 61 of cover 60 bearing against panel 37 of shield member 35. Latch arms 57, 67 are depressed toward the rear of the connector to achieve mating of the T-bar 58 and T-slot 68 with the T-slot 68 and T-bar 58 respectively of a like hermaphroditic connector. The mating of contacts 8 with like contacts causes disengagement of shorting bars 16 therewith, as described in detail in U.S. application Ser. No. 452,171.
The foregoing description is exemplary and not intended to limit the scope of the claims which follow.
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Shielded electrical connector for flat cable with shielded signal conductors and drain wires has terminal housing with terminals for signal conductors sandwiched between connector shield members. Bottom shield member has upstanding flange flanked by coplanar tabs; flange contacts exposed cable shield and tabs have slots for terminating drain wires. Top shield member has upstanding flange which contacts exposed shield opposite flange on bottom member and upstanding tabs flanking the flange in parallel planes perpendicular to the plane of said tabs on said bottom member. Tabs on top member flex inward against tabs on bottom member until inward facing detents on bottom tabs latch into apertures in top tabs.
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PRIOR APPLICATIONS
This is a continuation-in-part of Ser. No. 066,497 filed June 26, 1987.
SUBJECT MATTER OF INVENTION
The present invention relates to means for recording and displaying three-dimensional images by a system which utilizes one energy source and one energy detector.
BACKGROUND OF INVENTION
Prior art 3-dimensional displays rely on systems which capture two different images from two locations and presenting each image to each eye by means of well known devices such as stereoviewers or stereoscopes.
Most recently, the recording of two stereoscopically related images from a single point in space, but requiring two separated scanning beams to illuminate the scene, was described in application Ser. No. 537,514 filed Sept. 30, 1983.
Additionally, two dimensional video images of an object or a scene have been effected without using a camera. In such a system, the object is illuminated by scanning light, such as a laser beam, which moves over the scene in a raster similar to the movement of an electron beam in a CRT. The light from the laser beam reflected by the scene is picked up by a photomultiplier which controls the beam intensity of a cathode ray tube of a video monitor. Thus, as the laser beam scans the object the photomultiplier senses variations in the reflected light and generates an analog output which is coupled to the gun of the cathode ray tube of the video monitor. The movement of the electron beam emanating from the gun of the cathode ray tube is synchronized with the movement of the laser beam. Such systems are useful for generating two dimensional images on a monitor and have been used in the inspection of nuclear reactors and in scanning laser ophthalmoscopes. However, to date such systems have not been useful or adaptable for three dimensional displays.
In addition to such systems numerous efforts have been made to create a wide range of three dimensional imaging systems. Some of these systems have been described in a number of issued U.S. patents, including U.S. Pat. Nos. 1,372,646; 1,595,295; 2,235,743; 2,360,322; 2,568,327; 2,751,826; 3,039,358, 3,731,606; 3,810,213; 3,990,087; 4,009,951; 4,189,210; 4,290,675; and 3,431,299.
OBJECTS AND SUMMARY OF INVENTION
It is an object of the present invention to provide a novel system for generating three dimensional images as standard stereo pairs which may utilize an energy source selected from a wide frequency spectrum. Thus, the present invention is designed to generate three dimensional images utilizing visible light waves or other wave lengths such as infrared or ultraviolet, with a suitable detector. Additionally, the present invention is designed for use with other types of radiation sources different from electromagnetic waves such as x-rays or ultrasound.
A further object of the present invention is to provide a means for generating standard stereo pairs of images of an object, making use of an energy sensitive means, which generates a pair of signals which may be appropriately channelled for stereoscopic viewing.
A further object of the present invention is to provide an improved means for generating three dimensional images without the use of a pair of cameras and by means which may be adaptable for use in a variety of systems and for a variety of purposes.
A still further object of this invention is to provide an improved means and method that may be adopted for generating three dimensional images in video broadcasting or recording, video monitoring, and surveillance and reconnaissance systems.
The present invention provides an improved means for generating standard stereo pairs of images which may be detected and transmitted either in analog or digital form.
In the present invention 3-dimensional information of a scene is obtained by means of a single energy source such as a light source, and by means that differentiate the relative distance of objects in the scene as a function of the different time required by the energy to reach the object, reflect and reach the detector means.
In this invention an energy source used in conjunction with an energy sensor and suitably modified video equipment, renders 3-dimensional stereoscopic images when viewed with known stereo-viewing devices. One embodiment of the present invention consists of a scanning energy source such as a laser beam that scans a scene in the same way and in synchrony, as the raster beam in a CRT (Cathod Ray Tube), except that horizontal lines are scanned from right to left, left to right, right to left and so on instead of always in the same direction (right to left). The electron beam in the CRT is also made to scan the screen in synchrony in the same right-left-right . . . fashion. In this scanning sequence, the energy reflected from a far object is delayed, and therefore presented on the CRT screen more to the right of a nearer object when scanning from left to right and more to the left when scanning in the opposite direction. The horizontal displacement of the object on the CRT screen is equal to the velocity of the raster on the CRT screen multiplied by the extra time required by the energy to travel the extra distance and back. This time is equal to the relative depth of the object divided by the velocity of the illuminating energy beam.
In a second embodiment, the whole scene is illuminated uniformly with an energy by means such as a flood light, but the intensity of the energy is changed periodically, by suitable means such as a gas tube powered with alternating current. The phase of the reflected energy is a function of the distance of the reflecting object. Detecting the phase of such energy can be accomplished with a conventional phase detector applied to the reflected energy once converted to electrical energy or video signal by means of a conventional video camera.
If the output of the phase detector is used to shift the electron beam of a CRT, objects that are further in space will be shifted more than near ones. This is the same result as when viewing the scene with either eye (stereoscopic disparity). Therefore, if two images, shifted by different amounts (opposite phase), are presented separately to each eye, a sensation of stereoscopic depth arises.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are schematic top view of an embodiment of the present invention using a beam of energy scanning a scene in both directions alternately with images displayed on a screen for each direction of raster movement.
FIG. 2 depicts a schematic arrangement of the present invention using a scanning-beam to achieve a three-dimensional display in a radar station;
FIG. 3 illustrates the arrangement of components in an alternative form of the present invention using a conventional regular TV camera; and
FIG. 4 illustrates a preferred method for detection of phase (depth) for the arrangement illustrated in FIG. 3.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 illustrates the operation of one embodiment of the present invention. A beam of energy from energy source 3 scans a scene or objects 5 and 7 two dimensionally. The beam scans horizontally from left position 1 to right position 2, then from position 2 to position 1 on a lower scanning line or position and then from 2 to 1 again one scanning line lower and so on until the desired vertical field is scanned. The scanning sequence is illustrated by arrows A and B, with arrow B representing a scan line lower than arrow A. The scanning beam energy emanating from source 3 will hit the objects to be imaged and the energy will be reflected and will travel back to source 3 where a suitable energy detector 3A for such energy is located. The time required for the beam when in position 4 to travel to an object 5 and back will be longer than the time required by the beam when in position 6 to hit a point of object 7 and reflect back to the detector 3A since object 5 is more distant from object 7. The detector output signal from detector 3A modulates the intensity of a CRT electron beam moving in the same way and in synchrony with the beam of energy from source 3. As schematically illustrated, the output from detector 3A is fed through a modulator 10 to modulate the energy signal in the display means 11 which in this example is a cathode ray tube. The intensity of the reciprocating electron beam scan in the cathode ray tube 11 is thus varied by the modulator synchronously with the beam scanning from energy source 3. That beam is scanned in synchronous movement with the output energy from energy source 3 by suitable means such as synchronizer 12. Stereo pairs are detectable to an observer by segregating one by a variety of known techniques. For example, a pair of spectacles having alternating shutters for the lenses 12 and 13 may be provided. The shutters schematically illustrated at 14 are controlled for alternate covering of lenses 12 and 13 in synchronism with the output from detector 3A by synchronizer 12.
The CRT screen 11 thus presents to the observer two separate pictures, one to each eye of the observer, with the images illustrated in FIG. 1A as noted, different pictures depend from source 3 on the direction of movement of the raster: 8 when scanning from left to right and 9 when scanning from right to left. Far objects will be shifted with respect to nearer objects in the direction of the scanning beam, either to the right as depicted in 8 or to the left as shown in 9, the shift being the consequence of the delay of arrival of the energy reflected further away. Screens 8 and 9 comprise a stereoscopic pair and will give rise to depth perception when each screen is presented to each eye (8 to right and 9 to left eye). The angle of disparity can be easily derived from this figure and found to be: Disparity=4dw/v where d is the relative distance between objects 5 and 7, w is the angular velocity of the raster and v the velocity of travel of the energy used.
FIG. 2 illustrates an embodiment of the invention in which energy source 21 is a continuous-wave microwave scanning source, similar to those used in radar installations. A scanning beam 22 covers field 23 by scanning in a right-left-right fashion as described above in connection with FIG. 1. The beam of energy 22b reflected from an object 24 is detected by a microwave antenna 25. The signals detected by the antenna 25 is suitably amplified to control the electron beam intensity of CRT 26 while the deflection of such beam is controlled by deflection circuits 27 which are operated in synchrony with the deflection control 21 of the radar beam. The image on the screen of the CRT presents stereo pairs to an observer when the right and left scan are segregated and presented to each eye by conventional methods. These methods may include, as noted above, alternating shutter spectacles.
FIG. 3 depicts an alternative embodiment of the present invention for TV or video applications that does not require a scanning source. Instead, a flood light 31 is used whose intensity is modulated by a high frequency sinusoid generator 32. A detector means comprises a standard video camera 33 that generates a standard video signal 34 that is modulated by the sinewave generator 32. The phase of such modulating video component is proportional to the distance of the objects 35 and 36 as shown 34, and, therefore, a measure of such phase difference, obtained with phase detector 37, is a measure of their relative depth. The output voltage of phase detector 37 is added to or subtracted from the conventional sawtooth deflection voltage generated in generator 38 to produce a relative shift of objects 35 and 36 on the face of the CRT 39. When sawtooth and phase signals are added, objects 35 and 36 are imaged closer together and when subtracted they are shifted apart. When these images are presented to each eye by conventional means, stereoscopic depth sensation arises. Means such as previously described may be used to present separate images to each eye.
FIG. 4 describes a preferred embodiment of the present invention for television, teleoperation, or machine vision by which every pixel in the image has a corresponding digital range (depth) value as a result of phase detection with improved means.
Light source 41 is modulated with a periodical waveform by modulator 42 at frequency f. The image sensor in video camera 43 is shuttered on and off at the same frequency f, in synchrony and in phase with the light source for a video frame period. In this way, during half of the frame time, no light is collected and a digital image is formed and stored (44) from light received during the "on" time only. During the next frame, the on-off cycles are reversed so that they are in synchrony with the light source, but in opposed phase. A second and different digital image is temporarily stored in buffer 45.
Energy collected for an arbitrary pixel of buffer 44 is schematically depicted as 44A, while energy collected for the same pixel in buffer 45 is illustrated as 45A. The digital value for that pixel will be the total area of 44A (for buffer 44) or 45A (for buffer image 45) integrated during a frame time (1/60's for American TV).
The addition (pixel by pixel) of buffers 44 and 45 results in buffer 46 which contains a conventional image of the scene. The subtraction of buffers 44 and 45 results in buffer 47 containing phase information. It can be seen that the result of substracting total light energy for the same pixel in alternate frames (black areas of waveforms 44A and 45A) is clearly dependent on the time when switching occurs, and therefore the phase. Range (distance) is obtained at buffer 48 as phase measurement by dividing relative phase from buffer 47 by amplitude from buffer 46. Depending on the phase (distance) of the imaged pixel, the range measurement will vary between the values -1 and +1 for each pixel.
This invention is not limited to the energy sources or to the applications described above, but it can be used with other types of energy such as electromagnetic radiation, including light and infrared, sound, ultrasound, x-rays, etc., and in any propagation media, such as, but not limited to, air, water, space, soil, biological tissue, etc. This invention can therefore be used for multiple imaging applications, such as, but not limited to, broadcast and close circuit TV, land and air radar, sonar, depth sounders, ultrasonic medical imaging, and automated vision machines.
This invention, as opposed to conventional stereoscopic recording, offers the advantage of stereo effect independent of how far the objects are located, since the disparity angle is constant as shown above.
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A three dimensional display system in which a beam of energy is admitted from a single source with the beam reciprocally scanning an object. The reflected energy from the beam is detected and the reflected energy is separated and segregated by the direction of the scan. The two separately detected signals are then displayed separately to each eye of the viewer to create a stereoscopic image.
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TECHNICAL FIELD
[0001] The invention relates to a method and to an apparatus for watermarking successive sections of an audio signal, wherein the watermarking is controlled by a psycho-acoustical model.
BACKGROUND
[0002] Audio watermarking is the process of embedding information items (called watermark) into an audio signal in an inaudible manner.
[0003] An original audio signal c o can be considered as representing a channel for conveying watermark information m using a key k. In turn, watermarking can be modelled as a form of communication. There exist different ways of how to incorporate the original signal c o into the communication model. In a basic model the original signal c o is considered as a noise signal. The information about the host signal is not exploited in the modulation step. In advanced models the original audio signal is examined in the watermark encoder before adding a corresponding watermark signal w. This kind of processing is usually referred to as “watermarking with informed embedding” or simply “informed embedding”. In such case the watermark signal w is shaped according to a perceptual model and is then applied to the host signal in the modulation step.
SUMMARY OF INVENTION
[0004] Known informed embedding systems can implement different modulation modules f(m,k,c o ) for generating a watermarked original audio signal c w from the original audio signal c o , which however can result in robustness problems. This is the case in audio signals containing only minimal energy in low frequencies (like special sound effects in a movie), or in artificial signals containing time sections with digital zeroes. If the modulation f(m,k,c o ) consists of a multiplicative embedding rule, incorporating the host signal (see equation below), there is essentially nothing embedded.
[0000] c w =f ( m,k,c o )
[0000] c w =(1+ w ( m, k, c o ))× c o
[0005] The modulation of the original signal can be done in the media space (i.e. audio samples) or can be performed in a transformed domain (e.g. in the Fourier domain). Thus c o and c w can represent audio samples in time domain or Fourier magnitudes/phases in the transformed domain. The latter is performed in watermarking based on Spread Spectrum processing which are most widely used in audio watermarking.
[0006] Another important class of audio watermarking methods are time-spread echo hiding methods, for which the modulation function can be written as c w =c o *h(m,k,c o ) with the convolution operator ‘*’ and the echo kernel h(m,k,c o ), having the same difficulty if c o has sections containing digital zeroes. I.e., the two most important audio watermarking type classes have problems if the audio signal has very low signal energy or contains digital zero values.
[0007] In a one embodiment of the described processing, in case the original audio signal has parts of low signal energy, an alternative signal having a level or strength given by the psycho-acoustic model is combined with the original audio signal. The combined signal is watermarked with watermark data to be embedded.
[0008] This kind of processing represents a combination of a multiplicative embedding rule and an additive embedding rule.
[0009] The described processing improves the robustness of audio watermarking systems in particular for signal sections which have very low signal energy in the full time frequency range or in parts of the time frequency range, resulting in significantly improved audio watermark detection at decoder or receiver side. Advantageously, any suitable watermark detection at decoder or receiver side can be used without modification.
[0010] In principle, the described processing is suited for watermarking successive sections of an audio signal, comprising the steps:
calculating using a psycho-acoustical model a masking curve for a current section of said audio signal, and determining for said current section of said audio signal whether it contains low signal energy or parts of low signal energy; providing an alternative signal different from said audio signal, which is controlled by said low signal energy determination and the strength of which is controlled by said masking curve; combining said alternative signal with said audio signal in case said current section of said audio signal has low signal energy or parts of low signal energy, so as to provide a combined signal; watermarking said combined signal, controlled by watermark data to be embedded and by said masking curve, so as to provide a watermarked audio signal.
[0015] In principle the described apparatus is suited for watermarking successive sections of an audio signal, said apparatus comprising means being adapted for:
calculating using a psycho-acoustical model a masking curve for a current section of said audio signal, and determining for said current section of said audio signal whether it contains low signal energy or parts of low signal energy; providing an alternative signal different from said audio signal, which is controlled by said low signal energy determination and the strength of which is controlled by said masking curve; combining said alternative signal with said audio signal in case said current section of said audio signal has low signal energy or parts of low signal energy, so as to provide a combined signal; watermarking said combined signal, controlled by watermark data to be embedded and by said masking curve, so as to provide a watermarked audio signal.
BRIEF DESCRIPTION OF DRAWINGS
[0020] Exemplary embodiments of the processing are described with reference to the accompanying drawings, which show in:
[0021] FIG. 1 block diagram of a first embodiment for watermarking processing using the described processing;
[0022] FIG. 2 block diagram of a second embodiment for watermarking processing using the described processing.
DESCRIPTION OF EMBODIMENTS
[0023] Even if not explicitly described, the following embodiments may be employed in any combination or sub-combination.
[0024] The described processing improves the detection in audio watermarking systems that are using the audio signal itself as watermark carrier and the audio signal itself is transformed, but the watermark is not an external watermarked signal added to the audio signal where that external signal is watermarked independently from the current content of the audio signal.
[0025] The affected systems are for example multiplicative embedding systems as described e.g. in I. K. Yeo and H. J. Kim, “Modified patchwork algorithm: A novel audio watermarking scheme”, Proceedings of the IEEE International Conference on Information Technology: Coding and Computing, 2001, pp.237-242, 2-4 Apr. 2001.
[0026] Other systems which add a scaled and time delayed version of the original content as a watermark are echo hiding systems as described e.g. in B. S. Ko, R. Nishimura, Y. Suzuki, “Time-spread echo method for digital audio watermarking”, IEEE Transactions on Multimedia, vol.7, no.2, pp.212-221, April 2005, and in R. Petrovic, “Audio Signal Watermarking based on Replica Modulation”, 5th International Conference on Telecommunications in Modern Satellite, Cable and Broadcasting Service, pp.227-234, 19-21 September 2001.
[0027] It is common practice in audio signal processing to apply a short-time Fourier transform (STFT) for obtaining a time-frequency representation of the signal, so as to mimic the behavior of the ear. This results in a collection of DFT-transformed (discrete Fourier transform) and windowed overlapped audio signal section blocks (overlap-add-processing as such is well-known). For watermarking purposes each audio block is analyzed to calculate the (psycho-acoustically) allowed size of modification, and finally the audio block signal values are modified according to this analysis by embedding the watermark information.
[0028] However, this known kind of processing has its limits if the signal in a block has only very low signal energy in parts of the time-frequency range or in the full time-frequency range. A signal containing for example only digital zero amplitude values will not be watermarked at all if a multiplicative embedding rule is employed. An audio signal section containing only low frequencies, which often occurs as an effect in movies, can use only the low frequencies for the watermark-related modifications, which means that the watermark is less robust as compared to when the full frequency range can be used for the modifications.
[0029] According to the described processing, additive and multiplicative embedding rules are combined in a single watermarking system, by generating an alternative signal within the time-frequency range for signal sections in which the original audio signal does have low signal energy. This alternative signal is dependent on the data to be embedded and ensures high watermark detection strength. It is scaled or shaped using a psycho-acoustical model, such that inaudibility is ensured. Such alternative signals are different from the original audio signal and can be for examples white noise signals or pink noise signals. The alternative signal is combined with the watermarked audio signal and thereby produces the final watermarked audio signal. The combination rule can be for example adding or substituting, depending on the underlying watermarking principle.
[0030] Because of the combination with the alternative signal, watermarks can be embedded even in problematic audio signal sections, and the final encoder or transmitter audio output signal is more robust: the decoder or receiver side device can more reliably detect the watermark, without any noise from the alternative signal becoming audible. The watermark detection at decoder or receiver side requires no modification: for example, a known processing using correlation with candidate bit pattern sequences, detecting magnitude value peaks in the correlation result and selecting the watermark bit or word corresponding to that bit pattern sequence which leads to the highest peak value. While with the state of the art technology the detector would receive a ‘watermarked’ audio signal with digital zeros, it could not detect the current watermark symbol. With the described processing used, however, the detector receives a non-zero alternative signal which produces a good watermark symbol detection result.
[0031] In FIG. 1 successive sections of an original audio signal are fed to a low signal energy detector step or stage 11 , a psycho-acoustical model calculator step or stage 12 and a signal composer step or stage 14 . Psycho-acoustical model calculator 12 calculates a masking curve for every original audio signal section—even in silence two effects of the human auditory system can be exploited: the hearing threshold in quiet (the human ear is not able to hear signals having an energy below a frequency dependent energy threshold) and temporal masking (if the signal power drops suddenly to zero, the human ear is not able to hear a signal with an energy below a certain level which is dependent on the distance to the drop).
[0032] Signal composer 14 provides its output signal to a watermark embedding step or stage 15 which outputs a watermarked audio signal.
[0033] Low signal energy detector 11 determines low energy sections or partial low energy sections within time-frequency information, e.g. signal sections containing zero values, and provides an alternative signal provider step or stage 13 with such information. In case a low signal energy part is detected, alternative signal provider 13 generates an alternative signal for composing it in composer 14 with the original audio signal. The ‘alternative signal’ is a signal which produces the best detection results at detector or receiver side while at the same time being inaudible. An example alternative signal is white or pink noise generated according to the hearing threshold in quiet. To that alternative signal the above-described modulation with a multiplicative rule is applied according to the watermark data or symbol to be embedded. Watermark embedder 15 gets on one hand watermark data to be embedded and on the other hand a current masking curve from psycho-acoustical model calculator 12 .
[0034] The current masking curve is also provided to alternative signal provider 13 for controlling for which signal values of the original audio signal it outputs with which amplitude alternative signal values to be combined in step/stage 14 with original values of the original audio signal.
[0035] The watermark data to be embedded in watermark embedder 15 can be a bit sequence selected from a set of pseudo-random bit sequences modulated according to a watermark information bit value. The bit sequence can be used in step/stage 15 for correspondingly modulating the phase of the combined signal to be watermarked, e.g. in a manner described in WO 2007/031423 A1.
[0036] In FIG. 2 successive sections of an original audio signal are fed to a low signal energy detector step or stage 21 , a psycho-acoustical model calculator step or stage 22 and a watermark embedding step or stage 25 . Psycho-acoustical model calculator 22 calculates a masking curve for every original audio signal section. Watermark embedder 25 gets on one hand watermark data to be embedded and on the other hand a current masking curve from psycho-acoustical model calculator 22 .
[0037] Watermark embedder 25 provides its output signal to a signal composer step or stage 24 which outputs a watermarked audio signal.
[0038] Low signal energy detector 21 determines low energy sections or partial low energy sections within time-frequency information, e.g. signal sections containing zero values, and provides an alternative signal provider step or stage 23 with such information. In case a low signal energy part is detected, alternative signal provider 23 generates an alternative signal (e.g. white or pink noise) that is watermarked in a further watermark embedding step or stage 26 according to the watermark data to be embedded.
[0039] The further watermark embedder 26 provides its output signal to signal composer 24 which combines the watermarked alternative signal with the watermarked original audio signal. The current masking curve is also provided to alternative signal provider 23 for controlling for which signal values of the original audio signal it outputs with which amplitude alternative signal values to be watermarked in step/stage 26 and to be combined in step/stage 24 with original values of the original audio signal.
[0040] Watermark embedders 25 and 26 carry out the same kind of operation. The watermark data to be embedded in watermark embedders 25 and 26 can be a bit sequence selected from a set of pseudo-random bit sequences modulated according to a watermark information bit value. The bit sequence can be used in steps/stages 25 and 26 for correspondingly modulating the phase of the signals to be watermarked, e.g. in a manner described in WO 2007/031423 A1.
[0041] The described processing can be carried out by a single processor or electronic circuit, or by several processors or electronic circuits operating in parallel and/or operating on different parts of the described processing.
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Audio watermarking is the process of embedding watermark information items into an audio signal in an in-audible manner. In a first embodiment, in case the original audio signal has parts of low signal energy, an alternative signal having a level or strength given by the psycho-acoustic model is combined with the original audio signal. The combined signal is watermarked with watermark data to be embedded. In a second embodiment, in case the original audio signal has parts of low signal energy, an alternative signal having a level or strength given by the psycho-acoustic model is watermarked with watermark data to be embedded, and the audio signal is watermarked with the watermark data to be embedded. The watermarked alternative signal is combined with the watermarked audio signal.
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BACKGROUND OF THE INVENTION
The present invention relates to a method of producing a molded resin article. More particularly, the present invention relates to a method of producing a molded resin article composed of a mixture of thermoplastic and thermosetting materials.
In addition, the present invention relates to a method of fabricating a molded article from a composite material created by melting a thermosetting resin component and a thermoplastic resin component, kneading the components and immediately injecting the resultant composite material into a mold where the kneaded melt is given a desired shape.
Resins can be molded by various methods depending upon such factors as the physical properties of feed materials and those of the finished article. Thermoplastic resins are in most cases shaped by injection molding, in which a molten resin is injected at high pressure into a cavity between closed mold parts and given a desired shape. The injection molding process has a high production rate and great latitude in the selection of the shapes of molded articles.
The injection molding technique, however, has the following disadvantages: (1) a large clamping force must be used during molding and thus a bulky molding machine is required; (2) it is practically impossible to fabricate thin-Walled and large parts; and (3) the molten resin must have high temperature and pressure when it is injected into the mold cavity, such that simultaneous lamination of skin members such as fabrics and PVC leather cannot be achieved without high risk of damage to the texture of the skin members. The third problem is particularly pronounced in the case where napped fabrics are to be simultaneously laminated and flattening of naps is unavoidable. Electronic parts are often required to be sealed with resins. However, if injection molding is adopted to encapsulate the parts, displacement of parts, breaking of lead wires and other problems can occur owing to the high injection pressure employed. Furthermore, when molding resins are used as sealants of electronic parts, the resins are generally required to be fire-retardant. However, many of the fire-retardant resins available today have a tendency to decompose or deteriorate at elevated temperatures required for injection. Therefore, simultaneous lamination of skin members and resin molding of electronic parts are very difficult to accomplish by customary injection molding techniques. A fourth problem with the injection molding process is that since the resin material will pass through the whole length of the cylinder of a kneader at high speed under high pressure, long glass fibers cannot be incorporated without breaking into short lengths. In addition, use of a relatively high amount of glass fibers or inorganic fillers is difficult.
In order to cope with these problems, one needs to employ resin materials having a high melt index and inject them while in molten state into the mold cavity at low temperature and pressure, with the viscosity of the melt being reduced at the time of injection. In the case of thermoplastic resins, materials of high melt index are polymers of low molecular weights but articles molded from such low-molecular weight polymers are not satisfactory in many aspects including impact strength, fatigue strength, creep resistance, chemical and solvent resistance, and resistance to environmental stress cracking. In other words, in order to ensure that a resin feed solely composed of thermoplastic materials is injection molded at low temperature and pressure, the strength of the shaped article has to be sacrificed but such a sacrifice is not desired from a practical viewpoint.
Compared to thermoplastics, thermosets are low in viscosity when they are in a molten state but as a thermosetting reaction proceeds, they will cure and thus increase in viscosity. Therefore, to perform injection molding with an in-line machine, one of the following methods must be used: i) curing the resin by heating it after it has been injected into the mold cavity rather than in the injection cylinder; or ii) using a so-called "premix" prepared by compounding the ingredients after they have passed through a certain degree of reaction. However, the first method in which the resin is cured by heating in the mold cavity suffers from the disadvantage of extended molding cycles. The second method which involves the use of a premix is subject to significant limitations on such factors as the compounding formulation and the choice of starting materials.
A method that is commonly adopted in molding thermosetting resin materials having the problems described above includes first preparing a sheet molding compound (SMC) or bulk molding compound (BMC) which has a thermoset of interest, say, an unsaturated polyester impregnated in a glass mat or glass fibers, and then molding SMC or BMC by compression or with matched dies. However, this method is not suitable for high-volume production since the metering and supply of materials is not easily adaptable for automation or continuous processes.
Thermoplastic resins, typically polyurethanes, are often molded by reaction-injection molding (RIM) processes in which two liquid streams are pumped under high pressure into an impingement chamber where they are mixed intimately and then are immediately forced into a mold cavity where a rapid polymerization reaction occurs. However, the major disadvantage of the RIM process is a small freedom in the choice of compounding formulas because the materials that can be used are limited to those which are low in viscosity and high in reactivity. Furthermore, the viscosity of the resin is so low at the time of injection as to cause various troubles such as an increased chance of burring and formation of voids on account of bubble trapping, extensive bleeding in the bulk of fabrics to be laminated simultaneously, and difficulty in relatively highly loading reinforcements or fillers on account of the great tendency toward solid-liquid separation.
A possible alternative to injection molding of thermoplastics is stamping, in which a molten material is deposited onto an open matched mold and stamped by closing the mold. During stamping, the material flows, filling the mold cavity. Compared to injection molding, this method tolerates the use of low pressures and is suitable for fabricating large and thin-walled parts. However, so long as thermoplastics are used, there are limits on the effort toward temperature and viscosity reduction and the stamping method is still insufficient to completely eliminate the defects of the injection molding process.
As described above, all conventional methods for molding thermoplastic or thermosetting resins have their own problems and generally speaking, thermoplastics are adapted for high production processes. Another advantage of thermoplastics is that they can be molded into articles having a higher degree of toughness. In contrast, articles molded from thermosetting resins are almost brittle and prone to chipping but they are excellent in such properties as stiffness, heat resistance, stress cracking resistance and creep resistance. It is therefore expected that a molded article that is superior in production rate and physical properties will be obtained from thermoplastic and thermosetting resin materials that are blended in an appropriate composite form.
However, none of the molding methods currently in commercial use are capable of producing composites of desired thermoplastic and thermosetting resin materials in desired proportions. One of the practices that has been adapted extensively is to incorporate thermoplastic components as modifiers in SMC or BMC of unsaturated polyesters but the thermoplastic components that can be added have been limited to those which are soluble in the principal components of thermosets such as alkyds and styrene monomers. Besides this restricts compounding formulation, i.e. the contents of thermoplastic components that can be incorporated have been limited.
An attempt has also been made to fabricate thermoplastic resins by injection molding on an in-line machine after thermosetting components have been added. But in this case, too, the contents of thermosetting components that can be added are limited to low levels because if they are excessive, they undergo a curing reaction and the resulting mix becomes too viscous to be efficiently injected into the mold cavity.
As will be understood from the foregoing discussion, when thermoplastic and thermosetting resin materials are to be mixed and molded by previously known methods, either one type of resin serves as the principal component with the other being used merely as an additive, and it has been impossible for the two types of resins to be mixed in more or less comparable amounts, e.g. from 25:75 to 75:25, and directly subjected to a molding step.
In order to realize fabrication of large and thin-walled parts, simultaneous lamination of skin members, resin molding of electronic parts, high loading of glass fibers, or incorporation of long fibers, the molten material must be injected into a mold cavity not only at an optimum viscosity (e.g. lower than the viscosity encountered in ordinary injection molding of thermoplastics but higher than the viscosity encountered in RIM but also at low temperature and pressure. However, it has been impossible with conventional molding processes to accomplish the necessary adjustment or control of resin viscosity and temperature.
It is further noted that in order to attain a balance of high-level physical properties in a composite material, one of the ideal structures is a micro dispersion in which islands of a toughness imparting component are dispersed in a sea of a stiff and heat-resistant matrix. This ideal structure would be obtained by using a thermosetting resin as a component for stiffness and heat resistance of the matrix, and employing a thermoplastic resin as a component for toughness of the islands. It is desirable to use a rubber-like material as the thermoplastic resin component.
Conventional composite materials that are prepared by kneading two types of resin components, thermosets and thermoplastics, are characterized in that the thermoplastic resin component or rubber component is dispersed in a minor proportion in the thermosetting resin component. The rubber component is dissolved in the thermosetting resin component and when the solution changes from a fluid to a solid state upon reaction, the dissolved rubber component undergoes phase separation to form an emulsion in which the islands of the rubber component are microscopically dispersed in the sea of the thermosetting resin component. However, with conventional composite materials, the solubility of the rubber component is limited and it cannot be dissolved in an increased amount in the thermosetting resin component. Furthermore, the viscosity of the thermosetting resin component cannot be controlled with sufficient ease to enable efficient molding with customary machines including injection molding and extrusion machines. Even if a composite material in which the thermoplastic resin component and the thermosetting resin component are mixed in more or less comparable proportions is successfully molded, the islands of the thermoplastic resin component are not sufficiently dispersed microscopically in the sea of the thermosetting resin component to produce a molded article that attains a balance between stiffness, heat resistance and toughness at high levels. The following three principal reasons are offered to explain this problem: first, because of the nature of rubbery materials which form islands and are responsible for the toughness of the composite, considerable difficulty is involved in comminuting (pulverizing) the rubbery material into fine particles. Even if this is possible, the particles are so sticky as to experience frequent blocking, which makes it difficult to attain a particle size that is ideal for the formation of a desired dispersion; second, the island phase should generally be composed of particles on the submicron order but such fine particles tend to scatter as dust particles and this is detrimental not only to handling but also to the consistency of the supply of the rubber component through a feeder, etc.; and third, the rubber-like particles dispersed in the sea of the matrix resin will re-fuse during melt mixing under thermal effects, making it impossible to obtain an ideal dispersion.
SUMMARY OF THE INVENTION
The objects of the present invention are to solve the above-mentioned problems.
The principal object of a first aspect of the present invention is to enable the fabrication of a molded article from a resin composite in which thermoplastic and thermosetting resins are incorporated in more or less comparable proportions.
Another object of the present invention is to provide a molding method that is adapted for large-scale production of molded articles from a composite of thermoplastic and thermosetting resins.
Still another object of the present invention is to provide a method of producing a molded resin article which allows for optimal adjustment of the viscosity of a molten resin mix to be injected into a mold cavity, thereby limiting the temperature and pressure of the resin to lower levels.
A further object of the present invention is to provide a method of producing a molded composite resin article that allows for kneading with a screw-type extruder, thereby enabling the compounding of desired materials.
To attain these objects, in the inventive method, a plurality of materials including a thermoplastic component and a thermosetting component are successively fed into a kneader, with a time lag being provided between the first supplied material having a higher melting point, viscosity and stability relative to the next supplied material which has a lower viscosity and a higher reactivity, and kneaded in said kneader, and injecting the resulting blend to fill a mold cavity and give a desired shape.
The principal object of a second aspect of the invention is to provide a method of fabricating a molded article from a composite material that contains a thermosetting resin component and a thermoplastic resin component mixed in more or less comparable proportions (e.g. 25:75 to 75:25) and which yet features an island-in-sea structure in which the thermoplastic resin component is microscopically dispersed in the matrix of the thermosetting resin component to ensure a balance among high levels of stiffness, heat resistance and toughness.
The above-stated object of this second aspect of the invention can generally be attained by using a composite material that comprises more or less comparable proportions of a thermosetting resin component responsible for stiffness and heat resistance and a thermoplastic resin component responsible for toughness and in which the islands of said thermoplastic resin component having a particle size of 0.01-10 μm are microscopically dispersed in the sea of the thermosetting resin matrix to provide an island-in-sea structure. More specifically, the particles of the thermoplastic resin component are subjected to secondary agglomeration to produce larger particles of 10-1000 μm that can be dissociated by shearing, and such particles are kneaded under shear force with the portion of the thermosetting resin component which has a relatively low reactivity and a relatively high viscosity, thereby allowing the particles to be dispersed microscopically in that portion; thereafter, those portions of the thermosetting resin component which have a relatively high reactivity and a relatively low viscosity are successively added, with a time lag provided between the first supplied portion having the lower reactivity and the higher viscosity and the next supplied portion having the higher reactivity and the lower viscosity; after all the components have been kneaded, the mixture is immediately injected into a mold cavity where it is given a desired shape and allowed to solidify simultaneously with completion of the curing of the thermosetting resin component.
BRIEF DESCRIPTION OF THE FIGURE
The above and other objects, features and advantages of the inventive method will become more evident upon reading the detailed description set forth below in conjunction with the accompanying drawing.
FIG. 1 is a schematic side view of a molding apparatus for use in the practice of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
According to a first aspect of the invention, feed materials are inputted to a kneader, then kneaded into a mixture, and the mixture is injected into a mold for molding. The feed materials are inputted to the kneader generally in the order of decreasing viscosity and melting point yet increasing reactivity.
In general, in the molding process, the viscosity of the molten mixture when it is injected into a mold cavity is desirably controlled to be in a low range of 200-5000 poises. Such viscosity adjustments can be performed by properly selecting the conditions of supplying feed materials into the kneader, such as the timing of their supply, the temperature at which they are supplied and the proportions of the respective materials.
The kneader may be of a screw-type extruder. When a screw-type extruder is to be used, a plurality of feed supply inlets are provided in the axial direction and a material having a higher melting point, viscosity and stability is fed at a supply inlet which is remote from the discharge port of the extruder whereas a material having a lower melting point and viscosity and a higher reactivity is fed at a supply inlet nearer to the discharge port. However, the above mentioned melting point may be not always defined in the present invention because there exists materials with specific melting point characteristics.
When a screw-type extruder is used, it is also desirable to provide a viscosity gradient such that the melt viscosity of the plasticized mix in the cylinder decreases toward the discharge end of the extruder. Such a viscosity gradient can be readily produced by properly selecting the conditions under which feed materials are supplied. Such conditions include their proportions, the temperature and the degree of preliminary plasticization.
As described above, in the inventive method, a thermoplastic resin or material having a high melting point, viscosity and stability relative to the other feed materials is supplied into a kneader at the initial stage of the kneading step to allow for sufficient plasticization. By contrast a thermosetting resin or material having a low melting point and viscosity and a high reactivity relative to the other feed materials is supplied into the kneader at a later stage of the kneading step, so that its kneading time is sufficiently short to avoid curing that would otherwise occur owing to excessive reaction in the kneader. The thermosetting material in such a low-viscosity state is kneaded with the plasticized thermoplastic material and the resulting mix is injected to fill a mold cavity. Therefore, the viscosity of the mix when it is injected into the mold is sufficiently reduced to enable filling of the mold cavity at low temperature and pressure so as to facilitate the molding of the mix.
The method according to the present invention also enables thermoplastic and thermosetting materials to be incorporated in relatively high proportions. Furthermore, the molten feed materials are kneaded under high shear in the kneader, so that any compounding formulation can be used substantially independent of the miscibility and dispersibility of the feed materials used.
Hereinafter, the thermoplastic resin or material with the high melting point, viscosity and stability will be referred to as the high melting point, viscosity and stability material. This high melting point, viscosity and stability material has a melting point, viscosity and stability which are high relative to the other feed materials used in the molding process. In addition, the thermosetting resin or material with the low melting point and viscosity and high reactivity will be referred to as the low melting point and viscosity and high reactivity material. This material has a low melting point and viscosity and a high reactivity relative to the other feed materials. In the inventive method, preferably the material with the highest melting point, viscosity and stability is fed into the kneader first, and the material with the lowest melting point and viscosity and the highest reactivity is fed last, with any other feed materials being fed according to their relative melting points, viscosities and stabilities/reactivities.
If the melt viscosity of the kneaded mix is in the low range of 200-5000 poises when it is injected into the mold cavity, the feed materials will fill every part of the cavity even if the mold is shaped for fabricating a thin-walled product. At the same time, problems that would otherwise occur on account of undesirably low viscosities (e.g. lower than 200 poises) are minimized.
If the kneader is a screw-type extruder and if the material having a high melting point, viscosity and stability is supplied at a feed inlet that is remote from the discharge port of the extruder whereas the material having a low melting point and viscosity and a high reactivity is supplied at a feed inlet that is near to the discharge port, the material with the high melting point and viscosity and high stability will be fully plasticized as it is transferred toward the discharge port of the kneader whereas the material having a low melting point and viscosity and a high reactivity is kneaded together with the fully plastiziced material, and the mixture is immediately transferred into the mold cavity, with the mixture being held in a desired low-viscosity state (e.g. 200 to 5000 poises). In this way, a molded composite resin article is efficiently produced.
If a feed containing a substantial amount of thermosetting component is supplied into a conventional screw-type extruder, the viscosity of the feed will increase with time. This creates low viscosity at the feed supply end and high viscosity at the discharge end, with slippage in the extruder barrel occurring at the supply end of the extruder to make further transfer of the plasticized mixture impossible. To avoid this problem, an extruder that has a plurality of feed inlets along its axial direction is used and the viscosity of the feed is controlled to decrease toward the discharge end of the extruder by properly selecting various conditions. These conditions include the shape and type of the materials to be supplied at the various feed inlets, the temperature of the feed materials and/or inlets and the degree of preliminary plasticization of the feed materials. Thus, the inventive method includes the advantage that the materials can be transferred smoothly through the cylinder of the extruder.
Preferred embodiments of the present invention are described hereinafter with reference to FIG. 1 which is a schematic side view of a resin molding apparatus that may be employed in the inventive method. As is clear from FIG. 1, the molding apparatus has a screw-type extruder 1, a mold 2, and a clamp mechanism 3 for closing or opening the mold. The screw in the extruder 1 is rotatably driven by a motor 4, causing the feed in the cylinder to be plasticized and kneaded as it is transferred to the right in the drawing. The extruder 1 is equipped at discharge port 5 with a unit 6 that discharges a metered amount of the kneaded feed. The metering/discharging unit 6 is connected to the feed injection port of the mold 2 via a heat-insulated transfer pipe 7.
The operating conditions of the extruder 1, such as the rotational speed of the screw and the cylinder temperature, are controlled at an extruder control panel 8. The unit 6 and the clamp mechanism 3 are controlled at a control panel 9.
The extruder 1 has a plurality of feed supply inlets disposed at given spacings in its axial direction. In the embodiment of FIG. 1, five feed inlets 11-15 are provided. The first inlet 11 (the furthest from the discharge port 5) is chiefly adapted for the charging (feeding) of a pelletized thermoplastic material that is fed from a hopper or some other suitable device. The second inlet 12 is adapted for the supply of a granular or powdered thermoplastic component or a similar form, comparatively stable thermosetting component. The third inlet 13 is for a thermosetting component of a comparatively low reactivity that is in a granular, powdered or liquid form. Where the molded article is desired to include fibrous reinforcement (e.g. glass fiber), the fourth inlet 14, which is closer to the discharge port 5, is used for continuous supply of the reinforcement from a side feeder or other suitable means so that the reinforcement can be kneaded with the mixed materials of lower viscosity. The fifth inlet 15 (the nearest to the discharge port 5) is for the supply of such materials as unstable reactive fluids and peroxide catalysts.
Materials are supplied through the respective inlets 11-15 by various means such as a metering feeder and a metering/discharging pump. These feeding devices are controlled at a feeder control panel 10.
To fabricate the molded article from a resin composite made of a thermoplastic and a thermosetting resin, the feed inlets 11-15 on the cylinder of the extruder 1 are adjusted for predetermined temperatures. The first inlet 11 is set at a high temperature while the fifth inlet 15 is set at a low temperature, and the respective materials are supplied through the most appropriate inlets in view of their characteristics, as explained in more detail below.
Pellets of a thermoplastic resin which is a stable material having a high melting point and viscosity are supplied through the first inlet 11. Since the first inlet 11 is the most remote from the discharge port 5, the material supplied through this inlet will be in the extruder 1 for a long time before reaching the discharge port 5. Therefore, the material supplied will be subjected to a shear action by the screw sufficient to plasticize it to a desired extent, and the viscosity of the material will decrease toward the discharge end as plasticization proceeds.
A granular or powdered thermoplastic component or a similarly shaped thermosetting component of low reactivity is supplied through the second inlet 12. These materials, as they are heated within the extruder 1, will be rapidly plasticized and melted and thus become low in viscosity.
A liquid thermosetting material which has a comparatively high reactivity is supplied through the third inlet 13.
A liquid thermosetting material that is labile and has a very high reactivity, as well as a catalyst and so forth are supplied through the fifth inlet 15. Therefore, these materials will be pushed out of the extruder 1 within a short period of time.
As described above, stable materials that are high in melting point and viscosity are supplied through the first and second inlets 11 and 12 which are remote from the discharge port 5. If desired, these materials are supplied into the extruder 1 after they have been subjected to a preliminary plasticizing step to ensure that they will be plasticized and melted to a satisfactory degree in the extruder 1. By contrast, materials having a higher reactivity are supplied through inlets 13 and 15 which are closer to the discharge port 5. As a result, these materials will stay for only a short time within the extruder 1 thus avoiding excessive curing action from occurring in the extruder 1. Therefore, thermosetting resins can be incorporated in relatively high proportions without potential curing within the extruder 1.
Since materials of low viscosity are successively added to and kneaded with plasticized thermoplastic materials, the viscosity of the resulting mix will decrease toward the discharge end of the extruder. This is true even though the viscosity of the thermosetting components has a tendency to increase as a result of heating which occurs during kneading in the extruder 1, because any curing of these thermosetting components is sufficiently repressed to prevent elevation of the overall viscosity of the kneaded mixture.
For the reasons stated above, the viscosity gradient of the feed material in the extruder 1 is such that it is high in the area beneath the first inlet 11 and loW in the area adjacent the discharge port 5. This ensures that the materials fed into the extruder will be pushed by the action of the screw from the side of the first inlet 11 and constantly transferred toward the discharge port 5. The viscosity gradient of the feed material being transferred can be adjusted by properly selecting various conditions of its supply, including the type of materials, their shape, the proportions of the components, the positions of the feed inlets, as well as the temperature and viscosity of the materials fed through the inlets 11-15. These conditions of the supplied materials are also adjustable to control the viscosity of the feed material at the discharge port 5. The viscosity of the feed material at the port 5 may be determined in accordance with such parameters as the shape of the final article to be fabricated, its physical properties and the structure of the mold 2, but it is usually adjusted to lie within a low viscosity range of 200 to 5000 poises.
In accordance with the inventive method, the feed material in a molten state is kneaded under the high shear action exerted by the screw and is immediately injected into the mold to be given a desired shape. Therefore, a feed of any formulation can be provided with a desired mixed and dispersed state irrespective of the miscibility and dispersibility of the individual components of the feed. In other words, the inventive method allows greater latitude in the selection of feed materials.
Using the method described above, a plasticized mixture of low viscosity that has been prepared by kneading thermoplastic and thermosetting materials will emerge from the discharge port 5 of the extruder 1. The temperature of this plasticized mixture is held at a comparatively low level by controlling the temperature of the cylinder in the extruder 1. The plasticized mixture is metered in the unit 6 and discharged therefrom for injection into the mold 2 through the transfer pipe 7. Since the pipe 7 is heat-insulated, the materials in the plasticized mixture will not cure while passing through the pipe 7. If necessary, the pipe 7 may be heated or cooled for temperature control.
The plasticized mixture may be injected into the mold 2 in a closed state, as in ordinary injection molding machines. Alternatively, as in a stamping molding machine, the plasticized mixture may be injected into an open mold, which is thereafter closed and clamped. As already mentioned, the plasticized mixture which is injected into the mold 2 is in a low-viscosity state, so it will fill every part of the mold cavity even if it is injected at low pressure. As a further advantage, the mixture is injected into the mold at low temperature so that a skin member can be laminated simultaneously without thermal deterioration.
The plasticized mixture in the mold 2 is then shaped and cured in that state to produce a molded article of a desired shape.
If it is necessary to incorporate a fibrous reinforcement such as glass fibers in the article they are supplied through the fourth inlet 14 which is relatively close to the discharge port 5. By so doing, the time for which the reinforcement is subjected to the shearing action of the screw is sufficiently shortened to minimize any fiber breakage and to allow long fibers to retain their length while they are kneaded with the feed material and to emerge from the port 5. In addition, the feed material with which the reinforcement is to be kneaded has been fully plasticized to a low viscosity, so it can be incorporated in the feed material in a high proportion.
The embodiment described above assumes the use of the screw-type extruder 1 but it should be understood that a common kneader such as a batch-typed kneader can also be used in the inventive method. In this case, a material having a high melting point, viscosity and stability is first fed into the kneader and then plasticized. A material having a low melting point and viscosity and a high reactivity is supplied to the kneader with the previously supplied and plasticized material.
The method of the present invention is described hereinafter in greater detail with reference to specific examples of fabricating molded articles by the method.
EXAMPLE 1
A screw-type extruder having four feed inlets was connected to a vertical type stamping press for simultaneous lamination of a napped fabric. The screw-type extruder was supplied with the following materials: pellets of SBS (styrene-butadiene-styrene copolymer, a thermoplastic material) were supplied through the first feed inlet which was located further from the discharge end; granules of a thermosetting unsaturated polyester were supplied through the second inlet; a liquid bifunctional oligomer was supplied through the third inlet; and a peroxide catalyst was supplied through the fourth inlet which was the nearest to the discharge port. The first to fourth inlets were adjusted to respective temperatures of 110°, 100°, 90° and 80° C. The mold was adjusted to a temperature of 120°-150° C. on the core side and 60°-80° C. on the fabric side. The clamping pressure was set within a range of 20-50 kg/cm 2 . The feed material had a viscosity of 1000 poises at the time of injection into the mold.
The resulting molded article was homogeneous and defectless in the resin portion. There was an absence of flattened naps in any part of it, so the molded article was quite suitable for practical applications.
EXAMPLE 2
Caseless molding of a polypropylene film capacitor was performed using the same apparatus and materials as those employed in Example 1, except that the mold temperature was 120° C. In addition, the clamping pressure and the viscosity of the feed material upon injection into the mold was adjusted to values slightly lower than those employed in Example 1.
The resulting molded article was acceptable in that it was free from broken lead wires and shrinkage of the polypropylene film.
As will be understood from the foregoing explanation, the method of the present invention offers the following advantages. First, a thermoplastic material having a relatively high melting point, viscosity and stability is supplied into a kneading machine at the initial stage of the kneading step and kneaded for a sufficiently long period of time to ensure plasticization to a satisfactory degree. Second, a thermosetting material having a relatively low melting point and viscosity and a higher reactivity is supplied into the kneader at a later stage of the kneading step, so that this material can be kneaded without excessive curing in the kneader. Third, the supplied materials can be kneaded in a molten state without causing phase separation in the kneader. Therefore, even if thermoplastic and thermosetting resin materials are used in more or less comparable proportions, they can be kneaded and injected in a low-viscosity state to fill the mold. In this way, it is possible to fabricate a molded article from a composite resin that has both thermoplastic and thermosetting resin components incorporated in high proportions. Fourth, by properly selecting the supply conditions such as the type of materials, their shape, the proportions of the respective components and the timing of their supply, a plasticized mixture of the feed can be injected into a mold cavity at low temperature, pressure and viscosity. Therefore, the inventive method allows fabrication of thin-walled large parts, simultaneous lamination of skin members or even resin molding of electronic parts using a simple molding apparatus which requires a low clamping pressure.
According to a second aspect of the invention, a molded article is formed from more or less comparable proportions of a thermosetting resin and a thermoplastic resin to achieve a material with stiffness and heat resistance comparable to that of a thermosetting article and with toughness comparable to that of a thermoplastic resin.
It is effective for the purposes of the second aspect of the present invention to use a rubber-like component as the thermoplastic resin component. It is particularly effective to use a fine particulate rubber that is prepared by emulsion polymerization and has an anti-blocking property (achieved by appropriate processing well-known in the art). Alternatively, the rubber-like component may be formed of particles having either a core/shell structure or a salami-sausage structure. The term "salami-sausage structure" means a multi-core particle.
In order to attain a highly tough composite material of an island-in-sea structure, it is necessary that the microscopically dispersed island phase comprise particles of a size in the range of 0.01-10 μm, desirably 0.05-0.5 μm. Based on this observation, the particles of a thermoplastic resin component are subjected to secondary agglomeration to form larger particles of a size in the range of 10-1000 μm that can be dissociated by shearing but which will otherwise remain stable during molding cycles so that these particles will exhibit improved fluidity within the hopper on the molding machine and/or will not scatter. These large particles of the thermoplastic, resin component are kneaded under shear force with a portion of a thermosetting resin component which has a relatively low reactivity and a relatively high viscosity, thereby allowing these particles to be microscopically dispersed in the portion of the thermosetting resin. Thereafter, those portions of the thermosetting resin component which have a relatively high reactivity and a relatively low viscosity are successively added, with a time lag being provided between the first supplied portion having the lower reactivity and the higher viscosity and the next supplied portion having the higher reactivity and the lower viscosity, and all the components are kneaded to a satisfactory degree. The mixture is immediately injected into a mold cavity where it is given a desired shape and allowed to solidify simultaneously with completion of the curing of the thermosetting resin component. In this way, particles in the island phase of the thermoplastic resin component will have a size in the range of 0.01-10 μm.
If a twin-screw extruder is used as a means for applying shear force, kneading can be performed in such a way that the thermoplastic resin component forming an island phase is added after that portion of the sea-phase forming thermosetting resin component which has a relatively low reactivity and a relatively high viscosity is first melted by heating. Alternatively, the two components may be simultaneously supplied to the kneader. Thereafter, the high-reactivity portion of the thermosetting resin component, a catalyst and a curing agent are successively added at given time intervals and kneaded. In this way, a temperature that is adequately lower than the melting point of the thermoplastic resin component (serving as a toughness imparting component) can be maintained throughout the molding process and the particles of the thermoplastic resin component will be prevented from re-fusing under thermal effects thus ensuring a desired structure in which the islands of the thermoplastic resin component are microscopically dispersed in the sea of the thermosetting matrix.
The size of secondary particles that have been formed by agglomeration of primary particles is adjusted to lie within the range of 10-1000 μm. If their size is greater than 1000 μm, some secondary particles will remain in the matrix without being completely dissociated by the shear force exerted during kneading. If their size is smaller than 10 μm, the miscibility with the matrix is not very high. In addition, if materials are selected that differ greatly in viscosity, some of the agglomerated particles will remain incompletely dissociated. The exact reason for this insufficiency in the degree of dissociation is not clear. However, it is postulated that under the conditions described above, the necessary dissociating force will not work very effectively on the agglomerated particles.
If a fine particulate rubber, which has been processed to acquire an anti-blocking property, is prepared by emulsion polymerization and is used as a rubber-like component (i.e., as the thermoplastic component), its secondary particles can be dissociated and dispersed as ideally sized particles by kneading.
If desired, a rubber-like component having a core shell structure or a salami-sausage structure may be used as the thermoplastic resin component. In this case, by properly selecting the structure of the shell or skin layer, an improvement in wetting and adhesion at the interface between the thermoplastic and thermosetting resin components can be readily attained.
It is also possible to use a rubber-like material of a polymeric structure, e.g. chlorinated polyethylene, that has both microscopic crystalline and amorphous portions. In this case, the crystalline portion serves as a nuclear whereas the amorphous portion exhibits not only affinity for the sea phase but also toughness by itself, thereby imparting toughness to the resulting composite resin material.
The following example is provided only to further illustrate the present invention, and is not to be construed to limit the present invention or the scope of the appended claims.
EXAMPLE 3
Molded specimens were fabricated from composite materials by the method specified herein. In all specimens, an unsaturated alkyd resin (Polymal 6011 EH of Takeda Chemical Industires, Ltd.) was used as a thermosetting resin component which forms a matrix sea phase. As a toughness imparting thermoplastic resin component, one of the following four materials was used: powdered, partially crosslinked NBR (acrylonitrile-butadiene rubber) prepared by emulsion polymerization; powdered MBS (methacrylate-butadiene-styrene copolymer having a microscopic core shell structure); SBS (styrene-butadiene-styrene block copolymer); and powdered chlorinated polyethylene. The molding process was as follows: a selected rubber-like material and the unsaturated alkyd resin were supplied simultaneously into a twin-screw extruder through the first hopper throat; after a certain time, a nonvolatile bifunctional monomer serving as a crosslinking agent for the unsaturated alkyd resin was supplied through the second inlet, and finally a peroxide catalyst was supplied through the third inlet. After intimately kneading the supplied materials, the composition extruded from the nozzle at the end of the extruder was immediately injected into a mold where it was given a desired shape.
The specimens thus fabricated were subjected to various tests to evaluate the performance of the toughness imparting materials used. The results are shown in Table 1.
TABLE__________________________________________________________________________ Physical properties of molded articleToughness Size of Content of Flexural Flexural modulus Impact strengthimparting secondary toughness imparting strength of elasticity on DuPont testerRun No.component particle (μ) component (%) (kg/cm.sup.2) (kg/cm) g × cm__________________________________________________________________________1 NBR 400-700 30 700 11000 500 352 NBR 400-700 35 620 9500 1000 403 NBR 400-700 40 510 6000 1000 504 MBS 250-400 40 700 14000 300 155 SBS (Pellet) 40 340 7000 300 56 chlorinated 500-900 40 500 8000 1000 20polyethylene__________________________________________________________________________ NBR: JMN2 of Japan Synthetic Rubber Co., Ltd. MBS: Kaneace B56 of Kanegafuchi Chemical Industry Co., Ltd. SBS: TR2000 of The Nippon Synthetic Chemical Industry Co., Ltd. Chlorinated polyethylene: Elaslen 403A of Showa Denko K.K.
As is clear from Table 1 the powdered partly crosslinked NBR exhibited the greatest toughness imparting effect of all the compounds used and imparted a higher impact strength based on formulations that produced the same level of elastic modulus.
When MBS was compared with SBS, the former was superior in all aspects of flexural strength, flexural modulus of elasticity and impact strength (on DuPont tester) based on formulations that contained MBS and SBS in equal proportions. This shows that a toughness-imparting component having a core/shell structure was more effective than a mere block copolymer.
Chlorinated polyethylene had a high toughness imparting effect but at the same time, the specimen containing it experienced a substantial decrease in elastic modulus. It is therefore assumed that chlorinated polyethylene works as if it were a plasticizer.
Having the features described on the foregoing pages, the method of the present invention offers the following advantages: 1) The particles of a thermoplastic resin component are subjected to secondary agglomeration to form larger particles having a size in the range of 10-1000 μm, so they will not scatter about the molding machine during its operation and they have a sufficient flowability to be supplied consistently through the hopper on the molding machine; 2) The particles of the thermoplastic resin component which form the island phase have a size of 0.01-10 μm and are dispersed microscopically in the sea phase of a thermosetting matrix, so that subsequent to the kneading of the two resin components, a molded article can be directly fabricated from a composite material that attains a balance between high levels of stiffness heat resistance and toughness; and 3) If a rubber-like material composed of particles with a core/shell structure is used as the thermoplastic resin component, a molded article can be fabricated that is much better in toughness than a product that employs a mere block copolymer.
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A method of forming a composite material involves feeding materials to a kneader, kneading the materials, and injecting them from the kneader into a mold. The kneader is formed by a screw-type extruder having an ejection outlet at one end for extrusion into the mold. Various input ports are located axially along the extruder. Materials are fed into the kneader beginning at the inlet port most remote from the outlet end and proceeding successively to the inlet port nearest the outlet end. The materials are fed in successive order from those with the highest viscosity and lowest reactivity relative to the materials with the highest reactivity and lowest viscosity. For example, thermoplastic is fed to the inlet most remote from the outlet, and thermosetting resin is fed to the inlet nearest the outlet. In another aspect of the invention, in which thermoplastic and thermosetting resins are employed in roughly comparable amounts, an "island-in-sea" structure is desired. This structure is achieved by agglomerating thermoplastic material having a particle diameter of 0.05-0.5 μm into particles of 10-1000 μm diameter prior to kneading, then introducing the thermoplastic material into the kneader. The thermoset material is then added from least reactive and most viscous to most reactive and least viscous.
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This application claims the benefit of Ser. No. 60/200,804, filed May 1, 2000.
BACKGROUND OF THE INVENTION
During conventional fabrication of textile feedstock, especially of cotton pressed in bales, numerous health, technical and economic problems often arise.
These problems include the development of health threatening molds, especially aflatoxines in the leaves (bracts); insufficient moisture for subsequent treatment steps; and wild behavior of the delivered material in the processing machine or gin before subsequent treatment depending on the quality of the cotton gin, its previous storage condition, press condition and moisture content.
Attempts to pretreat the feedstock to address the problems have been unsuccessful for technical and/or economic reasons.
It is therefore a purpose of the present invention to provide a process to solve health and technical problems which have affected prior art textile feedstock fabrication processes.
It is a further purpose of the invention to provide a process which allows an improvement in the quality of the spun yarn, with a raised yield.
Yet a further purpose of the present invention is to provide a feedstock preparation method which is reproducible, efficient, and which produces a feedstock which is greatly restricted in its biological activity, especially insuring that only a minimal further development of mold fungi can occur, even in the case of a new contamination occurring by means of airborne spores.
BRIEF DESCRIPTION OF THE INVENTION
The foregoing and other objects of the invention are achieved by a heat treatment of the feedstock in a pressed state, i.e. in the bale. By a specific, gradual heat treatment of the bale at least partial sterilization and a conditioning of the feedstock is effected simultaneously.
The heat treatment of the present invention comprises placing the feedstock in a treatment chamber and subjecting the feedstock to a plurality of treatment cycles comprising the evacuation of the chamber to a reduced pressure, and the application of steam to the feedstock for a treatment period to allow the steam to penetrate into the interior of the bale. At least 4, and preferably 5 treatment cycles are conducted.
The heat treatment can be accomplished by a type of fractional conditioning (alternating evacuation and steaming with holding times) which may be carried out by conventional treating systems as marketed by Xorella AG, CH-5430 Wettingen, Switzerland under the trademark SYSTEM CONTEXOR.
It has been surprisingly found that the present invention makes it possible to successfully treat a heavily pressed cotton bale in an economically reasonable time with an economically justifiable expenditure of energy. The treatment installation is preferably operated according to WO 98/21390 and U.S. Pat. No. 6,094,840.
It has been found that a 5 cycle steaming procedure yields an ultimate temperature of about 80° C. in the inner part of the bale. Higher bale temperatures may be desired or utilized when required for sterilization or destruction of biologically active material.
BRIEF DESCRIPTION OF THE DRAWINGS
A fuller understanding of the invention will be achieved upon consideration of the following description of the invention when considered in connection with the annexed drawings, in which:
FIGS. 1 a-c are diagrams depicting the structure and placement of temperature probes in a cotton bale for test purposes.
DETAILED DESCRIPTION OF THE INVENTION
It is known in the art that the conditioning of textile feedstocks, and particularly by conditioning by steam treatments, improve the process ability and quality of the resulting fabric. Conditioned knitting yarns exhibit reduced unwinding tension and are of a softer quality than untreated yarn, reducing needle wear. Further, consistency of the finished products is improved with a substantial decrease in lint and fiber fly. Weaving processes utilizing yarns which have been subject to such conditioning have fewer breaks, improved strength and elongation qualities, and yield softer fabrics. Similarly, treated fabrics experience increased sewing efficiency with fewer needles breaks and improved needle wear. While conventional conditioning treatments are applied to the yarns and threads, the present invention provides an improved methodology for such general heat treatment, and is of particular benefit in connection with cotton, which in accordance with the invention may be treated in the bale, rather than in the form of yarn or finished fabric, thus increasing treatment efficiency. By applying a repeated procedure of evacuation and steam application treatment through the entirety of the bale can be effected in an economical manner.
In general, the present procedure comprises placing the cotton bale to be treated in a closed container, and evacuating the container to a reduced pressure in the range of about 50 to 200 mbar. Steam is then introduced, and the steam is allowed to permeate the bale for a treatment period typically between 5 and 15 minutes, during which steaming step the internal temperature of the bale increases to roughly between 600 and 80° C. The container is again evacuated, the remaining steam being simultaneously withdrawn and condensed exterior to the container, and the procedure is repeated. Preferably, the fabric is subjected to a minimum of 4 steaming cycles. The the end of the treatment the cotton bale is removed. After an appropriate cool-down period, during which time a small amount of residual moisture evaporates, the bale can be wrapped for shipment.
Each steam treatment step may be of a chosen duration, on the order of 5 minutes, which typically allows the interior of the bale to reach between 60° and 80° C., the bale temperature increasing with each steaming cycle. A final interior temperature of 80° C. is preferred to insure extermination or elimination of bacteria and/or mold. Temperature monitoring of the bale may be conducted using temperature sensor probes, with the treatment step time being dictated by the interior bale temperature desired. Similarly, the vacuum employed may be at levels of between about 50 and 200 mbar, with the greatest vacuum typically being applied in the initial treatment step. Vacuums of 50, 200, 2000 and 200 mbar for a five cycle process may be acceptable, the vacuum serving primarily to facilitate the entry of the steam deep into the bale and thus improving heat transfer between the steam and bale. Overall process time, including treatment steps and the time necessary to re-evacuate the chamber between treatment steps, is in the order of less than 2 hours.
The procedure may be carried out in a vacuum steamer chamber of the type known in the art having an internally located water bath which is heated to generate the steam. Alternatively, the steam can be generated exterior to the chamber and introduced to the evacuated chamber through appropriate valved piping. Vacuum pumps and condensers as known in the art establish the vacuum and exhaust the remaining water vapor/steam at the end of a steaming cycle. When an external steam source is used, as opposed to a heated water bath, it may be advantageous to have a drain to allow condensate to be withdrawn before or during vacuum establishment.
The following sets forth a series of tests carried out in accordance with the invention and are exemplary of the parameters which may be employed in connection therewith.
A bale having the dimensions 1380×530×900 mm, a volume V=660 cm 3 , weight G approx. 250 kg and a density y=0.38 kg/dm 3 was subjected to a treatment in accordance with the present invention. Temperature probes were inserted at different locations within the bale as depicted in FIGS. 1 a - 1 c . A Xorella CONTEXXOR treatment unit with a volume of 10.2 m 3 was utilized for the treatment process.
The bale was subjected to a steaming/evacuation program with four vacuum cycles, as follows:
Steaming Program
1st vacuum: 050mbar=95%
1st cycle: T1=600° C.—5 min.
Start 1st cycle with empty evaporator, or with cold water bath.
2nd vacuum: 100mbar=90%
2 nd cycle: T2=70° C.—5 min.
3rd vacuum: 100 mbar=90%
3 rd cycle: T3=80° C.—10 min.
4th vacuum: 200 mbar =80%
4 th cycle: T4=80° C.—15 min.
Total time: approx. 100 minutes
Weight Increase of Bale with 4 Measuring Probes and Pallet
Before conditioning: 258.60 kg=100% weight
05 minutes after conditioning: 268.90 kg=+3.98% weight increase.
90 minutes after conditioning: 267.40 kg=+3.40% weight increase.
Weight of measuring probes 1.25 kg.
Weight of pallet: 14.35 kg.
After a cooling time of 90 minutes, the measuring probes were removed and the bale was wrapped in foil with a pallet binder. In practice it takes about 1-1½ hours before the bales can be packed. A weight increase of 3.0% to a maximum of about 3.2% can therefore be expected.
Notes on Test Procedure
The test was erroneously carried out in 2 phases, because on startup and after the first cycle the CPU failed due to software intervention with the programming unit. After the first cycle (96%, 60° C.—5 min.) and after reaching the first intermediate vacuum, the program stopped when the heating was switched on, and the evaporator was vented. The process was then restarted. The process was restarted after correcting the above-mentioned fault. And the program ran according to the preselected process steps. In general, phase 1 had no effect on the test parameters. This test can be evaluated as a normal steam program with 4 cycles with a prior warm-up program
Vacuum
The startup vacuum of 50 mbar=95% of the vacuum was generated with a gas jet at the vacuum pump intake. The gas jet was not switched on until vacuum had reached 90%.
The intermediate vacuum up to 100 mbar was generated with a tube bank condenser at the vacuum pump intake.
Measuring point MP1 reached the setpoint temperature T1=60° C. after the first cycle, and followed the pre-selected temperatures in the subsequent cycles. Steam penetration to a depth of 100 mm occurred by the end of the first cycle.
Temperatures at depths of 150 and 200 mm respectively for MP 2 and MP 3 started to rise significantly during the warm-up phase of the second vacuum cycle to the setpoint temperature T2=70° C., although the setpoint temperatures was not yet reached. The MP2 setpoint temperature T=80° C. at the 150 mm depth was not reached until the holding phase of the third vacuum cycle.
The MP 3 setpoint temperature T=80° C. at the 200 mm depth was reached during the fourth vacuum cycle. By this time steam had penetrated the bale to a depth of about 200 mm.
The temperature rise at MP 4 inside the bale was slow. The temperature rose at 0.75° C. per minute on average. However, the temperature rise was steeper after the end of each vacuum cycle, indicating that steam penetration is accelerated by the intermediate
The setpoint temperature at measuring point MP 4 was reached 10 minutes after reaching the fourth cycle temperature.
Steam penetration is theoretically complete after reaching the setpoint temperature T4=80° C. side the bale. Further steaming time does not increase humidity since the entire bale is then heated up to a temperature of 80° C.
Weight Loss After Packaging
After a cooling time of 90 minutes, the measuring probes were removed and the bale was wrapped in foil with a pallet binder for storage. The temperature inside the bale was still high at this time, as shown by the following readings:
Measuring point MP 1: 70° C.
Measuring point MP 2: 76° C.
Measuring points MP 3,4: 78° C.
Weight loss of packaged bale No. 1 including pallet
Days
Weight w/pallet
Difference
Start
267.45 kg
(100%)
2
267.30 kg
0.15 kg = 0.00%
4
267.15 kg
0.30 kg = 0.11%
8
266.90 kg
0.55 kg = 0.20%
13
266.65 kg
0.80 kg = 0.30%
21
266.65 kg
0.80 kg = 0.30%
26
266.70 kg
0.75 kg = 0.30%
Weight loss of the packaged bale after 2 weeks of storage was 0.3% referred to the original weight of 267.45 kg. No weight change occurred during the following week.
Assuming that the wrapping foil is impermeable to air, no further weight losses are expected. The above-mentioned weight loss of 0.80 kg also includes that of the timber pallet weighing about 15 kg. Steaming increased the pallet weight by about 4% due to 0.60 kg additional water content, which evaporates during storage.
If this pallet weight loss: of about 0.60 kg is deducted from the total weight loss, weight loss attributable to the foil is practically negligible at only 0.20 kg or 0.075%.
Condensate Accumulation
After 2 hours of cooling time a condensate film is formed inside the packaging foil, which about 2 days later had consolidated into water drops. These water drops were still clearly visible two days later, but they were no longer visible when the weight measurement was taken 8 days after packaging.
The cotton bales cooled down within about 4 days, when evaporation ceased and the cotton bales reabsorbed the condensate drops. Cotton can absorb up to about 15% of its own weight in moisture at 100% air humidity.
Steam penetration can be accelerated by increasing the temperature as rapidly as possible to the setpoint value of about 80° C. after reaching 100 mbar vacuum. Since steam has a vapor saturation pressure of about 450 mbar at 80° C., the pressure differential is then 450−100=350 mbar; this helps to force steam into the bale more efficiently and rapidly.
Theoretical Considerations
The weight increase after steaming was 3.98%. This fact alone establishes that 100% of the bale mass was heated up by steaming.
The theoretical weight increase is calculated as follows based on the given data:
Net weight of bale: G=250.00 kg
Specific heat of cotton: c=1.3 kJ/kg° C.
Temperature differential: αT=80°−20°=60° C.
Vaporization heat of steam: r=2350 kJ/kg steam
Thermal energy Q required for cotton bale heating to 80° C.:
Q=c×G×ΔT
Q =1.3×250×60=19,500 kJ
The bale is heated with saturated steam The steam transfers its vaporization heat to the cotton through condensation. Cotton is hygroscopic and can store up to 18% by weight of moisture at 20° C. Since the cotton absorbs the condensate, its weight increases according to the amount of steam required.
With an evaporation heat of r=2309 kJ per kg steam, the following steam quantity D is required:
D=Q/r
D =19,500/2350=8.29 kg steam
8.29 kg of steam is therefore required to heat the cotton bale to 80° C. The steam then condenses into 8.29 kg of water, which is absorbed by the cotton. This weight increase of 8.29 kg corresponds to a 3.32% increase.
Since the above calculation does not take into account the original moisture content of about 6%, the actual weight increase is about 13% more than calculated, i.e. about 3.75%. The difference between this figure and the measured weight increase of 3.93%—which is greater than theoretically calculated—is attributable to weighing precision of the balance of +/−0.2 kg and of the physical data.
In a second test in accordance with the invention, a 5-cycle procedure was performed on a bale under the following conditions:
Steaming Program
1 st vacuum: 50 mbar=95%
1st cycle: T1=80° C.—2 min.
Start 1 st cycle with empty evaporator, or with cold waterbath.
2 nd vacuum: 200 mbar=80%
2 nd cycle: T2=80° C.—5 min.
3 rd vacuum: 200 mbar=80%
3 rd cycle: T3=80° C.—5 min.
4 th vacuum: 200 mbar=80%
4 th cycle: T4=80° C.—7 min.
5 th vacuum: 200mbar=80%
5 th cycle: T5=80° C.—9 min.
Total time: approx. 100 minutes.
Weight Increase of Bale Measuring Probes and with Pallet
Before conditioning: 260.80 kg=100% weight minutes after conditioning: 270.15 kg=3.58% weight increase.
After about 10 minutes the bale, probes and pallet were wrapped in foil.
Cooling of the wrapped bale
The cooling temperature readings were as follows:
After 1 day:
MP 2, 3, 4 interior 50° C.
MP 1 exterior 45° C.
After 2 days:
MP 2, 3, 4 interior 35° C.
MP 1 exterior 32° C.
Notes on Test Procedure
Control System
On OP 5 a 1-cycle program was programmed with T=80° C. for 99 minutes. During the holding time of 99 minutes the vacuum pump was switched on and off manually. The holding time for each cycle was maintained until it was clearly established that the temperatures at measuring points 1 to 4 either changed or remained unchanged.
Vacuum
Startup Vacuum—50 mbar
The startup vacuum of 50 mbar=95% was generated with a gas jet at the vacuum pump intake. The gas jet was not switched on until vacuum had reached 90%. The time required to reach the correct vacuum with cold water bath was rather long at 15 minutes. According to calculation (t=60×V/S×In p1/p2=60×10,2/400×3=5), the vacuum should be attained within about 5 minutes. With a cooling water temperature of 15° C. and dry air extraction, vacuum pump operating conditions were optimal. The long time required may be attributable to evaporator leakage or to vacuum pump power deficiency. Intermediate Vacuum—200 mbar
The intermediate vacuum up to 200 mbar was generated with a tube bank condenser at the vacuum pump intake. The first 2 vacuums after the 1 st and 2nd cycles lasted 7 minutes, and 8-9 minutes after the 3rd and 4th cycles. The reason for this longer vacuum time after cycles 3 and 4 was that part of the bale mass had already been heated up after the 3rd cycle and had to be cooled down again during the vacuum phase.
Measuring Point Temperature Sequence
Temperatures at the 4 measuring points were recorded during the process.
Measuring Point MP 1: Depth 100 mm (Black)
The temperature at this point did not begin to rise until the 2 nd cycle heating and holding phase. It reached the setpoint value at the beginning of the 3 rd cycle.
Measuring Point MP 2: Depth 150 mm (Green)
The temperature at this point did not begin to rise until the 3rd cycle heating and holding phase. It then rose in parallel with the steam temperature, but only reached the setpoint temperature at the beginning of the 5 th cycle heating phase. During the 4 th cycle holding phase the temperature no longer rose and remained constant. Extending the holding time would therefore have been pointless since the temperature would not have increased any
Measuring Point MP 3: Depth 200 mm (Blue)
This temperature characteristic was similar to that at MP 2, but at rather lower temperature level. The setpoint temperature was reached together with MP 2 at the beginning of the 5 th cycle heating phase.
The temperature characteristics at MP 2 and MP3 clearly show that 4 cycles are not enough: the fifth cycle is essential. The 4 th cycle holding time can however be shortened from 7 to 5 or even 3 minutes.
Measuring Point MP 4: Depth 250 mm (Brown)
As in test No. 1, the temperature at MP 4 inside the bale rose only slowly at approx. 0.75° C. per minute. The setpoint temperature was not reached until during the 5 th cycle holding time. Here again, the temperature rise was steeper after the end of each cycle.
Weight Loss After Packaging
After a short cooling time of only 10 minutes the bale was wrapped with the four probes inserted in order to record the temperature characteristics on cool down See comments on “Bale weight increase”.
The total weight of the wrapped bale including probes and pallet on the steaming day was 271.35 kg The probes (weight 1.25 kg) were removed after temperature measurements 6 days later. The starting weight (100% reference for weight loss measurements) was: 271.35 kg−1.25 kg=270.10 kg
Weight loss of packaged bale No. 3 including pallet
Day
Weight with pallet
Difference
Start
270.10 kg
None (100%)
6
269.15 kg
0.95 kg = 0.35%
12
269.10 kg
1.00 kg = 0.37%
The percentage weight loss of 0.37% after 12 days was 0.07% more, or 20% higher than in test No. 1. So even after 12 days, the percentage weight loss was still about 0.3%. This large difference may be attributable to a lower quality packaging with stretch-foil, or to weighing inaccuracy. It can also be due to higher vapor diffusion through the foil with excessively warm packing in the case of bale No. 3.
If the 0.60 kg pallet weight is deducted as with test No. 1, the weight loss after 12 days is 0.40 kg or 0.15%.
Condensation Inside the Packaging Foil
Condensate formed inside the foil and was re-absorbed by the cotton fibers within 5 to 6 days.
In order to reach steaming temperature as quickly as possible, direct steam injection is preferred. At T=80° C. the vapor pressure is about 500 mbar, so that steam is forced into the bale by a pressure differential of 300 mbar over the previous 200 mbar vacuum.
Direct steam injection can eliminate the problem of water batch contamination by cotton fibers.
At least four cycles are required. With adequate heating capacity, it should be possible to complete the process in no more than 2 hours.
Energy Consumption per Tonne of Cotton Fiber—Approx. 45 kWh
The theoretical energy consumption per tonne of yam with temperature rise A T=60° C. is 1.3×1000×60=78,000 kJ=22kWh. Taking into account the 4 to 5 reheating-required after the intermediate cycles, each time by about 20° C., as well as other losses, about 100% additional energy is required. In general we should expect here an optimistic energy consumption of about 45 kWh per tonne of yarn.
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A heat treatment process for fiber feedstock, comprises repeatedly subjecting the bale to a reduced pressure atmosphere followed by the introduction of steam which permeates the bale. The interior of the bale may ultimately reach a temperature of about 80° C., which conditions and sanitizes the cotton fibers. Reduced pressure in the range of 20-200 mbar and steam treatment time in the order of 5 minutes can be employed.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a process and an apparatus for guiding a coated material s trip in an initial drying zone, without requiring mechanical contact, by utilizing a heated gas.
2. Description of the Related Art
It is currently the state of the art to perform a surface treatment in floating film dryers for film or metal strips utilizing the aid of a supporting-air nozzle system which permits the material to be guided in the dryer without requiring mechanical contact. (journal "gas warm international", Volume 24 (1975), No. 12, pp. 527-531). In such dryers, the dryer air which is enriched with solvent is extracted directly in the nozzle zones in order to eliminate an undesired transversal flow. This produces so-called nozzle dryers or impact-jet dryers, in which a particular disadvantage is the impact of the point-like flow of individual nozzles, which tends, both in the case of laminar flow form and in the case of turbulent flow form, to cause flow-physical instabilities. The flow-physical instabilities, particularly in the case of low-viscosity liquid films, inevitably results in irreversible drying structures.
To avoid impact point-like flows in the beginning of the dryer apparatus, PCT Application WO 82/03450 discloses that the dryer air is directed out of an antespace, via suitable inlet openings and flow deflectors, and into a stabilized intermediate space. From the intermediate space, part of the dryer air passes via a porous filter element, arranged in the direct vicinity of the liquid jet, to the web to be dried. The operating principle of such drying is based on the fact that between the porous protective shield and the liquid film to be dried, there is formed a stabilized, yet highly solvent-enriched, weak air flow, which is constantly renewed by exchange with the residual air flowing transversely over the porous medium. Consequently, by virtue of the relatively short overall dryer length, a predrying of the liquid film with a reduced tendency for exhibiting mottling effects is accomplished.
This type of drying is predominantly characterized by the diffusion of the solvent vapor/air mixture through the porous protective shield. A complete drying out of the liquid film is only possible by having very great dryer lengths or by utilizing auxiliary dryers further downstream, because of the virtually complete lack of convective removal within the space that exists between strip and protective shield.
In the drying of products in web forms which have large surface areas on which liquid layers are applied, different drying processes and drying apparatuses have been used. Typical drying products are, for example, metal or plastic strips on which liquid layers are applied. As a rule, these liquid layers are composed of vaporizable components, which are removed from the liquid film during the drying process, and of non-vaporizable components, which remain on the base material after drying. In general, the webs which are to be dried are initially passed through an initial drying zone and subsequently through an actual drying zone. The coating gives the surfaces of the base materials special properties, which are not present in the form in which they are desired for later use until after the drying process. AS an example of this, mention can be made of the coating of metal strips, in particular aluminum strips, with light-sensitive layers, which are made into printing plates. The coating of metal strips or plastic sheets with a solvent-containing wet film, referred to hereinafter as a liquid film, and its subsequent drying, constitute an operation which requires special installations in order to ensure the desired product quality of the layers. What is essential in this case are the process steps of the initial drying and the final film drying as the final process measures of the coating.
The uniform drying of the blasting-sensitive coatings on the base material in dryers in which a dryer air flow runs parallel to the coated strip, is primarily disturbed by mechanical guide elements, such as rolls, for the base material and the coated metal strip. Very good drying results, with regard to the layer cosmetics, are obtained utilizing corresponding air conduction on the layer side that is to be dried if the material strip is guided in close proximity to the bottom of the dryer. If the material strip is passed, for example, over a level dryer bottom, which is composed for example of aluminum, there is the risk that so-called longitudinal scratches will occur on the underside of the material strip which can damage the coated material strip or even render it unusable.
If the bottom of the dryer is lined with a soft material,, such as for example a woven fabric, felt or a nonwoven fabric, the aforementioned longitudinal scratches are avoided. However, due to the different widths of the material strips, these lining materials are cut into. When the lining materials are cut into, particles of the lining material are formed which become deposited on the layer to be dried. Consequently, the layer to be dried becomes soiled and the lining materials become scored, which prevents a uniform contact with the guiding surface.
If the bottom of the dryer is lined with a material which has a substantially lower friction value than the material strip and which is temperature-resistant, such as for example polytetrafluoroethylene, this material will not remain mechanically resistant with respect to the edges of the material strip over an extended period.
SUMMARY OF THE INVENTION
An object of the invention is to provide a process and an apparatus so that a coated material strip can be contactlessly guided in an initial drying zone in such a way that the uniform initial drying of the liquid layer on the material strip is not impaired, and the effects of wear do not occur on the guiding means.
This object is achieved by a process which includes directing a gas stream to flow against a material strip in a direction which is perpendicular to a longitudinal and a running direction of the material strip, multiply interrupting the flow of the gas stream beneath the material strip so that it flows in the longitudinal direction of the material strip, creating a gas film due to the flow of the gas stream, and supporting the material strip by the gas film.
In a refinement of the process, first and second parts of the gas stream flow off in the running direction of the material and a direction opposite thereto, respectively. In addition, the material strip is guided over permeable guide elements, the gas stream is passed through the permeable guide elements, and the permeability of the guide elements is used to increase a pressure of the gas stream before the gas stream exits from the guide elements. Moreover, air is provided as the gas stream the air is at a temperature which is higher than a temperature of the drying zone.
In the inventive process, an air lubrication is accomplished between the material strip and the guide elements, with the lubrication taking place in very small spacings. The distance between the material strip and the guide elements is in this case substantially less than 1 mm, but may also be up to 1 mm. With appropriate material selection of the guide elements, which are generally air-permeable, the gas or air pressure to be preset is substantially lower than 1 bar. The relationship between the gas or air pressure to be preset for the lubrication and the gas or air permeability of the material for the guide elements is particularly important for creating a uniform and uninterrupted gas or air film between the material strip and the guide elements which are transverse to the through-running direction of the material strip. The exiting energy of the gas or the air from the guide elements must be quickly converted by the creation of microvortices into heat and pressure, which increase the effectiveness of the gas or air film. As a result, a flowing-around of the gas or air at the strip edges is avoided preventing damage to the blasting-sensitive liquid layer which can be caused by such a flow pattern.
An apparatus for guiding a coated material strip through a dryer has a plurality of guide elements disposed in the dryer so that the plurality of guide elements are equally spaced. The plurality of guide elements each have a gas-permeable guide face which faces an underside of the coated material strip. A device for supplying a gas to the plurality of guide elements is provided so that a gas stream passes through each of the gas-permeable guide faces and supports the coated material.
In a refinement of the apparatus according to the invention, each guide element includes a duct or supply tube which receives the gas, and the plurality of guide elements are all connected to the supplying device via a common supply line.
Moreover, the apparatus can also include an extraction line through which the gas stream which passes through each of the plurality of guide elements is drawn off.
In a further embodiment of the invention, an apparatus is provided wherein each of the plurality of guide elements includes a right-parallelepipedal air-permeable body which is disposed relative to its length transverse to a running direction of the material strip and a control duct. Moreover, the gas is a drying gas which flows via the control duct into the interior of the guide element along its longitudinal direction. Each of the air-permeable bodies is sintered metal or porous glass, and the three outer sides of each of the air-permeable bodies which do not face the material strip each have a barrier layer of lacquer or plastic thereon which seals the three outer sides and prevents the escape of the gas.
Since the gas or air supply which is applied underneath the material strip in accordance with the invention is not applied over its full surface area, an advantage is achieved in that a uniform sliding effect of the material strip is preserved over the entire web width, without the material strip being pushed up at the edges. In this case, interruptions of the airflow due to slight depressions in the sliding faces of the guide elements, which lie transverse to the material strip, have proven to be particularly advantageous.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is explained in more detail below with reference to graphically represented illustrative embodiments of the apparatus, in which:
FIG. 1 is a diagrammatic sectional view through a dryer having a number of guide elements according to the invention for the material strip,
FIG. 2 is a sectional view of a first embodiment of a guide element according to the invention,
FIG. 3 is a sectional view of a second embodiment of a guide element according to the invention, and
FIG. 4 is a sectional view of a third embodiment of a guide element according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, a dryer 13 having an air-lubricated guidance of a material strip 1 is shown. The material strip 1 runs from an inlet into the dryer 13 via a deflecting roll 11, opposite to which there lies an applying roll 19 for a liquid layer 2. Once the liquid layer 2 has been applied by the applying roll 19 to the material strip 1, the latter enters the dryer 13 through a gap and is horizontally led over guide elements 14. On the rear side of the dryer 13, the coated material strip 1 leaves from a gap and is led downward over a deflecting roll 12. The dryer 13 has a housing 15, through the underside of which a supply line 17 and an extraction line 18 pass. Each of the guide elements 14 is connected to supply line 17 through which gas or air is supplied. Normally, air is used as the guiding gas for the material strip 1 and the air typically has a higher temperature than the surrounding environment within the dryer 13. Each of the guide elements 14 includes a run-in duct 5 for receiving the gas or air being supplied. The supply line 17 is separate from a line 37 which supplies the drying air, and is also operated independently. A unit 16 (not shown in detail) for the air supply includes an air compressor with an upstream super-fine filter, and a downstream heat exchanger, as well as corresponding pipelines and fittings and a corresponding control system. The guide faces 9 of the guide elements 14 which face the material strip 1 are permeable to gas or air, so that the air flows in a perpendicular direction onto the material strip 1. Thus, an air film 7 is formed so that the coated material strip 1 with the blasting-sensitive liquid layer 2 slides without having any mechanical contact with the guide faces 9 of the guide elements 14.
The air pressure or gas pressure, prior to the exiting of the air or the gas from the guide elements 14, may increase up to 1 bar or more depending substantially on the permeability of the guide faces 9. The more permeable that these guide faces 9 are, the less the pressure increases within the guide elements 14 prior to the exiting of the air or the gas. The distance between the underside of the material strip 1 and the guide faces 9 is less than I mm, but may also be up to 1 mm in size. The air film 7 flows off in both the running direction of the material strip 1 and in a direction opposite thereto. The spaces which exist between any two adjacent guide elements, functions as a flowing-offregion for the air film 7. Since the amount of air flowing off is very small, the overall guiding and flowing behavior within the dryer 13 is not influenced, so that no disturbance of the layer cosmetics occurs during the initial drying of the liquid layer 2 on the material strip 1.
Through the run-in ducts 5, the air flows into the air-permeable bodies of the guide elements 14 and subsequently flows upward through the guide face 9 as guide air 10 against the material strip. To prevent the guide air 10 from flowing off laterally and downwardly through the outer walls of the guide elements, these outer walls are sealed off, as is further described in more detail below.
In FIGS. 2 to 4, different embodiments of guide elements 14, 32, 33 are represented, which in each case can be used in the dryer 13 of FIG. 1. FIG. 2 shows an individual guide element 14 of the dryer 13 in detail. The guide element 14 includes a right-parallelepipedal air-permeable body 3, which is supplied from the inside with superfine-filtered air via a central run-in duct. The air-permeable body 3, which is arranged in terms of its length transversely to the running direction of the material strip 1, is composed of sintered metal or porous glass. Three outer sides 24, 25, 26 of the body 3, which are not facing the material strip 1, are sealed off on the outside by a barrier layer 4 of lacquer or plastic to protect against the undesired escape of air from the body 3. The fourth outer side 27, which lies opposite the underside of the material strip 1 at a distance of less than or equal to 1 mm, and in particular at a distance which is considerably less than 1 mm, has outwardly lowered, sloping surfaces 30, 31, which respectively form with the underside of the material strip 1 flowing-off zones for the flowing off of the air. The guide air is conducted centrally through the run-in duct 5, along the guide face 9, and against the material strip 1. The air then flows offboth in and against the strip-running direction and into the neighboring flowing-offzones, thereby forming the air film 7. The surface of the guide face 9 is relatively rough.
FIG. 3 shows a second embodiment of a guide element 32, which includes a manifold 6 having passage openings 8 in the region of the guide face 9 and a jacket 20, which encloses the manifold 6. The jacket 20 is permeable to air and gas and is composed of a polytetrafluoroethylene-coated nonwoven fabric or felt. The guide air 10, which flows in through the manifold 6, exits through the passage openings 8, and flows through the jacket 20, and thereby forms between the circumferential face of the jacket 20 and the underside of the material strip 1 and air film 7. The air film 7 serves as a type oflubricating film and transports the material strip 1 by allowing it to slide over the guide elements 32. The guide air 10 primarily exits from the jacket 20 underneath the material strip 1 in the region of the guide face 9. Other materials which can be used for jacket 20 include polytetrafluoroethylene-coated woven fabric, glass or carbon fibers.
In FIG. 4, a third embodiment of the guide element 33 is shown, which includes a manifold 6 having passage openings 8 for the air, a jacket 34 of sintered metal or porous glass, sliding seals 21, and a protective jacket 22. The air-permeable jacket 34 is held at a distance from the manifold 6 by the sliding seals 21 which are attached to the manifold 6. The protective jacket 22 encloses the jacket 34, with the exception of a level polygonal face 35, which faces the underside of the material strip 1. On the inner side of the protective jacket 22 there is a continuous sliding seal 23 which, like the sliding seals 21, is composed, for example, of polytetrafluoroethylene. The sliding seals 21 and 23 may be adhesively attached, for example, to the manifold 6 or to the inner slide of the protective jacket 22. The air-permeable jacket 34 is rotatable with respect to the supply tube 6, so that the overall circumferential face of the air-permeable jacket 34 can be used. That is, when the inner or outer surface which faces the material strip 1 becomes soiled, the jacket 34 can be turned so that another polygonal face 35 faces the material strip 1.
The outer side of the jacket 34 comprises level polygonal faces 35, which are joined to one another by rounded-off transitional faces 36. These transitional faces 36 facilitate the turning of the jacket 34 with respect to the fixed protective jacket 22, since they are in contact with the sliding seal 23 over only a small surface and not over the entire face of the sliding seal.
The passage openings 8 of the fixed manifold 6 face the material strip 1, and two sliding seals 21 are in the direct proximity of the passage openings 8. The other two sliding seals 21 are attached to the manifold 6 at points diametrically opposite thereto.
It is thus apparent that by utilizing the guide elements 14, 32 or 33, the material strip 1 is guided in the dryer 13 without requiring the use of mechanical moving parts, such as rolls, and the blasting-sensitive liquid layer 2 is dried in a largely trouble free manner.
While several embodiments of the invention have been described, it will be understood that further modifications are still capable, and this application is intended to cover any variations, use or adaptation of the invention and including such departures from the present disclosure as to come within the knowledge of customary practice in the art to which the invention pertains, and as may be applied to the essential features hereinbefore set forth and following within the scope of the invention and the limits of the appended claims.
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An apparatus for guiding a coated material strip through a dryer has a plurality of guide elements disposed in the dryer so that the plurality of guide elements are equally-spaced. The plurality of guide elements each have a gas-permeable guide face which faces an underside of the coated material strip. A device for supplying a gas to the plurality of guide elements is provided so that a gas stream passes through each of the gas-permeable guide faces and supports the coated material.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional application of copending U.S. patent application Ser. No. 13/545,853, filed Jul. 10, 2012, which is a divisional application of U.S. patent application Ser. No. 12/092,253, filed Dec. 19, 2008, and issued as U.S. Pat. No. 8,237,019, which is a U.S. National Phase application filed under 35 U.S.C. §371 claiming priority to PCT Application No. PCT/EP2006/010535, filed Nov. 1, 2006 and which claims priority to PCT Application No. PCT/EP2005/011718, filed Nov. 1, 2005, each of which is incorporated herein in reference in their entirety.
[0002] The Sequence Listing associated with this application is filed in electronic format via EFS-Web and is hereby incorporated by reference into the specification in its entirety. The name of the text file containing the Sequence Listing is 123498_ST25.txt. The size of the text file is 90,740 bytes, and the text file was created on Dec. 5, 2012.
BACKGROUND OF THE INVENTION
[0003] The present invention relates to disease resistant plants, in particular plants resistant to organisms of the phylum Oomycota, the oomycetes. The invention further relates to plant genes conferring disease resistance and methods of obtaining such disease resistant plants for providing protection to Oomycota pathogens.
[0004] Resistance of plants to pathogens has been extensively studied, for both pathogen specific and broad resistance. In many cases resistance is specified by dominant genes for resistance. Many of these race-specific or gene-for-gene resistance genes have been identified that mediate pathogen recognition by directly or indirectly interacting with avirulence gene products or other molecules from the pathogen. This recognition leads to the activation of a wide range of plant defense responses that arrest pathogen growth.
[0005] In plant breeding there is a constant struggle to identify new sources of mostly monogenic dominant resistance genes. In cultivars with newly introduced single resistance genes, protection from disease is often rapidly broken, because pathogens evolve and adapt at a high frequency and regain the ability to successfully infect the host plant. Therefore, the availability of new sources of disease resistance is highly needed.
[0006] Alternative resistance mechanisms act for example through the modulation of the defense response in plants, such as the resistance mediated by the recessive mlo gene in barley to the powdery mildew pathogen Blumeria graminis f. sp. hordei . Plants carrying mutated alleles of the wildtype MLO gene exhibit almost complete resistance coinciding with the abortion of attempted fungal penetration of the cell wall of single attacked epidermal cells. The wild type MLO gene thus acts as a negative regulator of the pathogen response. This is described in WO9804586.
[0007] Other examples are the recessive powdery mildew resistance genes, found in a screen for loss of susceptibility to Erysiphe cichoracearum . Three genes have been cloned so far, named PMR6, which encodes a pectate lyase-like protein, PMR4 which encodes a callose synthase, and PMR5 which encodes a protein of unknown function. Both mlo and pmr genes appear to specifically confer resistance to powdery mildew and not to oomycetes such as downy mildews.
[0008] Broad pathogen resistance, or systemic forms of resistance such as SAR, has been obtained by two main ways. The first is by mutation of negative regulators of plant defense and cell death, such as in the cpr, lsd and acd mutants of Arabidopsis . The second is by transgenic overexpression of inducers or regulators of plant defense, such as in NPR1 overexpressing plants.
[0009] The disadvantage of these known resistance mechanisms is that, besides pathogen resistance, these plants often show detectable additional and undesirable phenotypes, such as stunted growth or the spontaneous formation of cell death.
[0010] It is an object of the present invention to provide a form of resistance that is broad, durable and not associated with undesirable phenotypes.
[0011] In the research that led to the present invention, an Arabidopsis thaliana mutant screen was performed for reduced susceptibility to the downy mildew pathogen Hyaloperonospora parasitica . EMS-mutants were generated in the highly susceptible Arabidopsis line Ler eds1-2. Eight downy mildew resistant (dmr) mutants were analysed in detail, corresponding to 6 different loci. Microscopic analysis showed that in all mutants H. parasitica growth was severely reduced. Resistance of dmr3, dmr4 and dmr5 was associated with constitutive activation of plant defence. Furthermore, dmr3 and dmr4, but not dmr5, were also resistant to Pseudomonas syringae and Golovinomyces orontii.
[0012] In contrast, enhanced activation of plant defense was not observed in the dmr1, dmr2, and dmr6 mutants. The results of this research have been described in Van Damme et al. (2005) Molecular Plant-Microbe Interactions 18(6) 583-592. This article does however not disclose the identification and characterization of the DMR genes.
BRIEF SUMMARY OF THE INVENTION
[0013] According to the present invention it was now found that DMR1 is the gene encoding homoserine kinase (HSK). For Arabidopsis five different mutant dmr1 alleles have been sequenced each leading to a different amino acid change in the HSK protein. HSK is a key enzyme in the biosynthesis of the amino acids methionine, threonine and isoleucine and is therefore believed to be essential. The various dmr1 mutants show defects in HSK causing the plants to accumulate homoserine The five different alleles show different levels of resistance that correlate to different levels of homoserine accumulation in the mutants.
[0014] The present invention thus provides a plant, which is resistant to a pathogen of viral, bacterial, fungal or oomycete origin, characterized in that the plant has an altered homoserine level as compared to a plant that is not resistant to the said pathogen.
[0015] This form of resistance is in particular effective against pathogens of the phylum Oomycota, such as Albugo, Aphanomyces, Basidiophora, Bremia, Hyaloperonospora, Pachymetra, Paraperonospora, Perofascia, Peronophythora, Peronospora, Peronosclerospora, Phytium, Phytophthora, Plasmopara, Protobremia, Pseudoperonospora, Sclerospora, Viennotia species.
[0016] The resistance is based on an altered level of homoserine in planta. More in particular, the resistance is based on an increased level of homoserine in planta. Such increased levels can be achieved in various ways.
[0017] First, homoserine can be provided by an external source. Second, the endogenous homoserine level can be increased. This can be achieved by lowering the enzymatic activity of the homoserine kinase gene which leads to a lower conversion of homoserine and thus an accumulation thereof. Alternatively, the expression of the homoserine kinase enzyme can be reduced. This also leads to a lower conversion of homoserine and thus an accumulation thereof. Another way to increase the endogenous homoserine level is by increasing its biosynthesis via the aspartate pathway. Reducing the expression of the homoserine kinase gene can in itself be achieved in various ways, either directly, such as by gene silencing, or indirectly by modifying the regulatory sequences thereof or by stimulating repression of the gene.
[0018] Modulating the HSK gene to lower its activity or expression can be achieved at various levels. First, the endogenous gene can be directly mutated. This can be achieved by means of a mutagenic treatment. Alternatively, a modified HSK gene can be brought into the plant by means of transgenic techniques or by introgression, or the expression of HSK can be reduced at the regulatory level, for example by modifying the regulatory sequences or by gene silencing.
[0019] In one embodiment of the invention, an increase (accumulation) in homoserine level in the plant is achieved by administration of homoserine to the plant. This is suitably done by treating plants with L-homoserine, e.g. by spraying or infiltrating with a homoserine solution.
[0020] Treatment of a plant with exogenous homoserine is known from WO00/70016. This publication discloses how homoserine is applied to a plant resulting in an increase in the phenol concentration in the plant. The publication does not show that plants thus treated are resistant to pathogens. In fact, WO00/70016 does not disclose nor suggest that an increase in endogenous homoserine would lead to pathogen resistance.
[0021] Alternatively, endogenous homoserine is increased by modulating plant amino acid biosynthetic or metabolic pathways.
[0022] In one embodiment, the increased endogenous production is the result of a reduced endogenous HSK gene expression thus leading to a less efficient conversion of homoserine into phospho-homoserine and the subsequent biosynthesis of methionine and threonine. This reduced expression of HSK is for example the result of a mutation in the HSK gene leading to reduced mRNA or protein stability.
[0023] In another embodiment reduced expression can be achieved by downregulation of the HSK gene expression either at the transcriptional or the translational level, e.g. by gene silencing or by mutations in the regulatory sequences that affect the expression of the HSK gene. An example of a method of achieving gene silencing is by means of RNAi.
[0024] In a further embodiment the increase in endogenous homoserine level can be obtained by inducing changes in the biosynthesis or metabolism of homoserine. In a particular embodiment this is achieved by mutations in the HSK coding sequence that result in a HSK protein with a reduced enzymatic activity thus leading to a lower conversion of homoserine into phospho-homoserine. Another embodiment is the upregulation of genes in the aspartate pathway causing a higher production and thus accumulation of L-homoserine in planta.
BRIEF DESCRIPTION OF THE DRAWINGS
[0025] FIG. 1 shows orthologous HSK sequences that have been identified in publicly available databases and obtained by PCR amplification on cDNA and subsequent sequencing. FIG. 1 shows the alignment of the amino acid sequences of the HSK proteins of Arabidopsis thaliana and orthologs from Citrus sinensis, Populus trichocarpa (1), Populus trichocapa (2), Solanum tuberosum (2), Vitis vinifera, Lactuca sativa, Solanum tuberosum (1), Solanum lycopersicum, Nicotiana benthamiana, Ipomoea nil, Glycine max, Phaseolus vulgaris, Cucumis sativus, Spinacia oleracea, Pinus taeda, Zea mays , and Oryza sativa using the CLUSTAL W (1.82) multiple sequence alignment programme (EBI). Below the sequences the conserved amino acids are indicated by the dots, and the identical amino acids are indicated by the asterisks. The black triangles and corresponding text indicate the amino acids that are substituted in the five Arabidopsis dmr mutants.
[0026] Table 2 shows the Genbank accession numbers and GenInfo identifiers of the Arabidopsis HSK mRNA and orthologous sequences from other plant species.
[0027] FIG. 2 shows the percentage of conidiophore formation by two Hyaloperonospora parasitica isolates, Cala2 and Waco9, on the mutants dmr1-1, dmr1-2, dmr1-3 and dmr1-4 and the parental line, Ler eds1-2, 7 days post inoculation. The conidiophores formed on the parental line were set to 100%.
[0028] FIG. 3 is a graphic overview of the three major steps in the cloning of DMR1. a) Initial mapping of dmr1 resulted in positioning of the locus on the lower arm of chromosome 2 between positions 7.42 and 7.56 Mb. Three insert/deletion (INDEL) markers were designed (position of the markers F6P23, T23A1 and F5J6 is indicated by the black lines). These markers were used to identify recombinants from several 100 segregating F2 and F3 plants. Primer sequences of these INDEL markers and additional markers to identify the breakpoints in the collected recombinants is presented in table 3. b) One marker, At2g17270 (indicated by the grey line), showed the strongest linkage with resistance. The dmr1 locus could be further delimited to a region containing 8 genes, at2g17250-at2g17290. The eight genes were amplified and sequenced to look for mutations in the coding sequences using the primers described in table 4. DNA sequence analysis of all 8 candidate genes led to the discovery of point mutations in the At2g17265 gene in all 5 dmr1 mutants. c) Each dmr1 mutant has a point mutation at a different location in the At2g17265 gene, which encodes homoserine kinase.
[0029] FIG. 4 shows a schematic drawing of the HSK coding sequence and the positions and nucleotide substitutions of the 5 different dmr1 mutations in the HSK coding sequence (the nucleotide positions, indicated by the black triangles, are relative to the ATG start codon which start on position i). The 5′UTR and 3′UTR are shown by light grey boxes. Below the nucleotide sequence the protein sequence is shown. The HSK protein contains a putative transit sequence for chloroplast targeting (dark grey part). The amino acid changes resulting from the 5 dmr1 mutations are indicated at their amino acid (aa) position number (black triangles) in the HSK protein.
[0030] FIG. 5 shows the position of the homoserine kinase enzyme in the aspartate pathway for the biosynthesis of the amino acids threonine, methionine and isoleucine.
[0031] FIG. 6 shows the number of conidiophores per Ler eds 1-2 seedlings 5 days post inoculation with two different isolates of H. parasitica , Waco9 and Cala2. The inoculated seedlings were infiltrated with dH2O, D-homoserine (5 mM) or L-homoserine (5 mM) at 3 days post inoculation with the pathogen. Seedlings treated with L-homoserine show a complete absence of conidiophore formation and are thus resistant.
[0032] FIG. 7 shows the growth and development of H. parasitica in seedlings treated with water, D-homoserine (5 mM), or L-homoserine (5 mM) as analysed by microscopy of trypan blue stained seedlings.
[0033] a: Conidiophore formation after HS treatment on Ler ed1-2 seedlings (10× magnification). No conidiophore formation was detected after L-homoserine infiltration, whereas control plants show abundant sporulation.
[0034] b: Haustorial development is affected by L-homoserine (5 mM) infiltration (40× magnification), but not in plants treated with water or D-homoserine.
[0035] FIGS. 8 and 9 show the nucleotide and amino acid sequence of the homoserine kinase gene (At2g17265, NM — 127281, GI:18398362) and protein (At2g17265, NP — 179318, GI: 15227800) of Arabidopsis thaliana , respectively (SEQ ID NOs: 99-100).
[0036] FIG. 10 shows the nucleotide and the predicted amino acid sequence of the homoserine kinase coding sequence (CDS) and protein, respectively, of Lactuca sativa (SEQ ID NOs. 101-102)
[0037] FIG. 11 shows the nucleotide and the predicted amino acid sequence of the homoserine kinase coding sequence (CDS) and protein, respectively, of Vitis vinifera (SEQ ID NOs: 103-104)
[0038] FIG. 12 shows the nucleotide and the predicted amino acid sequence of the homoserine kinase coding sequence (CDS) and protein, respectively, of Cucumis sativus (SEQ ID NOs: 105-106)
[0039] FIG. 13 shows the nucleotide and the predicted amino acid sequence of the homoserine kinase coding sequence (CDS) and protein, respectively, of Spinacia oleracea (SEQ ID NOs: 107-108)
[0040] FIG. 14 shows the nucleotide and the predicted amino acid sequence of the homoserine kinase coding sequence (CDS) and protein, respectively, of Solanum lycopersicum (SEQ ID NOs: 109-110)
DETAILED DESCRIPTION
[0041] This invention is based on research performed on resistance to Hyaloperonospora parasitica in Arabidopsis but is a general concept that can be more generally applied in plants, in particular in crop plants that are susceptible to infections with pathogens, such as Oomycota.
[0042] The invention is suitable for a large number of plant diseases caused by oomycetes such as, but not limited to, Bremia lactucae on lettuce, Peronospora farinosa on spinach, Pseudoperonospora cubensis on members of the Cucurbitaceae family, e.g. cucumber, Peronospora destructor on onion, Hyaloperonospora parasitica on members of the Brasicaceae family, e.g. cabbage, Plasmopara viticola on grape, Phytophthora infestans on tomato and potato, and Phytophthora sojae on soybean.
[0043] The homoserine level in these other plants can be increased with all techniques described above. However, when the modification of the HSK gene expression in a plant is to be achieved via genetic modification of the HSK gene or via the identification of mutations in the HSK gene, and the gene is not yet known it must first be identified. To generate pathogen-resistant plants, in particular crop plants, via genetic modification of the HSK gene or via the identification of mutations in the HSK gene, the orthologous HSK genes must be isolated from these plant species. Orthologs are defined as the genes or proteins from other organisms that have the same function.
[0044] Various methods are available for the identification of orthologous sequences in other plants.
[0045] A method for the identification of HSK orthologous sequences in a plant species, may for example comprise identification of homoserine kinase ESTs of the plant species in a database; designing primers for amplification of the complete homoserine kinase transcript or cDNA; performing amplification experiments with the primers to obtain the corresponding complete transcript or cDNA; and determining the nucleotide sequence of the transcript or cDNA.
[0046] Suitable methods for amplifying the complete transcript or cDNA in situations where only part of the coding sequence is known are the advanced PCR techniques 5′RACE, 3′RACE, TAIL-PCR, RLM-RACE and vectorette PCR.
[0047] Alternatively, if no nucleotide sequences are available for the plant species of interest, primers are designed on the HSK gene of a plant species closely related to the plant of interest, based on conserved domains as determined by multiple nucleotide sequence alignment, and used to PCR amplify the orthologous sequence. Such primers are suitably degenerate primers.
[0048] Another reliable method to assess a given sequence as being a HSK ortholog is by identification of the reciprocal best hit. A candidate orthologous HSK sequence of a given plant species is identified as the best hit from DNA databases when searching with the Arabidopsis HSK protein or DNA sequence, or that of another plant species, using a Blast programme. The obtained candidate orthologous nucleotide sequence of the given plant species is used to search for homology to all Arabidopsis proteins present in the DNA databases (e.g. at NCBI or TAIR) using the BlastX search method. If the best hit and score is to the Arabidopsis HSK protein, the given DNA sequence can be described as being an ortholog, or orthologous sequence.
[0049] HSK is encoded by a single gene in Arabidopsis and rice as deduced from the complete genome sequences that are publicly available for these plant species. In most other plant species tested so far, HSK appears to be encoded by a single gene, as determined by the analysis of mRNA sequences and EST data from public DNA databases, except for potato, tobacco and poplar for which two HSK homologs have been identified. The orthologous genes and proteins are identified in these plants by nucleotide and amino acid comparisons with the information that is present in public databases.
[0050] Alternatively, if no DNA sequences are available for the desired plant species, orthologous sequences are isolated by heterologous hybridization using DNA probes of the HSK gene of Arabidopsis or another plant or by PCR methods, making use of conserved domains in the HSK coding sequence to define the primers. For many crop species, partial HSK mRNA sequences are available that can be used to design primers to subsequently PCR amplify the complete mRNA or genomic sequences for DNA sequence analysis.
[0051] In a specific embodiment the ortholog is a gene of which the encoded protein shows at least 50% identity with the Arabidopsis HSK protein or that of other plant HSK proteins. In a more specific embodiment the homology is at least 55%, more specifically at least 60%, even more specifically at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95% or at least 99%.
[0052] After orthologous HSK sequences are identified, the complete nucleotide sequence of the regulatory and coding sequence of the gene is identified by standard molecular biological techniques. For this, genomic libraries of the plant species are screened by DNA hybridization or PCR with probes or primers derived from a known homoserine kinase gene, such as the above described probes and primers, to identify the genomic clones containing the HSK gene. Alternatively, advanced PCR methods, such as RNA Ligase Mediated RACE (RLM-RACE), can be used to directly amplify gene and cDNA sequences from genomic DNA or reverse-transcribed mRNA. DNA sequencing subsequently results in the characterization of the complete gene or coding sequence.
[0053] Once the DNA sequence of the gene is known this information is used to prepare the means to modulate the expression of the homoserine kinase gene in anyone of the ways described above.
[0054] More in particular, to achieve a reduced HSK activity the expression of the HSK gene can be down-regulated or the enzymatic activity of the HSK protein can be reduced by amino acid substitutions resulting from nucleotide changes in the HSK coding sequence.
[0055] In a particular embodiment of the invention, downregulation of HSK gene expression is achieved by gene-silencing using RNAi. For this, transgenic plants are generated expressing a HSK anti-sense construct, an optimized micro-RNA construct, an inverted repeat construct, or a combined sense-anti-sense construct, so as to generate dsRNA corresponding to HSK that leads to gene silencing.
[0056] In an alternative embodiment, one or more regulators of the HSK gene are downregulated (in case of transcriptional activators) by RNAi.
[0057] In another embodiment regulators are upregulated (in case of repressor proteins) by transgenic overexpression. Overexpression is achieved in a particular embodiment by expressing repressor proteins of the HSK gene from a strong promoter, e.g. the 35S promoter that is commonly used in plant biotechnology.
[0058] The downregulation of the HSK gene can also be achieved by mutagenesis of the regulatory elements in the promoter, terminator region, or potential introns. Mutations in the HSK coding sequence in many cases lead to amino acid substitutions or premature stop codons that negatively affect the expression or activity of the encoded HSK enzyme.
[0059] These and other mutations that affect expression of HSK are induced in plants by using mutagenic chemicals such as ethyl methane sulfonate (EMS), by irradiation of plant material with gamma rays or fast neutrons, or by other means. The resulting nucleotide changes are random, but in a large collection of mutagenized plants the mutations in the HSK gene can be readily identified by using the TILLING (Targeting Induced Local Lesions IN Genomes) method (McCallum et al. (2000) Targeted screening for induced mutations. Nat. Biotechnol. 18, 455-457, and Henikoff et al. (2004) TILLING. Traditional mutagenesis meets functional genomics. Plant Physiol. 135, 630-636). The principle of this method is based on the PCR amplification of the gene of interest from genomic DNA of a large collection of mutagenized plants in the M2 generation. By DNA sequencing or by looking for point mutations using a single-strand specific nuclease, such as the CEL-I nuclease (Till et al. (2004) Mismatch cleavage by single-strand specific nucleases. Nucleic Acids Res. 32, 2632-2641) the individual plants that have a mutation in the gene of interest are identified.
[0060] By screening many plants, a large collection of mutant alleles is obtained, each giving a different effect on gene expression or enzyme activity. The gene expression or enzyme activity can be tested by analysis of HSK transcript levels (e.g. by RT-PCR), quantification of HSK protein levels with antibodies or by amino acid analysis, measuring homoserine accumulation as a result of reduced HSK activity. These methods are known to the person skilled in the art.
[0061] The skilled person can use the usual pathogen tests to see if the homoserine accumulation is sufficient to induce pathogen resistance.
[0062] Plants with the desired reduced HSK activity or expression are then back-crossed or crossed to other breeding lines to transfer only the desired new allele into the background of the crop wanted.
[0063] The invention further relates to mutated HSK genes encoding HSK proteins with a reduced enzymatic activity. In a particular embodiment, the invention relates to the dmr1 alleles dmr1-1, dmr1-2, dmr1-3, dmr1-4 and dmr1-5.
[0064] In another embodiment, the invention relates to mutated versions of the HSK genes of Lactuca sativa, Vitis vinifera, Cucumis sativus, Spinacia oleracea and Solanum lycopersicum as shown in FIGS. 10-14 (SEQ ID NOs: 101-110).
[0065] The present invention demonstrates that plants having an increased homoserine level show resistance to pathogens, in particular of oomycete origin. With this knowledge the skilled person can actively modify the HSK gene by means of mutagenesis or transgenic approaches, but also identify so far unknown natural variants in a given plant species that accumulate homoserine or that have variants of the HSK gene that lead to an increase in homoserine, and to use these natural variants according to the invention.
[0066] In the present application the terms “homoserine kinase” and “HSK” are used interchangeably.
[0067] The present invention is illustrated in the following examples that are not intended to limit the invention in any way. In the examples reference is made to the following figures.
EXAMPLES
Example 1
Characterization of the Gene Responsible for Pathogen Resistance in dmr Mutants
[0068] Van Damme et al., 2005, supra disclose four mutants, dmr1-1, dmr1-2, dmr1-3 and dmr1-4 that are resistant to H. parasitica . The level of resistance can be examined by counting conidiophores per seedling leaf seven day post inoculation with the H. parasitica Cala2 isolate (obtainable from Dr. E. Holub (Warwick HRI, Wellesbourne, UK or Dr. G. Van den Ackerveken, Department of Biology, University of Utrecht, Utrecht, NL). For the parental line, Ler eds1-2 (Parker et al., 1996. Plant Cell 8:2033-2046), which is highly susceptible, the number of conidiophores is set at 100%. The reduction in conidiophore formation on the infected dmr1 mutants compared to seedlings of the parental line is shown in FIG. 2 .
[0069] According to the invention, the gene responsible for resistance to H. parasitaca in the dmr1 mutants of van Damme el al., 2005, supra has been cloned by a combination of mapping and sequencing of candidate genes.
[0070] DMR1 was isolated by map-based cloning. The dmr1 mutants were crossed to the FN2 Col-0 mutant to generate a mapping population. The FN2 mutant is susceptible to the H. parasitica isolate Cala2, due to a fast neutron mutation in the RPP7A gene (Sinapidou et al., 2004, Plant J. 38:898-909). All 5 dmr1 mutants carry single recessive mutations as the F1 plants were susceptible, and approximately a quarter of the F2 plants displayed H. parasitica resistance.
[0071] The DMR1 cloning procedure is illustrated in FIG. 3 and described in more detail below. The map location of the dmr1 locus was first determined by genotyping 48 resistant F2 plants to be located on the lower arm of chromosome 2. From an additional screen for new recombinants on 650 F2 plants ˜90 F2 recombinant plants between two INDEL (insertion/deletion) markers on BAC T24112 at 7.2 Mb and BAC F5J6 at 7.56 Mb (according to the TIGR Arabidopsis genome release Version 5.0 of January 2004) were identified, which allowed to map the gene to a region containing a contig of 5 BACs.
[0072] The F2 plants were genotyped and the F3 generation was phenotyped in order to fine map the dmr1 locus. The dmr1 mutation could be mapped to a ˜130 kb region (encompassing 3 overlapping BAC clones: F6P23, T23A1, and F5J6) between two INDEL markers located on BAC F6P23, at 7.42 Mb and F5J6 at 7.56 Mb (according to the TIGR Arabidopsis genome release Version 5.0 of January 2004). This resulted in an area of 30 putative gene candidates for the dmr1 locus, between the Arabidopsis genes with the TAIR codes AT2g17060 and AT2g17380. Additionally cleaved amplified polymorphic sequences (CAPS) markers were designed based on SNPs linked to genes AT2g17190, AT2g17200, AT2g17270, At2g17300, At2g17310 and At2g17360 genes.
[0073] Analyses of 5 remaining recombinants in this region with these CAPS marker data left 8 candidate genes, At2g17230 (NM — 127277, GI:30679913), At2g17240 (NM — 127278, GI:30679916), At2g17250 (NM — 127279, GI:22325730), At2g17260 (NM — 127280, GI:30679922). At2g17265 (NM — 127281, GI:18398362), At2g17270 (NM — 127282, GI:30679927), At2g17280 (NM — 127283, GI:42569096), At2g17290 (NM — 127284, GI:30679934). Sequencing of all the 8 genes resulted in the finding of point mutations in the AT2g17265 coding gene in the five dmr1 alleles: dmr1-1, dmr1-2, dmr1-3, dmr1-4 and dmr1-5, clearly demonstrating that AT2g17265 is DMR1. FIG. 3 shows a scheme of dnrl with point mutations of different alleles.
[0074] At2g17265 encodes the homoserine kinase (HSK) enzyme, so far the only Arabidopsis gene exhibiting this function.
[0075] In Arabidopsis , HSK is encoded by a single gene. At2g17265 (Lee & Leustek, 1999, Arch. Biochem. Biophys. 372: 135-142). HSK is the fourth enzyme in the aspartate pathway required for the biosynthesis of the amino acids methionine, threonine and isoleucine. HSK catalyzes the phosphorylation of homoserine to homoserine phosphate ( FIG. 5 ).
Example 2
Amino Acid Analysis
[0076] Homoserine phosphate is an intermediate in the production of methionine, isoleucine and threonine in Arabidopsis . Since homoserine kinase has a key role in the production of amino acids, free amino acid levels were determined in the parental line Ler eds1-2 and the four different dmr1 mutants. For this amino acids from total leaves were extracted with 80% methanol, followed by a second extraction with 20% methanol. The combined extracts were dried and dissolved in water. After addition of the internal standard, S-amino-ethyl-cysteine (SAEC) amino acids were detected by automated ion-exchange chromatography with post column ninhydrin derivatization on a JOEL AminoTac JLC-500/V (Tokyo, Japan).
[0077] Amino acid analysis of four different dmr1 mutants and the parental line, Ler eds 1-2 showed an accumulation of homoserine in the dmr1 mutants, whereas this intermediate amino acid was not detectable in the parental line Ler eds1-2. There was no reduction in the level of methionine, isoleucine and threonine in the dmr1 mutants (Table 1).
[0000] TABLE 1 Concentration (in pmol/mg fresh weight) of homoserine, methionine, threonine and isoleucine in above-ground parts of 2-week old seedlings of the parental line Ler eds 1-2 and the mutants dmr1-1, dmr1-2, dmr1-3 and dmr1-4. Homoserine Methionine Isoleucine Threonine dmr1-1 964 29 12 264 dmr1-2 7128 14 29 368 dmr1-3 466 11 16 212 dmr1-4 6597 11 32 597 Ler eds 1-2 0 7 10 185
Due to the reduced activity of the HSK in the dmr1 mutants, homoserine accumulates. This effect could be further enhanced by a stronger influx of aspartate into the pathway leading to an even higher level of homoserine. The high concentration of the substrate homoserine would still allow sufficient phosphorylation by the mutated HSK so that the levels of methionine, isoleucine and threonine are not reduced in the dmr1 mutants and the parental line, Ler eds1-2 (Table 1).
Example 3
Pathogen Resistance is Achieved by Application of L-Homoserine
[0078] To test if the effect is specific for homoserine the stereo-isomer D-homoserine was tested. Whole seedlings were infiltrated with water, 5 mM D-homoserine and 5 mM L-homoserine. Only treatment with the natural amino acid L-homoserine resulted in resistance to H. parasitica . Seedlings treated with water or D-homoserine did not show a large reduction in pathogen growth and were susceptible to H. parasitica . The infiltration was applied to two Arabidopsis accessions, Ler eds1-2 and Ws eds1-1, susceptible to Cala2 and Waco9, respectively. Conidiophore formation was determined as an indicator for H. parasitica susceptibility. Conidiophores were counted 5 days post inoculation with H. parasitica and 2 days post infiltration with water, D-homoserine or L-homoserine. ( FIG. 6 ). L-homoserine infiltration clearly results in reduction of conidiophore formation and H. parasitica resistance. This was further confirmed by studying pathogen growth in planta by trypan blue staining of Arabidopsis seedlings. Plants were inoculated with isolate Cala2. Two days later the plants were treated by infiltration with water, 5 mM D-homoserine, and 5 mM L-homoserine. Symptoms were scored at 5 days post inoculation and clearly showed that only the L-homoserine-infiltrated seedlings showed a strongly reduced pathogen growth and no conidiophore formation ( FIG. 7 ).
[0079] Microscopic analysis showed that only in L-homoserine treated leaves the haustoria, feeding structures that are made by H. parasitica during the infection process, are disturbed. Again it is shown that increased levels of homoserine in planta lead to pathogen resistance.
Example 4
Identification of HSK Orthologs in Crops
1. Screening of Libraries on the Basis of Sequence Homology
[0080] The nucleotide and amino acid sequences of the homoserine kinase gene and protein of Arabidopsis thaliana are shown in FIGS. 8 and 9 (SEQ ID NOs: 99-100).
[0081] Public libraries of nucleotide and amino acid sequences were compared with the sequences of FIGS. 8 and 9 (SEQ ID NOs: 99-100).
[0000] This comparison resulted in identification of the complete HSK coding sequences and predicted amino acid sequences in Citrus sinensis, Populus trichocarpa (1), Populus trichocarpa (2), Solanum tuberosum (2), Solanum tuberosum (1), Nicotiana benthamiana, Ipomnoea nil, Glycine max, Phaseolus vulgaris, Pinus taeda, Zea mays , and Oryza sativa . The sequence information of the orthologous proteins thus identified is given in FIG. 1 . For many other plant species orthologous DNA fragments could be identified by BlastX as reciprocal best hits to the Arabidopsis or other plant HSK protein sequences.
2. Identification of Orthologs by Means of Heterologous Hybridisation
[0082] The HSK DNA sequence of Arabidopsis thaliana as shown in FIG. 8 (SEQ ID NO: 99) is used as a probe to search for homologous sequences by hybridization to DNA on any plant species using standard molecular biological methods. Using this method orthologous genes are detected by southern hybridization on restriction enzyme-digested DNA or by hybridization to genomic or cDNA libraries. These techniques are well known to the person skilled in the art. As an alternative probe the HSK DNA sequence of any other more closely related plant species can be used as a probe.
3. Identification of Orthologs by Means of PCR
[0083] For many crop species, partial HSK mRNA or gene sequences are available that are used to design primers to subsequently PCR amplify the complete cDNA or genomic sequence. When 5′ and 3′ sequences are available the missing internal sequence is PCR amplified by a HSK specific 5′ forward primer and 3′ reverse primer. In cases where only 5′, internal or 3′ sequences are available, both forward and reverse primers are designed. In combination with available plasmid polylinker primers, inserts are amplified from genomic and cDNA libraries of the plant species of interest. In a similar way, missing 5′ or 3′ sequences are amplified by advanced PCR techniques, 5′RACE, 3′RACE, TAIL-PCR, RLM-RACE or vectorette PCR.
[0084] As an example the sequencing of the Lactuca sativa (lettuce) HSK cDNA is provided. From the Genbank EST database at NCBI several Lactuca HSK ESTs were identified using the tblastn tool starting with the Arabidopsis HSK amino acid sequence. Clustering and alignment of the ESTs resulted in a consensus sequence for a 5′HSK fragment and one for a 3′ HSK fragment. To obtain the complete lettuce HSK cDNA the RLM-RACE kit (Ambion) was used on mRNA from lettuce seedlings. The 5′ mRNA sequence was obtained by using a primer that was designed in the 3′HSK consensus sequence derived from ESTs (R1S1a: GCCTTCTTCACAGCATCCATTCC—SEQ ID NO: 1) and the 5′RACE primers from the kit. The 3′ cDNA sequence was obtained by using two primers designed on the 5′RACE fragment (Let3 RACEOut: CCOTTGCGGTTAATGAGATT—SEQ ID NO: 2, and Let3RACEInn: TCGTGTTGGTGAATCCTGAA—SEQ ID NO: 3) and the 3′RACE primers from the kit. Based on the assembled sequence new primers were designed to amplify the complete HSK coding from cDNA to provide the nucleotide sequence and derived protein sequence as presented in FIG. 10 (SEQ ID NOs: 101-102). A similar approach was a used for Solanum lycopersicum (FIG. 14 —SEQ ID NOs: 109-110) and Vitis vinifera (FIG. 11 —SEQ ID NOs: 103-104).
[0085] The complete HSK coding sequences from more than 10 different plants species have been identified from genomic and EST databases. From the alignment of the DNA sequences, conserved regions in the coding sequence were selected for the design of degenerate oligonucleotide primers (for the degenerate nucleotides the abbreviations are according to the IUB nucleotide symbols that are standard codes used by all companies synthesizing oligonucleotides, G=Guanine, A=Adenine, T=Thymine, C=Cytosine, R=A or G, Y=C or T, M=A or C, K=G or T, S=C or G, W=A or T, B=C or G or T, D=G or A or T, H=A or C or T, V=A or C or G, N=A or C or G or T).
[0086] The procedure for obtaining internal HSK cDNA sequences of a given plant species is as follows:
[0087] 1. mRNA is isolated using standard methods,
[0088] 2. cDNA is synthesized using an oligo dT primer and standard methods,
[0089] 3. using degenerate forward and reverse oligonucleotides a PCR reaction is carried out,
[0090] 4. PCR fragments are separated by standard agarose gel electrophoresis and fragments of the expected size are isolated from the gel,
[0091] 5. isolated PCR fragments are cloned in a plasmid vector using standard methods,
[0092] 6. plasmids with correct insert sizes, as determined by PCR, are analyzed by DNA sequencing.
[0093] 7. Sequence analysis using blastX reveals which fragments contain the correct internal HSK sequences,
[0094] 8. The internal DNA sequence can then be used to design gene- and species-specific primers for 5′ and 3′ RACE to obtain the complete HSK coding sequence by RLM-RACE (as described above).
[0095] As an example the sequencing of the Cucumis sativus (cucumber) HSK cDNA is provided. For cucumber two primer combinations were successful in amplifying a stretch of internal coding sequence from cDNA; combination 1: primer F1Kom (GAYTTTCYTHGGMTGYGCCGT—SEQ ID NO: 4) and M1RC (GCRGCGATKCCRGCRCAGTT—SEQ ID NO: 5), and combination 2: primer M1Kom (AACTGYGCYGGMATCGCYGC—SEQ ID NO: 6) and R1Kom (CCATDCCVGGAATCAANGGVGC—SEQ ID NO: 7). After cloning and sequencing of the amplified fragments cucumber HSK-specific primers were designed for 5′ RACE (Cuc5RACEOut: AGAGGATTTTACTAAGTTATTCGTG—SEQ ID NO: 8 and Cuc5RACEInn: AGACATAATCTCCCAAGCCATCA—SEQ ID NO: 9) and 3′ RACE (Cuc3RACEOut: TGATGGCTTGGGAGATATGTCT—SEQ ID NO: 10 and Cuc3RACEInn: CACGAATAAACTTAGTAAAAATCCTCT—SEQ ID NO: 11). Finally the complete cucumber HSK cDNA sequence was amplified and sequenced (FIG. 12 —SEQ ID NOs: 105-106). A similar approach was a used for spinach, Spinacia oleracea (FIG. 13 —SEQ ID NOs: 107-108).
[0096] Orthologs identified as described in this example can be modified using well-known techniques to induce mutations that reduce the HSK expression or activity. Alternatively, the genetic information of the orthologs can be used to design vehicles for gene silencing. All these sequences are then used to transform the corresponding crop plants to obtain plants that are resistant to Oomycota.
Example 5
Reduction of Homoserine Kinase Expression in Arabidopsis by means of RNAi
[0097] The production of HSK silenced lines has been achieved in Arabidopsis by RNAi. A construct containing two ˜750 bp fragments of the HSK exon in opposite directions was successfully transformed into the Arabidopsis Col-0 accession. The transformants were analysed for resistance to H. parasitica , isolate Waco9. Several transgenic lines were obtained that confer resistance to H. parasitica . Analysis of HSK expression and homoserine accumulation confirm that in the transformed lines the HSK gene is silenced, resulting in resistance to H. parasitica.
Example 6
Mutation of Seeds
[0098] Seeds of the plant species of interest are treated with a mutagen in order to introduce random point mutations in the genome. Mutated plants are grown to produce seeds and the next generation is screened for increased accumulation of homoserine. This is achieved by measuring levels of the amino acid homoserine, by monitoring the level of HSK gene expression, or by searching for missense mutations in the HSK gene by the TILLING method, by DNA sequencing, or by any other method to identify nucleotide changes.
[0099] The selected plants are homozygous or are made homozygous by selfing or inter-crossing. The selected homozygous plants with increased homoserine levels are tested for increased resistance to the pathogen of interest to confirm the increased disease resistance.
Example 7
Transfer of a Mutated Allele into the Background of a Desired Crop
[0100] Introgression of the desired mutant allele into a crop is achieved by crossing and genotypic screening of the mutant allele. This is a standard procedure in current-day marker assistant breeding of crops.
Tables
[0101]
[0000]
TABLE 2
GI numbers (GenInfo identifier) and Genbank accession number
for Expressed Sequence Tags (ESTs) and mRNA sequences of
the Arabidopsis HSK mRNA and orthologous sequences
from other plant species.
Species
Common name
Detail
GI number
Genbank
Arabidopsis thaliana
Thale cress
mRNA
39104571
AK117871
Citrus sinensis
Sweet Orange
ESTs
55935768
CV886642
28618675
CB293218
55935770
CV886643
28619455
CB293998
Glycine max
Soybean
ESTs
10846810
BF069552
17401269
BM178051
8283472
BE021031
16348965
BI974560
7285286
AW597773
58024665
CX711406
58017647
CX704389
20449357
BQ253481
16105339
BI893079
37996979
CF808568
37996460
CF808049
6072786
AW102173
26057235
CA800149
6455775
AW186458
6072724
AW102111
9203587
BE329811
Ipomoea nil
Japanese moming glory
ESTs
74407098
CJ761918
74402449
CJ757269
74402115
CJ756935
74388670
CJ743490
Nicotiana
Tobacco
ESTs
39880685
CK295868
Benthamiana
39859026
CK284950
39864851
CK287885
39864855
CK287887
39859024
CK284949
39864853
CK287886
39880683
CK295867
39864849
CK287884
Oryza sativa
Rice
mRNA
50916171
XM_468550
32970537
AK060519
Phaseolus vulgaris
Common Bean
ESTs
62708660
CV535256
62710636
CV537232
62708052
CV534648
62709395
CV535991
62710761
CV537357
62708535
CV535131
62708534
CV535130
62711318
CV537914
62707924
CV534520
62710733
CV537329
62709601
CV536197
62709064
CV535660
62708834
CV535430
Pinus taeda
Loblolly Pine
ESTs
70780626
DR690274
67490638
DR092267
48933532
CO162991
34354980
CF396563
67706241
DR117931
17243465
BM158115
34349136
CF390719
66981484
DR057917
48932595
CO162054
66689208
DR011702
48933450
CO162909
34350236
CF391819
67706323
DR118013
48932678
CO162137
66981399
DR057832
34354850
CF396433
Populus trichocarpa 1
Poplar
Genome v1.0, LG_IX,
149339-148242
Expression confirmed by ESTs
Populus trichocarpa 2
Poplar
Genome v1.0, scaffold_66,
1415935-1417032
Expression confirmed by ESTs
Solanum tuberosum 1
Potato
ESTs
66838966
DR037071
61238361
DN588007
39804315
CK251362
39801776
CK250065
9250052
BE340521
39832341
CK275363
21917848
BQ116921
9249876
BE340345
39815050
CK258070
39804985
CK251702
39804987
CK251703
39825384
CK268406
39832342
CK275364
66838967
DR037072
9250394
BE340863
39804317
CK251363
39825385
CK268407
21375072
BQ516203
Solanum tuberosum 2
Potato
ESTs
39813353
CK256373
39793361
CK246131
39793359
CK246130
39813352
CK256372
Zea Mays
Maize
ESTs
76071237
DT948407
76913306
DV165065
71446162
DR827212
71449720
DR830770
78117576
DV535963
91048486
EB158904
71439095
DR820145
76936546
DV174774
76012246
DT939416
78085419
DV513812
71766843
DR964780
76924795
DV170131
71449067
DR830117
91875652
EB405609
71450175
DR831225
78103551
DV521979
78090555
DV518929
78104654
DV523072
76926251
DV170768
78111568
DV529965
71773353
DR971257
71425952
DR807002
93282458
EB674722
78074199
DV502633
76293328
DV032896
78075462
DV503896
91054750
EB165168
86469295
DY235665
74243218
DT651132
74242899
DT650813
101384764
EB814428
91054750
EB165168
71440426
DR821476
78121780
DV540164
78103550
DV521978
86469794
DY235664
91877777
EB407734
67014441
CO443190
76924794
DV170130
76021236
DT948406
71446161
DR827211
78110960
DV529358
78074736
DV503170
71428043
DR809093
86469052
DY235422
71440425
DR821475
78121779
DV540163
78104653
DV523071
37400920
CF637820
78074198
DV502632
71449719
DR830769
Solanum lycopersicum
Tomato
58213736
BP877213
7333245
AW621598
4386685
AI482761
Unigene SGN-U223239
Sequence described in this patent
from Sol Genomics Network
application
Lactuca sativa
Lettuce
Sequence described in this patent
application
Vitis vinifera
Grape vine
Sequence described in this patent
application
Spinacia oleracea
Spinach
Sequence described in this patent
application
Cucumis sativus
Cucumber
Sequence described in this patent
application
A GI number (genInfo identifier, sometimes written in lower case, “gi”) is a unique integer which identifies a particular sequence. The GI number is a series of digits that are assigned consecutively to each sequence record processed by NCBI. The GI number will thus change every time the sequence changes. The NCBI assigns GI numbers to all sequences processed into Entrez, including nucleotide sequences from DDBJ/EMBL/GenBank, protein sequences from SWISS-PROT, PIR and many others. The GI number thus provides a unique sequence identifier which is independent of the database source that specifies an exact sequence. If a sequence in GenBank is modified, even by a single base pair, a new GI number is assigned to the updated sequence. The accession number stays the same. The GI number is always stable and retrievable. Thus, the reference to GI numbers in the table provides a clear and unambiguous identification of the corresponding sequence.
[0000]
TABLE 3
Primer sequences on insertion/deletion (INDEL, size difference indicated in brackets)
markers and cleaved amplified polymorphics sequences (CAP, polymorphic restriction
site indicated in brackets) used in the mapping of the DMR1 locus.
Primer name: BAC
Forward
SEQ
Reverse
SEQ
TYPE
GI number of
and/or TAIR At code
primer sequence
ID NO:
primer sequence
ID NO:
(size/enzyme)
TAIR At code
T24112
AATCCAAATTTCTT
12
AAACGAAGAGTGAC
13
INDEL
18398180
(At2g16670)
GCGAGAACACA
14
AATGGTTGGAG
15
(33)
F5J6
CCGTCAGATCAGTC
16
CAGAAGCTGATGAT
17
INDEL
23506018
(AT2g17370-80)
CTCATCTTGTT
18
CGTGGAAAGTA
19
(30)
30679966
F6P23
CGGTTTCATGTCGA
20
AAGAAGAGAACTGC
21
INDEL
22325728
(AT2g17060)
GGAAGATCATA
22
GTCAACCTTCC
23
(37)
T23A1
TCCTTCCATGTCCG
24
AACAAATTTGCTTC
25
INDEL
42570808
(AT2g17220-30)
AAACCA
26
CAGCCTTT
27
(26)
AT2g17190
GAATAGAGGTTGAT
28
CTCTTGTATGTTTT
29
CAP
30679898
GGAAATCAAGA
30
ACTGGGCTGAT
31
(MseI)
AT2g17200
CCTCTCCACCCATT
32
CGATCCATTTCGTC
33
CAP
30679902
TCTAATTTCG
34
AAGCAATCTAC
35
(MboII)
AT2g17270
GATGCAGCTAAATT
36
ACGAAAATATCAAA
37
CAP
30679927
ATCAGTGTGAA
38
AAGCTCCTTC
39
(NlaIII)
AT2g17300-05
AGGTAGGATGGTAT
40
GCATGTTTTCTCTA
41
CAP
30679937
TATGTTTGAACT
42
AGCGATAGAAG
43
(EcoRI)
22325732
AT2g17310
ATGGGTAACGAAAG
44
CACATGTATAAGGT
45
CAP
42569097
AGAGGATTAGT
46
CTTCCCATAGA
47
(MseI)
AT2g17360
CCAACAAGTATCCT
48
CCACATCAAACTTA
49
CAP
30679959
CTTTTGTTGTT
50
ATGAACTCCAC
51
(MaeIII)
[0000]
TABLE 4
Primer sequences used for amplifying and sequencing of eight candidate DMR1
genes for which the TAIR and GI codes are indicated
Primer name
Primer sequence
SEQ ID NO:
TAIR codes
GI codes
MvD17230_F
TTCCCGAAGTGTACATTAAAAGCTC
52
At2g17230
30679913
MvD17230_R
TATGTCATCCCCAAGAGAAGAAGAC
53
At2g17230
30679913
MvD17240_F
CAATAAAAGCCTTTAAAAGCCCACT
54
At2g17240
30679916
MvD17240_R
TAGCTTCTGAAACTGTGGCATTACA
55
At2g17240
30679916
MvD17250_1F
CATGATTTGAGGGGTATATCCAAAA
56
At2g17250
22325730
MvD17250_1R
GGAGGTGGGATTTGAGATAAAACTT
57
At2g17250
22325730
MvD17250_2F
TAGCCTAGAACTCTCTGTTCGCAAG
58
At2g17250
22325730
MvD17250_2R
CATTATTTTGCGTAGTTGTGAGTGG
59
At2g17250
22325730
MvD17250_3F
CGAAGAAATCCTACAATCAACCATC
60
At2g17250
22325730
MvD17250_3R
TCTCACAATTCCCATCTCTTACTCC
61
At2g17250
22325730
MvD17260_1F
TTACTCATTTGGGTGAACAGAACAA
62
At2g17260
30679922
MvD17260_1R
ATCATCCCTAATCTCTCTGCTTCCT
63
At2g17260
30679922
MvD17260_2F
GATTAAGATACGGGGAATGGAGTCT
64
At2g17260
30679922
MvD17260_2R
ATGCAGACAAATAAGATGGCTCTTG
65
At2g17260
30679922
MvD17260_3F
GTTGTTGCTCCTGTCACAAGACTTA
66
At2g17260
30679922
MvD17260_3R
GAACAAAGACGAAGCCTTTAAACAA
67
At2g17260
30679922
MvD17265_F
GAGGACTGCATCTAGAAGACCCATA
68
At2g17265
18398362
MvD17265_R
TGGGCTCTCAACTATAAAGTTTGCT
69
At2g17265
18398362
MvD17270_F1
TAACGGTAAAGCAACGAATCTATCC
70
At2g17270
30679927
MvD17270_R1
TCAAACTGATAACGAGAGACGTTGA
71
At2g17270
30679927
MvD17270_F2
TTGCGTTCGTTTTTGAGTCTTTTAT
72
At2g17270
30679927
MvD17270_R2
AAACCAGACTCATTCCTTTGACATC
73
At2g17270
30679927
MvD17280_F1
TTTAGGATCTCTGCCTTTTCTCAAC
74
At2g17280
42569096
MvD17280_R1
GAGAAATCAATAGCGGGAAAGAGAG
75
At2g17280
42569096
MvD17280_F2
GCTTAAATAGTCCTCCTTTCCTTGC
76
At2g17280
42569096
MvD17280_R2
TCTGCTGGTTCTCATGTTGATAGAG
77
At2g17280
42569096
MvD17290_F1
CTCTCCTTCATCATTTCACAAATCC
78
At2g17290
30679934
MvD17290_R1
TTCCTCTCGCTGTAATGACCTCTAT
79
At2g17290
30679934
MvD17290_F2
TGCCACAGGTGTTGACTATGC
80
At2g17290
30679934
MvD17290_R2
TGCTCTTAAACCCGCAATCTC
81
At2g17290
30679934
MvD17290_F3
GAAGATGGCTTTAAAGGTCAGTTTGT
82
At2g17290
30679934
MvD17290_R3
AGCAACAACAACTAAAAGGTGGAAG
83
At2g17290
30679934
|
The present invention relates to a plant, which is resistant to a pathogen of viral, bacterial, fungal or oomycete origin, wherein the plant has an increased homoserine level as compared to a plant that is not resistant to the said pathogen, in particular organisms of the phylum Oomycota. The invention further relates to a method for obtaining a plant, which is resistant to a pathogen of viral, bacterial, fungal or oomycete origin, comprising increasing the endogenous homoserine level in the plant.
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CROSS REFERENCE TO RELATED APPLICATION
The present application claims benefit of U.S. Ser. No. 60/642,058 filed on Jan. 7, 2005 which is incorporated by reference herein in its entirety.
FIELD OF THE INVENTION
The invention pertains to heteroaromatic compounds that serve as effective phosphodiesterase (PDE) inhibitors. The invention also relates to compounds which are selective inhibitors of PDE10. The invention further relates to intermediates for preparation of such compounds; pharmaceutical compositions comprising such compounds; and the use of such compounds in methods for treating certain central nervous system (CNS) or other disorders. The invention relates also to methods for treating neurodegenerative and psychiatric disorders, for example psychosis and disorders comprising deficient cognition as a symptom.
BACKGROUND OF INVENTION
Phosphodiesterases (PDEs) are a class of intracellular enzymes involved in the hydrolysis of the nucleotides cyclic adenosine monophosphate (cAMP) and cyclic guanosine monophosphates (cGMP) into their respective nucleotide monophosphates. The cyclic nucleotides cAMP and cGMP are synthesized by adenylyl and guanylyl cyclases, respectively, and serve as secondary messengers in several cellular pathways.
The cAMP and cGMP function as intracellular second messengers regulating a vast array of intracellular processes particularly in neurons of the central nervous system. In neurons, this includes the activation of cAMP and cGMP-dependent kinases and subsequent phosphorylation of proteins involved in acute regulation of synaptic transmission as well as in neuronal differentiation and survival. The complexity of cyclic nucleotide signaling is indicated by the molecular diversity of the enzymes involved in the synthesis and degradation of cAMP and cGMP. There are at least ten families of adenylyl cyclases, two of guanylyl cyclases, and eleven of phosphodiesterases. Furthermore, different types of neurons are known to express multiple isozymes of each of these classes, and there is good evidence for compartmentalization and specificity of function for different isozymes within a given neuron.
A principal mechanism for regulating cyclic nucleotide signaling is by phosphodiesterase-catalyzed cyclic nucleotide catabolism. There are 11 known families of PDEs encoded by 21 different genes. Each gene typically yields multiple splice variants that further contribute to the isozyme diversity. The PDE families are distinguished functionally based on cyclic nucleotide substrate specificity, mechanism(s) of regulation, and sensitivity to inhibitors. Furthermore, PDEs are differentially expressed throughout the organism, including in the central nervous system. As a result of these distinct enzymatic activities and localization, different PDEs' isozymes can serve distinct physiological functions. Furthermore, compounds that can selectively inhibit distinct PDE families or isozymes may offer particular therapeutic effects, fewer side effects, or both.
PDE10 is identified as a unique family based on primary amino acid sequence and distinct enzymatic activity. Homology screening of EST databases revealed mouse PDE10A as the first member of the PDE10 family of PDEs (Fujishige et al., J. Biol. Chem. 274:18438-18445, 1999; Loughney, K. et al., Gene 234:109-117, 1999). The murine homologue has also been cloned (Soderling, S. et al., Proc. Natl. Acad. Sci. USA 96:7071-7076, 1999)and N-terminal splice variants of both the rat and human genes have been identified (Kotera, J. et al., Biochem. Biophys. Res. Comm. 261:551-557, 1999; Fujishige, K. et al., Eur. J. Biochem. 266:1118-1127, 1999). There is a high degree of homology across species. The mouse PDE10A1 is a 779 amino acid protein that hydrolyzes both cAMP and cGMP to AMP and GMP, respectively. The affinity of PDE10 for cAMP (Km=0.05 μM) is higher than for cGMP (Km=3 μM). However, the approximately 5-fold greater Vmax for cGMP over cAMP has lead to the suggestion that PDE10 is a unique cAMP-inhibited cGMPase (Fujishige et al., J. Biol. Chem. 274:18438-18445, 1999).
The PDE 10 family of polypeptides shows a lower degree of sequence homology as compared to previously identified PDE families and has been shown to be insensitive to certain inhibitors that are known to be specific for other PDE families. U.S. Pat. No. 6,350,603, incorporated herein by reference.
PDE10 also is uniquely localized in mammals relative to other PDE families. mRNA for PDE10 is highly expressed only in testis and brain (Fujishige, K. et al., Eur J Biochem. 266:1118-1127, 1999; Soderling, S. et al., Proc. Natl. Acad. Sci. 96:7071-7076, 1999; Loughney, K. et al., Gene 234:109-117, 1999). These initial studies indicated that within the brain PDE10 expression is highest in the striatum (caudate and putamen), n. accumbens, and olfactory tubercle. More recently, a detailed analysis has been made of the expression pattern in rodent brain of PDE10 mRNA (Seeger, T. F. et al., Abst. Soc. Neurosci. 26:345.10, 2000) and PDE10 protein (Menniti, F. S., Stick, C. A., Seeger, T. F., and Ryan, A. M., Immunohistochemical localization of PDE10 in the rat brain. William Harvey Research Conference ‘Phosphodiesterase in Health and Disease’, Porto, Portugal, Dec. 5-7, 2001).
A variety of therapeutic uses for PDE inhibitors has been reported including obtrusive lung disease, allergies, hypertension, angina, congestive heart failure, depression and erectile dysfunction (WO 01/41807 A2, incorporated herein by reference).
The use of selected benzimidazole and related heterocyclic compounds in the treatment of ischemic heart conditions has been disclosed based upon inhibition of PDE associated cGMP activity. U.S. Pat. No. 5,693,652, incorporated herein by reference.
United States Patent Application Publication No. 2003/0032579 discloses a method for treating certain neurologic and psychiatric disorders with the selective PDE10 inhibitor papaverine. In particular, the method relates to psychotic disorders such as schizophrenia, delusional disorders and drug-induced psychosis; to anxiety disorders such as panic and obsessive-compulsive disorder; and to movement disorders including Parkinson's disease and Huntington's disease.
SUMMARY OF THE INVENTION
The present invention provides for compounds of formula I or pharmaceutical salts thereof,
wherein Z is
R 1 is each independently selected from a group consisting of hydrogen, halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 1 to C 8 haloalkyl, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, 4 to 7 membered heterocycloalkyl, C 1 to C 8 alkylthio, —NR 3 R 3 , —O—CF 3 , —S(O) n —R 3 , C(O)—NR 3 R 3 , and C 1 to C 8 alkyl substituted with a heteroatom wherein the heteroatom is selected from a group consisting of nitrogen, oxygen and sulfur and wherein the heteroatom may be further substituted with a substituent selected from a group consisting of hydrogen, C 1 to C 8 alkyl, C 3 to C 8 cycloalkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, and C 1 to C 8 haloalkyl;
each R 3 is independently selected from a group consisting of hydrogen, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 haloalkyl, C 3 to C 8 cycloalkyl;
R 2 is selected from the group consisting of hydrogen, C 1 to C 8 alkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 haloalkyl and C 3 to C 8 cycloalkyl;
HET 1 is selected from a group consisting of a monocyclic heteroaryl and a bicyclic heteroaryl, wherein the monocyclic and bicyclic heteroaryl may be optionally substituted with at least one R 4 and;
R 4 is selected from a group consisting of halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 1 to C 8 alkylthio, and C 1 to C 8 alkyl substituted with a substituent is selected from the group consisting of —OR 8 , —NR 8 R 8 , and —SR 8 , wherein R 8 is independently selected from the group consisting of hydrogen and C 1 to C 8 alkyl
HET 2 is a monocyclic or bicyclic heteroaryl, wherein the monocyclic and bicyclic heteroaryl optionally substituted with at least one R 5 , with the proviso that HET 2 is not tetrazole;
R 5 is independently selected from a group consisting of halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 1 to C 8 alkylthio, —NR 7 R 7 and C 1 to C 8 haloalkyl;
B 1 and B 2 are adjacent atoms in Het 1 which are independently selected from a group consisting of carbon and nitrogen;
bond j is a covalent bond between Z and B 2 ;
bond k is a covalent bond in Het 1 between B 1 and B 2 ;
X and X 1 are each independently selected from the group consisting of oxygen, sulfur, C(R 2 ) 2 and NR 2 ; provided that at least one of X or X 1 is carbon;
Y is selected from a group consisting of carbon and nitrogen, provided that when Y is carbon it is substituted with R 6 ;
wherein each R 6 is independently selected from a group consisting of hydrogen, halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 1 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 1 to C 8 alkylthio, C 1 to C 8 haloalkyl, —NR 7 R 7 , —O—CF 3 , —S(O)m-R 7 , and C(O)—NR 7 R 7 , C 1 to C 8 alkyl substituted with a heteroatom wherein the heteroatom is selected from a group consisting of nitrogen, oxygen and sulfur and wherein the heteroatom may be further substituted with a substituent selected from the group consisting of hydrogen, C 1 to C 8 alkyl, C 3 to C 8 cycloalkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl and C 1 to C 8 haloalkyl;
wherein each R 7 is independently selected from the group consisting of hydrogen and C 1 -C 8 alkyl; p is 1, 2 or 3; n is 0, 1 or 2; and m is 0, 1 or 2.
In another embodiment, the present invention provides for compounds of formula I or pharmaceutical salts thereof;
wherein Z is
R 1 is each independently selected from a group consisting of hydrogen, halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 1 to C 8 haloalkyl, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, 4 to 7 membered heterocycloalkyl, C 1 to C 8 alkylthio, —NR 3 R 3 , —O—CF 3 , —S(O) n —R 3 , C(O)—NR 3 R 3 , and C 1 to C 8 alkyl substituted with a heteroatom wherein the heteroatom is selected from a group consisting of nitrogen, oxygen and sulfur and wherein the heteroatom may be further substituted with a substituent selected from a group consisting of hydrogen, C 1 to C 8 alkyl, C 3 to C 8 cycloalkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, and C 1 to C 8 haloalkyl;
each R 3 is independently selected from a group consisting of hydrogen, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 haloalkyl, C 3 to C 8 cycloalkyl;
R 2 is selected from the group consisting of hydrogen, C 1 to C 8 alkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl C 2 to C 8 alkenyl, C 1 to C 8 haloalkyl and C 3 to C 8 cycloalkyl;
HET 1 is selected from a group consisting of a monocyclic heteroaryl and a bicyclic heteroaryl, wherein the monocyclic and bicyclic heteroaryl may be optionally substituted with at least one R 4 ;
R 4 is selected from a group consisting of C 1 to C 8 haloalkyl;
HET 2 is a monocyclic or bicyclic heteroaryl, wherein the monocyclic and bicyclic heteroaryl and may be substituted with at least one R 5 ;
R 5 is independently selected from a group consisting of halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 3 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 1 to C 8 alkylthio, —NR 7 R 7 , and C 1 to C 8 haloalkyl;
B 1 and B 2 are adjacent atoms in Het 1 which are independently selected from a group consisting of carbon and nitrogen;
bond j is a covalent bond between Z and B 2 ;
bond k is a bond in Het 1 between B 1 and B 2 ;
X and X 1 are each independently selected from the group consisting of oxygen, sulfur, C(R 2 ) 2 and NR 2 , provided that at least one of X or X 1 is carbon;
Y is selected from a group consisting of carbon and nitrogen, provided that when Y is carbon it is substituted with R 6 ;
wherein each R 6 is independently selected from a group consisting of hydrogen, halogen, hydroxyl, cyano, C 1 to C 8 alkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, C 1 to C 8 alkoxy, C 1 to C 8 cycloalkyl, C 3 to C 8 cycloalkyl-C 1 to C 8 alkyl, C 1 to C 8 alkylthio, C 1 to C 8 haloalkyl, NR 7 R 7 —O—CF 3 , —S(O)m-R 7 , and C(O)—NR 7 R 7 . C 1 to C 8 alkyl substituted with a heteroatom wherein the heteroatom is selected from a group consisting of nitrogen, oxygen and sulfur and wherein the heteroatom may be further substituted with a substituent selected from the group consisting of hydrogen, C 1 to C 8 alkyl, C 3 to C 8 cycloalkyl, C 2 to C 8 alkenyl, C 2 to C 8 alkynyl, and C 1 to C 8 haloalkyl;
wherein each R 7 is independently selected from the group consisting of hydrogen and C 1 -C 8 alkyl; p is 1, 2 or 3; n is 0, 1 or 2 and m is 0, 1 or 2.
In one aspect of the present invention, Y is selected from a group consisting of carbon and nitrogen, provided that not more than one Y is nitrogen.
In another aspect of the present invention, X 1 is carbon and X is oxygen.
In another aspect of the present invention all Y's are carbon (i.e., the heteroaryl is quinoline).
The present invention also provides compounds of formula I or pharmaceutical salts thereof, wherein HET 1 is a 5 membered heteroaryl group. Preferably, HET 1 is selected from a group consisting of pyrazole, isoxazole, triazole, oxazole, thiazole and imidazole.
The present invention also provides subgenera providing for number of ring members for HET 2 of formula I wherein HET 2 is selected from a group consisting of 4-pyridyl, 4-pyridazine and isoxazole. More preferably, HET 2 is 4-pyridyl.
In a preferred embodiment, the invention is directed to a compound of formula I(a)-I(k):
wherein j, k, Z HET 2 and R 4 are as defined above. More preferably, the compounds of formula I have the following general structure:
Most preferably, the compounds of formula I have the following general structure:
In another aspect, for the above compounds of Formula I, HET 1 is not tetrazole.
Compounds of the Formula I may have optical centers and therefore may occur in different enantiomeric and diastereomeric configurations. The present invention includes all enantiomers, diastereomers, and other stereoisomers of such compounds of the Formula I, as well as racemic compounds and racemic mixtures and other mixtures of stereoisomers thereof.
Pharmaceutically acceptable salts of the compounds of Formula I include the acid addition and base salts thereof.
Suitable acid addition salts are formed from acids which form non-toxic salts. Examples include, but are not limited to, the acetate, adipate, aspartate, benzoate, besylate, bicarbonate/carbonate, bisulphate/sulphate, borate, camsylate, citrate, cyclamate, edisylate, esylate, formate, fumarate, gluceptate, gluconate, glucuronate, hexafluorophosphate, hibenzate, hydrochloride/chloride, hydrobromide/bromide, hydroiodide/iodide, isethionate, lactate, malate, maleate, malonate, mandelates mesylate, methylsulphate, naphthylate, 2-napsylate, nicotinate, nitrate, orotate, oxalate, palmitate, pamoate, phosphate/hydrogen phosphate/dihydrogen phosphate, pyroglutamate, salicylate, saccharate, stearate, succinate, sulfonate, stannate, tartrate, tosylate, trifluoroacetate and xinofoate salts.
Suitable base salts are formed from bases which form non-toxic salts. Examples include, but are not limited to, the aluminium, arginine, benzathine, calcium, choline, diethylamine, diolamine, glycine, lysine, magnesium, meglumine, olamine, potassium, sodium, tromethamine and zinc salts.
Hemisalts of acids and bases may also be formed, for example, hemisulphate and hemicalcium salts.
For a review on suitable salts, see Handbook of Pharmaceutical Salts: Properties, Selection, and Use by Stahl and Wermuth (Wiley-VCH, 2002).
Pharmaceutically acceptable salts of compounds of Formula I may be prepared by one or more of three methods:
(i) by reacting the compound of Formula I with the desired acid or base;
(ii) by removing an acid- or base-labile protecting group from a suitable precursor of the compound of Formula I or by ring-opening a suitable cyclic precursor, for example, a lactone or lactam, using the desired acid or base; or
(iii) by converting one salt of the compound of Formula I to another by reaction with an appropriate acid or base or by means of a suitable ion exchange column.
All three reactions are typically carried out in solution. The resulting salt may precipitate out and be collected by filtration or may be recovered by evaporation of the solvent. The degree of ionization in the resulting salt may vary from completely ionised to almost non-ionised.
The compounds of the invention may exist in a continuum of solid states ranging from fully amorphous to fully crystalline. The term ‘amorphous’ refers to a state in which the material lacks long range order at the molecular level and, depending upon temperature, may exhibit the physical properties of a solid or a liquid. Typically such materials do not give distinctive X-ray diffraction patterns and, while exhibiting the properties of a solid, are more formally described as a liquid. Upon heating, a change from solid to liquid properties occurs which is characterised by a change of state, typically second order (‘glass transition’). The term ‘crystalline’ refers to a solid phase in which the material has a regular ordered internal structure at the molecular level and gives a distinctive X-ray diffraction pattern with defined peaks. Such materials when heated sufficiently will also exhibit the properties of a liquid, but the change from solid to liquid is characterised by a phase change, typically first order (‘melting point’).
The compounds of the invention may also exist in unsolvated and solvated forms. The term ‘solvate’ is used herein to describe a molecular complex comprising the compound of the invention and one or more pharmaceutically acceptable solvent molecules, for example, ethanol. The term ‘hydrate’ is employed when said solvent is water.
A currently accepted classification system for organic hydrates is one that defines isolated site, channel, or metal-ion coordinated hydrates—see Polymorphism in Pharmaceutical Solids by K. R. Morris (Ed. H. G. Brittain, Marcel Dekker, 1995). Isolated site hydrates are ones in which the water molecules are isolated from direct contact with each other by intervening organic molecules. In channel hydrates, the water molecules lie in lattice channels where they are next to other water molecules. In metal-ion coordinated hydrates, the water molecules are bonded to the metal iron.
When the solvent or water is tightly bound, the complex will have a well-defined stoichiometry independent of humidity. When, however, the solvent or water is weakly bound, as in channel solvates and hygroscopic compounds, the water/solvent content will be dependent on humidity and drying conditions. In such cases, non-stoichiometry will be the norm.
The compounds of the invention may also exist in a mesomorphic state (mesophase or liquid crystal) when subjected to suitable conditions. The mesomorphic state is intermediate between the true crystalline state and the true liquid state (either melt or solution). Mesomorphism arising as the result of a change in temperature is described as ‘thermotropic’ and that resulting from the addition of a second component, such as water or another solvent, is described as ‘lyotropic’. Compounds that have the potential to form lyotropic mesophases are described as ‘amphiphilic’ and consist of molecules which possess an ionic (such as —COO − Na + , —COO − K + , or —SO 3 − Na + ) or non-ionic (such as —N − N + (CH 3 ) 3 ) polar head group. For more information, see Crystals and the Polarizing Microscope by N. H. Hartshorne and A. Stuart, 4 th Edition (Edward Arnold, 1970).
Hereinafter all references to compounds of Formula I include references to salts, solvates, multi-component complexes and liquid crystals thereof and to solvates, multi-component complexes and liquid crystals of salts thereof.
The compounds of the invention include compounds of Formula I as hereinbefore defined, including all polymorphs and crystal habits thereof, prodrugs and isomers thereof (including optical, geometric and tautomeric isomers) as hereinafter defined and isotopically-labeled compounds of Formula I.
As indicated, so-called ‘prodrugs’ of the compounds of Formula I are also within the scope of the invention. Thus certain derivatives of compounds of Formula I which may have little or no pharmacological activity themselves can, when administered into or onto the body, be converted into compounds of Formula I having the desired activity, for example, by hydrolytic cleavage. Such derivatives are referred to as ‘prodrugs’. Further information on the use of prodrugs may be found in Pro-drugs as Novel Delivery Systems, Vol. 14, ACS Symposium Series (T. Higuchi and W. Stella) and Bioreversible Carriers in Drug Design, Pergamon Press, 1987 (Ed. E. B. Roche, American Pharmaceutical Association).
Prodrugs in accordance with the invention can, for example, be produced by replacing appropriate functionalities present in the compounds of Formula I with certain moieties known to those skilled in the art as ‘pro-moieties’ as described, for example, in Design of Prodrugs by H. Bundgaard (Elsevier, 1985).
Some examples of prodrugs in accordance with the invention include, but are not limited to,
(i) where the compound of Formula I contains a carboxylic acid functionality (—COOH), an ester thereof, for example, a compound wherein the hydrogen of the carboxylic acid functionality of the compound of Formula (I) is replaced by (C 1 -C 8 )alkyl;
(ii) where the compound of Formula I contains an alcohol functionality (—OH), an ether thereof, for example, a compound wherein the hydrogen of the alcohol functionality of the compound of Formula I is replaced by (C 1 -C 6 )alkanoyloxymethyl; and
(iii) where the compound of Formula I contains a primary or secondary amino functionality (—NH 2 or —NHR where R≠H), an amide thereof, for example, a compound wherein, as the case may be, one or both hydrogens of the amino functionality of the compound of Formula I is/are replaced by (C 1 -C 10 )alkanoyl.
Further examples of replacement groups in accordance with the foregoing examples and examples of other prodrug types may be found in the aforementioned references.
Moreover, certain compounds of Formula I may themselves act as prodrugs of other compounds of Formula I.
Also included within the scope of the invention are metabolites of compounds of Formula I, that is, compounds formed in vivo upon administration of the drug. Some examples of metabolites in accordance with the invention include, but are not limited to,
(i) where the compound of Formula I contains a methyl group, an hydroxymethyl derivative thereof (—CH 3 ->—CH 2 OH):
(ii) where the compound of Formula I contains an alkoxy group, an hydroxy derivative thereof (—OR->—OH);
(iii) where the compound of Formula I contains a tertiary amino group, a secondary amino derivative thereof (—NR 1 R 2 ->—NHR 1 or —NHR 2 );
(iv) where the compound of Formula I contains a secondary amino group, a primary derivative thereof (—NHR 1 ->—NH 2 );
(v) where the compound of Formula I contains a phenyl moiety, a phenol derivative thereof (-Ph->-PhOH); and
(vi) where the compound of Formula I contains an amide group, a carboxylic acid derivative thereof (—CONH 2 ->COOH);
(vii) where the compound contains an aromatic nitrogen atom or an tetrtiary aliphatic amine function, an N-oxide derivative thereof.
Compounds of Formual I having a nitrogen atom in a tertiary amine functional group may be further substituted with oxygen (i.e., an N-oxide);
Compounds of Formula I containing one or more asymmetric carbon atoms can exist as two or more stereoisomers. Where a compound of Formula I contains an alkenyl or alkenylene group, geometric cis/trans (or Z/E) isomers are possible. Where structural isomers are interconvertible via a low energy barrier, tautomeric isomerism (‘tautomerism’) can occur. This can take the form of proton tautomerism in compounds of Formula I containing, for example, an imino, keto, or oxime group, or so-called valence tautomerism in compounds that contain an aromatic moiety. It follows that a single compound may exhibit more than one type of isomerism.
Included within the scope of the present invention are all stereoisomers, geometric isomers and tautomeric forms of the compounds of Formula I, including compounds exhibiting more than one type of isomerism, and mixtures of one or more thereof. Also included are acid addition or base salts wherein the counterion is optically active, for example, d-lactate or l-lysine, or racemic, for example, dl-tartrate or dl-arginine.
Cis/trans isomers may be separated by conventional techniques well known to those skilled in the art, for example, chromatography and fractional crystallisation.
Conventional techniques for the preparation/isolation of individual enantiomers include chiral synthesis from a suitable optically pure precursor or resolution of the racemate (or the racemate of a salt or derivative) using, for example, chiral high pressure liquid chromatography (HPLC).
Alternatively, the racemate (or a racemic precursor) may be reacted with a suitable optically active compound, for example, an alcohol, or, in the case where the compound of Formula I contains an acidic or basic moiety, a base or acid such as 1-phenylethylamine or tartaric acid. The resulting diastereomeric mixture may be separated by chromatography and/or fractional crystallization and one or both of the diastereoisomers converted to the corresponding pure enantiomer(s) by means well known to a skilled person.
Chiral compounds of the invention (and chiral precursors thereof) may be obtained in enantiomerically-enriched form using chromatography, typically HPLC, on an asymmetric resin with a mobile phase consisting of a hydrocarbon, typically heptane or hexane, containing from 0 to 50% by volume of isopropanol, typically from 2% to 20%, and from 0 to 5% by volume of an alkylamine, typically 0.1% diethylamine. Concentration of the eluate affords the enriched mixture.
When any racemate crystallises, crystals of two different types are possible. The first type is the racemic compound (true racemate) referred to above wherein one homogeneous form of crystal is produced containing both enantiomers in equimolar amounts. The second type is the racemic mixture or conglomerate wherein two forms of crystal are produced in equimolar amounts each comprising a single enantiomer.
While both of the crystal forms present in a racemic mixture have identical physical properties, they may have different physical properties compared to the true racemate. Racemic mixtures may be separated by conventional techniques known to those skilled in the art—see, for example, Stereochemistry of Organic Compounds by E. L. Eliel and S. H. Wilen (Wiley, 1994).
The present invention includes all pharmaceutically acceptable isotopically-labelled compounds of Formula I wherein one or more atoms are replaced by atoms having the same atomic number, but an atomic mass or mass number different from the atomic mass or mass number which predominates in nature.
Examples of isotopes suitable for inclusion in the compounds of the invention include, but are not limited to, isotopes of hydrogen, such as 2 H and 3 H, carbon, such as 11 C, 13 C and 14 C, chlorine, such as 36 Cl, fluorine, such as 18 F, iodine, such as 123 I and 125 I, nitrogen, such as 13 N and 15 N, oxygen, such as 15 O, 17 O and 18 O, phosphorus, such as 32 P, and sulphur, such as 35 S.
Certain isotopically-labelled compounds of Formula I, for example, those incorporating a radioactive isotope, are useful in drug and/or substrate tissue distribution studies. The radioactive isotopes tritium, i.e. 3 H, and carbon-14, i.e. 14 C, are particularly useful for this purpose in view of their ease of incorporation and ready means of detection.
Substitution with heavier isotopes such as deuterium, i.e. 2 H, may afford certain therapeutic advantages resulting from greater metabolic stability, for example, increased in vivo half-life or reduced dosage requirements, and hence may be preferred in some circumstances.
Substitution with positron emitting isotopes, such as 11 C, 18 F, 15 O and 13 N, can be useful in Positron Emission Topography (PET) studies for examining substrate receptor occupancy.
Isotopically-labeled compounds of Formula I can generally be prepared by conventional techniques known to those skilled in the art or by processes analogous to those described in the accompanying Examples and Preparations using an appropriate isotopically-labeled reagent in place of the non-labeled reagent previously employed.
Pharmaceutically acceptable solvates in accordance with the invention include those wherein the solvent of crystallization may be isotopically substituted, e.g. D 2 O, d 6 -acetone, d 6 -DMSO.
Specific embodiments of the present invention include the compounds exemplified in the Examples below and their pharmaceutically acceptable salts, complexes, solvates, polymorphs, steroisomers, metabolites, prodrugs, and other derivatives thereof;
This invention also pertains to a pharmaceutical composition for treatment of certain psychotic disorders and conditions such as schizophrenia, delusional disorders and drug induced psychosis; to anxiety disorders such as panic and obsessive-compulsive disorder; and to movement disorders including Parkinson's disease and Huntington's disease, comprising an amount of a compound of formula I effective in inhibiting PDE 10.
In another embodiment, this invention relates to a pharmaceutical composition for treating psychotic disorders and condition such as schizophrenia, delusional disorders and drug induced psychosis; anxiety disorders such as panic and obsessive-compulsive disorder; and movement disorders including Parkinson's disease and Huntington's disease, comprising an amount of a compound of formula I effective in treating said disorder or condition.
Examples of psychotic disorders that can be treated according to the present invention include, but are not limited to, schizophrenia, for example of the paranoid, disorganized, catatonic, undifferentiated, or residual type; schizophreniform disorder; schizoaffective disorder, for example of the delusional type or the depressive type; delusional disorder; substance-induced psychotic disorder, for example psychosis induced by alcohol, amphetamine, cannabis, cocaine, hallucinogens, inhalants, opioids, or phencyclidine; personality disorder of the paranoid type; and personality disorder of the schizoid type.
Examples of movement disorders that can be treated according to the present invention include but are not limited to selected from Huntington's disease and dyskinesia associated with dopamine agonist therapy, Parkinson's disease, restless leg syndrome, and essential tremor.
Other disorders that can be treated according to the present invention are obsessive/compulsive disorders, Tourette's syndrome and other tic disorders.
In another embodiment, this invention relates to a method for treating an anxiety disorder or condition in a mammal which method comprises administering to said mammal an amount of a compound of formula I effective in inhibiting PDE 10.
This invention also provides a method for treating an anxiety disorder or condition in a mammal which method comprises administering to said mammal an amount of a compound of formula I effective in treating said disorder or condition.
Examples of anxiety disorders that can be treated according to the present invention include, but are not limited to, panic disorder; agoraphobia; a specific phobia; social phobia; obsessive-compulsive disorder; post-traumatic stress disorder; acute stress disorder; and generalized anxiety disorder.
This invention further provides a method of treating a drug addiction, for example an alcohol, amphetamine, cocaine, or opiate addiction, in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in treating drug addiction.
This invention also provides a method of treating a drug addiction, for example an alcohol, amphetamine, cocaine, or opiate addiction, in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in inhibiting PDE10.
A “drug addiction”, as used herein, means an abnormal desire for a drug and is generally characterized by motivational disturbances such a compulsion to take the desired drug and episodes of intense drug craving.
This invention further provides a method of treating a disorder comprising as a symptom a deficiency in attention and/or cognition in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in treating said disorder.
This invention also provides a method of treating a disorder or condition comprising as a symptom a deficiency in attention and/or cognition in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in inhibiting PDE10.
This invention also provides a method of treating a disorder or condition comprising as a symptom a deficiency in attention and/or cognition in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in treating said disorder or condition.
The phrase “deficiency in attention and/or cognition” as used herein in “disorder comprising as a symptom a deficiency in attention and/or cognition” refers to a subnormal functioning in one or more cognitive aspects such as memory, intellect, or learning and logic ability, in a particular individual relative to other individuals within the same general age population. “Deficiency in attention and/or cognition” also refers to a reduction in any particular individual's functioning in one or more cognitive aspects, for example as occurs in age-related cognitive decline.
Examples of disorders that comprise as a symptom a deficiency in attention and/or cognition that can be treated according to the present invention are dementia, for example Alzheimer's disease, multi-infarct dementia, alcoholic dementia or other drug-related dementia, dementia associated with intracranial tumors or cerebral trauma, dementia associated with Huntington's disease or Parkinson's disease, or AIDS-related dementia; delirium; amnestic disorder; post-traumatic stress disorder; mental retardation; a learning disorder, for example reading disorder, mathematics disorder, or a disorder of written expression; attention-deficit/hyperactivity disorder; and age-related cognitive decline.
This invention also provides a method of treating a mood disorder or mood episode in a mammal, including a human, comprising administering to said mammal an amount of a compound of formula I effective in treating said disorder or episode.
This invention also provides a method of treating a mood disorder or mood episode in a mammal, including a human, comprising administering to said mammal an amount of a compound of formula I effective in inhibiting PDE10.
Examples of mood disorders and mood episodes that can be treated according to the present invention include, but are not limited to, major depressive episode of the mild, moderate or severe type, a manic or mixed mood episode, a hypomanic mood episode; a depressive episode with atypical features; a depressive episode with melancholic features; a depressive episode with catatonic features; a mood episode with postpartum onset; post-stroke depression; major depressive disorder; dysthymic disorder; minor depressive disorder; premenstrual dysphoric disorder; post-psychotic depressive disorder of schizophrenia; a major depressive disorder superimposed on a psychotic disorder such as delusional disorder or schizophrenia; a bipolar disorder, for example bipolar I disorder, bipolar II disorder, and cyclothymic disorder.
This invention further provides a method of treating a neurodegenerative disorder or condition in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in treating said disorder or condition.
This invention further provides a method of treating a neurodegenerative disorder or condition in a mammal, including a human, which method comprises administering to said mammal an amount of a compound of formula I effective in inhibiting PDE10.
As used herein, and unless otherwise indicated, a “neurodegenerative disorder or condition” refers to a disorder or condition that is caused by the dysfunction and/or death of neurons in the central nervous system. The treatment of these disorders and conditions can be facilitated by administration of an agent which prevents the dysfunction or death of neurons at risk in these disorders or conditions and/or enhances the function of damaged or healthy neurons in such a way as to compensate for the loss of function caused by the dysfunction or death of at-risk neurons. The term “neurotrophic agent” as used herein refers to a substance or agent that has some or all of these properties.
Examples of neurodegenerative disorders and conditions that can be treated according to the present invention include, but are not limited to, Parkinson's disease; Huntington's disease; dementia, for example Alzheimer's disease, multi-infarct dementia, AIDS-related dementia, and Fronto temperal Dementia; neurodegeneration associated with cerebral trauma; neurodegeneration associated with stroke, neurodegeneration associated with cerebral infarct; hypoglycemia-induced neurodegeneration; neurodegeneration associated with epileptic seizure; neurodegeneration associated with neurotoxin poisoning; and multi-system atrophy.
In one embodiment of the present invention, the neurodegenerative disorder or condition comprises neurodegeneration of striatal medium spiny neurons in a mammal, including a human.
In a further embodiment of the present invention, the neurodegenerative disorder or condition is Huntington's disease.
This invention also provides a pharmaceutical composition for treating psychotic disorders, delusional disorders and drug induced psychosis; anxiety disorders, movement disorders, mood disorders, neurodegenerative disorders, obesity, and drug addiction, comprising an amount of a compound of formula I effective in treating said disorder or condition.
This invention also provides a method of treating a disorder selected from psychotic disorders, delusional disorders and drug induced psychosis; anxiety disorders, movement disorders, obesity, mood disorders, and neurodegenerative disorders, which method comprises administering an amount of a compound of formula I effective in treating said disorder.
This invention also provides a method of treating disorders selected from the group consisting of: dementia, Alzheimer's disease, multi-infarct dementia, alcoholic dementia or other drug-related dementia, dementia associated with intracranial tumors or cerebral trauma, dementia associated with Huntington's disease or Parkinson's disease, or AIDS-related dementia; delirium; amnestic disorder; post-traumatic stress disorder; mental retardation; a learning disorder, for example reading disorder, mathematics disorder, or a disorder of written expression; attention-deficit/hyperactivity disorder; age-related cognitive decline, major depressive episode of the mild, moderate or severe type; a manic or mixed mood episode; a hypomanic mood episode; a depressive episode with atypical features; a depressive episode with melancholic features; a depressive episode with catatonic features; a mood episode with postpartum onset; post-stroke depression; major depressive disorder; dysthymic disorder; minor depressive disorder; premenstrual dysphoric disorder; post-psychotic depressive disorder of schizophrenia; a major depressive disorder superimposed on a psychotic disorder comprising a delusional disorder or schizophrenia; a bipolar disorder comprising bipolar I disorder, bipolar II disorder, cyclothymic disorder, Parkinson's disease; Huntington's disease; dementia, Alzheimer's disease, multi-infarct dementia, AIDS-related dementia, Fronto temperal Dementia; neurodegeneration associated with cerebral trauma; neurodegeneration associated with stroke; neurodegeneration associated with cerebral infarct; hypoglycemia-induced neurodegeneration; neurodegeneration associated with epileptic seizure; neurodegeneration associated with neurotoxin poisoning; multi-system atrophy, paranoid, disorganized, catatonic, undifferentiated or residual type; schizophreniform disorder; schizoaffective disorder of the delusional type or the depressive type; delusional disorder; substance-induced psychotic disorder, psychosis induced by alcohol, amphetamine, cannabis, cocaine, hallucinogens, obesity, inhalants, opioids, or phencyclidine; personality disorder of the paranoid type; and personality disorder of the schizoid type, which method comprises administering an amounot of a compound of Formula I effecting in said disorders.
This invention also provides a method of treating psychotic disorders, delusional disorders and drug induced psychosis; anxiety disorders, movement disorders, mood disorders, neurodegenerative disorders, obesity, and drug addiction which method comprises administering an amount of a compound of formula I effective in inhibiting PDE10.
The term “alkyl”, as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, and t-butyl.
The term “alkenyl”, as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon double bond wherein alkyl is as defined above. Examples of alkenyl include, but are not limited to, ethenyl and propenyl.
The term “alkynyl”, as used herein, unless otherwise indicated, includes alkyl moieties having at least one carbon-carbon triple bond wherein alkyl is as defined above. Examples of alkynyl groups include, but are not limited to, ethynyl and 2-propynyl.
The term “alkoxy”, as used herein, unless otherwise indicated, as employed herein alone or as part of another group refers to an alkyl, groups linked to an oxygen atom.
The term “alkylthio” as used herein, unless otherwise indicated, employed herein alone or as part of another group includes any of the above alkyl groups linked through a sulfur atom.
The term “halogen” or “halo” as used herein alone or as part of another group refers to chlorine, bromine, fluorine, and iodine.
The term “haloalkyl” as used herein, unless otherwise indicated, refers to at least one halo group, linked to an alkyl group. Examples, of haloalkyl groups include, but are not limited, to trifluoromethyl, trifluoroethyl, difluoromethyl and fluoromethyl groups.
The term “cycloalkyl”, as used herein, unless otherwise indicated, includes non-aromatic saturated cyclic alkyl moieties wherein alkyl is as defined above. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl.
The term “aryl”, as used herein, unless otherwise indicated, includes an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, such as phenyl, naphthyl, indenyl, and fluorenyl. “Aryl” encompasses fused ring groups wherein at least one ring is aromatic.
The terms “heterocyclic”, “heterocycloalkyl”, and like terms, as used herein, refer to non-aromatic cyclic groups containing one or more heteroatoms, prefereably from one to four heteroatoms, each preferably selected from oxygen, sulfur and nitrogen. The heterocyclic groups of this invention can also include ring systems substituted with one or more oxo moieties. Examples of non-aromatic heterocyclic groups are aziridinyl, azetidinyl, pyrrolidinyl, piperidinyl, azepinyl, piperazinyl, 1,2,3,6-tetrahydropyridinyl, oxiranyl, oxetanyl, tetrahydrofuranyl, tetrahydrothienyl, tetrahydropyranyl, tetrahydrothiopyranyl, morpholino, thiomorpholino, thioxanyl, pyrrolinyl, indolinyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1,3-dioxolanyl, pyrazolinyl, dihydropyranyl, dihydrothienyl, dihydrofuranyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexanyl, 3-azabicyclo[4.1.0]heptanyl, quinolizinyl, quinuclidinyl, 1,4-dioxaspiro[4.5]decyl, 1,4-dioxaspiro[4.4]nonyl, 1,4-dioxaspiro[4.3]octyl, and 1,4-dioxaspiro[4.2]heptyl.
The term “heteroaryl”, as used herein, refers to aromatic groups containing one or more heteroatoms (preferably oxygen, sulfur and nitrogen), preferably from one to four heteroatoms. A multicyclic group containing one or more heteroatoms wherein at least one ring of the group is aromatic is a “heteroaryl” group. The heteroaryl groups of this invention can also include ring systems substituted with one or more oxo moieties. Heteroaryl groups containing a tertiary nitrogen may also be further substituted with oxygen (i.e., an N-oxide). Examples of heteroaryl groups are pyridinyl, pyridazinyl, imidazolyl, pyrimidinyl, pyrazolyl, triazolyl, pyrazinyl, quinolyl, isoquinolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, isothiazolyl, pyrrolyl, indolyl, benzimidazolyl, benzofuranyl, cinnolinyl, indazolyl, indolizinyl, phthalazinyl, triazinyl, isoindolyl, purinyl, oxadiazolyl, thiadiazolyl, furazanyl, benzofurazanyl, benzothiophenyl, benzotriazolyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, dihydroquinolyl, tetrahydroquinolyl, dihydroisoquinolyl, tetrahydroisoquinolyl, benzofuryl, furopyridinyl, pyrolopyrimidinyl, and azaindolyl. For clarity, the term heteroaryl includes the heteroaryl structure in substituent Z in Formula I (i.e., the heteroaryl structure containing Y).
Unless otherwise indicated, the term “one or more” substituents, or “at least one” substituent as used herein, refers to from one to the maximum number of substituents possible based on the number of available bonding sites.
Unless otherwise indicated, all the foregoing groups derived from hydrocarbons may have up to about 1 to about 20 carbon atoms (e.g. C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3 -C 20 cycloalkyl, 3-20 membered heterocycloalkyl; C 6 -C 20 aryl, 5-20 membered heteroaryl, etc.) or 1 to about 15 carbon atoms (e.g., C 1 -C 15 alkyl, C 2 -C 15 alkenyl, C 3 -C 15 cycloalkyl, 3-15 membered heterocycloalkyl, C 6 -C 15 aryl, 5-15 membered heteroaryl, etc.) , or 1 to about 12 carbon atoms, or 1 to about 8 carbon atoms, or 1 to about 6 carbon atoms.
“Neurotoxin poisoning” refers to poisoning caused by a neurotoxin. A neurotoxin is any chemical or substance that can cause neural death and thus neurological damage. An example of a neurotoxin is alcohol, which, when abused by a pregnant female, can result in alcohol poisoning and neurological damage known as Fetal Alcohol Syndrome in a newborn. Other examples of neurotoxins include, but are not limited to, kainic acid, domoic acid, and acromelic acid; certain pesticides, such as DDT; certain insecticides, such as organophosphates; volatile organic solvents such as hexacarbons (e.g. toluene); heavy metals (e.g. lead, mercury, arsenic, and phosphorous); aluminum; certain chemicals used as weapons, such as Agent Orange and Nerve Gas; and neurotoxic antineoplastic agents.
As used herein, the term “selective PDE10 inhibitor” refers to a substance, for example an organic molecule, that effectively inhibits an enzyme from the PDE10 family to a greater extent than enzymes from the PDE 1-9 families or PDE11 family. In one embodiment, a selective PDE10 inhibitor is a substance, for example an organic molecule, having a K i for inhibition of PDE10 that is less than or about one-tenth the K i that the substance has for inhibition of any other PDE enzyme. In other words, the substance inhibits PDE10 activity to the same degree at a concentration of about one-tenth or less than the concentration required for any other PDE enzyme.
In general, a substance is considered to effectively inhibit PDE10 activity if it has a K i of less than or about 10 μM, preferably less than or about 0.1 μM.
A “selective PDE10 inhibitor” can be identified, for example, by comparing the ability of a substance to inhibit PDE10 activity to its ability to inhibit PDE enzymes from the other PDE families. For example, a substance may be assayed for its ability to inhibit PDE10 activity, as well as PDE1A, PDE1B, PDE1C, PDE2, PDE3A, PDE3B, PDE4A, PDE4B, PDE4C, PDE4D, PDE5, PDE6, PDE7, PDE8, PDE9, and PDE11.
The term “treating”, as in “a method of treating a disorder”, refers to reversing, alleviating, or inhibiting the progress of the disorder to which such term applies, or one or more symptoms of the disorder. As used herein, the term also encompasses, depending on the condition of the patient, preventing the disorder, including preventing onset of the disorder or of any symptoms associated therewith, as well as reducing the severity of the disorder or any of its symptoms prior to onset. “Treating” as used herein refers also to preventing a recurrence of a disorder.
For example, “treating schizophrenia, or schizophreniform or schizoaffective disorder” as used herein also encompasses treating one or more symptoms (positive, negative, and other associated features) of said disorders, for example treating, delusions and/or hallucination associated therewith. Other examples of symptoms of schizophrenia and schizophreniform and schizoaffecctive disorders include disorganized speech, affective flattening, alogia, anhedonia, inappropriate affect, dysphoric mood (in the form of, for example, depression, anxiety or anger), and some indications of cognitive dysfunction.
The term “mammal”, as used herein, refers to any member of the class “Mammalia”, including, but not limited to, humans, dogs, and cats.
The compound of the invention may be administered either alone or in combination with pharmaceutically acceptable carriers, in either single or multiple doses. Suitable pharmaceutical carriers include inert solid diluents or fillers, sterile aqueous solutions and various organic solvents. The pharmaceutical compositions formed thereby can then be readily administered in a variety of dosage forms such as tablets, powders, lozenges, liquid preparations, syrups, injectable solutions and the like. These pharmaceutical compositions can optionally contain additional ingredients such as flavorings, binders, excipients and the like. Thus, the compound of the invention may be formulated for oral, buccal, intranasal, parenteral (e.g. intravenous, intramuscular or subcutaneous), transdermal (e.g. patch) or rectal administration, or in a form suitable for administration by inhalation or insufflation.
For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g. pregelatinized maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); fillers (e.g. lactose, microcrystalline cellulose or calcium phosphate); lubricants (e.g. magnesium stearate, talc or silica); disintegrants (e.g. potato starch or sodium starch glycolate); or wetting agents (e.g. sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents (e.g. sorbitol syrup, methyl cellulose or hydrogenated edible fats); emulsifying agents (e.g. lecithin or acacia); non-aqueous vehicles (e.g. almond oil, oily esters or ethyl alcohol); and preservatives (e.g. methyl or propyl p-hydroxybenzoates or sorbic acid).
For buccal administration, the composition may take the form of tablets or lozenges formulated in conventional manner.
The compounds of the invention may be formulated for parenteral administration by injection, including using conventional catheterization techniques or infusion. Formulations for injection may be presented in unit dosage form, e.g. in ampules or in multi-dose containers, with an added preservative. They may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulating agents such as suspending, stabilizing and/or dispersing agents. Alternatively, the active ingredient may be in powder form for reconstitution with a suitable vehicle, e.g. sterile pyrogen-free water, before use.
When a product solution is required, it can be made by dissolving the isolated inclusion complex in water (or other aqueous medium) in an amount sufficient to generate a solution of the required strength for oral or parenteral administration to patients. The compounds may be formulated for fast dispersing dosage forms (fddf), which are designed to release the active ingredient in the oral cavity. These have often been formulated using rapidly soluble gelatin-based matrices. These dosage forms are well known and can be used to deliver a wide range of drugs. Most fast dispersing dosage forms utilize gelatin as a carrier or structure-forming agent. Typically, gelatin is used to give sufficient strength to the dosage form to prevent breakage during removal from packaging, but once placed in the mouth, the gelatin allows immediate dissolution of the dosage form. Alternatively, various starches are used to the same effect.
The compounds of the invention may also be formulated in rectal compositions such as suppositories or retention enemas, e.g. containing conventional suppository bases such as cocoa butter or other glycerides.
For intranasal administration or administration by inhalation, the compound of the invention is conveniently delivered in the form of a solution or suspension from a pump spray container that is squeezed or pumped by the patient or as an aerosol spray presentation from a pressurized container or a nebulizer, with the use of a suitable propellant, e.g. dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. In the case of a pressurized aerosol, the dosage unit may be determined by providing a valve to deliver a metered amount. The pressurized container or nebulizer may contain a solution or suspension of the active compound. Capsules and cartridges (made e.g. from gelatin) for use in an inhaler or insulator may be formulated containing a powder mix of a compound of the invention and a suitable powder base such as lactose or starch.
Aerosol formulations for treatment of the conditions referred to above (e.g. migraine) in the average adult human are preferably arranged so that each metered dose or “puff” of aerosol contains about 20 mg to about 1000 mg of the compound of the invention. The overall daily dose with an aerosol will be within the range of about 100 mg to about 10 mg. Administration may be several times daily, e.g. 2, 3, 4 or 8 times, giving for example, 1, 2 or 3 doses each time.
A proposed daily dose of the compound of the invention for oral, parenteral, rectal or buccal administration to the average adult human for the treatment of the conditions referred to above is from about 0.01 mg to about 2000 mg, preferably from about 0.1 mg to about 200 mg of the active ingredient of formula I per unit dose which could be administered, for example, 1 to 4 times per day.
Assay methods are available to screen a substance for inhibition of cyclic nucleotide hydrolysis by the PDE 10 and the PDEs from other gene families. The cyclic nucleotide substrate concentration used in the assay is 1/3 of the K m concentration, allowing for comparisons of IC 50 values across the different enzymes. PDE activity is measured using a Scintillation Proximity Assay (SPA)-based method as previously described (Fawcett et al., 2000). The effect of PDE inhibitors is determined by assaying a fixed amount of enzyme (PDEs 1-11) in the presence of varying substance concentrations and low substrate, such that the IC 50 approximates the K i (cGMP or cAMP in a 3:1 ratio unlabelled to [ 3 H]-labeled at a concentration of 1/3 Km). ). The final assay volume is made up to 100 μl with assay buffer [50 mM Tris-HCl pH 7.5, 8.3 mM MgCl 2 , 1 mg/ml bovine serum albumin]. Reactions are initiated with enzyme, incubated for 30-60 min at 30° C. to give <30% substrate turnover and terminated with 50 μl yttrium silicate SPA beads (Amersham) (containing 3 mM of the respective unlabelled cyclic nucleotide for PDEs 9 and 11). Plates are re-sealed and shaken for 20 min, after which the beads were allowed to settle for 30 minutes in the dark and then counted on a TopCount plate reader (Packard, Meriden, Conn.). Radioactivity units can be converted to percent activity of an uninhibited control (100%), plotted against inhibitor concentration and inhibitor IC 50 values can be obtained using the “Fit Curve” Microsoft Excel extension.
Using such assay, compounds of the present invention were determined to have an IC 50 for inhibiting PDE10 activity of less than about 10 micromolar.
This invention also pertains to the preparation of compounds of formula I. The present invention also provides for methods for the synthesis compounds of formula I. For example, the present invention provides for a process for forming the compound of formula I, comprising a step of reacting a compound of formula II
with dimethoxymethyl-dimethyl amine and hydrazine or substituted hydrazine (e.g., such as R 20 —NHNH 2 where R 20 is alkyl).
The present invention also provides for a process for forming the compound of formula I, comprising a step of reacting a compound of formula III
with dimethyl oxalate and a hydrazine of formula HET 2 -NHNH 2 .
The present invention also provides for a process for forming the compound of formula I, comprising a step of reacting a compound of formula IV
with dimethoxymethyl-dimethyl amine and hydrazine or substituted hydrazine.
The present invention also provides for a process for forming the compound of formula I, comprising a step of reacting a compound of formula V
with a compound of formula VI
wherein Q is a hydroxyl or a halide.
DETAILED DESCRIPTION OF THE INVENTION
Scheme 1 depicts the preparation of the pyrazole class of compounds of this invention. Alkylation of a substituted phenol with 2-methyl chloro quinoline provides the desired ether. Hydrolysis of the ester and treatment with thionyl chloride provides the desired acid chloride. Addition of O,N-dimethyl hydroxyl amine hydrochloride provides the Weinreb amide for coupling (Weinreb et al, Tet Lett., 1981, 22(39) 3815). Anion generation with 4-picoline and LDA followed by addition of the Weinreb amide affords the ketone. The ketone can then be treated with dimethoxymethyl-dimethyl amine at reflux to form the enaminone intermediate. Treatment with various hydrazines affords the pyrazole analogues. A variety of ratios of the two isomers were obtained. These isomers were separated via, crystallization, Biotage MPLC, preparative TLC or preparative HPLC. This reaction scheme is general for a variety of starting substituted phenols, substituted quinolines and substituted hydrazines.
Alternatively, the substituted pyrazole compounds can be prepared by alkylation of the NH pyrazole. One set of conditions is the utilization of cesium carbonate as the base with an alkyl halide as the electrophile in a solvent such as dimethyl formamide. Some reactions require heating.
As depicted in Scheme 3, a variety of heterocycles can be prepared from the enaminone intermediate. Pyrimidines can be prepared by heating with substituted formamides in the presence of ethanol and sodium ethoxide. Isoxazoles are prepared by heating the enaminone with hydroxyl amine in methanol/acetic acid. Only one isomer in the isoxazole case is formed. By heating with amino pyroles, amino imidazoles or amino triazoles, 6-5 bicyclic systems can be formed.
A variety of 4-pyridyl heterocyclic replacements can be prepared according to scheme 4. Methyl heterocycles such as 3,5-dimethyl isoxazole and methyl pyridazine can be deprotated with lithium diisopropyl amide and added to a Weinreb amide (Weinreb et al, Tet Lett., 1981, 22(39) 3815) to provide the desired ketone. Sequential treatment with dimethoxymethyl-dimethyl amine and a hydrazine provides the heterocyclic pyrazoles. Pyrimidines and isoxazoles can also be prepared as described in Scheme 3.
N-pyridyl pyrazoles can be prepared according to Scheme 5. The starting ketones are prepared by alkylation of the phenol as depicted in Scheme 1. Treatment of the ketone with dimethoxymethyl-dimethyl amine followed by addition of 4-pyridyl hydrazine (see J. Med. Chem. 2002, 45(24) 5397) provides the desired compounds. Other heterocyclic replacements for 4-pyridyl can be prepared by using the requisite hydrazine.
As depicted in Scheme 6, 3-substituted-N-pyridyl pyrazoles can be prepared by literature methods. (see J. Med. Chem. 2004, 47, 2180). Treatment of the acetophenone (prepared according to scheme 1) with sodium methoxide and dimethyl oxalate provides the ester intermediate. Addition of 4-pyridyl hydrazine (see J. Med. Chem. 2002, 45(24) 5397) provides the pyrazole with an ester at the 3-position. This ester can be converted to amides by hydrolysis and coupling with amines. It can be converted to ethers by reduction to the alcohol and alkylation. Amine formation is capable by amide formation followed by reduction or conversion to the aldehyde followed by reductive amination. All of these transformations can be carried out by those skilled in the art of organic chemistry.
The benzyl intermediates can be prepared by the method shown in scheme 1. The benzyl ether can be removed via treatment with hydrogen gas over a palladium catalyst such as palladium on carbon or palladium hydroxide in a variety of solvents. The phenol can then be alkylated using a benzylic chloride in acetone heating with potassium carbonate. Also Mitsunobu chemistry (Hughes, D. L., The Mitsunobu Reaction. Organic Reactions. Vol. 42. 1992, New York. 335-656.) can be applied to couple the phenol with alcohols.
Many benzylic halides or alcohols are commericially available or are known in the literature. General ways to make these intermediates by those skilled in the art are reduction of an ester, acid or aldehyde to form an alcohol. One general procedure is the oxidation of a benylic site with selenium dioxide to provide an aldehyde that is subsequentially reduced with sodium borohydride. Benzylic halide can be formed vial halogenation (see Syn. Comm. 1995, 25(21) 3427-3434).
Triazole analogues can be prepared in many ways. One way is depicted in Scheme 9. Treatment of a hydrazide with dimethyl formamide dimethyl acetal to form an intermediate, which is subsequently treated with an amine or aniline with the addition of heat and acetic acid provides the 1,2,4 triazoles (see Org. Lett, 2004, 6(17), 2969-2971). The regioisomeric triazoles can be prepared by interchanging the functionality of the starting materials.
Other triazole isomers can be prepared according to scheme 10 by starting with the carboxyamides and treating with dimethyl formamide dimethyl acetal followed by the addition of aromatic hydrazines. The regioisomeric triazoles can be prepared by interchanging the functionality of the starting materials.
The inverted ketone isomer can be prepared according to Scheme 11. (Bunting et al. JACS, 1988, 110, 4008.) The starting aldehyde is coupled with a phosphonate to provide the enaminone. The enaminone is hydrolyzed to provide the desired ketone. The ketone can then be utilized according to Scheme 1,2 and 3 to provide the desired compounds
Scheme 12 depicts a method for synthesizing a 4,5-diaryl oxazole. In the illustrated case, 4-benzyloxy-benzaldehyde and 4-methylbenzenesulfinic acid are heated with formamide to generate a substituted formamide as shown. This transformation is known in the literature. [J. Med Chem., 2002, 45, 1697] Dehydration of the formamide in a reaction mediated by POCl3 gives a tosylmethyl isocyanate. This class of compound can be treated with an aldehyde and a base to yield an oxazole. In the illustrated case, the tosylmethylisocyanate is treated with isonicotinaldehyde and potassium carbonate. The product of this reaction is an oxazole possessing a 4-benzyloxyphenyl group at the 4-position of the oxazole ring, and a 4-pyridyl substituent at the 5-position. These substituents can be substituted with other aryl groups simply by utilizing different aryl-aldehydes for steps one and three of the sequence. Cleavage of the benzyloxy group is achieved by the standard method of catalytic hydrogenation, and the resultant phenol is easily alkylated by treatment with an alkyl halide, such as 2-(chloromethyl)quinoline, and cesium fluoride in DMF. The method is not limited to the illustrated case as the relative positions of the phenyl and pyridyl rings can be switched, and said rings may comprise a variety of aryl groups displaying various substitution patterns.
Scheme 13 depicts a method for preparing 4,5-substituted oxazoles possessing alkyl group substitution in the 2-position of the oxazole ring. In the illustrated case, 1-(4-Benzyloxy-phenyl)-2-pyridin-4-yl-ethanone is brominated by treatment with bromine in acetic acid according to traditional methods. The resultant α-bromoketone is then treated with ammonium acetate and sodium acetate in acetic acid, which yields the methyl-substituted oxazole ring as disclosed in the patent literature (WO 9513067). The methyl group can be replaced by other alkyl groups. For example, substitution of ammonium ethanoate, sodium ethanoate, and ethanoic acid acid would yield ethyl group substitution. Cleavage of the benzyloxy group is achieved by the standard method of catalytic hydrogenation, and the resultant phenol is easily alkylated by treatment with an alkyl halide as described above. The method is not limited to the illustrated case as the relative positions of the phenyl and pyridyl rings can be switched, and said rings may comprise a variety of aryl groups displaying various substitution patterns.
Step 1 of Scheme 14 is an imine formation/heterocycle formation. A compound of formula 2A wherein R1 is alkyl, benzyl, or allyl, is condensed with 4-pyridine carboxaldehyde in solvent such as toluene and is heated to reflux with a Dean-Stark apparatus attached to remove water for about 40 hours. After removal of toluene, the crude imine is mixed with tosylmethylisocyanide and a base such as potassium carbonate, in a solvent mixture of 1,2-dimethoxyethane and methanol, and is heated at reflux for about 3 hours to afford 3A.
Step 2 of Scheme 14 is a phenol dealkylation. If R1 is methyl, the dealkylation can be effected with boron tribromide (BBr3) in a non-coordinating solvent such as methylene chloride at about 20-40° C. for about 3-48 hours, where about 24 hours is preferred to yield 4A. If R2 is benzyl, the dealkylation can be effected with in neat trifluoracetic acid with anisole at a temperature of about 75° C. for about 3-48 hours, where about 24 hours is preferred to yield 4A. If R1 is allyl, the dealkylation can be effected with a palladium catalyst, such as dichloropalladium bis(triphenylphosphine) of palladium acetate, where dichloropalladium bis(triphenylphosphine) is preferred, with a reducing agent such as n-butylammonium formate, in a solvent such as tetrahydrofuran, 1,2-dichloroethane, methylene chloride, or an alkanol, where 1,2-dichloroethane is preferred, in a temperature range from about 20° C. to 75° C., to yield 4A.
Step 3 of Scheme 14 is a phenol alkylation. Treatment of 4A with a base such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, or potassium hydride, where cesium carbonate or sodium hydride are preferred, in a solvent such as tetrahydrofuran, 1,2-dimethoxyethane, N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, or dimethylsulfoxide, where dimethylsulfoxide or N,N-dimethylformamide are preferred, at a temperature from about 20° C. to 70° C., where about 23° C. is preferred, for about 3-48 hours, where about 24 hours is preferred, affords 1A.
Step 4 of Scheme 14 is an imidazole deprotonation/electrophilic trapping. Treatment of 3A with a base such as lithium diisopropyl amide or lithium 2,2,6,6-tetramethylpiperidine, where lithium diisopropylamide is preferred, in a solvent such as tetrahydrofuran, at a temperature from about −78° C. to 0° C., where about −20° C. is preferred, for about 5 minutes to 30 minutes, where about 10 minutes is preferred, followed by addition of the desired electrophile R3-1, affords 3B.
Step 5 of Scheme 14 is a phenol dealkylation and uses the same methods as described for Step 2 above to produce 4B.
Step 6 of Scheme 14 is a phenol alkylation and uses the same methods as described for Step 3 above to produce 1B.
Step 1 of Scheme 15 is an acylation of an amine to form an amide. Compound 2A, wherein R1 can be methyl, benzyl, or allyl, is treated with an acid chloride or a carboxylic acid in the presence of a coupling reagent, such as tri-n-propylphosphonic anhydride or dicyclohexyl carbodiimide, where tri-n-propylphosphonic anhydride is preferred, in the presence of a base such as sodium hydroxide, potassium or sodium carbonate, triethylamine, or diisopropylethylamine, where diisopropylethylamine is preferred, in a solvent system such as water/methylene chloride, water/ethyl acetate, ethyl acetate, tetrahydrofuran, or methylene chloride, where ethyl acetate is preferred, at a temperature from about 0° C. to 50° C., where about 20° C. to 30° C. is preferred, to yield 5A.
Step 2 consists of a chlorination to form an iminochloride, reaction with an amine to form an amidine, followed by treatment with acid to form an imidazole. Compound 5A is treated with a chlorinating agent such as PCl 5 /POCl 3 at a temperature of about 120° C. for about 4 hours. The chlorinating agent is removed in vacuo and an excess of 1,1-diethoxy-2-ethylamine in a solvent such as isopropanol is added and the mixture is stirred for about 5-24 hours at about 23° C. The solvent is removed in vacuo and concentrated hydrochloric acid and isopropanol is added and the mixture is heated to about 90° C. for about 24 hours to yield 6A.
Step 3 of Scheme 15 is a phenol dealkylation. If R1 is methyl, the dealkylation can be effected with boron tribromide (BBr3) in a non-coordinating solvent such as methylene chloride at about 20-40° C. for about 3-48 hours, where about 24 hours is preferred to yield 7A. If R2 is benzyl, the dealkylation can be effected with in neat trifluoracetic acid with anisole at a temperature of about 75° C. for about 3-48 hours, where about 24 hours is preferred to yield 7A. If R1 is allyl, the dealkylation can be effected with a palladium catalyst, such as dichloropalladium bis(triphenylphosphine) of palladium acetate, where dichloropalladium bis(triphenylphosphine) is preferred, with a reducing agent such as n-butylammonium formate, in a solvent such as tetrahydrofuran, 1,2-dichloroethane, methylene chloride, or an alkanol, where 1,2-dichloroethane is preferred, in a temperature range from about 20° C. to 75° C., to yield 7A.
Step 4 of Scheme 15 is a phenol alkylation. Treatment of 7A with a base such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, or potassium hydride, where cesium carbonate is preferred, in a solvent such as tetrahydrofuran, 1,2-dimethoxyethane, N,N-dimethylformamide, dimethylacetamide, N-methylpyrrolidinone, or dimethylsulfoxide, where dimethylsulfoxide is preferred, at a temperature from about 20° C. to 70° C., where about 23° C. is preferred, for about 3-48 hours, where about 24 hours is preferred, affords 1C.
The quinolyl benzaldehyde can be coupled with the ketone in the presence of refluxing piperidine to provide the desired olefin. Treatment with hydrazine affords the NH-pyrazole. This can be further elaborated by treatment with sodium hydride and an electrophile such as methyl iodide to provide substituted pyrazoles.
As depicted in scheme 17, the alkyne and iodide can be coupled via a Sonagashira coupling and the methyl ether deprotected with boron tribromide in dichloromethane. Alkylation of the phenol with 2-chloromethylquinoline according to the methods described above provides the penultimate intermediate. Treatment with trimethyl silyl azide in a sealed tube at 70-190° C., preferably about 150° C., for 24-72 h, provides the desired triazole.
General Experimental
Organic solutions were dried with magnesium or sodium sulfate if not otherwise specified. Room temperature is abbreviated as RT. HPLC-MS system 1 consisted of Zorbax Bonus-RP™ 4.6×150 mm column, 1.0 mL/min, solvent A=MeCN, solvent B=0.1% aqueous formic acid, linear gradient of 1:9 A:B to 95:5 A:B over 10 min, using a Hewlett-Packard 1100 HPLC system equipped with diode array and mass detectors. HPLC system 2 used a linear gradient of 3:7 A:B to 95:5 A:B over 15 min. When purification by RP-HPLC is indicated, a Shimadzu preparative HPLC instrument equipped with X-Terra™ 50×50 mm column, solvent A=acetonitrile, solvent B=water, each containing either 0.1% trifluoroacetic acid (“acidic conditions”) or 0.1% concentrated ammonium hydroxide (“basic conditions”), linear gradient of 25%-85% A:B over 10 min.
The following Examples illustrate the present invention. It is to be understood, however, that the invention, as fully described herein and as recited in the claims, is not intended to be limited by the details of the following Examples.
Experimental Procedures
Preparation 1
4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester
To a solution of 2-Chloromethyl quinoline. (2 g, 9.3 mmole) in acetone (47 ml, 0.2M) was added 4-hydroxy benzoic acid methyl ester (1.42 g, 1.0 eq.) and potassium carbonate (3.86 g, 3 eq.). The reaction mixture was heated at 60° C. for 16 h under N 2 atmosphere, cooled to ambient temperature and poured into 1N sodium hydroxide (50 ml)/ethyl acetate (100 ml). The layers were separated and the organic layer dried magnesium sulfate, filtered and concentrated. Biotage MPLC was run using a 5-30% ethyl acetate/hexane gradient on a 40 M column to provide the title compound as a white solid (1.66 g, 61%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.18 (d, J=8.7 Hz, 1 H), 8.07 (d, J=8.3 Hz, 1 H), 7.95 (M, 2H), 7.82 (d, J=7.9 Hz, 1 H), 7.74 (dt, J=7.1, 1.7 Hz, 1 H), 7.62 (d, J=8.3 Hz, 1 H), 7.55 (dt, J=7.9, 1.2 Hz, 1 H), 7.03 (d, J=9.1, 2 H), 5.41 (s, 2 H), 3.84 (s, 3 H); MS: (M + H m/z=294.2).
Preparation 2
4-(Quinolin-2-ylmethoxy)-benzoic acid
To a solution of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester (500 mg, 1.7 mmole) in tetrahydrofuran (8.5 ml) and methanol (3 ml) was added 1N NaOH (3.4 ml, 2 eq.). The reaction mixture was stirred at ambient temperature for 16 h. To the reaction mixture was added 50 ml of brine and the pH was adjusted to 3 with 1N HCl to provide a white precipitate which was filtered and dried to provide the title compound as a white solid (463 mg, 98%). 1 H NMR (400 MHz, DMSO) δ 8.39 (d, J=8.3 Hz, 1 H), 7.99 (m, 2 H), 7.81 (M, 2H), 7.76 (dt, J=8.3, 1.7 Hz, 1 H), 7.64 (d, J=8.3 Hz, 1 H), 7.60 (dt, J=7.9, 1.3 Hz, 1 H), 7.12 (M, 2 H), 5.41 (s, 2 H); MS: (M + H m/z=280.2).
Preparation 3
N-Methoxy-N-methyl4-(quinolin-2-ylmethoxy)-benzamide
To a solution of 4-(Quinolin-2-ylmethoxy)-benzoic acid (25.98 g, 93 mmole) was added 250 ml of thionyl chloride under N 2 . The reaction mixture stirred 3 h and the excess thionyl chloride was removed under vacuum. The acid chloride was dissolved in tetrahydrofuran (450 ml) and triethylamine (50 ml, 4 eq.) was slowly added. O,N-dimethyl hydroxyl amine hydrochloride (27 g, 3 eq.) was added and the reaction stirred 18 h. The reaction mixture was placed on a rotovap to remove the solvent, partitioned between 1N NaOH and methylene chloride, separated, dried magnesium sulfate, filtered and concentrated. The crude product was filtered through silica gel eluting with 30-70% ethyl acetate/hexane to proved the title compound as a brown oil (26.26 g, 87%); 1 H NMR (400 MHz, CDCl 3 ) δ 8.17 (d, J=8.7 Hz, 1 H), 8.06 (d, J=8.3 Hz, 1 H), 7.81 (d, J=8.3 Hz, 1H), 7.67 (m, 3 H), 7.63 (d, J=8.3 Hz, 1 H), 7.52 (m, 1 H), 7.01 (M, 2 H), 5.39 (s, 2 H), 3.52 (s, 3 H) 3.31 (s, 2H); MS: (M + H m/z=323.2).
Preparation 4
2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone
To a solution of Lithium diisopropyl amide (1.0M) in tetrahydrofuran was added 4-picoline dropwise (7.55 ml, 5 eq.) at 0° C. under N 2 . After 30 min the anion was cooled to −78° C. In a separate round bottom flask N-Methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide (5.0, 15.5 mmole) was dissolved in tetrahydrofuran (77 ml, 0.2M) and cooled to −78° C. under N 2 . 1.2 eq. of the 4-picoline anion was added dropwise to the amide solution. After 45 min, 1 eq. more of the 4-picoline anion was added. After an addition 30 min, acetic acid (40 ml) was added dropwise and the reaction was slowly warmed to ambient temperature. The solid product (acetate salt) was filtered and partitioned between saturated sodium bicarbonate and dichloromethane. The layers were separated, dried magnesium sulfate filtered and concentrated to provide the title compound as a tan solid (4.41 g, 80%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.52 (d, J=5.8 Hz, 2 H), 8.19 (d, J=8.7 Hz, 1 H), 8.07 (d, J=8.7 Hz, 1H), 7.93 (m, 2 H), 7.82 (d, J=8.3 Hz, 1 H), 7.75 (m, 1 H), 7.61 (d, J=8.3 Hz, 1 H), 7.54 (dt, J=7.9, 1.0 Hz, 1 H), 7.23 (m, 2 H) 7.07 (m, 2H), 5.42 (s, 2H), 4.19 (s, 2H); MS: (M + H m/z=355.2).
Preparation 5
3-Dimethylamino-2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl}-propenone
To 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone (4.0 g, 11.3 mmole) was added dimethoxymethyl-dimethyl amine (10 ml) and the reaction mixture was heated at reflux for 1 hr. Concentrated to give a quantitative yield of the title compound which was used as is in the next step. LC/MS: RT=1.4 min, MS: (M + H m/z=410.2).
EXAMPLE 1
2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 3-Dimethylamino-2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl}-propenone (9.57 g, 27 mmole) in methanol was added hydrazine hydrate (3.33 g, 40.5 mmole) and the reaction mixture was heated at reflux for 1 h. The solvent was evaporated to yield a white solid. The solid was washed with water and ethyl ether. The solid was recystallized from hot ethanol/ethylacetate (10 ml/g) to give 8.34 g of the title compound (82%). 1 H NMR (400 MHz, DMSO) δ 8.41 (m, 3 H), 8.16 (s, 1 H), 7.97 (m, 2H), 7.86 (s, 1 H), 7.75 (t, J=7.9 Hz, 1 H), 7.68 (d, J=8.3 Hz, 1 H), 7.60 (t, J=7.5 Hz, 1 H), 7.33 (m, 2 H), 7.18 (m, 2 H) 7.15 (d, J=8.3 Hz, 1H), 7.06 (d, J=8.3 Hz, 1H), 5.38 (s, 2H); MS: (M + H m/z=379.2).
EXAMPLE 2
2-[4-(2-Methyl-4-pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline (1.72 g) in ethanol (20 ml) was added methyl hydrazine (3.5 ml, 1.5 eq.) and concentrated sulfuric acid (0.1 ml). The reaction mixture was stirred 1 h at ambient temperature and solvent evaporated. The reaction mixture was partitioned between methylene chloride and saturated sodium bicarbonate. The layers were separated and the organic layer dried magnesium sulfate, filtered and concentrated. Preparative HPLC chromatography provided the title compound (minor isomer) as a white solid (0.30 g, 17%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.31 (d, J=5.4 Hz, 2 H), 8.21 (d, J=8.7 Hz, 1 H), 7.80 (d, J=8.3 Hz, 1H), 7.77 (s, 1 H), 7.66 (m, 3 H), 7.53 (m, 1H), 7.19 (d, J=8.7 Hz, 2 H), 7.11 (d, J=8.7 Hz, 2H), 7.01 (d, J=6.2 Hz, 2H) 5.40 (s, 2H), 3.69 (s, 3H); MS: (M + H m/z=393.3).
EXAMPLE 3
2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline (1.72 g) in ethanol (20 ml) was added methyl hydrazine (3.5 ml, 1.5 eq.) and concentrated sulfuric acid (0.1 ml). The reaction mixture was stirred 1 h at ambient temperature and solvent evaporated. The reaction mixture was partitioned between methylene chloride and saturated sodium bicarbonate. The layers were separated and the organic layer dried magnesium sulfate, filtered and concentrated. Preparative HPLC chromatography provided the title compound (major isomer) as a clear oil (0.97 g, 56%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (d, J=5.0 Hz, 2 H), 8.17 (d, J=8.7 Hz, 1 H), 8.05 (d, J=8.3 Hz, 1H), 7.81 (d, J=7.9 Hz, 1 H), 7.70 (m, 1 H), 7.66 (d, J=8.7 Hz, 1H), 7.54 (s, 1H), 7.53 (m, 1H), 7.37 (d, J=8.7 Hz, 2H) 7.15 (d, J=5.0, 2H), 7.00 (d, J=8.7 Hz, 2H), 5.38 (s, 2H), 3.93 (s, 3H); MS: (M + H m/z=393.3).
EXAMPLE 4
2-[4-(2-Ethyl-4-pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting ethyl hydrazine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.35 (bs, 2H), 8.23 (d, J=8.3 Hz, 1 H), 8.08 (d, J=8.3 Hz, 1 H), 7.85 (d, J=7.4 Hz, 1H), 7.83 (s, 1 H), 7.74 (m, 2 H), 7.57 (t, J=7.9 Hz, 1H), 7.21 (d, J=8.7 Hz, 2 H), 7.14 (d, J=9.1 Hz, 2 H), 7.04 (m, 2H) 5.42 (s, 2H), 4.03 (q, J=7.5 Hz, 2H), 1.36 (t, J=7.5 Hz, 3H); MS: (M + H m/z=407.3).
EXAMPLE 5
2-[4-(1-Ethyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting ethyl hydrazine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.35 (bs, 2H), 8.19 (d, J=8.3 Hz, 1 H), 8.07 (d, J=9.1 Hz, 1 H), 7.82 (d, J=7.9 Hz, 1H), 7.73 (t, J=8.3 Hz, 1H), 7.67 (d, J=8.3 Hz, 2 H), 7.62 (s, 1H), 7.55 (t, J=7.9 Hz, 1 H), 7.37 (d, J=9.1 Hz, 2H), 7.21 (bs, 2 H), 7.01 (d, J=8.7 Hz, 2H) 5.39 (s, 2H), 4.24 (q, J=7.5 Hz, 2H), 1.56 (t, J=7.5 Hz, 3H); MS: (M + H m/z=407.3).
EXAMPLE 6
Dimethyl-(2-{4-pyridin-4-yl-3-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-ethyl)-amine
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting (2-hydrazino-ethyl)-dimethyl-amine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (dd, J=4.6, 1.7, Hz, 2 H), 8.18 (d, J=8.3 Hz, 1 H), 8.06 (d, J=8.3 Hz, 1H), 7.82 (d, J=8.7 Hz, 1 H), 7.71 (m 2H), 7.55 (t, J=7.1 Hz, 1H), 7.38 (d, J=8.7 Hz, 2H), 7.15 (d, J=6.2 Hz, 2H) 7.00 (d, J=8.7 Hz, 2H), 5.38 (s, 2H), 4.25 (t, J=6.6 Hz, 2H), 2.82 (t, J=6.6 Hz, 2H), 2.28 (s, 6H); MS: (M + H m/z=450.4).
EXAMPLE 7
Dimethyl-(2-{4-pyridin-4-yl-5-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-ethyl)-amine
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting (2-hydrazino-ethyl)-dimethyl-amine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.35 (d, J=6.2 Hz, 2 H), 8.22 (d, J=8.3 Hz, 1 H), 8.08 (d, J=8.7 Hz, 1H), 7.85 (m, 2 H), 7.73 (m 2H), 7.57 (t, J=7.1 Hz, 1H), 7.23 (m, 2H), 7.17 (d, J=9.1 Hz, 2H) 7.00 (d, J=6.2 Hz, 2H), 5.42 (s, 2H), 4.05 (t, J=6.6 Hz, 2H), 2.66 (t, J=7.1 Hz, 2H), 2.10 (s, 6H); MS: (M + H m/z=450.4).
EXAMPLE 8
2-{4-[-Pyridin4-yl-2-(2,2,2-trifluoro-ethyl)-2H-pyrazol-3-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting (2,2,2-trifluoro-ethyl)-hydrazine provided the title compound. MS: (M + H m/z=461.2).
EXAMPLE 9
2-{4-[-Pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline
To a solution of 2-[4-(4-Pyridin4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline (26.5 g) in dimethyl formamide (140 mL) was added 1,1,1-Trifluoro-2-iodo-ethane (21 mL, 2.0 eq.) and cesium carbonate (68.3 g, 3 eq.) and the reaction mixture heated at 60° C. for 24 h. The reaction mixture was diluted with water, extracted 3× methylene chloride, dried with magnesium sulfate, filtered and concentrated. Purification via flash chromatography eluting with 5% methanol/70% ethyl acetate/hexanes provided the title compound 20.85 g as an 8:1 regioisomeric mixture. Preparative HPLC eluting with acetonitile/methanol (98:2) on a chiralpak AD column with a flow rate of 430 ml/Min provided the pure title compound as a free base 13.4 g. 1 H NMR (400 MHz, CDCl 3 ) δ 8.45 (m, 2 H), 8.16 (d, J=8.3 Hz, 1 H), 8.04 (d, J=8.3 Hz, 1H), 7.96 (s, 1H), 7.79 (d, J=8.3 Hz, 1 H), 7.69 (m, 1 H), 7.64 (d, J=8.3 Hz, 1 H), 7.50 (m, 1H), 7.36 (d, J=8.7 Hz, 2 H), 7.14 (d, J=6.2 Hz, 2H), 6.98 (d, J=9.1 Hz, 2 H), 5.35 (s, 2H), 4.75 (q, J=8.3 Hz, 2 H); MS: (M + H m/z=427.1).MS: (M + H m/z=461.2).
EXAMPLE 10
1-{4-Pyridin-4-yl-3-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-propan-2-ol
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-hydrazino-propan-2-ol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (bs, 2 H), 8.20 (d, J=8.3 Hz, 1 H), 8.08 (d, J=8.3 Hz, 1H), 7.83 (d, J=8.3 Hz, 1 H), 7.75 (m 2H), 7.67 (d, J=8.3 Hz, 1H), 7.56 (t, J=8.3 Hz, 1H), 7.36 (d, J=8.7 Hz, 2H) 7.30 (m, 2H), 7.03 (d, J=9.1 Hz, 2 H), 5.40 (s, 2H), 4.49 (m, 1H), 4.23 (m, 1H), 4.02 (m, 1H), 1.83 (m, 1H), 1.28 (d, J=6.2 Hz, 3H); MS: (M + H m/z=437.2).
EXAMPLE 11
1-{4-Pyridin-4-yl-5-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-propan-2-ol
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-hydrazino-propan-2-ol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.37 (d, J=6.2 Hz, 2 H), 8.23 (d, J=8.7 Hz, 1 H), 8.08 (d, J=8.3 Hz, 1H), 7.84 (m, 2 H), 7.75 (m 2H), 7.57 (t, J=6.6 Hz, 1H), 7.20 (d, J=9.1 Hz, 2H), 7.13 (d, J=8.7 Hz, 2H) 7.00 (dd, J=6.2, 1.7 Hz, 2H), 5.42 (s, 2H), 4.17 (m, 1H), 3.94 (m, 2H), 3.86 (m, 1H), 1.12 (d, J=6.6 Hz, 3H); MS: (M + H m/z=437.3).
EXAMPLE 12
2-[4-(2-Isopropyl-4-pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting isopropyl hydrazine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.33 (bs, 2 H), 8.24 (d, J=8.3 Hz, 1 H), 8.08 (d, J=8.3 Hz, 1H), 7.86 (s, 1H) 7.83 (m, 1 H), 7.72 (m 2H), 7.58 (t, J=7.9 Hz, 1H), 7.20 (d, J=8.7 Hz, 2H), 7.15 (d, J=9.1 Hz, 2H) 7.04 (m, 2H), 5.43 (s, 2H), 4.31 (m, 1H), 1.43 (d, J=6.6 Hz), 6H); MS: (M + H m/z=421.2).
EXAMPLE 13
2-[4-(4-Pyridin-4yl-isoxazol-5-yl)-phenoxymethyl]-quinoline
2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone (200 mg, 0.56 mmole) was heated at reflux in dimethoxymethyl-dimethyl amine (1 ml) for 1 h and concentrated. The crude product was dissolved in methanol/water (3:1, 4 ml) and hydroxyl amine hydrochloride (43 mg, 1.1 eq.) was added. After 1 h, acetic acid was added (0.016 ml) and the reaction was heated at reflux for 1h. Cooled to ambient temperature poured into saturated sodium bicarbonate, extracted with methylene chloride, dried magnesium sulfate, filtered and concentrated. Biotage MPLC was run on a 25S column elution with 3% methanol/1% ammonium hydroxide/ethyl acetate 50% in hexanes to provide the title compound as a tan solid (94 mg, 45%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.59(dd, J=6.2, 1.7 Hz, 2 H), 8.36 (s, 1H), 8.20 (d, J=8.3 Hz, 1H), 8.07 (d, J=8.7 Hz, 1 H), 7.82 (d, J=9.1 Hz, 1H), 7.73 (dt, J=7.1, 1.7 Hz, 1H), 7.64 (d, J=8.3 Hz, 1H), 7.54 (m, 3H), 7.28 (d, J=4.2 Hz, 2H) 7.05 (d, J=9.1, 2H), 5.40 (s, 2H); MS: (M + H m/z=380.2).
EXAMPLE 14
2-[4-(5-Pyridin-4-yl-pyrimidin-4-yl)-phenoxymethyl]-quinoline
2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone (200 mg) was heated at reflux in dimethoxymethyl-dimethyl amine (1 ml) for 1 h and concentrated. The crude reaction mixture was dissolved in ethanol (3 ml) and formamidine hydrochloride (90 mg, 2 eq.) was added. In a separate flask sodium (40 mg) was added to ethanol 3 ml and stirred 10 min. The sodium ethoxide solution was added to the reaction mixture and was heated at reflux for 1 h. The reaction mixture was concentrated and purified via Biotage MPLC chromatography on a 25S column eluting with 40-100% ethyl acetate/hexane to provide the title compound (83 mg, 38%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.53(m, 3 H), 8.14 (d, J=8.7 Hz, 1H), 8.03 (d, J=8.3 Hz, 1H), 7.79 (d, J=7.9 Hz, 1 H), 7.70 (m, 1 H), 7.58 (d, J=8.7 Hz, 1H), 7.50 (m, 1H), 7.33 (d, J=9.1 Hz, 2H) 7.10 (d, J=6.2, 2H), 6.91(d, J=9.1 Hz, 2H), 5.34 (s, 2H) 2.77 (s, 3H); MS: (M + H m/z=391.2).
EXAMPLE 15
2-[4-(2-Methyl-5-pyridin-4-yl-pyrimidin-4-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-pyrimidin-4-yl)-phenoxymethyl]-quinoline but substituting acetamidine hydrochloride provide the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 9.21 (s, 1H), 8.63 (S, 1H), 8.58(m, 2 H), 8.17 (d, J=8.7 Hz, 1H), 8.04 (d, J=8.7 Hz, 1H), 7.81 (d, J=8.3 Hz, 1 H), 7.70 (m, 1 H), 7.60 (d, J=8.3 Hz, 1H), 7.52 (m, 1H), 7.37 (m, 2H) 7.15 (d, J=6.2, 2H), 6.93 (d, J=9.1 Hz, 2H), 5.35 (s, 2H); MS: (M + H m/z=405.2).
EXAMPLE 16
2-[4-(2-Methyl-6-pyridin-4-yl-pyrazolo[1,5-a]pyrimidin-7-yl)-phenoxymethyl]-quinoline
To a solution of 3-Dimethylamino-2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl}-propenone (229 mg, 0.56 mmole) in ethanol (3 ml) was added piperidine (2 eq.) and 5-methyl-2H-pyrazol-3-ylamine (108 mg, 2 eq.) and the reaction mixture was heated at reflux for 3 h. The reaction mixture was cooled to RT, filtered and product washed with ethanol and hexane to provide the title compound (96 mg, 39%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.51 (d, J=7.9 Hz, 2H), 8.46 (S, 1H), 8.30(m, 1 H), 8.18 (m, 1H), 7.89 (d, J=8.3 Hz, 1H), 7.78 (m, 1 H), 7.71 (m, 1 H), 7.60 (m, 1 H), 7.41 (d, J=8.7, 2H), 7.21 (m, 2H) 7.07 (d, J=8.7, 2H), 6.60 (s, 1H), 5.50 (s, 2H) 2.48 (s, 3H); MS: (M + H m/z=444.2).
EXAMPLE 17
2-[4-(2-Methyl-6-pyridin-4-yl-[1,2,4]triazolo[1.5-a]pyrimidin-7-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(2-Methyl-6-pyridin-4-yl-pyrazolo[1,5-a]pyrimidin-7-yl)-phenoxymethyl]-quinoline but substituting 5-Methyl-2H-[1,2,4]-triazol-3ylamine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.75 (s, 1H), 8.55 (m, 2H), 8.21(d, J=8.3 Hz, 1 H), 8.06 (d, J=7.5 Hz, 1H), 7.84 (d, J=7.1 Hz, 1H), 7.73 (m, 1H), 7.64 (d, J=8.3 Hz, 1 H), 7.55 (m, 1H), 7.42 (d, J=8.7, 2H), 7.08 (m, 4H), 5.39 (s, 2H) 2.60 (s, 3H); MS: (M + H m/z=445.2).
Preparation 6
2-Pyridazin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 4-methyl pyridazine for 4-picoline provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 9.12 (d, J=5.4 Hz, 1 H), 9.08 (d, J=8.7 Hz, 2.1 H), 8.20 (d, J=8.3 Hz, 1H), 8.07 (d, J=8.3 Hz, 1 H), 7.96 (m, 2 H), 7.83 (d, J=7.9 Hz, 1 H), 7.76 (m, 1 H), 7.62 (d, J=8.3 Hz, 1 H), 7.55 (m, 1 H) 7.38 (dd, J=5.4, 2.5 Hz, 1H), 7.09 (m, 2H), 5.44 (s, 2H) 4.23 (s, 2H); MS: (M + H m/z=356.2).
Preparation 7
3-Dimethylamino-2-pyridazin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone
Following the procedure for the preparation of 3-Dimethylamino-2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl}-propenone but substituting 2-Pyridazin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone provided the title compound. LC/MS: RT=1.8 min, MS: (M + H m/z=411.2).
EXAMPLE 18
2-[4-(4-Pyridazin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline but substituting 3-Dimethylamino-2-pyridazin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 9.11 (s, 1H), 9.01 (d, J=5.0 Hz, 1H), 8.34(d, J=8.7 Hz, 1 H), 8.25 (d, J=8.7 Hz, 1H), 7.89 (m 2H), 7.81 (d, J=8.3 Hz, 1 H), 7.79 (m, 2 H), 7.61 (t, J=7.6 Hz, 1H), 7.34 (m, 1H), 7.31 (d, J=8.7 Hz, 2H), 7.05 (d, J=8.7, 2H), 5.49 (s, 2H); MS: (M + H m/z=380.2).
EXAMPLE 19
2-[4-(1-Methyl-4-pyridazin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 3-Dimethylamino-2-pyridazin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 9.11 (d, J=2.5 Hz, 1H), 8.96 (d, J=5.4 Hz, 1H), 8.19(d, J=8.7 Hz, 1H), 8.06 (d, J=8.3 Hz, 1H), 7.82 (d, J=7.9 Hz, 1H), 7.73 (t, J=7.1 Hz, 1 H), 7.67 (m, 2H), 7.55 (t, J=7.1 Hz, 1H), 7.34 (d, J=9.1 Hz, 2H), 7.24 (m, 1H), 7.02 (d, J=6.6 Hz, 2H), 5.39 (s, 2H) 3.97 (s, 3H); MS: (M + H m/z=394.2).
EXAMPLE 20
2-[4-(2-Methyl-4-pyridazin4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 3-Dimethylamino-2-pyridazin4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 8.99 (d, J=2.5 Hz, 1H), 8.90 (d, J=5.4 Hz, 1H), 8.24(d, J=8.7 Hz, 1H), 8.08 (d, J=8.7 Hz, 1H), 7.89 (s, 1H), 7.85 (d, J=8.3 Hz, 1 H), 7.75 (t, J=7. 1 Hz, 1 H), 7.70 (d, J=8.3 Hz, 1H), 7.57 (t, J=7.1 Hz, 1H), 7.21 (d, J=8.7 Hz, 2H), 7.15 (d, J=9.1 Hz, 2H), 7.11 (m, 1 H), 5.43 (s, 2H) 3.73 (s, 3H); MS: (M + H m/z=394.2).
EXAMPLE 21
2-[-4-(4-Pyrimidin-4yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline and making the necessary chemical substitutions provided the title compound as a white solid. LC/MS: RT=1.8 min, MS: (M + H m/z=380.2).
EXAMPLE 22
2-[4-(4-Pyridazin-3-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline and making the necessary chemical substitutions provided the title compound as a white solid. LC/MS: RT=1.7 min, MS: (M + H m/z=380.2).
Preparation 8
2-(3-Methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 3,5-dimethyl isoxazole for 4-picoline provided the title compound. LC/MS: RT=2.3 min, MS: (M + H m/z=359.2).
Preparation 9
3-Dimethylamino-2-(3-methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone
Following the procedure for the preparation of 3-Dimethylamino-2-pyridin4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl}-propenone but 2-(3-Methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone provided the title compound. LC/MS: RT=2.1 min, MS: (M + H m/z=414.2).
EXAMPLE 23
2-{4-[4-(3-Methyl-isoxazol-5-yl)-2H-pyrazol-3-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline but substituting 3-Dimethylamino-2-(3-methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.23 (d, J=8.7 Hz, 1H), 8.12 (d, J=8.7 Hz, 1H), 7.94(s, 1 H), 7.84 (d, J=7.1 Hz, 1H), 7.74 (m, 1H), 7.69 (d, J=8.3 Hz, 1 H), 7.57 (t, J=6.6 Hz, 2 H), 7.46 (d, J=8.87 Hz, 2H), 7.08 (d, J=8.7 Hz, 2H), 5.88 (s, 1H), 5.42 (s, 2H), 2.23 (s, 3H); MS: (M + H m/z=383.2).
EXAMPLE 24
2-{4-[2-Methyl-4-(3-methyl-isoxazol-5-yl)-2H-pyrazol-3-yl]-phenoxymethyl)-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 3-Dimethylamino-2-(3-methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 8.25 (d, J=8.7 Hz, 1H), 8.12 (d, J=8.3 Hz, 1H), 7.89(s, 1 H), 7.85 (d, J=8.3 Hz, 1H), 7.74 (m, 2H), 7.57 (t, J=7.1 Hz, 1 H), 7.28 (s, 1 H), 7.26 (d, J=10.4 Hz, 2H), 7.16 (d, J=8.7 Hz, 2H), 5.45 (s, 2H), 3.71 (s, 3H), 2.16 (s, 3H); MS: (M + H m/z=397.2).
EXAMPLE 25
2-{4-[1-Methyl-4-(3-methyl-isoxazol-5-yl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 3-Dimethylamino-2-(3-methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ 8.18 (d, J=8.3 Hz, 1H), 8.07 (d, J=8.7 Hz, 1H), 7.81(d, J=7.1 Hz, 1 H), 7.77 (s, 1H), 7.74 (t, J=7.1 Hz, 1H), 7.67 (d, J=8.7 Hz, 1 H), 7.54 (t, J=7.1 Hz, 1H), 7.48 (d, 8.7 Hz, 2 H), 7.07 (d, J=8.7 Hz, 2H), 5.81 (s, 1H), 5.41 (s, 2H), 3.92 (s, 3H), 2.20 (s, 3H); MS: (M + H m/z=397.2).
EXAMPLE 26
2-{4-[2-Methyl-5-(3-methyl-isoxazol-5-yl)-pyrimidin-4-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-pyrimidin-4-yl)-phenoxymethyl]-quinoline but substituting acetamidine hydrochloride and 3-Dimethylamino-2-(3-methyl-isoxazol-5-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone provided the title compound as the hydrochloride salt. 1 H NMR (400 MHz, CDCl 3 ) δ 8.87 (s, 1H), 8.18 (d, J=8.3 Hz, 1H), 8.06 (d, J=8.3 Hz, 1H), 7.82(d, J=8.3 Hz, 1 H), 7.72 (t, J=7.1 Hz, 1H), 7.63 (d, J=8.7 Hz, 1H), 7.53 t, J=6.6 Hz, 1 H), 7.45 (d, J=9.1 Hz, 2H), 7.05 (d, J=9.1 Hz, 2H), 5.79 (s, 1H), 5.40 (s, 2H), 2.78 (s, 3H), 2.23 (s, 3H); MS: (M + H m/z=409.2).
Preparation 10
1-[4-(Quinolin-2-ylmethoxy)-phenyl]-ethanone
To a solution of 2-Chloromethyl quinoline (2.5 g, 14 mmole) in acetone (47 ml) was added 4-hydroxy acetophenone (1.92 g, 1.0 eq.) and potassium carbonate (2.5 g, 2 eq.). The reaction mixture was heated at 60° C. for 16 h under N 2 atmosphere, cooled to ambient temperature and poured into 1N sodium hydroxide (50 ml)/ethyl acetate (100 ml). The layers were separated and the organic layer dried magnesium sulfate, filtered and concentrated. Biotage MPLC was run using a 5-40% ethyl acetate/hexane gradient on a 40 M column to provide the title compound as a white solid (2.75 g, 71%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (d, J=8.7 Hz, 1 H), 8.07 (d, J=8.7, 1H), 7.91 (m, 2H), 7.82 (dd, J=8.3, 1.3 1H), 7.73 (t, J=7.1 Hz, 1 H), 7.62 (d, J =8.3 Hz, 1 H), 7.54 (t, J=7.1 Hz, 1 H), 7.06 (m, 2H), 5.42 (s, 2 H), 2.51 (s, 3 H); MS: (M + H m/z=278.3).
Preparation 11
3-Dimethylamino-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone
1-[4-(Quinolin-2-ylmethoxy)-phenyl]-ethanone (1.0 g, 3.61 mmole) was stirred in dimethoxymethyl-dimethyl amine (5 ml) and heated at reflux for 18 h. The reaction mixture was cooled to RT and a tan precipitate formed. It was filtered and washed with ethyl ether to provide the title compound 840 mg, 71%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.39 (d, J=8.3 Hz, 1 H), 7.97 (m, 2H), 7.91 (m, 2H), 7.84 (m, 2H), 7.75 (t, J=6.6 Hz, 1 H), 7.62 (m, 3H), 7.05 (d, J=8.7 Hz, 2 H), 5.77 (d, J=12.0, 1H), 5.40 (s, 2 H), 3.07 (bs, 3 H), 2.84 (bs, 3H); MS: (M +H m/z= 333.3).
EXAMPLE 27
2-[4-(2-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 3-Dimethylamino-1-[4-(quinolin-2-ylmethoxy)-phenyl]-propenone (46 mg) in ethanol (0.7 ml) was added water (0.7 ml), acetic acid (0.05ml) and 4-pyridyl hydrazine (25 mg, 1 eq.). The reaction mixture was heated at 100° C. for 3 h, cooled to RT, poured into 1 N NaOH, extracted with chloroform, dried magnesium sulfate, filtered and concentrated. Biotage MPLC was run on a 25S column eluting with 20-80% ethyl acetate/hexane to provide the title compound as a tan solid (31 mg, 61%). 1 H NMR (400 MHz, CDCl 3 )δ 8.51 (bs, 2H), 8.24 (d, J=8.7 Hz, 1 H), 8.11 (d, J=8.7, 2H), 7.84 (d, J=8.3 Hz, 1H), 7.74 (m, 2H), 7.69 (d, J=8.7 Hz, 1 H), 7.58 (t, J=7.1, 1H), 7.32 (bs, 2H), 7.19 (d, J=6.6 Hz, 2H), 7.04 (d, J=6.6, 2H), 5.40 (s, 2 H), 6.45 (s, 1H), 5.42 (s, 2H); MS: (M + H m/z=379.2).
EXAMPLE 28
2-[4-(3-Methyl-5-pyridin-4-yl [1,2,4]triazol-4-yl)-phenoxymethyl]-quinoline
To a solution of isonicotinic hydrazide (1.04 g, 1.12 eq.) in acetonitrile (30 ml) was added N,N-dimethylacetamide dimethyl acetal (1.1 eq.) and the reaction mixture was heated at 50° C. for 3 h. The reaction mixture was cooled to ambient temperature and concentrated. 4-(Quinolin-2-ylmethoxy)-phenylamine (1.70 g) was added along with acetic acid (30 ml) and the reaction mixture was heated at reflux for 3 h, and cooled to ambient temperature. The reaction mixture was concentrated on a rotovap and purified via combiflash MPLC to provide the title compound as a tan solid (56%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.51 (d, J=6.2 Hz, 2H), 8.24 (d, J=8.7 Hz, 1 H), 8.08 (d, J=8.7, 1H), 7.85 (d, J=7.9 Hz, 1H), 7.76 (t, J=8.3 Hz, 1H), 7.67 (d, J=8.7 Hz, 1 H), 7.58 (t, J=7.1, 1H), 7.29 (d, J=6.2 Hz, 2 H), 7.17 (d, J=9.1 Hz, 2H), 7.12 (d, J=9.1 Hz, 2 H), 5.43 (s, 2 H), 2.31 (s, 3H); MS: (M + H m/z=394.3).
Preparation 12
4-benzyloxy-N-methoxy-N -methyl-benzamide
Following the procedure for the preparation of N-Methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide but substituting 4-benzyloxy benzoic acid provided the title compound as a waxy solid. MS: (M + H m/z=272.3).
Preparation 13
1-(4-Benzyloxy-phenyl)-2-pyridin-4-yl-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 4-benzyloxy-N-methoxy-N-methyl-benzamide provided the title compound. MS: (M + H m/z=304.2).
Preparation 14
4-[3-(4-Benzyloxy-phenyl)-1-methyl-1H-pyrazol-4-yl]-pyridine
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-(4-Benzyloxy-phenyl)-2-pyridin-4-yl-ethanone provided the title compound. MS: (M + H m/z=342.2).
Preparation 15
4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenol
To a solution of 4-[3-(4-Benzyloxy-phenyl)-1-methyl-1H-pyrazol-4-yl]-pyridine (1.28 g) in ethanol (50 ml)/ethyl acetate (50 ml) in a parr bottle was added Palladium hydroxide (500 mg). The parr bottle was charged to 40 psi on a shaker for 6 h. The reaction mixture was filtered and concentrated. MPLC biotage chromatography eluting with methanol (1-7%)/chloroform provided the title compound (860 mg, 91%). 1 H NMR (400 MHz, DMSO) δ 9.53 (s, 1H), 8.39 (d, J=5.8 Hz, 2 H), 7.15 (m, 4H), 6.72 (d, J=8.7 Hz, 1H), 3.84 (s, 3H); MS: (M + H m/z=252.2).
EXAMPLE 29
2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoxaline
To a solution of 4-(1-Methyl4-pyridin-4-yl-1H-pyrazol-3-yl)-phenol (50 mg) in dioxane (2 ml) was added triphenylphosphine (84 mg), quinoxaline-2-yl-methanol (48 mg) and di-t-butyl-aza-dicarboxylate (73 mg) and the reaction mixture was heated at 60° C. for 18 h. The reaction mixture was poured into 1N NaOH, extracted 3× methylene chloride, dried magnesium sulfate, filtered and concentration Purification via MPLC biotage chromatography provided the title compound (54 mg, 67%). 1 H NMR (400 MHz, CDCl 3 ) δ 9.09 (s, 1H), 8.45 (d, J=6.2 Hz, 2H), 8.10 (m, 2 H), 7.77 (m, 2H), 7.55 (s, 1H), 7.37 (d, J=9.1 Hz, 2H), 7.10 (d, J=6.9 Hz, 2 H), 7.01 (d, J=8.7, 2H), 5.41 (s, 2 H), 3.94 (s, 3H); MS: (M + H m/z=394.4).
EXAMPLE 30
7-Chloro-2-[4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline hydrogen chloride
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting 4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenol and 7-chloro-2-chloromethyl-quinoline provided the title compound. 1 H NMR (400 MHz, DMSO) δ 8.66 (d, J=6.6 Hz, 2H), 8.54 (s, 1 H), 8.47 (d, J=8.3, 2H), 8.04 (m, 2H), 7.70 (m, 2H), 7.65 (m, 1H), 7.36 (d, J=8.7 Hz, 2H), 7.12 (d, J=8.7, 2H), 5.38 (s, 2H), 3.90 (s, 3 H); MS: (M + H m/z=427.1).
EXAMPLE 31
6-Fluoro-2-[4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline hydrogen chloride
Following the procedure for the preparation of 7-Chloro-2-[4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline hydrogen chloride but substituting 2-chloromethyl-6-fluoro-quinoline provided the title compound. 1 H NMR (400 MHz, DMSO) δ 8.67 (d, J=6.6 Hz, 2H), 8.55 (s, 1 H), 8.42 (d, J=8.3, 1H), 8.04 (m, 1H), 7.82 (m, 1H), 7.71 (m, 4H), 7.36 (d, J=8.7 Hz, 2H), 7.12 (d, J=8.7, 2H), 5.37 (s, 2H), 3.91 (s, 3 H); MS: (M + H m/z=411.2).
Preparation 16
3-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid quinolin-2-ylmethyl ester
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting 3-fluoro-4-hydroxy-benzoic acid provided the title compound. MS: (M + H m/z=439.0).
Preparation 17
3-Fluoro-4-(quinolin-Z-ylmethoxy)-benzoic acid
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid but substituting 3-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid quinolin-2-ylmethyl ester provided the title compound. MS: (M + H m/z=298.2).
Preparation 18
3-Fluoro-N-methoxyl-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide
Following the procedure for the preparation of N-Methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide but substituting 3-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid provided the title compound. MS: (M + H m/z=341.2).
Preparation 19
1-[3-Fluoro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 3-Fluoro-N-methoxyl-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide provided the title compound. MS: (M + H m/z=373.1).
EXAMPLE 32
2-[2-Fluoro-4-(4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline but substituting 1-[3-Fluoro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (bs, 2H), 8.19 (d, J=8.7 Hz, 1H), 8.05 (d, J=8.3 Hz, 1 H), 7.71 (m, 4H), 7.54 (t, J=7.1 Hz, 1H), 7.18 (m, 3H), 7.07 (m, 2 H), 5.42 (s, 2 H); MS: (M + H m/z=397.0).
EXAMPLE 33
2-[2-Fluoro-4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-[3-Fluoro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (d, J=6.2 Hz, 2H), 8.21 (d, J=8.3 Hz, 1H), 8.05 (d, J=8.7 Hz, 1 H), 7.83 (d, J=7.9 Hz, 2H), 7.72 (m, 2H), 7.55 (m, 2H), 7.16 (m, 2 H), 7.07 (m, 1H), 6.99 (m, 2H), 5.45 (s, 2 H), 3.95 (s, 3H); MS: (M + H m/z=411.0).
Preparation 20
2,3-Difluoro-4-(quinolin-2-ylmethoxy)-benzoic acid quinolin-2-yl methyl ester
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting 2,3-difluoro-4-hydroxy-benzoic acid provided the title compound. MS: (M + H m/z=457.1).
Preparation 21
2,3-Difluoro-4-(quinolin-2-ylmethoxy)-benzoic-acid
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid but substituting 2,3-Difluoro-4-(quinolin-2-ylmethoxy)-benzoic acid quinolin-2-yl methyl ester provided the title compound. MS: (M + H m/z=316.1).
Preparation 22
2,3-Difluoro-N-methoxy-N -methyl-4-(quinolin-2-ylmethoxy)-benzamide
Following the procedure for the preparation of N-Methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide but substituting 2,3-Difluoro-4-(quinolin-2-ylmethoxy)-benzoic acid provided the title compound. MS: (M + H m/z=359.1).
Preparation 23
1-[2,3-Difluoro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 2,3-Difluoro-N-methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide provided the title compound. MS: (M + H m/z=391.1).
EXAMPLE 34
2-[2,3-Difluoro-4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-[2,3-Difluoro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (bs, 2H), 8.22 (d, J=8.7 Hz, 1H), 8.06 (d, J=8.7 Hz, 1 H), 7.84 (d, J=7.9 Hz, 1H), 7.70 (m, 2 H), 7.66 (s, 1H), 7.56 (t, J=7.9 Hz, 1H), 7.08 (m, 3H), 6.88 (m, 1H), 5.48 (s, 2H); MS: (M + H m/z=429.1).
Preparation 24
2-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid quinolin-2-ylmethyl ester
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting 2-fluoro-4-hydroxy-benzoic acid provided the title compound. MS: (M + H m/z=439.0).
Preparation 25
2-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid but substituting 2-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid quinolin-2-yl methyl ester provided the title compound. MS: (M + H m/z=298.2).
Preparation 26
2-Fluoro-n-methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide
Following the procedure for the preparation of N-Methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide but substituting 2-Fluoro-4-(quinolin-2-ylmethoxy)-benzoic acid provided the title compound. MS: (M + H m/z =341.2).
Preparation 27
1-{2-Fluoro-4-(quinolin-2-ylmethoxy)-phenyl}-2-pyridin-4-yl-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 2-Fluoro-n-methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide provided the title compound. MS: (M + H m/z=373.0).
EXAMPLE 35
2-[3-Fluoro-4-(4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[-4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl}-quinoline but substituting 1-{2-Fluoro-4-(quinolin-2-ylmethoxy)-phenyl}-2-pyridin-4-yl-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (d, J=6.5 Hz, 2H), 8.22 (d, J=8.3 Hz, 1H), 8.08 (d, J=8.7 Hz, 1 H), 7.84 (s, 1H), 7.82 (m, 1H), 7.74 (m, 1H), 7.65 (d, J=8.7 Hz, 1 H), 7.55 (m, 1 H), 7.25 (m, 1 H), 7.18 (d, J=6.2 HZ, 2H), 6.85 (d, J=10.9, 2 H), 5.38 (s, 2 H); MS: (M + H m/z=397.2).
Preparation 28
4-(Quinolin-2-ylmethoxy)-benzaldehyde
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting 4-Hydroxy-benzaoldehyde provided the title compound. MS: (M + H m/z=264.2).
Preparation 29
1-Pyridin-4-yl-2-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone
To a solution of 4-pyridine carboxaldehyde (10.8 g) in 2-propanol (50 ml) was added aniline (9.3 g). After 15 min, the phenyl-pyridin-4-ylmethylene-amine product (68%) was filtered and used crude. To a solution of the imine in ethoanol (35 ml) was added diphenyl phosphite (13.1 ml) and stirred 1 h. Ethyl ether (200 mL) was added and the (Phenylamino-pyridin-4-yl-methyl-phosphonic acid diphenyl ester (5.06 g) was filtered. The phophonic ester (0.98 g) in THF (25 ml) was stirred at −40° C. under N 2 . A solution of KOH/methanol (0.146 g/10%) was added followed by 4-(Quinolin-2-ylmethoxy)-benzaldehyde (0.62 g). The crude reation mixture was warmed to ambient temperature for 1 h and concentrated. The crude product was stirred in acetonitrile (1 mL)/1 ml conc. HCl for 1 h, quenched with sat'd sodium bicarbonate, extracted with chloroform, dried magnesium sulfate, filtered and concentrated. Purification via MPLC combiflash provided the title compound. MS: (M + H m/z=355.1).
EXAMPLE 36
2-[4-(5-Pyridin-4-yl-1H-pyrazol-4-yl)-phenoxymethyl]-quinoline
1-Pyridin-4-yl-2-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone (168 mg) was heated in diethoxymethyl-dimethyl amine (1 ml) at reflux for 2 hours. The reaction mixture was concentrated and dissolved in methanol (1 ml) and hydrazine hydrate (0.023 ml) was added and the reaction mixture was heated at 65° C. for 1 h. The reaction mixture was concentrated and purified by combiflash MPLC chromatography to provide the title compound (90%). 1 H NMR (400 MHz, CDCl 3 ) δ 8.37 (bs, 2H), 8.18 (d, J=8.7 Hz, 1 H), 7.99 (d, J=8.7 Hz, 1H), 7.78 (d, J=8.3 Hz, 1 H), 7.66 (m, 2 H), 7.54 (s, 1 H), 7.48 (m, 1 H), 7.36 (m, 2 H), 7.11 (d, J=7.1 Hz, 2H), 6.94 (d, J=8.3 Hz, 2H), 5.29 (s, 2H); MS: (M + H m/z=379.2).
EXAMPLE 37
2-[4-(1-Methyl-5-pyridin-4-yl-1H-pyrazol-4-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-1H-pyrazol-4-yl)-phenoxymethyl]-quinoline but substituting methyl hydrazine provided the title compound and 2-[4-(1-Methyl-3-pyridin-4-yl-1H-pyrazol4-yl)-phenoxymethyl]-quinoline. 1 H NMR (400 MHz, CDCl 3 ) δ 8.66 (bs, 2 H), 8.17 (d, J=8.7 Hz, 1H), 8.05 (d, J=7.9 Hz, 1 H), 7.81 (d, J=8.3 Hz, 1H), 7.70 (m, 1 H), 7.63 (m, 2 H), 7.53 (t, J=7.1 Hz, 1 H), 7.21 (m, 2 H), 7.03 (d, J=9.1 Hz, 2H), 6.89 (d, J=8.7 Hz, 2H), 5.32 (s, 2H), 3.80 (s, 3H); MS: (M + H m/z=393.2).
EXAMPLE 38
2-[4-(1-Methyl-3-pyridin-4-yl-1H-pyrazol-4-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-1H-pyrazol-4-yl)-phenoxymethyl]-quinoline but substituting methyl hydrazine provided the title compound and 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-4-yl)-phenoxymethyl]-quinoline. 1 H NMR (400 MHz, CDCl 3 ) δ 8.49 (bs, 2 H), 8.20 (d, J=8.3 Hz, 1 H), 8.07 (d, J=8.3 Hz, 1 H), 7.83 (d, J=8.3 Hz, 1H), 7.74 (m, 2 H), 7.55 (t, J=7.1 Hz, 1 H), 7.42 (m, 2H), 7.38 (s, 1H), 7.17 (d, J=8.7 Hz, 2H) 7.00 (d, J=8.7Hz, 2H), 5.38 (s, 2H), 3.95 (s, 3H); MS: (M + H m/z=393.2).
EXAMPLE 39
2-Methyl-1-{4-pyridin-4-yl-3-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-propan-2-ol
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-Hydrazino-2-methyl-propan-2-ol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (d, J=6.2 Hz, 2 H), 8.19 (d, J=8.7 Hz, 1 H), 8.07 (d, J=8.7 Hz, 1 H), 7.82 (d, J=7.9 Hz, 1H), 7.74 (t, J=8.3 Hz, 1H), 7.68 (d, J=8.7 Hz, 1 H), 7.62 (s,1H), 7.55 (t, J=7.1 Hz, 1 H), 7.39 (d, J=8.7 Hz, 2H), 7.17 (m, 2H), 7.01 (d, J=8.7 Hz, 2H), 5.39 (s, 2H) 4.09 (s, 2H), 1.23 (s, 2H); MS: (M + H m/z=451.2).
EXAMPLE 40
2-Methyl-1-{4-pyridin-4-yl-5-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-propan-2-ol
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-Hydrazino-2-methyl-propan-2-ol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.37 (d, J=5.8 Hz, 2 H), 8.24 (d, J=8.3 Hz, 1 H), 8.09 (d, J=9.1 Hz, 1 H), 7.87 (s, 1H), 7.85 (d, J=7.9 Hz, 1H), 7.76 (m, 1 H), 7.72 (m, 1H), 7.17 (m, 4 H), 7.00 (d, J=6.2 Hz, 2H), 5.42 (s, 2H) 3.89 (s, 2H), 1.04 (s, 6H); MS: (M + H m/z=451.2).
EXAMPLE 41
(R)-1-{4-Pyridin-4-yl-3-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-propan-2-ol
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting (R)-1-Hydrazino-propan-2-ol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.42 (m, 2 H), 8.18 (d, J=8.3 Hz, 1 H), 8.06 (d, J=8.4 Hz, 1 H), 7.81 (d, J=8.3 Hz, 1H), 7.73 (m, 1H), 7.66 (d, J=8.7 Hz, 1H), 7.61 (s, 1 H), 7.54 (m, 1H), 7.36 (d, J=9.1 Hz, 2 H), 7.12 (m, 2H), 6.99 (d, J=8.7 Hz, 2H) 5.37 (s, 2H), 4.30 (m, 1H), 4.21 (dd, J=13.6, 2.5 Hz, 1H), 4.03 (dd, J=13.6, 7.9 Hz, 1H), 1.26 (d, J=6.2 Hz, 3H); MS: (M + H m/z=437.2).
EXAMPLE 42
(S)-1-{4-Pyridin-4-yl-3-[4-(quinolin-2-ylmethoxy)-phenyl]-pyrazol-1-yl}-propan-2-ol
Following the procedure for the preparation of 2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting (S)-1-Hydrazino-propan-2-ol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.42 (m, 2 H), 8.18 (d, J=8.3 Hz, 1 H), 8.06 (d, J=8.4 Hz, 1 H), 7.81 (d, J=8.3 Hz, 1H), 7.73 (m, 1H), 7.66 (d, J=8.7 Hz, 1H), 7.61 (s, 1 H), 7.54 (m, 1H), 7.36 (d, J=9.1 Hz, 2 H), 7.12 (m, 2H), 6.99 (d, J=8.7 Hz, 2H) 5.37 (s, 2H), 4.30 (m, 1H), 4.21 (dd, J=13.6, 2.5 Hz, 1H), 4.03 (dd, J=13.6, 7.9 Hz, 1H), 1.26 (d, J=6.2 Hz, 3H), MS: (M + H m/z=437.2).
EXAMPLE 43
2-[4-(1-Isopropyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenoxymethyl]-quinoline (0.075 g) in dimethyl formamide (2 ml) was added cesium carbonate (0.098 g) and 2-iodo propane (0.030 ml) and the reaction mixture heated at 60° C. for 72 h. The reaction mixture was poured into water and extracted with methylene chloride, dried magnesium sulfate, filtered and concentrated. Purification via Prep TLC eluting with 2% methanol/1% saturated ammonium hydroxide/67% ethyl acetate/30% hexane provided the title compound (60 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 8.43 (d, J=6.2 Hz, 2 H), 8.16 (d, J=8.7 Hz, 1 H), 8.05 (d, J=9.1 Hz, 1 H), 7.80 (d, J=8.3 Hz, 1H), 7.70 (m, 1H), 7.65 (d, J=8.7 Hz, 1 H), 7.59 (s, 1H), 7.53 (t, J=7.1 Hz, 1 H), 7.38 (d, J=9.1 Hz, 2H), 7.15 (d, J=8.7 Hz, 2H), 6.99 (d, J=8.7 Hz, 2H), 5.38 (s, 2H) 4.51 (m, 1H), 1.54 (d, J=6.6 Hz, 6H); MS: (M + H m/z=421.2).
EXAMPLE 44
2-[4-(1-Isobutyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(1-Isopropyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-Iodo-2-methyl-propane provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.44 (m, 2H), 8.18 (d, J=8.7 Hz, 1H), 8.06 (d, J=8.3 Hz, 1 H), 7.83 (d, J=6.6 Hz, 1 H), 7.73 (t, J=6.6 Hz, 1H), 7.54 (s,1H), 7.52 (m, 1H), 7.38 (d, J=9.1 Hz, 2 H), 7.15 (m, 2H), 7.00 (d, J=8.7 Hz, 2 H), 5.38 (s, 2H) 3.93 (d, J=7.5 Hz, 2 H), 4.29 (m, 1H), 0.95 (d, J=6.6 Hz, 6H); MS: (M + H m/z=435.2).
EXAMPLE 45
2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-[1.8]Naphthyridine
To a solution of 4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenol (72 mg) in dioxane 1.5 ml, was added triphenyl phosphine (121 mg), [1,8]Naphthyridin-2-yl-methanol (69 mg) and di-t-butyl-diazacarboxalate (106 mg) and the reaction mixture heated at 60° C. for 24 h. The reaction mixture was poured into 1 N NaOH, extracted with methylene chloride, dried magnesium sulfate and concentrated. Purification via Prep TLC eluting with 15% methanol/70%ethyl acetate/15% hexanes provided the title compound (9.8 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 9.13 (dd, J=4.2, 1.7 Hz, 1H), 8.45 (d, J=5.8 Hz, 2H), 8.23 (d, J=8.3 Hz, 1H), 7.21 (dd, J=8.5, 2.1 Hz, 1 H), 7.79 (d, J=8.7 Hz, 1H), 7.57 (s, 1H), 7.52 (m, 1H), 7.37(d, J=9.1 Hz, 2 H), 7.16 (d, J=6.2 Hz, 2H), 7.01 (d, J=8.7 Hz, 2 H), 5.47 (s, 2H), 3.94 (s, 3 H); MS: (M + H m/z=394.0).
Preparation 30
4-(2-Quinolin-2-yl-ethyl)-benzoic acid methyl ester
To a solution of 4-[Triphenyl-phophanyl)-methyl]-benzoic acid methyl ester (1.87 g) in THF (16 ml) under N 2 atmosphere at 0° C. was added sodium hydride (165 mg (60%)). After 30 min, quinoline-2-carbaldehyde (0.50 g) was added and the reaction stirred at ambient temperature for 2 h. The reaction mixture was quenched with brine, extracted with chloroform, dried magnesium sulfate, filtered and concentrated to provide the crude alkene. The crude product was placed on a parr shaker in ethanol (15 ml) with palladium hydroxide (200 mg) as the catalyst under 10 PSI of H 2 . After 40 min, the reaction mixture was filtered through celite and concentrated. Biotage MPLC chromatography eluting with 10-20% ethyl acetate/hexane provided the title compound. MS: (M + H m/z=292.1).
Preparation 31
4-(2-Quinolin-2-yl-ethyl)-benzoic acid
To a solution of 4-(2-Quinolin-2-yl-ethyl)-benzoic acid methyl ester (680 mg) in THF (11 ml)/methanol (3 ml) was added 1N sodium hydroxide solution (4.67 ml). The reaction mixture stirred for 4 h. and the pH adjusted to 3. The white solid was filtered to provide the title compound (550 mg, 86%). MS: (M + H m/z=278.1).
Preparation 32
N-Methoxy-N-methyl-4-(2-quinolin-2-yl-ethyl)-benzamide
To a solution of 4-(2-Quinolin-2-yl-ethyl)-benzoic acid (530 mg) in dioxane 5 ml/acetonitrile 5 ml was added triethylamine (0.60 ml) and O,N-Dimethyl-hydroxylamine hydrogen chloride (240 mg). After 72 h, the reaction mixture was poured into 1N sodium hydroxide solution and extracted with chloroform, dried magnesium sulfate, filtered and concentrated. Biotage MPLC chromatography eluting with 20-50% ethyl acetate provided the title compound (516 mg, 88%). MS: (M + H m/z=321.1).
Preparation 33
2-Pyridin-4-yl-1-[4-(2-quinolin-2-yl-ethyl)-phenyl]-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting N-Methoxy-N-methyl-4-(2-quinolin-2-yl-ethyl)-benzamide provided the title compound. MS: (M + H m/z=353.1).
EXAMPLE 46
2-{2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenyl]-ethyl}-quinoline
To 2-Pyridin-4-yl-1-[4-(2-quinolin-2-yl-ethyl)-phenyl]-ethanone (53 mg) was added 3 ml of Diethoxymethyl-dimethyl-amine and the reaction mixture heated at 100° C. After 3 h, the reaction mixture as concentrated and methanol (3 ml) and hydrazine (0.02 ml) was added. The reaction mixture was heated at 60° C. for 3 h and concentrated. Biotage MPLC purification eluting with 1-3% methanol/0.5% saturated ammonium hydroxide in chloroform provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (d, J=6.2 Hz, 2 H), 8.05 (d, J=8.3 Hz, 2 H), 7.80 (s, 1H), 7.78 (d, J=8.3 Hz, 2 H), 7.70 (t, J=7.1 Hz, 1H), 7.51 (t, J=7.1 Hz, 1 H), 7.32 (d, J=8.3 Hz, 2 H), 7.24 (m, 3H), 7.19 (d, J=6.2 Hz, 2H), 3.31 (m, 2H), 3.22 (m, 2H), MS: (M + H m/z=377.1).
EXAMPLE 47
2-(2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenyl]-ethyl]-quinoline
Following the procedure for the preparation of 2-{2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenyl]-ethyl}-quinoline but substituting methyl hydrazine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.45 (d, J=6.2 Hz, 2 H), 8.06 (t, J=10.4 Hz, 2 H), 7.77 (d, J=7.1 Hz, 1 H), 7.70 (t, J=8.3 Hz, 1 H), 7.57 (s, 1H), 7.50 (t, J=9.1 Hz, 1 H), 7.35 (d, J=8.3 Hz, 2H), 7.24 (m, 3H), 7.20 (d, J=5.0 Hz, 2H), 3.97 (s, 3H), 3.31 (m, 2H), 3.18 (m, 2H); MS: (M +H m/z= 391.0).
Preparation 34
2-(2-Chloro-pyridin-4-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 2-chloro-4-methyl pyridine provided the title compound. MS: (M + H m/z=389.0).
EXAMPLE 48
2-{4-[4-(2-Chloro-pyridin-4-yl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-{2-[4-(4-Pyridin4-yl-2H-pyrazol-3-yl)-phenyl]-ethyl}-quinoline but substituting 2-(2-Chloro-pyridin-4-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.23 (m, 2 H), 8.08 (d, J=8.7 Hz, 1 H), 7.83 (d, J=8.3 Hz, 1 H), 7.80 (s, 1H), 7.75 (t, J=7.1 Hz, 1 H), 7.67 (d, J=8.3 Hz, 1H), 7.57 (t, J=7.1 Hz, 1 H), 7.33 (d, J=9.1 Hz, 2H), 7.05 (m, 4H), 5.40 (s, 2H); MS: (M + H m/z=413.1).
EXAMPLE 49
2-{4-[4-(2-Chloro-pyridin-4-yl)-1-methyl-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenyl]-ethyl}-quinoline but substituting methyl hydrazine and 2-(2-Chloro-pyridin-4-yl)-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.19 (m, 2 H), 8.07 (d, J=8.3 Hz, 1 H), 7.83 (d, J=8.3 Hz, 1 H), 7.74 (t, J=8.3 Hz, 1H), 7.67 (d, J=8.3 Hz, 1 H), 7.58 (s, 1H), 7.55 (t, J=8.3 Hz, 1 H), 7.36 (d, J=8.7 Hz, 2H), 7.20 (s, 1H), 7.03 (m, 3H), 5.40 (s, 2H) 3.95 (s, 3H); MS: (M + H m/z=427.0).
EXAMPLE 50
2-{4-[1-Methyl-4-(2-methyl-pyridin-4-yl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline
To a solution of 2-{4-[4-(2-Chloro-pyridin-4-yl)-1-methyl-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline (100 mg) in dioxane (1.2 ml) was added methyl boroxine (0.066 ml), palladium tetrakis (41 mg) and 2N sodium carbonate solution (0.234 ml). The reaction mixture was heated at 100° C. for 8 h, poured into 1 N NaOH, extracted with chloroform, dried magnesium sulfate, filtered and concentrated. Prep TLC run with 3% methanol/0.5% saturated ammonium hydroxide/80% ethyl acetate in hexanes provided the free base material. The produce was stirred in ethyl acetate and 2 eq. of succinic acid was added to give a white precipitate which was filtered to provide the title compound as a white solid succinate salt (20 mg). 1 H NMR (400 MHz, DMSO) δ 8.40 (d, J=8.3 Hz, 2 H), 8.25 (d, J=5.0 Hz, 2 H), 8.07 (s, 1H), 8.00 (t, J=7.9 Hz, 2 H), 7.77 (t, J=6.6 Hz, 1 H), 7.67 (d, J=8.7 Hz, 2H), 7.60 (t, J=6.6 Hz, 1 H), 7.29 (d, J=9.1 Hz, 2H), 7.03 (m, 3 H), 6.92 (m, 1H), 5.35 (s, 2H), 3.85 (s, 3H), 2.37 (s, 4H) 2.31 (s, 3H); MS: (M + H m/z=407.0).
EXAMPLE 51
Dimethyl-(4-{1-methyl-3-[4-(quinolin-2-ylmethoxy)-phenyl]-1H-pyrazol-4-yl}-pyridin-2-yl)-amine
To a solution of 2-{4-[4-(2-Chloro-pyridin-4-yl)-1-methyl-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline (100 mg) in dimethyl formamide (1 ml) was added diethanolamine (0.035 ml) and the reaction mixture heated at 130° C. for 72 h. The reaction mixture was poured into water and extracted with ethyl ether, dried magnesium sulfate, filtered and concentrated. Prep TLC eluting with 60% ethyl acetate/hexane provided the title compound as a Free base. The product was stirred in ethyl acetate and 1 eq. of succinic acid was added. After 18 h, the white precipitate was filtered to provide the succinate salt (24 mg). 1 H NMR (400 MHz, DMSO) δ 8.40 (d, J=8.3 Hz, 1 H), 8.03 (s, 1 H), 7.98 (m, 2 H), 7.90 (d, J=5.4 Hz, 1 H), 7.77 (m, 1H), 7.65 (d, J=8.3 Hz, 1 H), 7.59 (m, 1 H), 7.31 (d, J=6.6 Hz, 2H), 7.04 (d, J=9.1 Hz, 2 H), 6.37 (m, 2 H), 5.35 (s, 2H), 3.84 (s, 3H), 2.80 (s, 6H) 2.37 (s, 4H); MS: M + H m/z=436.0).
Preparation 35
3-Dimethylamino-1-pyridin-4-yl-propenone
To 1-Pyridin-4-yl-ethanone(1.62 g) was added N,N-dimethylformamide diethylacetal (10 ml) and the reaction mixture heated at 120° C. for 2 h and concentrated to provide the title compound. MS: (M + H m/z=177.0).
Preparation 36
4-[2-(4-Benzyloxy-phenyl-2H-pyrazol-3-yl]-pyridine
To a solution of 3-Dimethylamino-1-pyridin-4-yl-propenone (590 mg) in methanol (10 ml) was added acetic acid (0.5 ml) and (4-Benzyloxy-phenyl)-hydrazine hydrogen chloride (836 mg) and the reaction mixture heated to 60° C. for 6 h. The reaction mixture was poured into saturated sodium bicarbonate, extracted with ethyl acetate, dried magnesium sulfate, filtered and concentrated. Purification via combiflash MPLC provided the title compound (795 mg). MS: (M + H m/z=328.1).
Preparation 37
4-(5-Pyridin-4-yl-pyrazol-1-yl)-phenol
To a solution of 4-[2-(4-Benzyloxy-phenyl-2H-pyrazol-3-yl]-pyridine (610 mg) in ethyl acetate (15 ml)/ethanol (15 ml) was added palladium hydroxide (20%, 343 mg). The reaction mixture was placed on a parr shaker under 45 psi of H 2 gas for 18 h. The reaction mixture was filtered through celite and concentrated. Purification via chromatotron (2 mm silica, 5% methanol/chloroform) provided the title compound (259 mg). MS: (M + H m/z=238.1).
EXAMPLE 52
2-[4-(5-Pyridin-4-yl-pyrazol-1-yl)-phenoxymethyl]-quinoline
To a solution of 4-(5-Pyridin-4-yl-pyrazol-1-yl)-phenol (82 mg) in acetone was added potassium carbonate (153 mg) and 2-Chloromethyl-quinoline (95 mg) and the reaction mixture heated at 60° C. for 18 h. The reaction mixture was poured into brine and extracted with ethyl acetate, dried magnesium sulfate, filtered and concentrated. Purification via combiflash MPLC provided the title compound (91 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 8.51 (m, 2 H), 8.20 (d, J=8.7 Hz, 1 H), 8.06 (d, J=8.7 Hz, 1 H), 7.83 (d, J=7.1 Hz, 1H), 7.74 (m, 2H), 7.65 (d, J=8.7 Hz, 1 H), 7.57 (m, 1H), 7.20 (d, J=8.7 Hz, 2 H), 7.09 (d, J=5.8 Hz, 2H), 7.02 (d, J=9.1 Hz, 2H), 6.60 (d, J=1.7 Hz, 1H), 5.39 (s, 2H); MS: (M + H m/z=379.0).
EXAMPLE 53
2-[4-(3-Methyl-5-pyridin-4-yl-pyrazol-1-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-pyrazol-1-yl)-phenoxymethyl]-quinoline but substituting (1,1-Dimethoxy-ethyl)-dimethyl-amine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.49 (d, J=6.2 Hz, 2 H), 8.20 (d, J=8.3 Hz, 1 H), 8.06 (d, J=8.7 Hz, 1 H), 7.83 (d, J=8.3 Hz,1H), 7.74 (m,1H), 7.64 (d, J=8.3 Hz, 1 H), 7.54 (m, 1H), 7.18 (d, J=8.7 Hz, 2 H), 7.07 (d, J=6.2 Hz, 2H), 7.00 (d, J=9.1 Hz, 2H), 6.40 (s, 1H), 5.38 (s, 2H), 2,35 (s, 3H); MS: (M + H m/z=393.4).
Preparation 38
3-Chloro-4-(quinolin-2-ylmethoxy)-benzoic acid methyl ester
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting 3-Chloro-4-hydroxy-benzoic acid methyl ester provided the title compound. MS: (M + H m/z=328.0).
Preparation 39
3-Chloro-4-(quinolin-2-ylmethoxy)-benzoic acid
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid but substituting 3-Chloro-4-(quinolin-2-ylmethoxy)-benzoic acid methyl ester provided the title compound. (M + H m/z=314.0).
Preparation 40
3-Chloro-N-methoxy-N-methyl4-(quinolin-2-ylmethoxy)-benzamide
Following the procedure for the preparation of N-Methoxy-N-methyl-4-(2-quinolin-2-yl-ethyl)-benzamide but substituting 3-Chloro4-(quinolin-2-ylmethoxy)-benzoic acid provided the title compound. (M + H m/z=356.9).
Preparation 41
1-[3-Chloro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 3-Chloro-N-methoxy-N-methyl-4-(quinolin-2-ylmethoxy)-benzamide provided the title compound. (M + H m/z=389.0).
EXAMPLE 54
2-[2-Chloro4-(4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-{2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenyl]-ethyl}-quinoline but substituting 1-[3-Chloro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone provided the title compound. 1 H NMR (400 MHz, CD 3 OD) δ 8.37 (m, 4 H), 8.02 (d, J=8.7 Hz, 2 H), 7.93 (d, J=8.3 Hz, 2H), 7.78 (m, 2 H), 7.61 (t, J=7.1 Hz, 1 H), 7.31 (m, 2H), 7.21 (m, 1 H), 5.44 (s, 2H); MS: (M + H m/z=413.0).
EXAMPLE 55
2-[2-Chloro-4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-{2-[4-(4-Pyridin-4-yl-2H-pyrazol-3-yl)-phenyl]-ethyl}-quinoline but substituting methyl hydrazine and 1-[3-Chloro-4-(quinolin-2-ylmethoxy)-phenyl]-2-pyridin-4-yl-ethanone provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.47 (d, J=6.2 Hz, 2 H), 8.21 (d, J=8.3 Hz, 1 H), 8.04 (d, J=7.5 Hz, 1H), 7.83 (d, J=8.3 Hz, 1 H), 7.78 (d, J=8.7 Hz, 1 H), 7.72 (m, 1H), 7.56 (m, 3 H), 7.21 (m, 1H), 7.14 (d, J=6.2 Hz, 2 H), 6.97 (d, J=8.7 Hz, 1 H), 5.46 (s, 2H), 3.95 (s, 3H); MS: (M + H m/z=427.1).
Preparation 42
4-(4-Pyridin-4-yl-4H-[1,2,4]triazol-3-yl)-phenol
To a solution of 4-Methoxy-N-pyridin-4-yl-benzamide (75 mg) in POCl 3 (3 ml) was added PCl 5 (68 mg) and the reaction mixture heated at reflux for 5 h. The reaction mixture was concentrated and dissolved in dimethyl formamide (2 ml) and Formic acid hydrazide (5 eq, 100 mg) was added and stirred for 2 h. The reaction mixture was concentrated and diluted with isopropanol (3 mL) and 0.25 ml of conc. HCl was added. The reaction mixture stirred for 18 h, quenched with 1 NaOH, extracted with dichloromethane, dried magenesium sulfate and concentrated. The crude product dissolved in methylene chloride (2 mL) and boron tribromide (0.63 mL 1.0M hexanes) was added at 0° C. The reaction mixture was warmed to ambient temperature and stirred for 18 h. The reaction mixture was quenched with 1 N NaOH and pH adjusted to 9, extracted with dichloromethane, dried magnesium sulfate, filtered and concentrated. Purification via Biotage MPLC chromatography eluting with 0-20% methanol/methylene chlroride provided the title compound (32 mg, 55%). MS: (M + H m/z=239.2).
EXAMPLE 56
2-[4-(4-Pyridin-4-yl-4H-[1,2,4]triazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 4-(4-Pyridin-4-yl-4H-[1,2,4]triazol-3-yl)-phenol (44 mg) in dimethyl formamide (1 ml) in a 7 ml Teflon capped vial was added cesium carbonate (185 mg) and 2-Chloromethyl-quinoline (37 mg) and the reaction mixture heated on a shaker plate at 60° C. for 18 h. The reaction mixture was poured into water and extracted with methylene chloride, dried magnesium sulfate, filtered and concentrated to provide the title compound (45 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 8.87 (s, 1H), 8.65 (d, J=6.0 Hz, 2 H), 8.37 (d, J=8.3 Hz, 1 H), 8.03 (d, J=8.7 Hz, 1H), 7.94 (d, J=7.9 Hz, 1H), 7.78 (m, 1 H), 7.70 (d, J=8.3 Hz, 1 H), 7.61 (t, J=5.8 Hz, 1 H), 7.40 (m, 4H), 7.14 (d, J=9.1 Hz, 2 H), 5.38 (s, 2H); MS: (M + H m/z=380.2).
Preparation 43
[4-(Quinolin-2-ylmethoxy)-phenyl]-hydrazine
To a suspension of 4-(Quinolin-2-ylmethoxy)-phenylamine (1.73 g) in 30 mL of concentrated HCl at 0° C. was added sodium nitrite (531 mg). After 3 h, tin chlrodie (3.95 g) was dissolved in 20 mL of concentrated HCl and added slowly dropwise and the reaction mixture stirred at ambient temperature for 18 h. The reaction mixture was filtered and the solid dried to provide the title compound as the HCL salt (3.94 g). MS: (M + H m/z=266.3).
EXAMPLE 57
2-[4-(5-Pyridin4-yl-[1,2,4]triazol-1-yl)-phenoxymethyl]-quinoline
Isonicatinamide (4.15 g) was heated in 35 ml of N,N-Dimethylformamide diethyl acetal at reflux for 3 h. The reaction mixture was cooled to ambient temperature and concentrated to give 5.02 g of N-Dimethylaminomethylene-isonicotinamide. To a solution of [4-(Quinolin-2-ylmethoxy)-phenyl]-hydrazine (3.16 g) in methanol (30 mL) and acetic acid (2.5 mL) was added N-Dimethylaminomethylene-isonicotinamide (1.10 g) and the reaction mixture heated at reflux for 72 h. The reaction mixture was concentrated onto silica gel and purified by flash chromatography to provided the title compound (514 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 8.60 (d, J=5.8 Hz, 2 H), 8.22 (d, J=8.7 Hz, 1 H), 8.10 (s, 1H), 8.07 (d, J=8.7 Hz, 1H), 7.85 (d, J=7.1 Hz, 1H), 7.76 (m, 1 H), 7.66 (d, J=8.3 Hz, 1 H), 7.56 (m, 1 H), 7.56 (m, 1H), 7.38 (d, J=6.2 Hz, 2 H), 7.26 (d, J=8.7Hz, 2H), 7.11 (d, J=9.1 Hz, 2H), 5.42 (s, 2H); MS: (M + H m/z=380.3).
Preparation 44
[4-(Quinolin-2-ylmethoxy)-phenyl]-hydrazine
Following the procedure for the preparation of (4-(Quinolin-2-ylmethoxy)-phenyl]-hydrazine but substituting 4-(Quinolin-2-ylmethoxy)-phenylamine provided the title compound. MS: (M + H m/z=266.2).
EXAMPLE 58
2-[4-(3-Methyl-5-pyridin-4-yl-[1,2,4]triazol-1-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-[1,2,4]triazol-1-yl)-phenoxymethyl]-quinoline but substituting N,N-dimethylacetamide dimethyl acetal provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.58 (d, J=6.2 Hz, 2 H), 8.22 (d, J=8.3 Hz, 1 H), 8.08 (d, J=8.3 Hz, 1H), 7.84 (d, J=7.7 Hz, 1H), 7.74 (m, 1 H), 7.65 (d, J=8.3 Hz, 1 H), 7.56 (m, 1 H), 7.36 (d, J=6.2 Hz, 2 H), 7.25 (d, J=9.1 Hz, 2H), 7.09 (d, J=8.7 Hz, 2H), 5.41 (s, 2H), 2.48 (s, 3H); MS: (M + H m/z=394.4).
Preparation 45
4-(Quinolin-2-ylmethoxy)-benzamide
To a solution of 2-Chloromethyl-quinoline (1.57 g) and 4-Hydroxy-benzamide (995 mg) in dimethyl formamide (20 mL) was added cesium carbonate (7.3 g) and the reaction mixture heated at 80° C. for 18 h. The reaction mixture was poured into water and extracted with chloroform, dried magnesium sulfate, filtered and concentrated to provided the title compound (909 mg). MS: (M + H -m/z=279.3).
EXAMPLE 59
2-[4-(2-Pyridin-4-yl-2H-[1,2,4]triazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-[1,2,4]triazol-1-yl)-phenoxymethyl]-quinoline but substituting 4-(Quinolin-2-ylmethoxy)-benzamide and Pyridin-4-yl-hydrazine provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.65 (d, J=6.2 Hz, 2 H), 8.21 (d, J=8.3 Hz, 1 H), 8.08 (s, 1H), 8.07 (d, J=7.9 Hz, 1H), 7.84 (d, J=8.3 Hz, 1H), 7.73 (m, 1 H), 7.65 (d, J=8.7 Hz, 1 H), 7.55 (m, 1 H), 7.43 (d, J=9.1 Hz, 2H), 7.32 (d, J=6.2 Hz, 2 H), 7.05 (d, J=8.7Hz, 2H), 5.40 (s, 2H); MS: (M + H m/z=380.2).
EXAMPLE 60
2-[4-(5-Methyl-2-pyridin-4-yl-2H-[1,2,4]triazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-[4-(5-Pyridin-4-yl-[1,2,4]triazol-1-yl)-phenoxymethyl]-quinoline but substituting 4-(Quinolin-2-ylmethoxy)-benzamide, Pyridin4-yl-hydrazine and N,N-dimethylacetamide dimethyl acetal provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.61 (d, J=6.2 Hz, 2 H), 8.21 (d, J=8.7 Hz, 1 H), 8.07 (d, J=7.9 Hz, 1H, 7.83 (d, J=8.3 Hz, 1H), 7.75 (m, 1 H), 7.64 (d, J=8.3 Hz, 1 H), 7.55 (m, 1 H), 7.56 (m, 1H), 7.41 (d, J=9.1 Hz, 2 H), 7.29 (d, J=6.2 Hz, 2H), 7.05 (d, J=8.7 Hz, 2H), 5.40 (s, 2H), 2.47 (s, 3H); MS: (M + H m/z=394.3).
Preparation 46
4-[3-(4-Benzyloxy-phenyl)-1H-pyrazol-4-yl]-pyridine
To a solution of 1-(4-Benzyloxy-phenyl)-2-pyridin-4-yl-ethanone (1.58 g) was added toluene (26 ml) and 1.6 g of Diethoxymethyl-dimethyl-amine and the reaction mixture heated at reflux for 1 h. The reaction mixture was concentrated, dissolved in methanol (26 ml) and hydrazine (0.64 g) and the reaction mixture was heated at reflux for 1 h. The reaction mixture was concentrated and purified via biotage MPLC eluting with 5% methanol/chloroform/0.5% ammonium hydroxide to provided the title compound (0.89 g). MS: (M + H m/z=328.1).
Preparation 47
4-[3-(4-Benzyloxy-phenyl)-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol4-yl]-pyridine
To a solution of 4-[3-(4-Benzyloxy-phenyl)-1H-pyrazol-4-yl]-pyridine (0.42 g) in dimethyl formamide (7 ml) was added cesium carbonate (0.65 g) and 1,1,1-Trifluoro-2-iodo-ethane (0.29 ml). The reaction mixture was heated at 60° C. for 24 h, poured into water and extracted 3× with dichloromethane. Purification via biotage MPLC chromatography, eluting with 5% methanol/0.5% ammonium hydroxide/70% ethyl acetate/hexane provided the title compound. MS: (M + H m/z=410.0).
Preparation 48
4-[4-Pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenol
Following the procedure for the preparation of 4-(1-Methyl4-pyridin4-yl-1H-pyrazol-3-yl)-phenol but substituting 4-[3-(4-Benzyloxy-phenyl)-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-4-yl]-pyridine provided the title compound. MS: (M + H m/z=320.1)
EXAMPLE 61
2-{4-[4-Pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoxaline
To a solution of 4-[4-Pyridin4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenol (79 mg) and Quinoxalin-2-yl-methanol (50 mg) in dioxane (2 ml) was added triphenylphosphine (105 mg) and di-t-butyldiazacarboxalate (92 mg) and the reaction mixture heated at 60° C. After 18, the reaction mixture was poured into 1N NaOH, extracted with methylene chloride, dried magnesium sulfate, filtered and concentrated. Purification with MPLC biotage eluting with 2% methanol/0.5% ammonium hydroxide/60% ethyl acetate/hexanes provided the title compound (54 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 9.09 (s, 1 H), 8.52 (m, 2H), 8.13 (m, 1H), 8.10 (m, 1H), 7.79 (m, 2 H), 7.73 (s, 1 H), 7.40 (d, J=8.7, Hz, 2 H), 7.24 (m, 2H), 7.04 (d, J=8.7 Hz, 2 H), 5.32 (s, 2H), 4.79 (q, J=8.3 Hz, 2 H); MS: (M + H m/z=462.1).
EXAMPLE 62
8-Methoxy-2-[4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-{4-[4-Pyridin4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoxaline but substituting 4-(1-Methyl4-pyridin4-yl-1H-pyrazol-3-yl)-phenol and (8-Methoxy-quinolin-2-yl)-methanol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.45 (d, J=6.2 Hz, 2 H), 8.15 (d, J=8.7 Hz, 1H), 7.73 (d, J=8.3 Hz,1H), 7.55 (s, 1H), 7.44 (m, 1 H), 7.37 (m, 3 H), 7.15 (d, J=5.8, Hz, 2 H), 7.07 (d, J=7.5 Hz, 1H), 6.99 (d, J=8.7 Hz, 2 H), 5.46 (s, 2H), 4.08 (s, 3 H), 3.94 (s, 3H); MS: (M + H m/z=423.1).
EXAMPLE 63
2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-pyrido[1,2-a]pyrimidin-4-one
Following the procedure for the preparation of 2-[4-(4-Pyridin-4-yl-4H-[1,2,4]triazol-3-yl)-phenoxymethyl]-quinoline but substituting 2-Chloromethyl-pyrido[1,2-a]pyrimidin4-one provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 9.01 (d, J=7.1 Hz, 1 H), 8.43 (m, 2H), 7.72 (m, 1H), 7.59 (d, J=8.7 Hz, 1H), 7.53 (s, 1H), 7.37 (d, J=9.1 Hz, 2H), 7.12 (m, 3H), 6.93 (d, J=8.7Hz, 2H), 6.68 (s, 1 H), 5.05 (s, 2H), 3.92 (s, 3H); MS: (M + H m/z=410.1).
EXAMPLE 64
2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinazoline
Following the procedure for the preparation of 2-[4-(4-Pyridin-4-yl-4H-[1,2,4]triazol-3-yl)-phenoxymethyl]-quinoline but substituting 2-Chloromethyl-quinazoline provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 9.43 (s, 1H), 4.43 (d, J=4.6 Hz, 2 H), 8.07 (d, J=8.3 Hz, 1H), 7.93 (d, 2H), 7.69 (t, J=7.9 Hz, 1H), 7.55 (s, 1 H), 7.36 (d, J=8.7 Hz, 2 H), 7.15 (d, J=6.2, Hz, 2 H), 7.05 (d, J=8.7 Hz, 2H), 5.48 (s, 2H), 3.94 (s, 3H); MS: (M + H m/z=394.2)
Preparation 49
4-Benzyloxy-2-fluoro-benzoic acid benzyl ester
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid methyl ester but substituting two equivalents of benzyl bromide and 2-Fluoro4-hydroxy-benzoic acid provided the title compound. MS: (M + H m/z=337.2).
Preparation 50
4-Benzyloxy-2-fluoro-benzoic acid
Following the procedure for the preparation of 4-(Quinolin-2-ylmethoxy)-benzoic acid but substituting 4-Benzyloxy-2-fluoro-benzoic acid benzyl ester provided the title compound. MS: (M + H m/z=247.1).
Preparation 51
4-Benzyloxy-2-fluoro-N-methoxy-N-methyl-benzamide
Following the procedure for the preparation of N-Methoxy-N-methyl4-(quinolin-2-ylmethoxy)-benzamide but substituting 4-Benzyloxy-2-fluoro-benzoic acid provided the title compound. MS: (M + H m/z=290.2).
Preparation 52
1-(4-Benzyloxy-2-fluoro-phenyl)-2-pyridin-4-yl-ethanone
Following the procedure for the preparation of 2-pyridin-4-yl-1-[4-(quinolin-2-ylmethoxy)-phenyl]-ethanone but substituting 4-Benzyloxy-2-fluoro-N-methoxy-N-methyl-benzamide provided the title compound. MS: (M + H m/z=322.1).
Preparation 53
4-[3-(4-Benzyloxy-2-fluoro-phenyl)-l -methyl-1H-pyrazol-4-yl]-pyridine
Following the procedure for the preparation of 4-[3-(4-Benzyloxy-phenyl)-1-methyl-1H-pyrazol4-yl]-pyridine but substituting 1-(4-Benzyloxy-2-fluoro-phenyl)-2-pyridin4-yl-ethanone provided the title compound. MS: (M + H m/z=360.1).
Preparation 54
3-Fluoro-4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenol
Following the procedure for the preparation of 4-(1-Methyl4-pyridin-4-yl-1H-pyrazol-3-yl)-phenol but substituting 4-[3-(4-Benzyloxy-2-fluoro-phenyl)-1-methyl-i H-pyrazol4-yl]-pyridine provided the title compound. MS: (M + H m/z=270.1).
EXAMPLE 65
2-[3-Fluoro-4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 3-Fluoro-4-(1-methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenol (450 mg) in dimethylformamide (10 ml) was added cesium carbonate (2 g) and 2-chloro methyl quinoline (481 mg) and the reaction mixture was heated at 60° C. for 18 h. The reaction mixture was poured into 1N NaOH, extracted with methylene chloride, dried magnesium sulfate, filtered and concentrated. Biotage MPLC purification eluting with methanol 2%/0.5% ammonium hydroxide/70% ethyl acetate/hexanes provided the title compound. The free base was stirred in ethyl acetate and 1.1 equivalents of succinic acid was added. The white precipitate was filtered and dried to provide the title compound as the succinate salt (280 mg). 1 H NMR (400 MHz, DMSO) δ 8.43 (d, J=8.3 Hz, 1 H), 8.37 (d, J=6.2 Hz, 2H), 8.26 (s, 1H), 8.00 (m, 2H), 7.78 (t, J=7.1 Hz, 1H), 7.70 (d, J=8.3 Hz, 1 H), 7.61 (t, J=6.6 Hz, 1 H), 7.38 (t, J=8.3, Hz, 1 H), 7.10 (d, J=6.2 Hz, 2H), 7.00 (m, 2H), 5.40 (s, 2H), 3.88 (s, 3 H), 2.38 (s, 4H), MS: (M + H m/z=411.1).
Preparation 55
4-[3-(4-Benzyloxy-2-fluoro-phenyl)-1H-pyrazol-4-yl]-pyridine
Following the procedure for the preparation of 2-[4-(4-Pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 1-(4-Benzyloxy-2-fluoro-phenyl)-2-pyridin-4-yl-ethanone provided the title compound. MS: (M + H m/z=346.3).
Preparation 56
4-[3-(4-Benzyloxy-2-fluoro-phenyl)-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-4-yl]-pyridine
Following the procedure for the preparation of 2-{4-[-Pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline but substituting 4-[3-(4-Benzyloxy-2-fluoro-phenyl)-1H-pyrazol4-yl]-pyridine provided the title compound. MS: (M + H m/z=428.4).
Preparation 57
3-Fluoro-4-[4-pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenol
To 4-[3-(4-Benzyloxy-2-fluoro-phenyl)-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-4-yl]-pyridine (900 mg) was added trifluoroacetic acid (5.25 ml) and anisole (1.15 ml) and the reaction mixture heated at reflux for 18 h. The reaction mixture was quenched with with 1N NaOH, extracted 3× tetrahydrofuran, dried magnesium sulfate, filtered and concentrated. Purification via Biotage MPLC eluting with 5% methanol/1% ammonium hydroxide/ethyl acetate provided the title compound (552 mg). MS: (M + H m/z=338.2).
EXAMPLE 66
2-{3-Fluoro-4-[4-pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoline
Following the procedure for the preparation of 2-[3-Fluoro4-(1-methyl4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 3-Fluoro4-[4-pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenol and acetone as the solvent provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.46 (m, 2 H), 7.80 (s, 1H), 7.31 (t, J=8.3 Hz, 1H), 7.24 (m, 5 H), 6.72 (dd, J=8.3, 2.5 Hz, 1 H), 6.50 (dd, J=11.6, 2.1 Hz, 1 H), 4.81 (q, J=8.4 Hz, 2H); MS: (M + H m/z=479.2).
EXAMPLE 67
2-{3-Fluoro-4-[4-pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoxaline
Following the procedure for the preparation of 2-[3-Fluoro4-(1-methyl4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline but substituting 3-Fluoro4-[4-pyridin4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenol, 2-Chloromethyl-quinoxaline and acetone as the solvent provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 9.09 (s, 1 H), 8.46 (m, 2H), 8.15 (m, 1H), 8.09 (m, 1 H), 7.81 (m, 3H), 7.43 (t, J=8.7Hz, 1H), 7.12 (d, J=6.2 Hz, 2H), 6.93 (dd, J=7.9, 2.0 Hz, 1 H), 6.81 (dd, J=11.6, 2.5 Hz, 1 H), 5.43 (s, 2H), 4.80 (q, J=8.3 Hz, 2H); MS: (M + H m/z=480.1).
EXAMPLE 68
4-Chloro-2-[4-(1-methyl4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
Following the procedure for the preparation of 2-{4-[4-Pyridin-4-yl-1-(2,2,2-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoxaline but substituting 4-(1-Methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenol and (4-Chloro-quinolin-2-yl)-methanol provided the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ 8.43 (d, J=4.6 Hz, 2 H), 8.18 (d, J=8.7 Hz, 1H), 8.04 (d, J=7.9 Hz, 1H), 7.73 (m, 2H), 7.60 (t, J=7.1 Hz, 1 H), 7.52 (s, 1 H), 7.37 (d, J=9.1, Hz, 2 H), 7.12 (d, J=6.2 Hz, 2H), 6.98 (d, J=8.7 Hz, 2 H), 5.30 (s, 2H), 3.90 (s, 3 H); MS: (M + H m/z=427.1).
EXAMPLE 69
4-Methoxy-2-[4-(1-methyl-4-pyridin4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline
To a solution of 4-Chloro-2-[4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline (125 mg) in methanol (4 mL) was added phenanthroline (78 mg), cesium carbonate (143 mg) and copper iodide (5 mg). The reaction mixture was heated in a microwave reactor at 165° C. with 50 W of power for 20 min. The reaction mixture was filtered through celite and concentrated. Purification via MPLC biotage chromatography, eluting with 5% methanol/1% ammonium hydroxide/methylene chloride provided the title compound (74 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 8.45 (d, J=5.4 Hz, 2 H), 8.18 (d, J=8.3 Hz, 1H), 7.97 (d, J=8.3 Hz, 1H), 7.68 (m, 1H), 7.55 (s, 1H), 7.49 (t, J=7.1 Hz, 1 H), 7.37 (d, J=9.1, Hz, 2 H), 7.15 (d, J=6.2 Hz, 2H), 7.01 (m, 3H), 5.32 (s, 2H), 4.02 (s, 3 H), 3.95 (s, 3H); MS: (M + H m/z=423.3).
EXAMPLE 70
Dimethyl-{2-[4-(1-methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinolin-4-yl}-amine
To a solution of 4-Chloro-2-[4-(1-methyl4-pyridin-4-yl-1H-pyrazol-3-yl)-phenoxymethyl]-quinoline (135 mg) in tetrahydrofuran (4 mL) was added dimethylamine (2N in methanol, 0.32 mL), cesium fluoride (5 mg), diisopropyl ethyl amine (62 mg) and tetrabutyl ammonium iodide (12 mg). The reaction mixture was heated in a microwave reactor at 180° C. with 100 W of power for 40 min. The reaction mixture was filtered through celite and concentrated. Purification via MPLC biotage chromatography, eluting with 5% methanol/1% ammonium hydroxide/methylene chloride provided the title compound (36 mg). 1 H NMR (400 MHz, CDCl 3 ) δ 8.45 (d, J=6.2Hz, 2 H), 8.04 (d, J=8.3 Hz, 1H), 7.99 (d, J=8.3 Hz, 1H), 7.62 (m, 1H), 7.56 (s, 1H), 7.42 (m, 1 H), 7.38 (d, J=9.1 Hz, 2 H), 7.15 (d, J=6.2 Hz, 2H), 7.01 (m, 3H), 5.29 (s, 2H), 3.95 (s, 3 H), 3.03 (s, 6H); MS: (M + H m/z=436.3).
Preparation 58
N-Methoxy-N-methyl-4-triisopropylsilanyloxymethyl-benzamide
Following the procedure for the preparation of 4-benzyloxy-N-methoxy-N-methyl-benzamide but substituting 4-Triisopropylsilanyloxymethyl-benzoic acid provided the title compound. MS: (M + H m/z=352.1).
Preparation 59
2-Pyridin-4-yl-1-(4-triisopropylsilanyloxymethyl-phenyl)-ethanone
Following the procedure for the preparation of 1-(4-Benzyloxy-phenyl)-2-pyridin-4-yl-ethanone but substituting N-Methoxy-N-methyl-4-triisopropylsilanyloxymethyl-benzamide provided the title compound. MS: (M + H m/z=384.1).
Preparation 60
4-[1-Methyl-3-(4-triisopropylsilanyloxymethyl-phenyl)-1H-pyrazol-4-yl]-pyridine
Following the procedure for the preparation of 4-[3-(4-Benzyloxy-phenyl)-1-methyl-1H-pyrazol-4-yl]-pyridine but substituting 2-Pyridin-4-yl-1-(4-triisopropylsilanyloxymethyl-phenyl)-ethanone provided the title compound. MS: (M + H m/z=422.2).
Preparation 61
[4-(l -Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenyl]-methanol
To a solution of 4-[1-Methyl-3-(4-triisopropylsilanyloxymethyl-phenyl)-1H-pyrazol-4-yl]-pyridine (1.75 g) in THF (16.2 mL) was added TBAF (1.0M THF, 5.2 mL) and the reaction mixture stirred at ambient temperature under inert atmosphere for 1 h. The reaction mixture was poured into saturated sodium bicarbonate, extracted 3× with chloroform, dried magnesium sulfate filtered and concentration. Purification via MPLC biotage chromatography eluting with 2% methanol/0.5% saturated ammonium hydroxide/50% ethyl acetate/hexanes provided the title compound (920 mg, 84%). MS: (M + H m/z=266.1).
EXAMPLE 71
2-[4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-benzyloxy]-quinoline di succinic acid
Following the procedure for the preparation of 2-{4-[4-Pyridin4-yl-1-(2,212-trifluoro-ethyl)-1H-pyrazol-3-yl]-phenoxymethyl}-quinoxaline but substituting [4-(1-Methyl-4-pyridin-4-yl-1H-pyrazol-3-yl)-phenyl]-methanol and Quinolin-2-ol provided the title compound. 1 H NMR (400 MHz, DMSO) δ 8.42 (d, J=5.0 Hz, 2 H), 8.25 (d, J=8.7 Hz, 1H), 8.14 (s, 1H), 7.88 (d, J=7.9 Hz, 1H), 7.78 (d, J=7.9 Hz, 1H), 7.66 (t, J=7.1 Hz, 1 H), 7.51 (d, J=7.5 Hz, 2 H), 7.40 (m, 3 H), 7.19 (d, J=4.6 Hz, 2H), 7.07 (d, J=8.7 Hz, 1H), 5.49 (s, 2H), 2.38 (s, 8 H); MS: (M + H m/z=393.1).
Preparation 62
N-((4-(Benzyloxy)phenyl)(tosyl)methyl)formamide
A mixture of 4-methylbenzenesulfinic acid (3.1 g, 19.9 mmol), 4-(benzyloxy)benzaldehyde (4.2 g, 19.9 mmol), and formamide (4.5 mL ) was heated at 60° C. for 20 h. The mixture was diluted with methanol and stirring was continued for 1 h at rt. The resultant solid was filtered and dried to give 3.81 g (49%) of a white solid. The product was used in the next step without future purification.
Preparation 63
1-((4-(Benzyloxy)phenyl)isocyanomethylsulfonyl)-4-methylbenzene
To a solution of N-((4-(Benzyloxy)phenyl)(tosyl)methyl)formamide (3.2 g, 8.1 mmol) in 43 mL of DME (dimethoxy ethane) at 0° C. was added POCl 3 (2.27 mL) followed by the dropwise addition of triethylamine (5.6 mL ). The resultant solution was then stirred at 0° C. for 3 h and finally poured into cooled water. The precipitate was collected and dried to give 3.3 g of pale yellow solid. MS m/z: 378 [M+1] + .
Preparation 64
4-(4-(4-(Benzyloxy)phenyl)oxazol-5-yl)pyridine
A mixture of 1-((4-(Benzyloxy)phenyl)isocyanomethylsulfonyl)4-methylbenzene (4.3 g, 11.4 mmol), isonicotinaldehyde (1.34 g, 12.5 mmol) and K 2 CO 3 (3.15 g, 22.8 mmol) in methanol (96 mL ) and DME (30 mL) was heated at reflux for 5 h. After removal of solvent, the residue was purified by silica gel chromatography (2:1 hexane/EtOAc) to provide 2.29 g (84%) of a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ: 5.12v (s, 2H), 7.03 (d, 2H), 7.46 (m, 6H), 7.56 (d, 2H), 7.61 (d, 2H), 8.02 (s, 1H), 8.58 (d, 2H). MS m/z: 329 [M+1] + .
Preparation 65
4-(5-(pyridin-4-yl)oxazol-4-yl)phenol
To a solution of 4-(4-(4-(Benzyloxy)phenyl)oxazol-5-yl)pyridine (300 g, 0.91 mmol) was added 20% Pd(OH) 2 /C (30 mg) and ammonium formate (115 mg, 1.83 mmol) in methanol (8 mL ). The solution was heated at 60° C. for 20 min. The catalyst was removed by filtration and the filtrate was concentrated to give 208 mg (96%) of the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ: 6.92 (m, 2H), 7.46 (m, 2H), 7.57 (d, 2H), 8.02 (s, 1H), 8.58 (m, 2H). MS m/z: 239 [M+1] + .
EXAMPLE 72
2-((4-(5-(pyridin-4-yl)oxazol-4-yl)phenoxy)methyl)quinoline
To a solution of compound 4-(5-(pyridin4-yl)oxazol4-yl)phenol (90 mg, 0.38 mmol) in 1 mL of dry DMF was added CsF (115 mg, 0.76 mmol). After stirring for 0.5 h, 2-(chloromethyl)quinoline (67 mg, 0.38 mmol) was added and the reaction was heated at 80° C. for 48 h. Upon removal of DMF under vacuum, the residue was purified by PTLC (1:2 hexane/EtOAc) to give 29 mg (20%) of the title compound as a white solid. 1 H NMR (400 MHz, CDCl 3 ) δ: 5.47 (s, 2H), 7.11 (m, 2H), 7.56 (m, 5H), 7.70 (d, 1H), 7.78 (t, 1H), 7.86 (d, 1H), 8.01 (s, 1H), 8.12 (d, 1H), 8.26 (d, 1H), 8.57 (d, (2H). MS m/z: 380 [M+1] + .
Preparation 66
1-(4-(benzyloxy)phenyl)-2-bromo-2-(pyridin-4-yl)ethanone
To a solution of 1-(4-(benzyloxy)phenyl)-2-(pyridin-4-yl)ethanone (1.39 g, 4.58 mmol) in acetic acid was added a solution of bromine (0.72 g, 4.58 mmol) in acetic acid (3 mL). After stirring 2 h, the solid was collected via filtration and washed with acetic acid to provide 1.67 g (96%) of the title compound as a pale yellow solid. 1 H NMR (400 MHz, DMSO) δ: 5.21 (s, 1H), 7.15 (d, 2H), 7.42 (m, 3H), 7.87 (m, 1H), 8.06 (d, 2H), 8.77 (m, 1H). MS m/z: 382 [M+1] + .
Preparation 67
4-(4-(4-(benzyloxy)phenyl)-2-methyloxazol-5-yl)pyridine
To a mixture of sodium acetate (323 mg, 2.38 mmol) and ammonium acetate (304 mg, 3.95 mmol) in acetic acid (10 mL) was added 1-(4-(benzyloxy)phenyl)-2-bromo-2-(pyridin-4-yl)ethanone (302 mg, 0.79 mmol). The resulting mixture was then refluxed for 48 h. After removal of the solvent under vacuum, the residue was dissolved in ethyl acetate and the solution was washed with satd NaHCO3. The organic phase was dried and concentrated in vacuum to give an oil, which was purified via silica gel chromatography (1:3 EtOAc/n-hexane) to provide 111 mg (41%) of the title compound. 1 H NMR (400 MHz, CDCl 3 ) δ: 2.58 (s, 3H), 5.15 (s, 2H), 7.01 (d, 2H), 7.39 (m, 7H), 7.56 (d, 2H), 8.57 (d, 2H). MS m/z: 343 [M+1] + .
Preparation 68
4-(2-methyl-5-(pyridin-4-yl)oxazol-4-yl)phenol
4-(4-(4-(Benzyloxy)phenyl)-2-methyloxazol-5-yl)pyridine was hydrogenated in the presence of ammonium formate and Pd(OH) 2 in methanol for 1 h at 50° C. The catalyst was removed via filtration and the filtrate was concentrated. The resultant residue was dissolved in methylene chloride and dried with Na 2 SO 4 . Evaporation of the solvent gave 69 mg (86%) of the title compound as a brown solid. MS m/z: 253.
EXAMPLE 73
2-((4-(2-methyl-5-(pyridin-4-yl)oxazol-4-yl)phenoxy)methyl)quinoline
To a solution of 4-(2-methyl-5-(pyridin-4-yl)oxazol-4-yl)phenol (21 mg, 0.083 mmol) in 2.5 mL of dry DMF was added Cs 2 CO 3 (54 mg, 0.17 mmol). After stirring for 0.5 h, 2- (chloromethyl)quinoline (17.8 mg, 0.100 mmol) was added and the mixture was stirred at 85° C. for 12 h. After removal of the DMF under vacuum, the residue was purified by PTLC (1:2 hexane/EtOAc) to give 13 mg (40%) of the title compound as a pale yellow solid. 1 H NMR (400 MHz, CDCl 3 ) δ: 2.54 (s, 3H), 5.41 (s, 2H), 7.06 (m, 2H), 7.41 (m, 2H), 7.53 (m, 3H), 7.68 (d, 1H), 7.80 (t, 1H), 7.83 (d, 1H), 8.05 (d, 1H), 8.20 (d, 1H), 8.53 (m, 2H). MS m/z: 394 [M+1] + .
Preparation 69
4-(4-((quinolin-2-yl)methoxy)phenyl)-3-(pyridin-4-yl)but-3-en-2-one
A mixture of 4-((quinolin-2-yl)methoxy)benzaldehyde (2.5 g, 9.5 mmol), 1-(pyridin-4-yl)propan-2-one (1.3 g, 9.5 mmol) and piperidine (162 mg, 1.9 mmol) in toluene (50 mL) was heated at reflux for 18 h, concentrated, and the residue chromatographed on silica eluting with a gradient of ethyl acetate in hexanes giving impure title substance (2.4 g) as a yellow solid which was chromatographed again on silica eluted with 1% and 2% methanol in dichloromethane containing 0.5% concentrated ammonium hydroxide giving a 3:1 mixture of the title substance contaminated with the pyridyl starting material. Yield 2.0 g, 55%. The title substance appeared to be a 10:1 mixture of two isomers by NMR. 1 H NMR (CDCl 3 , 400 mHz, partial) δ 2.35 (s, 3H, major isomer), 2.23 (s, 3H, minor isomer). HPLC-MS 6.09 min, m/e 381 (MH+).
EXAMPLE 74
2-((4-(3-Methyl-4-(pyridin-4-yl)-1H-pyrazol-5-yl)phenoxy)methyl)quinoline
A mixture of 4-(4-((quinolin-2-yl)methoxy)phenyl)-3-(pyridin-4-yl)but-3-en-2-one (1.00 g, 2.60 mmol) and p-toluensulfonylhydrazine (484 mg, 2.6 mmol) in acetic acid (14 mL) was heated at reflux for 10 h. Additional p-toluenesulfonylhydrazine (242 mg, 0.5 mmol) was added and the mixture heated at reflux 2 h. The mixture was concentrated, the residue dissolved in dichloromethane and the resulting solution washed with water (2×25 mL), dried and concentrated. The residue was chromatographed on silica eluted with 1%, 2%, and 3% methanol in dichloromethane containing 0.5% concentrated ammonium hydroxide giving a solid which was triturated with ether and dried. Yield 293 mg, 29%. 1 H NMR (CDCl 3 , 400 mHz) δ 8.51 (m, 2H), 8.18 (d, 1H, J=8.7 Hz), 8.06 (d, 1H, J=7.9 Hz), 7.81 (d, 1H, J=8.3 Hz), 7.72 (m, 1H), 7.64 (d, 1H, J=8.3 Hz), 7.54 (m, 1H), 7.24 (m, 2H), 7.13 (m, 2H), 6.96 (m, 2H), 5.36 (s, 2H), 2.33 (s, 3H). HPLC-MS (system 1) 4.65 min, m/e 393 (MH+).
EXAMPLE 75
2-((4-(1,3-dimethyl-4-(pyridin-4-yl)-1H-pyrazol-5-yl)phenoxy)methyl)quinoline
A solution of 2-((4-(3-methyl-4-(pyridin-4-yl)-1H-pyrazol-5-yl)phenoxy)methyl)quinoline (150 mg, 0.38 mmol) in anhydrous dimethylformamide (2 mL) was treated at 0° C. with sodium hydride dispersion (30 mg, 0.76 mmol of 60% NaH in oil) followed after 20 min with methyl iodide (54 mg, 0.38 mmol), and the stirred mixture was allowed to warm to RT overnight. Water was added and the mixture extracted with dichloromethane (3×20 mL). The organic layer was dried, concentrated, and the residue chromatographed on silica eluted with an ethyl acetate-hexane gradient containing 1% triethylamine, giving fractions containing two isomeric substances. The less polar isomer (18 mg) was thus obtained (methylation regiochemistry tentatively assigned by NMR). 1 H NMR (CDCl 3 , 400 mHz) δ 8.41 (m, 2H), 8.21 (d, 1H, J=8.7 Hz), 8.07 (d, 1H, J=8.3 Hz), 7.84 (d, 1H, J=9.5 Hz), 7.74 (ddd, 1H), 7.67 (d, 1H, J=8.3 Hz), 7.55 (ddd, 1H), 7.12 (m, 2H), 7.05 (m, 2H), 7.0 (m, 2H), 5.40 (s, 2H), 3.71 (s, 3H), 2.37 (s, 3H). HPLC-MS 4.81 min, m/e 407 (MH+).
EXAMPLE 76
2-((4-(1,5-dimethyl-4-(pyridin-4-yl)-1H-pyrazol-3-yl)phenoxy)methyl)quinoline
The more polar fractions obtained from the sodium hydride/methyl iodide alkylation of 2-((4-(3-methyl-4-(pyridin-4-yl)-1H-pyrazol-5-yl)phenoxy)methyl)quinoline gave 26 mg of impure title substance which was recrystallized from 10:1 ethyl acetate-hexanes giving isomerically pure material whose methylation regiochemistry was tentatively assigned by NMR. 1 H NMR (CDCl 3 , 400 mHz) δ 8.51 (m, 2H), 8.17 (d, 1H, J=8.7 Hz), 8.05 (d, 1H, J=8.3 Hz), 7.85 (d, 1H, J=8.3 Hz), 7.72 (ddd, 1H), 7.65 (d, 1H, J=8.7 Hz), 7.53 (t, 1H, J=7.5 Hz), 7.27 (m, 2H), 7.12-7.11 (m, 2H), 6.93 (m, 2H), 5.36 (s, 2H), 3.87 (s, 3H), 2.30 (s, 3H), HPLC-MS 4.78 min, m/e 407 (MH+).
Preparation 69a
1-(quinolin-2-yl)ethanol
A solution of methylmagnesium bromide (17.6 mL of 1.4 M in toluene, 24.7 mmol) was added at <10° C. to a solution of quinoline-2-carboxaldehyde (3.0 g, 19 mmol) in anhydrous tetrahydrofuran (50 mL). The mixture was stirred at RT for 1 h and poured into saturated aqueous ammonium chloride (100 mL), and the resulting mixture was extracted with ethyl acetate (3×150 mL). The extracts were dried, concentrated, and the residue chromatographed on silica eluted with 30% and 40% ethyl acetate-hexanes giving a yellow solid. Yield 2.46 g, 75%. 1 H NMR (CDCl 3 , 400 mHz) δ 8.15 (d, 1H, J=8.7 Hz), 8.07 (d, 1H, J=8.7 Hz), 7.81 (dd, 1H, J=1, 8 Hz), 7.71 (ddd, 1H, J=1, 7, 8.5 Hz), 7.51 (ddd, 1H, J=1, 7, 8.3 Hz), 7.33 (d, 1H, J=8.3 Hz), 5.07-4.99 (m, 2H), 1.56 (d, 3H, J=6.2 Hz).
EXAMPLE 77
2-(1-(4-(1-methyl-4-(pyridin-4-yl)-1H-pyrazol-3-yl)phenoxy)ethyl)quinoline
A mixture of 4-(1-methyl-4-(pyridin-4-yl)-1H-pyrazol-3-yl)phenol (75 mg, 0.30 mmol) and 1-(quinolin-2-yl)ethanol (78 mg, 0.45 mmol) in p-dioxane (2 mL) was treated sequentially at RT with triphenylphosphine (126 mg, 0.48 mmol) and di-t-butyldiazodicarboxylate (110 mg, 0.48 mmol) and the mixture was heated at 60° C. for 4 h. Aqueous 2N NaOH was added and the mixture extracted with dichloromethane. The organic layers were dried, concentrated, and the residue purified on silica gel eluted with a gradient of ethyl acetate-hexanes giving a yellow solid. Yield 36 mg, 29%. 1 H NMR (CDCl 3 , 400 mHz) δ 8.40 (m, 2H), 8.10 (d, 1H, J=8.7 Hz), 8.06 (d, 1H, J=7.5 Hz), 7.77 (d, 1H, J=8.3 Hz), 7.71 (ddd, 1H), 7.55 (d, 1H, J=8.3 Hz), 7.53-7.49 (m, 2H), 7.25 (m, 2H), 7.10 (m, 2H), 6.88 (m, 2H), 5.59 (q, 1H, J=6.6 Hz), 3.91 (s, 3H), 1.75 (d, 3H, J=6.6 Hz). HPLC-MS (system 1) 4.73 min, m/e 407 (MH+).
Preparation 70
2-((4-(2-(pyridin-4-yl)ethynyl)phenoxy)methyl)quinoline
A mixture of 4-(2-(pyridin-4-yl)ethynyl)phenol (335 mg, 1.72 mmol), 2-(chloromethyl)quinoline hydrochloride (385 mg, 1.8 mmol), and cesium carbonate (2.2 g, 6.87 mmol) was stirred in dimethylformamide (8 mL) at 65° C. for 3 h. Water (20 mL) was added and the mixture was extracted with dichloromethane (3×15 mL). The organic layers were dried, concentrated, and the residue chromatographed on silica eluted with a gradient of 10% to 80% ethyl acetate-hexanes giving 450 mg (78%) of a yellow solid. 1 H NMR (CDCl 3 , 400 mHz) δ 8.56 (m, 2H), 8.20 (d, 1H, J=8.7 Hz), 8.08 (d, 1H, J=8.3 Hz), 7.82 (d, 1H, J=7.9 Hz), 7.74 (ddd, 1H, J=8.4, 7, 1Hz), 7.63 (d, 1H, J=8.7 Hz), 7.55 (ddd, 1H, J=8, 7, 1 Hz), 7.47 (m, 2H), 7.35 (m, 2H), 7.01 (m, 2H), 5.41 (s, 2H). MS (AP+) m/e 337 (MH+).
Preparation 71
4-(2-(pyridin-4-yl)ethynyl)phenol
Boron tribromide (1M in dichloromethane, 9.7 mL, 9.7 mmol) was added at 0° C. to a solution of 4-(2-(4-methoxyphenyl)ethynyl)pyridine (810 mg, 3.88 mmol) in dichloromethane (10 mL) and the mixture was stirred at RT for 5 h. Aqueous 1 N sodium hydroxide (20 mL) was added and after 40 min the pH was brought between 7 and 8 by addition of 1 N HCl. The resulting mixture was extracted with 4:1 dichloromethane:2-propanol (3×30 mL). The organic layers were dried, concentrated and evaporated and the residue chromatographed on silica in a gradient from 25% to 80% ethyl acetate-hexanes giving a brown solid. Yield 450 mg, 60%. 1 H NMR (CDCl 3 containing CD 3 OD, 400 mHz) δ 8.50 (br, 2H), 7.38 (br, 2H), 7.37 (d, 2H, J=8.7 Hz), 6.77 (d, 2H, J=8.7 Hz), 3.11 (br, 2H, OH+H2O). MS (AP+) m/e 196 (MH+).
Preparation 72
4-(2-(4-methoxyphenyl)ethynyl)pyridine
A mixture of 4-methoxyphenylacetylene (2.86 g, 21.7 mmol), 4-iodopyridine (4.44 g, 21.7 mmol), cuprous iodide (206 mg, 1.08 mmol), bis(triphenylphosphine)palladium(II) dichloride (758 mg, 1.08 mmol) in tetrahydrofuran (40 mL) and triethylamine (20 mL) was heated at reflux for 2 h. The mixture was filtered, concentrated, and the residue chromaptographed on silica in 1:1 ethyl acetate-hexanes giving 2.45 g (54%) of a yellow solid. 1 H NMR (CDCl 3 , 400 mHz) δ 9.2 (very broad, 2H), 7.57 (br, 2H), 7.48 (d, 2H, J=8.7 Hz), 6.88 (d, 2H, J=8.7 Hz), 3.82 (s, 3H). MS (AP+) m/e 210 (MH+).
EXAMPLE 78
2-((4-(5-(pyridin-4-yl)-1,2,3-triazol-4-yl)phenoxy)methyl)quinoline
Trimethylsilylazide (730 mg, 6.4 mmol) and 2-((4-(2-(pyridin-4-yl)ethynyl)phenoxy)methyl)quinoline (360 mg) were combined in a screw cap sealed tube and heated behind a safety shield in a 150° C. bath for 72 h. The mixture was concentrated and the yellow residue triturated with ether (2×10 mL) leaving a yellow solid (346 mg) which was chromatographed on silica eluted with a gradient of 0.5%-2% methanol in dichloromethane giving a yellow solid (210 mg,52%). 1 H NMR (CDCl 3 with a drop of CD 3 OD, 400 mHz) δ 8.54 (d, 2H, J=6.2 Hz), 8.23 (d, 1H, J=8.7 Hz), 8.07 (d, 1H, J=8.7 Hz), 7.84 (d, 1H, J=7.9 Hz), 7.74 (ddd, 1H, J=8.4, 7, 1Hz), 7.69 (d, 1H, J=8.7 Hz), 7.63 (d, 2H, J=6.2 Hz), 7.56 (ddd, 1H), 7.41 (m, 2H), 7.09 (m, 2H), 5.41 (s, 2H). MS (AP+) m/e 380 (MH+).
Preparation 73
4-(2-methyl-5-(pyridin-4-yl)-2H-1,2,3-triazol-4-yl)phenol
A solution of 4-(5-(4-methoxyphenyl)-2-methyl-2H-1,2,3-triazol-4-yl)pyridine (203 mg, 0.76 mmol) in dichloromethane (5 mL) was treated at 0° C. with boron tribromide (2.3 mL of 1M in dichloromethane) and the mixture stirred 18 h at RT. Methanol (3 mL) was added and the mixture was concentrated and extracted using dichloromethane and aqueous sodium bicarbonate. The organic extracts were dried and concentrated giving a yellow solid which was chromatographed on silica (gradient of 0.5%-3% methanol in dichloromethane) giving two substances. The more polar substance (88 mg) was assigned 4-(2-methyl-5-(pyridin4-yl)-2H-1,2,3-triazol-4-yl)phenol. 1 H NMR (CDCl 3 , 400 mHz, partial) δ 8.57 (br, 2H), 7.59 (d, 2H, J=5.2 Hz), 7.32 (m, 2H), 6.90 (m, 2H), 4.26 (s, 3H). HPLC-MS (system 1) 3.96 min, m/e 253 (MH+). The less polar substance (80 mg) was assigned to be the corresponding boronate as it was found to convert on treatment with aqueous NaOH to the less polar substance.
Preparation 74
4-(5-(4-methoxyphenyl)-2-methyl-2H-1,2,3-triazol-4-yl)pyridine, 4-(5-(4-methoxyphenyl)-1-methyl-1H-1,2,3-triazol-4-yl)pyridine, and 4-(5-(4-methoxyphenyl)-3-methyl-3H-1,2,3-triazol-4-yl)pyridine
Sodium hydride (240 mg of 60% oil dispersion, 6.0 mmol) was added to a solution of 4-(5-(4-methoxyphenyl)-1,2,3-triazol-4-yl)pyridine (755 mg, 3.0 mmol) in dimethylformamide (10 mL) at 0° C. and the mixture was stirred 30 min. Methyl iodide (425 mg) was added and the mixture was stirred at 0° C. for 2.5 h, quenched with water (20 mL), and extracted with dichloromethane (3×20 mL). The organic layers were dried over magnesium sulfate and concentrated. The residue was chromatographed on silica eluted with a gradient of 50% to 100% ethyl acetate-hexanes providing three isomeric substances of increasing polarity. Each showed a mass of m/e 267 (MH+) by HPLC-MS. Each structure was assigned by single crystal X-ray on crystals grown from either ethyl acetate or acetonitrile. The least polar substance (454 mg of yellow solid), 4-(5-(4-methoxyphenyl)-2-methyl-2H-1,2,3-triazol-4-yl)pyridine, 1 H NMR (CDCl 3 , 400 mHz) δ 8.59 (br, 2H), 7.52 (br, 2H), 7.41 (m, 2H), 6.93 (m, 2H), 4.26 (s, 3H), 3.84 (s, 3H). The middle-polarity substance (235 mg yellow solid), 4-(5-(4-methoxyphenyl)-1-methyl-1H-1,2,3-triazol-4-yl)pyridine, 1 H NMR (CDCl 3 , 400 mHz) δ 8.49 (d, 2H, J=6.22), 7.52 (m, 2H), 7.24 (m, 2H), 7.06 (m, 2H), 3.91 (s, 3H), 3.89 (s, 3H). The most polar substance (50 mg yellow solid), 4-(5-(4-methoxyphenyl)-3-methyl-3H-1,2,3-triazol-4-yl)pyridine, 1 H NMR (CDCl 3 , 400 mHz) δ 8.59 (br, 2H), 7.52 (br, 2H), 7.41 (m, 2H), 6.93 (m, 2H), 4.26 (s, 3H), 3.84 (s, 3H).
Preparation 75
4-(5-(4-methoxyphenyl)-1,2,3-triazol-4-yl)pyridine
4-(2-(4-methoxyphenyl)ethynyl)pyridine (1.48 g, 7.1 mmol) and trimethylsilylazide (2.5 g, 21.3 mmol) were combined in a sealed tube which was heated 48 h in a 150° C. oil bath. The mixture was chromatographed on silica using an ethyl acetate-hexanes gradient giving a yellow solid (950 mg, 53%). 1 H NMR (CDCl 3 , 400 mHz) δ 8.50 (d, 2H, J=5.8 Hz), 7.60 (d, 2H, J=5.8 Hz), 7.36 (d, 2H, J=8.7 Hz), 6.92 (d, 2H, J=8.7 Hz), 3.81 (s, 3H), 2.80 (br, 1H). MS (AP+) m/e 253 (MH+).
EXAMPLE 79
2-((4-(2-methyl-5-(pyridin-4-yl)-2H-1,2,3-triazol-4-yl)phenoxy)methyl)quinoline
A mixture of 4-(2-methyl-5-(pyridin-4-yl)-2H-1,2,3-triazol-4-yl)phenol (80 mg, 0.32 mmol), 2-(chloromethyl)quinoline hydrochloride (71 mg, 0.33 mg), and cesium carbonate (414 mg, 1.27 mmol) in dimethylformamide was heated at 65° C. for 20 h, filtered, the filtrate concentrated and chromatographed on silica eluted with ethyl acetate-hexanes providing material containing starting phenol. This was dissolved in ethyl acetate, washed with aqueous NaOH, dried and concentrated giving a colorless solid (100 mg, 80%). 1 H NMR (CDCl 3 , 400 mHz) δ 8.56 (d, 2H, J=6.2 Hz), 8.24 (d,1H, J=8.3 Hz), 8.12 (d, 1H, J=8.3 Hz), 7.85 (d, 1H, J=8.3 Hz), 7.75 (ddd, 1H, J=8.5, 7, 1.6 Hz), 7.70 (d, 1H, J=8.7 Hz), 7.65 (d, 2H, J=6.2 Hz), 7.57 (m, 1H), 7.41 (m, 2H), 7.08 (m, 2H), 5.45 (s, 2H), 4.27 (s, 3H). MS (AP+) m/e 394 (MH+).
Preparation 76
4-(3-methyl-5-(pyridin-4-yl)-3H-1,2,3-triazol-4-yl)phenol
A solution of 4-(5-(4-methoxyphenyl)-1-methyl-1H-1,2,3-triazol-4-yl)pyridine (170 mg, 0.64 mmol) in dichloromethane (5 mL) was treated at RT With boron tribromide (1.27 mL of 1M in dichloromethane) and the mixture was stirred overnight. Aqueous 1N NaOH (10 mL) was added, and after being stirred 1 h the mixture was extracted with dichloromethane (20 mL). The aqueous layer was acidified to pH 7 with 2N HCl, and extracted with ethyl acetate (2×15 mL). The extracts were dried with sodium sulfate and concentrated giving a yellow solid (142 mg, 88%). 1 H NMR (CDCl 3 , 400 mHz) δ 1 H NMR (CDCl 3 , 400 mHz) δ 8.39 (d, 2H, J=5-6 Hz), 7.49 (d, 2H, J=5-6 Hz), 7.09 (d, 2H, J=8.7 Hz), 6.95 (d, 2H, J=8.7 Hz), 3.87 (s, 3H). MS (AP−) 351 (M−H).
EXAMPLE 80
2-((4-(3-methyl-5-(pyridin-4-yl)-3H-1,2,3-triazol-4-yl) phenoxy)methyl)quinoline
A mixture of 4-(3-methyl-5-(pyridin-4-yl)-3H-1,2,3-triazol-4-yl)phenol (88 mg, 0.35 mmol), 2-(chloromethyl)quinoline hydrochloride (82 mg, 0.38 mmol), and cesium carbonate (455 mg, 1.4 mmol) in dimethylformamide was stirred at 65° C. for 20 h, filtered, and concentrated. The residue was chromatographed on silica eluting with a gradient of 50% to 100% ethyl acetate in hexanes giving a light yellow solid (100 mg, 73%). 1 H NMR (CDCl 3 , 400 mHz) δ 8.48 (d, 2H, J=6.2 Hz), 8.24 (d, 1H, J=8.3 Hz), 8.09 (d, 1H, J=8.3 HZ), 7.85 (d, 1H, J=7.9 Hz), 7.76 (ddd, 1H, J=8.5, 7, 1Hz), 7.70 (d, 1H, J=8.7 Hz), 7.57 (m, 1H), 7.54 (m, 2H), 7.24 (m, 2H), 7.20 (m, 2H). 5.46 (s, 2H), 3.90 (s, 3H). MS (AP+) m/e 394 (MH+).
Preparation 77
4-(1-(pyridin-4-yl)-1H-imidazol-2-yl)phenol
According to the procedure for preparation of 4-(3-methyl-5-(pyridin-4-yl)-3H-1,2,3-triazol-4-yl)phenol, except that 4:1 dichloromethane:2-propanol was used in place of ethyl acetate to extract the product, 4-(2-(4-methoxyphenyl)-1H-imidazol-1-yl)pyridine (125 mg, 0.5 mmol) was treated with 1.25 mmol of boron tribromide to give 90 mg of a colorless solid. 1 H NMR (CDCl 3 , 400 mHz) δ 8.52 (d, 2H, J=6 Hz), 7.14 (m, 2H), 7.11-7.08 (m, 4H), 6.79 (m, 2H), 2.94 (br, 1 H).
Preparation 78
4-(2-(4-methoxyphenyl)-1H-imidazol-1-yl)pyridine
Phosphorus pentachloride (572 mg, 2.75 mmol) was added to a mixture of 4-methoxy-N-(pyridin-4-yl)benzamide (626 mg, 2.75 mmol) in phosphorus oxychloride (3 mL) and the mixture was heated a 105° C. oil bath for 4 h. The mixture was concentrated to dryness. To the residue was added 2,2-dimethoxyethylamine (3.1 g) in methanol, and the mixture was stirred at RT. After more than one hour the mixture was partially concentrated to remove most of the methanol, stirred at RT overnight and concentrated to dryness. Isopropyl alcohol (10 mL) and conc. HCl (15 mL) were added and the mixture was heated at 80° C. for 24 h. Solid sodium bicarbonate was added to bring the pH to 7-8, and the mixture was extracted with dichloromethane (3×50 mL) which was dried (sodium sulfate) and concentrated. Chromatography on silica eluted with 25% to 100% ethyl acetate-hexanes gave 130 mg (20%) of a yellow solid. 1 H NMR (CDCl 3 , 400 mHz) δ 8.55 (d, 2H, J=6 Hz), 7.22 (d, 2H, J=9Hz), 7.17 (s, 1H), 7.12 (s, 1H), 7.05 (d, 2H, J=6 Hz), 6.75 (d, 2H, J=9 Hz), 3.72 (s, 3H).
Preparation 79
4-methoxy-N-(pyridin-4-yl)benzamide
4-Aminopyridine (1.94 g, 20.6 mmol) was added to a solution of p-anisoyl chloride (3.5 g, 20.6 mmol) and triethylamine (8.6 mL, 62 mmol) in dichloromethane (100 mL) at 0° C. The mixture was stirred 3 h at RT, and then extracted successively with 1N NaOH, water and brine, dried over sodium sulfate, and concentrated. Chromatography on silica (gradient of 30% to 100% ethyl acetate-hexanes) gave 3.8 g (81%) of a colorless solid. 1 H NMR (CDCl 3 , 400 mHz) δ 8.49 (m, 2H), 8.19 (br, 1H), 7.85 (m, 2H), 7.59 (m, 2H), 6.95 (m, 2H), 3.85 (s, 3H), MS (AP+) 229 (MH+).
EXAMPLE 81
2-((4-(1-(pyridin-4-yl)-1H-imidazol-2-yl)phenoxy)methyl)quinoline
According to the procedure for preparation of 2-((4-(3-methyl-5-(pyridin-4-yl)-3H-1,2,3-triazol-4-yl)phenoxy)methyl)quinoline, 4-(1-(pyridin-4-yl)-1H-imidazol-2-yl)phenol (90 mg), 2-(chloromethyl)quinoline hydrochloride (81 mg) and cesium carbonate (495 mg) gave 120 mg as an off-white solid (84%). 1 H NMR (CDCl 3 , 400 mHz) δ 8.59 (m, 2H), 8.16 (d, 1H, J =8.3 Hz), 8.04 (d, 1H, J=8.3 Hz), 7.79 (d, 1H, J=7.9 Hz), 7.70 (ddd, 1H), 7.60 (d, 1H, J=8.3 Hz), 7.52 (ddd, 1H), 7.28 (m, 2H), 7.22 (d, 1H, J=1 Hz), 7.15 (d, 1H, J=1 Hz), 7.11 (m, 2H), 6.94 (m, 2H), 5.34 (s, 2H). HPLC-MS (system 1) 4.53 min, m/e 379 (MH+).
Preparation 80
4-(1-(4-methoxyphenyl)-1H-imidazol-5-yl)pyridine
4-Methoxyaniline (2.46 g, 20 mmol) and pyridine-4-carboxaldehyde (1.9 mL, 10 mmol) in toluene (110 mL) in a flask attached to a Dean-Stark trap and reflux condensor was heated at reflux. After 40 hours, the reaction was complete by infrared spectral analysis and mass spectral analysis. The toluene was removed via distillation through the Dean-Stark sidearm, the residue was dissolved in methanol (100 mL) and ca. ½ of the crude imine (ca. 10 mmol, 50 mL of methanol solution) was diluted with methanol (20 mL) and 1,2-dimethoxyethane (20 mL). The solution was then treated with potassium carbonate (2.76 g, 20 mmol) and tosylmethylisocyanide (TOSMIC, 2.93 g, 15 mmol) and was heated at reflux for 3 hours. After cooling to room temperature, the solvent was removed in vacuo, and the residue was dissolved in methylene chloride and was washed with brine. The brine layer was extracted with methylene chloride and the combined organic layers were dried (MgSO 4 ), were filtered, and were concentrated in vacuo. The residue was purified by silica gel chromatography with ethyl acetate—hexanes—methanol (80:20:0 to 76:19:5) to afford 1.4 g (56% yield) of the title compound; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 160.039, 150.161, 141.009, 137.240, 130.839, 129.179, 127.287, 121.597, 115.106, 55.801; MS (AP/Cl) 252.4 (M + H)+.
Preparation 81
4-(1-(4-(benzyloxy)phenyl)-1H-imidazol-5-yl)pyridine
The title compound was prepared using the method described for Preparation 80, substituting 4-benzyloxyaniline for 4-methoxyaniline, and afforded 4-(1-(4-(benzyloxy)phenyl)-1H-imidazol-5-yl)pyridine in 54% yield; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 159.195, 150.132, 141.001, 137.263, 136.403, 130.892, 130.735, 129.389, 128.932, 128.521, 127.751, 127.317, 121.627, 116.078, 70.637; MS (AP/Cl) 328.4 (M+H)+.
Preparation 82
4-(1-(4-methoxyphenyl)-2-methyl-1H-imidazol-5-yl)pyridine
A solution of diisopropyl amine (0.51 mL, 3.6 mmol) in tetrahydrofuran (12 mL) at −20° C., was treated with n-butyl lithium (2.5 M in hexanes, 1.45 mL, 3.6 mmol) and the solution was stirred for 10 minutes. A solution of Preparation 80 (4-(1-(4-methoxyphenyl)-1H-imidazol-5-yl)pyridine, 730 mg, 2.9 mmol) in tetrahydrofuran was added and the solution became dark orange. The solution was stirred for 30 minutes as the temperature was allowed to rise to 0° C. After cooling to −20° C., methyl iodide (0.54 mL, 8.7 mmol) in tetrahydrofuran (12 mL) was added and the solution was stirred for 30 min at −20° C. and for 2 hr at 23° C. The solvent was removed in vacuo, the residue was diluted with brine and was extracted with ethyl acetate. The organic layer was then dried (MgSO 4 ), was filtered, and was concentrated in vacuo. The residue was purified by silica gel chromatography using ethyl acetate-hexanes-methanol (63:32:5 to 72:18:10) to afford 555 mg (72% yield) of the title compound; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 160.144, 150.034, 149.197, 137.749, 131.265, 129.463, 128.985, 128.828, 120.849, 115.233, 55.78, 14.203; MS (AP/Cl) 266.4 (M+H)+.
Preparation 83
4-(2-ethyl-1-(4-methoxyphenyl)-1H-imidazol-5-yl)pyridine
The title compound was prepared using the method described for Preparation 82 with ethyl iodide used in the place of methyl iodide and afforded 83% yield of 4-(2-ethyl-1-(4-methoxyphenyl)-1H-imidazol-5-yl)pyridine; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 160.144, 150.147, 149.990, 137.786, 129.239, 129.037, 128.992, 121.597, 120.909, 115.181, 55.771,21.097,12.348; MS (AP/Cl) 280.5 (M+H)+.
Preparation 84
4-(5-(pyridin-4-yl)-1H-imidazol-1-yl)phenol
A solution of Preparation 81 (4-(1-(4-(benzyloxy)phenyl)-1H-imidazol-5-yl)pyridine, 2 g, 6.1 mmol) and anisole (13 mL, 122 mmol) in trifluoracetic acid (50 mL) was heated at 75° C. for 24 h. The solvent was removed in vacuo and the residue was purified via silica gel chromatography with chloroform-methanol-ammonium hydroxide (94:5:1) to afford 1.27 g (88%) of the title compound; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 158.402, 149.145, 141.061, 138.018, 120.600, 129.822, 127.482, 127.370, 121.933, 116.497; MS (AP/Cl) 238.3 (M+H)+.
Preparation 85
4-(2-methyl-5-(pyridin-4-yl)-1H-imidazol-1-yl)phenol
A solution of boron tribromide (1 M in methylene chloride, 2.1 mL, 2.1 mmol) was added dropwise to a solution of Preparation 82 (4-(1-(4-methoxyphenyl)-2-methyl-1H-imidazol-5-yl)pyridine, 220 mg, 0.83 mmol) in methylene chloride (5 mL) at 0° C. After stirring at 23° C. for 24 h, aqueous sodium hydroxide solution (1 N, 15 mL) was added and the mixture was stirred at 23° C. for 1 h. The pH was adjusted to 7 by the addition of aqueous hydrochloric acid (1N), the mixture was extracted with methylene chloride/isopropanol (4:1, 3×30 mL), the combined organic layers were dried (MgSO 4 ), were filtered, and were concentrated in vacuo. The residue was purified by silica gel chromatography using chloroform-methanol (20:1 to 10:1) to afford 150 mg (72% yield ) of the title compound; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 159.337, 149.548, 149.302, 138.302, 131.131, 128.760, 128.170, 127.310, 121.163, 117.237, 13.881; MS (AP/Cl) 252.4 (M+H)+.
Preparation 86
4-(2-ethyl-5-(pyridin-4-yl)-1H-imidazol-1-yl)phenol
The title compound was prepared using Preparation 4 as the starting material and the method for Preparation 85. This yielded 4-(2-ethyl-5-(pyridin-4-yl)-1H-imidazol-1-yl)phenol in 70% yield; diagnostic 13 C NMR signals (100 MHz, CD 3 OD/CDCl 3 ) δ 158.574, 149.182, 149.002, 138.511, 130.877, 128.895, 128.200, 127.340, 121.253, 116.692, 20.656, 12.020; MS (AP/Cl) 266.4 (M+H)+.
EXAMPLE 82
2-((4-(5-(pyridin-4-yl)-1H-imidazol-1-yl)phenoxy)methyl)quinoline
A mixture of Preparation 84 (4-(5-(pyridin-4-yl)-1H-imidazol-1-yl)phenol, 95 mg, 0.4 mmol), 2-chloromethylquinoline hydrochloride (128 mg, 0.6 mmol), and cesium carbonate (391 mg, 1.2 mmol) in dimethylsulfoxide (2 mL) was stirred at 23° C. for 24 h. The mixture was diluted with ethyl acetate/n-butanol (100 mL/5 mL), was washed with water and then brine, and the organic layer was dried (MgSO 4 ), was filtered, and was concentrated in vacuo. The residue was purified by silica gel chromatography using chloroform/methanol (50:1) to afford 150 mg (99% yield) of the title compound; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 158.940, 157.116, 149.990, 147.836, 141.054, 137.405, 130.989, 130.204, 129.650, 129.239, 127.953, 127.871, 127.392, 127.011, 121.627, 119.324, 116.198, 71.990; MS (AP/Cl) 379.4 (M+H)+.
EXAMPLE 83
2-((4-(2-methyl-5-(pyridin-4-yl)-1H-imidazol-1-yl)phenoxy)methyl)quinoline
The title compound was prepared using Preparation 85 and the method described in Example 82; 88% yield; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 159.060, 157.078, 150.004, 147.836, 137.689, 137.397, 130.204, 129.934, 129.239, 128.962, 127.968, 127.871, 127.385, 127.011, 120.886, 119.354, 116.273, 71.975, 14.225; MS (AP/Cl) 393.49 (M+H)+.
EXAMPLE 84
2-((4-(2-ethyl-5-(pyridin-4-yl)-1H-imidazol-1-yl)phenoxy)methyl)quinoline
The title compound was prepared using Preparation 86 and the method described in Example 82; 92% yield; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 159.090, 157.078, 150.147, 149.930, 147.836, 137.734, 137.405, 130.211, 129.680, 129.232, 129.127, 128.970, 127.968, 127.886, 127.392, 127.018, 120.961, 119.354, 116.243, 71.968, 21.090, 12.333; MS (AP/Cl) 407.5 (M+H)+.
Preparation 87
N-(4-methoxyphenyl)isonicotinamide
A solution of p-anisidine (2.46 g, 20 mmol) and triethylamine (13.9 mL, 100 mmol) in ethyl acetate (200 mL) was treated with isonicotinic acid (2.46 g, 20 mmol) followed by 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 15.1 mL, 24 mmol). After stirring at 23° C. for 4 h, the reaction mixture was diluted with ethyl acetate, was washed with water and with brine, and the organic layer was dried (MgSO 4 ), was filtered, and was concentrated in vacuo. Purification by silica gel chromatography with chloroform-methanol (40:1) gave 4 g (88% yield) of the title compound; diagnostic 13 C NMR signals (100 MHz, CD 3 OD/CDCl 3 ) δ 164.825, 157.213, 149.758, 143.349, 130.989, 123.085, 122.068, 55.285; MS (AP/Cl) 229.3 (M+H)+.
Preparation 88
4-(1-(4-methoxyphenyl)-1H-imidazol-2-yl)pyridine
Preparation 87 (N-(4-methoxyphenyl)isonicotinamide, 1 g, 4.39 mmol) was dissolved in phosphorous oxychloride (POCl 3 ) (5 mL) then phosphorous pentachloride (913 mg, 4.39 mmol) was added. The mixture was heated at 120° C. for 4 h. The POCl 3 was removed in vacuo, aminoacetaldehyde dimethyl acetal (9.5 mL, 87.8 mmol) and isopropanol (10 mL) were added, and the mixture was stirred at 23° C. for ca. 16 h. The reaction mixture was concentrated in vacuo and concentrated hydrochloric acid (36.5%, 25 mL) in isopropanol (15 mL) was added. The reaction mixture was heated at 90° C. for 24 h. After cooling to 23° C., aqueous sodium hydroxide (1N) and aqueous sodium bicarbonate were added to obtain pH=8. The mixture was extracted with methylene chloride, was dried (MgSO 4 ), and was filtered and concentrated in vacuo. The residue was purified by silica gel chromatography with ethyl acetate/hexanes/methanol (80:20:0 to 76:19:5) to afford 811 mg (74% yield) of the title compound; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 160.069, 149.952, 144.142, 137.853, 131.004, 129.882, 127.414, 124.977, 122.195, 115.114, 55.808; MS (AP/Cl) 252.4 (M+H)+.
Preparation 89
4-(2-(pyridin-4-yl)-1H-imidazol-1-yl)phenol
The title compound was prepared using the method outlined in Preparation 85 with the substitution of Preparation 88 for Preparation 82; 86% yield; diagnostic 13 C NMR signals (100 MHz, CD 3 OD/CDCl 3 ) δ 158.372, 149.145, 143.641, 138.257, 129.232, 128.985, 127.347, 125.418, 122.666, 116.505; MS (AP/Cl) 238.4 (M+H)+.
EXAMPLE 85
2-((4-(2-(pyridin-4-yl)-1H-imidazol-1-yl)phenoxy)methyl)quinoline
The title compound was prepared using the method outlined in Example 82 with the substitution of Preparation 89 for Preparation 84; 98% yield; diagnostic 13 C NMR signals (100 MHz, CDCl 3 ) δ 158.948, 157.108, 149.847, 147.814, 137.868, 137.420, 131.445, 130.226, 129.942, 127.968, 127.871, 127.534, 127.026, 124.954, 122.247, 119.339, 116.190, 71.968; MS (AP/Cl) 379.4 (M+H)+.
The invention described and claimed herein is not to be limited in scope by the specific embodiments herein disclosed, since these embodiments are intended as illustrations of several aspects of the invention. Any equivalent embodiments are intended to be within the scope of this invention. Indeed, various modifications of the invention in addition to those shown and described herein will become apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
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The invention pertains to heteroaromatic compounds that serve as effective phosphodiesterase (PDE) inhibitors. In particular, the invention relates to said compounds which are selective inhibitors of PDE10. The invention also relates to intermediates for preparation of said compounds; pharmaceutical compositions comprising said compounds; and the use of said compounds in a method for treating certain central nervous system (CNS) or other disorders.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to an opening and closing mechanism with a damper for use in a western style stool or piano.
[0002] Heretofore, as shown in FIG. 5 , in the western style stool, a pair of hinge elements 4 , 6 is provided at the side of the stool proper member 2 , and a pair of hinge members 10 , 12 is provided at the side of an opening and closing member 8 of a lavatory seat or lavatory lid. Hinge member 10 is disposed at the right side of hinge element 4 of the stool proper member 2 . Hinge member 12 is disposed at the left side of hinge element 6 . Hinge element 4 and hinge member 10 , and hinge element 6 and hinge member 12 are connected by rotary dampers 14 and 16 , respectively. The damping power of rotary members 14 , 16 has a direction property of asymmetry type which was disclosed in the official gazette of Japanese Patent Kokai H-10-20167 70.
[0003] In FIG. 5 , a mounting member 14 b with rotation skid face is formed on a cylindrical housing 14 a of rotary damper 14 . Mounting member 14 b is tied to a mounting portion 4 a with rotation skid face that is formed on the side of hinge element 4 . A mounting member 14 d with rotation skid face is formed on an axial portion of a rotary member 14 c which projects from housing 14 a , and mounting member 14 d is tied to mounting portion 10 a with rotation skid face formed on the side of hinge member 10 .
[0004] A relationship between rotary damper 16 , hinge element 6 , and hinge member 12 resembles the mounting structure mentioned above. Rotary dampers 14 and 16 are disposed on an identical axis and are disposed on the left and right sides, respectively, of the opening and closing mechanism shown in FIG. 5 .
[0005] As shown in FIG. 5 , a construction is illustrated wherein hinge members 10 and 12 are disposed at different sides of hinge elements 4 and 6 , respectively. Hinge element 4 and hinge member 10 , and hinge element 6 and hinge member 12 are of a bilateral symmetry. However, rotary damper 14 disposed between hinge element 4 and hinge member 10 and rotary damper 16 disposed between hinge element 6 and hinge member 12 , end up with a relationship whose relative rotating direction against the housing of the rotary member is reversed.
[0006] Namely, in FIG. 5 , when the cover portion (illustration is omitted) of opening and closing member 8 is swiveled about rotary dampers 14 and 16 to a standing up position from the cover closed position where it extends perpendicular to the page, rotary member 14 c rotates in a clockwise direction relative to housing 14 a , and rotary member 16 c rotates in a counterclockwise direction relative to housing 16 a.
[0007] Accordingly, when a rotary damper whose damping power is of asymmetric type is used, two kinds of rotary damper are required, one whose damping direction is for clockwise rotation and another whose damping direction is for counterclockwise rotation. For this reason, control of component parts becomes complicated, and moreover, mass production cannot be expected. Furthermore, in the case of mounting the rotary damper, when two rotary dampers of different types are erroneously installed in each other's proper locations, the proper rotation cannot be transmitted to the rotary damper and the desired damping characteristic cannot be obtained.
[0008] An object of the present invention is to solve the foregoing problems.
SUMMARY OF THE INVENTION
[0009] In one aspect of the invention, at least two hinge elements are provided at the side of a proper member and are separated by a predetermined interval. At least two hinge members are provided on an opening and closing member side and correspond to each of the hinge elements. Each of the hinge members is disposed in opposition to the same side of the respective hinge element. A mounting member for a rotary damper is provided at each hinge member. The rotary damper has asymmetric damping power, mounting members at both ends, and is disposed between the hinge elements of the proper member and the hinge members of the opening and closing member which are disposed in opposition. The mounting member at one side of the rotary damper is tied to the mounting portion provided at a hinge element of the proper member, and the mounting member of the other side of the rotary damper is tied to the mounting portion provided on a hinge member of the opening and closing member. In the foregoing construction, the opening and closing member is swivelly journalled at the proper member with the axis of rotary damper 30 as a rotation center, and the damping power of the rotary damper is applied to the swiveling motion of the opening and closing member with the rotary damper as the pivot.
[0010] Furthermore, the present invention is constructed such that the rotary damper is composed of a cylindrical housing and a rotary member rotatably housed in the housing that rotates relative to the housing. A mounting member of the rotary damper is formed at an end portion of the housing, and another mounting member of the rotary damper is formed at another end portion of the housing. The shape of the mounting member at one end of the rotary damper and of the mounting member at the other end is symmetric.
[0011] The present invention is constructed such that during operation each of a plurality of dampers rotates in the same direction regardless of orientation. It should be appreciated that using one kind of rotary damper is sufficient for achieving the objects of the invention, and that using one kind of rotary damper facilitates easier control of component parts and facilitates mass production of the opening and closing mechanism.
[0012] Furthermore, during assembly, there is no apprehension of making a mistake with respect to the mounting positions of the right and left rotary dampers, and as a result, the assembly process can be efficiently carried out.
[0013] Moreover, during assembly, workers may disregard the fitting directions of the rotary dampers which facilitates efficient assembly of the opening and closing mechanism.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a cross-sectional view showing an embodiment of the present invention.
[0015] FIGS. 2A , 2 B, and 2 C are a plan view, a left end view and a right end view, respectively, of an explanatory drawing of an appearance of the rotary damper.
[0016] FIGS. 3A-3D are sectional views illustrating the operation of the rotary damper.
[0017] FIG. 4 is a cross-sectional view showing another embodiment of the present invention.
[0018] FIG. 5 is a cross-sectional view of a conventional opening and closing mechanism.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention will be described in detail by referring to the attached drawings. In FIG. 1 , reference numeral 18 denotes a proper member composed of proper members such as a western style stool or piano and a variety of storage boxes with a lid or cover. Hinge elements 22 , 24 consist of projecting members. The hinge elements 22 and 24 are provided on proper member 18 at locations corresponding to attachment locations of an opening and closing member 20 . Opening and closing member 20 may be, for example, a stool seat or a stool lid of proper member 18 or a lid of a piano. The attachment locations are spaced at a predetermined interval.
[0020] In the exemplary embodiment, two hinge elements 22 and 24 are provided. However, it should be appreciated that more than two hinge elements may be provided in other embodiments. Hinge members 26 and 28 are formed on opening and closing member 20 , are separated by a predetermined interval, and are in correspondence to hinge elements 22 and 24 of the proper member 18 . The hinge members 26 and 28 of opening and closing member 20 are disposed adjacent to the left sides S 1 and S 2 of hinge elements 22 and 24 , respectively. It should be understood that in other embodiments, hinge members 26 and 28 of opening and closing member 20 may be arranged adjacent to the right sides of hinge elements 22 and 24 , respectively.
[0021] Housing storing portions 34 and 36 , and 38 and 40 , store a cylindrical housing 30 a of a rotary damper 30 . Housing storing portions 34 and 36 are bored in hinge element 22 and hinge member 26 , respectively. Likewise, housing storing portions 38 and 40 are bored in hinge element 24 and hinge member 28 , respectively. Housing storing portions 34 and 36 are adjacent and opposed to each other about an identical axis. Similarly, housing storing portions 38 and 40 are adjacent and opposed to each other about the identical axis.
[0022] Furthermore, damper mounting portions 22 a and 26 a have mutually identical shapes with rotation skid faces, and are bored in housing storage portions 34 and 36 , respectively. Likewise, damper mounting portions 24 a and 28 a have mutually identical shapes with rotation skid faces, and are bored in housing storage portions 38 and 40 , respectively. Damper mounting portions 22 a and 26 a , and 24 a and 28 a , are bored to align on the identical axis. Damper mounting portions 22 a and 24 a open to sides S 1 and S 2 , respectively, of hinge elements 22 and 24 . Damper mounting portions 26 a and 28 a open to sides S 3 and S 4 , respectively, of hinge members 26 and 28 . Rotary damper 30 is mounted from these open sides. Each rotary damper 30 is composed of a housing 30 a of a cylindrical type that is filled with oil, and a rotary member 30 b that fits rotatably in housing 30 a . In the exemplary embodiment, rotary damper 30 is an asymmetrical type rotary damper that outputs different damping characteristics determined by the rotating direction of a structure illustrated in FIG. 3 . The asymmetrical type rotary damper has damping power that works on the load by a relative rotating direction of rotary member 30 b against housing 30 a . The asymmetrical type rotary damper 30 has torque working on rotary housing 30 a that changes sequentially from a first low torque to a second low torque, from the second low torque to a first high torque, and then from the first high torque to a second high torque as shown in FIGS. 3(A) , 3 (B), 3 (C) and 3 (D), respectively. Rotary member 30 b makes a relative rotation from an initial position shown in FIG. 3A clockwise against housing 30 a.
[0023] When rotary member 30 b rotates relative to rotary housing 30 a counterclockwise against housing 30 a from the second high torque shown in FIG. 3D , the torque working on rotary member 30 b sequentially changes from the second high torque shown in FIG. 3D , to the first high torque shown in FIG. 3C , to the second low torque shown in FIG. 3B , and to the first low torque shown in FIG. 3A . The internal structure of the asymmetric type rotary damper 30 as shown in FIG. 3 is disclosed in the official gazette of Japanese patent laid open publication (TOKKAI) 2001-349364, and is hitherto open to the public, and moreover, the present invention is not particularly limited to the rotary damper housing of the internal structure shown in FIG. 3 so that its detailed description is omitted.
[0024] In the exemplary embodiment, each rotary damper 30 includes mounting members 30 c and 30 e that are axially positioned at the left and right sides, respectively, of housing 30 a , as shown in FIG. 2A . Thus configured, housing 30 a and mounting members 30 c and 30 e form a bilaterally symmetric rotary damper 30 . Mounting members 30 c and 30 e are identically shaped, include an axial skid face “a”, and rotate on the identical axis of housing 30 a . It should be appreciated that each housing 30 a includes a viscous fluid for producing a damping effect and includes a cap 30 d.
[0025] Each housing 30 a is rotatably fitted and disposed in housing storing portions 34 and 36 , and 38 and 40 . Specifically, mounting members 30 c and 30 e are fitted, disposed on, and tied to corresponding mounting portions 26 a and 22 a , and 28 a and 24 a , respectively. A stopper 42 is positioned on proper member 18 proximate a left side of hinge member 28 to prevent opening and closing member 20 from moving left towards hinge element 22 .
[0026] In the foregoing construction, when the lid portion (illustration omitted) of opening and closing member 20 is swiveled to open from a closed position where it is oriented perpendicular to the page of FIG. 1 , it rotates counterclockwise about hinge elements 22 and 24 as viewed from the arrow mark direction A of FIG. 1 . At this time, housing 30 a of rotary damper 30 on the left side rotates counterclockwise relative to left side rotary member 30 b . Similarly, housing 30 a of rotary damper 30 on the right side rotates counterclockwise relative to right side rotary member 30 b . As a result, the rotating directions of rotary dampers 30 of the right and left sides is identical.
[0027] For this reason, the same kind of asymmetric type rotary damper 30 can be used for the right and left side hinge members 26 and 28 , respectively. Rotary dampers 30 are mounted on the right and left sides of FIG. 1 , respectively. Rotary dampers 30 are mounted in hinge elements 22 and 24 such that each mounting member 30 e is oriented on the right side of each damper 30 and is positioned within one of mounting portions 22 a and 24 a . Similarly, each mounting member 30 c is oriented on the left side of each damper 30 and is positioned within one of mounting portions 26 a and 28 a . However, it should be appreciated that dampers 30 may be oriented differently by rotating them through one-hundred-eighty degrees such that mounting members 30 c and 30 e face in opposite directions. That is, mounting members 30 c and 30 e face in left and right directions of FIG. 1 , respectively. Thus, the orientation of dampers 30 is optional.
[0028] FIG. 4 shows an alternative embodiment of the opening and closing mechanism. Specifically, the opening and closing mechanism includes left and right side rotary dampers 30 mounted such that the left side rotary damper 30 is oriented to have mounting members 30 c face left and mounting member 30 e face right, and such that the right side rotary damper 30 is rotated one-hundred-eighty degrees such that mounting member 30 c faces right and mounting member 30 e faces left. In this alternative embodiment, when opening and closing member 20 is swiveled open from the closed position, rotary member 30 b of right side rotary damper 30 rotates counterclockwise as viewed from the arrow mark direction A. Moreover, housing 30 a of the right side rotary damper 30 rotates counterclockwise relative to rotary member 30 b , and as a result, the left and right side rotary dampers 30 rotate in identical directions. Consequently, during assembly, workers have the option of installing or mounting right and left side rotary dampers 30 in more than one orientation between hinge element 22 and hinge member 26 , and between hinge element 24 and hinge member 28 , respectively. The asymmetric type rotary dampers 30 to be used in this invention are such as the rotary damper disclosed in the Japanese official gazette of publicly known TOKKAI H-282039 or other types such as the rotary dampers of a structure with different torque characteristics depending on the rotating direction.
[0029] It should be appreciated that although the exemplary embodiments describe rotary dampers 30 as having bilateral symmetry, in other embodiments, rotary dampers 30 are not limited to the embodiment of a bilateral symmetry. In another alternative embodiment, mounting members 30 c and 30 e are of different shape, mounting portions 26 a and 28 a are formed so as to be suitable for the shape of mounting member 30 c , and mounting portions 22 a and 24 a are formed so as to be suitable for the shape of mounting member 30 e.
[0030] In yet another alternative embodiment, mounting members 30 c and 30 e are formed in a different shape, mounting portions 22 a and 24 a are formed in a different shape, and mounting portions 26 a and 28 a may be formed in a structure suitable to the shape of the mounting member 30 e . Furthermore, mounting member 30 c may be shaped to a shape suitable for any of the mounting portions 22 a , 24 a , 26 a , 28 a . If mounting member 30 e has a shape suitable for any of mounting portions 22 a , 24 a , 26 a , 28 a , the same operation and effect identical with the case of using rotary damper 30 wherein mounting member 30 c and mounting member 30 e , shown in FIG. 2 are identical, can be obtained, although mounting member 30 c and mounting member 30 e are not necessarily of identical shape. Furthermore, in this case, mounting member 30 c and mounting member 30 e of mutually different shapes may be made suitable for any of mounting portions 22 a , 24 a , 26 a 28 a with the use of adapters and the like.
CROSS REFERENCE TO RELATED APPLICATION
[0031] This application is a divisional of Application No. 11/237,914, filed Sep. 29, 2005.
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An opening and closing member with a rotary damper for use in a western style stool or piano and the like which facilitates easy control of the rotary damper and easy assembly. Hinge members corresponding to an opening and closing member side are adjacently disposed at the same side of respective hinge members on a side of a proper member. The rotary damper having a particular directivity is disposed between hinge members facing each other. The opening and closing member is swivellably journalled on the proper member about an axis of rotation of the rotary dampers, and the damping power of the rotary damper is applied to the swiveling motion as the opening and closing member swivels with the rotary damper on its axis.
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CROSS REFERENCE TO RELATED APPLICATIONS
The present application is related to U.S. patent application Ser. No. 12/547,042 filed Aug. 25, 2009, incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to wireless digital networks, and in particular, to the problem of traffic forwarding in mesh networks.
Wireless digital networks commonly have a controller to which are attached one or more access points. Each access point supports a number of wireless clients. In most situations, each access point connects to its controller using a wired connection. Such wired connections, for example using 803.2 Ethernet and often 802.3af power over Ethernet, provide a high capacity channel between controller and access points.
In some situations, however, it is not possible to provide wired data connections to access points. Examples include large outdoor installations, such as rail yards, cargo terminals, and large college campuses. In such situations mesh networks are used. In a mesh network, only a few, perhaps only one access point has a wired connection to a controller. This access point may be referred to as a portal, or a root node. All other access points in the mesh network communicate wirelessly, access point to access point. Access points are organized into a mesh, a network usually represented topologically as a tree with its origin, or root, the access point with the wired connection to the controller.
In the operation of a mesh network, traffic from a client connected to an access point passes through the mesh in a directed fashion from access point to access point until the traffic finally reaches the root node. Similarly, traffic flows through the root node, and through a succession of access points until it reaches the access point to which the client is attached.
For various engineering reasons, mesh networks typically operate using a single radio channel for transferring data within the mesh, that is, from access point to access point. In many installations, this same channel may also be used in communicating between the access point and the wireless client.
The use of the shared channel leads to a problem where some mesh access points obtain a larger portion of the channel capacity for their transmissions compared to some other mesh access points that get a smaller portion. This imbalance causes data packets to accumulate at certain mesh access points eventually leading to data loss. To characterize the problem further, we need to consider both directions in which traffic flows through the mesh network—“downstream” from the portal (or root) towards the edge of the network, and “upstream” from the edge of the network towards the portal. To illustrate how the imbalance can affect downstream traffic, FIG. 1 shows a mesh network in which access point 200 is the root node of the mesh, access points 201 through 207 are mesh nodes, and 300 through 303 are wireless clients attached to nodes in the mesh.
Consider mesh access point 206 . If parent node 205 has a steady stream of data destined to client node 302 and succeeds in getting access to the channel whenever it has data to send, then data packets will accumulate at 206 since 206 does not get a chance to forward the data downstream to client 302 . In the upstream direction, the tree structure of the mesh causes a problem when traffic flows from multiple wireless clients up to the portal or root node. If an upstream node such as 205 does not get timely access to the channel for its transmissions, the memory capacity of that access point will be exceeded, and packets comprising the traffic must be dropped.
What is needed is a way of prioritizing traffic within access points in the mesh in both the upstream and downstream directions.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention may be best understood by referring to the following description and accompanying drawings that are used to illustrate embodiments of the invention in which:
FIG. 1 shows a mesh network.
DETAILED DESCRIPTION
Embodiments of the invention relate to methods of prioritizing traffic flow in a wireless mesh network. In an embodiment of the invention for wireless networks practicing carrier sense multiple access collision avoidance (CSMA/CA) with backoff, such as IEEE 802.11 wireless networks, access points in a mesh network are represented in a tree topology with the root or portal node as level 0 of the tree, and each successive level of access points having a level of one plus the level of the access point to which they connect. Wireless traffic is prioritized by having access points use a backoff time that depends on several factors such as the number of packets waiting in the upstream and downstream queues, the number of hops these packets have traversed, and the level or distance of the mesh node to the root or portal node.
CSMA/CA with exponential backoff is specified as part of the IEEE 802.11 standard, IEEE-Std 802.11-1999 (R2003) incorporated herein by reference, and is practiced by devices operating in accordance with the standard.
FIG. 1 shows a mesh network in which controller 100 connected to wired network 150 supports a plurality of access points forming a mesh network. A wired connection is provided between controller 100 and access point 200 , the root node of the mesh. Access points 201 , 202 , 203 , 204 , 205 , 206 , 207 operate as mesh nodes and connect wirelessly as shown to root 200 . Client devices 300 , 301 , 302 , 303 connect wirelessly through the mesh.
As shown in FIG. 1 , client 300 connects wirelessly to access point 202 which in turn connects wirelessly to access point 201 which in turn connects wirelessly to access point 200 , the root of the mesh.
Controller 100 is a purpose-built digital device having a CPU 110 , memory hierarchy 120 , and a plurality of network interfaces 130 . CPU 110 may be a MIPS-class processor from companies such as Raza Microelectronics or Cavium Networks, although CPUs from companies such as Intel, AMD, IBM, Freescale, or the like may also be used. Memory hierarchy 120 includes read-only memory for device startup and initialization, high-speed read-write memory such as DRAM for containing programs and data during operation, and bulk memory such as hard disk or compact flash for permanent file storage of programs and data. Wired network interfaces 130 and 140 are typically IEEE 802.3 Ethernet interfaces to copper, although high-speed optical fiber interfaces may also be used. Controller 100 typically operates under the control of purpose-built embedded software, typically running under a Linux operating system, or an operating system for embedded devices such as VXWorks. Controller 100 may have dedicated hardware for encryption, and/or for routing packets between network interfaces. Memory hierarchy 120 may also contain a Trusted Platform Module (TPM), an industry-standard device for providing secure storage.
Access points 200 - 207 are also a purpose-built digital devices having a CPU 210 , memory hierarchy 220 , a first wired interface 230 , and wireless interface 240 . As with controller 100 , the CPU commonly used for such access nodes is a MIPS-class CPU such as one from Raza Microelectronics or Cavium Networks, although processors from other vendors such as Intel, AMD, Freescale, and IBM may be used. Memory hierarchy 220 comprises read-only storage such as ROM or EEPROM for device startup and initialization, fast read-write storage such as DRAM for holding operating programs and data, and permanent bulk file storage such as compact flash memory. Memory hierarchy 220 may also contain a TPM. Remote access points 200 - 207 typically operate under control of purpose-built programs running on an embedded operating system such as Linux or VXWorks. Wireless interface 240 is typically an interface operating to the family of IEEE 802.11 standards including but not limited to 802.11a, b, g, and/or n.
Many wireless digital networks, such as IEEE 802.11 wireless networks practice carrier sense multiple access with collision avoidance (CSMA/CA) as a method of sharing a common channel among multiple devices. In CSMA/CA schemes, a device listens on the channel prior to transmitting, waiting for the channel to be idle. If the channel is busy, the device waits, or backs off, a predetermined period of time before checking again. When the channel is sensed as idle, the device also waits, or backs off, a predetermined period of time before transmitting. According to the IEEE 802.11 standard, this backoff time is random, and increases exponentially with subsequent attempts. This backoff process seeks to avoid collisions.
According to the present invention, access points in a mesh network calculate a backoff time using a formula or algorithm based on their current state in such a way that a node that is a more deserving candidate to transmit computes a smaller backoff time compared to a node that is less deserving. A node is considered more deserving if by transmitting it reduces the probability of data loss due to queue overflow in the network. The algorithm can be described as follows:
Node Rank Calculation: Each node gets a rank from 1 through N where N is a positive integer. The higher the rank of a node, the more deserving it is which translates to a smaller backoff time.
Downstream and Upstream Rank Components: If a node has data to transmit downstream, it calculates a downstream rank. If a node has data to transmit upstream it calculates an upstream rank. The sum of the two ranks is the overall rank of the node. The sum of the two ranks cannot exceed N. In the description below the downstream and upstream ranks are limited to N/2 which represents an equal weighting for downstream and upstream traffic. However other weightings are possible.
DEFINITIONS
CurrentMaxHops: This is the maximum hopcount among all packets in the downstream transmit queue of the node. The hopcount of a packet is the number of hops it has already traversed to arrive at this node.
MaxTreeHops: This is the maximum number of levels in the tree (root has level of 0).
DownstreamBufferRatio: If ‘MaxDownstreamBufferAllocation’ is the amount of buffer space allocated for downstream packets, and ‘CurrentDownstreamBufferUsage’ is the space occupied by downstream packets, then the ratio CurrentDownstreamBufferUsage/MaxDownstreamBufferAllocation is the ‘DownstreamBufferRatio’ (it is a number between 0 and 1)
NodeLevelRatio: We refer to the level of a node in the tree as ‘NodeLevel’ and we define the ‘NodeLevelRatio’ as (1−NodeLevel/MaxTreeHops). Nodes closer to the root will have a higher value.
UpstreamBufferRatio: This is similar to DownstreamBufferRatio defined earlier except it refers to space occupied by packets destined upstream.
Downstream Rank: This is the sum HopRank+BufferRank where HopRank is defined as (CurrentMaxHops/MaxTreeHops)*N/4 and BufferRank is defined as Downstream BufferRatio*(N/4)
Upstream Rank: This is the sum LevelRank+BufferRank where LevelRank=NodeLevelRatio*(N/4) and BufferRank=Upstream BufferRatio*(N/4)
TotalNodeRank: This is the sum UpstreamRank+DownstreamRank
What the above algorithm seeks to achieve is that the rank of nodes dynamically adjusts to ensure that traffic keeps moving through the mesh without accumulating at any node. For example, as traffic moves downstream through the mesh, its priority increases at each hop since its HopRank increases. This ensures that traffic already in transit through the mesh is “drained out” before the mesh accepts new traffic from the wired side. Likewise, as upstream traffic gets closer to the root of the tree, the LevelRank increases and it “bubbles up” faster to the root.
Finally, we map the rank to a backoff delay. A higher rank translates to a smaller backoff delay. If the value N is less than the maximum delay M that standard 802.11 devices use, then the backoff delay can simply be chosen as (M−N). Other ways of mapping the rank are possible as long as a higher rank translates to a smaller delay.
Note that the shortened periods that the algorithm calculates are shorter than those practiced by devices practicing the 802.11 standard. This has the effect of placing a higher priority on traffic being transmitted by mesh access nodes.
The level of a node in the tree may be calculated in a number of ways known to the art. In one embodiment, access points forming the mesh are enumerated by walking the tree formed by the mesh. This process may be incorporated into the process of organizing nodes into the mesh, or reorganizing nodes in the mesh when the mesh topology changes. Walking or coloring the tree, as is known to the art, assigns levels to the access points, with the root or portal being level 0, the access points connecting to the root are level 1, and so on. Depth first searches and breadth first searches are approaches to walking the tree and assigning levels. As an example the numbering of access points 201 through 207 in FIG. 1 are the result of a depth-first search. A similar protocol header field in each packet can be used to calculate the number of hops a packet has traversed which is used in the calculation of CurrentMaxHops.
In another embodiment, nodes in the mesh use a dedicated field in a protocol header to count how many hops a packet takes through the mesh, The header could be the mesh header as described in IEEE-80211s/D2.0 Part 11 or it could be a higher level protocol header such as TCP/IP. The header field is incremented each time a node forwards a packet. In such an embodiment, a node may determine its level in the mesh by examining this field in packets coming from root node 200 .
Once levels have been assigned to access points in the mesh, this level is used as the distance to the root.
Examining FIG. 1 , all traffic to and from client devices 302 and 303 must pass through access point 205 . When client 302 wishes to send a packet to a service on network 150 , it transmits that packet to access point 206 on the mesh. Access point 206 then transmits the packet to access point 205 on the mesh, which sends it to access point 200 .
If client devices 302 and 303 are generating substantial amounts of upstream traffic, access point 205 is going to be very busy. While it is common for access points to incorporate queues for holding data to be transmitted, particularly in a mesh environment, it is easy for those queues to be filled.
According to the 802.11 standard, when the shared radio channel used by mesh nodes 200 - 207 goes idle, stations wishing to transmit wait a randomized period of time with exponential backoff according to the algorithm specified in the standard. At the end of that interval, if the channel is still idle, the station begins transmitting. This insures fairness.
According to the present invention, access points in the mesh calculate their wait and backoff times using the rank calculation algorithm described above and do so in a manner which results in shorter times than those specified in the standard.
According to the present invention, if both access points 205 and 206 have traffic to transmit upstream, when the shared channel goes idle, access point 205 at level 1 of the mesh will generate a wait time that is less than the wait time generated by access point 206 which is at level 2 of the mesh. Similarly, access point 206 will generate a wait time for upstream traffic which is less than the wait time generated by client device 302 . This has the effect, then, of prioritizing upstream traffic transmissions by access points closer to the root of the mesh. Similar arguments apply to the downstream traffic where nodes further away from the root calculate a higher rank and smaller backoff delay for transmissions directed downstream
The present invention may be realized in hardware, software, or a combination of hardware and software. The present invention may be realized in a centralized fashion in one computer system, or in a distributed fashion where different elements are spread across several interconnected computer systems. Any kind of computer system or other apparatus adapted for carrying out the methods described herein is suited. A typical combination of hardware and software may be a general purpose computer system with a computer program that, when being loaded and executed, controls the computer system such that it carries out the methods described herein.
The present invention also may be embedded in a computer program product, which comprises all the features enabling the implementation of the methods described herein, and which when loaded in a computer system is able to carry out these methods. Computer program in the present context means any expression, in any language, code or notation, of a set of instructions intended to cause a system having an information processing capability to perform a particular function either directly or after either or both of the following: a) conversion to another language, code or notation; b) reproduction in a different material form.
This invention may be embodied in other forms without departing from the spirit or essential attributes thereof. Accordingly, reference should be made to the following claims, rather than to the foregoing specification, as indicating the scope of the invention.
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Prioritizing traffic forwarding in a wireless mesh network. In a wireless mesh network using carrier detect multiple access—collision avoidance with backoff, such as mesh networks supporting IEEE 802.11 clients, access points in the mesh calculate a node rank based on downstream and upstream rank components. Access points in the mesh then generate backoff times inversely proportional to their node rank. This has the effect of prioritizing traffic at nodes that have higher rank. The downstream and upstream rank components take into account the amount of space occupied by downstream and upstream traffic, respectively, and are weighted by their position in the mesh tree.
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CLAIM OF PRIORITY
This application claims priority under 35 U.S.C. §119(e) to provisional U.S. Patent Application 61/783,425, filed on Mar. 14, 2013, the entire contents of which are hereby incorporated by reference.
BACKGROUND
Various methods can be used to establish or verify the identity and authority of an individual. For example, people use physical badges to identify themselves and establish their authority or permissions in a variety of contexts. For example, a person may present an employee badge to gain access to an employer's secure building.
Paper documents can be signed to associate a person with the document in a reasonably verifiable manner. The document may have different significance or meaning depending on the identity and authority of a person who signs the document.
SUMMARY
In one aspect of the present disclosure, a method performed by one or more processing devices includes receiving a content item. The method may further include receiving a request to electronically sign the content item by a user by associating the content item with a credential associated with the user, the request comprising data identifying the credential from among a set of credentials that are associated with the user. The method may further include generating a package comprising the content item and data for the identified credential.
Implementations of the disclosure can include one or more of the following features. In some implementations, a digital signature for the package is determined and the package may be transmitted or stored with the digital signature. The digital signature may be determined based in part on a private key that corresponds to a public key associated with an entity that manages the set of stored credentials for a plurality of users. Generating the package may further include including, in the package, data reflecting a time associated the request to electronically sign. Generating the package may further include including, in the package, data reflecting a geographic location associated with the request to electronically sign. The request to electronically sign may be received from a first device associated with the user. The package may be transmitted with the digital signature to a second device associated with a different user. The data for the identified credential may be retrieved from a data storage device that is local to the one or more processing devices. The data for the identified credential may be retrieved from a remote processing device associated with an entity that issued the credential. A QR code within which a reference to the data for the identified credential is encoded may be embedded in the content item. The data for the credential may include a photograph of a user associated with the credential. A request to electronically sign the content item by the user, by associating the content item with a second credential associated with the user, may be received. The request may include data identifying the second credential from among the set of credentials that are associated with the user. Generating the package may further include including data for the second credential in the package. The identified credential and the second credential may be issued by different entities. The identified credential may be issued by a first entity and the second credential may also issued by the first entity. A request to electronically sign the content item, by associating the content item with a second credential, may be received. The request may include data identifying the second credential from among a set of credentials that are associated with a different user. Generating the package may further include including data for the second credential in the package. A condition for electronic signature associated with the identified credential may be checked to determine whether the condition is satisfied by the request to electronically sign the content item. The package may be generated responsive to determining that the condition is satisfied. The condition may require the request to electronically sign the content item to be sent within one or more specified periods of time. The condition may require the request to electronically sign the content item to be sent from within one or more specified geographic regions. An annotation may be applied to the content item before adding the content item to the package. The annotation may include an image of a handwritten signature of the user.
In still another aspect of the disclosure, one or more machine-readable media are configured to store instructions that are executable by one or more processing devices to perform operations including receiving a content item. The operations may further include receiving a request to electronically sign the content item by a user by associating the content item with a credential associated with the user, the request comprising data identifying the credential from among a set of credentials that are associated with the user. The operations may further include generating a package comprising the content item and data for the identified credential.
In still another aspect of the disclosure, an electronic system includes one or more processing devices; and one or more machine-readable media configured to store instructions that are executable by the one or more processing devices to perform operations including: receiving a content item. The operations may further include receiving a request to electronically sign the content item by a user by associating the content item with a credential associated with the user, the request comprising data identifying the credential from among a set of credentials that are associated with the user. The operations may further include generating a package comprising the content item and data for the identified credential.
All or part of the foregoing can be implemented as a computer program product including instructions that are stored on one or more non-transitory machine-readable storage media, and that are executable on one or more processing devices. All or part of the foregoing can be implemented as an apparatus, method, or electronic system that can include one or more processing devices and memory to store executable instructions to implement the stated functions.
The details of one or more implementations are set forth in the accompanying drawings and the description below. Other features will be apparent from the description and drawings, and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an example of a graphical user interface for displaying a list of electronically signed content items.
FIG. 2 illustrates an example of a graphical user interface for acquiring or creating a content item that may be electronically signed.
FIG. 3 illustrates an example of a graphical user interface for reviewing a captured image file.
FIGS. 4-6 illustrate examples of graphical user interfaces for electronically signing a content item.
FIGS. 7A-7C illustrate examples of graphical user interfaces for applying an annotation to a content item.
FIG. 8 illustrates an example of a graphical user interface for displaying a list of electronically signed content items shared with a user by other users.
FIGS. 9-10 illustrate examples of graphical user interfaces for displaying an electronically signed content item with information about a credential used to electronically sign the content item.
FIGS. 11A-11B illustrate examples of graphical user interfaces for displaying a badge representing a credential.
FIG. 12 is a block diagram of an example of a network environment enabling electronic signing of content items with credentials.
FIG. 13 is a block diagram showing examples of components of a network environment enabling electronic signing of content items with credentials.
FIG. 14 is a flowchart showing an example of a process for electronically signing a content item with a credential and sharing the electronically signed content item.
FIG. 15 is a flowchart showing an example of a process for electronically signing a content item with a credential.
DETAILED DESCRIPTION
A system consistent with this disclosure provides an application through which users may electronically sign and share content items (e.g., photographs, text files, video files, audio files, etc.). In some implementations, the application enables a user to manage and utilize multiple credentials, each potentially issued by a different credential issuing body. The application also may enable the user to select one or more of the credentials available on the user's mobile device to use to apply an electronic signature to a content item such that the electronic signature later can be used by another user to identify the one or more credentials that the user used to electronically sign the content item.
In some implementations, a content item is electronically signed by generating a package that includes the content item and information indicative of a credential that has been selected for signing the content item. Additionally or alternatively, the package may be digitally signed using a private key held by a trusted server system that manages credentials of many users.
In some implementations, an annotation may be applied to a content item. For example, an image of a user's handwritten signature or initials may be overlaid on a visual representation of a content item.
Furthermore, in some implementations, a content item may be electronically signed by multiple users. In such implementations, information corresponding to credentials of each of the signers may be included in a package to form an electronically signed content item.
In an illustrative example, employees may electronically sign content items with credentials issued by their employer, as described below. An employee may have other credentials, such as a gym membership credential or a museum membership credential, among others. All of these credentials may be managed by a credential management application server, and the employee may access and utilize the credentials using a client application that runs on the employee's mobile phone (or other computing device). The employee may generate a content item by taking a photograph with the employee's mobile phone. The employee's handwritten initials may be overlaid on the photograph as an annotation. The employee may then electronically sign the photograph using one or more of the employee's credentials. Once the photograph has been electronically signed by the employee, the employee may share the electronically signed photograph with another user of the credential management application. For example, the employee may share the electronically signed photograph with a coworker of the employee.
When the coworker receives the electronically signed photograph, the coworker is able to view both the photograph and information about the credential that the employee used to electronically sign the photograph. For example, the coworker may be able to view a badge on the coworker's mobile device that represents the employee's credential that was used to electronically sign the photograph. The coworker also may electronically sign the photograph with a credential associated with the coworker. Thereafter, the coworker may share the content item, electronically signed by both the employee and the coworker, with a third user.
A content item as described herein may be any data that can be provided over an electronic communications network. Examples of content items include image files, video files, streamed video, audio files, streamed audio, webpages, text files, and portable document format (PDF) files, among others.
FIG. 1 illustrates an example of a graphical user interface 100 for displaying a list of content items ( 102 , 104 , 106 , and 108 ) that have been electronically signed by a user (as described below). In the example of FIG. 1 , graphical user interface 100 is displayed on a client device through an application, including, e.g., an application for managing credentials. In the example of FIG. 1 , graphical user interface 100 includes a tab 110 for accessing the list of content items that have been electronically signed by the user. In some implementations, the content items ( 102 , 104 , 106 , and 108 ) listed may be stored on a remote server (e.g., a credential management application server), and the server may make the content items available to the user through the use of the application running on the client device. Graphical user interface 100 may also include an add document icon 120 , that may be selected by the user to add a new document that will be electronically signed by the user using one or more of his credentials.
FIG. 2 illustrates an example of a graphical user interface 200 for adding a content item to the list of content items electronically signed by the user. In an example, graphical user interface 200 is displayed, e.g., following selection of icon 120 of graphical user interface 100 ( FIG. 1 ). In the example of FIG. 2 , the user is presented with a number of options for creating or accessing content items that may be electronically signed, including: a camera icon 202 for creating a photograph using a camera integrated in the user's mobile device; a text icon 204 for launching a text editor interface that facilitates the creation of a text file; a gallery icon 206 for browsing existing content items available on the users mobile device; an e-mail icon 212 for importing content items (e.g., an e-mail or an attachment to an e-mail) from an e-mail application; and an “other apps” icon 214 for importing content items from other applications installed on the user's mobile device. For example, by selecting camera icon 202 , a user may launch a camera application on the mobile device for facilitating capture of a photograph by the mobile device.
FIG. 3 illustrates an example of a graphical user interface 300 for reviewing a captured image file. After a new image 302 has been captured, the user may preview the image to confirm that the image meets the user's needs. In this example, a captured photograph of a drawing and a collection of sticky-notes on a white board is presented for review in graphical user interface 300 . If the image is not acceptable, the user may select a “retake” icon 306 to make another attempt at capturing a new image. If the image is acceptable, the user may select a “use” icon 310 to proceed to electronically signing the new content item, in this example, photograph 302 .
FIG. 4 illustrates an example of a graphical user interface 400 for electronically signing a content item (e.g., photograph 302 ). Graphical user interface 400 may facilitate selection of one or more of the user's credentials ( 402 , 404 , and 406 ) for use in electronically signing the content item. Graphical user interface 400 also includes a display of the current time 410 and the current location 412 of the user's mobile device during the electronic signing process. The time and location of the electronic signature may be stored as part of an electronically signed content package.
FIG. 5 illustrates an example graphical user interface 500 that displays a content item along with information for a credential selected for an electronic signature. In this example, the user has selected credential 404 in graphical interface 400 . Once a credential has been selected for signing the content item (e.g., a photograph), the content item may be displayed along with information 502 about the credential that will be used to electronically sign the content item. Graphical user interface 500 may also display a time 510 and a location 512 that will be recorded as part of the electronic signature that may indicate the time and location at which the electronic signing process was carried out. If the proposed electronic signature with the selected credential is acceptable, the user may select the “confirm” icon 520 . Pressing confirm icon 520 may cause the proposed electronically signed content item to be generated, for example, by a credential management application server.
In some implementations, a code (e.g., a QR code) that references the credential used to sign the document may be embedded within the content item. In such implementations, if the content item subsequently is printed or otherwise converted into physical form, the code may be printed on the hardcopy version of the content item. The code then can be scanned and decoded to access information about who signed the document. For example, responsive to receipt of the decoded code from a client device, the credential management application server may return information to the client device about the credential used to sign the document.
FIG. 6 illustrates an example of a graphical user interface 600 for displaying a confirmation message that indicates the electronically signed content item has been successfully generated by, for example, a credential management application server. The confirmation message includes an indication 606 of which of the user's credentials was used to electronically sign the content item. In the example of FIG. 6 , graphical user interface 600 includes a “share the document” icon 610 that, when selected by a user, facilitates sharing the document with other users. For example, selecting icon 610 may cause an address book of other users to be displayed that may be used to select one or more proposed recipients of the new electronically signed content item. When recipients of an electronically signed content item are selected, the electronically signed content item may be shared with those recipients. The recipients may receive a message notifying the recipient that the electronically signed content item is accessible to the recipient (e.g., through access to the credential management application server).
As an alternative to the example illustrated in FIGS. 1-6 , in some implementations, when a user intends to electronically sign a photograph, the user may select a credential to be used to electronically sign the photograph prior to taking the photograph instead of after taking the photograph. In such implementations, the photograph may be automatically electronically signed using the selected credential as part of the photograph capture or import process.
FIG. 7A illustrates an example of a graphical user interface for applying an annotation to a content item. In this example, graphical user interface 700 facilitates the selection of one or more credentials (e.g., credentials 702 , 704 , and/or 706 ) for electronically signing a content item 708 that has been imported from a gallery or another application. For example, graphical user interface 700 may be displayed responsive to user selection of icon 206 in graphical user interface 200 . Graphical user interface 700 also includes an icon 710 for adding an annotation to the content item 708 . An annotation may be added to the content item before the user electronically signs the content item.
When the add annotation icon 710 is selected by a user, graphical user interface 720 of FIG. 7B is presented to the user to facilitate application of an annotation to the content item 708 . Graphical user interface 720 includes an expandable annotation selection icon 730 that, when expanded as illustrated in FIG. 7B , displays a list of available annotations associated with a user or one or more credentials of the user. In this example, four annotations are available for application to the content item, including a handwritten signature 732 associated with a user, handwritten initials 437 of the user, a printed name 736 of the user, and a current date and time display 738 . In some implementations, annotations available to be applied to the content item may be stored locally on a user's mobile device and/or annotations available to be applied to the content item may be stored on a server. In some implementations, selection of the printed name annotation icon 736 may open a text editor that allows a user to enter text for the user's name (or other text) that is added to the content item as an annotation.
When one of the annotations (e.g., the handwritten initials 734 ) is selected by the user, a corresponding annotation 750 is applied to the content item 708 , as shown in graphical user interface 740 of FIG. 7C . The annotation may be superimposed over the image of the content item 708 at a desired location. In some implementations, the application may enable the user to adjust the size of the annotation and/or drag the annotation to a desired location within the image of the content item 708 . For example, the application may enable the user to size and/or position the annotation using gestures entered through a touch-screen display. Graphical user interface 740 also includes a collapsed expandable annotation selection icon 754 , which may be selected and expanded to facilitate selection of an additional annotation for application to the content item 708 . After the annotation has been applied, a user may select the done icon 758 to return to graphical user interface 700 of FIG. 7A and electronically sign the document using one of the credentials ( 702 , 704 , 706 ) according to the techniques described above.
In the examples described above, the graphical user interfaces of FIGS. 1-6 and 7 A- 7 C are presented to a first user, John Doe, who interacts with the graphical user interfaces to electronically sign content items, including photograph 302 . Continuing with the examples described above, after electronically signing photograph 302 , the first user, John Doe, shares the electronically signed photograph 302 with a second user who is able to access the electronically signed photograph 302 , including information about the credential that the first user, John Doe, used to electronically sign the photograph 302 , through the graphical user interfaces of FIGS. 8-10 and 11 A- 11 B.
FIG. 8 illustrates an example of a graphical user interface 800 for displaying a list of electronically signed content items ( 802 , 804 , 806 , and 808 ) that have been shared with a user by other users. In this example, signed content item 802 is the signed and shared version of photograph 302 described above in connection with FIGS. 3-6 that has been shared with the user by John Doe. The list of shared content items ( 802 , 804 , 806 , and 808 ) may be displayed in a “shared with me” tab 810 of graphical user interface 800 . The user who has received these shared content items ( 802 , 804 , 806 , and 808 ) may select a content item (e.g., content item 804 ) from the list to cause the selected content item to be displayed along with information about a credential that was used to electronically sign the content item.
In some implementations, the recipient of an electronically signed content item that has been shared with the recipient only may be allowed to access the content item (or view information about a credential used to electronically sign the content item) if the recipient possesses the same credential as was used to electronically sign the content item (or a credential issued by the same credential issuing organization as the credential that was used to electronically sign the content item).
FIG. 9 illustrates an example of a graphical user interface 900 for displaying an electronically signed content item 902 with information about a credential 906 that has been used to electronically sign the content item. In this example, graphical user interface 900 is presented responsive to the selection of signed content item 802 in graphical user interface 800 . When a recipient of a shared electronically signed content item 902 accesses the content item, the content item is displayed with an indication of the credential 906 that was used to electronically sign the content item overlaid on the display of the content item 902 .
In some implementations, when a code (e.g., QR code) has been embedded within the content item as described above, the code is displayed embedded within the signed content item 902 in graphical user interface 900 .
The selection of the indication of credential 906 that was used to electronically sign the content item may cause more information about the electronic signature to be displayed, as shown in the example graphical user interface 1000 of FIG. 10 . Graphical user interface 1000 may include an icon 1004 identifying the credential used to electronically sign the content item, an indication of the time 1006 when the content item was electronically signed, an indication of the location 1008 where the content item was electronically signed, and information about the electronically signed content item, such as the file size 1010 . Graphical user interface 1000 may also include an icon 1030 for causing the electronically signed content item 902 to be removed from the recipient user's list of shared content items.
When the icon 1004 is selected, it may cause additional information about the credential used to electronically sign the content item 902 to be presented in the form of a badge representing the credential, as shown in the example graphical user interface of FIGS. 11A and 11B .
FIG. 11A illustrates an example graphical user interface 1100 on a client device that is used to display a portion of a badge that represents a credential used to electronically sign content item 902 . In this example, the user, “John Doe,” has electronically signed the content item 902 using an employee credential issued by his employer. A portion of the badge that may correspond to the front of a physical badge is displayed in graphical user interface 1100 . Graphical user interface 1100 includes an identifier 1102 (e.g., a distinctive mark) of the credential issuing organization that issued the credential (e.g., the signing user's employer). Graphical user interface 1100 may also include the name 1106 and a photograph 1110 of a user associated with the credential. Graphical user interface 1100 may also include information about the credential and/or the associated user 1114 , such as an employee's title and an employee identification number.
Graphical user interface 1100 may also include a “details” icon 1122 that, when selected by a user, causes graphical user interface 1150 of FIG. 11B to be displayed. For example, graphical user interface 1150 may correspond to the back of a physical badge. For example, graphical user interface 1100 may include a name for the credential 1152 , a name of a user 1154 associated with the credential, a title of the user 1156 associated with the credential, a name of an organization 1158 associated with the credential, an indication of an expiration date 1160 for the credential, an office number 1162 of the user associated with the credential, and a telephone number 1164 of the user associated with the credential. When an icon displaying the name of the organization associated with the credential is selected by a user, additional information about the organization may be displayed.
FIG. 12 is a block diagram of an example network environment 1200 enabling sharing and electronic signing of content items with credentials. Network environment 1200 includes network 1210 , client devices 1204 , 1206 , credential management application system 1222 , data repository 1216 , and credential issuing organization systems 1217 , 1218 . Network environment 1200 may include many thousands of data repositories, client devices, application systems, and credential issuing organization systems, which are not shown.
In an example, client device 1204 is associated with user 1202 . In this example, user 1202 may electronically sign content items and share those contents items and/or receive electronically signed content items shared by other users. Client device 1206 is associated with user 1208 . In this example, user 1208 may electronically sign content items and share those contents items and/or receive electronically signed content items shared by other users.
In the example of FIG. 12 , application system 1222 includes a system that hosts applications, including, e.g., application 1220 . In this example, application 1220 is an application that manages credentials for users and facilitates electronic signing of content items by the users using one or more of their credentials. In an example, client devices 1204 , 1206 may download a client application 1212 for interacting with application 1220 from credential management application system 1222 (or another system). In another example, client devices 1204 , 1206 may use a web browser to access application 1220 from credential management application system 1222 , e.g., rather than downloading a client application for interacting with application 1220 onto client devices 1204 , 1206 . In an example, application 1220 and/or a client application 1212 for interacting with application 1220 may be configured to render one or more of graphical user interfaces 100 , 200 , 300 , 400 , 500 , 600 , 700 , 720 , 740 , 800 , 900 , 1000 , 1100 , and 1150 , as shown in FIGS. 1-11B , respectively. In this example, through application 1220 and/or a client application 1212 for interacting with application 1220 , users 1202 , 1208 of client devices 1204 , 1206 , respectively, may electronically sign content items using credentials managed by merchant system 1222 (e.g., a credential issued by credential issuing organization system 1218 ) and share the electronically signed content items with other users, including each other.
Credentials may be issued to users by one or more credential issuing organizations. For example, an employer may be a credential issuing organization that issues credentials to its employees (e.g., a credential that is specific to an employee's job function(s)). Some other examples of credential issuing organizations are a government agency, a telecommunications service provider, a banking or other financial services institution, a gym, or a museum, among others. Credentials may be used by credential holders to gain access to service or facilities provided by a credential issuing organization and/or to act on behalf of a credential issuing organization.
Credential issuing organization system 1218 may be operated by a credential issuing organization (e.g., an employer of users 1202 , 1208 ). Credential management application system 1222 may provide an interface (e.g., via communications over network 1210 ) to the credential issuing organization system 1218 to allow for the specification of credential properties and issuing of credentials to users. In some implementations, credential issuing organization system 1218 provides a user (e.g., user 1202 ) with a token that matches data associated with a credential that is communicated to the credential management application system 1222 through its credential issuing organization interface. The user may then present the token to the credential management application system 1222 as part of a credential registration request sent from the user's client device (e.g., client device 1204 ) to associate the credential with the user's client device.
The credential management system 1222 may enable users (e.g., users 1202 , 1208 ) to store, manage, and/or access various different credentials issued by one or more different credential issuing organizations through credential management system 1222 . An individual user may have credentials from multiple credential issuing organizations (e.g., credential issuing organization 1217 and credential issuing organization 1218 ). For example, a user (e.g., user 1202 ) may have credentials issued by the user's employer, a government agency (e.g., a driver's license, passport, or other identity card), and a bank where the user has an account. An individual user may also have multiple credentials issued by the same credential issuing organization. For example, an employer may issue multiple credentials to an employee user (e.g., user 1202 ). Different credentials from the employer may provide different permissions and/or authority to the user, corresponding to different job functions that the user performs as an employee.
Credential management application system 1222 stores, in data repository 1216 , information about credentials managed by application 1220 . For example, when user 1202 registers a new credential, the credential management application system 1222 stores, in data repository 1216 , a credential record 1226 , including, e.g., information indicative of the assignment of the new credential to user 1202 . In this example, the credential record 1226 includes information identifying a credential 1228 that has been issued by credential issuing organization system 1218 , information specifying conditions 1230 associated with the credential (e.g., conditions associated with the use of the credential), and user information 1232 that identifies a user identity for user 1202 (e.g., a unique identification code for a user identity or a pointer to a user identity record in the data repository 1216 or remote data storage system). In some implementations, the user information 1232 also includes (or points to) data for the assigned user that may be relayed through the application 1220 to another user when a shared content item electronically signed by the user 1202 is accessed. For example, the user information 1232 may include a name for user 1202 , a photograph of user 1202 , demographic information for user 1202 , or other personally identifying information for user 1202 , including, e.g., a biometric identifier for user 1202 .
The credential record 1226 may enable identification of the user based on the credential ID 1228 . For example, a received credential may be cross referenced against credentials (or information related to credentials) stored in credential records to find user information 1232 .
In some implements, conditions 1230 for a credential may include an expiration date, after which the credential may no longer be accessed and used by user 1202 . Additionally or alternatively, conditions 1230 for a credential may include limitations on the time(s) or location(s) where a credential may be accessed and/or used. For example, a condition 1230 may require that a user's device (e.g., client device 1204 ) be located in one of a list of allowed locations (e.g., an employer's offices) in order for the credential to be accessed and/or used. In some implementations, allowed or disallowed locations may be defined as areas within a predefined radius of a point location (e.g., a pair of latitude longitude coordinates or a fixed wireless communications antenna). Additionally or alternatively, a condition 1230 may require that a credential be accessed and/or used during certain times of the day (e.g., during regular business hours). For example, conditions 1230 for a credential may be specified by credential issuing organization system 1218 via communications with credential management application system 1222 through a dedicated interface.
Users 1202 , 1208 may access their credentials using a client application 1212 running on their client devices 1204 , 1206 that interfaces with application 1220 running on credential management application system 1222 . In some implementations, client application 1212 interfaces with application 1220 to allow a user (e.g., user 1208 ) to validate a credential used by another user (e.g., user 1202 ).
Application 1220 may enable users (e.g., users 1202 , 1208 ) to upload and store content items (e.g., photographs, text files, audio files, video files, etc.) onto the credential management system 1222 and to electronically sign an uploaded content item using a credential managed by application 1220 . For example, uploaded content items may be stored in data repository 1216 . When an uploaded content item is electronically signed, it may be stored as part of a package that includes the content item and information identifying one or more credentials that have been used to electronically sign the content item.
Application 1220 may also enable users (e.g., users 1202 , 1208 ) to share electronically signed content items with other users of application 1220 . In some implementations, a recipient of an electronically signed content item that has been shared is able to access the electronically signed content item using client application 1212 , which displays the accessed content item along with an indication of one or more credentials that have been used to electronically sign the content item.
For example, application 1220 and/or a client application 1212 for interacting with application 1220 may be configured to render one or more of graphical user interfaces 800 , 900 , 1000 , 1100 , and/or 1150 , as shown in FIGS. 8-10 and 11 A- 11 B, respectively to facilitate sharing of the electronically signed content item.
In an example scenario, user 1202 may register a credential issued by credential issuing organization system 1218 with application 1220 running on credential management application system 1222 . User 1202 may thereafter use client device 1204 to create a content item (e.g., by taking a photograph) and use client application 1212 to upload the content item to credential management application system 1222 . In addition, user 1202 may use client application 1212 to transmit to credential management application system 1220 an electronic signature request 1224 that identifies the uploaded content item and a particular one of the user's 1202 credentials to be used to electronically sign the uploaded content item (e.g., the credential issued by credential issuing organization system 1218 ).
In some implementations, a client device (e.g., client device 1204 ) may store indications of the different credentials available to the user to be used to sign a content item and enable the user to select one or more of these credentials to use to sign the content item. Additionally or alternatively, a server (e.g., credential management system 1222 ) may store the indications of the different credentials available to the user to be used to sign a content item and enable the user to select one or more of these credentials to use to sign the content item.
Upon receiving the electronic signature request 1224 , the application 1220 running on credential management application system 1222 may access the credential record 1226 for the identified credential and check that any conditions 1230 for the credential are satisfied. If the conditions 1230 attached to the credential (if any) are satisfied, then the application 1220 may electronically sign the content item by generating a package that includes the content item and information identifying the credential (e.g., credential ID 1228 and/or some of the user information 1232 stored in credential record 1226 ). In some implementations, a confirmation message may be transmitted from the credential management system 1222 to the client device 1204 in response to the electronic signature request 1224 . The confirmation message may include a copy of the electronically signed content item 1244 , which includes the generated package.
In some implementations, at the time of the electronic signing, the credential management application system 1222 may request from the credential issuing organization 1218 that issued the credential selected to be used to electronically sign the content item information about the credential (e.g., if the credential management application system 1222 does not cache the credential record 1226 for the selected credential and/or if the credential management application system 1222 has not updated the credential record 1226 for the selected credential within a defined period of time).
For example, application 1220 and/or a client application 1212 for interacting with application 1220 may be configured to render one or more of graphical user interfaces 100 , 200 , 300 , 400 , 500 , 600 , as shown in FIGS. 1-6 , respectively to facilitate uploading and electronic signing of a content item. In some implementations, application 1220 also enables the application of annotations to content items. For example, application 1220 and/or a client application 1212 for interacting with application 1220 may be configured to render one or more of graphical user interfaces 700 , 720 and 740 , as shown in FIGS. 7A-7C , respectively to facilitate applying an annotation to content item. The application of an annotation to a content item may precede the electronic signing of the content item.
User 1202 may then choose to share the electronically signed content item with user 1208 . In some implementations, a sharing invitation may be transmitted from client device 1204 to client device 1206 . The sharing invitation may refer to a copy of the electronically signed content item stored in the data repository 1216 by application 1220 and may cause an icon for the electronically signed content item to be presented to user 1208 by client application 1212 running on client device 1206 in a list of signed content items that have been shared with user 1208 . In some implementations, when the electronically signed content item is shared with the user 1208 , a record may be created in data repository 1216 that indicates that user 1208 is authorized to access the content item. Consequently, when client application 1212 connects to the credential management application system 1222 while user 1208 is logged in, an indication that the electronically signed content item has been shared with user 1208 may be displayed by client application 1212 (e.g., as an icon within a list of icons representing content items that have been shared with user 1208 ).
If a user 1208 selects the electronically signed content item from this list, then a copy of the electronically signed content item 1244 including the generated package may be transmitted from credential management application system 1222 to client device 1206 . The content item may then be presented to user 1208 in a display of client device 1206 and information identifying the credential used to electronically sign the content item (e.g., credential ID 1228 and or user information 1232 ) may also be presented in the same display.
In some implementations, the electronically signed content item 1244 may be digitally signed by application 1220 using a private key of the application that is paired with a public key that is associated with the credential management application system 1222 . Client devices (e.g. client device 1204 and client device 1206 ) may store or otherwise have access to the public key and may use the public key to confirm the validity of the digital signature generated using the private key. In this manner, the digital signature may provide assurance that the electronically signed content item 1244 was generated by and properly received from the credential management application system 1222 .
FIG. 13 is a block diagram showing examples of components of network environment 1200 enabling sharing and electronic signing of content items with credentials. In the example of FIG. 13 , users 1202 , 1208 , electronic signature request 1224 and electronically signed content item 1244 are not shown.
Application system 1222 can be a variety of computing devices capable of receiving data and running one or more services, including, e.g., application 1220 , which can be accessed by one or more of client devices 1204 , 1206 . In an example, application system 1222 can include a server, a distributed computing system, a desktop computer, a laptop, a cell phone, a rack-mounted server, and the like. Application system 1222 can be a single server or a group of servers that are at a same position or at different positions. Application system 1222 and each of client devices 1204 , 1206 , and credential issuing organization systems 1217 , 1218 can run programs having a client-server relationship to each other.
Application system 1222 can receive data from each of client devices 1204 , 1206 , and credential issuing organization systems 1217 , 1218 through input/output (I/O) interface 1300 . I/O interface 1300 can be a type of interface capable of receiving data over a network, including, e.g., an Ethernet interface, a wireless networking interface, a fiber-optic networking interface, a modem, and so forth. Application system 1222 also includes a processing device 1302 and memory 1304 . A bus system 1306 , including, for example, a data bus and a motherboard, can be used to establish and to control data communication between the components of application system 1222 .
Processing device 1302 can include one or more microprocessors. Generally, processing device 1302 can include an appropriate processor and/or logic that is capable of receiving and storing data, and of communicating over a network (not shown). Memory 1304 can include a hard drive and a random access memory storage device, including, e.g., a dynamic random access memory, or other types of non-transitory machine-readable storage devices. As shown in FIG. 13 , memory 1304 stores computer programs that are executable by processing device 1302 . These computer programs may include a data engine (not shown) for implementing the operations and/or the techniques described herein. The data engine can be implemented in software running on a computer device (e.g., application system 1222 ), hardware or a combination of software and hardware.
FIG. 14 is a flowchart showing an example of a process 1400 for electronically signing and sharing a content item. In FIG. 14 , process 1400 is split into parts 1402 , 1404 , 1406 , 1408 . Part 1402 may be performed by credential issuing organization (CIO) system 1218 . Part 1404 may be performed by credential management application (CMA) system 1222 (and/or by application 1220 ). Part 1406 may be performed by client device 1204 . Part 1408 may be performed by client device 1206 .
In operation, client device 1204 obtains and uploads 1410 a content item to the CMA system 1222 . In some implementations, the content item is obtained by using a camera to take a photograph. In some implementations, the content item is obtained by using a text editor to create a text file. In some implementations, the content item is obtained by retrieving the content item from a gallery of content items stored on client device 1204 . In some implementations, the content item is obtained by retrieving the content item from another application (e.g., an e-mail application) running on the client device 1204 . The CMA system 1222 receives 1412 the uploaded content item and may store the content item (e.g., in data repository 1216 . Alternatively, in some implementations, the content item already may be stored by the CMA system 1222 before a request to sign the content item is received. For example, the content item previously may have been shared with the user by another user.
The client device 1204 may transmit 1420 a request to electronically sign the content item with a credential registered to a user in the CMA system 1222 . The request to sign may identify the content item and a credential that will be used to electronically sign the content item. In some implementations, the request to sign may also indicate a time and/or a location where client device 1204 was located at the time of the request to electronically sign. For example, client device 1204 may determine a time of the request using a clock maintained by the client device 1204 at the time the request to electronically sign is initiated by a user. Alternatively, in some implementations, client device 1204 may determine a time of the request using a trusted timestamp it obtains from a separate time stamping authority (e.g., a time stamping authority computer device or system) at the time the request to electronically sign is initiated by a user, or the credential management application system 1222 may determine the time of an electronic signature based on the time when the request to electronically sign is received. Furthermore, client device 1204 may determine a location of the request using a global positioning system (GPS) receiver integrated in the client device 1204 at the time the request to electronically sign is initiated by a user.
Upon receiving 1422 the request to electronically sign the content item, the CMA system 1222 may retrieve 1424 data for the identified credential. In some implementations, data for the identified credential is retrieved 1424 from a credential record stored in the data repository 1216 . Additionally or alternatively, the CMA system may retrieve 1424 some or all of the data for the identified credential from CIO system 1218 , which provides 1430 credential and/or user information for credentials that is has issued.
A package is generated 1440 that includes the content item and some or all of the retrieved credential data, including data identifying the credential used to electronically sign the content item. Additionally or alternatively, in some implementations, the package may include a reference (e.g., a link) to information about the credential used to electronically sign the content item such that the credential information for the credential used to electronically sign the content item may be retrieved by interaction with the reference. In some implementations, the package may also include an indication of a time and/or a location where the document was electronically signed (e.g., where the client device requesting the electronic signature was located at the time). In some implementations, the package may use predefined internal structures to contain the content item and the retrieved credential data.
Furthermore, in some implementations, a digital signature is determined 1450 for the generated package. The digital signature may be determined 1450 based in part on a private key paired with a public key that is associated with the CMA system 1222 . The digital signature may be transmitted and/or stored 1456 along with the package to provide assurance to a recipient that a received electronically signed content item was truly generated by the CMA system 1222 as it appears in a received transmission.
An electronic signature confirmation message may be transmitted 1456 to client device 1204 in response to the request to electronically sign the content item. The confirmation message may include or be accompanied by a copy of the electronically signed content item with the digital signature for the package.
After the content item has been electronically signed, a user of client device 1204 may request that the electronically signed content item be shared with one or more other users. For example, client device 1204 may transmit 1460 to the CMA system 1222 a request to share the electronically signed content item with one or more other users, including a user associated with client device 1206 . In response to receiving the request to share the electronically signed content item, the CMA system 1222 may transmit 1470 to client device 1206 the package along with the digital signature of the CMA system 1222 . In some implementations, when the electronically signed content item is shared with a recipient, a record on the CMA system 1222 may be updated to reflect that the electronically signed content item has been shared with the recipient. Consequently, an indication that the electronically signed content item has been shared with the recipient may be provided to the recipient. Thereafter, the CMA system 1222 may provide the recipient with access to the document responsive to interaction with the provided indication that the electronically signed content item has been shared with the recipient.
Client device 1206 may receive 1476 the package with the digital signature from the CMA system 1222 . Client device 1206 may use the public key associated with the CMA system 1222 to check the digital signature and confirm that the CMA system 1222 created the received package. The content item and data identifying the credential from the package may then be presented in a display of client device 1206 . Client device 1206 may allow a user to access additional data regarding the credential used to electronically sign the content item and/or a user associated with the credential.
FIG. 15 is a flowchart showing an example of a process 1500 for electronically signing a content item with a credential. A package is generated including the content item and data identifying one or more credentials that are used to electronically sign the content item. In some implementations, an annotation may be applied to the content item that is incorporated in the package. In some implementations, the package may be digitally signed by a system that is trusted to manage the credentials. For example, process 1500 may be performed by application system 1222 .
The process 1500 may include receiving 1502 a content item. For example the content item may include a text file, an image file (e.g., a photograph), a video file, or an audio file, among other types of data. In some implementations, the content item is obtained by a user using a client application (e.g., client application 1212 ) running on a client device and uploaded to a server system that manages credentials. For example, a physical document (e.g., a page from a book) may be converted into a digital document that may be electronically signed by taking a photograph of the physical document. For example, the content item may be received 1502 through network interface 1300 of application system 1222 .
A request to electronically sign the content item is received 1504 that includes data identifying one or more credentials that will be associated with the content item to electronically sign the content item. The identified credential(s) may be selected from among a set of multiple stored credentials that are associated with a single user. For example, an interface similar to graphical user interface 400 of FIG. 4 may be used by a user to select from among the user's own credentials in forming the request to electronically sign the content item. The request to electronically sign the content item may be received 1504 from a client device associated with a user registered to use the identified one or more credentials. The request to electronically sign the content item may also include a time and/or location associated with the request to electronically sign. For example, the request to electronically sign the content item may be received 1504 through network interface 1300 of application system 1222 .
Data for the credential(s) identified in the request to electronically sign the content item may be retrieved 1508 . In some implementations, data for a credential is retrieved from a record for the credential that is maintained in a storage device that is local to the one or more processing devices (e.g., from credential record 1226 in data repository 1216 ). In some implementations, data for a credential is retrieved 1508 from a credential issuing organization that issued the credential (e.g., from credential issuing organization system 1218 . A request for data regarding the credential may be transmitted to a credential issuing organization system. For example, data for the identified credential(s) may be retrieved 1508 through network interface 1300 of application system 1222 .
In some implementations, the data retrieved for a credential may include one or more conditions on the use of the credential for electronic signing of content items. These condition(s) may be checked to determine if they are satisfied. In some implementations, a condition requires a request to electronically sign the content item to be sent within one or more specified periods of time (e.g., before a deadline, during business hours, on the last day of a financial quarter). In some implementations, a condition requires a request to electronically sign the content item to be sent from within one or more specified geographic regions (e.g., from a user's home, from one of an employer's offices, or from within certain designated countries). If the conditions for use of the credential are satisfied, then the electronic signing process 1500 may proceed.
In some implementations, a request to apply an annotation to the content item may be received. For example, during the electronic signature request process on a client device running client application 1212 , a user electronically signing the content item may be presented with the option to apply an annotation to the content item as described in relation to FIGS. 7A-7C . If annotation of the content item is requested 1510 , then a selected annotation may be applied 1512 to the content item. In some implementations, an annotation is an image that is superimposed or overlaid on a visual component of a content item. In the case of an audio file, an annotation may be overlaid on a visual representation of the audio file that is displayed by an audio file player application. For example, an annotation may be applied 1512 to the content item by application 1220 running on application system 1222 .
In some implementations, the annotation includes an image of a handwritten set of initials for a user associated with one or more of the credential(s) that will be used to electronically sign the content item. An annotation may include other information about a user associated with one or more of the credential(s) that will be used to electronically sign the content item, such as printed name of the user. In some implementations, the annotation includes an indication of the time and/or location where the request to electronically sign the content item was generated.
In some implementations, the annotations available to be applied to a content item may depend upon the particular credential of the user selected to be used to electronically sign the content item. For example, each credential available to the user may be associated with a selection of different annotations that can be applied to the content item such that different annotations may be available depending on which credential is being used to sign the content item. In alternative implementations, annotations may be associated with an individual user more generally rather than with particular credentials of the user. In such implementations, the user may select an annotation that generally is associated with the user to be applied to the content item before selecting a credential to use to electronically sign the content item.
A package may be generated 1520 that includes the content item and data identifying one or more credentials that are being used to electronically sign the content item. The package may be generated to include a credential identifier (e.g., credential ID 1228 ) and/or data reflecting characteristics of the user associated with the credential. In some implementations, the package may be generated to include a photograph of a user associated with the credential, which may be displayed to another user who reviews the electronically signed content item.
In some implementations, the package may be generated to include data reflecting a time associated the request to electronically sign the content item. In some implementations, the package may be generated to include data reflecting a geographic location associated the request to electronically sign the content item. This time and location data for the electronic signature may also be presented to a user with whom the electronically signed content item is shared.
In some implementations, the request to electronically sign the content item identifies multiple credentials associated with the same user to be used to electronically sign the content item. Additionally or alternatively, the user may submit a series of multiple requests to sign the same content item with different ones of the user's credentials. For example, if the user requests to electronically sign the content item with a second credential of the user, the package may be generated to include data for a second credential in addition to the data for the first credential of the user. In some cases, the second credential may be issued by the same credential issuing organization as the first credential used to electronically sign the content item. In other cases, the second credential may be issued by a different credential issuing organization than the first credential used to electronically sign the content item. For instance, referring again to the examples introduced above in connection with FIGS. 1-6 and 7 A- 7 C, the user John Doe may request to electronically sign photograph 302 using his employee credential 404 . In addition, John Doe also may request to electronically sign the photograph 302 with his college alumni association credential 406 . The resulting electronically signed content item then may be shared with and displayed to other users with indications of both credentials 404 , 406 being presented with the photograph 302 .
In some implementations, multiple users may electronically sign the same content item. In such cases, multiple requests to electronically sign the content item may be received from multiple different users. For example, first and second requests to electronically sign the content item may be received from different users. In such cases, the package may be generated to include data for the credential of the first user and data for the credential of the second user. For example, a purchase order may need to be approved by two employees of a company before it can be processed for payment by the company's finance department. A first employee may electronically sign a purchase order using the first employee's employee credential and then share the electronically signed purchase order with a second employee of the company. The second employee may review the purchase order and then electronically sign the purchase order using the second employee's employee credential. The second employee then may share the purchase order with the two electronic signatures with a third employee in the finance department for processing.
In some implementations, the package is generated by appending the data identifying the one or more credentials to the content item in a larger file or other data structure. For example, the package may be generated 1520 by application 1220 running on application system 1222 .
In some implementations, a digital signature is determined 1530 for the package. The digital signature may be determined based in part on a private key that corresponds to a public key associated with an entity that manages the set of stored credentials for a group of users. For example, the digital signature may be determined based on a hash function that is applied to the package and the result of the hash function may be encrypted with the private key. When a user receives the electronically signed content item (e.g., as a shared document), the user's client device (e.g., running client application 1212 ) may confirm that the package was correctly received from an entity that manages the credentials by checking the digital signature with the public key associated with that entity. For example, the user's client device may apply the same hash function to the received package and compare the result to the result of decrypting the digital signature with the public key. If the results match, then the package may be considered to have been generated by the trusted entity that manages the credentials. For example, the digital signature for the package may be determined 1530 by application 1220 running on application system 1222 .
The package may be transmitted or stored 1540 with the digital signature for the package. For example, the package and the digital signature may be transmitted 1540 to a client device associated with the user requesting the electronic signature and/or a client device associated with a different user that will receive the electronically signed content item as a shared content item. For example, the package with the digital signature may be transmitted 1518 through network interface 1300 of application system 1222 .
Implementations of the subject matter and the functional operations described in this specification can be implemented in digital electronic circuitry, in tangibly-embodied computer software or firmware, in computer hardware, including the structures disclosed in this specification and their structural equivalents, or in combinations of one or more of them. Implementations of the subject matter described in this specification can be implemented as one or more computer programs, i.e., one or more modules of computer program instructions encoded on a tangible program carrier for execution by, or to control the operation of, a processing device. Alternatively or in addition, the program instructions can be encoded on a propagated signal that is an artificially generated signal, e.g., a machine-generated electrical, optical, or electromagnetic signal that is generated to encode data for transmission to suitable receiver apparatus for execution by a processing device. The machine-readable medium can be a machine-readable storage device, a machine-readable storage substrate, a random or serial access memory device, or a combination of one or more of them.
The term “processing device” encompasses all kinds of apparatus, devices, and machines for processing data, including by way of example a programmable processor, a computer, or multiple processors or computers. The processing device can include special purpose logic circuitry, e.g., an FPGA (field programmable gate array) or an ASIC (application-specific integrated circuit). The processing device can also include, in addition to hardware, code that creates an execution environment for the computer program in question, e.g., code that constitutes processor firmware, a protocol stack, a database management system, an operating system, or a combination of one or more of them.
A computer program (which may also be referred to as a program, software, a software application, a script, or code) can be written in any form of programming language, including compiled or interpreted languages, or declarative or procedural languages, and it can be deployed in any form, including as a stand-alone program or as a module, component, subroutine, or other unit suitable for use in a computing environment. A computer program may, but need not, correspond to a file in a file system. A program can be stored in a portion of a file that holds other programs or data (e.g., one or more scripts stored in a markup language document), in a single file dedicated to the program in question, or in multiple coordinated files (e.g., files that store one or more modules, sub-programs, or portions of code). A computer program can be deployed to be executed on one computer or on multiple computers that are located at one site or distributed across multiple sites and interconnected by a communication network.
The processes and logic flows described in this specification can be performed by one or more programmable computers executing one or more computer programs to perform functions by operating on input data and generating output. The processes and logic flows can also be performed by, and apparatus can also be implemented as, special purpose logic circuitry, e.g., an FPGA (field programmable gate array) or an ASIC (application-specific integrated circuit).
Computers suitable for the execution of a computer program include, by way of example, general or special purpose microprocessors or both, or any other kind of central processing unit. Generally, a central processing unit will receive instructions and data from a read-only memory or a random access memory or both. The essential elements of a computer may be a central processing unit for performing or executing instructions and one or more memory devices for storing instructions and data. Generally, a computer will also include, or be operatively coupled to receive data from or transfer data to, or both, one or more mass storage devices for storing data, e.g., magnetic, magneto-optical disks, or optical disks. However, a computer need not have such devices. Moreover, a computer can be embedded in another device, e.g., a mobile telephone, a personal digital assistant (PDA), a mobile audio or video player, a game console, a Global Positioning System (GPS) receiver, or a portable storage device (e.g., a universal serial bus (USB) flash drive), to name just a few.
Computer-readable media suitable for storing computer program instructions and data include all forms of non-volatile memory, media and memory devices, including by way of example semiconductor memory devices, e.g., EPROM, EEPROM, and flash memory devices; magnetic disks, e.g., internal hard disks or removable disks; magneto-optical disks; and CD-ROM and DVD-ROM disks. The processor and the memory can be supplemented by, or incorporated in, special purpose logic circuitry.
To provide for interaction with a user, implementations of the subject matter described in this specification can be implemented on a computer having a display device, e.g., a CRT (cathode ray tube) or LCD (liquid crystal display) monitor, for displaying data to the user and a keyboard and a pointing device, e.g., a mouse or a trackball, by which the user can provide input to the computer. Other kinds of devices can be used to provide for interaction with a user as well; for example, feedback provided to the user can be any form of sensory feedback, e.g., visual feedback, auditory feedback, or tactile feedback; and input from the user can be received in any form, including acoustic, speech, or tactile input. In addition, a computer can interact with a user by sending documents to and receiving documents from a device that is used by the user; for example, by sending web pages to a web browser on a user's client device in response to requests received from the web browser.
Implementations of the subject matter described in this specification can be implemented in a computing system that includes a back-end component, e.g., as a data server, or that includes a middleware component, e.g., an application server, or that includes a front-end component, e.g., a client computer having a graphical user interface or a Web browser through which a user can interact with an implementation of the subject matter described in this specification, or any combination of one or more such back-end, middleware, or front-end components. The components of the system can be interconnected by any form or medium of digital data communication, e.g., a communication network. Examples of communication networks include a local area network (“LAN”) and a wide area network (“WAN”), e.g., the Internet.
The computing system can include clients and servers. A client and server are generally remote from each other and typically interact through a communication network. The relationship of client and server arises by virtue of computer programs running on the respective computers and having a client-server relationship to each other.
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any of what may be claimed, but rather as descriptions of features that may be specific to particular implementations. Certain features that are described in this specification in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable sub-combination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub-combination or variation of a sub-combination.
Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. In certain circumstances, multitasking and parallel processing may be advantageous. Moreover, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described program components and systems can generally be integrated together in a single software product or packaged into multiple software products.
Particular implementations of the subject matter have been described. Other implementations are within the scope of the following claims. For example, the actions recited in the claims can be performed in a different order and still achieve desirable results. As one example, the processes depicted in the accompanying figures do not necessarily require the particular order shown, or sequential order, to achieve desirable results. In certain implementations, multitasking and parallel processing may be advantageous.
Furthermore, in some implementations, an electronic signature as described herein may be applied at a client device rather than at a server system. For example, a package for the electronically signed content item including the content item and information about the credential used to electronically sign the content item may be generated by a client device in response to user commands received at the client device. Additionally or alternatively, in such implementations, the client device may apply a digital signature to the content item using a private key associated with the credential selected as the credential to be used to electronically sign the content item. Other users with whom the digitally signed content item subsequently is shared then can confirm the validity of the digital signature using the public key paired with the private key associated with the credential used to electronically sign the content item. In some such implementations, the public key only may be accessible to other users who also hold the same credential as the credential used to electronically sign the content item (or other users who hold a credential issued by the same credential issuing organization as the credential used to electronically sign the content item).
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This specification describes technologies relating to applying electronic signatures to content items. In general, one aspect of the subject matter described in this specification can be embodied in methods that include receiving a content item and receiving a request to electronically sign the content item by a user by associating the content item with a credential associated with the user, the request comprising data identifying the credential from among a set of credentials that are associated with the user. The method may further include generating a package comprising the content item and data for the identified credential.
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CROSS REFERENCE TO RELATED APPLICATIONS
This is a continuation-in-part of application Ser. No. 644,768, filed Dec. 29, 1975 now abandoned as a continuation application of application Ser. No. 546,277, filed Feb. 3, 1975, now U.S. Pat. No. 3,944,092, issued 3/16/76 which was a continuation of application Ser. No. 471,845, filed May 21, 1974 and now abandoned.
BACKGROUND OF THE INVENTION
The background of the invention will be set forth in two parts.
1. Field of the Invention
The present invention pertains generally to the field of trash handling devices and more particularly to a new and useful device for collecting trash and depositing it in a trash-hauling vehicle through an elevated access opening in the vehicle body.
2. OF THE Description of the Prior Art
Blakeley, et al U.S. Pat. No. 3,773,197; Owen U.S. Pat. No. 3,790,011 and applicants' U.S. Pat. No. 3,910,434 disclose container emptying devices including container engaging mechanisms having the capability of horizontal movement from the side of a vehicle to a trash container.
Nelson U.S. Pat. No. 2,877,910 discloses a trash container having support abutment means in the form of an arm affixed to each sidewall of the container in a horizontal plane. Each arm has a free end extending beyond the front wall of the container. A roller is rotatably mounted on the free end of each arm for rolling engagement with a vertical plate on the truck as cables, which may be hooked onto the horizontal arms, pull the container up the side of the truck.
OBJECTS AND SUMMARY OF THE INVENTION
It is a primary object of the present invention to provide a new and useful trash handling device exemplifying improvements over this prior art.
Another object of the present invention is to provide a container engaging mechanism of the type disclosed in U.S. Pat. No. 3,910,434 which is designed to coact with support abutment means of the type disclosed in U.S. Pat. No. 2,877,910 so that trash or refuse may be transferred from a container to a vehicle through an elevated access opening efficiently, expeditiously and economically.
Yet another object of the invention is to provide an interchangeable container emptying device which may be easily and speedily attached to an elevator device on a vehicle and which includes a new and useful locking container emptying device when the container is tipped to a dumping position adjacent an elevated access opening in the body of the vehicle.
According to the present invention, a new and useful apparatus for emptying the contents of trash and/or refuse containers into a vehicle through an elevated access opening in the vehicle body is provided. The apparatus may be used in combination with a vehicle having power supply means to empty trash and/or refuse containers.
The apparatus includes elevator means for raising and lowering the container. The elevator means includes an upper end adjacent the elevated access opening and a lower end adjacent a surface supporting the containers.
The apparatus also includs means connecting the elevator means to the power supply means for moving at least the lower end of the elevator means over the surface between a first position closely adjacent the vehicle and a second position spaced laterally outwardly from the vehicle and closely adjacent the container.
A container engaging means is connected to the elevator means for mechanically engaging support abutment means on the container when the elevator means is moved to the second position by the power supply means. The support abutment means on the container may include arms and rollers of the type disclosed in U.S. Pat. No. 2,877,910 and may be engaged by the open-throat portions of U-shaped members provided on the container engaging means.
The apparatus also includes locking means for automatically locking the support abutment means to the container engaging means so that the container will remain in connected relationship with the container engaging means when it is inverted adjacent the elevated access opening to empty the container.
In one form of the invention, the locking means is swingably connected to the container engaging means by suitable shaft means and includes lock bar means for bridging the open-throat portions of the U-shaped members. The locking means also includes bumper means engageable by the container for swinging the locking means about the shaft means upon movement of the container to the inverted position, so that the lock bar means will move to the bridging position. In this form of the invention, the rollers on the container are engaged by the U-shaped members.
In a modified form of the invention, the U-shaped members occupy a position on a container engaging means at right angles to the positions occupied by the U-shaped members in the first form of the invention so that the U-shaped members in the modified form will engage the arms behind the rollers. The locking means in the modified form of the invention includes a lock bar which is forced into engagement with each arm adjacent an associated one of the open-throat portions of the U-shaped members.
The features of the present invention which are believed to be novel are set forth with particularity in the appended claims. The present invention, both as to its organization and manner of operation, together with further objects and advantages thereof, may best be understood by reference to the following description, taken in connection with the accompanying drawings in which like reference characters refer to like elements in the several views.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view of a container emptying device constituting a first form of the present invention having portions thereof foreshortened for clarity and showing the device in position on the side of a vehicle shown in side elevation with portions broken away;
FIG. 2 is an enlarged, perspective view, showing a portion of the container-engaging and the locking portions of the device shown in FIG. 1;
FIG. 3 is an enlarged, cross-sectional view taken along line 3--3 of FIG. 2;
FIG. 4 is an enlarged, partial elevational view of the locking device portion shown in FIG. 2;
FIG. 5 is an enlarged, cross-sectional view taken along line 5--5 of FIG. 1;
FIG. 6 is an enlarged, partial side-elevational view showing a container connected to the device with the container in a tipped-dumping position;
FIG. 7 is an enlarged, partial perspective view of the device of FIG. 1 showing bolt means for connecting the container-engaging portion of the device to the elevator portion of the device;
FIG. 8 is a rear elevational view showing the device of FIG. 1 in position closely adjacent the truck of FIG. 1 in solid lines and in a laterally outward position in broken lines adjacent a partial elevational view of a container to be engaged by the device;
FIG. 9 is an enlarged elevational view, with parts broken away to show internal construction, of the device of FIG. 1 showing the container-engaging portion of the device in engagement with a container;
FIG. 10 is an enlarged partial perspective view showing the container-engaging portion of the device connected to the elevator portion of the device;
FIG. 11 is a front elevational view of a container emptying device constituting a modified form of the present invention having portions thereof foreshortened for clarity and showing the device in position on the side of a vehicle shown in side elevation with portions broken away;
FIG. 12 is an enlarged, perspective view, showing a portion of the container-engaging and the locking portions of the device shown in FIG. 11;
FIG. 13 is an enlarged cross-sectional view taken along line 13--13 of FIG. 11;
FIG. 14 is an enlarged, partial perspective view of the device of FIG. 11 showing hook means connecting the container-engaging portion of the device to the elevator portion of the device;
FIGS. 14A and 14B are partial, side-elevational views of the portion of the container-engaging mechanism shown in FIG. 14;
FIG. 15 is a rear elevational view showing the device of FIG. 11 in position closely adjacent the truck of FIG. 11 in solid lines and in a laterally outward position in broken lines adjacent a partial elevational view of a container to be engaged by the device;
FIG. 16 is an enlarged elevational view, with parts broken away to show internal construction, of the device of FIG. 11 showing the device detached from the truck and showing the container-engaging portion of the device in engagement with a container;
FIG. 17 is an enlarged, partial perspective view showing the container-engaging portion of the device connected to the elevator portion of the device; and
FIG. 18 is an enlarged, partial perspective view of a portion of the container-engaging and the locking portions of the device of FIG. 11 with parts in an elevated position.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring again to the drawings, and more particularly to FIGS. 1 and 8, a container emptying device constituting a presently preferred embodiment of the invention, generally designated 10, is shown, for purposes of illustration, but not of limitation, in combination with a vehicle 12 having a suitable power supply, indicated schematically in FIG. 9 and 14 and fully illustrated and described in U.S. Pat. No. 3,910,434.
The container emptying device 10 is adapted to empty the contents of a trash container 16 (FIGS. 6, 8 and 9) into vehicle 12 through an elevatd access opening 18 provided therein. Device 10 includes a suitable elevator means 20 for raising and lowering container 16 and including an upper end 22 adjacent access opening 18 and a lower end 24 adjacent a supporting surface 26 which supports container 16 laterally outwardly from vehicle 12.
Container emptying device 10 also includes a suitable connecting means, indicated generally at 28 in FIG. 9, for connecting the elevator means 20 to the vehicle power supply 14 for moving at least the lower end 24 of elevator means 20 over surface 26 between a first position closely adjacent vehicle 12, as shown in solid lines in FIG. 8, and a second position spaced laterally outwardly from vehicle 12 and closely adjacent container 15, as shown in broken lines in FIG. 8
Device 10 also includes a container-engaging means 30 which may be quickly and easily connected to elevator means 20 by a plurality of bolts 32, 34, 36 and 38 facilitating interchanging container-engaging means 30 with other container engaging means like, for example the container engaging means shown in said U.S. Pat. No. 3,910,434. Container engaging means 30 is adapted to mechanically engage a suitable outwardly extending, transversely aligned abutment means which forms supporting means 40 provided on container 16 (FIGS. 6, 8 and 9) when the elevator means 20 is moved to the position shown in broken lines in FIG. 8 by power transmitted from vehicle power supply 14 to connecting means 28.
As best shown in FIGS. 2, 6, 8, 9 and 10, container-engaging means 30 includes a pair of hooks or U-shaped members 42, 44 having open-throat portions 46, 48, respectively, through which an associated one of the support abutment means 40, may pass when container engaging means 30 is elevated while in its FIG. 8 broken-line position. Container-engaging means 30 may then be moved inwardly to its FIG. 8 solid-line position by actuatng vehicle power supply 14 to move the lower end 24 of elevator means to its FIG. 8 solid-line position closely adjacent vehicle 12. Elevator means 20 may then be energized to raise container 16 to a position adjacent access opening 18 where suitable means, to be hereinafter described, will tip container 16 to the inverted position shown in FIG. 6. In this position, a suitable locking means 50 automatically locks the container to container engaging means 30 so that the support abutment means will not pass through open-throat U-shaped members 42, 44, as shown in FIG. 6. Locking means 50 includes a pair of lock bars 52, 54, adapted to bridge open-throat U-shaped members 42, 44, respectively. Lock bars 52, 54 are swingably connected to container-engaging means 30 by a shaft 56 having a first end 58 journalled in a hollow boss 60 affixed to U-shaped member 42 by a suitable weldment 62 (FIG. 3) and a second end journalled in a hollow boss 66 affixed to the U-shaped member 44. Shaft 56 includes first and second intermediate portions 68, 70 (FIG. 1) journaled in bearings 72, 74, respectively, rigidly affixed to a rectangular, tubular member or mounting bar 76 by brackets 246, respectively. Lock means 50 also includes a bumper bar 82 engageable by container 14 (FIG. 6) for swinging lock bars 52, 54 about shaft 56, upon movement of container 16 to the substantially inverted position shown in FIG. 6 whereby the lock bars 52, 54 will move into bridging positions in open-throat portions 46, 48.
The lock bars 52, 54 are each affixed to a bracket 84 (FIG. 2) by a suitable weldment 86. Bracket 84 is secured to a sleeve 88 by a weldment 90 and sleeve 88 is rotatably mounted on a fixed shaft 92, which shaft, in turn, is rigidly affixed to a pair of arms 94, 96 by suitable weldments, like the one shown at 98 for arm 94. Arms 94, 96 have upper ends 100, 102 respectively, affixed to bumper bar 82 by suitable weldments, such as the one shown at 104 for arm 94, and lower ends 106, 108, respectively, affixed to shaft 56 by suitable weldments like the one shown at 110 for arm 94. Longitudinal movement of sleeve 88 on shaft 92 is limited by a pair of thrust washers 112, 114 (FIG. 4) secured to the shaft 92 by weldments 116, 118, respectively. Each sleeve 88 carries an L-shaped arm 120 having a lower end 122 affixed to sleeve 88 by a weldment 124 and an upper, bifurcated end 126 having a roller 128 rotatably mounted thereon by a bolt 130. Rollers 128 are adapted to engage container 16 when it is inverted (FIG. 6) to prevent lock bars 52, 54 from swinging counterclockwise about shaft 92 due to the action of gravity. Rollers 128 have at least an elastomeric face thereon, and each roller forms an abutment to move lock bars 52, 54 across the respective open-throat portions 46, 48.
Each arm 94 carries a cam roller 132, rotatably connected thereto by a bolt 134, and a bracket 135, affixed thereto by a weldment 138 (FIGS. 2 and 5). A compression spring 140 has a first end 142 bearing against bracket 136 and a second end 144 bearing against tubular member 76 for biasing cam rollers 132 into engagement with an associated one of the inturned flanges 146 provided on a pair of upstanding masts 150, 152, respectively, forming part of elevator means 20. Masts 150, 152, each includes upper end 22 and lower end 24 of elevator means 20 and are maintained in spaced-apart relationship by an upper transverse tubular brace 156 (FIGS. 1, 6 and 9), an intermediate brace 158 (FIG. 10) and a lower brace 160 (FIG. 1). Each lower end 24 is affixed to a rectangular tubular member 162 (FIGS. 9 and 10) reciprocably mounted in a channel 164 attached to the frame 164 (FIG. 8) of vehicle 12 by a pair of upstanding brackets 166, 168 (FIG. 9) each having a lower 170 affixed to an associated one of the channels 164 by weldments 172, 174. Tubular member 162 is reciprocated by connecting means 28 which comprises an hydraulic cylinder 176 connected to vehicle power supply 14 by a pair of conduits 173, 175 and having a piston rod 178 connected to tubular member 162 by a transverse bar 180, affixed to tubular member 162 by a weldment 182, and a clevis pin 184. Reciprocating friction on tubular member 162 is minimized by a lower roller 186 and an upper roller 188 carried by brackets 190, 192, respectively, affixed to each channel 164 by weldments 194, 196, respectively.
A gear reduction unit 198 is mounted on lower end 24 of mast 152 for receiving the output from an hydraulic motor 200 receiving power from vehicle power supply 14 in the form of hydraulic fluid passing through conduits 202 and 204, as is described in detail in said U.S. Pat. No. 3,910,434. As best seen in FIGS. 1 and 5, a driven shaft 206 has a first end 208 connected to gear reduction unit 198 and a second end 210 journalled in a bearing cup 212 affixed to the lower end 24 of mast 150 by bolts 214. The ends 208, 210 of shaft 206 each carries a sprocket 216 keyed thereto for driving an associated one of a pair of elevator chains 218 trained about an associated upper sprocket 220 keyed to a shaft 222 having a first end 224 journalled in a bearing cup 226 affixed to the upper end 22 of mast 150 by bolts 228 and a second end 240 journalled in a bearing cup 232 affixed to the upper end 22 of mast 148 by bolts 234. Each chain 218 is also trained around an idler sprocket 236 (FIG. 9) carried by a shaft 238 rotatably mounted on masts 150, 152.
Referring now to FIGS. 1, 5, 7, 9 and 10, elevator means 20 includes a channel 240 having flanges 242, 244 between which the rectangular tubular mounting bar 76 on container-engaging means 30 is mounted. An arcuate plate 246 is affixed to each end of channel 240 and includes an upper end 248 which is pivotally connected to elevator chain 218 by a link 250 (FIG. 7). An abutment plate 252 is rigidly affixed to the upper end 248 of each arcuate plate 246 for forming a stop to complimentally engage an elastomeric bumper 254 which is secured to the transverse tubular brace 156 and which prevents further downward movement of container 16 when it is in an inverted position adjacent access opening 18. Abutment plates 252 may be brought into engagement with bumper 254 repeatedly to jar the contents from container 16, if necessary. Each plate 246 also includes a lower end 256 to which an end of a shaft 258 is affixed by a weldment 260. A similar shaft 262 has the ends thereof affixed to the upper end 248 of each plate 246 by weldments, like that shown at 264 in FIG. 7. Each end of the shaft 258, 262 extends through its associated plate 246 where it rotatably receives a guide roller 266 adapted to ride in channel 268 formed by associated ones of the flanges 146, 148 and 270, 272 provided on the masts 150, 152, respectively, for guiding container engaging means 30 during its travel along the upright portions of masts 150, 152 to the upper ends of flanges 272. At this point, the inturned flanges 146, 148 each takes a 180° turn, as shown at 276 in FIG. 9 for the flange 148, so that guide rollers 266 will move container-engaging means 30 on a course which inverts container 16, as shown in FIG. 6. When container 16 moves over the arcs at the upper ends 222 of masts 150, 152, the container 16 will be an elastomeric guide and support roller 278 encompassing a shaft 280 having a first end 282 extending through U-shaped member 42 and journaled in bearing 285, and a second end 184 extending through the U-shaped member 44 and journaled in a bearing 285. A set collar 286 may then be secured to each of the end 282, 284.
OPERATION
Operation of the first form of the device will be readily understood. Assuming that the parts are in the position shown in solid lines in FIG. 8, vehicle power supply 14 (FIG. 9) may be energized to supply fluid under pressure through conduit 175 to hydraulic cylinder 176 causing piston rod 178 to move container-engaging means 30 laterally outward from vehicle 12 over surface 26 to a position whereby the elastomeric guide and support roller 278 is moved into contact rolling relation with container 16 which will position the open-throat portions 46, 48 of the U-shaped members 42, 44 beneath support abutment means 40 on container 16, like the abutment means shown at 40 in FIG. 8, with the elastomeric guide and support rollers 278 being moved into contact relation with the container 16, as shown in dashed outline in FIG. 8. This will position the open-throat portions 46, 48 directly below the abutment support means 40, whereupon, by upward movement of the container engaging means 30, by elevator chains 218, the open-throat portions 46, 48 are guided into engagement with abutment support means 40, without the operator having to rely on manual skill to properly engage the container engaging means 30 with the container 16. The elastomeric roller minimizes the noise, and furthermore, it provides a friction surface to insure that the roller will roll upwardly along the side of the container 16 to cause proper engagement of the container engaging means 30 with the container 16.
The vehicle power supply 14 may then be controlled as more fully explained in said U.S. Pat. No. 3,910,434, to discontinue flow of hydraulic fluid through conduit 175 to cylinder 176 and direct the fluid, under pressure, through conduit 204 (FIG. 9) to hydraulic motor 200 transmitting power through gear reduction unit 198 to shaft 206 (FIG. 1) causing container engaging means 30 to move upwardly in guided relation to elastomeric guide and support roller 278 into engagement with container 16 to lift the container slightly above surface 26. The flow of fluid through conduit 204 to hydraulic motor 200 may then be terminated and cylinder 176 may be pressurized by fluid flowing through conduit 173 to move container-engaging means 30 and container 16 inwardly to a position closely adjacent vehicle 12. The flow of hydraulic fluid to cylinder 176 may then be terminated and fluid may be directed through conduit 204 to hydraulic motor 200 to again elevate container-engaging means 30 and container 16. Guide roller 266 will guide container-engaging means 30 during the upward movement thereof. When guide rollers 266 enter the 180° turn 276, container 16 will be supported by elastomeric guide and support roller 276 until guide rollers 266 start down the other side of the 180° turn 276. Also the respective cam rollers 132 will engage the outer side of the respective flanges 146, 148, simultaneously with the cam rollers 132 entering onto the respective 180° turns 276, will cause a change of distance between the guide rollers 266, and the cam rollers will move the arms 94, 96 outward, due to the change in distance between the cam rollers 132 and the guide rollers 266. This movement will pivot locking means 50 (including arms 94, 96) about the axis of shaft 56 to urge rollers 128 against the side of the container 16 to move bumper bar 82 into contact with container 16. Upon rollers 128 engaging container 16, simultaneously with the cam rollers entering onto the respective 180° turns 276, will cause the pivoting of sleeves 88, the pair of arms 84 and the L-shaped arms 120 to pivot about the axis of shafts 92 to move the lock bars 52, 54 in biased relation into open-throat portions 46, 48 respectively of U-shaped members 42, 44 to retain support abutment means therein. The double pivot action of shaft 56 and sleeve 88 is effective to impart sufficient movement to lock bars 52, 54 to move the lock bars into biased relation in U-shaped members 42, 44 to retain support abutment means 40 in open-throat portions 46, 48 respectively, to automatically lock container-engaging means 30.
Container engaging means 30 will continue its downward movement until abutment plates 252 engage elastomeric bumper 254, whereupon the contents from container 16 should have passed through access opening 18. If necessary, however, the flow of fluid to hydraulic motor 200 may be reversed briefly moving abutment plates 252 away from the elastomeric bumper 254 a short distance, whereupon, the flow of fluid to motor 200 may again be reversed causing plates 252 to re-engage bumper 254 for jarring the contents from container 16. Motor 200 may again be reversed so that elevator chains 218 will carry container-engaging means 20 and container 16 back up around turn 276 and back down the upright portions of masts 150, 152 to the position shown in solid lines in FIG. 8, whereupon motor 200 may be de-energized while container 16 is still slightly above surface 25. Hydraulic cylinder 176 may then again be energized to move masts 150, 152 to the position shown in FIG. 8 in broken lines, whereupon, motor 200 may be energized to lower container 16 to surface 26.
A modified form of the container emptying device is indicated generally at 10A in FIGS. 11-18. Device 10A may be used in combination with vehicle 12 in place of the device 10.
The container emptying device 10A is adapted to empty the contents of trash container 16 (FIGS. 15 and 16) into vehicle 12 through an elevated access opening 18 provided therein. Device 10A includes a suitable elevator means 20A for raising and lowering container 16 and including an upper end 22A adjacent access opening 18 and a lower end 24A adjacent supporting surface 26.
Container emptying device 10A also includes a suitable connecting means, indicated generally at 28A in FIG. 17, for connecting the elevator means 20A to the vehicle power supply, shown at 14 in FIG. 9, for moving at least the lower end 24A of elevator means 20A over surface 26 between a first position closely adjacent to vehicle 12, as shown in solid lines in FIG. 15, and a second position spaced laterally outwardly from vehicle 12 and closely adjacent container 16, as shown in broken lines in FIG. 15.
Device 10A includes a container-engaging means 30A which may be quickly and easily connected to elevator means 20A by a plurality of bolts 32, 34, 36 and 38 facilitating interchanging container engaging means 30A with other container-engaging means. Container-engaging means 30A is adapted to mechanically engage the abutment means 40 when the elevator means 20A is moved to the position shown in broken lines in FIG. 15 by power transmitted from vehicle 12 to connecting means 28A. Abutment means 40 includes an arm 41 affixed to each sidewall 16A, 16B of container 16 and a roller 43 rotatably mounted on the free end 41A of each arm 41. Each free end 41A extends to a position in front of container 16 and the axis of rotation of each roller 43 is normal to the longitudinal axis of its associated arm, whereby a stop member is provided normal to each arm at its free end.
As best shown in FIGS. 11-13 and 15-18, container-engaging means 30A includes a pair of hooks or U-shaped members 42A, 44A having open-throat portions 46A, 48A, respectively, through which an associated one of the free ends 41A may pass when container engaging means 30A is elevated while in its FIG. 15 broken-line position. Container-engaging means 30A may then be moved inwardly to its FIG. 15 solid-line position by actuating vehicle power supply 14 (FIG. 9) to move the lower end 24A of elevator means 20A to its FIG. 15 solid-line positon closely adjacent vehicle 12. Elevator means 20A may then be energized to raise container 16 to a position adjacent access opening 18 where suitable means, to be hereinafter described, will tip container 16 to the inverted position shown in FIG. 16. In this position, a suitable locking means 50A automatically locks the container to container engaging means 30A so that free ends 41A will not pass through open-throat portions 46A, 48A of U-shaped members 42A, 44A. Locking means 50A includes a pair of lock bars 52A, 54A, adapted to engage free ends 41A. Lock bars 52A, 54A are swingably connected to container-engaging means 30A by pins 56A each journaled in a bracket 60A affixed to a rectangular, tubular member or mounting bar 76A by weldments 62A.
The U-shaped members 42A, 44A each includes a short leg 45, a long leg 47 and a bight portion 49. Long leg 47 is affixed to mounting bar 76A by a weldment 51 (FIG. 17) in a manner such that legs 45, 47 and bight portion 49 lie in a plane normal to the plane of arm 41, as best seen in FIG. 12. It may be noted that this position of members 42A, 44A is also normal to the position of members 42, 44 in the first form of the invention. Each leg 45 has an upper end 53 which is curved outwardly to facilitate engaging roller 43 behind leg 45, which is re-enforced by a gusset plate 55. As is clear from FIGS. 12, 15 and 16, leg 45 engages roller 43 between the roller and container 16. Each leg 47 has an upwardly, outwardly extending member 57 which diverge from each other to faciltate aligning container engaging means 30A. Each leg 47 is re-enforced by a gusset plate 288 which is provided with a slot 59 extending downwardly from adjacent the rear edge 61 to the front edge 63 to accomodate an associate one of the lock bars 52A, 54A and the path taken thereby when it moves to its locking position against its arm 41.
Lock bars 52A, 54A each includes a shaft 64 affixed to a hollow boss 65 encompassing an associated one of the pins 56A, which are inclined slightly outwardly away from elevator means 20A as shown in FIG. 17, so that lock bars 52A, 54A will swing downwardly toward arms 41, in a manner to be hereinafter described. A first collar 290 is affixed to each shaft 64 near its boss 65 and a second collar 67 is affixed to an intermediate portion of each shaft for controlling the axial position of a first sleeve 292 rotatably mounted on shaft 64. A third collar 69 is affixed to each shaft 64 at its free end and a fourth collar 294 is affixed to shaft 64 a predetermined distance from collar 67 for controlling the axial position of a second sleeve 71 rotatably mounted on the free end (not shown) of each shaft 64. A lug 296 is affixed to each shaft 64 between sleeves 292, 71 and includes a front face 73 and a rear face 298.
Lock bars 52A, 54A are each normally maintained in the retracted position shown in FIGS. 13 and 17 by a compression spring 300 having a first end 302 bearing against face 73 of lug 296 and a second end 304 bearing against leg 47 of an associated one of the U-shaped members 42A, 44A. Each lock bar may be moved to the container-locking position shown in FIG. 18 for bar 52A by a roller-type cam 306 (FIGS. 11-13 and 17-18) rotatably mounted on a bolt 308 secured to a bracket 310 by a nut 312 and lubricated through a pair of grease fittings 314, 316. Bracket 310 is affixed to sleeve 292 and cam 306 lightly engages an associated one of the inturned flanges 146A, 148A on a pair of upstanding masts 150A, 152A, respectively, forming part of elevator means 20A. Thus, when container-engaging means 30A starts over the upper end 22A of elevator means 20A, the weight of container 16 will bring cams 306 into engagement with their associated flanges 146A, 148A with sufficient force to impart a rotating force to each sleeve 292 on its shaft 46. A torsion spring 318 translates this rotating force on each sleeve into a swinging of each shaft 46 on its pin 56A for overcoming the bias of compression springs 300 so that each lock bar 52A, 54A will move down its slots 59 and into engagement with its aim 41. Each torsion spring 318 has first and second ends 320, 322, respectively, engaging an associated one of the brackets 310 and lugs 296, respectively. Each spring 318 and its associated parts permits each cam and its bracket to move forward (as viewed in FIG. 13) without moving an associated one of the lock bars 52A, 54A when the bars are in a position where damage would be caused by their movement.
A grease fitting 324 may be provided on the free end of each shaft 64 for lubricating sleeves 292, 71. Cams 306 and sleeves 71 may be covered with a suitable elastomeric material if desired.
Masts 150A, 152A are maintained in spaced-apart relationship by an upper transverse tubular brace 156A (FIGS. 11 and 16), an intermediate brace 158A (FIG. 17) and a lower brace 160A (FIG. 11). Each lower end 24A is affixed to a rectangular tubular member 162A (FIG. 17) reciprocably mounted in a channel 164A attached to vehicle 12 in the manner described in connection with the first form of the invention. Tubular members 162A is reciprocated by connecting means 28A which comprises an hydraulic cylinder 176A (FIG. 11) connected to the aforementioned vehicle power supply and having a piston rod 178 connected to tubular member 162A by a transverse bar 180A affixed to tubular member 162A by a clevis pin 184A. Reciprocating friction on tubular member 162A is minimized by a lower roller 186A (FIG. 17) carried by a bracket 190A affixed to each channel 164A by a weldment 194A.
A gear reduction unit 198A (FIGS. 11 and 13) is mounted on lower end 24A of mast 152A for receiving the output from an hydraulic motor 200A receiving power from the vehicle power supply in the form of hydraulic fluid passing through conduits 202A and 204A as is described in detail in said patent No. 3,910,434. As best seen in FIGS. 11 and 13, a driven shaft 206A has a first end 208A connected to gear reduction unit 198A and a second end 210A journaled in a bearing cup 212A affixed to the lower end 24A of mast 150A by bolts 214A. The ends 208A, 210A of shaft 206A each carries a sprocket 216A keyed thereto for driving an associated one of a pair of elevator chains 218A trained about an associated upper sprocket 220A keyed to a shaft 222A having a first end 224A journaled in a bearing cup 226A affixed to the upper end 22A of mast 150A by bolts 228A and a second end 230A journaled in a bearing cup 232A affixed to the upper end 22A of mast 152A by bolts 234A. Each chain 218A is also trained around an idler sprocket 236A (FIG. 16) carried by a shaft 238A rotatably mounted on masts 150A, 152A.
Referring now to FIGS. 11-14B and 16-18, elevator means 20A includes a first arcuate plate 326 provided with a channel 240A having flanges 242A, 244A between which the rectangular tubular mounting bar 76A on container-engaging means 30A is mounted. Another arcuate plate 246A is affixed to each end of the first plate 326 and includes an upper end 248A which is connected to elevator chain 218A by a bracket 250A extending from end 248A. An abutment plate 252A is rigidly affixed to the upper end 248A of each arcuate plate 246A for forming a stop to complimentally engage an elastomeric bumper 254A (FIG. 16) which is secured to the transverse tubular brace 156A and which prevents further downward movement of container 16 when it is in an inverted position adjacent access opening 18. Abutment plates 252A may be brought into engagement with bumper 254A repeatedly to jar the contents from container 16, if necessary. Each plate 246A also includes a lower end 256A (FIGS, 14, 14B and 16) to which an end of a shaft 258A is affixed. A similar shaft 262A has its ends affixed to the upper end 248A of each plate 246A (FIGS. 13, 14, 14A, 16 and 17) and each end of the shafts 258A, 262A extends through its associated plate 245A where it rotatably receives a guide roller 266A adapted to ride in channel 268A formed by associated ones of the flanges 146A, 148A and 270A, 272A provided on the masts 140A, 152A respectively, for guiding container engaging means 30A during its travel along the upright portions of masts 150A, 152A to the upper ends 327 (FIG. 16) of flanges 270A, 272A. At this point, the inturned flanges 146A, 148A each takes a 180° turn, as shown at 276A in FIG. 16 for the flange 148A, so that guide rollers 266A will move container-engaging means 30A on a course which inverts container 16, as shown in FIG. 16. When container engaging means 30A moves over the arcs at the upper ends 22A of masts 150A, 152A, brackets 250A on plates 246A will be engaged in notches provided in upper sprockets 220A, as shown at 328 for sprocket 220A on mast 152A (FIG. 16). Thus, sprockets 220A will carry the weight of container 16 and container engaging means 30A
While the particular container emptying devices herein shown and described in detail are fully capable of attaining the objects and providing the advantages hereinbefore stated, it is to be understood that they are merely illustrative of the presently preferred embodiments of the invention, and that no limitations are intended to the details of construction or design herein shown and described, other than as defined in the appended claims, which form a part of this disclosure. Whenever the term "means" is employed in these claims is to be interpreted as defining the corresponding structure illustrated and described in this specification or the equivalent of the same.
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An interchangeable container emptying device on the side of a trash-hauling vehicle to a position adjacent support abutment means on a trash container to move open-throat portions of U-shaped members upwardly into engagement with support abutment means, elevates container, automatically blocks open-throat portions of the U-shaped members to prevent disengagement of support abutment means when container reached an arcuate turn at the top, inverts container to a dumping position, dumps container, moves container to an upright position, lowers container, and then moves container outwardly to its original position.
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FIELD OF THE INVENTION
This invention relates to the field of video image processing, and, more particularly, to video coders compliant with the MPEG-2 standard.
BACKGROUND OF THE INVENTION
The concept of motion estimation is that a set of pixels of a field of a picture may be placed in a position of the subsequent picture obtained by translating the preceding one. These transpositions of objects may expose to the video camera parts that were not visible before as well as changes of their shape, e.g., zooming.
The family of algorithms suitable to identify and associate these portions of images is generally referred to as motion estimation. Such an association permits calculation of the portion of a difference image by removing the redundant temporal information making more effective the subsequent process of compression by DCT, quantization and entropic coding. A typical example of such a method is found in the MPEG-2 standard. A typical block diagram of a video MPEG-2 coder is depicted in FIG. 1 . Such a system is made up of the following functional blocks.
Field ordinator. This block includes one or more field memories outputting the fields in the coding order required by the MPEG-2 standard. For example, if the input sequence is I B B P B B P etc., the output order will be I P B B P B B . . . . The intra-coded picture I is a field and/or a semifield containing temporal redundance. The predicted-picture P is a field and/or a semifield from which the temporal redundance with respect to the preceding I or P (previously co-decoded) picture has been removed. The biredictionally predicted-picture B is a field and/or a semifield whose temporal redundance with respect to the preceding I and subsequent P (or preceding P and successive P) picture has been removed. In both cases, the I and P pictures must be considered as already co/decoded. Each frame buffer in the format 4:2:0 occupies the following memory space: standard PAL 720 × 576 × 8 for the luminance ( Y ) = 3 , 317 , 760 bit 360 × 288 × 8 for the chrominance ( U ) = 829 , 440 bit 360 × 288 × 8 for the chrominance ( V ) = 829 , 440 bit _ total Y + U + V = 4 , 976 , 640 bit standard NTSC 720 × 480 × 8 for the luminance ( Y ) = 2 , 764 , 800 bit 360 × 240 × 8 for the chrominance ( U ) = 691 , 200 bit 360 × 240 × 8 for the chrominance ( V ) = 691 , 000 bit _ total Y + U + V = 4 , 147 , 200 bit
Motion Estimator. This block removes the temporal redundance from the P and B pictures.
DCT. This block implements the cosine-discrete transform according to the MPEG-2 standard. The I picture and the error pictures P and B are divided in 8*8 blocks of pixels Y, U, V on which the DCT transform is performed.
Quantizer Q. An 8*8 block resulting from the DCT transform is then divided by a quantizing matrix to reduce the magnitude of the DCT coefficients. In such a case, the information associated to the highest frequencies less visible to human sight tends to be removed. The result is reordered and sent to the successive block.
Variable Length Coding (VLC). The codification words output from the quantizer tend to contain a large number of null coefficients, followed by nonnull values. The null values preceding the first nonnull value are counted, and the count figure forms the first portion of a codification word. The second portion represents the nonnull coefficient. These paired values tend to assume values more probable than others. The most probable ones are coded with relatively short words composed of 2, 3 or 4 bits. The least probable ones are coded with longer words. Statistically, the number of output bits is less than in the case such methods are not implemented.
Multiplexer and Buffer. Data generated by the variable length coder, the quantizing matrices, the motion vectors and other syntactic elements are assembled for constructing the final syntax examined by the MPEG-2 standard. The resulting bitstream is stored in a memory buffer. The limit size of which is defined by the MPEG-2 standard and cannot be overfilled. The quantizer block Q respects such a limit by making the division of the DCT 8*8 blocks dependent upon the filling limit of such a memory buffer, and on the energy of the 8*8 source block taken upstream of the motion estimation and the DCT transform process.
Inverse Variable Length Coding (I-VLC). The variable length coding functions specified above are executed in an inverse order.
Inverse Quantization (IQ). The words output by the I-VLC block are reordered in the 8*8 block structure, which is multiplied by the same quantizing matrix that was used for its preceding coding.
Inverse DCT (I-DCT). The DCT transform function is inverted and applied to the 8*8 block output by the inverse quantization process. This permits passing from the domain of spatial frequencies to the pixel domain.
Motion Compensation and Storage. At the output of the I-DCT block the following may alternatively be present. A decoded I picture or semipicture that must be stored in a respective memory buffer for removing the temporal redundance with respect to subsequent P and B pictures. A decoded prediction error picture or semipicture P or B that must be summed to the information removed previously during the motion estimation phase. In case of a P picture, such a resulting sum stored in a dedicated memory buffer is used during the motion estimation process for the successive P pictures and B pictures. These field memories are generally distinct from the field memories that are used for re-arranging the blocks.
Display Unit. This unit converts the pictures from the format 4:2:0 to the format 4:2:2, and generates the interlaced format for displaying the images. Arrangement of the functional blocks depicted in FIG. 1 into an architecture implementing the above-described coder is shown in FIG. 2. A distinctive feature is that the field ordinator block, the motion compensation and storage block for storing the already reconstructed P and I pictures, and the multiplexer and buffer block for storing the bitstream produced by the MPEG-2 coding are integrated in memory devices external to the integrated circuit of the core of the coder. The decoder accesses the memory devices through a single interface suitably managed by an integrated controller.
Moreover, the preprocessing block converts the received images from the format 4:2:2 to the format 4:2:0 by filtering and subsampling the chrominance. The post-processing block implements a reverse function during the decoding and displaying phase of the images.
The coding phase also uses the decoding for generating the reference pictures to make operative the motion estimation. For example, the first I picture is coded, then decoded, stored as described in the motion compensation and storage block, and used for calculating the prediction error that will be used to code the subsequent P and B pictures. The play-back phase of the data stream previously generated by the coding process uses only the inverse functional blocks I-VLC, I-Q, I-DCT, etc., never the direct functional blocks. From this point of view, it may be said that the coding and the decoding implemented for the subsequent displaying of the images are nonconcurrent processes within the integrated architecture.
A description of the exhaustive search motion estimator is provided in the following paragraphs. The P field or semifield is first addressed. Two fields of a picture are considered and the same applies to the semifields. Q 1 at the instant t, and the subsequent field Q 2 at the instant t+(kp)*T are considered. The constant kp is dependant on the number of B fields existing between the preceding I and the subsequent P, or between two Ps. T is the field period which is {fraction (1/25)} sec. for the PAL standard and {fraction (1/30)} sec. for the NTSC standard. Q 1 and Q 2 are formed by luminance and chrominance components. The motion estimation is applied only to the most energetic, and therefore richer of information component, such as the luminance, which is representable as a matrix of N lines and M columns. Q 1 and Q 2 are divided in portions called macroblocks, each of R lines and S columns.
The results of the divisions N/R and M/S must be two integer numbers, but not necessarily equal to each other. Mb 2 (i,j) is a macroblock defined as the reference macroblock belonging to the field Q 2 and whose first pixel, in the top left part thereof is at the intersection between the i-th line and the j-th column. The pair (i,j) is characterized by the fact that i and j are integer multiples of R and S, respectively. FIG. 2 b shows how the reference macroblock is positioned on the Q 2 picture while the horizontal dash line arrows indicate the scanning order used for identifying the various macroblocks on Q 2 . MB 2 (i,j) is projected on the Q 1 field to obtain MB 1 (i,j). On Q 1 , a search window is defined having its center at (i,j) and composed of the macroblocks MBk[e,f], where k is the macroblock index. The k-th macroblock is identified by the coordinates (e,f), such that −p<=(e−i)<=+p and −q<=(f−j)<=+q. The indices e and f are integer numbers.
Each of the macroblocks are said to be a predictor of MB 2 (i,j). For example, if p=32 and q=48, the number of predictors is (2p+1)*(2q+1)=6,305. For each predictor, the norm L 1 with respect to the reference macroblock is calculated. Such a norm is equal to the sum of the absolute values of the differences between common pixels belonging to MB 2 (i,j) and to MBk (e,f). Each sum contributes R*S values, the result of which is called distortion. Therefore, (2p+1)*(2q+1) values of distortion are obtained, among which the minimum value is chosen, thus identifying a prevailing position (e•,f•).
The motion estimation process is not yet terminated because in the vicinity of the prevailing position, a grid of pixels is created for interpolating those that form Q 1 . For example, if Q 1 is composed of:
. . .
p 31 p 32 p 33 p 34 p 35 . . .
p 41 p 42 p 43 p 44 p 45 . . .
. . .
After interpolation, the following is obtained: p31 11 p32 … 12 13 14 … p41 15 p42 …
where 11=(p 31 +p 32 )/2
12=(p 31 +p 41 )/2
13=(p 31 +p 32 +p 41 +p 42 )/4
14=(p 32 +p 42 )/2
15=(p 41 +p 42 )/2
The above noted algorithm is applied in the vicinity of the prevailing position by assuming, for example, p=q=1. In such a case, the number of predictors is equal to 8 and are formed by pixels that are interpolated starting from the pixels of Q 1 . Let's identify the predictor with minimum distortion with respect to MB 2 (i,j). The predictor more similar to MB 2 (i,j) is identified by the coordinates of the prevailing predictor through the above noted two steps of the algorithm. The first step tests only whole positions while the second step tests the sub-pixel positions. The vector formed by the difference components between the position of the prevailing predictor and of MB 2 (i,j) is defined as the motion vector, and describes how MB 2 (i,j) derives from a translation of a macroblock similar to it in the preceding field. It should be noted that other measures may be used to establish whether two macroblocks are similar. For example, the sum of the quadratic values of the differences (norm L 2 ) may be used. Moreover, the sub-pixel search window may be wider than that specified in the above example. All this further increases the complexity of the motion estimator.
In the example described above, the number of executed operations per pixel is equal to 6,305+8=6,313, wherein each operation includes a difference between two pixels plus an absolute value identification plus a storage of the calculated result between the pair of preceding pixels of the same macroblock. This means that to identify the optimum predictor, there is a need for 6.313*S*R parallel operators at the pixel frequency of 13.5 MHZ. By assuming R=S=16, as defined by the MPEG-2 standard, the number of operations required: is 6,313*16*16=1,616,128. Each operator may function on a time division basis on pixels that belong to different predictors. Therefore, if each of these predictors operated at a frequency 4*13.5=54 MHz, the number of operators required would be 1,616,128/4=404,032.
The B field or semifield is addressed next. Three picture fields are considered, and the same applies also to semifields QP n−1 at the instant t, QBk B at the instant t+(k B )*T, and QP n at the instant t+(k p )*T with k P and k B dependant on the number of B fields or semifields preventively selected. T is the field period with {fraction (1/25)} sec. for the PAL standard and {fraction (1/30)} sec. for the NTSC standard. QP n−1 , QBk B and QP n are formed by luminance and chrominance components. The motion estimation is applied only to the most energetic, and therefore richer of information component, such as the luminance, which is representable as a matrix of N lines and M columns. QP n−1 , QBk B and Qp n are divided into portions called macroblocks, each of R lines and S columns. The results of the divisions N/R and M/S must be two integer numbers, but not necessarily equal.
MB 2 (i,j) is a macroblock defined as the reference macroblock belonging to the field Q 2 and whose first pixel, in the top left part thereof, is at the intersection between the i-th line and the j-th-column. The pair (i,j) is characterized by the fact that i and j are integer multiples of R and S, respectively. MB 2 (i,j) is projected on the fQP n−1 field to obtain MB 1 (i,j), and on the Qp n to obtain MB 3 (i,j).
On QP n−1 a search window is defined with its center at (i,j) and composed of the macroblocks MB 1 k[e,f], and on Qp n a similar search window whose dimension may also be different, or in any case predefined. This is made up by MB 3 k[e,f], where k is the macroblock index. The k-th macroblock on the QP n− is identified by the coordinates (e,f), such that −p 1 <=(e−i)<=+p 1 and −q 1 <=(f−j)<=+q 1 . This is while the k-th macroblock on the QP n field is identified by the coordinates (e,f), such that −p 3 <=(e−i)<=+p 3 and −q 3 <=(f−j)<=+q 3 . The indexes e and f are integer numbers.
Each of the macroblocks are said to be a predictor of MB 2 (i,j). There are in this case two types of predictors for MB 2 (i,j). One is on the field that temporally precedes the one containing the block to be estimated (I or P). This is referred to as forward. The second type is those obtained on the field that temporally follows the one containing the block to be estimated (I or P). This is referred to as backward. For example, if p 1 =16, q=32, p 2 =8, q 2 =16, the numbers of predictors is (2p 1 +1)*(2q 1 +1)+(2p 2 +1)*(2q 2 +1)=2,706.
For each predictor, the norm L 1 with respect to the reference macroblock is calculated. Such a norm is equal to the sum of the absolute values of the differences between common pixels belonging to MB 1 (i,j), and to MB 1 k (e,f), or MB 3 k (e,f). Each sum contributes R*S values, the result of which is called distortion. Hence, we obtain the forward distortion values (2p 1 +1)*(2q 1 +1), among which the minimum value is chosen. This identifies a prevailing position (e F •,f F •) on the field QP n−1 , (2p 2 +1)*(2q 2 +1) backward distortion values among which the minimum value is again selected identifying a new prevailing position (e B •,f B •) on the QP n field.
The motion estimation process is not yet attained because in the vicinity of the prevailing position, a grid of pixels is created to interpolate those that form QP n−1 and QP n . For example if QP n−1 is
. . .
p 32 p 33 p 34 p 35 . . .
p 42 p 43 p 44 p 45 . . .
. . .
After intertpolation, we have: p31 11 p32 … 12 13 14 … p41 15 p42 …
11=(p 31 +p 32 )/2
12=(p 31 +p 41 )/2
13=(p 31 +p 32 +p 41 +p 42 )/4
14=(p 32 +p 42 )/2
15=(p 41 +p 42 )/2
The above noted algorithm is applied in the vicinity of the prevailing position by assuming, for example, p=q=1. In such a case, the number of predictors is equal to 8, and are formed by pixels that are interpolated starting from the pixels of QP n−1 . The predictor with minimum distortion with respect to MB 2 (i,j) is nonidentified. In the same way we proceed for the QP n field. The predictor more similar to MB 2 (i,j) on QP n−1 and on QP n is identified by the coordinates of the prevailing predictor through the above stated two steps of the algorithm predicted on each field. The first step tests only whole positions while the second the sub-pixel positions. At this point we calculate the mean square errors of the two prevailing predictors (forward and backward). That is, the sums of the square of the differences pixel by pixel between the MB 2 (i,j) with (e F •,f F •) and with (e B •,f B •).
Moreover, the mean square error between MB 2 (i,j) is calculated with a theoretical macroblock obtained by linear interpolation of the two prevailing predictors. Among the three values thus obtained, we select the lowest. MB 2 (i,j) may be estimated using only (e F •,f F •) or just (e B •,f B •) or both, though averaged.
The vector formed by the components is a difference between the position of the prevailing predictor and of MB 2 (i,j). The vectors are defined as the motion vectors and describe how MB 2 (i,j) derives from a translation of a macroblock similar to it in the preceding and/or successive field. In the example described above, the number operations carried out for each pixel is equal to 2,706+8*2=2,722, where each operation includes a difference between two pixels plus an absolute value plus an accumulation of the calculated result between the pair of preceding pixels and comprised in the same macroblock. This means that for identifying the optimum predictor, there is a need for 2,722*R*S parallel operators at the pixel frequency of 13.5 MHz. By assuming R=S=16, as defined by the MPEG-2 standard, the number of operations required is 2,722*16*16=696,832.
Each operator may function on a time division basis on pixels belonging to different predictors. Therefore, if each of them operated at a frequency of 4*13.5=54 MHz, the number of operators required would be 696,832/4=174,208. A high level block diagram of a known motion estimator based on an exhaustive search technique is depicted in FIG. 3, wherein the DEMUX block conveys the data coming from the field memory to the operators. In addition, the MIN block operates on the whole of distortion values for calculating the minimum one.
SUMMARY OF THE INVENTION
An object of the present invention is to reduce the complexity of a motion estimator as used, for example, in an MPEG-2 video coder.
As an illustration of an efficient implementation of the method and architecture of the motion estimator of the present invention, a coder for the MPEG-2 standard will be taken into consideration. Using the motion estimator of the invention, it is possible, for example, to use only 6,5 operations per pixel to find the best predictor of the portion of a picture currently being subjected to motion estimation. This is for an SPML compressed video sequence of either PAL or NTSC type. In contrast, the best result that may be obtained with a motion estimator of the prior art would require execution of 569 operations per pixel. This is in addition to the drawback of requiring a more complex architecture.
The method of the invention implies a slight loss of quality of the reconstructed video images for the same compression ratio. Nevertheless, such a degradation of the images is practically undetectable to human sight because the artifaxes are distributed in regions of the images having a substantial motioncontent. The details of which practically pass unnoticed by the viewer.
The following paragraphs provide a description of a hierarchical recursive motion estimator of the invention. The number of operations per pixels required by the coding process may be significantly reduced once the use of vectors calculated by the motion estimation process for macroblocks, spatially and temporally in the vicinity of the current macroblock, are received.
The method herein disclosed is based on the correlation that exists among motion vectors associated to macroblocks in a common position in temporally adjacent images. Moreover, the motion vectors also associated to macroblocks belonging to the same picture, spatially adjacent to the current one, may represent with small errors the motion of the current macroblock.
The process of motion estimation of the invention meets the following requirements. The integration of the required number of operators necessary for implementing the method of motion estimation, together with auxiliary structures such as memories for allowing the reuse of precalculated vectors, must be significantly less burdensome than that of motion estimators that do not include the method of the invention. The loss of quality of the reconstructed images for a given compression ratio must be practically negligible as compared to motion estimators that do not implement the method of the invention.
In the ensuing description of the method for motion estimation, reference is made to a whole fields equal in number to the distance imposed beforehand and equal to M between two subsequent P or I fields. Included is a total number of fields equal to M+2, which will then be taken into consideration, according to the scheme of FIG. 2 b . The temporal distance between two successive pictures are equal to a period of a field. In particular, let us assume to have already considered the first QP n−1 , motion estimation with respect to the preceding (Q 0 ) motion estimation. Its association is also considered to a motion field per macroblock. The motion field is generated by using the same method of the first step, as described below.
With respect to the first step, the prevailing macroblock predictor MBQB (i,j) belonging to the QB 1 field is searched on Qpn− 1 . That is, the portion of Qp n−1 that more resembles it. The method is applied to all the QB 1 macroblocks preceding it following a scanning order from left to right, and from the top to bottom. According to FIG. 2 c , mv_MB 5 (i, j+S) is the motion vector associated to the macroblock belonging to QP n−1 and identified by the coordinates (i, j+S). mv_MB 6 (i+R, j) is the motion vector associated to the macroblock belonging to QP n−1 and identified by the coordinates (i+R, j). mv_MB 3 (i, j−S) is the motion vector associated to the macroblock belonging to QB 1 and identified by the coordinates (i, j−S). mv_MB 4 (i−R, j) is the motion vector associated to the macroblock belonging to QB 1 and identified by the coordinates (i−R, j).
Let us consider, by way of example, to use the above vectors for identifying, during a first phase, four predictors starting from the projection of MBQB 1 on Qp n−1 . The prevailing predictor is identified by using the norm L 1 or the norm L 2 , etc. Generally, it is possible to use more than two predictors belonging to QP n−1 , and also in a different number from those belonging to QB 1 . The above noted example is very effective during simulation. The norm associated to the prevailing predictor is thereafter compared with precalculated thresholds derived from statistical considerations. Such thresholds identify three subsets, each composed of F pairs of vectors. Each pair, for example, is composed of vectors having components equal in terms of absolute value, but opposite in sign. In the second step, such F pairs are summed to the vector that represents the prevailing predictor. They also identify other 2*F predictors among which there may also be sub-pixels positions.
The prevailing predictor, in the sense of the norm, is the predictor of MBQB 1 (i,j) on Qp n−1 . This is the difference between their common coordinates associated with the motion vector. The norm is calculated starting from the result obtained by subsampling the macroblock according to a quincux scheme, or by interpolating the pixels of QP n−1 for generating predictor macroblocks disposed in sub-pixels positions. The quincux grid is obtained by eliminating a pixel every two from the macroblock according to the following scheme: source macroblock _ A1 A2 A3 A4 A5 A6 … B1 B2 B3 B4 B5 B6 … C1 C2 C3 C4 C5 C6 … subsampled macroblock _ A1 A3 A5 B2 B4 B6 C1 C3 C5
In this way, the operations necessary for calculating the norm are reduced by 50% compared to the case of an exhaustive search technique of a known motion estimator. The method used for interpolating the pixels of QP n−1 , thus generating the sub-pixels thereof, is the one used in the exhaustive search estimator of the prior art. The description above for QB 1 also applies for the successive fields QB 2 . . . QB(M−1). QP n calculates the predictors of each of the respective fields immediately preceding temporally to obtain a motion estimator for each field of the partial sequence considered. The motion estimators must be stored in a suitable structure to enable the second step.
For the second step, the QP n field (type P) is coded, and this requires a spreading of its macroblocks with respect to the QP n−1 field positioned at a temporal distance equal to M field periods. To perform this estimation let us consider the MBP n (i,j) block belonging to QP n , where i and j represent the position of the first top left pixel of the above mentioned macroblock with respect to the top left corner of the field it belongs to. It is assumed that all the preceding QP n macroblocks have already been submitted to such a process according to the scanning order.
By referring to FIG. 2 d , let us consider the two blocks of coordinates (i, j−S) immediately to the left and above (coordinates (i−R, j)) the block to be estimated MBP n (i,j). Both belong to QP n and have already been submitted to motion estimation. They are therefore associated with two motion vectors which will identify, on QP n−1 , two spatial predictors macroblocks. Moreover, let us consider the field immediately preceding in a temporal sense the current one. QB(M−1) has been already submitted to motion estimation with respect to its own previous field, QB(M−2). Each of its macroblock has an associated translation vector. A portion of such vectors may be considered to identify, properly scaled in terms of the temporal distance existing between QP n−1 and QP n , the new MBP n (i,j). This is referred to as temporal predictors. These predictors are positioned on QP n−1 .
In particular, the positions identified by the motion vectors associated to the macroblocks as indicated in the figure with T 1,2 are tested if the temporal distance to estimate is of one field period.
In this case, only the vectors. associated with T 1 having coordinates (i, j+S) and (i+R, j) will be used. Otherwise, those indicated by T 2 should also be considered and whose coordinates are (i+R, j+2*S), (i+2*R, j+S), (i+2*R, j−S), (i+R, j−2*S). The number of these temporal predictors may also be different from the number indicated. However, this choice is made based on the best experimental results.
Among all the indicated predictors, only one is chosen using the criterion of the norm L 1 . This norm is then compared with precalculated thresholds derived from statistical considerations. These thresholds identify 3 sub-sets of pairs of vectors, whose components are equal in absolute value, but with opposite signs. The number of such pairs is taken equal to F, and F is the function of the temporal distance to cover by the estimation (F=F(T_dist)). In the second phase, such pairs are added to the vector that identifies the prevailing predictor and identifies other 2*F predictors among which there may be also subpixel positions. The prevailing norm is the predictor of MBP n (i,j) on QP n−1 , and the difference between their common coordinates identifies the motion vector to it associated.
For example, the number of operations per pixel according to the above described method for the P fields is equal to:
first step
12
second step
24
coordinate position (i-0, j-0)
1
partial total
37
(without quincux
subsampling)
final total
18.5
(with quincux
subsampling)
This is followed by the estimation of the B fields. The procedure considers that the estimate is to be carried out both for the P or I field that temporally precedes the one to be estimated. This is with respect to both the I or P field that follows. As for the estimation of the preceding I or P field, the process is similar to that described above. For the estimation of the successive field P or I, there are some differences in using the temporal predictors. In this case, this term is used to identify the motion vectors associated to the macroblocks positioned in the same positions as described above for the temporal predictors of the P fields. They belong to the immediately successive field in a temporal sense to the one to be estimated. Accordingly, they always move in the estimate direction. For example, to estimate QB(M−2) with respect to Qp n , the vectors associated to the QB(M−1) field are used. The latter are calculated during the implementation of the first algorithmic step.
It is necessary that such vectors are symmetrically overturned with. respect to the origin, because they identify the position of a block belonging to a future field as compared to a previous field. It is also necessary to scale them in a proper manner as a function of the temporal distance between the current field and the field to be estimated. At this point, the best backward predictor is chosen between the two spatial and temporal ones, for example, 2 or 6. A certain number of pairs of small vectors symmetrical with respect to the origin are again chosen. Such a number is also a function of the temporal distance to cover. They are chosen within the predefined whole by comparing the norm found with some thresholds as defined by statistical considerations. Such pairs of vectors, added to the prevailing one found above, will identify new predictors among which there may also be sub_pixel positions.
The prevailing norm is the final backward predictor for the block subject to estimation.
Finally, for each macroblock, two predictors are identified. One on the I or P field that temporally precedes QB(M−2), and one on the successive I or P field. A third predictor is also identified and obtained by linear interpolation of the pixels belonging to the above cited predictors. Out of the three predictors one is chosen based on the norm L 1 . The latter will be the final predictor which is subtracted from the reference block, which is the one submitted to estimation. In this way, the prediction error is obtained.
For example, the number of operations per pixel, according to the above described method, is equal to:
first step
12
second step
33
coordinate position (i-0, j-0)
1
partial total
46 (without quincux subsampling)
final total
23 (with quincux subsampling)
In these conditions, the performance in terms of signal/noise ratio obtained is equivalent to that of the known exhaustive search estimator (see FIG. 3 ), while the complexity of the hardware implementation is significantly reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
The different aspects and advantages of the invention will become even more evident through the following description of an embodiment and by referring to the attached drawings, wherein:
FIG. 1 is a basic diagram of a video coder MPEG-2 MPML including the motion estimator block, according to the prior art;
FIG. 2 shows the architecture of the coder MPEG-2 MPML of FIG. 1;
FIG. 2 a is a reference scheme of the relative position of the macroblock taken into consideration in the description of the known method of motion estimation, according to the prior art;
FIG. 2 b shows the temporal scheme of whole fields equal in number to a certain distance between subsequent P or I fields, according to the prior art;
FIG. 2 c is a reference scheme of the relative position of the macroblock of pixels taken into consideration in an example calculation, according to the present invention;
FIG. 2 d shows the relative position of the spatial and temporal macroblock predictors, according to the present invention;
FIG. 3 is a block diagram of the calculator of the norm between predictors and reference macroblocks, wherein highlighted is the array of parallel operator blocks that conduct the calculation of the norm L 1 , according to the present invention;
FIG. 4 shows the architecture of the hierarchical recursive motion, according to the present invention;
FIG. 5 shows the architecture of the estimator of FIG. 4, relative to the first coding phase;
FIG. 6 is a scheme of the quincux subsampler and interpolator, according to the present invention;
FIG. 7 shows the diagram of the M.A.E. comparator block for addressing the ROM illustrated in FIG. 8, according to the present invention;
FIG. 8 is the diagram of the block representing random addressing of macroblocks, according to the present invention;
FIG. 9 shows the memory architecture for the motion fields, according to the present invention;
FIG. 10 is the architectural scheme of the estimator of FIG. 4, relative to the second coding phase;
FIG. 11 shows the architecture of the estimator of FIG. 4, relative to the implementation of the conclusive coding phase; and
FIG. 12 shows the block representing random addressing of the macroblocks of FIG. 11 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The architecture of the hierarchical recursive motion estimator of the invention is described in the following paragraphs. A block diagram of the hierarchical recursive motion estimator of the invention is depicted in FIG. 4 . In particular, there are three blocks. The first block carries out the first step of the procedure, which is the initialization and convergence of the motion fields. The third block carries out the second step of the algorithm which is the coding of the MPEG-2 fields. The above cited blocks interact through a memory that contains the two motion fields of the fields comprised between the first I or P field, and a successive one of the same type.
The block referred to as R.M.E. Coarse is shown in FIG. 5 . This identifies a memory of (N*M)/(R*S) cells, each of T bits, containing the motion vectors associated to the macroblocks preceding the current one, and disposed on the same field and on the preceding one. Moreover, there is also a memory for storing the predictors belonging to the current field. This memory has dimensions G*H*R*S*8, and permits limitation to the number of accesses to the external memory. This would otherwise need to be accessed every time a predictor is required to feed the motion estimator. This increments the passband. By referring again to the same example described above, let us consider step 1 during which the four motion vectors are mv MB 5 (i, j+S), mv MB 6 (i+R, j), mv_MB 3 (i, j−S), and mv_MB 4 (i−R, j).
Depending on the position (i,j) of the macroblock which is being subjected to motion estimation, and the reference macroblock, the motion vectors are acquired by the block memory of the motion vectors. They are used for addressing the macroblock memory, from which the four macroblocks are fed, one at a time to the quincux subsampling block. These subsampled macroblocks, eventually interpolated for defining the sub-pixel position, thereafter feed the block that calculated the norm L 1 or L 2 , etc. between the predictor and the reference predictor. The norm, by identifying the prevailing predictor of step 1 of the processing, permits the M.A.E. comparator to address a ROM, wherein vectors to be summed to the one associated to the prevailing predictor are stored.
The ROM is contained in the block called random addressing of macroblocks. The output of this block provides the addresses that are used for singling out the predictors in the macroblocks memory. These predictors feed the same blocks described in relation to step 1 . At the end of step 2 , the motion vector V is obtained, and is stored in a register, and made available to the coding process.
The number of parallel operators are reduced. Thus, the implementation of the structure shown in FIG. 3 is significantly less cumbersome and simpler because the required number of operators is halved. The structure of the block in FIG. 4 called MV cache is shown in FIG. 9 . The motion vector provided by the first block is conveyed to one of the six memories intended to contain the motion fields. Each memory has a number of cells equal to (N*M)/(R*S) of T bits each. Such memories provide the motion fields used in the subsequent final estimation. In particular, we have two output lines. One supplies the forward predictors, and one supplies the temporally backward predictors.
The structure of the last block of FIG. 4, called R.M.E. fine, is shown in FIG. 10 . It is possible to see how the motion vectors may be appropriately scaled as a function of the estimate direction (forward or backward) and of the temporal distance. They are then made available to the two forward and backward estimation blocks operating in parallel, and whose structures are represented in FIG. 11 . The structure of the above cited estimation blocks is substantially similar to the one that operates the completion of the first estimation step as described in FIG. 5 . However, this is with the exception of the absence of the memory dedicated to contain the motion field, which is contained in the MV cache.
Furthermore, the structure of the block random addressing is new, and its structure is shown in FIG. 12 . The adders exist in greater number as compared to the similar block existing in the structure of the first estimating step of FIG. 8 . The adders serve to apply some small variations to the prevailing vector formed by testing the spatial and temporal predictors. However, only a certain number of such adders are used. The selection is carried out based on the temporal distance to cover by the estimation. The greater the distance, the greater is the number of adders used. The selection of the type of variation is made by reading a ROM addressed by the MAE obtained from the MAE comparator. This ROM contains all the possible variations to be applied and is obtained through statistical considerations.
FIGS. 6 and 7 respectively show the embodiments of the quincux subsampler and of the MAE comparator of the scheme of FIG. 11 . The respective calculator of the norm L 1 has a functional scheme substantially identical to the one already shown in FIG. 3 . With reference to the scheme of FIG. 6, the quincux subsampler is formed by a plurality of 8-bit registers commanded, by way of a multiplexer, by two signals having the same frequency, but in opposite phase. The interpolator is formed by a plurality of T registers. This permits access to the sampled pixels at different instants, which makes them available for the downstream blocks of multiplication and addition. The coefficients C 0 , C 1 , C 2 , C 3 , C 4 may, for example, take the following values, if applied to the source pixels p 31 , p 32 , p 41 , p 42 :
p31
p32
p41
p42
½
½
0
0
—I1
½
0
½
0
—I2
0
0
½
½
—I5
0
½
0
½
—I4
¼
¼
¼
¼
—I3
0
0
0
0
—quincux
subsampling
implementation
The multiplexer finally selects the output, depending on the type of predictor required.
With reference to the diagram of FIG. 3, the calculation circuit of the norm L 1 , among predictors and the reference macroblock, is composed of a demultiplexer that provides the predictors and the reference macroblock toward the appropriate operator. For example, if the macroblock has a 16*16 size, and by defining the norm L 1 as the sum of the absolute values of the differences between common pixels (predictor/reference), the precision at the output of the subtractor block may be defined in 9 bits. The precision of the absolute value block is defined in bits, and the precision of the accumulation block is defined in 16 bits. The latter is formed by an adder and a 16-bit register. The outputs of the operators feed a block that calculates the minimum value, outputting the minimum value which is also called Mean Absolute Error (MAE).
With reference to the scheme of FIG. 7 which shows the architecture of the MAE comparator for addressing the ROM of the scheme shown in FIG. 9, the MAE must be comprised in one of the three subsets defined by the values 0÷c_ 1 ÷c_ 1 ÷c_ 2 , and c_ 2 ÷c_ 3 . Consequently, an address is produced at the output.
FIG. 8 shows the architecture of the macroblocks random addressing. The address produced by the block of FIG. 7 addresses a ROM which outputs 8 addresses, called motion vectors. These vectors are summed to the motion vector defined during step 1 , as described above. These sums are multiplexed for addressing the macroblocks memory.
FIG. 9 shows the memory architecture of the motion fields. A demultiplexer controlled by a counter addresses the memory position for storing the single motion vector prevailing from the first step of the algorithm. The content of the single cache is written. At an output, two multiplexers, both controlled by appropriate counters, select the vectors needed for the following estimation to be implemented in the second algorithmic step. They are required simultaneously at the most two motion vectors. That is, one for the forward estimation, and one for the backward estimation.
FIG. 10 shows the implementing architecture of the second coding step, which is the estimation direction. This includes forward or backward estimation, and the temporal distance to cover. The sign and module are respectively modified according to appropriate coefficients contained in the ROM. The temporal motion vectors are read from the MV cache. The vectors will then be used by the downstream structure, which performs the final estimate phase. This phase returns, as output, the prevailing vector and the motion vector associated to it. Finally, it should be noted that the two predictors (forward and backward) are added to generate the interpolated predictor.
FIG. 11 shows the architecture of the final phase block of the motion estimation, which is similar to that of the analogous block of FIG. 5 . This is relative to the implementation of the first algorithmic step, with the exception of the macroblocks random addressing block. This has a further input of T_dist which is required for the selection of the total number of variations to be applied to the prevailing vector, following the spatial/temporal predictors test.
FIG. 12 shows the random addressing macroblock, wherein the prevailing motion vectors are added to the variations selected on statistical factors, direction of the estimate, and the temporal distance to cover. The embodiments and applications of the motion estimator of the invention are numerous, among these the following can be mentioned. The motion estimation may be implemented by extracting predictors from a temporally preceding picture, and also from a temporally successive picture. If both estimations are implemented in parallel, replicas of the structure of FIG. 4, operating in parallel, may be used. The use of replicas of the motion vector memory and of the macroblocks memory is also considered. Applications include coders for recording on digital video disks (DVD RAM), camcorders, and digital coders, even if not based on the MPEG-2 standard, but requires a step of motion estimation.
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Relaying on a temporal correlation among successive pictures and using a hierarchical recursive motion estimation algorithm, the hardware complexity of video coders complying with the MPEG-2 standard can be significantly reduced without an appreciable loss of quality of the video images being transferred. Relaying on a temporal correlation among successive pictures is also performed on a spatial correlation of motion vectors of macroblocks of the currently processed picture.
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BACKGROUND OF THE INVENTION
This invention relates to covers for padlocks or the like and is particularly concerned with protective covers for lock boxes, or key safes.
There are many situations in modern living where it is desired to limit or control access to vehicles, utility rooms, security areas, etc. A particular example is found in connection with the sale of real estate where a number of agents may be showing the property to prospective buyers at different times. It is both impractical and undesirable to provide each agent with a key to the premises, and requiring an agent to obtain a key from the head sales office is often inconvenient. This problem has been solved by providing what is known as a "key safe," which is a hollow cast metal box adapted to contain a single key in the interior; see, e.g., U.S. Pat. No. 3,436,937, the disclosure of which is incorporated herein by reference. One source of key safes is Supra Products, Inc. This box has a front panel that is closed with a lock, especially a combination lock. The key safe is also provided with an external shackle that is slipped over a door knob, mounted on a vehicle door handle or other exterior hardware, or snapped into a link fence. Once installed, the key safe can be removed only with a key or combination that opens the shackle. By unlocking the front panel of the key safe, an authorized person gains access to the key contained in its interior.
Useful and convenient though key safes are, they suffer from one serious drawback. Of necessity they are made of heavy and sturdy metal, and they tend to bang against nearby surfaces, e.g., the front door or molding of a house, the door panel of an automobile, etc. In the process, paint is often chipped, arcuate scratch marks are imparted, and dents may be produced, all to the annoyance of the person whose property is being protected.
Some heavy key safes have been provided with a vulcanized rubber moulding that surrounds the base in order to prevent the problems just discussed. Although scratching and denting are reduced, the rubber tends to cause unattractive black marks. Further, the rubber moulding is expensive to produce and, since it is not absolutely essential for the key safe to function, customers resist buying it.
BRIEF DESCRIPTION
The present invention provides a simple, convenient, and inexpensive way of solving the problems discussed above. Key safes (lock boxes) are provided with a light weight, non-marking, removable moisture-resistant, flexible, resiliently stretchable, compressible polymeric jacket that functions as a shock absorber. The hollow key safe is provided with a jacket having the general form of a unitary open shallow box having a back panel, two end panels, and two side panels, the interior dimensions of the jacket corresponding to the exterior dimensions of the back, ends, and sides of the key safe. The jacket is made of material that is capable of retaining its shape prior to being applied to the key safe, preferably flexible, resiliently stretchable, compressible, shock-absorbing closed cell polymeric foam. Fitting snugly around the back, ends, and sides of the key safe, it prevents the key safe from marking, denting, or scratching the surface that it contacts in normal use.
BRIEF DESCRIPTION OF THE DRAWING
Understanding of the invention will be enhanced by referring to the accompanying drawing, in which like numbers refer to like parts in the several views, and in which:
FIG. 1 is a perspective view of the jacket of the invention,
FIG. 2 is a perspective view of a key safe on which is mounted the jacket of FIG. 1; and
FIG. 3 is a side view of the key safe and jacket shown in FIG. 2, some parts being shown in section.
DETAILED DESCRIPTION
In the drawing, protective jacket 10 has the general shape of a shallow open box, comprising back panel 11, left side panel 12, right side panel 13, bottom end panel 14, and top end panel 15. Top panel 15 is provided with holes 16, slit 17 extending from at least one hole 16 to the open edge of panel 15.
Turning to FIGS. 2 and 3, key safe 20 has rear, side, and end panels (not shown) and front panel 21, which is fitted with removable plate 22, combination dial 23 being mounted on plate 22 and providing a means of removing it. When the proper combination is entered, button 24, mounted on plate 22, can be slid downward to provide access to the interior of key safe 20.
Extending from the top of key safe 20 is inverted U-shaped shackle 25, typically covered with rubber or vinyl tubing to minimize marring of the door knob or other hardware to which shackle 25 may be attached. One leg of shackle 25 remains in the interior of key safe 20 at all times, but shackle 25 is usually spring loaded so that unlocking it causes it to pop upward, releasing one leg, and enabling it to rotate around the other leg.
When jacket 10 is mounted on key safe 20, one hole 16 may be threaded over shackle 25 and seated at the location where the permanently located leg emerges from the top of key safe 20. The other hole 16 is then positioned over the hole in the top of key safe 20 through which shackle 25 is inserted. The remainder of jacket 10 is then maneuvered around the back, sides, and bottom end of key safe 20. In this arrangement, shackle 25 ensures that jacket 10 will remain in position on key safe 20. If desired, the mounting of jacket 10 on key safe 20 can be simplified by providing slit 17 from hole 16 to the open edge of top panel 15; slit 17 permits easier mounting of jacket 10, the permanently anchored leg of shackle 25 merely being forced through slit 17 into hole 16. It is feasible, of course, to have a slit 17 extending from each hole, so that jacket 10 can be readily installed on key safe 20 even when the shackle is closed, as when the key safe is already positioned for use.
Jacket 10 is preferably formed of extremely light weight, tough, resilient closed cell polymeric foam, especially crosslinked polyethylene foam weighing 1.5-12 lbs./ft 3 . Suitable white or pastel foams are commercially available from Dow Chemical Company under the trade designation "Ethofoam" XL and from Voltek under the trade designation "Volare" 4A. Sheets of foam initially 1/8" thick and weighing 4 lbs./ft 3 can be thermoformed to the shape of jacket 10, the resultant wall thickness being about 0.080 inch. This particular foam is durable, inexpensive, and shock-absorbing, and has a clinging texture that helps it to adhere to the metal exterior of a key safe. If desired, however, one or more of the interior surfaces of the panels of jacket 10 may be provided with adhesive 30, e.g., a spot of pressure-sensitive adhesive, to help maintain jacket 10 in position.
It is recognized that others have previously applied covers to padlocks; see, e.g., U.S. Pat. Nos. 1,662,612, 4,134,280, 4,317,344, 4,534,190, and 4,555,920, but it is believed that no one has heretofore recognized the unusual utility of a simple jacket of the type described for a key safe.
A number of modifications of the described jacket can be made without departing from the spirit of the invention. For example, the jacket may be formed to extend around the outer portion of the key safe's front panel; indeed, it may be desirable to help maintain the jacket in place by providing it with a strap or flap that extends across the front panel.
Similarly, for aesthetic or strengthening purposes, it may be desirable to incorporate ribs, bosses, ripples, etc., into the shell of the key safe. For similar reasons, it may be desirable to incorporate dye or pigment into the foam, or to coat the exterior with a colored skin to impart an appearance other than the white presented by the foam. It may even be possible to form a jacket by injection molding a foamable polymer or a suitable vinyl polymer.
Numerous other variations will undoubtedly occur to those skilled in the art without departing from the spirit of the invention. Accordingly, the scope of the invention is defined by the appended claims.
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A lock box, or key safe, is provided with a light weight, flexible, shock-absorbing jacket to minimize or eliminate marking, denting, or other damage caused by the box's inadvertently contacting areas adjacent to where it is mounted. The presently preferred jacket material is crosslinked closed cell polyethylene foam.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of the present invention is that of turbine engines and in particular compressors of these turbine engines.
2. Description of the Related Art
Aeronautical turbine engines conventionally consist of a group of assembled modules comprising, in the air circulation direction, one or more compressors, a combustion chamber, one or more turbines which drive the compressor or compressors via drive shafts by extracting power from the gas leaving the combustion chamber, and at the outlet either a nozzle into which the burned gasses are ejected to produce thrust or a free turbine which recovers the energy from the gas to produce mechanical power.
The compressors are conventionally either of the axial flow type where the air flows through them in a substantially axial direction from the inlet to the outlet, or of the centrifugal type where the air enters axially to emerge in a radial direction. In the case of a centrifugal compressor, the air is collected at the impeller outlet by a radial part called a diffuser, then transferred to a second part called a guide vane which returns the compressed air flow to a substantially axial direction before it is introduced into the combustion chamber.
Several configurations have been proposed for these parts on existing aeronautical turbine engines. Engines are known in which the guide vane consists of a part used in combination with the external compressor housing to form a duct to guide the flow. This type of guide vane has the drawback of an imperfect connection between the diffuser and the guide vane and a poor quality of seal at the guide vane.
Monoblock guide vanes are also known which are bolted to flanges linked to the structure of the engine, but these configurations are characterized by additional parts, which entails a penalty in terms of mass. Also these flanges can deform under the effect of vibration or thermal expansion and not ensure perfect continuity of the stream between the diffuser and the guide vane.
Finally monoblock guide vanes are known which are mounted directly onto the diffuser by a hooping type connection which joins the two parts rigidly. Hooping is the assembly of two parts by a shrink fit. The assembly is produced with machining tolerances which prevent its manual assembly or even assembly on a press, and generally means are required for heating or cooling the parts to be assembled. Although this solution brings a benefit in terms of mass and continuity of the stream, it is difficult to disassemble without suitable means and the solution cannot be produced by an operator equipped with conventional tooling only.
BRIEF SUMMARY OF THE INVENTION
The aim of the present invention is to rectify these drawbacks by proposing a device for connection between the diffuser and the guide vane which does not have at least some of the drawbacks of the prior art, and in particular is light, easy to assemble and disassemble, and guarantees good alignment of the air circulation ducts at the compressor outlet.
To this end the object of the invention is an assembly comprising a diffuser and a guide vane at the outlet from a centrifugal compressor of a turbine engine, said diffuser having substantially the form of a double annular disk oriented radially and said guide vane being a double toroidal part positioned in the extension of the double diffuser disk and curved to divert the air flow towards the downstream side of the engine, characterized in that said guide vane is fixed to said diffuser by a connection which is positioned immediately next to the contact surface of the two parts and can be disassembled using standard tooling, with the exclusion of any other means of support.
Such a connection eliminates the risk of misalignment of the two parts while remaining easy to disassemble without the operator needing to use means other than those usually available. Standard tooling must be understood as tooling which can be transported by the operator and is suitable for use at the turbine engine assembly or disassembly station.
Advantageously the connection is a connection by bolt and nut.
Preferably the diffuser comprises on one of its disks, at its contact surface with said guide vane, a flange parallel to said disk and delimiting with said disk a groove able to receive the head of said bolt and comprising at least one notch to allow passage of the stem of said bolt.
In a particular embodiment the guide vane, at its contact surface with said diffuser, comprises a toroidal ferrule, the section of which comprises a first L-shaped part which surrounds the end of the diffuser followed by a second part in the form of a flange which comes to surround the corresponding flange of the diffuser.
Advantageously the guide vane, at its surface intended to cooperate with the diffuser disk opposite the disk carrying said flange, comprises a toroidal ferrule with L-shaped section.
In another particular embodiment the diffuser, on its disk opposite that carrying said flange, comprises an L-shaped flange which extends axially towards the outside of the diffuser and projects radially so as to constitute a transverse stop flange for the guide vane.
Preferably the bolt on its head comprises a truncated part to constitute an anti-rotation element by cooperation with the base of the groove.
The invention also concerns a compressor module for a turbine engine comprising a diffuser-guide vane assembly as described above, and finally a turbine engine comprising such a diffuser-guide vane assembly positioned at the outlet from a centrifugal compressor.
The invention will be better understood and further objectives, details, characteristics and advantages thereof will appear more clearly during the detailed explanatory description below of one embodiment of the invention, given as a purely illustrative and non-limiting example with reference to the attached schematic drawings.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
In these drawings:
FIG. 1 is a section view of a diffuser-guide vane assembly for a centrifugal compressor according to one embodiment of the invention;
FIG. 2 is a section view of the diffuser-guide vane connection according to one embodiment of the invention;
FIG. 3 is a perspective view of an assembly bolt of the diffuser-guide vane connection according to one embodiment of the invention;
FIG. 4 is a perspective view of a notch in the diffuser flange for production of a connection according to one embodiment of the invention;
FIG. 5 is a perspective view of an assembly bolt in place in the groove of a diffuser for a connection according to one embodiment of the invention;
FIG. 6 is a perspective view of a diffuser-guide vane connection according to one embodiment of the invention before installation of the clamping nut;
FIG. 7 is a perspective view of a diffuser-guide vane connection according to one embodiment of the invention after installation of the clamping nut.
DETAILED DESCRIPTION OF THE INVENTION
With reference to FIG. 1 , a diffuser 1 placed at the outlet from the blade wheel of a centrifugal compressor (not shown) is visible, and a guide vane 2 which diverts the compressed air flow by around 120° to guide it in the direction of a combustion chamber, also not shown. The diffuser 1 has approximately the shape of a double annular disk oriented radially, in the center of which is inserted the impeller and which forms a compressed air collector duct. The guide vane 2 is a toroidal part with two faces which is positioned in the extension of the double diffuser disk and curved to divert the air flow to the downstream side of the engine (the downstream side being shown on the right on FIG. 1 ).
With reference to FIG. 2 , we see the detail of the connection between the diffuser 1 and the guide vane 2 . The downstream disk 3 of the diffuser comprises a flange 4 positioned on the outside of the diffuser parallel to the downstream disk 3 , which flange runs over the entire periphery of the disk and is connected to the downstream disk by a bridge so as to create a groove 5 between the flange 4 and the downstream disk 3 .
On FIGS. 1 and 2 , the flange 4 is positioned against the downstream disk i.e. at the disk accessible last on assembly in the present configuration; it is evident that this type of connection can comprise a flange 4 mounted on the upstream disk if the latter is accessible last on assembly of the engine.
On the upstream side, the disk of the diffuser 1 ends in an L-shaped flange 6 which first extends axially towards the outside of the diffuser so as not to disrupt the circulation of the air flow within said diffuser, then projects radially so as to constitute a transverse stop flange for the guide vane. It should be noted that throughout the present document, the term axial is used with reference to the axis of rotation of the rotating elements of the turbine engine and the direction of circulation of the gas flow.
The guide vane 2 is terminated at its junction with the diffuser 1 on the upstream side by a toroidal upstream ferrule 7 of L-shaped section, the axial extension of which cooperates with the L-shaped flange 6 of the diffuser, and on the downstream side by a downstream ferrule 8 , also toroidal. The section of the downstream ferrule 8 has a first L-shaped part 8 a which surrounds the end of the diffuser and continues in a second part 8 b in the form of a flange which caps the corresponding flange 4 of the diffuser 1 .
The guide vane 2 is held on the diffuser 1 by a bolt 9 , the head of which is placed in the groove 5 and which extends perpendicular to the wall of the downstream disk 3 . This bolt passes firstly through the flange 4 of the diffuser at a notch 11 made in said flange, and secondly through the second part 8 b of the downstream ferrule 8 at a drill-hole 12 . The assembly is clamped by a nut 10 which cooperates with the bolt 9 and rests on the second part 8 b.
FIGS. 3 and 4 show the bolt 9 , the head of which is truncated to produce a flat 13 , and the notch 11 made in the wall of the flange 4 of the diffuser.
FIGS. 5 to 7 show the sequence of operations for assembly of a guide vane 2 on a diffuser 1 .
In FIG. 5 , the head of the bolt 9 is positioned in the groove 5 of the diffuser 1 with its flat 13 against the base of the groove to ensure an anti-rotation function on tightening. The stem of the bolt 9 is positioned perpendicular to the flange 4 and passes through the notch 11 made in this flange.
In FIG. 6 , the guide vane 2 has been installed on the diffuser 1 by an axial translation movement. For reasons of clarity of FIGS. 6 and 7 , the downstream ferrule 8 is here shown transparently. The first part 8 a of the ferrule extends backward in the extension of the downstream disk 3 while the second part 8 b covers the flange 4 of the diffuser. The stem of the bolt 9 passes through the second part 8 b via the drill-hole 12 provided to this end.
FIG. 7 shows the diffuser-guide vane assembly already assembled. The nut 10 is bolted to the stem of the bolt 9 and firmly connects the ferrule 8 of the guide vane with the flange 4 of the diffuser.
The improvements made to the function and use of a diffuser-guide vane assembly joined by a connection according to the invention will now be described, by comparison with known configurations of the prior art.
With regard to production of the two parts, the diffuser 1 is preferably produced from a part cut from a solid piece, the groove 5 being machined in an over-thickness left on the downstream disk 3 . After the groove is machined, notches are then made in the flange of the diffuser and are a priori distributed regularly over the circumference of said flange.
The guide vane 2 is produced by a separate sheet which recreates the air stream, to which are welded or brazed the upstream ferrule 7 and downstream ferrule 8 which ensure the connection with the diffuser 1 . This method of manufacture allows production of the guide vane independently of the other parts of the turbine engine, and in particular the possibility of recreation of the weld bead of the ferrules in the case of overflow of said bead, before assembly of the guide vane 2 on the diffuser 1 . Thus it can be ensured that no burrs provoked by welding protrude into the air stream and disrupt the flow, causing undesirable pressure losses or turbulence.
The first improvement made by the invention lies in the perfect alignment of the two parts which remain aligned whatever the operating conditions and in particular whatever the vibration or thermal deformation level of the parts. This characteristic results from the shrink-fitting of the ferrule 8 of the guide vane between firstly the radial extension of the L-shaped flange 6 and secondly the flange 4 of the diffuser. The tightening of the bolt 9 furthermore applies a stress on this ferrule which is held by the L-shaped flange and pressed against the flange 4 by the nut 10 . This application of stress guarantees good resistance of the ferrule 8 and the perfect alignment of the ducts which direct the air stream.
Also the guide vane 2 is mounted directly on the diffuser 1 without flanged connection to the structure of the engine, which prevents deformation due to flexibility of these support flanges as is found in the prior art. Similarly the positioning of the clamping means of the guide vane 2 as close as possible to its connection with the diffuser 1 contributes to this improvement in rigidity of assembly and constancy of alignment of the ducts. Thus the multiplicity of support devices for the guide vane and the associated mass are avoided.
Finally the principle of assembly by bolting guarantees the possibility of easy disassembly and consequently facilitates the replacement of the various elements which could be damaged during the life of the part.
Although the invention has been described in relation to a particular embodiment, it is evident that it comprises all technical equivalents of the means described and their combinations if falling within the context of the invention.
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An assembly including a diffuser and an airflow rectifier at an outlet of a centrifugal compressor of a turbine engine, the diffuser being substantially in a shape of a radially positioned double annular disc, and the rectifier being a double toroidal part, arranged as an extension of the double disc of the diffuser and curved such as to divert the airflow in the downstream direction of the engine. The rectifier is attached to the diffuser by a connection positioned immediately adjacent to the contact surface of the two parts and is removable using a standard tool, excluding any other supporting mechanism.
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BACKGROUND
The present invention relates to electronic communication systems and, more particularly, to sleep modes in asynchronous data communication schemes.
In the last decades, progress in radio and VLSI technology has fostered widespread use of radio communications in consumer applications. Mobile radios and other portable devices are common consumer devices.
Presently, the primary focus of wireless communication technology is on voice communication. This focus will likely expand in the near future to provide inexpensive radio equipment which can be easily integrated into mobile and stationary devices. For instance, radio communication can be used to create wireless data links and thereby reduce the number of cables used to connect electronic devices. Recently, a new radio interface called Bluetooth was introduced to replace the cables used to connect laptop computers, headsets, PDAs, and other electronic devices. Some of the implementation details of Bluetooth are disclosed in this application, while a detailed description of the Bluetooth system can be found in “BLUETOOTH—The universal radio interface for ad hoc, wireless connectivity,” by J. C. Haartsen, Ericsson Review No. 3, 1998.
Radio communication systems for personal use differ significantly from radio systems like the public mobile phone network. Public mobile phone networks use a licensed band which is fully controlled by the network provider and guarantee a substantially interference-free channel.
In contrast, personal radio communication equipment operates in an unlicensed spectral band and must contend with uncontrolled interference. One such band is the globally-available ISM (Industrial, Scientific, and Medical) band at 2.45 GHz. The band provides 83.5 MHz of radio spectrum. Since the ISM band is open to anyone, radio systems operating in this band must cope with several unpredictable sources of interference, such as baby monitors, garage door openers, cordless phones, and microwave ovens. Interference can be avoided using an adaptive scheme that finds an unused part of the spectrum. Alternatively, interference can be suppressed by means of spectrum spreading. In the U.S., radios operating in the 2.45 GHz ISM band are required to apply spectrum-spreading techniques if their transmitted power levels exceed about 0 dBm.
Bluetooth radios use a frequency-hop/time-division-duplex (FH/TDD), spread spectrum access scheme. This radio technology supports low-cost, low-power implementations. Frequency-hop systems divide the frequency band into several hop channels. During a connection, radio transceivers hop from one channel to another in a pseudo-random fashion. The instantaneous (hop) bandwidth is small in frequency-hop radios, but spreading is usually obtained over the entire frequency band. This results in low-cost, narrowband transceivers with strong immunity to interference. Occasionally, interference jams a hop channel, causing faulty reception. When this occurs, error-correction schemes in the link can recover lost data.
The channel is divided into time slots, or intervals of 625 μs, wherein a different hop frequency is used for each slot. This results in a nominal hop rate of 1,600 hops per second. One packet can be transmitted per interval/slot. Subsequent slots are alternately used for transmitting and receiving, which results in a TDD scheme.
The channel makes use of several, equally spaced, 1 MHz hops. With Gaussian-shaped frequency shift keying (FSK) modulation, a symbol rate of 1 Mbit/s can be achieved. In countries where the open band is 80 MHz or broader, 79 hop carriers have been defined. On average, the frequency-hop sequence visits each carrier with equal probability.
Bluetooth radio communications are based on peer communications and ad-hoc networking. In peer communications, all units are equal and a hierarchical network with a fixed infrastructure of base stations and portable terminals is not required. There is no centralized control that provides resource and connection management and other support services. In ad-hoc networks, which are usually based on peer communications, any unit can establish a connection to any other unit within range.
One application for Bluetooth-enabled communication units is the replacement of cables that connect computing or communication devices, such as computers, printers, mobile terminals, and the like. For systems such as Bluetooth to replace cables, data traffic over the radio interface must be very flexible. The enabling protocol must support both symmetric and asymmetric traffic flows and synchronous and asynchronous clocking schemes. In Bluetooth, a flexible communication channel is achieved using a slot structure without an overriding multi-slot frame structure. Bluetooth divides the time domain into slots and Bluetooth-enabled units are free to allocate the slots as necessary for transmission or reception.
As in other mobile radio communication systems, one important issue in peer-to-peer and ad-hoc communications is power conservation in mobile terminals. Since the radio communication typically takes place between portable and mobile equipment, low power consumption is essential to preserve battery life.
In communication networks, like cellular networks, low power modes are supported by the control channels of the network base stations. Such power conservation schemes are described in U.S. Pat. No. 5,794,146 to Sevcik et al., U.S. Pat. No. 5,758,278 to Lansdowne, commonly-assigned U.S. Pat. No. 5,883,885 to Raith, and International Patent Publication No. WO 00/04738. The base stations are typically fixed and not subject to power limitations. Once the terminal is synchronized to the base station, the terminal can enter a very low power mode. While in a low power mode, the terminal periodically scans for a signal from the base station, with each scan lasting for a short period of time. The base station, which is not constrained by power limitations, can broadcast the control channel or beacon continuously. The terminal can reduce its standby power considerably without sacrificing response time. Similar techniques are used on cellular asynchronous data channels, such as General Packet Radio Service (GPRS), which uses a control channel to schedule packet deliveries. A method of power conservation in a battery-operated, portable device is also described in European Patent Publication No. EP 0 944 273 A1.
Ad-hoc radio communications schemes like Bluetooth lack a control channel concept. Reducing power consumption while the device is in idle mode (i.e., not connected) has been described in commonly assigned U.S. Pat. No. 5,940,431 entitled “Access Technique of Channel Hopping Communications System,” to J. C. Haartsen and P. W. Dent, the disclosure of which is incorporated here by reference. However, reducing power consumption while terminals are connected but during pauses between asynchronous data bursts presents technical problems that are not trivial, particularly when both units have to minimize power consumption.
Accordingly, there is a need in the art for a system and method to reduce power consumption in radio units engaged in asynchronous data services. More particularly, there is a need for a system and method that allows the radio units to enter a sleep mode without requiring extra overhead.
SUMMARY
In peer-to-peer radio communications supporting asynchronous services, it is desired to reduce the power consumption in mobile terminals during pauses between data bursts. When there is no traffic on the channel for a predetermined amount of time, the units enter a low duty cycle sleep mode in which they sleep most of the time and wake up periodically, with a period T, to scan the channel for a brief time. A unit can restart communications only at specific points in time which relate to the sleep period T. The scan cycle of one unit preferably corresponds to the restart cycle of the other unit. If, for several sleep cycles, traffic does not return, T can be increased. This process may be carried out in both units, but without the units communicating to each other when the adaptation occurs. Since the two units may not update T exactly at the same time, T cannot be varied in an arbitrary fashion and cannot be based on relative timing. Instead, the scan time is based on absolute timing. Switching from one sleep/scan period to another sleep/scan period is allowed only at predetermined points in time. To prevent collisions when both units want to restart communications, the scan/restart cycles should be staggered. Once communication has restarted, the sleep mode is left. Only a predetermined period of silence on the channel can force the unit(s) into the sleep mode, starting with the smallest T.
In accordance with the present invention, there is a system for conserving power in a portable radio device. The system includes a first unit having at least a transmitter, a second unit having at least a receiver, and a communication channel through which the first unit and the second unit can communicate. Each receiver is activated for a period of time to enable the unit to receive a signal followed by a period of time in which the receiver is deactivated and the unit is unable to receive the signal. A first timing means is associated with the first unit and a second timing means associated with a second unit. Each timing means is used to measure an amount of elapsed time since the signal was last received. The system includes a plurality of time thresholds wherein the period of time for which the receiver is deactivated is increased by a time interval associated with one of the plurality of time thresholds when the amount of elapsed time exceeds the time threshold.
In accordance with another aspect of the present invention, the first unit transmits a signal to the second unit to initiate communications. The signal is transmitted more than one time. A time interval between successive attempts by the transmitter to initiate communications is determined by the amount of elapsed time since the last communication with the second unit. The time interval is associated with a time threshold exceeded by the amount of elapsed time since the last communication.
In accordance with another aspect of the present invention, there is a system for conserving power in a portable radio network. The system includes a plurality of communication devices wherein at least one of the communication devices has a transmitter and at least one of the communication devices has a receiver. There is a communication channel through which the plurality of communication devices can communicate. Each receiver is activated for a period of time to enable the communication device to receive a signal followed by a period of time in which the receiver is deactivated and the communication device is unable to receive a signal. A first timing means is associated with one of the plurality of communication devices and a second timing means is associated with another of the plurality of communication devices. Each timing means is used to measure an amount of elapsed time since the signal was last received. The system includes a plurality of time thresholds wherein the period of time for which the receiver is deactivated is increased by a time interval associated with one of the plurality of time thresholds when the amount of elapsed time exceeds the time threshold.
In accordance with another aspect of the present invention, there is a method for conserving power in a portable radio device. The method comprises the steps of measuring a period of elapsed time beginning with the end of a transmission; comparing the period of elapsed time with a threshold; increasing a time period between successive activations of a radio transmitter if the elapsed time exceeds a threshold period; and increasing a time period between successive activations of a radio receiver if the elapsed time exceeds a threshold period.
In accordance with another aspect of the present invention, there is a communication system including a first communication device having at least a transmitter, a second communication device having at least a receiver, and a communication channel through which the first communication device and the second communication device can communicate. Each receiver is activated for a period of time to enable the communication device to receive a signal followed by a period of time in which the receiver is deactivated and the communication device is unable to receive a signal. A first timing means is associated with the first communication device and a second timing means associated with a second communication device. Each timing means is used to measure an amount of elapsed time since the signal was last received. A plurality of time thresholds wherein the period of time for which the receiver is deactivated is increased by a time interval associated with one of the plurality of time thresholds when the amount of elapsed time exceeds the time threshold.
In accordance with another aspect of the present invention, there is a communication device which includes a receiver capable of interfacing with a communication channel through which the communication device can receive a signal. The receiver is activated for a period of time to enable the communication device to receive a signal followed by a period of time in which the receiver is deactivated and the communication device is unable to receive a signal. A timing means is associated with the communication device wherein the timing means is used to measure an amount of elapsed time since the signal was last received. The timing means compares the amount of elapsed time with a plurality of time thresholds wherein the period of time for which the receiver is deactivated is increased by a time interval associated with one of the plurality of time thresholds when the amount of elapsed time exceeds the time threshold.
In accordance with another aspect of the present invention, there is a method of operating a communication system having a transmitting device, a receiving device, a first timing means associated with the transmitting device, a second timing means associated with the receiving device, and a communication channel through which the transmitting device transmits a signal to the receiving device. The method comprising the steps of activating the receiving device at periodic intervals; increasing the period between successive activations of the receiving device based on an elapsed time since the last communication with the transmitting device; activating the transmitting device at periodic intervals to establish communication with the receiving device; and adjusting the period between successive activations of the transmitting device to coincide with the periods of activation of the receiving device.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic depiction of a timing diagram of a slotted time-division-duplex communication channel with asynchronous traffic flow;
FIG. 2 is a schematic depiction of a timing diagram that illustrates entering a low-power mode according to the present invention;
FIG. 3 is a schematic depiction of a timing diagram that illustrates a staggered start-restart timing scheme for two units according to the present invention;
FIG. 4 is a schematic depiction of a timing diagram that illustrates staggered scan/restart timing schemes for multiple devices according to the current invention;
FIG. 5 is a schematic depiction of a timing diagram that illustrates several scan/restart timing schemes according to the present invention;
FIG. 6 is a schematic depiction of a timing diagram that illustrates switching between several scan/restart timing schemes according to the present invention;
FIG. 7 is a flow diagram illustrating operation of sleep modes; and
FIG. 8 is a schematic depiction of a timing diagram that illustrates non-aligned switching between several scan/restart timing schemes according to the present invention.
DETAILED DESCRIPTION
In the following description, the invention is described in terms of a Bluetooth communication system, but it will be understood that Applicant's invention is not so limited. The invention is broadly applicable to peer-to-peer communication networks and can be embodied in other types of communication systems that have appropriate features.
FIG. 1 depicts a timing diagram of an ideal slotted, packet-based radio interface between two peer units, A and B. Packets 100 start at a slot boundary 102 and can last for a generally unrestricted period of time 104 . As shown in FIG. 1, unit A transmits packet 100 a beginning at slot boundary 102 a and lasting for a duration 104 a. Likewise, packet 100 b begins at slot boundary 102 b and lasts for a duration 104 b. In this example, packet 100 b has a shorter duration than packet 100 a. As can be appreciated, unit B transmits its packets 100 e, 100 f, 100 g, and 100 h beginning at respective slot boundary 102 e, 102 f, 102 g, and 102 h. By design, unit A and unit B do not transmit at the same time.
Bluetooth implements a variation of this type of channel, in which the packet length can vary and the packet can occupy between one and five slots. Preferably, a priority scheme exists among the units so that each unit knows when it is permitted to transmit on the channel. Such a scheme is described in commonly-assigned U.S. Provisional Patent Application No. 60/226,965, entitled “Method and Apparatus for Medium Access on a Radio Channel,” filed Aug. 8, 2000, incorporated herein by reference. In this priority scheme, timeslots are defined at regular intervals and the units are allowed to start transmission unconditionally. Each unit will have a different priority timeslot assigned, thereby preventing collisions due to simultaneous transmissions. Since there is no distinct uplink and downlink in peer communications, time division duplexing (TDD) is preferably used. In a TDD-enabled system, only one unit transmits while all other units listen. When the first unit has finished transmitting (either because it has transmitted its full message or it has transmitted for the maximum allowed time), the first unit releases the communication channel and other units are allowed to transmit. Using TDD obviates the need for expensive duplexers in radio transceiver equipment. TDD also simplifies the integration of a transmitter and a receiver on a single chip, since both sections of the chip never operate simultaneously. Accordingly, using TDD results in cost-effective equipment.
As shown in FIG. 2, if the channel is idle for a period of time, the radio transceivers enter a low-power “sleep” mode and occasionally wake up to listen to the channel to see if communications have resumed. To determine when to enter a sleep mode, each unit begins measuring a time-out period once the unit is idle (i.e., not transmitting or receiving). If the unit resumes transmitting or receiving during the time-out period, then the time-out period restarts once communication ceases. When the time-out period has elapsed, the unit enters a low-power mode.
A unit wishing to resume communications may need to determine the timing of the sleep interval of a unit in low power mode, so that the unit can determine when the low-power unit is scanning and can be activated. In addition, the unit will need to determine when the unit is permitted to transmit. Accordingly, the scan cycle (indicating the periods when a unit is scanning) of one unit should be aligned with the restart cycle (indicating the periods when a unit may transmit to restart communication with another unit) of the other unit. The time position t=t s during which the scan starts in one unit, and the time position t=t r during which the restart operation starts in the other unit, should be aligned, and preferably is based on an absolute time t given by:
t modulo T _sleep=offset (1)
where T_sleep is the interval between two consecutive scan periods.
Ideally, the period of the scan cycle is the same as the period of the restart cycle. The offset value is a time offset which is preferably smaller than T_sleep. Each unit preferably has a different offset value to prevent two units from trying to restart at the same time. The offset is preferably referenced to an absolute time. The absolute time is known by both units, provided they are synchronized. Bluetooth, for example, requires time synchronization between the participating units to implement a frequency hopping scheme.
FIG. 2 illustrates how two units A and B enter low-power mode after a time out period during which no communication has taken place. Because the scan/restart cycle is based on absolute time, the units need not enter the low-power “sleep” mode at the same time. In FIG. 2 it is assumed that only unit A can restart communications. In real peer-to-peer communications, each unit can restart communications and both should be scanning and have potential restart positions.
To prevent both units from simultaneously attempting to resume communications, the scan cycle of one unit should be staggered in time with respect to the scan cycle of another unit, as shown in FIG. 3 . This is accomplished by choosing the offset value in equation 1 properly. For example, the group of offset values may be an orthogonal set, thereby ensuring that no two units will transmit at the same time. If several units on the channel enter sleep mode, each unit should have a different offset value. The staggering offset could be negotiated at connection setup and may depend on a variety of factors, such as the unit's address. If more than two units are involved, the potential restart positions corresponding to the priority slots should be staggered to prevent simultaneous transmissions and data collisions. On a potential restart position of unit i, all units j (where j≠i) scan to check whether unit i wants to resume communication. The restart and scan cycles would relate to each other as illustrated in FIG. 4 for three users. As can be appreciated, if the offset values are sufficiently small, a single scan duration could encompass the potential restart opportunities of all of the units, allowing the unit to sleep for a longer duration of time.
The sleep mode schemes illustrated in FIG. 1 through FIG. 3 have a fixed sleep interval T_sleep. The choice of T_sleep depends on a trade-off between power consumption and latency. Increasing T_sleep results in a lower duty cycle and therefore a lower power consumption. But during T_sleep, the unit cannot be activated and the response time or latency (defined as the interval between the time when one unit wants to activate a unit in sleep mode and the time the sleeping unit responds) increases. A fixed value can be chosen for T_sleep if the latency requirements are fixed. Latency may depend on a variety of factors, such as the application, traffic conditions, and may even vary in time.
For example, an application with a mouse or a pointer requires a very small latency when the user is handling (i.e., moving) the mouse. While at work, short movements are alternated by periods of idleness. The response time during these periods of idleness should be short since the user should not experience any delay while at work (although “at work” does not mean he continuously moves the mouse). However, if the user leaves his work place for a while and then returns, the response time may have grown much longer during the time of absence. The user will accept a long delay the first time he moves the mouse again, as long as the delay is reduced while he is working. In general, a response time which increases when the idle time increases is acceptable, provided the maximum delay is limited and the response time reduces to a short period as soon as work is resumed.
In bursty communication systems, the same kind of procedures can be followed. Dynamically changing T_sleep facilitates balancing power consumption and latency at any moment in time. One crucial aspect is that the scan cycles and restart cycles remain aligned. As T_sleep varies, both units should change their timing, preferably at approximately the same time. In addition, the timing change must be accomplished without the units exchanging information.
In the following description, only two units are considered. However, the procedure can easily be extended to more than two units. The procedures is based on a sleep/scan cycle which includes several substates with fixed relative time relationships. The first substate ST 1 has the highest duty cycle and the shortest sleep interval. The time interval between two consecutive scan periods in this first substate is T 1 . The second substate ST 2 has a time interval between consecutive scan periods which is T 2 =N 2 ×T 1 where N 2 is an integer and T 1 the interval of substate ST 1 . The third substate ST 3 has an inter-scan interval T 3 =N 3 ×T 2 =N 3 ×N 2 ×T 1 . In general, substate STk has an inter-scan interval of T k =N k ×T k−1 .
FIG. 5 illustrates an example of a timing scheme with four substates corresponding to the case where N 4 =N 3 =N 2 =2. In this case, the duty cycle is reduced exponentially when going to a higher substate. The substates are all aligned, which means that all scan periods of substate STk occur at the same time as some of the scan periods of substate STk−1. Since STk−1 is aligned with STk−2 and so on, all higher substates are aligned with all lower substates. The substate timing is based on an absolute timing. The scan period of STk will start at time t
t modulo T k =offset (2)
where T k is the period in scheme STk and offset is a fixed time offset smaller than T k .
FIG. 5 shows the scan/sleep cycle. In correspondence with this scheme, there is a restart cycle which is used by a unit that wants to resume communications with the unit in the sleep mode. This restart scheme has exactly the same substates. However, instead of scan periods, the restart scheme indicates the potential restart points where a unit can start transmitting data and resume communications.
FIG. 6 illustrates a timing scheme in which A and B, have established a communication channel. Assume that unit B is a power sensitive device that needs to save as much power as possible. If the channel has been silent for time Tidle 1 1 , then unit B will enter the ST 1 low-power state. Unit B will sleep for most of the time, but every T 1 seconds will wake up and scan to determine if unit A has something to send. If the channel is still silent, then unit B will enter the ST 2 low power state if the silent period has exceeded Tidle_ 2 seconds (using the same reference as for determining Tidle_ 1 , e.g., the end of the last information packet exchanged on the channel). As shown in FIG. 6, this can continue with Tidle_ 3 , ST 3 , etc.
Note that for a switch from STk−1 to STk, Tidle_k is used which is preferably based on the same absolute reference that defined the end of the active state. If each new time out had been based on the previous time out period, then an accumulation of inaccuracies would arise, deteriorating the alignment between the sleep and restart cycles as discussed below.
If there is information on the channel during a scan period, then unit B leaves the low power mode and enters the active state. If the channel becomes idle again, then the sleep-mode timing scheme begins all over again starting with low-power mode ST 1 .
The activity of unit B is generally described in the flow diagram shown in FIG. 7 . The unit begins in the active state. Once the communication channel remains idle for more than Tidle_ 1 , the unit advances to the first substate and begins periodic scans according to the timing diagram in FIG. 6 . If the channel remains idle for Tidle_ 2 , then the unit advances to the second substate. This progression through the substates continues as the idle time reaches the threshold for each substate. If the channel becomes active during a scan period, the unit returns to the active state. Accordingly, a subsequent idle period of sufficient duration (i.e., Tidle_ 1 ) will cause the unit to again enter the first substate.
Since the low-power scheme is based on absolute timing, unit A can determine when unit B's scan periods occur (provided unit A knows unit B's offset). However, unit A may not know exactly which substate unit B is operating in. This is because unit A cannot know precisely when unit B determined that the channel was idle and determined when to switch substates. That is, unit A does not track when unit B last transmitted or received a message. Due to communication errors, unit A may assume a reference which is different from the reference used by unit B. However, unit A will know the trend (ST 1 to ST 2 to ST 3 etc.) and the exact scan positions of STk. Accordingly, unit A can activate unit B, although it may take a little longer than if unit A had knowledge of the substate in which unit B is operating.
FIG. 8 a and FIG. 8 b illustrate the situation when unit A assumes that unit B is operating in a substate different from the substate unit B is actually operating in. In FIG. 8 a, unit A may wait unnecessarily for unit B to wake up during the time that unit B is in ST 1 but unit A assumes that unit B is operating in ST 2 . In FIG. 8 b, unit A may transmit unnecessarily since unit B is not scanning as frequently when it is in ST 2 , but unit A assumes unit B is operating in ST 1 . Note that this situation only arises for a time period where units A and B use different substates. This time period corresponds to the time offset between the references times used in units A and B, respectively. In another embodiment, unit A may always use STk−1 when it predicts that unit B is in STk. In this way, the shortest response time for the mode unit A resides in is guaranteed, but at the expense of possible extra transmissions.
The previous scheme is a one-directional procedure between one recipient (unit B in the above example) and an activator (unit A). The procedure can equally well be established in the opposite direction (unit B activator and unit A recipient). The sleep periods N×T 1 do not have to be the same in both directions. If they are, preferably, the offset value is chosen differently for each direction so that the schemes are staggered. This means that the restart timing points do not overlap and there is no possibility of a collision when both units want to activate each other. If more than two units are involved, each should chooses a different offset value, similar as was shown in FIG. 5 .
The invention has been described in accordance with a single preferred embodiment. In light of this disclosure, those skilled in the art will likely make alternate embodiments of this invention. These and other alternate embodiments are intended to fall within the scope of the claims which follow.
It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, integers, steps, or components but does not preclude the presence or addition of one or more other features, integers, steps, components, or groups thereof
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A system and method for conserving power in a radio communication network wherein a radio receiver periodically scans for a transmitted signal. If a signal is not received after a predetermined period of time, the period between scans is increased. In a multi-unit system, the scan periods are offset from an absolute time reference to prevent more than one unit from transmitting at the same time.
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RELATED APPLICATIONS
The present application is a continuation application of application Ser. No. 09/578,240 filed on May 29, 2000, now granted as U.S. Pat. No. 6,415,949.
BACKGROUND OF THE INVENTION
This invention relates generally to the field of dispensing devices and systems. More particularly, this invention relates to the field of devices and systems for dispensing paper products such as napkins, towels, bath tissue, etc.
Various types of dispensers for paper products have been developed to provide ready availability of the paper products to users. Such dispensers are often provided in public places such as restaurants or rest rooms where customers remove from the dispenser a desired amount of paper products for personal use. In some high traffic areas, such as fast food restaurants, a large number of customers may use a paper product dispenser such as a napkin dispenser in a short period of time. Therefore, dispensers have been developed that hold a large number of paper products for use by a large number of consumers.
Unfortunately, large dispensers are subject to a number of drawbacks. First, it is difficult to uniformly dispense individual paper products or a controlled amount of paper products from a large dispenser without dispensing more paper products than necessary to a user. Thus, too many paper products are removed by a user, and some of the paper products are wasted. If too many paper products are removed from a dispenser, the benefits provided by a larger dispenser are eliminated as the dispenser is emptied more rapidly.
Second, many dispensers are difficult to load, and that difficulty can increase with the size of the dispenser. If paper products are not properly loaded into the dispenser, the paper products may jam as they are removed thereby preventing further removal of paper products by users. Also, a person refilling a large dispenser is more likely, due to the larger number of paper products involved, to drop some of the paper products onto a floor. Any dropped paper products are then unsanitary and must be discarded, thereby creating more waste and again defeating the benefits of the larger dispenser.
Third, for many currently available dispensers regardless of size, it is impossible to determine without opening the dispenser how many paper products remain within the dispenser. Thus, a person must either periodically check the dispenser to determine how many paper products remain or be vigilant to refill the dispenser as soon as it is empty. Both alternatives involve much personal attention and, especially during peak usage, can lead to empty dispensers if the dispensers are not vigilantly monitored.
Some dispensers may be adapted to dispense paper products from preloaded cartridges. One drawback of these types of dispensers that the cartridge itself is designed to be loaded into and dispensed from a specific configuration of dispenser. This requires the facility to stock the appropriate cartridge for each type of dispenser used. Thus, the facility is required to monitor more than one reserve supply of paper products and to dedicate storage space for each type of preloaded cartridge used.
OBJECTS AND SUMMARY OF THE INVENTION
It is a principle object of the present invention to provide an improved cartridge for dispensing controlled amounts of paper products from a dispenser housing, the improved cartridge being readily adapted to various applications.
Another object of the present invention is to provide a cartridge for dispensing paper products that is simple and inexpensive to manufacture, and that is reliable in use.
Still another object of the present invention is to provide a cartridge for dispensing paper products that provide metered delivery of individual paper products or a controlled amount of paper products.
Yet another object of the present invention is to provide a cartridge for dispensing paper products that reduce the incidence of waste of the paper products, either due to dispensing of too many paper products to a user or due to dropping of the paper products during refilling of a container.
Still another object of the present invention is to provide a cartridge for dispensing paper products that provides an indication of the remaining amount of the paper products ready for dispensing to users.
Yet another object of the present invention is to provide a cartridge for dispensing paper products that reduces the incidence of jamming of paper products and the resultant inability to dispense further paper products.
Yet another object of the present invention is to provide a cartridge for dispensing paper products that can be used in more than one embodiment of dispenser housings or containers.
To achieve these objects and in accordance with the purposes of the invention, as embodied and broadly described herein, a cartridge for holding and dispensing a plurality of paper products includes a cartridge body having cartridge walls and may further include removable sections defined in the cartridge body.
Generally speaking, the cartridge includes a cartridge body having cartridge walls, the cartridge being insertable into an interior area of a dispenser housing. The cartridge may further include removable sections defined in the cartridge body, removal of at least a portion of the removable portions creating openings in the cartridge. In some embodiments, the cartridge wall may include a first slit, slot, orifice or channel that may serve to control access to the paper products held within. Desirably, the first slit is defined by a rear wall and a top wall of the cartridge. However, it is contemplated that other locations may be used.
The first slit is desirably sized so that its horizontal dimension or width is about the same as or slightly greater than the width of the paper products within the cartridge and its vertical dimension or height is large enough to permit the passage of a limited number of paper products. For example, if the paper products are in the form of folded paper napkins, the vertical dimension of the first slit may be sized so that a limited number of folded paper napkins may extracted. This could be achieved by making the vertical dimension some multiple of the thickness of an individual folded paper napkin (e.g., greater than about two and less than about ten thicknesses).
The paper product may be accessed by a thumb slot and/or a finger slot. Desirably, the thumb and finger slots are located on the rear and top walls of the cartridge.
It should be understood that any reference to topographical features used to describe the container are meant to provide relative placement of one feature with respect to another feature and are not meant to designate absolute locations. As such, disposed in a bottom wall of the cartridge or the wall opposite the wall comprising the first slit, may be a second slit, slot, orifice or channel that also may serve to control access to the paper products held within. Desirably, the second slit is wholly contained by a bottom wall of the cartridge. However, it is contemplated that other locations may be used.
The second slit is sized so that only a portion of the face of a paper product is exposed to the user. By exposing only a portion of the paper product, the paper product will be caused to dispense one at a time. For example, if the paper products are in the form of folded paper napkins, the second slit may be sized to enable a user to grasp an exposed face of a single napkin, extract that napkin from the cartridge, leaving the next napkin in the stack exposed.
The cartridge may further define at least one other slot through one of the cartridge walls, the slot being visible from outside a dispenser housing when the cartridge is placed within the interior area of such a dispenser housing. An amount of paper products contained within the cartridge being determinable by visually inspecting the amount of paper products through the slot.
Desirably, other openings are provided in the cartridge for receiving protrusions situated in a dispenser housing. A first group of such protrusions is envisioned to include bumpers adapted to extend into an interior area of the carton to contact paper products and thereby oppose or slow the progression of the paper products in a dispensing direction. A second group of such protrusions is envisioned to include rib members adapted to extend into an interior area of the carton to contact paper products for spacing, slowing, aligning and supporting the paper products as they are moved in the dispensing direction.
It is also contemplated that the cartridge may have at least one additional opening corresponding to a key, rib, pin, or projection of some form located on an interior section of the dispenser housing. The key would permit the cartridge to be loaded properly into the dispenser housing. If a custodian were to attempt to incorrectly load the cartridge into the dispenser or attempt to load the cartridge in the wrong orientation, the key would not engage the opening in the cartridge thus preventing the cartridge from seating within the dispenser.
The above structure enables the cartridge, which has been preloaded with a stack of paper products, to be used with a dispenser adapted to dispense a controlled or limited number of paper products at each dispense or dispensing event. Alternatively the cartridge may be used with a dispenser adapted to dispense paper products one at a time, i.e., single dispensing. The dual use is accommodated desirably by flipping the cartridge end for end so that the front wall is placed in the rear and the rear wall is placed in the front, while switching the orientation of the top and bottom walls as well. As such this configuration would enable dispensing from each end of the stack of paper products.
Additional objects and advantages of the invention will be set forth in part in the following description, or may be obvious from the description, or may be learned through the practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be more fully understood from the following detailed description, taken in conjunction with the accompanying drawings, wherein like reference numerals refer to like parts, and in which:
FIG. 1 is a perspective view of an exemplary cartridge for holding a plurality of paper products and dispensing the same therefrom.
FIG. 2 is a rear elevation view of the FIG. 1 cartridge, which has been rotated 180 degrees end to end about the x-axis.
FIG. 3 is a front elevation view of the FIG. 1 cartridge oriented as shown in FIG. 1 .
FIG. 4 is a top elevation view of the FIG. 1 cartridge depicting an exemplary slit adapted for the removal of a limited number of paper products in one dispensing event.
FIG. 5 is a bottom elevation view of the FIG. 1 cartridge depicting an exemplary slit adapted for the removal of a single paper product at a time.
FIG. 6 a is a perspective view of the FIG. 1 cartridge inserted into one variant of an exemplary dispenser housing, specifically a dispenser housing adapted to dispense a limited number of paper products.
FIG. 6 b is a front elevation view of the FIG. 1 cartridge inserted into another variant of an exemplary dispenser housing, specifically a dispenser housing adapted to dispense individual paper products or one-at-a-time dispensing.
FIG. 6 c is a front elevation view of the FIG. 1 cartridge inserted into yet another variant of dispenser housing, specifically an alternative variant of an exemplary dispenser housing adapted to dispense individual paper products or one-at-a-time dispensing.
FIG. 7 a is a perspective view of one exemplary form of dispenser housing for use with the FIG. 1 cartridge.
FIG. 7 b is a perspective view of another exemplary form of dispenser housing for use with the FIG. 1 cartridge.
FIG. 8 is an enlarged cross-sectional view (not to scale) of the lower portion of a cartridge and dispenser housing assembly.
DETAILED DESCRIPTION
Reference will now be made in more detail to the presently preferred embodiments of the invention, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the invention and not meant as a limitation of the invention. For example, features illustrated or described as part of one embodiment or figure can be used on another embodiment or figure to yield yet another embodiment. It is intended that the present invention include such modifications and variations.
As broadly embodied in FIGS. 1-5, one desirable embodiment of a cartridge 10 is disclosed in which paper products 12 are placed and from which paper products 12 are dispensed. The paper products 12 may be paper napkins, paper towels, toilet tissue, or any other similar material. The cartridge 10 comprises a plurality of cartridge walls 18 including a first wall, top wall, or end 24 and a corresponding second wall, bottom wall, or end 34 . It should be understood that the terms “top” and “bottom” are used only to describe the relative positions of each wall or end. During use in a dispenser housing, either end of the cartridge 10 may be located at a bottom or dispensing end of the dispenser housing.
As illustrated in FIGS. 6 a , 6 b , and 6 c , the cartridge 10 is adapted to be inserted into the interior area of a dispenser housing 100 , the cartridge 10 is further adapted for holding or containing the paper products 12 to be dispensed. Looking to FIGS. 6 a , 6 b , and 6 c it can be seen that the cartridge 10 is sized to fit snugly within an interior area of the dispenser housing 100 .
Looking back to FIGS. 1-5, in general, the cartridge 10 may include a plurality of removable portions 14 , the removal of which creates openings 16 through the cartridge 10 . The removable portions 14 are disposed in outside walls 18 of the cartridge 10 so that, once the removable portions 14 are removed, the openings 16 encompass and receive protrusions from the dispenser housing 100 that may extend into the cartridge 10 . Thus, upon removal of the removable portions 14 and placement of the cartridge 10 into the appropriate dispenser housing 100 , portions of the dispenser housing 100 protrude through the openings 16 to contact the paper products 12 within cartridge 10 .
FIGS. 2 and 4 depict one desirable dispenser opening in the cartridge 10 . A slit, slot, orifice or channel, referred to hereafter as a dispensing throat 20 serves to control access to the paper products 12 contained within the cartridge 10 . The dispensing throat 20 is desirably configured to dispense a limited quantity of paper products at each dispense.
FIGS. 3 and 5 depict another desirable dispenser opening in the cartridge 10 . A different slit, slot, orifice or channel, referred to hereafter as a dispensing throat 32 serves to control access to the paper products 12 contained within the cartridge 10 . Unlike the dispensing throat 20 , the dispensing throat 32 is desirably configured to dispense a single paper product at each dispense.
In either case, the cartridge 10 can be provided such that each dispensing throat 20 and 32 is provided with removable portions 14 . This enables a user to select which dispensing throat the paper products 12 are to be dispensed from and to only access that throat.
Before discussing the cartridge 10 in greater detail, it is important to understand that the cartridge 10 includes both a first dispensing throat 20 and a second dispensing throat 32 . These throats may be located at opposite ends of the cartridge 10 or at least at different dispensing zones within the cartridge 10 as can be at least partially observed in FIG. 1 . This feature enables a single cartridge 10 to be used in different types of dispenser housings, for example, a dispenser housing adapted to dispense a controlled plurality of paper products as well as a dispenser housing adapted to dispense paper products singly, i.e., one-at-a-time.
It is also important to note that FIG. 2 depicts the dispensing throat 20 in dispensing zone 500 at a bottom portion of the cartridge 10 . Similarly, FIG. 3 also depicts the dispensing throat 32 in dispensing zone 600 at a bottom portion of the cartridge 10 . Since it is more desirable to dispense the paper products 12 from the bottom of the dispenser 100 , the cartridge 10 is made to be flipped 180 degrees end for end along the x-axis. Though not required, it is also contemplated that the container could be flipped end for end along the y-axis and/or the z-axis as well. The dispensing throats 20 and 32 could be relocated accordingly to accommodate numerous variations. In either case, the cartridge 10 , once flipped is capable of dispensing from either embodiment of the dispenser housing 100 . Positioning the cartridge 10 as shown in FIG. 2 such that paper products 12 are dispensed from the dispensing throat 20 allows the cartridge 10 to be used with a dispenser 100 similar to that shown in FIG. 6 a or 6 c whereas the FIG. 3 position using the dispensing throat 32 is adapted to be used with a dispenser 100 similar to that shown in FIG. 6 b.
To minimize any potential for confusion, all terms referring to the topographical features of the dispenser 10 , including the terms “front”, “rear” or “back”, “top”, and “bottom” are used only to refer to their respective positions as depicted in FIG. 1 . As such, looking more specifically at FIGS. 2 and 4, it can be seen that the dispensing throat 20 is defined by the cartridge rear wall 22 and top wall 24 of the cartridge. However, it is contemplated that other locations may be used.
The dispensing throat 20 is desirably sized so that it has a horizontal dimension “H” that is about the same as or slightly greater than the width of the paper products 12 within the cartridge 10 and a vertical dimension “V” that is large enough to permit the passage of a limited number of paper products 12 . For example, if the paper products 12 are in the form of folded paper napkins, the vertical dimension “V” of the dispensing throat may be sized so that a limited number of folded paper napkins may be extracted. This could be achieved by making the vertical dimension “V” some multiple of the thickness of an individual folded paper napkin (e.g., desirably greater than about 2 and less than about 10 thicknesses, even more desirably greater than about 2 and less than about 6 thicknesses).
Generally speaking, this first dispensing throat 20 provides for the reliable and trouble free dispensing of a corresponding amount of paper products in a single dispensing event. That is, the first dispensing throat 20 may be configured to allow from about 2 to about 10 paper products to dispense in one pull, i.e., dispensing event.
The paper product may be accessed by a thumb slot 26 and/or a finger slot 28 . Desirably, these slots are located on the top and rear walls of the cartridge and may be centered with respect to the dimensions of the cartridge 10 or the dimensions of the slot 20 . However, whether the thumb slot 26 is located on the rear wall or top wall is a matter of preference. The point to note is that the slot 20 is desirably expanded to include the thumb and/or finger slot(s).
Looking now more particularly to FIGS. 3 and 5, it can be seen that the dispensing throat 32 is defined by the cartridge bottom wall 34 of the cartridge. However, it is contemplated that other locations may be used. The dispensing throat 32 may have many shapes within the scope of the present invention, as long as the throat provides easy access for a user and delivery of paper products 12 for “one-at-a-time” or single product dispensing.
To permit visual inspection of the amount of paper products 12 remaining in the cartridge 10 , the cartridge 10 may define at least one additional slot 30 through one of the cartridge walls 18 . More desirably, at least one such slot 30 is visible from outside a dispenser housing 100 when the cartridge 10 is in the interior area of the dispenser housing 100 . Since the cartridge 10 can be loaded in more than one orientation, it is desirable to provide at least one such slot 30 on the rear wall 22 and at least one such slot 30 on the front wall 36 , an amount of paper products 12 disposed within the cartridge 10 being determinable by visually inspecting the amount of paper products 12 through the slot 30 . As shown in FIGS. 6 a an 6 b , two slots 30 may be provided in the rear wall 22 and in the front wall 36 to provide a greater range of visual inspection. Note that FIGS. 1-3, and 6 c reflect an embodiment having only one such slot 30 located in the rear wall 22 and in the front wall 36 . In fact, any number or arrangement of slots is possible within the scope of the invention.
Further in accordance with the invention, at least some of the openings 16 may have removable portions 14 corresponding to a first group of slots 38 and a second group of slots 40 . The first group of slots 38 , as shown in FIGS. 7 a and 7 b , are adapted to receive at least one protrusion 102 , which is generally an attachment to or a part of the dispenser housing 100 . These protrusions 102 extend from the dispenser housing 100 , through the slot or slots 38 to contact the paper products 12 . By contacting the paper products 12 , the protrusions 102 impede, without actually prohibiting, the movement of the paper products 12 in a dispensing direction “D 1 ”, i.e., toward the dispensing zones 500 or 600 and the dispensing throats 20 or 32 depending upon the dispenser housing used to dispense the paper products 12 .
The second group of slots 40 may be provided in the cartridge walls 18 to adapt the cartridge 10 for use in dispenser housings wherein the dispenser housing 100 contains a rib or ribs 104 designed to protrude through the cartridge walls 18 , also to contact the paper products 12 . These second group of slots 40 are preferably disposed at least partly in the top wall 24 and/or the bottom wall 34 of the cartridge 10 and are adapted to receive the rib members 104 which are mounted or otherwise attached to the dispenser housing 100 . These slots 40 enable the rib members 104 to space, slow, align, and support the paper products 12 as they are moved in a dispensing direction “D”.
Some of these slots 40 can be of a different size than other of slots 40 . In fact, it may be desirable in at least the top wall 24 , to make the slots 40 smaller near a centerline of the dispenser 10 and larger near the outer edges of the dispenser 10 as depicted in FIG. 4 . This configuration is adapted to accommodate rib members 104 of differing heights. The rib members 104 closest to the centerline are shorter or protrude less distance into the cartridge 10 than do the outermost rib members 104 . This has the effect of bowing the center portions of the paper products toward the dispenser throat 20 .
Looking further to FIG. 4, it is also contemplated that the cartridge may have at least one additional opening 42 . This opening 42 corresponds to a key 44 located on the dispenser housing 10 as shown in FIG. 7 b . The key 44 would provide the cartridge 10 with a device minimizing the possibility that the cartridge could be improperly loaded into the dispenser housing 100 . It is desirable that the key 44 be associated with only one of the dispenser housing variations, i.e., either the configuration designed to dispense a limited quantity of paper products at each dispense or the configuration designed to dispense a single paper product at each dispense. In that way, in the event a custodian were to attempt to incorrectly load the cartridge 10 into a dispenser housing 100 , or alternatively attempt to load the cartridge 10 in the wrong orientation, the key 44 would not engage the opening 42 in the cartridge 10 thus preventing the cartridge 10 from seating within the dispenser housing 100 .
Generally speaking, removable portions 14 may either be removed or simply not formed in the cartridge walls 18 or ends 24 and/or 34 during manufacture of the cartridge 10 . Depending upon the circumstances desired, these removable portions 14 can be removed during installation of the cartridge 10 in the appropriate dispenser housing 10 . If the removable portions 14 are to be removed (or simply not formed) as part of the manufacturing process, the cartridge 10 may be shipped to the user wrapped, for example in a polyethylene bag, to prevent contamination and/or to preserve the sterility of the paper products 12 in the cartridge 10 . If the removable portions 14 are to be removed as part of the installation process, the edges of the removable portions 14 should be weakened, scored, etc. for easy removal. In one embodiment, it is desirable that the removable portions 14 are either not formed or are removed prior to shipment to the consumer. This minimizes the work necessary in loading the cartridge 10 into a dispenser.
Additional features which could be desirable, are that at least the top wall 24 and/or the bottom wall 34 of the cartridge 10 be disposed at an angle with respect to the front wall 36 and the rear wall 22 of the cartridge 10 as can be seen in FIGS. 3, 6 b , and 6 c . However, as depicted in FIGS. 1 and 6 a it may be more desirable to have the top wall 24 , or that wall comprising the dispensing throat 20 to be perpendicular to its adjacent walls. In any case, it is desirable to dispense the paper products 12 from the dispensing throat 20 or 32 so that a face of the paper products 12 is parallel to the top wall 24 or bottom wall 34 from which the paper products 12 are being dispensed.
FIGS. 6 a and 7 a depict dispenser housings 100 adapted to work with a perpendicular wall embodiment whereas FIGS. 6 b , 6 c , and 7 b depict dispenser housings 100 adapted to work with an angled wall embodiment. Furthermore, the cartridge 10 is preferably made of heavy paper or cardboard, but may be made of any other suitable material within the scope of the invention.
FIG. 8 depicts an enlarged cross-sectional view (not to scale) of the lower portion of the cartridge 10 inserted into a dispenser 100 as embodied in FIG. 6 a . Though not necessary to practice the invention, the paper products 12 contained within the cartridge 10 are desirably interfolded or tab interfolded napkins to provide metered feeding of one or a number of such individual napkins at any one time. As explained above, and as can be seen in the enlarged and expanded view, the slot 950 has a vertical dimension “V” which is generally some multiple of the thickness of a single layer or ply or fold of the paper product 12 . A dispensing direction “D” is identified as generally perpendicular to the housing and cartridge assembly. If the paper product is, for example, an interfolded paper napkin or tissue, a leading flap or tail 960 can be seen extending out of the slot 950 for a user to grasp. Pulling the leading flap 960 will result in one-at-a-time dispensing of the product.
Whereas gripping the interfolded product between lower grip point 1000 and a first upper grip point 1002 engages two of the interfolded paper products (e.g., napkins, tissues, wipes, etc.) for dispensing. One of which has a visible tail 960 extending from the slot 950 (or dispensing throat 20 ) and the other still located inside the cartridge but accessible through the finger slot 954 . Pulling the product engaged at grip points 1000 and 1002 in the dispensing direction “D” will result in two of the interfolded paper products to be dispensed at a time. This result will be consistent provided the interfolding of the product is consistent and the grip areas 1000 and 1002 remain accessible.
Pulling the product engaged at grip points 1000 and 1004 in the dispensing direction “D” will result in four of the interfolded paper products to be dispensed at a time. This result will be consistent provided the interfolding of the product is consistent and the grip areas 1000 and 1004 remains accessible.
Pulling the product engaged at grip points 1000 and 1006 in the dispensing direction “D” will result in six of the interfolded paper products to be dispensed at a time. This result will be consistent provided the interfolding of the product is consistent and the grip areas 1000 and 1006 remains accessible. This can be described mathematically for interfolded products as N=F f ×2 where N=the number of products dispensed, F f =the number of forward folds (F f ) falling between the identified grip points and which are gripped by the user. The number of forward folds (F f ) available for gripping is generally limited only by the vertical dimension of the slot “V ” and the size of the finger and/or thumb slots. Generally speaking, the “stack” of product dispensed will be in a folded configuration except for the leading and trailing edge or flap. Of course, if the product is dispensed one-at-a-time, it will be in an unfolded configuration.
If a non-interfolded product is used in the cartridge, the dispensing direction “D” remains the same. However, there will be no leading flap as in the interfolded format. Generally speaking, the number of products dispensed will be the same as the number of forward folds gripped unless the product is double or triple folded.
Thus, it can be seen how the cartridge 10 may be used in dispenser housings 100 designed to dispense a controlled amount of paper products 12 . The cartridge 10 may also be used in dispenser housings 100 designed to dispense paper products singly, i.e., one at a time. This could be accomplished by providing access only to a portion of the face of the paper product 12 . For example, if the paper products are in the form of folded paper napkins, and only an exposed face of a single napkin is accessible to a user, extracting that napkin from the cartridge 10 leaves the next napkin in the stack exposed.
RELATED APPLICATIONS
This application is one of a group of commonly assigned patent applications which have been previously filed. This group includes application Ser. No. 09/991,669 filed on Dec. 15, 1997 by Paul Tramontina, application Ser. No. 09/156,230 filed on Sep. 18, 1998 by Paul Tramontina, and application Ser. No. 09/206,956 filed on Dec. 8, 1998 by Paul Tramontina et al. The subject matter of these applications is hereby incorporated herein by reference.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention. It is intended that the present invention include such modifications and variations as come within the scope of the appended claims and their equivalents.
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A reversible cartridge holding a plurality of paper products and for dispensing a controlled amount of the same from a dispenser housing. The cartridge includes a cartridge body having cartridge walls, the cartridge being insertable into an interior area of a dispenser housing. The cartridge may further include removable sections defined in the cartridge body, removal of at least a portion of the removable portions creating openings in the cartridge. The exterior walls define an interior surface and an interior area within the interior surface for receiving a cartridge holding a plurality of paper products. The cartridge further includes two dispensing throats, a first dispensing throat for dispensing multiple paper products, and the second dispensing throat for dispensing single paper products one at a time. Additional openings could be provided for controlling the dispensing and alignment of the paper products within the cartridge.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a semiconductor memory device, such as a MASK ROM or the like.
[0003] 2. Description of the Prior Art
[0004] In a semiconductor memory device, such as a conventional MASK ROM, as one of the techniques for reducing current consumption, in order to appropriately control a readout operation time, a replica circuit including a dummy sense amplifier circuit and a dummy memory cell circuit having the same configuration as that of a normal sense amplifier circuit and memory cell circuit has been utilized. Hereinafter, referring to the drawings, an operation method of the replica circuit in the conventional MASK ROM will be explained.
[0005] FIG. 7 is a diagram of a readout circuit of the conventional MASK ROM. A sense amplifier circuit 1 includes a P-type transistor 2 receiving a precharge signal NPR as a gate input, an N-type transistor 3 connected to the P-type transistor 2 in series, an inverter 4 receiving a source node SA of the N-type transistor 3 , and supplying an output to a gate input of the N-type transistor 3 , an inverter chain 5 receiving the SA and outputting an SOUTO, and a charge circuit 6 receiving the NPR and outputting the SA. The charge circuit 6 is composed of a P-type transistor 6 ( 1 ) and an N-type transistor 6 ( 2 ). A column gate 7 is composed of n (n in number) N-type transistors 8 ( 1 ) through 8 ( n ), which receive column selection signals CL 1 through CLn as gate inputs, respectively, and are connected between the SA and bit lines BL 1 through BLn. A memory cell array 9 is composed of memory cells 10 ( 1 , 1 ) through 10 (n, m) (m in number) arranged in an array form, which receive word lines WL 1 through WLm as gate inputs, and whose sources are connected to a ground potential. As for these memory cells, according to data to be stored, whether or not the drains thereof are connected to the bit lines is determined during the manufacturing process. Here, it is assumed that the drains of all memory cells are connected to the bit lines. A column selection circuit 16 receives a Y address signal ADY, and outputs the column selection signals CL 1 through CLn. A row selection circuit 17 receives an X address signal ADX, and outputs the word lines WL 1 through WLm.
[0006] In a control signal generating circuit 60 , a dummy sense amplifier circuit 11 has a configuration similar to that of the sense amplifier circuit 1 . A dummy column gate 12 is composed of transistors 13 ( 1 ) and 13 ( 2 ) having the same configuration as that of the column gate 7 , wherein the gate inputs of the transistors are connected to a power supply. A dummy memory cell array 14 is composed of dummy memory cells 15 ( 1 , 1 ) through 15 ( 2 , m) having the same configuration as that of the memory cells 10 , for example, one bit line has one bit or more dummy memory cells, wherein the gates of the dummy memory cells are connected to a ground potential and the dummy memory cells are connected to dummy bit lines DBL 1 and DBL 2 . A NAND gate 18 receives an external clock signal CLK and an output of an inverter 20 , and outputs the NPR. The inverter 20 receives the output SOUTD of the dummy sense amplifier 11 . An inverter 19 receives the clock signal CLK, and outputs an NDPR as an input to the dummy sense amplifier circuit 11 .
[0007] FIG. 8A is a plan view of a conventional memory cell array, and FIG. 8B , FIG. 8C , and FIG. 8D are a cross-sectional view taken along line A-A of FIG. 8A , a cross-sectional view taken along line B-B of FIG. 8A , and a cross-sectional view taken along line C-C of FIG. 8A , respectively. This memory cell array includes N-type impurity diffusion regions 31 and 21 , which are a source region and a drain region formed on a P-type substrate 32 , respectively, a channel region disposed between the source region and the drain region, a gate insulating film 33 formed on the channel region, a gate electrode 27 formed on the gate insulating film 33 , an isolation region 22 for isolating between memory cell pairs, contact and via holes 28 , 29 , and 30 provided in interlayer insulation films for interconnecting between the drain region 21 and an upper interconnection, metal electrodes 23 and 24 , a bit line 25 composed of a metal interconnection, a metal interconnection 26 , which is arranged in parallel with the gate electrode 27 and has the same potential as that of the gate electrode 27 , a source potential supply interconnection 39 arranged in parallel with the bit line 25 , a P-type impurity diffusion region 40 for supplying a substrate potential, contact and via holes 34 , 35 , and 36 for interconnecting between the source potential supply interconnection 39 and the P-type impurity diffusion region 40 for supplying the substrate potential, metal electrodes 37 and 38 , and contact and via holes 41 , 42 , and 43 for supplying the source potential.
[0008] Hereinafter, referring to a timing chart of FIG. 9 , the circuit operation of FIG. 7 will be explained. When the CLK signal is changed from L level to H level at to, the precharge signal NPR via the NAND gate 18 becomes L level. As a result, the P-type transistor 2 turns on and the SA is charged. However, since the drain of the memory cell that is selected by the column signals CL 1 through CLn selected by the column selection circuit 16 and by the word lines WL 1 through WLm selected by the row selection circuit 17 is connected to the bit line, the level of the SA is not charged to a determination level of the inverter chain 5 , so that L level is outputted to the SOUTO. At that time, a penetration current continues to flow via the memory cell 10 while the precharge signal NPR stays in L level. Similarly, when the CLK signal is changed from L level to H level at t 0 , the precharge signal NDPR via the inverter 19 is becomes L level, and a DSA is charged. Since all dummy memory cells 15 ( 1 , 1 ) through 15 ( 2 , m) are connected to the dummy bit lines DBL 1 and DBL 2 , and all dummy word lines are fixed to the ground potential, the level of the DSA is charged to the determination level of the inverter chain, and H level is outputted to the SOUTD. Since the SOUTD is inputted to the NAND gate 18 via the inverter 20 , the precharge signal NPR is changed to H level to thereby turn off the P-type transistor 2 , leading the penetration current to be stopped.
[0009] As described above, during the operation period of the sense amplifier, since the replica circuit using the dummy sense amplifier circuit and the dummy memory cell circuit having the same configuration as the normal sense amplifier circuit and the memory cell circuit is configured, the proper timing can be obtained. Moreover, in order to prevent a malfunction due to a completion of the readout operation of the replica circuit prior to a completion of the normal sense amplifier operation owing to a variation in operation caused by the manufacturing variation or the like, a large number of dummy bit lines are provided to thereby secure the timing margin (for example, refer to Japanese Unexamined Patent Publication (Kokai) No. 08-036895).
[0010] In recent years, since an off leakage current of a transistor has been significantly increased with the advance of a microfabrication technology, and in the conventional replica circuit in particular, a plurality of dummy bit lines to which all dummy memory cells are connected are utilized, a current supplied from the charge circuit to the dummy bit line has been too short to charge the dummy bit line to the predetermined potential, so that there has been a problem that the desired timing margin has not been able to be secured.
SUMMARY OF THE INVENTION
[0011] In order to solve the aforementioned problem, there is provided a semiconductor memory device of the present invention, including
[0012] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0013] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0014] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0015] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0016] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array, and
[0017] a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0018] wherein in the second memory cell array, among the plurality of bit lines simultaneously selected by the second column selection circuit, all memory cells are connected to at least one row of the bit line, and at lease one row of the bit line does not connect one bit or more memory cells.
[0019] According to the aforementioned configuration, a current from a charge circuit to a plurality of dummy bit lines is supplied so sufficiently that a dummy bit can be charged to a predetermined potential, thereby making it possible to secure a desired timing margin.
[0020] In the aforementioned configuration, as means for not connecting the memory cell of the second memory array to the bit line, there is provided a configuration in which a drain of the memory cell is not connected to the bit line.
[0021] In the configuration described above, as means for not connecting the memory cell of the second memory array to the bit line, there is provided a configuration in which by using the same mask as that for writing data to a MASK ROM, a drain of the memory cell and the bit line are not connected.
[0022] In the configuration described above, as means for not connecting the memory cell of the second memory array to the bit line, there is provided a configuration in which a source of the memory cell is not connected to a ground potential.
[0023] In the aforementioned configuration, as means for not connecting the memory cell of the second memory cell array to the bit line, there is provided a configuration in which a gate of the memory cell is not arranged.
[0024] According to another means for solving the problem, there is provided a semiconductor memory device of the present invention, including
[0025] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0026] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0027] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0028] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0029] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array, and
[0030] a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0031] wherein in the second memory cell array, the plurality of bit lines simultaneously selected by the second column selection circuit do not connect at least one bit or more memory cells.
[0032] In the aforementioned configuration, as means for not connecting the memory cell of the second memory cell array to the bit line, there is provided a configuration in which a drain of the memory cell is not connected to the bit line.
[0033] In the aforementioned configuration, as means for not connecting the memory cell of the second memory cell array to the bit line, there is provided a configuration in which by using the same mask as that for writing data to a MASK ROM, a drain of the memory cell and the bit line are not connected.
[0034] In the aforementioned configuration, as means for not connecting the memory cell of the second memory cell array to the bit line, there is provided a configuration in which a source of the memory cell is not connected to a ground potential.
[0035] In the aforementioned configuration, as means for not connecting the memory cell of the second memory cell array to the bit line, there is provided a configuration in which a gate of the memory cell is not arranged.
[0036] According to still another means for solving the problem, there is provided a semiconductor memory device of the present invention, including
[0037] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0038] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0039] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0040] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0041] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array, and
[0042] a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0043] wherein a charge current of the second bit line charge circuit is set larger compared with that of the first bit line charge circuit.
[0044] According to still another means for solving the problem, there is provided a semiconductor memory device of the present invention, including
[0045] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0046] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0047] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0048] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0049] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array, and
[0050] a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0051] wherein in the second memory cell array, among the plurality of bit lines simultaneously selected by the second column selection circuit, at least one row of the bit line connects all memory cells, and a threshold voltage of the memory cell connected to at least one row of the bit line is higher than that of the other transistors.
[0052] According to still another means for solving the problem, there is provided a semiconductor memory device of the present invention, including
[0053] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0054] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0055] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0056] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0057] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array, and
[0058] a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0059] wherein in the second memory cell array, among the plurality of bit lines simultaneously selected by the second column selection circuit, at least one row of the bit line connects all memory cells, and a negative voltage is supplied to a gate of the memory cell connected to at least one row of the bit line.
[0060] According to still another means for solving the problem, there is provided a semiconductor memory device of the present invention, including
[0061] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0062] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0063] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0064] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0065] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array,
[0066] and a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0067] wherein in the second memory cell array, threshold voltages of at least one bit or more memory cells connected to the plurality of bit lines simultaneously selected by the second column selection circuit are higher than those of the other transistors.
[0068] According to still another means for solving the problem, there is provided a semiconductor memory device of the present invention, including
[0069] a first memory cell array arranging a plurality of memory cells equivalent to memory capacity in a matrix form in a bit line direction and a word line direction,
[0070] a first column selection circuit and row selection circuit for respectively selecting a bit line and a word line of the first memory cell array corresponding to an address input,
[0071] a plurality of first bit line charge circuits which are connected to the first column selection circuit and respectively charge a plurality of the bit lines selected by the first column selection circuit,
[0072] a second memory cell array arranging a plurality of memory cells in a matrix form in a bit line direction and a word line direction,
[0073] a second column selection circuit for simultaneously selecting a plurality of bit lines of the second memory cell array, and
[0074] a single second bit line charge circuit which is connected to the second column selection circuit and charges the plurality of bit lines of the second memory cell array,
[0075] wherein in the second memory cell array, a negative potential is supplied to gates of at least one bit or more memory cells connected to a plurality of bit lines simultaneously selected by the second column selection circuit.
BRIEF DESCRIPTION OF THE DRAWINGS
[0076] FIG. 1A is a plan view of a dummy memory cell array in accordance with a first embodiment of the present invention;
[0077] FIG. 1B is a cross-sectional view taken along line A-A of FIG. 1A ;
[0078] FIG. 1C is a cross-sectional view taken along line B-B of FIG. 1A ;
[0079] FIG. 1D is a cross-sectional view taken along line C-C of FIG. 1A ;
[0080] FIG. 1E is a cross-sectional view taken along line D-D of FIG. 1A ;
[0081] FIG. 2A is a plan view of a dummy memory cell array in accordance with a second embodiment of the present invention;
[0082] FIG. 2B is a cross-sectional view taken along line A-A of FIG. 2A ;
[0083] FIG. 2C is a cross-sectional view taken along line B-B of FIG. 2A ;
[0084] FIG. 2D is a cross-sectional view taken along line C-C of FIG. 2A ;
[0085] FIG. 2E is a cross-sectional view taken along line D-D of FIG. 2A ;
[0086] FIG. 3A is a plan view of a dummy memory cell array in accordance with a third embodiment of the present invention;
[0087] FIG. 3B is a cross-sectional view taken along line A-A of FIG. 3A ;
[0088] FIG. 3C is a cross-sectional view taken along line B-B of FIG. 3A ;
[0089] FIG. 3D is a cross-sectional view taken along line C-C of FIG. 3A ;
[0090] FIG. 3E is a cross-sectional view taken along line D-D of FIG. 3A ;
[0091] FIG. 4 is a replica circuit diagram in accordance with a fourth embodiment of the present invention;
[0092] FIG. 5 is a replica circuit diagram in accordance with a fifth embodiment of the present invention;
[0093] FIG. 6 is a replica circuit diagram in accordance with a sixth embodiment of the present invention;
[0094] FIG. 7 is a replica circuit diagram of a conventional semiconductor memory device;
[0095] FIG. 8A is a plan view of a memory cell array of the conventional semiconductor memory device;
[0096] FIG. 8B is a cross-sectional view taken along line A-A of FIG. 8A ;
[0097] FIG. 8C is a cross-sectional view taken along line B-B of FIG. 8A ;
[0098] FIG. 8D is a cross-sectional view taken along line C-C of FIG. 8A ; and
[0099] FIG. 9 is a timing chart of a replica circuit of a conventional semiconductor memory device.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0100] Hereinafter, referring to the drawings, embodiments according to the present invention will be explained.
[0101] A semiconductor memory device according to a first embodiment of the present invention will be explained referring to the FIG. 1 . FIG. 1A is a plan view of a dummy memory cell array in accordance with the first embodiment, and FIG. 1B , FIG. 1C , FIG. 1D , and FIG. 1E are a cross-sectional view taken along line A-A of FIG. 1A , a cross-sectional view taken along line B-B of FIG. 1A , a cross-sectional view taken along line C-C of FIG. 1A , and a cross-sectional view taken along line D-D of FIG. 1A , respectively. In the drawings, since the component having the same reference numeral as that of FIG. 8A , FIG. 8B , FIG. 8C , and FIG. 8D serves a similar function, only different components will be explained.
[0102] In FIG. 1 , the cross-sectional view taken along line D-D of FIG. 1A , namely FIG. 1E , is different from that of FIG. 8 . A portion for interconnecting between a dummy bit line and a drain region of the dummy memory cell is composed of via holes 49 and 50 corresponding to the via holes 29 and 30 , metal electrodes 44 and 45 corresponding to the metal electrodes 23 and 24 , and a second bit line 46 arranged in parallel with the first dummy bit line 25 , while a contact hole corresponding to the contact hole 28 between the drain region 21 of the N-type impurity region and the metal electrode 23 is not provided between a drain region 47 and a metal electrode 44 .
[0103] As a result of this, among two dummy bit lines charged by the charge circuit, all dummy memory cells are connected to one dummy bit line, while the dummy memory cell is not connected to the other, so that the off leakage current of the dummy memory cell is not excessively increased with respect to the current supply of the charge circuit, thereby making it possible to make the charge potential of the dummy bit line equivalent to that of the normal bit line in the memory array.
[0104] Incidentally, in FIG. 1 , it is configured in such a way that the contact holes are eliminated by dummy bit line, but even when it is configured in such a way that by the number of a range that the off leakage current generated in two dummy bit lines by the dummy memory cell becomes equivalent to the current of the normal bit line in the memory array by the current supply of the charge circuit, the dummy memory cells are arbitrarily connected to the dummy bit line, and the contact holes of the remaining dummy memory cells are eliminated therefrom, the same effect will be obtained.
[0105] Alternatively, even when it is configured in such a way that the via hole 49 or the via hole 50 is eliminated, the same effect may be obtained.
[0106] A semiconductor memory device according to a second embodiment of the present invention will be explained referring to FIG. 2 . FIG. 2A is a plan view of a dummy memory cell array in accordance with the second embodiment, and FIG. 2B , FIG. 2C , FIG. 2D , and FIG. 2E are a cross-sectional view taken along line A-A of FIG. 2A , a cross-sectional view taken along line B-B of FIG. 2A , a cross-sectional view taken along line C-C of FIG. 2A , and a cross-sectional view taken along line D-D of FIG. 2A , respectively. In the drawings, since the component having the same reference numeral as that of FIG. 8A , FIG. 8B , FIG. 8C , FIG. 8D and FIG. 1 serves a similar function, only different components will be explained.
[0107] In the second embodiment, unlike the first embodiment, a contact hole 48 is provided on the drain region 47 , a source region 51 of the dummy bit line 46 is kept in a floating state without being connected with others, and a source region 58 of the dummy bit line 25 is isolated from a source region 59 of the source potential supply interconnection 39 used as the ground potential.
[0108] As a result of this, among two dummy bit lines charged by the charge circuit, all dummy memory cells are connected to one dummy bit line, and the other does not generate the off leakage current since the source region of the dummy memory cell is kept in a floating state, so that the off leakage current of the dummy memory cell is not excessively increased with respect to the current supply of the charge circuit, thereby making it possible to make the charge potential of the dummy bit line equivalent to that of the normal bit line in the memory array.
[0109] Incidentally, in FIG. 2 , it is configured in such a way that the source region is kept in a floating state by dummy bit line, but even when it is configured in such a way that by the number of a range that the off leakage current generated in two dummy bit lines by the dummy memory cell becomes equivalent to the current of the normal bit line in the memory array by the current supply of the charge circuit, the dummy memory cells are arbitrarily connected to the dummy bit line, and the source regions of the remaining dummy memory cells are kept in a floating state, the same effect will be obtained.
[0110] A semiconductor memory device according to a third embodiment of the present invention will be explained referring to FIG. 3 . FIG. 3A is a plan view of a dummy memory cell array in accordance with the third embodiment, and FIG. 3B , FIG. 3C , FIG. 3D , and FIG. 3E are a cross-sectional view taken along line A-A of FIG. 3A , a cross-sectional view taken along line B-B of FIG. 3A , a cross-sectional view taken along line C-C of FIG. 3A , and a cross-sectional view taken along line D-D of FIG. 3A , respectively. In the drawings, since the component having the same reference numeral as that of FIG. 8A , FIG. 8B , FIG. 8C , FIG. 8D and FIG. 2 serves a similar function, only different component will be explained.
[0111] In this embodiment, without forming the gate electrode 27 (refer to FIG. 8 ) of the dummy memory cell, the source and drain regions 21 and 31 (refer to FIG. 8 ) are connected in common in a bit line direction to form a diffusion region 52 .
[0112] As a result of this, among two dummy bit lines charged by the charge circuit, all dummy memory cells are connected to one dummy bit line, and the off leakage current is not generated from the other dummy bit line since the dummy memory cell is not formed as the transistor in the other, so that the off leakage current of the dummy memory cell is not excessively increased with respect to the current supply of the charge circuit, thereby making it possible to make the charge potential of the dummy bit line equivalent to that of the normal bit line in the memory array.
[0113] Incidentally, in FIG. 3 , it is configured in such a way that the dummy memory cell is not formed by dummy bit line, but even when it is configured in such a way that by the number of a range that the off leakage current generated in two dummy bit lines by the dummy memory cell becomes equivalent to the current of the normal bit line in the memory array by the current supply of the charge circuit, the dummy memory cells are arbitrarily connected to the dummy bit line, and the transistors are not formed in the remaining dummy memory cells, the same effect will be obtained.
[0114] A semiconductor memory device according to a fourth embodiment of the present invention will be explained referring to FIG. 4 . FIG. 4 is a readout circuit diagram of a MASK ROM in accordance with the fourth embodiment. In the drawings, since the component having the same reference numeral as that of FIG. 7 serves a similar function, only different components will be explained.
[0115] A dummy memory cell array 61 is composed of dummy memory cells 15 ( 1 , 1 ) through 15 ( 1 , m) and dummy memory cells 54 ( 2 , 1 ) through 54 ( 2 , m), and threshold voltages of the dummy memory cells 54 ( 2 , 1 ) through 54 ( 2 , m) are set higher than those of the other memory cells and dummy memory cells.
[0116] As a result of this, among two dummy bit lines charged by the charge circuit, one dummy bit line does not generate a large amount of off leakage currents since the threshold voltage of the dummy memory cell is set higher, so that the off leakage current of the dummy memory cell is not excessively increased with respect to the current supply of the charge circuit, thereby making it possible to make the charge potential of the dummy bit line equivalent to that of the normal bit line in the memory array.
[0117] Incidentally, in FIG. 4 , it is configured in such a way that the threshold voltage of the dummy memory cell is set higher by dummy bit line, but even when it is configured in such a way that by the number of a range that the off leakage current generated in two dummy bit lines by the dummy memory cell becomes equivalent to the current of the normal bit line in the memory array by the current supply of the charge circuit, the threshold voltage of the dummy memory cell is arbitrarily set higher, the same effect will be obtained.
[0118] A semiconductor memory device according to a fifth embodiment of the present invention will be explained referring to FIG. 5 . FIG. 5 is a readout circuit diagram of a MASK ROM in accordance with the fifth embodiment. In the drawings, since the component having the same reference numeral as that of FIG. 7 serves a similar function, only different components will be explained.
[0119] A dummy memory cell array 64 is composed of dummy memory cells 15 ( 1 , 1 ) through 15 ( 1 , m) and dummy memory cells 63 ( 2 , 1 ) through 63 ( 2 , m). A negative voltage generating circuit 62 connects a negative voltage signal DWL which serves as a negative potential to a source potential of the dummy memory cells 63 ( 2 , 1 ) through 63 ( 2 , m) with the gates of the dummy memory cells 63 ( 2 , 1 ) through 63 ( 2 , m) composed of a part of the transistors of the dummy memory cell array 64 in a control signal generating circuit 57 .
[0120] As a result of this, among two dummy bit lines charged by the charge circuit, one dummy bit line does not generate a large amount of off leakage currents since a potential which is a negative potential to the source of the dummy memory cell is supplied to the gate of the dummy memory cell, so that the off leakage current of the dummy memory cell is not excessively increased with respect to the current supply of the charge circuit, thereby making it possible to make the charge potential of the dummy bit line equivalent to that of the normal bit line in the memory array.
[0121] Incidentally, in FIG. 5 , it is configured in such a way that the potential which is the negative potential to the source of the dummy memory cell is inputted to the gate of the dummy memory cell by dummy bit line, but even when it is configured in such a way that by the number of a range that the off leakage current generated in two dummy bit lines by the dummy memory cell becomes equivalent to the current of the normal bit line in the memory array by the current supply of the charge circuit, the gate of the dummy memory cell is arbitrarily set to a negative potential, the same effect will be obtained.
[0122] A semiconductor memory device according to a sixth embodiment of the present invention will be explained referring to FIG. 6 . FIG. 6 is a readout circuit diagram of a MASK ROM in accordance with the sixth embodiment. In the drawings, since the component having the same reference numeral as that of FIG. 7 serves a similar function, only different components will be explained.
[0123] In a dummy sense amplifier 55 , a current capacity of a P-type transistor 56 is set higher than that of the P-type transistor 6 ( 1 ) of the sense amplifier 1 by two times.
[0124] As a result of this, without causing a potential effect from the off leakage current generated by the current supplied from the charge circuit between the two dummy bit lines, the current of the dummy bit line can be equivalent to that of the normal bit line in the memory array.
[0125] Incidentally, in the present invention, as means for not connecting the memory cells to the bit line, it is possible to provide a configuration in which by using the same mask as that for writing data to the MASK ROM, a drain of the memory cell and the bit line are not connected.
[0126] The semiconductor memory device according to the present invention has advantages allowing the off leakage current of the dummy bit line to be suppressed, the proper timing margin in the readout operation to be secured, or the like, and is useful for the MASK ROM or the like.
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According to a conventional semiconductor memory device, in a replica circuit composed of a plurality of dummy bit lines, an off leakage current of a transistor has been significantly increased with the advance of a semiconductor microfabrication technology, so that the dummy bit line has not been able to be charged to a desired potential due to the off leakage current when charging. As a result of this, since a charging period or a discharging period of the dummy bit line is also different from a desired period, the optimal operation timing may not be set.
In a dummy memory cell array, in order to connect a drain region 21 and a first dummy bit line 25 , the first dummy bit line 25 is connected via contact and via holes 28 through 30 and metal electrodes 23 and 24 , while a second dummy bit line 46 does not contact to a drain region 47.
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CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent application Ser. No. 13/420,017 filed Mar. 14, 2012, which is a continuation of U.S. patent application Ser. No. 12/407,199, filed Mar. 19, 2009, which claims the benefit of German Application DE 10 2008 015 869.0, filed Mar. 26, 2008, the entire contents of all of which are incorporated herein by reference as if fully set forth.
BACKGROUND
[0002] The invention relates to a jet regulator which can be inserted with its jet regulator housing into the water outlet of a sanitary outlet fitting from the direction of the outlet end side and which, in the use position, can be releasably fastened or fixed in the water outlet.
[0003] It is already known for a jet regulator which is to form a homogenous, non-sputtering water jet to be mounted on the water outlet of a sanitary outlet fitting. Such jet regulators are usually inserted into an outlet mouthpiece which can be detachably screwed to the water outlet of the sanitary outlet fitting.
[0004] Since the configuration of the outlet mouthpiece in designing the surface of the sanitary outlet fitting may involve a considerable amount of expenditure, and since the gap remaining between the outlet mouthpiece and the outlet fitting is often perceived as a problem, jet regulators of the type mentioned in the introduction have already been created which can be inserted into the water outlet of a sanitary outlet fitting from the direction of the outlet end side without an additional outlet mouthpiece being necessary for fastening the jet regulator.
[0005] The aesthetic demand on the external appearance of sanitary outlet fittings is ever-increasing. For example, outlet fittings have also been created whose water outlet is formed by a tube which is rectangular in cross section. To be able to fix the jet regulator, whose shape is matched in terms of its outline to the rectangular tube cross section, in the water outlet of the previously known outlet fitting, a set screw which serves as a retaining element is provided, which set screw extends through a passage opening provided on the periphery of the fitting housing and engages, with its end region protruding into the housing interior of the fitting housing, on the jet regulator so as to fix the latter. In order that the passage opening and the set screw which is screwed therein do not adversely affect the external appearance of the known outlet fitting, the passage opening is arranged on the flat side, which faces away from the visible side, of the fitting housing.
[0006] However, outlet fittings have also already been created in which the visible side of the band-shaped fitting housing forms one of the two narrow sides. Here, a passage opening which is arranged on at least one of the two side surfaces and which is designed for a set screw which extends up to the jet regulator could be objectionable.
SUMMARY
[0007] It is therefore the object to create a jet regulator which can be inserted into the water outlet from the direction of the outlet end side and which can be releasably fixed in the water outlet without the required fastening means having an objectionable appearance in any way.
[0008] This object is achieved according to the invention with the jet regulator of the type mentioned in the introduction in particular in that the jet regulator can be releasably latched in the water outlet.
[0009] The jet regulator according to the invention can be releasably latched in the water outlet. Since the jet regulator according to the invention can be releasably latched in the water outlet of a sanitary outlet fitting, it is possible to dispense with an outlet mouthpiece which can be screwed to the water outlet and which holds the jet regulator. Also, since no rotational movement is required for mounting and dismounting the jet regulator according to the invention, it is possible for the jet regulator housing of the jet regulator according to the invention to have a round cross section or if appropriate also a rectangular cross section. Here, the fastening means required for fastening the jet regulator in the water outlet are not visible from the outside and therefore also cannot have an objectionable appearance.
[0010] To create a comfortable, practical and resilient latching connection, it is advantageous if at least one spring arm is integrally formed on the housing outer periphery of the jet regulator housing, which at least one spring arm, in the use position, engages with its free arm end behind an undercut on the inner periphery of the water outlet. The undercut which is required on the inner periphery of the fitting housing can then be provided in a particularly simple manner in particular if the fitting housing is embodied as a comparatively thick-walled cast part, such as will often be the case with a high-grade outlet fitting.
[0011] In order that the dismounting of the jet regulator according to the invention is also as simple as possible, it may be advantageous if the free arm end of the at least one spring arm is spaced apart from the housing outer periphery of the jet regulator housing in such a way that a release and/or removal tool can be inserted into the free space between said at least one spring arm and the housing outer periphery. In such an embodiment, the insertion movement of the release and/or removal tool which initiates the dismounting of the jet regulator is facilitated since the release and/or removal tool is guided here between the housing outer periphery of the jet regulator housing on one side and the spring arm on the other side.
[0012] It is possible for the at least one spring arm to point with its free arm end counter to the flow direction. It is duly the case in an embodiment of this type that the spring arms are deflected radially inward slightly, and are therefore released from the latching connection, as a result of the insertion of a release and/or removal tool into the free space remaining between the spring arms at the one side and the housing inner periphery of the jet regulator housing at the other side. In contrast, a particularly resilient and nevertheless structurally simple, preferred embodiment provides that the at least one spring arm is aligned in the flow direction of the water jet emerging from the outlet fitting and/or with its free arm end in the outlet direction.
[0013] To make it possible for the at least one spring arm which is provided on the jet regulator housing to be deflected radially inward, and released from its latching connection, it is advantageous if the at least one spring arm can, through the use of a pulling movement on the release and/or removal tool which can be applied to the outer side of the spring arm, be acted on with pressure in the outlet direction in such a way that the free arm end which is arranged opposite at the outflow side can be deflected inward. In this embodiment, a pulling movement on the release and/or removal tool is therefore converted into a radial deflecting movement of the at least one spring arm from its use or retaining position into its removal position; here, the removal movement of the jet regulator is additionally assisted by the pulling movement on the release and/or removal tool.
[0014] The transmission of the tensile force applied to the jet regulator by the release and/or removal tool and the removal of said jet regulator from the water outlet of the sanitary outlet fitting is additionally promoted if a tool stop is provided at the outside on the free arm section of at least one spring arm, which tool stop interacts with the release and/or removal tool in such a way that a pulling force on the release and/or removal tool can be transmitted to the spring arm and to the jet regulator housing which is connected thereto. Here, it is not strictly necessary for each of the spring arms provided on the housing outer periphery of the jet regulator housing to have a tool stop of said type.
[0015] The release and/or removal tool may, with an end section which is for example angled in the shape of a hook, be engaged in a particularly simple manner on the outer side of the spring arm, which is to be deflected for dismounting, if a run-on bevel which tapers counter to the pulling direction is provided, for the release and/or removal tool, upstream of the tool stop at the inflow side on the outside of at least one spring arm. In this embodiment, the release and/or removal tool need therefore merely be inserted into the water outlet beyond the run-on bevel before the release and/or removal tool can then be applied to the outer side of the at least one spring arm by means of the run-on bevel until the spring arm is deflected inward and can be released from its latching connection in the water outlet.
[0016] The insertion and retraction movement of the release and/or removal tool is facilitated considerably if at least one molded-out or molded-in portion with at least one axially aligned guide wall is provided on the housing outer periphery of the jet regulator housing, which at least one molded-out or molded-in portion interacts with a counterpart guide surface on the release and/or removal tool.
[0017] Here, an embodiment according to the invention which is specified merely by way of example but which is preferable provides that at least one molded-in portion with axially aligned guide walls is provided on the housing outer periphery of the jet regulator housing, which molded-in portion interacts with counterpart guide surfaces provided at both sides on the release and/or removal tool.
[0018] It is particularly expedient if at least one spring arm is provided in the region of at least one molded-in portion.
[0019] If a plurality of spring elements are provided on the jet regulator housing, the spring elements may also each serve as latching means independently of one another. One particularly resilient design which is simultaneously easy to handle provides that at least two spring arms are connected to one another by means of a tool stop or similar connecting web.
[0020] One preferred embodiment according to the invention provides that the at least one spring arm is of L-shaped design and a run-on bevel is provided in the region of the transverse web of the L shape. Here, it is particularly expedient if the L-shaped spring arms are assigned to one another in pairs and are of mirror-symmetrical design with respect to one another.
[0021] The features according to the invention may particularly advantageously be used in a jet regulator which has a non-circular, in particular elongate and/or rectangular outline.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Further features of the invention can be gathered from the following description of the figures in connection with the claims. The invention is described in more detail below on the basis of one advantageous exemplary embodiment. In the figures:
[0023] FIG. 1 shows a jet regulator on its inflow side in a perspective view, which jet regulator can be inserted into the water outlet of a sanitary outlet fitting and can be releasably latched there, wherein for this purpose, the jet regulator has, on the outer periphery of its jet regulator housing, two spring arms which are connected to one another and which, with their free arm ends, engage behind an undercut on the inner periphery of the water outlet,
[0024] FIG. 2 shows the jet regulator from FIG. 1 on the inflow side in a perspective illustration rotated through 180°,
[0025] FIG. 3 shows the jet regulator from FIGS. 1 and 2 on the outlet end side in a perspective, longitudinal section view,
[0026] FIG. 4 shows the jet regulator from FIGS. 1 to 3 on the inflow side in a perspective, longitudinal section view,
[0027] FIG. 5 shows the jet regulator from FIGS. 1 to 4 on its inflow side in a plan view,
[0028] FIG. 6 shows the jet regulator from FIGS. 1 to 5 in a longitudinal section, extending parallel to the longitudinal extent of said jet regulator, through section plane VI-VI in FIG. 5 ,
[0029] FIG. 7 shows the jet regulator from FIGS. 1 to 6 in a longitudinal section through section plane VII-VII in FIG. 6 ,
[0030] FIG. 8 shows the jet regulator from FIGS. 1 to 7 in its use position, situated in the water outlet of a sanitary outlet fitting, in a perspective longitudinal section,
[0031] FIG. 9 shows the jet regulator from FIGS. 1 to 8 in a perspective longitudinal section, with a release and/or removal tool applied to the jet regulator,
[0032] FIG. 10 shows the jet regulator from FIGS. 1 to 9 in a perspective illustration with the release and/or removal tool applied to the jet regulator,
[0033] FIG. 11 shows the release and/or removal tool associated with the jet regulator from FIGS. 1 to 10 in a perspective view, and
[0034] FIG. 12 shows the release and/or removal tool from FIGS. 9 to 11 in a further perspective view.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0035] FIGS. 1 to 10 illustrate a jet regulator 1 which can be inserted into the water outlet 2 of a sanitary outlet fitting 3 from the direction of the outlet end side, in order to form a homogenous, sparkling, soft and non-sputtering water jet there. To be able to fasten and fix the jet regulator 1 in its use position, the jet regulator 1 can be releasably latched in the water outlet 2 . For this purpose, two spring arms 5 , 6 are integrally formed on the housing outer periphery of the jet regulator housing 4 , which spring arms 5 , 6 engage behind a groove-like undercut 8 on the inner periphery of the fitting housing which surrounds the water outlet 2 .
[0036] The spring arms 5 , 6 are aligned in the flow direction of the water jet emerging from the outlet fitting 3 and are arranged with their free arm ends 7 in the outlet direction.
[0037] It is clear from FIGS. 9 and 10 that, for the purpose of dismounting the jet regulator 1 from the water outlet 2 , a release and/or removal tool 9 can be applied to the outer side of the spring arms 5 , 6 in such a way that the free arm ends 7 of the spring arms 5 , 6 can deflected radially inward, and released from their latching connection with the outlet fitting 3 , by means of a pulling movement on the release and removal tool 9 in the outlet direction. The spring arms 5 , 6 have, on their free arm section 7 , a common tool stop 10 which interacts with the release and/or removal tool 9 in such a way that a pulling force on the release and/or removal tool 9 can be transmitted to the spring arms 5 , 6 and to the jet regulator housing 4 which is connected thereto.
[0038] From a comparison of FIGS. 1 , 4 and 7 , it is clear that in each case one run-on bevel 11 which tapers counter to the pulling direction is provided, for the release and/or removal tool 9 , on the outer sides of the spring arms 5 , 6 . The release and/or removal tool 9 can therefore be pushed with its T-shaped tool head 12 beyond the run-on bevels 11 into the intermediate space provided between the jet regulator housing 4 and the inner periphery of the fitting housing, before running onto the run-on bevels 11 , as a result of a subsequent pulling movement of the T-shaped transverse web of the tool head 12 in the outlet direction, until the spring arms 5 , 6 are deflected inward and are released from their latching connection. Here, the T-shaped tool head is pushed through the opening which is bordered between the spring arms 5 , 6 , the tool stop 10 and the jet regulator housing 4 until the tool head can be pulled along the outside of the spring arms 5 , 6 to the tool stop 10 .
[0039] In FIGS. 1 , 4 , 7 and 10 , it can be seen that the spring arms 5 , 6 which are connected by the tool stop 10 are arranged in the region of a molded-in portion 13 which is provided on the outer periphery of the jet regulator housing 4 . The molded-in portion 13 has axially aligned guide walls 14 , 15 which interact with counterpart guide surfaces 16 , 17 provided at both sides on the release and removal tool 9 .
[0040] FIG. 1 illustrates that the spring arms 5 , 6 are formed in an L-shape and have the run-on bevels 11 in the region of the transverse web. Here, the spring arms 5 , 6 which are assigned to one another in pairs and which are connected to one another here by means of the common tool stop 10 are of mirror-symmetrical design with respect to one another.
[0041] The jet regulator 1 illustrated in FIGS. 1 to 10 is designed as an aerated jet regulator in which air is admixed to the water jet. To be able to draw the air required for admixture into the housing interior of the jet regulator 1 , an aeration duct 18 which is open in the direction of the outlet end side of the water outlet 2 is bordered between the molded-in portion 13 on the jet regulator housing 4 and the inner periphery of the outlet fitting 3 . The aeration duct 18 opens out in the region of aeration openings 19 which are provided in the jet regulator housing 4 . From a comparison of FIGS. 1 to 3 , it is clear that the jet regulator 1 has a jet regulator housing 4 with a peripheral push-in opening 21 . Here, at least one push-in guide 22 which is aligned transversely with respect to the jet regulator longitudinal axis is provided in the housing interior of the jet regulator housing 4 , such that the insert parts 23 required for forming the water jet can be pushed into the push-in guide or push-in guides 22 from the direction of the push-in opening 21 . To be able to form the water jet over the entire cross section thereof, the plate-shaped insert parts 23 extend substantially over the entire clear passage cross section of the jet regulator housing 4 . It can be seen from FIGS. 3 and 4 and 6 to 9 that the insert parts 23 which serve here as a homogenization device have a jet-forming sieve or grate structure.
[0042] A jet diffuser device 24 which is designed as a perforated plate is integrally formed in the jet regulator housing 4 upstream of the push-in opening 21 at the inflow side. To prevent undesired leakage currents between the jet regulator housing 4 on the one hand and the fitting inner periphery on the other hand, an annular seal 25 is provided between the jet regulator 1 and the fitting inner periphery. The annular seal 25 which is supported by the jet regulator housing 4 in the region of the jet diffuser device 24 can bear sealingly against the fitting housing without the risk of a deformation of the jet regulator housing 4 in said region, since the jet diffuser device 24 serves to stiffen the jet regulator housing 4 and counteracts an undesired deformation.
[0043] It can be seen from FIGS. 2 to 4 and 7 that the push-in opening 21 of the jet regulator 1 can be closed off by means of a cover which is formed from a plurality of cover partial regions 26 , 27 which are integrally formed on the insert parts 23 . Pressing projections (not shown in any more detail) can be integrally formed on said cover partial regions 26 , 27 at the outside, which pressing projections act on the fitting inner periphery. As the jet regulator 1 is inserted, said pressing projections are clamped between the fitting inner periphery and the jet regulator housing 4 in such a way that the pressing projections press the cover partial regions 26 , 27 against the peripheral edge region, which delimits the push-in opening 21 , of the jet regulator housing 4 with a sufficient sealing action.
[0044] The insert parts 23 can be pushed with lateral guide rails 28 into the push-in openings 22 which are designed at both sides as guide grooves. Here, the guide rails 28 and the guide grooves of the push-in guides 22 form a dovetail-like groove connection.
[0045] A sieve or grate structure 30 is integrally formed on the jet regulator housing 4 of the jet regulator 1 at the outlet side, which sieve or grate structure firstly serves as a flow straightener and secondly also constitutes a manipulation prevention device which is intended to prevent unauthorized manipulation of the insert parts 23 situated in the housing interior of the jet regulator housing 4 .
[0046] It is particularly advantageous if the sieve or grate structures of the insert parts 23 which are positioned in series with one another to be aligned with the gaps of the adjacent structures. Even if the insert parts 23 are of identical design, this is possible by means of a lateral offset of the sieve or grate structures for example by approximately half of a mesh width. Instead, it is also possible to use asymmetrical sieve or grate structures which can be aligned with the gaps of the adjacent structures by means of a simple rotation of the identically-designed insert parts 23 .
[0047] In each case one ancillary sieve 29 is positioned upstream of the jet regulators 1 at the inflow side, which ancillary sieve 29 filters out the dirt particles contained in the water.
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A jet regulator, having a non-circular profile when viewed in a flow direction, is provided. The jet regulator includes a jet regulator housing configured to be inserted into a water outlet of a sanitary outlet fitting from an outlet end side. The housing includes a latching part, which has at least one spring arm integrally formed on an outer periphery of the jet regulator housing, the at least one spring arm extending tangentially away from the housing, in the flow direction, toward a free arm end. The at least one spring arm is resiliently biased away from the housing.
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TECHNICAL FIELD
[0001] The present invention generally concerns methods and apparatus for use in multi-server web sites and web browsers and more specifically concerns methods and apparatus that improve the perceived responsiveness of multi-server web sites and web environments.
BACKGROUND
[0002] Users seeking content (such as, for example, web pages) from a web site often are confronted by delays. The sought web page may take tens of seconds to load, even if the user has a high-speed connection. The situation may not improve with each successive web page requested from the web site. Each successive web page may similarly load slowly. The perceived lack of responsiveness of the web site may be a source of dissatisfaction for a user. In fact, it might lead the user to conclude that the web site is poorly designed and managed. In view of such a conclusion, the user may seek another web site providing the same information or service.
[0003] What users may not understand is the perceived lack of responsiveness of the web site may not be the fault of the web site itself but may actually be caused by other elements of the web that are separate from the web site. For example, servers associated with the Domain Name System (hereinafter “DNS”) of the web often are consulted to service a request for web content. These servers are not part of the web site providing the content, but often provide address information needed to properly address requests to the web site for content. Delays in the DNS system in providing the address information may be mistakenly be attributed to the web site.
[0004] In more detail, DNS servers typically have associated address caches where address information for recently visited web sites is stored. For example, when a web client issues a request for a web page maintained by a web site that has not been recently visited, the web client will issue a DNS request to the DNS system for the address information. Depending upon the DNS server used by the client, the DNS request resolution time can vary. For DNS servers that serve a large number of clients, the address for the web site may already be in the cache of a local DNS server. In such a situation, the DNS system simply provides the address information to the web client from the cache of the local DNS server. For a DNS server that services a small number of clients, the server typically will not have the DNS entry within its local cache, resulting in a so-called “DNS cache miss”. When a DNS cache miss occurs, the local DNS server used by the client must make requests to additional DNS servers. These additional DNS requests can result in a long wait period for the web client.
[0005] This problem is increased when a web client visits a page that consists of many URLs that each have different hostnames, even if the hostnames are within the same network domain. Each different hostname requires a DNS request and response. If there is a DNS delay, this can give the user the false impression that the web site is at fault when in fact it is the DNS system that is causing the delay.
[0006] Similar problems may be encountered when a web page is produced using multiple content elements stored on web servers having different hostnames. If there is a delay in receiving any of the content elements, depending on the browser used, either the entire web page may be delayed in rendering, or the web page may be only partially rendered leaving blanks where content (such as, for example, images; text; dynamic elements) should appear.
[0007] Thus, those skilled in the art seek improvements for use in multi-server web sites and web environments that improve the perceived responsiveness of the web sites and web environments to users. In particular, those skilled in the art seek improvements that reduce the likelihood that delays occurring in the DNS system will actually be perceived by a user. DNS cache misses and resulting DNS delays may still occur, but those skilled in the art seek improvements that mask the delays from the user so that the user does not realize that delays are occurring.
SUMMARY OF THE INVENTION
[0008] The foregoing and other problems are overcome, and other advantages are realized, in accordance with the following embodiments of the invention.
[0009] A first embodiment of the invention is a method. In the method, movement from a first web page to a second web page is identified as an expected transition. It is assumed that the first web page is stored on a first server having a first hostname, and the second web page is stored on a second server having a second hostname different from the first hostname. Then, identification information is selected for the second web page that can be used to issue a DNS request for address information needed to service a web request for the second web page. Next, the first web page is associated with identification information for the second web page. Then, the association of the first web page with identification information for the second web page is saved to computer memory.
[0010] A second embodiment of the invention is a method occurring in a multi-server web environment. In the second method, a first web request is received from a web client for web content. Then, a response to the first web request is generated, wherein the response comprises the web content sought by the first web request and additional information. The additional information can be used by the web client to issue at least one DNS request for address information that will be needed to service an anticipated second web request. It is expected that the web client will issue the anticipated second web request after the first web request. Next, the response containing the web content sought by the first web request and the additional information is transmitted to the web client.
[0011] A third embodiment of the invention is a computer program product comprising a signal bearing medium tangibly embodying a computer readable program executable by digital processing apparatus. The computer readable program, when executed by digital processing apparatus, is configured to receive a first web request from a web client for a first web page; to generate a response to the first web request, wherein the response comprises the web page sought by the first web request and content element identification information identifying additional web content that will be needed to reproduce a second web page; and to transmit the response to the web client.
[0012] A fourth embodiment of the invention is a system comprising: a web site incorporating a plurality of web servers, at least first and second web servers of the plurality having URLs with hostnames different from one another; a computer memory coupled to the web site, the computer memory storing a computer program configured to perform operations for managing the web site when executed by digital processing apparatus; and a digital processing apparatus coupled to the web site and the computer memory, the digital processing apparatus configured to execute the computer program. Each of the first and second web servers with hostnames different from one another provides content used to produce a particular web page. When the computer program is executed by the digital processing apparatus, the system is configured to identity that the particular web page is produced using content provided by the first and second servers, wherein the first and second servers have different hostnames; to change the hostname associated with content used in the particular web page provided by the second web server to the hostname of the first web server; and to copy the content with the changed hostname to the first web server.
[0013] In conclusion, the foregoing summary of the various embodiments of the present invention is exemplary and non-limiting. For example, one or ordinary skill in the art will understand that one or more aspects or steps from one embodiment can be combined with one or more aspects or steps from another embodiment to create a new embodiment within the scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The foregoing and other aspects of these teachings are made more evident in the following Detailed Description of the Invention, when read in conjunction with the attached Drawing Figures, wherein:
[0015] FIG. 1 is a block diagram depicting a multi-server web environment in which methods and apparatus of the invention may be practiced;
[0016] FIG. 2 is a flowchart depicting a method operating in accordance with the invention;
[0017] FIG. 3 is a flowchart depicting a method operating in accordance with the invention;
[0018] FIG. 4 is a flowchart depicting a method operating in accordance with the invention; and
[0019] FIG. 5 is flowchart depicting a method operating in accordance with the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0020] One embodiment of the invention is practiced in a situation when a web client issues a request for a series of web pages. Ordinarily, before any web page request can be issued the web client must first obtain the DNS entry for the web page server (the IP address of the web server) that contains the web page. Methods and apparatus of this invention anticipate this by including URLs for web pages likely to be requested later in a series of requests for web pages in web pages responsive to initial requests. When the contents of the initial web pages are delivered to the web client, the web pages contain embedded URLs that consist of other hostnames within the website that the web client will likely visit. By including URLs in the first or initial web pages that contains the hostnames that the web client will likely need in order to make further requests for subsequent web pages, the web client can get a head start on resolving hostnames. This process will allow the web client to skip the DNS request/response steps when a subsequent web page is requested from one of the other web servers because the web client will already have saved the DNS entry within its local DNS cache. The included URLs are encoded as “hidden” images or other web objects which allow the initial page to be rendered without having to wait for the hidden images or objects to be downloaded from the site. These hidden images could be one pixel images that appear at the end of the page or off-screen from the page.
[0021] By including the hidden images within a web page, this forces any web client to pre-fetch DNS entries which the web client will likely need for a subsequent HTTP request.
[0022] In one embodiment, the present invention is a method and apparatus for providing information to a web client so that the web client can pre-resolve DNS entries. Embodiments of the present invention also allow website creators to normalize the network load over a series of web pages by copying embedded URLs contained within the pages. Embodiments of the invention further allow creators of websites to minimize the number of TCP connections that a client must use in order to view a particular web page.
[0023] FIG. 1 depicts a typical network environment showing a website 101 consisting of multiple web servers 103 , 105 , 107 and 109 . A web client 111 will make a series of HTTP requests 113 , 115 , 117 and 119 to the website 101 . Before each one of the web requests 113 , 115 , 117 and 119 is made to the corresponding web server 103 , 105 , 107 and 109 a DNS request 121 is made by the web client 111 to a local DNS server 123 . The DNS server 123 may make additional DNS requests to other DNS servers (not shown) in order to satisfy the DNS request 121 . When the DNS server issues a reply 125 to the web client 111 the web client 111 can then send the HTTP request 113 to the web server 103 and the web server 103 will reply 127 back to the web client 111 with the contents of the web page 139 . The same process occurs for the other web servers, HTTP requests and web pages.
[0024] The web site 101 consists of four web servers 103 , 105 , 107 and 109 that may have the same Internet domain name but may each have a different hostname.
[0025] If the local DNS server 123 does not have the address entry for each of the web servers 103 , 105 , 107 , 109 when the web client 111 makes each of the DNS requests 121 there can be a delay as the DNS server 123 obtains the address for the web client 111 . The delay can occur for each request for each web server within the web site. This delay is not the fault of the website 101 but rather the DNS server that the web client 111 is using.
[0026] In order to improve a user's experience of the website 101 the author of the website 101 can make improvements in accordance with the invention to speed up the resolution of DNS names.
[0027] The first step is to create a set of possible transitions from one web page to another. A transition occurs between a pair of web pages where an initial web page of the pair is web page that a user would be expected to view first and the later page is a web page that the user would be expected to view after the user has viewed the initial web page. For web site 101 this would result in a transition set of: (Welcome 139 to Logon 141 ), (Logon 141 to Authenticate 143 ), (Authenticate 143 to E-mail 145 ). Depending on implementation, the transition set can consist of all possible transitions or just the most popular. “Most popular” can be manually chosen or determined from past history of the web site 101 .
[0028] Using the set of web page transitions, URLs can be added to each web page, where the URLs refer to a future page, or to a future series of web pages. The embedded URLs can be a “hidden” image file that appears out of the normal view of the user. By using a hidden image it will allow the web page to render on the screen while the DNS request 121 and the response 125 are taking place for the hostname that contains the hidden image. There is typically some “think time” when a page is rendered on a screen when the user must view the page. During this think time the DNS request 121 and the response 125 can occur making the user unaware of the delay.
[0029] Referring to FIG. 1 , a hidden image is included within the Welcome page 139 on the web server 103 that refers to web server 105 . When the user clicks on a URL from within the Welcome page 139 to request the contents of the Logon page 141 , the web client 111 will already have the DNS entry due to the hidden image that forced the web client 111 to “pre-resolve” the hostname for web server 105 . In this example, web page 141 on web server 105 is the most likely request to follow after the web page 139 on web server 103 .
[0030] In other embodiments, URLs for multiple web pages in a sequence can be included in a web page likely to be requested first. In the example of FIG. 1 , this can be accomplished by including hidden image URLs for websites 107 and 109 within the Welcome page 139 as well.
[0031] The hidden image can be something such as a 1 pixel image or an image that appears off the screen or out of view of the user. In addition other objects could be used instead of an image URL such as a script file. Anything that causes the web client 111 to make a DNS request for the desired hostname could be used.
[0032] In alternate embodiments, actual physical address information may be provided. This can be done when it is known that the address of an item is unlikely to change. This totally eliminates in certain circumstances the need for a DNS query. Since addresses for many items can be expected to change, though, it is better in other instances to provide identification information (URLs) so the DNS system can be queried for an up-to-date address.
[0033] In addition, the web site creator can use the identified set of web page transitions to normalize the network load over the set of web servers 103 , 105 , 107 , 109 within website 101 . This process would occur by moving content that appears on subsequent web pages to previous pages. For example, if an image file is shown on the logon page 141 on web server 105 then a hidden URL can be placed on the welcome page 139 for the web server 103 . Doing this results in a web client 111 pre-fetching the image for the logon page 141 before the actual logon page 141 is requested by the web client 111 . This image when requested as part of the Welcome page 139 would be hidden from the user. When the HTTP request 115 is made for the Logon page, the web client 111 will already have the image within its cache and will not have to request the image in order to render the Logon page 141 .
[0034] In a variation of this embodiment where security is a concern, providing content in anticipation of future need can be selectively disabled either by the web site or web client. For example, the web client can signal the web site that address information or content should not be provided in anticipation of future need.
[0035] A third improvement provided by embodiments of the invention is obtained by reducing the number of TCP connections needed to render a web page. The number of TCP connections is equal to the number of unique hostnames found within all of the URLs of a web page. Using this technique, if an image file URL within the Welcome page 139 on web server 103 is located on another web server ( 105 , 107 , 109 ) within the web site 101 then that image could be copied from the other web server to web server 103 . This process would allow a web client 111 to render a web page with only one TCP connection using multiple HTTP requests over the same TCP connection (Known as HTTP 1.1)
[0036] The three improvements just described can be automated by including the methods within a web site authoring application.
[0037] In summary, FIGS. 2-5 depict methods operating in accordance with the invention that can be practiced alone or in combination. In the method depicted in FIG. 4 , at step 210 web pages accessible from different web servers of a web site like that depicted in FIG. 1 are analyzed to identify likely web page sequences. A “web page sequence” is a series of web pages likely to be serially accessed by a user, such as the sequence comprising the welcome web page 139 ; logon web page 141 ; authenticate web page 143 ; and e-mail web page 145 depicted in FIG. 1 . In step 210 , as an example, a movement from a first web page to a second web page is identified as an expected transition. It is assumed that the first web page is stored on a first server having a first hostname and the second web page is stored on a second server having a second hostname, wherein the second hostname of the second server is different from the first hostname of the first server. Then, at step 220 , identification information is selected for the second web page that can be used to issue a DNS request for address information needed to service a web request for the second web page. Next, at step 230 , identification information for the second web page is associated with the first web page in some manner such as, for example, by creating a data entry memorializing the association. Then, at step 240 , the association of the identification information for the second web page with the first web page is saved to computer memory.
[0038] In one variant of the embodiment depicted in FIG. 2 , associating the identification information for the second web page with the first web page further comprises incorporating the identification information for the second web page in the first web page and saving the association of the identification information further comprises saving the first web page in a form incorporating the identification information for the second web page.
[0039] Typically, the identification information for the second web page comprises a URL. Further, in typical embodiments, the URL comprising the identification information for the second web page is hidden so that when the first web page is displayed the URL for the second web page is not visible.
[0040] In another variant of the method depicted in FIG. 4 additional steps are performed at the first web server of the web site. In the additional steps, the first web server receives a first web request for the first web page from a web client; and the first web server transmits the first web page, wherein the first web page incorporates the identification information for the second web page. In one typical example of this variant the first web request comprises an HTTP request.
[0041] In a further variant of the method depicted in FIG. 4 additional steps are performed at the web client. In this variant, the web client receives the first web page; recovers the identification information (such as, for example, a URL) for the second web page from the first web page; and prior to receiving a request for the second web page, the web client issues a DNS request for address information using the identification information for the second web page recovered from the first web page. In contrast to the prior art, the ability to issue a DNS request for address information needed to service a request for the second web page before such a request is actually received often avoids delays typically attributed to a web site but which are, in fact, caused by DNS cache system misses.
[0042] Yet another variant of the method depicted in FIG. 4 can be practiced in combination with the steps of the method of FIG. 4 or alone. The preceding steps sought to eliminate delays associated with requesting address information needed to service a request for a web page from the DNS system. The following steps seek to eliminate delays associated with requesting content elements needed to reproduce a web page by requesting the content elements before a request for the web page is received. In this variant the following additional steps are performed: after identifying movement from the first web page to the second web page as an expected transition, at least one content element needed to reproduce the second web page is identified; and content element identification information (such as, for example, a URL) identifying the at least one content element needed to reproduce the second web page is added to the first web page. Performing the steps of this variant is done to normalize traffic between the web and servers of the web site by causing web clients to request content stored on the second server needed to reproduce the second web page before the web client issues a request for the second web page.
[0043] In a still further variant, the first web server receives a first web request for the first web page from a web client; and the first web server transmits the web page in response to the web request. As indicated previously, the first web page has been amended to incorporate content element identification information identifying a content element needed to reproduce a second web page. Accordingly, upon receipt of the first web page, the web client treats the URLs in the first web page (including the URL corresponding to the content element needed to reproduce the second web page) like any other URL and requests the content corresponding to the URLs. In this manner, the web client issues a request for the content element needed to reproduce the second web page before the web client receives a request for the second web page from the user.
[0044] In another variant of the method depicted in FIG. 4 steps can be taken at the web site depicted in FIG. 1 to reduce the number of TCP connections needed to reproduce a web page resident on one of the web servers of the web site. In this variant additional steps are performed, the steps comprising: identifying that the first web page is produced using content provided by the first and second servers; changing the hostname associated with the content used to produce the first web page provided by the second server to the hostname of the first server; and copying the content with the changed hostname originally provided by the second server to the first server. As indicated, these steps are performed to reduce the number of TCP connections need to produce a web page.
[0045] Another embodiment of the aspect of the invention that provides identification information that can be used to issue a DNS request for address information needed to service a web request for a web page before the web request is actually received is depicted in FIG. 3 . In contrast to the method depicted in FIG. 2 the steps of which are performed typically during the construction of the web site, the steps of FIG. 3 can also be performed on the fly as web requests are received. In the method of FIG. 3 at step 310 a web site comprising a plurality of web servers receives a first web request from a web client for web content. Then, at step 320 , a response is generated to the first web request, wherein the response comprises the web content sought by the first web request and additional information for use by the web client to issue at least one DNS request for address information that will be needed to service an anticipated second web request likely to be issued by the web client after the first web request. Next, at step 230 , the response is transmitted to the web client.
[0046] In a variant of the method depicted in FIG. 3 further steps are performed at the web client. In a first further step, the web client recovers the additional information from the response. In a second further step that occurs prior to receipt of the anticipated second web request, the web client uses the additional information to issue at least one DNS request for address information that will be needed to service the anticipated second web request when it is received.
[0047] As indicated, the method depicted in FIG. 3 can operate on the fly or in a predetermined fashion. In a variant of the method depicted in FIG. 3 operating in a predetermined fashion, additional steps are performed prior to receipt of the first web request. The additional steps comprise: identifying movement from the first web page to the second web page as an expected transition; selecting the additional information that can be used to issue a DNS request for address information needed to service the anticipated second request; and saving the additional information to a computer memory.
[0048] In another variant of the method depicted in FIG. 3 operating in a predetermined fashion, additional steps are performed to identify a plurality of transitions. In this variant the following additional steps are performed: identifying a plurality of expected transitions from initial web pages to later web pages, wherein different hostnames are used within URLs associated with the initial web page and later web page of each transition pair; selecting additional information that can be used to issue a DNS request for address information needed to service web requests seeking the later web pages; and saving the additional information to computer memory.
[0049] FIG. 4 depicts another method similar to a foregoing variant described with respect to FIG. 2 . In the method, it is determined that a second web request seeking a second web page is typically issued after a first web request seeking a first web page. It is also true that the first web page and associated content is stored on a first server with a first hostname and that the second web page and associated content is stored on a second server with a second hostname different from the first hostname. As described previously, in certain circumstances it is desirable to normalize traffic between the web client and the first and second servers by causing the web client to request content elements needed to reproduce a web page before the web client receives a request for the web page when it is known that a request for the web page will likely follow a request for an earlier web page.
[0050] In the method of FIG. 4 , at step 410 the first web server receives a first web request from a web client for a first web page. Then, at step 420 , the web client generates a response to the first web request, wherein the response comprises the web page sought by the first web request and content element identification information identifying a content element needed to reproduce a second web page. Then, at step 430 , the first web server transmits the response to the web client.
[0051] In a variant of the method depicted in FIG. 4 additional steps are performed at the web client. In the additional steps the web client receives the response comprising the first web page and the content element identification information identifying a content element needed to reproduce a second web page; recovers the content element identification information from the response; and issues a web request for the content element needed to reproduce the second web page.
[0052] In another variant of the method depicted in FIG. 4 , the content element identification information comprises a URL that is added to the first web page in such a manner that neither the URL nor the content corresponding to the URL is visible to a user when the user views the web page. Nonetheless, the incorporation of a URL corresponding to a content element needed to reproduce a second web page in the first web page causes the web client to issue a request for the content element before a request for the second web page is received.
[0053] FIG. 5 depicts another embodiment of the invention somewhat similar to a variant described with respect to FIG. 2 . The embodiment depicted in FIG. 5 corresponds to a method that seeks to reduce the number of TCP connections needed to reproduce a web page. As described previously, it is not unusual for a web page to include content elements that are stored in different servers having different hostnames. In such a situation, it is necessary to establish a TCP connection with each server having a different hostname in order to recover the content necessary to reproduce accurately the web page. It is desirable to reduce or even minimize the number of TCP connections required to reproduce a web page, and the method in FIG. 5 accomplishes this end.
[0054] At step 510 of the method, it is identified that a particular web page is produced using content provided by first and second servers, wherein the first and second servers have different hostnames. Then, at step 520 , the hostname associated with the content used in the particular web page provided by the second web server is changed to the hostname of the first web server. Next, at step 530 , the content with the changed hostname originally stored in the second web server is copied to the first web server. These operations reduce the number of TCP connections needed to reproduce the particular web page by one. If the content needed to produce the particular web page is only provided by the first and second web servers, the method depicted in FIG. 5 also minimizes the number of TCP connections needed to reproduce the web page.
[0055] One of ordinary skill in the art will understand that methods depicted and described herein can be embodied in a computer program storable in a tangible computer-readable memory medium or signal bearing medium. Instructions embodied in the tangible computer-readable memory or signal-bearing medium perform the steps of the methods when executed. Tangible computer-readable memory media include, but are not limited to, hard drives, CD- or DVD ROM, flash memory storage devices or in a RAM memory of a computer system.
[0056] In addition, apparatus associated with a web site such as the one depicted in FIG. 1 can be configured to perform operations corresponding to those depicted and described with respect to FIGS. 2-5 . Such apparatus would comprise a computer readable memory storing a computer program configured to cause the apparatus to perform operations similar to those depicted in FIGS. 2-5 when executed and digital processing apparatus to perform the operations.
[0057] Thus it is seen that the foregoing description has provided by way of exemplary and non-limiting examples a full and informative description of the best apparatus and methods presently contemplated by the inventors for improving interactions between web sites comprised of servers having different hostnames and web clients. One skilled in the art will appreciate that the various embodiments described herein can be practiced individually; in combination with one or more other embodiments described herein; or in combination with web environments differing from those described herein. Further, one skilled in the art will appreciate that the present invention can be practiced by other than the described embodiments; that these described embodiments are presented for the purposes of illustration and not of limitation; and that the present invention is therefore limited only by the claims which follow.
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Disclosed herein are methods and apparatus that improve the perceived responsiveness of a multi-server web site or web environment to web requests issued by web browsers. In one aspect, the methods and apparatus operate by determining a likely sequence of web pages to be accessed by users. The methods and apparatus then incorporate information identifying web pages and web page content likely to be requested later in the sequence in web pages responsive to web page requests received earlier in the sequence. In one such method, the URL of a second web is incorporated in a first web page that is expected to be requested before the second web page. A web client receiving the first web page will then issue a DNS request for address information corresponding to the URL of the second web page even if no request has been received for the second web page. Thus, the probability of a DNS system cache miss occurring when a web request for the second web page is actually received by the web client is significantly reduced.
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FIELD OF THE INVENTION
The present invention is directed towards a tar sands extraction process and, in particular, a counter-current decantation (CCD) process for the extraction of bitumen from bitumen froth generated from a tar sands using a water process.
BACKGROUND OF THE INVENTION
Throughout the world, considerable oil reserves are locked in the form of tar sands, also called bitumen sands. For example, the Athabasca tar sands deposit, located in northeastern Alberta, Canada, is the largest of the four major Alberta deposits and contains oil reserves exceeding 146 billion cubic meters over a total area of 32,000 square kilometers. Another such tar sands deposit exists in the Tar Sand Triangle located in a triangularly shaped area between the Dirty Devil River and the Colorado River in southeastern Utah. The Tar Sand Triangle deposit contains reserves of 12-16 billion barrels of oil in place and covers an area of approximately 518 square kilometers. However, the fact that the oil, in the form of bitumen, is intimately mixed with sand, water, sand silt, complicates its efficient extraction therefrom.
Various methods have been proposed to separate the bitumen product from the tar sands as a single component. In one method, the bitumen separated from the sands is coked to produce coker distillate which may be later refined in accordance with conventional refinery practice. In the alternative, it has been proposed that the raw tar sands be treated in a retort in either a moving or fluid bed to produce a coker distillate in which the coke which deposits on the sand is burned to provide process heat.
However, the foregoing processes have their disadvantages in that during coking, the distillate is cracked. While cracking may be desirable for obtaining economic yields, there is usually some degradation of the distillate quality.
One attempt to overcome these disadvantages is disclosed and claimed in U.S. Pat. No. 2,871,180. The method described in this patent for separating crude oil from bituminous sands in a deasphalted oil enriched layer and an asphaltene enriched layer is to provide an aqueous pulp of the sands into a vertical extraction zone. A low molecular weight paraffinic hydrocarbon (propane) is then introduced into the extraction zone at a level below the point of introduction of the aqueous bituminous sand pulp.
Essentially, the low molecular weight paraffinic hydrocarbon flows upwardly through the extraction zone while the heavier aqueous bituminous sand pulp flows downwardly. These opposing upward and downward flows result in the formation of a deasphalted oil and solvent phase (i.e., the product phase), an asphaltenes phase diluted with a lesser portion of the solvent, a water phase, and a substantially oil-free sand phase, said phases having increasing specific gravities in the order presented. The phases are then taken off for further treatment. However, this process presented several economic disadvantages that limited its use and commercial applicability.
Conventionally, the hot water extraction process, which avoids some of the disadvantages presented by the above methods, is utilized in the recovery of bitumen from the sand and other material in which it is bound. After the bitumen is recovered, it is then treated to obtain oil products therefrom. One such example of this process is disclosed by U.S. Pat. No. 5,626,743, which is incorporated herein by reference.
In the prior art water extraction process, tar sands are first conditioned in large conditioning drums or tumblers with the addition of caustic soda (NaOH) and water at a temperature of about 85° C. The tumblers provide means for steam injection and positive physical action to mix the resultant slurry vigorously, causing the bitumen to be separated and aerated to form a bitumen froth.
The slurry from the tumblers is then screened to separate out the larger debris and passed to a separating cell where settling time is provided to allow the slurry to separate. As the slurry settles, the bitumen froth rises to the surface and the sand particles and sediments fall to the bottom. A middle viscous sludge layer, termed middlings, contains dispersed clay particles and some trapped bitumen that is not able to rise due to the viscosity of the sludge. Once the slurry has settled, the froth is skimmed off for froth treatment and the sediment layer is passed to a tailings pond. The middlings is often fed to a secondary flotation stage for further bitumen froth recovery.
U.S. Pat. No. 5,626,793 discloses a modified prior art water extraction process termed the hydrotransport system. In this system, the tar sands are mixed with water and caustic soda at the mine site and the resultant slurry is transported to the extraction unit in a large pipe. During the hydrotransport, the tar sands are conditioned and the bitumen is aerated to form a froth. This system replaces the manual or mechanical transport of the tar sands to the extraction unit and eliminates the need for tumblers.
The bitumen froth from either process contains bitumen, solids, and trapped water. The solids that are present in the froth are in the form of clays, silt, and some sand and contains about 60% by weight bitumen, which is in itself composed of about 10 to 20% by weight asphaltenes, about 30% by weight water, and about 10% by weight solids. From the separating cell, the froth is passed to a defrothing or deaerating vessel where the froth is heated and broken to remove the air. Typically, naphtha is then added to solvate the bitumen thus reducing the density of the bitumen and facilitating separation of the bitumen from the water by means of a subsequent centrifugation treatment. The centrifuge treatment first involves a gross centrifuge separation followed by a series of high-speed centrifuge separations. The bitumen collected from the centrifuge treatment usually contains about 5 wt % water and solids and can be passed to the refinery for upgrading and subsequent hydrocracking. The water and solids released during the centrifuge treatment are passed to the tailings pond.
The very nature of bitumen renders it difficult to process. This is because bitumen is a complex mixture of various organic species comprising of about 44 wt % white oils, about 22 wt % resins, about 17 wt % dark oils, and about 17 wt % asphaltenes (Bowman, C. W. "Molecular and Interfacial Properties of Athabasca Tar Sands". Proceedings of the 7 th World Petroleum Congress. Vol. 3 Elsevier Publishing Co. 1967).
When bitumen is treated using the conventional naphtha dilution and centrifugation extraction process, considerable problems are encountered. The reason for this is actually two-fold: Firstly, the naphtha diluted bitumen product can contain up to 5 wt % water and solids. Secondly, the naphtha diluent solvates the bitumen as well as the unwanted and dirty asphaltenes contained in the bitumen froth. Because hydrocracking requires a homogeneous feed which is very low in solids and water, the naphtha diluted bitumen product cannot be fed directly to the hydrocracker. In order to utilize the naphtha diluted bitumen product, it must first be coked to drive off the naphtha solvent and drop out the asphaltenes and solids. Unfortunately, this coker upgrading represents an enormous capital outlay and also results in a loss of 10-15% of the bitumen initially available for hydrocracking.
One way to avoid the problems presented by the naphtha dilution of the bitumen is to use a different solvent such as a paraffinic diluent. However, the use of a paraffinic diluent results in the precipitation of a major proportion of asphaltenes from the diluted bitumen. Therefore, when the paraffinically diluted bitumen is fed to the centrifugation system, the precipitated asphaltenes may tend to "plug up" the centrifuges which results in increased maintenance due to the necessity of shutting down and cleaning the fouled centrifuges. The increased centrifuge maintenance therefore results in reduced throughput and unsatisfactory process economics. Furthermore, centrifugation equipment is highly capital and maintenance intensive even during smooth operation.
The tailings produced via the conventional extraction process present further problems. The tailings in the tailings pond are largely a sludge of caustic soda, sand, water, and some bitumen. During the initial years of residence time, some settling takes place in the upper layer of the pond, releasing some of the trapped water. The water released from the ponds can be recycled back into the water tar sands treatment process. However, the major portion of the tailings remains as sludge indefinitely. The sludge contains some bitumen and high percentages of solids, mainly in the form of suspended silt and clay.
The tailings ponds are costly to build and maintain, and the size of the ponds and their characteristic caustic condition creates serious environmental problems. In addition, environmental concerns exist over the large quantity of water which is required for the extraction and which remains locked in the tailings pond after use.
It is known that sludge is formed in the initial conditioning of the tar sands when caustic soda attacks the sand and clay particles. The caustic soda causes the clays, such as montinorillonite clays, to swell and disperse into platelets that are held in suspension and form the gel-like sludge. Since such sludge inhibits the flotation of the bitumen froth in the extraction process, lower grade tar sands containing large amounts of expanding clays cannot be treated satisfactorily using the conventional water caustic soda process.
Therefore, the need exists for an extraction process which would not require the use of caustic soda in the tar sands conditioning process, which would result in a reduction in the production of sludge and therefore an increase in the water available for recycling and a decrease in the sheer volume of tailings present in the tailings ponds. It would also be highly desirable to avoid to use of naphtha based solvents for bitumen extraction and preclude the necessity of coker upgrading of the bitumen product prior to hydrocracking. It would also be desirable to avoid the use of centrifuges with paraffinically diluted bitumen and the inherent asphaltenes plugging of such centrifuges by utilizing a non-capital intensive process which can efficiently treat a diluted bitumen containing precipitated asphaltenes while maintaining a high throughput, low maintenance, and improved process economics.
Processes to utilize alternative conditioning reagents other than caustic soda have been proposed. U.S. Pat. No. 4,120,777 and U.S. Pat. No. 5,626,743 disclose two such processes. While the former utilizes soluble metal bicarbonates in place of caustic soda, the latter teaches the use of mixtures of sodium and potassium bicarbonates in the presence of calcium and magnesium ion sources. The aim of both of these patents is to avoid the use of caustic soda in the hot water tar sands conditioning process and therefore reduce clay dispersion and subsequent sludge formation.
U.S. Pat. No. 4,349,633 avoids entirely the use of a conditioning reagent in the tar sands conditioning process and instead teaches the use of a suspension of oxidase-synthesizing hydrocarbon metabolizing microorganisms to facilitate the separation or release of bitumen from the sand, clays, and water in the tar sands.
However, such processes have not been adopted by the industry due to the fact that they substantially increase the cost of bitumen extraction from tar sands due to the higher cost of reagents employed. Furthermore, such processes often result is lower tar sands conditioning rates and thus adversely affect product throughput. Finally, although such processes may avoid the production of sludges and their inherent problems, none of the prior art addresses the problem of coker upgrading of naphtha diluted bitumen or the centrifuge plugging resulting from paraffinically diluted bitumen.
SUMMARY OF THE INVENTION
A unique, efficient, and novel process has been developed for the extraction of bitumen from bitumen froth generated from tar sands. According to the novel inventive process, bitumen froth is extracted from tar sands using a water process. The froth is then treated in a counter-current decantation circuit utilizing a paraffmic hydrocarbon as a solvent to remove precipitated asphaltenes, water, and solids from the bitumen froth.
Surprisingly, the present invention results in the production of a final dilute bitumen product having a water and solids content of about 0.01 to about 1.00% by weight which can be directly fed to a hydiocracker. This process provides an improved and alternative route to the conventional process of diluting bitumen with naphtha and, in addition, the expensive coker upgrading required to render the bitumen amenable to hydrocracking. The invention also provides an alternative bitumen extraction process that avoids centrifuge plugging encountered with paraffinically diluted bitumen products. Advantageously, the present invention does not require the use of caustic soda to condition the tar sands and thereby avoids clay dispersion and the attendant formation of sludge. Moreover, temperatures much lower that 85° C. normally used can be used to treat tar sands. Typically, the tar sands conditioning step of the present invention range in temperature between approximately 25 and 55° C. and preferably at a temperature of about 35° C. The decrease in the temperature required for tar sands conditioning results in lower energy costs and improved process economics.
According to another aspect of the present invention, a process is provided for the extraction of bitumen from bitumen froth generated from a tar sands conditioning process using water without requiring the use of caustic soda. The process comprises:
(a) treating the bitumen froth concentrate in a counter-current decantation process with a hydrocarbon solvent, e.g., a paraffmic hydrocarbon, by means of which a dilute bitumen product is produced with substantially reduced water, solids, and precipitated asphaltenes and a bitumen froth tailings or residuum, comprising either separately or intimately mixed residual bitumen, solvent, water, solids, and precipitated asphaltenes;
(b) subjecting the bitumen froth tailings comprising very dilute bitumen, solvent, water, solids, and precipitated asphaltenes, to a first gravity separation step and thus form a very dilute bitumen phase, a mixed very dilute bitumen, precipitated asphaltenes, and water phase, and a water and solids phase;
(c) recycling said very dilute bitumen phase produced in the first gravity separation step to the counter-current decantation system;
(d) subjecting the mixed very dilute bitumen, precipitated asphaltenes, and water phase produced in said first gravity separation step to a second gravity separation step to produce a very dilute bitumen phase, a solvent and precipitated asphaltenes phase, and a water phase;
(e) filtering the water and solids phase produced in said first gravity separation step and thereby produce filtered solids which are discarded as tails and a water filtrate which is recycled to the tar sands treatment process;
(f) recycling the very dilute bitumen phase produced in said second gravity separation to said first gravity separation step;
(g) subjecting said solvent and precipitated asphaltenes phase produced in the second gravity separation step to distillation to produce a vapor of the solvent which is condensed and then recycled to said first gravity separation step and thereby produce precipitated asphaltenes solid substantially free of solvent which may be discarded as tails; and
(h) finally recycling the water phase produced in the second gravity separation step to the tar sands treatment process.
According to one embodiment of the present invention a process is provided for the extraction of bitumen from bitumen froth produced from a tar sands water conditioning counter-current decantation process using a paraffinic hydrocarbon as the solvent which dilutes the bitumen and substantially removes the water, solids, and precipitated asphaltenes therefrom.
According to a fiuther aspect of the present invention a process is provided for the extraction of bitumen from bitumen froth produced from a tar sands water conditioning process in which the paraffinic hydrocarbon utilized as the solvent in the counter-current decantation process has a chain length from 4 to 8 carbons.
In a still further embodiment of the present invention, a process is provided for the extraction of bitumen from bitumen froth produced from a tar sands water conditioning process in which the paraffinic hydrocarbon utilized as the solvent comprises a major proportion of said paraffinic solvent in intimate mixture with a minor proportion of aromatic solvent.
According to a still further aspect of the present invention, a process is provided for the extraction of bitumen from bitumen froth produced from a tar sands water conditioning process wherein the paraffinic hydrocarbon utilized as the solvent in the counter-current decantation process is comprised of a mixture of pentane and hexane.
According to a still ftrther aspect of the present invention, a process is provided for the extraction of bitumen from bitumen froth produced from a tar sands water conditioning process in which the paraffinic hydrocarbon utilized as the solvent comprises a mixture of about 50% by weight pentane and about 50% by weight hexane.
Because the present invention does not require the use of caustic in the initial tar sands conditioning process and utilizes a CCD circuit in place of centrifugation for bitumen recovery from the froth concentrate, it is able to efficiently extract bitumen from tar sands without producing clay dispersion sludges and without utilizing centrifuges which are prone to plugging by precipitated asphaltenes following dilution. Since the instant invention utilizes a paraffinic hydrocarbon as a solvent for the bitumen, an exceptionally clean diluted bitumen product having about 0.01 to about 1.00 wt % water and solids is obtained which may be fed directly to a hydrocracker thereby avoiding the necessity of pre-hydrocracker upgrading through the conventional coking process. Finally, because the instant invention utilizes a series of gravity separation stages followed by several material recycle routes for treating the precipitated asphaltenes waste product, a more efficient and environmentally friendly tar sands treatment process results.
The objects and advantages of the instant invention will be more fully understood from the following detailed description of the invention, taken in conjunction with the accompanying drawing and example.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawing is a flow sheet of the process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The instant invention has as its main aim the production of a paraffinically diluted bitumen product produced by means of a counter-current decantation process in which the solids and water content comprise approximately 0.01 to about 1.00 wt %. Thus, the diluted bitumen product can be fed directly to a hydrocracker without intermediate upgrading. The present invention has as its object the extraction of bitumen from bitumen froth produced in a tar sands water-conditioning process without requiring the use of caustic soda as called for in the prior art. The present invention substantially minimizes, if not avoids, the production of tailings sludge, that is to say, clay dispersions. Thirdly, by utilizing a series of gravity separation stages followed by several material recycle routes for treating the precipitated asphaltenes waste product, the instant invention significantly reduces the amount of wastes produced in conventional tar sands treatment processes. However, it should be understood that the instant invention might be practiced to extract bitumen from bitumen froth produced by any known means.
In the following description of the instant invention it should be understood that the term "paraffinic hydrocarbon" used herein refers to the light paraffinic hydrocarbon utilized in the extraction of the bitumen values from the bitumen froth.
In a preferred embodiment, the light paraffinic hydrocarbon utilized in the counter-current decantation process has a chain length from 4 to 8 carbons. In an alternate embodiment, the solvent utilized in the counter-current decantation process comprises a major proportion of a paraffinic solvent in intimate mixture with a minor proportion of an aromatic solvent. In a preferred embodiment, as stated herein, the light paraffinic hydrocarbon utilized in the counter-current decantation process comprises a mixture of pentane and hexane, most preferably a mixture of about 50% by weight pentane and about 50% by weight hexane.
Referring to the Figure, a process flow diagram of the process of the present invention is illustrated. A raw tar sands feed originating from a tar sands deposit is fed through a suitable conduit 1 to a tar sands conditioning mixer 3 where the raw tar sands are mixed with process water which is fed to the mixer 3 through a suitable conduit 2 and any water recycle 4. This mixing occurs at a temperature between about 25 and 55° C. and preferably at a temperature of about 35° C. The reduced conditioning temperature, when compared to a conventional conditioning temperature of about 85° C., results in reduced energy cost and improved process economics. Furthermore, by not requiring the use of caustic soda for tar sands conditioning in mixer 3, the production of sludges through clay dispersion is substantially reduced, if not avoided.
After an amount of time sufficient to mechanically separate, by mixing, the bitumen from the tar sands solids and water, the water/tar sands slurry 5 is transported to flotation cell 6. Air transported by suitable conduit 7 to the flotation cell 6 aerates the water/tar sands slurry producing a bitumen froth 9 and a tar sands tails which is transported to a tailings impoundment via suitable conduit 8.
Bitumen froth 9 produced from flotation cell 6 is then transported via a suitable conduit 10 to deaerator 11 where the froth is heated in order to release trapped air. Preferably, the deaerated bitumen froth contains about 60% by weight bitumen, which is in itself composed of about 10 to 20% by weight asphaenes, about 30% by weight water, and about 10% by weight solids. The deaerated bitumen froth 12 produced by deaerator 11 is then fed to primary mixer 13 where it is mixed with secondary settler overflow produced from the secondary settler 22 and fed to the primary mixer through suitable conduit 15. At this point it may be enlightening to explain the general concepts of counter-current decantation (CCD) and its relation to the present invention.
The primary method of separating pregnant liquor (i.e., the diluted bitumen) from gangue (i.e., the precipitated asphaltenes, water, and solids or in other words the residuum) in the present invention is termed counter-current decantation. The basic aim of gravitational sedimentation through CCD is the increase in gangue concentration and the subsequent decrease in gangue concentration contained in the pregnant liquor (Dahlstrohm, D. A. and Emmet, Jr., R. C. "Solid-Liquid Separations". SME Mineral Processing Handbook, Vol. 2, pp. 13-26 to 13-33. Society of Mining Engineers. 1985.). However, the concentration of underflow solids, or residuum, will generally range from 20-60 wt % and, therefore, contain large quantities of solution. Accordingly, this slurry is diluted again and resettled to recover further the dissolved values. As most hydrometallurgical circuits require dissolved value recoveries of 95-99.5% in the final pregnant liquor this operation must be repeated several times. If the diluting solvent were to be employed for each separation step (even if available) the pregnant liquor volume would become too large, with a consequent increase in recovery cost and a considerable loss in chemicals. Accordingly a counter-current method is employed where the solids move in the opposite direction from the liquid, and dilution solution is added only to the last one or two separation steps (in the instant invention, the solvent is added to the last stage only). Basically, as the liquid moves forward from the last separation stage it is increasing in dissolved value concentration, while the liquid portion of the solids decreases in dissolved values as it passes towards the final separation stage. Accordingly, separation is actually achieved by dilution and solids concentration through sedimentation at each stage.
Again by inspecting the Figure, the CCD circuit of the present invention can be compared to the explanation given above. As explained above, the finction of the CCD circuit of the instant invention is to increase the concentration of the precipitated asphaltenes, solids, and water while simultaneously washing the bitumen through dilution with a solvent from the precipitated asphaltenes, solids, and water contained in the bitumen froth. The instant invention, however, differs from the above description in that each separation stage or settler is coupled with a mixing stage. This is because in order for there to be adequate washing and separation of diluted bitumen from the highly viscous precipitated asphaltenes, the underflow, or residuum, from each settler, excluding the bitumen froth tailings from the tertiary settler 27, must be remixed in the following mixer.
Again, attention should be directed to the Figure. As explained above, the deaerated bitumen froth 12 produced by deaerator 11 is fed to primary mixer 13 where it is mixed with secondary settler overflow produced from the secondary settler 22, containing a large proportion of diluted bitumen and solvent, fed through suitable conduit 15. During mixing in primary mixer 13, the secondary settler overflow 15, containing diluted bitumen and solvent, solvates a portion of the bitumen contained in the bitumen froth and precipitates a portion of the contained asphaltenes. This mixture then flows through conduit 14 into the primary settler 16 where the gangue, containing some bitumen, precipitated asphaltenes, water, and solids, is separated from the diluted bitumen which flows through conduit 17 and is collected as a dilute bitumen product. Surprisingly, it has been found that this dilute bitumen product contains approximately 0.01 to about 1.00 wt % solids and water which renders it amenable to direct hydrocracking, thereby avoiding expensive upgrading through coking.
It is also important to point out that the dilute bitumen product contains a solvent to bitumen ratio of about 2 to 1. By utilizing a solvent to bitumen ratio of 2 to 1, a large amount of the dirty asphaltenes are precipitated out and removed from the diluted bitumen product while the lower molecular weight asphaltenes, which add to the value of the bitumen, are conserved in the dilute bitumen product and contribute to the overall oil recoveries from the tar sands.
A proposed mechanism of this bitumen dilution and asphaltenes precipitation can be understood by first considering the makeup of the heavy hydrocarbon feedstock (i.e., the bitumen). The bitumen is essentially a mixture of a solvent, composed of light hydrocarbons and aromatics, and heavy hydrocarbons, containing the asphaltenes, which are held in solution with the lighter hydrocarbons by the aromatics. Upon the addition of a light paraffinic hydrocarbon such as pentane or hexane, which has a low solvency power for the asphaltic materials, the solvency power of the light hydrocarbons contained in the bitumen is reduced. Effectively, the addition of the light paraffinic hydrocarbon diluent results in its dissolution into the bitumen. Upon continued addition of the light paraffinic hydrocarbon diluent, the asphaltic materials begin to precipitate out of solution when the peptizing action of the aromatics in the feed is lost. In essence, the light paraffinic hydrocarbon diluent acts as an anti-solvent throwing the asphaltic materials out of the bitumen. It has been found that this asphaltenes precipitation occurs at a diluent to bitumen ratio of about 0.7 to 1, when hexane is utilized as the light paraffinic hydrocarbon diluent.
As more hydrocarbon diluent is added, further precipitation of the asphaltenes will occur. However, continued increases in the amount of diluent added results in the re-dissolving of some of the earlier precipitated materials. This is because although the light paraffinic hydrocarbon diluent is an anti-solvent, it has some solvency power for the heavy hydrocarbon material, and if present in excess, will start to dissolve more of the precipitated heavy hydrocarbons until it is saturated. The point at which the light paraffinic hydrocarbon diluent switches from an anti-solvent to a solvent occurs at a diluent to bitumen ratio of about 2 to 1.
Because the instant invention utilizes this asphaltenes precipitation phenomena occurring at a low diluent ratio for effective bitumen extraction, a reduction in the amount of diluent to be pumped around the system and ultimately recovered is achieved. This is a definite advantage of the instant invention because a low inventory of diluent results in a commercial scale plant with smaller unit operations rendering the process less capital intensive. Furthermore, as mentioned above, the precipitation of the heaviest and dirtiest asphaltenes by the instant invention results in a dilute bitumen product amenable to direct hydrocracking.
Again, attention should be directed to the Figure and primary settler 16 illustrated therein. The streams exiting primary settler 16 are dilute bitumen product 17 and primary settler underflow transported via conduit 18 to the secondary mixer 19. Upon entering secondary mixer 19, the solids underflow from the primary settler 16 are mixed with the overflow from tertiary settler 27 and fed to the secondary settler 22 through conduit 20. The effective diluent to bitumen ratio achieved in secondary mixer 19 is approximately 20 to 1. The high diluent content of the tertiary settler overflow acts to dissolve a large proportion of the hydrocarbons contained in the primary settler underflow via the mechanism explained above.
The mixture produced in secondary mixer 19 is then transferred via conduit 20 to the secondary settler 22 for separation again into a diluted bitumen and diluent phase and a solids phase. The diluted bitumen and diluent phase exiting the secondary settler 22 through conduit 15 enters primary mixer 13 for mixing with the deaerated bitumen froth 12. The underflow from the secondary settler 22 is transferred through conduit 23 to the tertiary mixer 24.
Upon entering tertiary mixer 24, the solids underflow from the secondary settler 22 is mixed with fresh solvent fed to the tertiary mixer through conduit 26. The effective diluent to bitumen ratio achieved in tertiary mixer 24 is approximately 70 to 1. This extremely high diluent to bitumen ratio acts to scrub the solids underflow of secondary settler 22 by dissolving a major proportion of the contained hydrocarbons but excluding the dirtiest and heaviest precipitated asphaltenes. In this way, all of the valuable hydrocarbons contained in the bitumen are extracted leaving behind only those hydrocarbons which are extremely heavy and dirty and which, if extracted, would render the dilute bitumen product unsuitable for direct hydrocracking.
After mixing in tertiary mixer 24, the mixture is transferred via conduit 25 to the tertiary settler where the diluted bitumen and diluent phase is separated from the solids phase containing the heaviest and dirtiest asphaltenes, sand, clay, silt, water, residual bitumen, and diluent. The overflow from tertiary settler 27 flows through conduit 21 into the secondary mixer 19 where it is mixed with the underflow from the primary settler 16.
The underflow, or residuum, from the tertiary settler 27, now termed bitumen froth tailings 28, is then transferred to the primary gravity separation 30 where the bitumen froth tailings 28 separate into three separate phases; the very dilute bitumen phase 31, the very dilute bitumen/precipitated asphaltenes/water phase 32, and a water/solids phase 33. From the primary gravity separation 30, the very dilute bitumen phase 31 is transferred via conduit 34 and combined with the deaerated bitumen froth 12 entering the primary mixer 13 of the CCD circuit. The very dilute bitumen/precipitated asphaltenes/water phase 32 is transferred via conduit 35 to the secondary gravity separation unit 37 with the water/solids phase 33 exiting the primary gravity separation 30 via conduit 36 to the filter 43.
The water/solids phase 33 entering the filter 43 is filtered to produce a solids tails containing sand, clays, and silt, and a water filtrate. The solids tails exiting the filter 43 are conveyed to tailings impoundment through conduit 44. The water filtrate produced by filter 43 is transferred through conduit 45 into water recycle conduit 4, returning it to tar sands processing mixer 3.
The very dilute bitumen/precipitated asphaltenes/water phase 32 transferred to secondary gravity separation 37 is separated into three phases; a very dilute bitumen phase 38, a solvent and precipitated asphaltenes phase 39 and a water phase 40. The very dilute bitumen phase 38 exits the secondary gravity separation 37 through conduit 41 to the very dilute bitumen recycle conduit 29 and combined with the bitumen froth tailings 28 which is fed to the primary gravity separation. The solvent and precipitated asphaltenes phase 39 exits secondary gravity separation 37 through conduit 42 and is fed to solvent and precipitated asphaltenes distillation 46. The water phase 40 exits the secondary gravity separation 37 and is combined with water filtrate 45 and fed as water recycle 4 to the tar sands processing mixer 3.
The solvent and precipitated asphaltenes phase 39, upon entering solvent/precipitated asphaltenes distillation 46 is separated into an asphaltenes tails which exits solvent and precipitated asphaltenes distillation 46 through conduit 48 and is discarded. The solvent vapor 47 exiting solvent and precipitated asphaltenes distillation 46 enters condenser 49 and exits as a condensed solvent recycle 50 which is combined with the very dilute bitumen exiting the primary gravity and bitumen froth tailings 28 and fed to primary gravity separation 30.
The process of the present invention is further described in the following example, which is non-limiting with respect to the scope of the process of the present invention.
EXAMPLE 1
This example illustrates the product streams produced by the present invention. The deaerated bitumen froth utilized as feed in this example was prepared from an Athabasca tar sands sample which was treated in a water conditioning process without the use of caustic soda. In this example, the paraffinic hydrocarbon utilized as the solvent in the three-stage counter-current decantation process was comprised of a mixture of about 50% by weight pentane and about 50% by weight hexane with the extraction proceeding at a temperature of about 25° C.
After extraction, the C 5 asphaltenes content of the bitumen froth feed, the diluted bitumen product, and bitumen froth tailings was determined by dissolving a portion of each in an excess amount of pentane. The amount of asphaltenes precipitated from each of these components was then separated and weighed giving the relative C 5 asphaltenes contents of each of the streams.
The bitumen, water, and solids content of the bitumen froth feed, the diluted bitumen product, and bitumen froth tailings was determined utilizing the Dean Stark method. The mass distributions of solvent, bitumen, water, solids, and C 5 asphaltenes in the solvent feed, bitumen froth feed, dilute bitumen product, and bitumen froth tailings are given below in Table 1.
TABLE 1__________________________________________________________________________Mass Distributions of Components. Solvent Bitumen Water Solids C.sub.5 Asphaltenes Total Stream (g) (g) (g) (g) (g) (g)__________________________________________________________________________Solvent Feed 1148.00 0.00 0.00 0.00 0.00 1148.00 Bitumen Froth Feed 0.00 490.00 184.00 172.00 147.00 993.00 Dilute Bitumen 1013.77 457.72 0.05 0.05 98.00 1569.59 Product Bitumen Froth 134.23 32.28 183.95 171.95 49.00 571.41 Tailings__________________________________________________________________________
As can be seen from Table 1, above, the majority of the bitumen contained in the bitumen froth reported to the dilute bitumen product while the water and solids contained in the feed reported to the bitumen froth tailings. The weight percentages of each of the components contained in the dilute bitumen product and bitumen froth tailings are given in Table 2, below:
TABLE 2______________________________________Weight Percentage Distribution of Components. Solvent Bitumen Water Solids C.sub.5 Asphaltenes Stream (wt. %) (wt. %) (wt. %) (wt. %) (wt. %)______________________________________Dilute Bitumen 88.31 93.41 0.03 0.03 66.67 Product Bitumen Froth 11.69 6.59 99.97 99.97 33.33 Tailings Total 100.00 100.00 100.00 100.00 100.00______________________________________
As can be seen from Table 2, above, the weight percentages of water and solids in the dilute bitumen product are exceptionally low rendering it amenable to direct hydrocracking. Furthermore, as evidenced by the bitumen content of the diluted bitumen product, it can be seen that this example of the inventive process resulted in better than 93% bitumen recovery from the bitumen froth. Therefore, it is seen by example that the inventive process results in an high-grade, ultra-clean dilute bitumen product and a bitumen froth tailings containing substantially all of the water and solids contaminants present in the bitumen froth.
The invention, as disclosed, utilizes a series of three mixer-settler units in the CCD circuit. However, it should be understood that any number of mixer-settler pairs could be utilized depending upon the ease or difficulty of the bitumen extraction from the particular deaerated bitumen froth feed. That is, deaerated bitumen froths that are more easily treated may not require three stages and may only require two. Conversely, deaerated bitumen froths representing more difficult separation could require more than three stages for effective bitumen extraction.
It should be understood that another separation method such as flotation may be utilized in place of the disclosed first and second gravity separation steps for treatment of the bitumen froth tailings produced from the CCD circuit. That is, although the present invention has been described in conjunction with preferred embodiments, it is to be understood that modifications and variations may be resorted to without departing from the spirit and scope of the invention as those skilled in the art will readily understand. Such modifications and variations are considered to be within the purview and scope of the invention and the appended claims.
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A process for the extraction of bitumen from bitumen froth generated from tar sands is presented. In this process bitumen froth, extracted from tar sands using a water process not requiring the use of caustic soda, is treated in a counter-current decantation circuit with a paraffinic solvent to remove precipitated asphaltenes, water, and solids from the bitumen froth. The instant invention produces a dilute bitumen product having final water and solids content of about 0.01 to about 1.00% by weight rendering the dilute bitumen product amenable to direct hydrocracking. This process provides an alternative route to the conventional process utilizing centrifuges to separate bitumen from precipitated asphaltenes, water, and solids thereby avoiding the high capital and operating costs associated with the conventional bitumen froth treatment by centrifugation. Because the invention utilizes bitumen froth produced from a water process that does not require the use of caustic soda, it advantageously avoids the production of tailings sludges through clay dispersion. Furthermore, because the diluted bitumen product can be directly hydrocracked, the instant invention avoids the conventional and capital intensive upgrading steps, such as coking, which are required for treatment of the dilute bitumen product produced in the traditional naphtha dilution and centrifugation bitumen extraction process.
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FIELD
There is described a method of increasing the efficiency of a Y strainer and a Y strainer that has been modified in accordance with the teachings of the method.
BACKGROUND
Y strainers are used to capture particulate matter in piping systems. They are so named due to their Y shaped configuration. Y strainers have also been referred to as Y “filters”. Whether a label of a Y “strainer” or Y “filter” is given to the device depends upon aperture size. As a general rule, Y devices which only are capable of capturing contaminants larger than 200 microns are termed “strainers” and Y devices apertures which are capable of capturing contaminants smaller than 200 microns are terms “filters”. For the purpose of this paper, no such distinction will be made and the term of Y strainer will be used in its broader more inclusive sense to denote the configuration.
When a hydrocarbon producing well has a sand problem, there are known sand separators that can be placed on the well. These sand separators are expensive units costing over $100,000.00 and are, therefore, only placed on wells that clearly have a long term, as opposed to a temporary sand problem.
When formation conditions are appropriate, hydrocarbon producing wells are stimulated by fracturing the formation with sand, a technique known as “fracing”. For this fracing procedure, very fine abrasive sand is used. Problems are being experienced with some of this fine abrasive sand appearing, without warning, in well production. The problem is not apparent until it manifests itself and sand starts appearing in the equipment. When it occurs, it can be difficult to determine whether the formation is merely “burping” small amounts of sand periodically or whether there is a more serious sand problem requiring a sand separator. The problem cannot be ignored. Even when present in small quantities, sand can damage equipment. When present in larger quantities, abrasive sand can wear through pipes and cause serious problems resulting in leakage into the environment and the threatening the lives of oil field workers.
Attempts have been made to use Y strainers until the magnitude of any sand problem can be determined. These attempts have been unsuccessful. The Y strainers presently available are not able to deal with the fine abrasive sand. There will now be described a method that was used to make the Y strainer more efficient in dealing with fine sand and a form of Y strainer that was built in accordance with the teachings of the method.
SUMMARY
According to one aspect, there is provided a method of increasing efficiency of a Y strainer. The Y strainer is of the type that has a filter cartridge receiving inflow through one end and outflow through apertures in a peripheral sidewall. The method involves slowing a velocity of fluids entering the filter cartridge of the Y strainer by having the fluids pass from a first bore of a first diameter into a second bore of a second diameter which is at least 50% larger than the first diameter prior to entering the filter cartridge. The filter cartridge also has the second diameter.
It was determined that by having fluids pass into a larger bore, the velocity of the fluids was reduced and a Y strainer that had previously had been ineffective captured a majority (over 75%) of the sand.
It was subsequently determined that the velocity of fluids entering the filter cartridge of the Y strainer could be further slowed by positioning a physical barrier across an inlet pipe, such that the fluids strike the physical barrier prior to entering the filter cartridge. The physical barrier used was a deflector plate. The deflector plate was originally added to protect the filter element. However, it was determined that the addition of the deflector plate also served to increase efficiency by bringing the amount of sand captured to over 90%.
According to another aspect, there is provided a Y strainer assembly constructed in accordance with the teachings of the method. The Y strainer has an inlet pipe having a first portion of a first diameter and a second portion of a second diameter that is 50% larger than the first diameter. An outlet pipe of similar construction is provided having a first portion of the first diameter and a second portion of the second diameter. A cartridge receiving pipe of the second diameter is in fluid communication with the second portion of the inlet pipe and the second portion of the outlet pipe. Fluids pass from the inlet pipe into the cartridge receiving pipe and from the cartridge receiving pipe into the outlet pipe. The cartridge receiving pipe has a closure which can be opened to facilitate insertion of a filter cartridge. A filter cartridge is provided having an inlet at an inlet end for receiving an inflow of fluids from the inlet pipe and apertures in a peripheral sidewall through which an outflow of fluids pass into the outlet pipe.
As described in relation to the method, the operation of the Y strainer assembly can be enhanced through the use of a deflector. It is preferred that the filter cartridge support a deflector, such that fluids flowing along the inlet pipe strike the deflector and are deflected into the inlet end of the filter cartridge.
In order to further improve performance, the filter cartridge has been modified to include an inner sleeve with flow apertures and a flexible mesh filter which is retained between the inner sleeve and the peripheral sidewall. The inner sleeve both supports and protects the flexible mesh filter. The flexible mesh filter can readily be inspected for wear and replaced.
In order to further improve performance, the filter cartridge has been modified so that the inlet end of filter cartridge defines a wedge. The wedge at the inlet end is wedged into the inlet pipe to make a connection through which fluids flow from the inlet pipe into the inlet end of the filter cartridge.
In order to monitor sand accumulation, an upstream sensor is positioned in the inlet pipe upstream of the filter cartridge and a downstream sensor is positioned in the outlet pipe downstream of the filter cartridge. A differential in output between the upstream sensor and the downstream sensor providing an indication of sand accumulation within the filter cartridge.
In order to empty the filter cartridge, a blow down valve is positioned in the closure of the cartridge receiving pipe. This allows service personnel to rapidly purge sand accumulations from the filter cartridge.
It is also preferred that valves are positioned on the inlet pipe and the outlet pipe. These valves can be used for a variety of purposes. One purpose is to selectively isolate the Y strainer. Another purpose is injection of chemicals, such as methanol.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features will become more apparent from the following description in which reference is made to the appended drawings, the drawings are for the purpose of illustration only and are not intended to be in any way limiting, wherein:
FIG. 1 is a top plan view of a Y strainer assembly.
FIG. 2 is a front elevation view of the Y strainer assembly shown in FIG. 1 .
FIG. 3 is an exploded view of the cartridge receiving pipe and filter cartridge.
FIG. 4 is an exploded view of a filter cartridge.
FIG. 5 is a top plan view of the cartridge receiving pipe and filter cartridge.
FIG. 6 is an exploded view of a variation of the cartridge receiving pipe and filter cartridge.
FIG. 7 is a top plan view of a variation of a Y strainer assembly.
FIG. 8 is a front elevation view of the variation of the Y strainer assembly shown in FIG. 7 .
FIG. 9 is an exploded view of a filter cartridge used in the Y strainer assembly shown in FIG. 7 .
DETAILED DESCRIPTION
A Y strainer assembly generally identified by reference numeral 10 , will be described with reference to FIG. 1 through 5 . A variation of the Y strainer assembly generally identified by reference numeral 100 , will be described with reference to FIG. 6 through FIG. 9 .
Structure and Relationship of Parts:
Referring to FIG. 1 , a Y strainer assembly 10 has an inlet pipe 12 with a first portion 14 of a first diameter and a second portion 16 of a second diameter that is 50% larger than the first diameter. An outlet pipe 18 has a first portion 20 of the first diameter and a second portion 22 of the second diameter. Referring to FIG. 2 and FIG. 5 , a cartridge receiving pipe 26 of the second diameter is in fluid communication with the second portion 16 of the inlet pipe 12 and the second portion 22 of the outlet pipe 18 . When filter cartridge 30 is in position, fluids are unable to pass directly from inlet pipe 12 to outlet pipe 18 without first passing through filter cartridge 30 . With filter cartridge 30 in position, fluids pass from the inlet pipe 12 into the cartridge receiving pipe 26 and from the cartridge receiving pipe 26 into the outlet pipe 18 . The cartridge receiving pipe 26 has a closure 28 which can be opened to facilitate insertion of filter cartridge 30 . Referring to FIG. 3 , filter cartridge 30 has an inlet 32 at an inlet end 34 for receiving an inflow of fluids from the inlet pipe 12 and apertures 36 in a peripheral sidewall 44 through which an outflow of fluids pass into the outlet pipe 18 . An end plate 33 with a centrally positioned blow down opening 31 is positioned at the opposite end 35 from inlet end 34 of filter cartridge 30 . Blow down valve 52 is passed through blow down opening 31 when closure 28 is in the closed position.
In the embodiment shown, filter cartridge 30 supports a deflector 38 . Fluids flowing along the inlet pipe 12 , strike the deflector 38 and are deflected into the filter cartridge 30 . Referring to FIG. 4 , filter cartridge 30 has an inner sleeve 40 with flow apertures 42 and a flexible mesh filter 43 which is retained between the inner sleeve 40 and the peripheral sidewall 44 . Referring to FIG. 3 , inlet end 34 of filter cartridge 30 defines a wedge 45 which is wedged into the inlet pipe 12 to make a connection through which fluids flow from the inlet pipe 12 into the inlet end 34 of the filter cartridge 30 .
Referring to FIG. 1 and FIG. 2 , an upstream sensor 46 is positioned in the inlet pipe 12 upstream of the filter cartridge 30 and a downstream sensor 48 is positioned in the outlet pipe 18 downstream of the filter cartridge 30 . A differential sensor 50 compares the outflow between the upstream sensor 46 and the downstream sensor 48 which provides an indication of sand accumulation within the filter cartridge 30 . The above described sensors can be isolated from fluid flow, for servicing by closing valves 49 . Referring to FIG. 1 , a blow down valve 52 is positioned in the closure 28 of the cartridge receiving pipe 26 ; to permit a conduit 53 to be attached through which sand accumulations on the filter cartridge 30 may be purged. Referring to FIG. 1 and FIG. 2 , valves 54 are positioned on the inlet pipe 12 and the outlet pipe 18 to permit the injection of fluids either upstream or downstream of filter cartridge 30 of Y strainer assembly 10 . Valves 55 are positioned at either end of Y strainer assembly 10 and provide means of isolating Y strainer assembly 10 during servicing and maintenance.
Operation:
Referring to FIG. 3 , closure 28 is opened and a cartridge 30 is inserted into cartridge receiving pipe 26 such that inlet end 34 of filter cartridge 30 receives an inflow of fluids from the inlet pipe 12 and an outflow of fluids into the outlet pipe 18 must pass through filter cartridge 30 . Referring to FIG. 1 , fluid flows through inlet pipe 12 through first portion 14 into second portion 16 . Due to the difference in diameter between first portion 14 and second portion 16 , the velocity of fluid is slowed. Fluid strikes deflector 38 , which deflects the fluid into cartridge 30 and further slows the velocity of the fluid. Referring to FIG. 1 and FIG. 2 , upstream sensor 46 senses the pressure of fluid flowing through inlet 12 and downstream sensor 48 senses the pressure of fluid flowing through outlet 18 . Differential 50 provides an indication of sand accumulation within the filter cartridge 30 by comparing the outflow between the upstream sensor 46 and the downstream sensor 48 . Valves 55 may be used to selectively isolate the Y strainer. Valves 54 may be used inject chemicals into Y strainer assembly 10 , either upstream or downstream of filter cartridge 30 . Valves 57 may be used to selectively isolate the upstream sensor 46 and the downstream sensor 48 from the Y strainer assembly 10 to allow for maintenance or replacement of sensors 46 and 48 . Referring to FIG. 1 , periodically conduit 53 may be attached to blow down valve 52 and sand that has accumulated within the filter cartridge 30 may be purged using either system pressure or a circulation of fluids through valves 54 .
The velocity of fluids entering the filter cartridge 30 is slowed as fluids pass from first portion 14 of inlet pipe 12 to second portion 16 which has a larger diameter prior to entering the filter cartridge 30 . The velocity is further slowed by deflector 38 which is positioned across inlet pipe 12 at the inlet into filter cartridge 30 . The slowing of the velocity of the fluids passing through Y strainer assembly 10 has a dramatic effect on the ability of the Y strainer assembly to remove the sand. The use of the deflector 38 also helps to protect the filter elements in filter cartridge 30 .
When building test units going from a 4 inch diameter to a 6 inch diameter worked well. However, when a unit was built going from a 4 inch diameter to an 8 inch diameter it worked even better.
Advantages:
The Y strainer described above provides a number of advantages:
There are devices that will work either when there is sand in gas or when there is sand in oil, but not both. The Y strainer described above can work with either gas or oil. There are devices that are adversely affected by the presence of hydrates and condensates. The Y strainer described is not particularly sensitive to the presence of hydrates and condensates. There are devices that can only operate efficiently within specified flow rate parameters and pressure level parameters. The Y strainer described above can work over a wide variety of flow rates and pressure levels. Competitive sand removal devices are very expensive in comparison to the Y strainer described above. The foot print of the Y strainer is relatively small and installation relatively simple, when compared to other sand removal technologies. The Y strainer can be rapidly blown down in situ, to remove accumulated sand and place the Y strainer back into service. The Y strainer can have sensors attached to determine the amount of sand accumulated. This can be as simple as an upstream and downstream pressure gauge that can be viewed by personnel on site or can be sensors that tie into a SCADA system for remote monitoring. There are other devices with respect to which replacing worn parts can be relatively expensive. The primary consumable with the Y strainer described above is the flexible mesh. The flexible mesh costs approximately $10.00 and can be changed out in 15 to 20 minutes. The “wedge” seating of the canister ensures correct placement. The flexible mesh is protected by both the deflector plate and the interior sleeve.
Variations:
A variation of a Y strainer assembly, generally referenced as numeral 100 will now be described with reference to FIG. 6 and FIG. 7 .
Referring to FIG. 7 , Y strainer assembly 100 has an inlet pipe 102 with a first portion 104 of a first diameter and a second portion 106 of a second diameter that is 50% larger than the first diameter. An outlet pipe 108 has a first portion 120 of the first diameter and a second portion 122 of the second diameter. A cartridge receiving pipe 126 of the second diameter is in fluid communication with the second portion 106 of the inlet pipe 102 and the second portion 122 of the outlet pipe 108 . When filter cartridge 130 is in position, fluids are unable to pass directly from inlet pipe 102 to outlet pipe 108 without first passing through filter cartridge 130 . With filter cartridge 130 in position, fluids pass from the inlet pipe 102 into the cartridge receiving pipe 126 and from the cartridge receiving pipe 126 into the outlet pipe 108 . The cartridge receiving pipe 126 has a closure 128 which can be opened to facilitate insertion of filter cartridge 130 .
Referring to FIG. 6 , filter cartridge 130 has an inlet 132 at an inlet end 134 for receiving an inflow of fluids from the inlet pipe 102 and apertures 136 in a peripheral sidewall 144 through which an outflow of fluids pass into the outlet pipe 108 . Referring to FIG. 9 , filter cartridge 130 has an inner sleeve 140 with flow apertures 142 and a flexible mesh filter 143 which is retained between the inner sleeve 140 and the peripheral sidewall 144 . Referring to FIG. 6 , an end plate 133 is positioned at the opposite end 135 from inlet end 134 of filter cartridge 130 . End plate 133 has a blow down opening 131 in an off center position along a lower side 137 when filter 130 is in position at an angle. This off center position allows for removal of virtually all of the sand on blow down. It was discovered during field tests that with a centrally positioned blow down opening a residue of sand would remain trapped along the edges of filter cartridge 130 . A blow down opening 131 in an off center position removes a greater amount of sand along the edges of filter cartridge 130 as sand from above falls to the lower side of filter cartridge 130 and a blow down through opening 131 directs the blow down to the lower side of filter cartridge 130 . In the embodiment shown, filter cartridge 130 supports a deflector 138 . Fluids flowing along the inlet pipe 102 , strike the deflector 138 and are deflected into the filter cartridge 130 .
Referring to FIG. 7 and FIG. 8 , an upstream sensor 146 is positioned in the inlet pipe 102 upstream of the filter cartridge 130 and a downstream sensor 148 is positioned in the outlet pipe 108 downstream of the filter cartridge 130 . A differential sensor 150 compares the outflow between the upstream sensor 146 and the downstream sensor 148 which provides an indication of sand accumulation within the filter cartridge 130 . Valves 157 may be used to selectively isolate the upstream sensor 146 and the downstream sensor 148 from the Y strainer assembly 100 to allow for maintenance or replacement of sensors 146 and 148 . Referring to FIG. 8 , the above described sensors can be isolated from fluid flow, for servicing by closing valves 149 . Referring to FIG. 7 , valves 154 are positioned on the inlet pipe 102 and the outlet pipe 108 to permit the injection of fluids either upstream or downstream of filter cartridge 130 of Y strainer assembly 100 . Valves 155 are positioned at either end of Y strainer assembly 100 and provide means of isolating Y strainer assembly 100 during servicing and maintenance. A series of valves 158 and 160 are positioned beyond closure 128 and in communication with a drain 162 and blow down opening 131 that enables a blow down procedure to be performed by opening and closing valves 158 and 160 to utilize system pressure. Beneficial results have been seen when valve 158 is a ball valve and valve 160 is a choke valve, however it will be understood that different types of valves may be used. This allows everything to remain online during the blow down to optimize production capacity of assembly 100 .
In this patent document, the word “comprising” is used in its non-limiting sense to mean that items following the word are included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one of the elements.
The following claims are to be understood to include what is specifically illustrated and described above, what is conceptually equivalent, and what can be obviously substituted. Those skilled in the art will appreciate that various adaptations and modifications of the described embodiments can be configured without departing from the scope of the claims. The illustrated embodiments have been set forth only as examples and should not be taken as limiting the invention. It is to be understood that, within the scope of the following claims, the invention may be practiced other than as specifically illustrated and described.
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A method of increasing efficiency of a Y strainer and Y strainer modified in accordance with the method. The Y strainer is of the type that has a filter cartridge receiving inflow through one end and outflow through apertures in a peripheral sidewall. The method involves slowing a velocity of fluids entering the filter cartridge of the Y strainer by having the fluids pass from a first bore of a first diameter into a second bore of a second diameter which is at least 50% larger than the first diameter prior to entering the filter cartridge. The filter cartridge also has the second diameter. This modification has been found to dramatically improve the performance of the Y strainer.
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BACKGROUND OF THE INVENTION
The present invention relates to a game device, a control method for a game and a program, and particularly relates to technology for implementing a ball game such as, for example, a soccer game or basketball game etc. with one or a plurality of game characters constituting a first team made to correspond to a first region, one or a plurality of game characters constituting a second team made to correspond to a second region, and a ball being arranged at a field provided with the first region and the second region, with the ball being made to move on the field, in such a manner that the ball is caused to move to within goals arranged at the first region or second region corresponding to the opposing team on a computer etc.
Degree of ball penetration for during the game is calculated in software for implementing a soccer game on a computer, and is used for reference displaying. The software determines which game character of which team is in possession of the ball during games, the penetration factor is calculated by adding up this time, and this is displayed.
The degree of ball penetration can frequently be used as one factor for determining which team is superior. However, the degree of ball penetration rises when possession of the ball takes place in defensive regions even if an attack does not take place. The degree of ball penetration and progress therefore do not always coincide, and this is therefore not always appropriate in progress analysis.
SUMMARY OF THE INVENTION
In order to resolve the aforementioned problems, the present invention provides a game device, game control method and program capable of evaluating and displaying progress in a more reliable manner in the case of implementing a soccer game or basketball game etc.
In order to resolve the aforementioned problems, a game device of the present invention, with one or a plurality of game characters constituting a first team made to correspond to a first region, one or a plurality of game characters constituting a second team made to correspond to a second region, and a ball being arranged at a field provided with the first region and the second region, with the ball being made to move on the field, for executing a ball game where the ball is caused to move to within goals arranged at the first region or second region corresponding to the opposing team, comprises means for storing progress variables expressing extent of superiority of the first team, means for determining which team is in possession of the ball, means for acquiring the ball position and the position of the game character in possession of the ball as a possession position, progress variable updating means for executing processing to enable the progress variable to approach a prescribed first fixed value when the first team is in possession of the ball and the ball is within a first attacking preparation region common to part or all of the first region, and executing processing to increase the progress variable when the first team is in possession of the ball and the possession position is outside of the first attacking preparation region, and means for displaying according to the progress variable.
Further, a control method for a game of the present invention for enabling games to function on a game device with one or a plurality of game characters constituting a first team made to correspond to a first region, one or a plurality of game characters constituting a second team made to correspond to a second region, and a ball being arranged at a field provided with the first region and the second region, with the ball being made to move on the field, for executing a ball game where the ball is caused to move to within goals arranged at the first region or second region corresponding to the opposing team, comprises a step of storing progress variables expressing extent of superiority of the first team, a step of determining which team is in possession of the ball, a step of acquiring the ball position and the position of the game character in possession of the ball as a possession position, a progress variable updating step of executing processing to enable the progress variable to approach a prescribed first fixed value when the first team is in possession of the ball and the ball is within a first attacking preparation region common to part or all of the first region, and executing processing to increase the progress variable when the first team is in possession of the ball and the possession position is outside of the first attacking preparation region and a step of displaying according to the progress variable.
Further, a program of the present invention, with one or a plurality of game characters constituting a first team made to correspond to a first region, one or a plurality of game characters constituting a second team made to correspond to a second region, and a ball being arranged at a field provided with the first region and the second region, with the ball being made to move on the field, for executing a ball game where the ball is caused to move to within goals arranged at the first region or second region corresponding to the opposing team, comprises instructions for causing a computer to function as means for storing progress variables expressing extent of superiority of the first team, means for storing progress variables expressing extent of superiority of the first team, means for determining which team is in possession of the ball, means for acquiring the ball position and the position of the game character in possession of the ball as a possession position, progress variable updating means for executing processing to enable the progress variable to approach a prescribed first fixed value when the first team is in possession of the ball and the ball is within a first attacking preparation region common to part or all of the first region, and executing processing to increase the progress variable when the first team is in possession of the ball and the possession position is outside of the first attacking preparation region, and means for displaying according to the progress variable. The computer may be, for example, a personal computer, a server computer, a household game, an office game, a mobile game, a mobile telephone, or a mobile information terminal, etc. The program may be stored on a computer-readable information storage medium such as, for example, a CD-ROM, DVD-ROM, memory card, or hard-disc, etc.
The game of the present invention is provided with a field, with a first region and second region being provided at the field. For example, compartment lines may be drawn at the center of the field, and first and second regions may be provided to the left and right via the compartment lines. The first team is made to correspond to the first region and the second team is made to correspond to the second region. Goals are arranged at each region. Further, each team is configured of one or a plurality of game characters, and these game characters are arranged at the field together with the ball. The game characters are then operated on the field in accordance with, for example, operations by the controller and computer algorithms and move the ball on the field, with both teams competing to move the ball into the goal arranged at the region corresponding to the opposing team. The aforementioned game may be configured, for example, as a soccer game or basketball game etc., and may be realized using so-called three-dimensional computer graphics or two-dimensional computer graphics.
In the present invention, variables expressing extent of superiority of the first team are stored. The progress variable, is, for example, numeric information of a prescribed range. It is then determined whether or not the team in possession of the ball is the first team or the second team. This determination can be easily implemented utilizing publicly-known technology taking conditions of, for example, the distance between the ball and each game character, the game character in possession of the ball up to this point, whether or not the ball is on the field, or whether or not each game character has come into contact with the ball in a valid manner, etc.
Further, in the present invention, the position of the ball on the field, and the position of the game character in possession of the ball are acquired as a possession position. When the ball is in the possession of the first team, if the ball is within a first attacking preparation region set at the field with the possession position being in common with part or all of the first region, processing is executed to ensure that the progress variable approaches a prescribed first fixed value. Further, if the possession position is outside of the first attacking preparation region, processing is executed to increase the progress variable. Displaying is then carried out according to the progress variable.
According to the present invention, when the first team is in possession of the ball, if the possession position is within the first attacking preparation region, the progress variable approaches a first fixed value. Further, if the first team is in possession of the ball and the possession position is outside of the first attacking preparation region, the progress variable is increased. When game characters constituting the first team remain in possession of the ball and are in the first attacking preparation region sharing part of all of the first region (partially or completely overlapping), the progress variable expressing the degree of superiority of the first team converges on a first fixed value, and the progress of the game can be more accurately evaluated and indicated.
In an aspect of the present invention, the progress variable updating means executes processing to enable the progress variable to approach a prescribed second fixed value the same as or differing from the first fixed value when the second team is in possession of the ball and the ball is within the second attacking preparation region common to part or all of the first region, and executes processing to reduce the progress variable when the second team is in possession of the ball and the possession position is outside of the second attacking preparation region. According to this, when the second team is in possession of the ball, if the possession position is within the first attacking preparation region, the progress variable approaches a second fixed value. Further, if the possession is outside of the second attacking preparation region, the progress variable approaches that expressing that the second team is superior. When game character constituting the second team remain in possession of the ball and are in the second attacking preparation region sharing part of all of the second region (partially or completely overlapping), the progress variable expressing the degree of superiority of the first team converges on a second fixed value, and the progress of the game can be more accurately evaluated and indicated.
Further, in an aspect of the present invention, the game is a soccer game. The progress of the soccer game can therefore be evaluated in a more accurate manner and this may then be displayed.
Further, the first attacking preparation region may also be the same region as the first region. Similarly, the second attacking preparation region may also be the same region as the second region.
Moreover, in an aspect of the present invention, the progress variable has a maximum value and a minimum value, and the first fixed value and the second fixed value are both set to be intermediate values of the maximum value and the minimum value. In doing this, if one team keeps possession of the ball but stays in the attacking preparation region corresponding to this team, the progress variable shows that it cannot be said that either team is superior.
Further, in an aspect of the present invention, the progress variable updating means contains means for increasing and decreasing the progress variable according to the occurrence of a prescribed event if the prescribed event occurs when the ball is in the possession of the first team or the second team. In doing so, it is possible to evaluate the game conditions and display these in a more accurate manner.
Further, an aspect of the present invention further comprises past progress variable storage means for storing a prescribed number of current values for the progress variable every prescribed time and comparison display means for displaying images in order of storage to the past progress variable storage means according to each progress condition stored in the past progress variable storage means in comparison manner. In doing so, it is possible to display changes in progress in a manner that is easy to understand.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view showing a hardware configuration for a game device of an embodiment of the present invention.
FIG. 2 is a perspective view showing a virtual three-dimensional space.
FIG. 3 is a view showing an example of a game screen.
FIG. 4 is a view showing an enlarged progress display image.
FIG. 5 is a block view showing functions of a game device of the embodiment of the present invention.
FIG. 6 is a view showing storage content of the progress variable storage.
FIG. 7 is a flowchart showing progress display processing for the first embodiment of the present invention.
FIG. 8 is a further flowchart showing progress display processing for the first embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The following is a detailed description based on the drawings of a preferred embodiment of the present invention.
FIG. 1 is a view showing a hardware configuration for a game device of an embodiment of the present invention. The game device 10 of FIG. 1 is installed with a DVD-ROM 25 and memory card 28 constituting information storage media at the household game 11 and a monitor 18 and speaker 22 are connected. A household television is used as the monitor 18 with built-in speakers of the television used as the speakers 22 . Further, a DVD-ROM 25 is used to supply the program to the household game 11 but any other information storage media such as CD-ROMs or ROM cards etc. may also be used. Moreover, the program may also be supplied to the household game 11 from a remote location via a data communication network such as the Internet, etc.
The household game 11 is a well-known computer game system including a microprocessor 14 , image processor 16 , main memory 26 , input/output processor 30 , audio processor 20 , controller 32 , and DVD-ROM player 24 . The microprocessor 14 , image processor 16 , main memory 26 , and input/output processor 30 are connected so as to be capable of mutual data communication using a bus 12 , with the controller 32 , audio processor 20 , DVD-ROM player 24 and memory card 28 being connected to the input/output processor 30 . Each configuration element of the household game 11 other than the controller 32 is housed in a case.
The microprocessor 14 controls each part of the household game 11 based on an operating system housed in a ROM (not shown), a program read from the DVD-ROM 25 , and saved data read from the memory card 28 , and provides the game to the player. The bus 12 is for exchanging addresses and data with each part of the household game 11 . The main memory 26 , for example, has a configuration including RAM, which is written with programs read out from the DVD-ROM 25 and saved data read out from the memory card 28 as necessary. The main memory 26 can also be used in operations of the microprocessor 14 for work space. The image processor 16 has a configuration including VRAM. The image processor 16 receives image data sent from the microprocessor 14 , depicts this as a game image on the VRAM based on this, and converts this content to a video signal for output at the monitor 18 at a prescribed timing.
The input/output processor 30 is an interface enabling the microprocessor 14 to access the controller 32 , the audio processor 20 , the DVD-ROM player 24 , and the memory card 28 . The audio processor 20 includes a sound buffer and reads out various audio data such as game music, game effect sounds, and messages etc. from the DVD-ROM 25 and plays back these sounds from the speaker 22 . The DVD-ROM player 24 reads programs recorded on the DVD-ROM 25 in accordance with instructions from the microprocessor 14 . The controller 32 is a general-purpose operation input means for enabling a player to input various game operations. The memory card 28 includes non-volatile memory (for example, EEPROM) and is detachable from the household game 11 . Saved data for various games etc. is stored in the memory card 28 .
A description is now given of technology for displaying the progress of a soccer game constituting a computer game using a game device 10 have the above configuration.
FIG. 2 is a view showing an example of virtual three-dimensional space constructed in a main memory 26 for the game device 10 of this embodiment. At the game device 10 , a soccer game program is stored in the DVD-ROM 25 , and the soccer game is provided at the game device 10 as a result of a microprocessor 14 executing the program. As shown in FIG. 2 , a soccer field object 56 is arranged in the virtual three-dimensional space 50 constructed in the main memory 26 at the game device 10 , and a plurality of soccer player objects (game character objects) 52 and a soccer ball object 54 are arranged on the soccer field object 56 . Similarly, only one soccer player object 52 is shown in FIG. 2 but in reality twenty-two soccer player objects 52 are arranged in the virtual three-dimensional space 50 , with eleven belonging to (corresponding to) a first team and the remaining eleven players belonging to (corresponding to) a second team.
The soccer field object 56 is a rectangular plane-shaped object, depicted to the left and right from the center. Here, the left side is a first region 55 a and the right side is a second region 55 b. A goal object 53 a is provided at an end of the first region 55 a, and a goal object 53 b is provided at an end of the second region 55 b. The first region 55 a and the goal object 53 a correspond to the first team. Further, the second region 55 b and the goal object 53 b correspond to the second team. In this soccer game, each soccer player object 52 is then made to play soccer on the soccer field object 56 in accordance with operation signals inputted using the controller 32 or in accordance with instructions given by the microprocessor 14 . Both teams then compete to move the ball object 54 into the goal objects 53 a or 53 b corresponding to that of the opposing team.
A viewpoint (not shown) is set in the virtual three-dimensional space 50 , and the game device 10 puts the situation of the virtual three-dimensional space 50 as viewed from this viewpoint in the form of an image and displays this on the monitor 18 . FIG. 3 shows an example of a game screen displayed in this manner. As shown in FIG. 3 , a situation is shown where soccer player objects 52 on a soccer field object 56 arranged in the virtual three-dimensional space 50 play soccer is displayed on a game screen 60 , with a progress display image 58 being displayed at the lower left of the game screen 60 .
As shown in an enlarged manner in FIG. 4 , the progress display image 58 contains fifteen graphical images 74 that are strips of the same shape and size extending in a horizontal direction of the screen. The graphical images 74 are arranged with their long sides connecting to each other and with their left and right ends coinciding, and express progress for a certain one minute of soccer carried out in respective virtual three-dimensional spaces 50 . Specifically, each graphical region 74 is formed of two regions where the display conditions such as color etc. are different to the left and right, with the length of a region (here, the hatched region) 70 of one display state indicating the extent of superiority of the first team. Further, the length of a region (here, the whited out region) 68 for another display situation showing the extent to which the second team is superior. When the length of both regions is the same, regions for which the display conditions are different are formed to the left and right from the centers of the graphical images 74 . In this case, neither the first team nor the second team can be said to be superior. The graphical images 74 are arranged from the lower side to the upper side in order of graphical images 74 expressing the oldest state of progress. At the progress display image 58 , an arrow image 66 for displaying a direction for the passage of time is displayed at a position crossing at a central position of each graphical image 74 .
Further, regions 64 for which the display conditions are still different are formed at the left and right end of one part of a graphical image 74 . In the case where a region 64 is formed at a left end, this shows that processing for a tactical change relating to the first team is carried out at a time zone corresponding to this graphical image 74 . Further, in the case where a region 64 is formed at a right end, this shows that processing for a tactical change relating to the second team is carried out at a time zone corresponding to this graphical image 74 .
Further, a score marker image 62 is arranged at the left side and right side of a part of the graphical images 74 . When this score marker image 62 is displayed, it is displayed that there has been a goal at the time zone corresponding to a graphical image 74 arranged to the side of this image. Specifically, when the marker 62 is displayed at the left side of the graphical image 74 , this indicates that the first team has scored a goal at the time zone corresponding to this graphical image 74 . When the marker 62 is displayed at the right side of the graphical image 74 , this indicates that the second team has scored a goal at the time band corresponding to this graphical image 74 .
Further, at the upper side of the graphical image 74 , a strip-shaped current graphical image 72 of the same shape and size as each graphical image 74 is arranged at the upper side of the graphical images 74 so as to come into contact with the long edge of the uppermost graphical image 74 and coincide with the left and right edges.
The following is a specific description of processing for displaying the progress display image 58 described above on a monitor 18 for a soccer game.
FIG. 5 is a functional block view showing the relationship between each software function implemented by the game device 10 . FIG. 5 is a view centering on those functions of the functions implemented by the game device 10 that relate to the present invention. These functions are implemented as a result of programs stored on a DVD-ROM 25 being executed on household game 11 constituting a computer system.
As shown in FIG. 5 , space information storage 90 , progress variable storage 88 , a progress variable update timing monitoring section 86 , a game controller 80 and a progress display section 84 are contained in functions executed using the game device 10 . An event monitoring section 82 is also contained in the game controller 80 . First, the space information storage 90 is configured so as to contain storage means such as a DVD-ROM 25 and main memory 26 etc. and stores various types of data indicating the state of the virtual three-dimensional space 50 . This stores the current position and posture of each soccer player object 52 , the position of the ball object 54 , the goals the first team and second team have up to present point, information identifying the soccer player object 52 currently in possession of the ball object 54 and the team to which this soccer player object belongs, and whether or not a match is in progress.
The game controller 80 implements the soccer game and displays a game screen ( FIG. 3 etc.) for the soccer game on the monitor 18 based on storage content of the space information storage 90 and operation signals inputted by the controller 32 . Further, the game controller 80 updates storage content of the space information storage 90 . An event monitoring section 82 in particular contains the game controller 80 . The event monitor 82 monitors the occurrence of events such as the case where one of the teams scores a goal, the case where processing in order to change tactics relating to one of the teams, or the case where one of the teams shoots (the case where the ball object 54 is kicked strongly towards the goal object 53 a or 53 b in accordance with an operation of a soccer player object 52 belonging to one of the teams) or centers (the case where a soccer player object 52 belonging to one of the teams kicks the ball object 54 a long way towards the front of the goal object 53 a or 53 b corresponding to the opposing team from a corner of the first region 55 a or the second region 55 b corresponding to the opposing team), and gives notification to the progress display section 84 when one of these events occurs.
The progress variable storage 88 contains storage means such as the main memory 26 , etc., and stores progress variables indicating extent of superiority of the first team in the soccer game. The progress variables are numerical data having a range of 0 to 100. FIG. 6 is a view showing storage content of the progress variable storage 88 . As shown in FIG. 6 , the progress variable storage 88 specifically stores a progress variable I corresponding to a current graphical image 72 , past progress variables I 1 to I 15 duplicating and storing progress variables I every one minute, and a numerical value n identifying which of the past progress variables I 1 to I 15 is finally stored. The past progress variables I 1 to I 15 are used to determine lengths of the regions 70 of each graphical image 74 . Further, a numerical value n is used to determine the order of arrangement of the graphical images 74 . Further, the progress variable I is used to determine the length of the region 70 of the current graphical image 72 .
Returning to FIG. 5 , the progress variable update timing monitoring section 86 is for monitoring timing of updating the progress variable I. With this game device 10 , in principle (with the exception of updating according to the occurrence of a prescribed event), updating of the progress variable I is limited to being every prescribed period of time. As a result, the progress variable update timing monitoring section 86 monitors progress variable update timing decided in advance every ten seconds. The progress display section 84 generates the progress display image 58 based on notification content from the event monitor 82 , storage content of the space information storage 90 , and monitoring conditions at the progress variable update timing monitoring section 86 and displays this on the monitor 18 .
FIG. 7 and FIG. 8 are flowcharts illustrating the details of processing of the progress display section 84 . The processing shown in FIG. 7 and FIG. 8 is executed at prescribed times (for example, every 1/60 seconds) based on the program stored in the DVD-ROM 25 .
As shown in FIG. 7 , at the progress display section 84 , first, a determination is made as to whether or not either team is in possession of the ball object 54 (S 101 ). Which soccer payer object 52 of which team is currently in possession of the ball object 54 is stored in the space information storage 90 , and together with this information, the progress display section 84 determines which team is currently in possession of the ball object 54 . It is possible to determine which team is currently in possession of the ball object 54 in a straightforward manner using publicly known technology by taking conditions such as, for example, distance between the ball object 54 and each soccer player object 52 , the soccer player object 52 in possession of the ball object unit 54 until immediately before, whether or not the ball object 54 is within the soccer field object 56 , and whether or not each soccer player object 52 effectively comes into contact with the ball object 54 .
When it is determined that neither team is in possession of the ball object 54 , S 111 is proceeded to. On the other hand, when it is determined that one or other of the teams is in possession of the ball object 54 , next, the possession position of the ball object 54 is acquired, and a determination is made as to whether or not the possession position is within an attacking preparation region (the first region 55 a or the second region 55 b ) corresponding to the team in possession of the ball object 54 (S 102 ). Here, the attacking preparation region is taken to be the region of the first region 55 a or the second region 55 b corresponding to the team, i.e. the defensive region of that team. The possession position of the ball object 54 may be, for example, the current position of the ball object 54 , or may be the current position of the soccer payer object 52 in possession of the ball object 54 . This data may also be read from the space information storage 90 .
If there is then a possession position with a region corresponding to the team in possession of the ball object 54 , a determination is made as to whether or not the current time is the update time for the progress variable I using the progress variable update timing monitoring section 86 (S 103 ). If this is the update timing, a determination is made as to whether or not the progress variable I is less than 50 (S 104 ). If the progress variable I is less than 50, 1 is added to the progress variable I, and the storage contents of the progress variable storage 88 are updated (S 105 ). Further, if the progress variable I is 50 or more, 1 is subtracted from the progress variable I, and the storage content of the progress variable storage 88 is updated (S 106 ). If the progress variable I is 50, this calculation is not carried out.
On the other hand, in S 102 , when it is determined that the ball object 54 is not within an attacking preparation region, a determination is then made as to whether or not the current time is the update time for the progress variable I. If the current time is the update timing, S 108 to S 110 are skipped, and S 111 is gone to. On the other hand, if the current time is the update timing, a determination is made as to whether the noted team (which is the first team here) is in possession of the ball object 54 , or the team opposing the noted team (which is the second team here) is in possession of the ball object 54 (S 108 ). When the noted team is in possession of the ball object 54 , 1 is added to the progress variable I, the storage content of the progress variable storage 88 is updated, and S 111 is gone to. If the progress variable I has reached 100 , this calculation is not carried out. Conversely, when the noted team is not in possession of the ball object 54 , 1 is subtracted from the progress variable I, the storage content of the progress variable storage 88 is updated, and processing advances to S 111 . If the progress variable I is 0, this calculation is not carried out.
Next, FIG. 8 is proceeded to, and the progress display section 84 determines whether or not notification of the occurrence of a prescribed event has been given by the event monitoring section 82 (S 111 ). If a prescribed event has occurred, the progress variable I is updated using a prescribed method (S 112 ). For example, when an event occurs where the first team takes aim at the goal of the second team and shoots, the progress variable I is increased by a prescribed value, and the storage content of the progress variable storage 88 is updated. Further, for example, when an event occurs where the second team takes aim at the goal of the first team and shoots, the progress variable I is reduced by a prescribed value, and the storage content of the progress variable storage 88 is updated. Moreover, when, for example, the ball object 52 is positioned outside of the soccer field object 56 , in the case of a player substitution, or when there is a foul (illegal conduct) etc., processing is carried out so that the progress variable I approaches 50 . If a prescribed event has not occurred, S 112 is skipped.
Next, it is determined whether or not one minute has passed since the last time when the progress variable I is copied to any one of the past progress variables 11 to 115 (S 113 ). If one minute has passed, the progress variable I is copied to the numerical value N in the past progress value 11 to 115 which is judged to store the oldest progress condition (S 114 ). This numerical value n is then updated with that specifying this copied past progress variable (S 115 ). If one minute has not elapsed, the above processing is skipped.
After this, the progress display image 58 is generated in accordance with the storage content of the progress variable storage 88 , and this is depicted in VRAM provided at the image processor 16 (S 116 ). The image depicted in the VRAM is then converted to a video signal and outputted to the monitor 18 . The progress display image 58 displayed at the game screen is then updated at prescribed time periods.
According to the game device 10 described above, when the first team is in possession of the ball object 54 , if the possession position is within the first attacking preparation region, the progress variable I approaches 50 . Further, if the first team is in possession of the ball and the possession position is outside of the first attacking preparation region, the progress variable I is increased. When game character object 52 constituting the first team remain in possession of the ball object 54 and are in the first attacking preparation region sharing part or all of the first region (partially or completely overlapping), the progress variable I expressing the degree of superiority of the first team converges on 50 , and the progress of the game can be more accurately evaluated and displayed. Further, a prescribed number ( 15 ) of current values for the progress variable I are stored every minute, and each graphical image 74 is compared and displayed at the progress display image 58 in order of storage according to the stored progress variables. This means that changes in progress can be displayed in a manner that is easy to understand.
The present invention is by no means limited to the above embodiment. For example, in the above description, a description is given of an example of the present invention applied to a soccer game, but the present invention may also be applied to ball games such as basketball games etc. Further, in the above description, in S 104 to S 106 , the progress variable I converges on 50 but may also converge on another numerical value. Moreover, in the above description, the first attacking preparation region is taken to be the same as the first region, but may be a region different to the first region providing this region is a region is common to part of or all of the first region. The same also applies fro the second attacking preparation region.
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To provide a game device capable of evaluating and displaying progress in a more reliable manner in the case of implementing a soccer game or basketball game etc., there is provided means for determining which team is in possession of the ball, means for acquiring the ball position and the position of the game character in possession of the ball as a possession position, progress variable updating means for executing processing to enable the progress variable to approach a prescribed first fixed value when the first team is in possession of the ball and the ball is within a first attacking preparation region common to part or all of the first region, and executing processing to increase the progress variable when the first team is in possession of the ball and the possession position is outside of the first attacking preparation region, and means for displaying a progress display image according to the progress variable.
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This is a division of application Ser. No. 08/429,727, filed on Apr. 27, 1995, issued as U.S. Pat. No. 5,510,296.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to a fabrication method used for semiconductor devices, and more specifically to an improved process for polycide coating of contact holes in a dielectric layer.
(2) Description of Prior Art
The trend in the semiconductor industry to smaller, higher performance silicon devices, has been influenced by the ability of specific semiconductor disciplines to achieve micro-miniaturazation. Advances in photolithography, via more sophisticated exposure cameras, as well as development of more sensitive photoresist materials, have allowed sub-micron images in photoresist materials to be routinely achieved. Comparable breakthroughs in the dry etching technology have allowed the sub-micron images in photoresist to be successfully transferred to underlying semiconductor materials via anisotropic reactive ion etching, (RIE), procedures. Other semiconductor fabrication disciplines, such as low pressure chemical vapor deposition, (LPCVD), and ion implantation, (I/I), have also contributed to the attainment of smaller, higher performing silicon devices.
However with the use of sub-micron feature, for specific elements of a semiconductor device, specific vulnerabilities, in terms of yield and reliability, arise. For example a device feature, needed to be reduced to successfully achieve micro-miniaturazation, is the contact or via hole, used to electrically connect; either two levels of wiring, or an active device region in silicon to an overlying wiring level. With the trend to sub-micron images, contact holes with diameters as small as 0.35 uM have been used. The decreased contact hole diameter, although successful in allowing for the fabrication of smaller silicon chips, has put special demands on the properties of the materials used to fill these small openings. First the material has to inherently possess excellent current carrying capabilities. The excellent electromigration resistance of refractory metals, such as tungsten, and also silicides such as tungsten silicide, has made these materials leading candidates for contact hole filling. An area of concern is the inability of the refractory or silicide, to completely fill the contact, that is the filling process supply adequate step coverage. This becomes more imperative as the contact hole diameter decreases. A solution to the filling criteria is offered by Cleeves, et al, in U.S. Pat. No. 5,366,929, in which a selective fill is described using a sputter etch clean followed by a selective deposition. This solution, although presenting possiblities of optimum fills, is complex and costly. Another area of concern with the use of refractory or silicide fills is the ability to achieve adhesion between the fill material and the contact hole materials. Many solutions have been offered, such as the use of titanium or titanium nitride films as adhesion layers, used to coat the contact hole prior to the fill deposition. Hasegawa, et al, in U.S. Pat. No. 5,374,591, offer a titanium nitride adhesion layer, followed by an etch back of the titanium nitride, at the edges of the contact, again directed at improving the subsequent fill process. Again, however this process is complex and costly. The fabrication process now described in this invention will offer an improved adhesion layer, as well as an optimized fill method enabling simple, reliable and non-costly contacts to be used.
SUMMARY OF THE INVENTION
It is an object of this invention to provide an optimized process for coating narrow diameter contact holes with conductive materials.
It is another object of this invention to use an underlying adhesion layer of amorphous silicon, prior to coating the narrow contact hole with a conductive material.
It is yet another object of this invention to coat the contact hole with tungsten silicide, obtained using silane as one of the reactants.
It is still yet another object of this invention to anneal the polycide filled contact hole, using a high flow of nitrogen.
In accordance with this present invention a method is described for fabricating semiconductor devices, using small diameter contact holes or vias to interconnect specific levels, in which the contacts or vias are partially filled with a polycide material, obtained using an optimized fill process. A small diameter contact hole is provided in a dielctric layer, to active device regions in a semiconductor substrate. After a surface clean, in a dilute hydrofluoric acid solution, a thin layer of amorphous silicon is deposited. An ion implantation process is used to dope the amorphous silicon layer, again followed by a dilute hydrofluoric acid surface clean. A deposition of tungsten silicide, partially filling the small diameter contact hole, is next performed, creating the tungsten polycide, the tungsten silicide-amorphous silicon composite. After patterning of the polycide to obtain the desired image, via RIE procedures, an anneal using a high flow of nitrogen is performed to improve the contact resistance of the polycide to the underlying regions.
BRIEF DESCRIPTION OF THE DRAWINGS
The object and other advantages of this invention are best described in the preferred embodiment with reference to the attached drawings that include:
FIG. 1, which schematically illustrates, in cross-sectional style, a metal oxide semiconductor field effect transistor, (MOSFET), device, prior to the initiation of the optimized polycide contact process.
FIGS. 2-6, which schematically illustrate, in cross-sectional style, the specific fabrication stages for the optimized polycide contact process.
FIGS. 7-8, which in bar graph representation, illustrates the improvement in specific device paramaters obtained via the use of the optimized polycide contact process.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The method of fabricating MOSFETs using the optimized polycide contact process will now be covered in detail. The optimized polycide contact process can be used as part of MOSFET devices that are currently being manufactured in industry, therefore only the specific areas unique to understanding this invention will be described in detail.
FIG. 1 shows a typical NFET, (N type field effect transistor), to which the optimized polycide contact process will be used with. A substrate, 1, composed of P type, single crystal silicon, with a <100>orientation, is used. A thick field oxide region, 2, (FOX) is formed surrounding the region where the device is to be built. Briefly the method used to create the FOX isolation region is to use an oxidation mask of silicon nitride, overlaying a thin thermal silicon dioxide layer. The desired FOX region is etched open in the composite dielectric, while leaving the subsequent device region protected, using conventional photolithographic and dry etching procedures. After removal of the masking photoresist, and a wet chemical clean, a field oxide is thermally grown, typically to a thickness between about 4000 to 6000 Angstroms. After removal of the oxidation mask, using a hot phosphoric acid solution, for the silicon nitride layer, and a buffered hydrofluoric acid solution for the underlying silicon dioxide layer, a gate oxide, 3, is grown at a temperature between about 850° to 950° C., to a thickness between about 70 to 250 Angstroms. Next a polysilicon layer, 4, is deposited, using LPCVD processing, at a temperature between about 550° to 750° C., to a thickness between about 2000 to 4000 Angstroms. An ion implantation procedure is then used to dope polysilicon layer, 4, using phosphorous, at an energy between about 50 to 100 Kev., at a dose between about 1E13 to 5E14 atoms/cm2. Standard photolithographic, and reactive ion etching, (RIE), processing, using SF6 as an etchant, are next used to create the polysilicon gate structure, 4, shown in FIG. 1.
The MOSFET fabrication process continues by photoresist removal, followed by careful wet chemical cleans. An N type, lightly doped source and drain region, 5, is then created in the semiconductor substrate via ion implantation of phoshorous, at an energy between about 50 to 100 Kev., at a dose between about 1E13 to 5E13 atoms/cm2. A silicon oxide layer is next produced via LPCVD processing, using tetraethylorthosilicate as a source, at a temperature between about 650° to 750° C., to a thickness between about 2000 to 4000 Angstroms. A selective anisotropic RIE procedure is then employed, using CHF3, to form the oxide sidewall spacer, 6. The N+ source and drain regions, 7, are now created via ion implantation of arsenic, at an energy between about 75 to 150 Kev., at a dose between 1E15 to 5E15 atoms/cm2, followed by an activation cycle using either conventional furnace procedures, at a temperature between 850° to 950° C., for a time of between about 10 to 30 min., or via rapid thermal annealing, (RTA), again at a temperature between about 850° to 950° C., but for a time between about 10 to 60 sec.
A silicon oxide layer, 8, is formed on the MOSFET structure, using LPCVD processing at a temperature between about 400° to 600° C., to a thickness between about 3000 to 4000 Angstroms. Photolithographic and RIE procedures, using CHF3, or CF4, are used to create contact hole, 9, in silicon oxide layer, 8, exposing source and drain region, 7, in the semiconductor substrate. This is shown schematically in FIG. 2. After photoresist removal, followed by careful organic cleans, the structure is subjected to a 200:1, dilute hydrofluoric, (DHF), acid solution, at a temperature between about 20° to 25° C., for a time between about 60 to 120 sec, for purposes of removing any native oxide from the surface of the N+ source and drain region, 7. A deposition of amorphous silicon, 10, shown in FIG. 3, is then performed, using LPCVD processing at a temperature between about 500° to 550° C., to a thickness between about 300 to 700 Angstroms, and preferably 500 Angstroms. The use of amorphous silicon as an underlay, or adhesion layer for a subsequent overlying silicide layer, rather then polycrystalline grained silicon, is based on the ability of the amorphous seed layer to assist in the growth of the overlying tungsten silicide, to a higher degree then counterparts fabricated with polycrystalline underlying seed layers. The thin amorphous silicon layer, 10, is then subjected to an ion implantation step, using phosphorous at an energy between about 30 to 40 Kev., at dose between about 1E15 to 5E15 atoms/cm2.
A pre-clean, again using DHF, at a temperature between about 20° to 25° C., for a time between 60 to 120 sec., is used to remove any native oxide from the amorphous silicon layer, 10. An LPCVD process, using tungsten hexafluoride and silane, at a temperature between about 300° to 400° C., is used to deposit a layer of tungsten silicide, 11, shown in FIG. 4, to a thickness between about 1000 to 2000 Angstroms, and preferably 1500 Angstroms. It is critical that the deposition conditions result in excellent step coverage, partially filling contact hole, 9. The use of these deposition conditions, in addition to the use of an amorphous silicon underlay, allowed the above requirements to be met.
The tungsten silicide-amorphous silicon composite, referred to as the tungsten polycide, can be used as either a contact metallurgy, or as both a contact and interconnect metallization. If the latter is desired the patterning of the tungsten polycide is accomplished using standard photolithographic and RIE procedures. The selective RIE process is carried out using SF6, to etch the tungsten polycide and stop on the underlying oxide layer, 8. After photoresist removal the resulting contact--interconnect metallization is shown schematically in FIG. 5. A critical anneal is now performed in an nitrogen ambient, at a temperature between about 750° to 850° C., and preferably 800° C., for a time between about 30 to 60 min. The anneal step is performed using a high nitrogen flow, between about 25 to 30 slm, and preferably 28 slm, which is critical in not allowing deleterious oxidation formation to occur at tungsten silicide-amorphous Si interface. These conditions, amorphous silicon underlay, tungsten silicide deposition using silane, and a nitrogen anneal at high flow rates, have allowed this process to be successfully used for contact hole diameters as small as 0.35 uM.
FIG. 6 describes the completion of the MOSFET structure, fabricated using the optimized tungsten polycide contact process. An oxide layer, 12, is deposited to a thickness between about 5000 to 10000 Angstroms. Conventional photolithographic and RIE procedures are used to open via, 13, in oxide layer, 12, to the tungsten polycide contact metallization. After photoresist removal, and careful wet chemical cleans, a deposition of Al--Cu is performed to a thickness between 8000 to 12000 Angstroms. Again standard photolithographic and dry etching is employed to create metal interconnect, 14.
Finally FIGS. 7-8, indicate the benefits of this invention. It can be ssen in FIG. 7 that the tungsten silicide yield is dramatically improved, specifically for the smallest contact hole size, via the use of annealing in a high N2 flow. It can also be observed that the resistance in the contact is minimized as a result of an anneal using a high N2 flow. FIG. 8, shows the highest yield and lowest contact resistance resulting via the use of amorphous silicon underlays, as compared to counterparts fabricated using grainy silicon underlays.
This invention, an optimized, manufacturable tungsten polycide contact metallization, although shown as a part of an N type, (NFET), MOSFET device, can also be applied to P type, (PFET), MOSFET devices, and complimentary, (CMOS), and BiCMOS structures.
While this invention has been particularly shown and described with reference to, the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of this invention.
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A method for creating manufacturable polycide contacts, for use in advanced semiconductor designs using images as small as 0.35 uM, has been developed. An amorphous silicon film, is used as an underlay, to assist in the growth of an overlying tungsten silicide layer. The tungsten silicide deposition is performed using tungsten hexafluoride and silane, and in conjunction with the amorphous silicon underlay, results excellent step coverage in the narrow contact hole. A nitrogen anneal, using high flow rates, optimizes the adhesion characteristics of the tungsten polycide structure.
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BACKGROUND OF THE INVENTION
The invention is directed to improvements in fuel injection pumps for internal combustion engines, in particular an in-line injection pump for Diesel engines.
In a known fuel injection pump of this type having a hydraulic control mechanism (French patent No. 2 082 346), the control element that specifies the pump fuel injection rate is adjusted by an amount calculated by the control unit, as a function of engine operating parameters, so that the injection rate is adjusted to an optimal value for the instantaneous operating state of the engine. To lengthen the adjusting travel of the control element, the inlet switching valve disposed in the inlet to the control mechanism is opened, preferably in clocked fashion, and to shorten the control path, the return switching valve disposed in the return from the control mechanism to the fuel tank is opened, preferably intermittently, while the inlet switching valve is closed. The pressure in the control chamber is thus raised or lowered, and as a result the control piston is extended farther, counter to the force of the restoring spring, or retracted again. The suction chamber of the fuel injection pump, from which the quantity of fuel to be injected is drawn in the intake stroke of the pump piston, is filled with fuel continuously by a fuel feed pump driven in common with the pump piston. The suction chamber communicates via an overflow valve with the fuel tank, so that when the fuel feed pump is pumping continuously, a constant pressure is maintained in the suction chamber.
From German Offenlegungsschrift No. 33 04 335, a fuel injection pump having an electrohydraulic injection pump governor is known, which in addition to or instead of the feed pump driven in common with the pump piston has a separately driven electric feed pump. For rapid shutdown of the engine, upon the occurrence of a lasting control deviation at the control member, the feed direction of the fuel feed pump is reversed by reversing the polarity of the reversible drive motor, thereby partly emptying the suction chamber. The pump piston of the fuel injection pump cannot aspirate any more fuel from the suction chamber, and the engine comes to a stop.
OBJECT AND SUMMARY OF THE INVENTION
It is an object of the fuel injection pump according to the invention to provide an advantage that when the engine ignition is shut off and hence the supply of current is shut off as well, the engine is shut down relatively quickly, because on the one hand the supply of fuel to the suction chamber is stopped and on the other the hydraulic control mechanism is returned to its zero and stopping position. The electrical and constructional provisions required for this are relatively simple, so that the fuel injection pump does not become markedly more expensive. The relief device may be embodied by electromechanical, hydromechanical or simply mechanical components. Filling of the suction chamber is disrupted by shutting off the feed pump. Subsequent intake strokes of the pump piston of the fuel injection pump that continue to occur empty the suction chamber, so that the engine comes to a stop with a delay, as soon as a partial vacuum of approximately 0.3 bar of absolute pressure is attained.
A check valve between the feed pump and the fuel reservoir of the hydraulic control mechanism prevents fuel from the reservoir from being fed into the suction chamber when the feed pump is stopped, which would make the engine take longer to come to a stop.
It is more expensive in terms of circuitry to reverse the feed direction of the feed pump, rather than simply shutting it off, but it shortens the delay between the time the engine is shut off and when it actually stops, because the suction chamber of the fuel injection pump is emptied faster.
The relief device connected to the control chamber becomes operative in the shutoff situation and causes the pressure in the control chamber to drop, so that the control piston is returned, under the influence of the restoring spring and with the control member at the same time returned to its zero or stopping position, so that the injection quantity is reduced to zero.
For the shutoff situation, the relief device may be embodied as a locking circuit for maintaining the current supply at the control unit; this circuit is finally shut off when the control piston reaches the zero or stopping position and the injection quantity is hence at zero.
The relief device may also be embodied so as to be operative not only in the shutoff situation, but whenever the return switching valve is without current or in other words closed, on the condition that in addition, the fuel feed pump is always shut off whenever a lasting control deviation occurs in the control member. A control deviation of this kind can occur as a result of a current failure (switching valves constantly closed) or if the control member becomes stuck. In such malfunctions as well, the engine is brought to a stop, and the hydraulic control mechanism is shifted to its zero or stopping position.
In the simplest case, the relief device can be embodied as a throttle that bypasses the return switching valve. This throttle may be disposed in a bypass line, or be integrated with the return switching valve itself.
Providing the relief device as a non-return valve in a connecting line between the control chamber of the control mechanism and the fuel tank avoids leakage losses that arise with a throttle, and the fuel feed pump can be smaller. The non-return valve should be controlled such that it is always closed in normal operation but is opened in shutoff and malfunction situations. Various possible embodiments of such non-return valves are described hereinafter.
The invention will be better understood and further objects and advantages thereof will become more apparent from the ensuing detailed description of preferred embodiments taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block circuit diagram of a fuel injection pump in a first exemplary embodiment;
FIG. 2 is a circuit diagram of a control unit and a locking circuit for the fuel injection pump in FIG. 1; and
FIGS. 3-5 are respective block circuit diagrams for three different exemplary embodiments of a fuel injection pump.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first exemplary embodiment, shown schematically in FIG. 1, shows the circulation of fuel in a fuel injection pump 10 for a Diesel engine, and an associated hydraulic control mechanism 11 for actuating a governor rod 12, suggested by dot-dash lines, which in turn controls the fuel injection quantity metered by the fuel injection pump 10 per pump piston stroke. 13 indicates a suction chamber of the fuel injection pump 10, which is filled with fuel by a feed pump 14 and from which fuel is aspirated for injection upon each pump piston stroke. The suction chamber 13 is connected via a one-way overflow valve 70 to a return line 74 leading to a fuel tank 16, as a result of which the suction chamber pressure is kept at a constant value. The feed pump 14 is electrically driven and communicates on the intake side with the fuel tank 16 via a suction line 15 and on the compression side with the suction chamber 13 via a pressure line 17. Disposed in the pressure line 17 are a fuel filter 18 and a one-way check valve 19; the direction of flow through the one-way check valve 19 is toward the suction chamber 13 of the fuel injection pump 10. The pressure line 17 is also connected via a one-way check valve 20, having a blocking direction toward the pressure line, to a fuel return line 21. The feed pump 14 is driven by an electric motor 22.
The hydraulic control mechanism 11 has a control cylinder 23, in which a control piston 24 is axially displaceably guided. With one piston face, the control piston 24 engages the governor rod 12 by means of a coupling rod 25. The piston also defines a control chamber 26, and on its piston face remote from the control chamber 26, the piston is loaded by a restoring spring 27 supported in the control cylinder 23 which urges the control piston 24 in the direction of a minimal control chamber volume. The control chamber 26 communicates via an inlet 28 with a fuel reservoir 29 and via a return 30 with the fuel return line 21. The fuel reservoir 29 is connected via a second pressure line 31 to the outlet of the fuel filter 18, and has a spring-loaded diaphragm 32, which defines a reservoir chamber 33. Upon fuel feeding by the feed pump 14, the reservoir chamber 33 is filled with fuel, as the diaphragm 32 retracts, thus putting pressure on the fuel reservoir 29. A one-way check valve 34 is disposed between the fuel filter 18 and the fuel reservoir 29; the direction of flow through this check valve is toward the fuel reservoir 29.
Disposed in the inflow 28 to the control chamber 26 of the control mechanism 11 is a first switching valve 35, hereinafter the electro-magnetic inflow switching valve 35, and in the return 30 from the control chamber 26 to the fuel return line 21 a second electro-magnetic switching valve 36, hereinafter known as the return switching valve 36. Both switching valves 35, 36 are embodied as 2/2-way magnetic valves, the control inputs of which are connected to an electronic control unit 37. The electronic control unit 37, sketched in the block circuit diagram in FIG. 2, has a microprocessor 38 having an input 39 for an actual-value signal, dictating the injected fuel quantity, and two outputs 40, 41 for switching valve control signals, which via two end stages 59, 60 send exciter current signals to the exciter coils of the switching valves 35, 36. The microprocessor 38 calculates a set-point fuel injection quantity as a function of the instantaneous operating parameters of the Diesel engine and after comparison with the actual-value signal present at the input 39, generates switching signals for the two switching valves 35, 36. To this end, the input 39 is connected via a signal line 42 to a sensor 42a, which generates an electrical sensor signal corresponding to the actually injected fuel quantity. The actual position of the governor rod 12, for instance, may be sensed as the actual-value signal. The supply voltage for the electronic control unit 37 is picked up from a vehicle battery 43 and applied via the driving or ignition switch 44 to the electronic control unit 37. Via a further output 73, the microprocessor 38 is connected to a switching device 45 for the drive motor 22. A switching signal is present at this output whenever the governor rod 12 indicates a persistent control deviation, that is, whenever a difference btween the calculated set-point position of the governor rod 12 and the actual position is no longer controlled to zero. This switching signal passes via a signal line 46 to the switching device 45, where, depending upon the embodiment of the switching device 45, the switching signal effects either a shutoff of the electric motor 22, or a reversal of the polarity of the electric motor 22, so that the feed pump 14 reverses in its pumping direction, causing an ensuing shutoff of the drive motor 22, after an interval of time. The supply of current to the switching device 45 and from here for the electric motor 22 is again provided via the driving or ignition switch 44.
For shutoff of the Diesel engine 44, the driving or ignition switch 44 is opened. This shuts off the supply of current for the electric control unit 37 and the drive motor 22 of the feed pump 14. The feed pump 14 pumps no further fuel into the suction chamber 13, and once this chamber is largely emptied, by the pumping piston of the fuel injection pump, the engine stops. To return the control mechanism 11 to its zero or stopping position in the shutoff situation as well, a relief device 47 is disposed between the control switch 44 and the electronic control unit 37; in the shutoff situation, the relief device 47 supplies a current to the electromagnet of the switch 36 which opens switch 36 to connect the control chamber 26 with the fuel tank 16, relieving the control chamber 26 and causing the restoring spring 27 to press the control piston 24 back into its zero or stopping position, thereby expelling fuel from the control chamber 26; in this position, the volume of the control chamber is minimal, and the governor rod 12 assumes its "zero injection quantity" position.
In FIG. 1, the relief device 47 is embodied, using the return switching valve 36, by a so-called self-locking circuit 48, which keeps up the supply of current to the electric control unit 37 long enough, after the opening of the driving switch 44, for the governor rod 12 to reach its "zero injection quantity" position. By keeping up the current supply to the control unit 37, this unit is capable, in the shutoff situation, of generating an opening signal for the return switching valve 36, so the return switching valve 36 remains open after the opening of the ignition switch 44 long enough for all the fuel to drain out of the control chamber 26 into the fuel tank 16. The "zero injection quantity" position of the governor rod 12 is indicated by the actual-value signal present at the input 39 of the microprocessor 38, which at that time becomes zero. The self-locking circuit 48 is shown in the circuit diagram of FIG. 2. It includes a switching relay 49 having a switch contact 50 embodied as a closing means, a series circuit of two diodes 51 and 52 of opposite polarity, and a p-n-p transistor 53. Of the two inputs 54, 55 of the control unit 37 for the direct-current supply, the positive-potential input 54 is connected via the switching contact 50 of the switching relay 49 to the positive terminal of the battery 43, bypassing the driving switch 44. The output of the driving switch 44 is connected to a further input 75 of the control unit 37 and from there is likewise carried to the microprocessor 38. The series circuit of the diodes 51, 52 is connected to the input 75 and to the negative-potential input 55 of the control unit 37. The transistor 53 is connected between the connection point 56 of the two diodes 51, 52 and the positive-potential input 54 of the control unit 37. Its control input is connected to an output 57 of the microprocessor 38, at which an output signal that triggers the transistor 53 is present as long as the actual-value signal at the input 39 of the microprocessor 38 is greater than zero. The relay winding 58 of the switching relay 49 is connected to the connecting point 56 and to the zero-potential input 55 of the control unit 37.
The self-locking circuit 48 functions as follows:
When the driving switch 44 is actuated, the switching relay 49 is excited via the diode 51; the switch contact 50 closes, and the control unit is supplied with direct voltage. If the driving switch 44 is opened, for shutting off the engine, the supply of current to the relay winding 58 is maintained via the opened transistor 53. The shutoff situation is recognized by the microprocessor 38 by the falloff of the voltage at the input 75 of the control unit 37. The microprocessor 38 generates an opening signal, which via the output 41 and the end stage 50 opens the return switching valve 36. By the time the control mechanism 11 has attained its zero or stopping position, by means of the return of the control piston 24 to its stop position, on the left as seen in FIG. 1, the governor rod 12 has returned to its "zero injection quantity" position. The actual-value signal at the input 39 of the microprocessor 38 becomes zero, and the control signal at the output 57 of the microprocessor 38 vanishes. The transistor 53 thus prevents current flow; the excitation of the switching relay 49 ends; and the switch contract 50 opens. The supply of current to the control unit 37 is thus switched off. Upon the opening of the driving switch, as already mentioned, the drive motor 22 has been shut off and the feed pump 14 accordingly shut off. The engine comes to a stop, once the suction chamber 13 is partly emptied, after a few intake strokes of the pump piston of the fuel injection pump 10, and once the pressure in the suction chamber 13 has therefore dropped to approximately 0.3 bar of absolute pressure. The diode 52 serves as a recovery diode.
Instead of the self-locking circuit 48, which is somewhat expensive in terms of circuitry, a simple throttle 61 may be used as the relief device 47, which in the shutoff situation and with the immediate disappearance of the supply of current to the control unit 37 bypasses the return switching valve 36, which is closed when there is no current, and thus establishes communication between the control chamber 26 and the fuel return line 21. As shown in dashed lines in FIG. 1, this throttle 61 may be disposed in a bypass line 62 around the return switching valve 36; however, it may also be integrated with the return switching valve 36 itself. To this end, the valve seat of the return switching valve 36 may for example be embodied as a throttle that is operative in the closing state of the valve, which is readily done by providing a certain lack of tightness of the valve seat. The throttle 61, like the embodiments of the relief device 47 to be described below, has the advantage that not only in the shutoff situation but also in the event of a malfunction, it is always operative whenever the feed pump 14 is shut off and so assures a return of the control mechanism 11 to its zero or stopping position.
The exemplary embodiment shown in FIG. 3 is largely like that of FIG. 1, and the same elements are identified by the same reference numerals. Only the relief device 47 is modified in FIG. 3, as compared with the relief device 47 of FIG. 1. Here the relief device comprises a connecting line 63, connected between the control chamber 26 and the pressure-side outlet of the feed pump 14, in which is disposed a non-return one-way valve 64 in the form of a flutter valve or check valve having a bias of approximately 0.5 bar. The non-return direction of the non-return valve 64 is toward the control chamber 26 of the control cylinder 23. The switching device 45 for the feed pump 14 is embodied such that in the shutoff situation, or opening of the driving switch 44, as well as in a malfunction, i.e., upon a persistent control deviation caused by sticking of the governor rod 12 or jamming of the inflow and/or return switching valve 35 or 36, the feed pump 14 briefly reverses its pumping direction and then is shut off. If the switching device 45 is designed such that in the situations mentioned only the feed pump 14 is shut off, then the relief device 47 also includes a bypass 65 between the pressure side of the feed pump and the fuel tank 16, in which a bypass throttle 66 is disposed. During the operation of the fuel injection pump 10, the feed pressure of the feed pump 14 locks the non-return valve 64, so that the control chamber 26 is closed and no fuel can drain out via the non-return valve 64. If the feed pump 14 is shut down, then the connecting line 63 empties via the bypass throttle 66. If there is no bypass 65, the reversal of the feed direction of the feed pump 14 once again effects the emptying of the connecting line 63. The non-return valve 64 thus opens, and fuel can drain from the control chamber 26, until the control piston 24 has attained its zero or stopping position.
In the third exemplary embodiment shown by FIG. 4, once again only the relief device 47 has been modified. All the other components match those of FIGS. 1 and 3, so that they are identified by the same reference numerals. The relief device 47 here is embodied as a hydraulically controllable switching valve 67, which is disposed in a bypass line 68 around the return switching valve 36. The switching valve 67, shown schematically in FIG. 4 with a hydraulically actuated displacement piston 69, is preferably a 2/2-way valve embodied as a slide valve. The switching valve 67 is embodied such that in its basic position, that is without action upon its hydraulic control chamber, it is in its open position and uncovers the bypass line 68. The hydraulic control input of the switching valve 67 is connected to the suction chamber 13 of the fuel injection pump 10. During operation of the fuel injection pump 10, the suction chamber 13 is filled with fuel. The suction chamber pressure is kept to a constant value in the usual manner via an overflow valve 70. Via a connecting line 71 between the suction chamber 13 and the control input of the switching valve 67, this suction chamber pressure also acts upon the displacement piston 69 of the switching valve 67, which closes, blocking the bypass line 68. In the shutoff situation or in the event of a malfunction (persistent control deviation of the governor rod 12) the feed pump 14 is shut off via the switching device 45, as described above. The suction chamber 13 of the fuel injection pump is emptied by means of repeated aspiration of fuel by the pump piston. The suction chamber pressure drops, and the switching valve 67 opens. This establishes a connection via the bypass line 68 between the control chamber 26 and the fuel return line 21, and the control piston 24 that is displaced under the influence of the restoring spring 27 expels the fuel out of the control chamber 26 into the fuel tank 16. The governor rod 12 is returned to its zero or stopping position. The engine is shut down. The shutdown of the engine is accelerated, if in the shutoff or malfunction situation the feed pump 14, prior to shutoff, is briefly operated with a reversed pumping direction.
In the exemplary embodiment shown by FIG. 5, only the relief device 47 has been modified. Components matching those of the other embodiments are again identified by the same reference numerals. The relief device 47 here has an electrically controllable switching valve 72, which is opened when in its basic position without electric current. The switching valve 72 is preferably embodied as a 2/2-way magnetic valve and is connected with its electrical control input to the electronic control unit 37. The switching valve 72 is again disposed in a bypass line 68 around the return switching valve 36. The switching valve 72 is now triggered by the electronic control unit 37 such that when the current supply is applied to the electronic control unit 37, the switching valve 72 receives current, from the closure of the driving switch 44, and thereby blocks the bypass line 68. If the supply of current is shut off again by the opening of the driving switch, then the switching valve 72 receives no current and establishes the communication between the control chamber 26 and the fuel tank 16. A persistent control deviation of the governor rod 12, that leds to the generation of a shut-off signal for the switching device 45 of the feed pump 14 by means of the electric control unit 37, is also utilized for shutting off the current to the switching valve 72, so that even in the event of a malfunction, with the attendant shutoff of the feed pump 14, the switching valve 72 is opened.
If the opening cross section of the valve openings of the switching valves 67 and 72 in the exemplary embodiments of FIGS. 4 and 5 is made larger than the opening cross section of the inflow switching valve 35, then even if the inflow switching valve 35 should stick in its open position, a shift of the control mechanism 11 to its zero or stopping position is attained, because upon the opening of the switching valves 67 and 72, the fuel can drain out of the control chamber 26 to the fuel tank 16 faster than it is being replenished from the fuel reservoir 29 into the control chamber 26.
The foregoing relates to preferred exemplary embodiments of the invention, it being understood that other variants and embodiments thereof are possible within the spirit and scope of the invention, the latter being defined by the appended claims.
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A fuel injection pump for internal combustion engines having a hydraulic control mechanism includes a control cylinder with a control piston actuating a control member, a hydraulic work chamber and one switching valve each for an input and an output controlled by a valve control unit. The inflow to and return from the work chamber is provided with the control valves in order to shut down the engine upon a shutoff or a malfunction in the hydraulic control mechanism. The fuel feed pump is electrically driven, and the hydraulic work chamber communicates with the fuel tank via a relief device. The supply of current to the valve control unit and the feed pump is switched on and off, along with the rest of the current supply to the engine, via a driving switch. Additionally, the valve control unit is embodied such that upon the appearance of a persistent control deviation of the control member, the valve control unit shuts off the feed pump. The relief device includes various variant embodiments operative upon shutoff of the current supply or the occurrence of a malfunction and enables the restoration of the control mechanism to its zero or stopping position.
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[0001] This application claims the benefit of U.S. Provisional Application No. 61/596,618, filed Feb. 8, 2012, the entirety of which is incorporated by reference herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention is a balloon catheter for angioplasty procedures, comprising an elastic constraining structure mounted over the balloon where the structure has a mechanism of expansion to control the balloon inflation.
[0004] Conventional angioplasty balloons expand in an artery lesion at the least resistant areas of the lesion causing “dog bone” effect at the lesion ends and overexpansion in the softer areas, resulting in trauma to the vessel wall. Conventional angioplasty is associated with vessel displacement and its main mechanism of action is plaque compression where the vessel is significantly displaced or “pushed out” before reaction force can be generated and plaque compression takes place. During this process the balloon may expand in the axial direction (in addition to radial), a phenomenon that accelerates propagation of “cracks” in the vessel wall (dissections). This elongation continues after the balloon engages the lesion and the vessel wall and cause longitudinal stretch
[0005] This mechanism of action causes a high rate of failure due to the vessel trauma (randomize studies in legs arteries document up to 40% acute failure rate and poor long term results with 20%-40% patency in one year). Attempts to modify the mechanism of action were mainly aimed at increasing the local force by adding cutting blades, wires or scoring elements that can penetrate into the vessel wall and create pre defined dissection plans. Those devices are used when encountering resistant lesions otherwise hard to crack open with conventional balloons. None of those technologies was designed to provide an alternative mechanism that leads to a gentler dilatation by minimizing vessel displacement and reducing the radial forces during balloon dilatation.
SUMMARY OF THE INVENTION
[0006] According to the present invention, a device that modifies the properties of an angioplasty balloon in order to provide uniform inflation and extraction of longitudinal forces in order to facilitate plaque extrusion and minimize vessel trauma. In the device presented herein, a novel constraining structure prevents non-cylindrical expansion using constraining rings that are spaced apart along the balloon working length leading to creation of small balloon segments (pillows) separates by grooves that facilitate plaque extrusion. The constraining structure also prevents longitudinal elongation of the balloon since it has a structure that shortens during expansion and constrains the balloon in both longitudinal and radial directions.
[0007] Computer simulation shows a decrease in radial forces using a balloon with the constraining structure. The constraining structure causes reduction in the rate of vessel dissections and perforations thru formation of an array of balloon pillows that provide gentle contact with the vessel wall and thru the formation of channels between these pillows that allow plaque flow and strain relief areas in the vessel wall.
[0008] Conventional balloon angioplasty does not provide strain relief to the vessel wall and suffer from high rate of dissections.
[0009] Other devices, such as cutting balloons and scoring devices (for example U.S. Pat. No. 7,691,119 Farnan) made to address resistant lesions by adding elements that can cut or score into the vessel wall and significantly, increase the local force (“focus force angioplasty”), but do not provide strain relief and gentle contact with the vessel wall. On the contrary, these devices include aggressive metallic components that are made to break hard plaque and mark their metal footprint on the vessel wall.
[0010] The constraining structure of the present invention takes advantage of the fact that by forcing the balloon into pillows topography the excessive length of the balloon is directed into a three dimensional shape and the surface area of the balloon increases. This mechanism shortens the overall balloon length during inflation and minimized longitudinal vessel stretch. Other devices such as stents or scoring cages that have structures over a balloon are using the balloon as an “activator” or expandable shell designed to increase the diameter of the stent or scoring stent and allow the balloon to inflate in full both radially and longitudinally and are therefore designed to expand as big as the inflated balloon, while the design present herein is made smaller than the inflated balloon, specifically aimed to modify, restrict and control the balloon inflated shape and size.
[0011] The combination of the advantages of the device described herein result in controlled non aggressive and predictable lesion dilation that addresses a major health concern.
[0012] All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The novel features of the invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present invention will be obtained by reference to the following detailed description that sets forth illustrative embodiments, in which the principles of the invention are utilized, and the accompanying drawings of which:
[0014] FIG. 1 show the layout of the constraining structure design adjacent to the balloon scheme, where the distal and proximal ends of the constraining structure are placed over the balloon legs, the constraining rings are spaced apart along the balloon length over the working length of the balloon, and an array of longitudinal waved struts interconnect between the constraining rings and the ends.
[0015] FIG. 2 shows a scheme of the inflated device with circumferential and longitudinal pattern of channels and pillows.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0016] A balloon catheter comprising a catheter shaft and an inflatable balloon at its distal end and an elastic constraining structure is mounted over the balloon. The constraining structure is made from an elastic material such as Nitinol, elastic polymers or high strength fibers or mesh.
[0017] The device natural configuration is collapsed. Unlike “self-expending stents” it is not “self-expending” but to the contrary “self-closing”: prior to expansion the constraining structure is tightly closed on the folded balloon. When the balloon is inflated the constraining structure is expanded by the balloon force up to a diameter smaller than the free inflated diameter of the balloon. The structure will self compressed back to a small diameter when the balloon is deflated. Typically the distal end and a proximal end of the constraining structure are fixedly attached to the catheter at both sides of the balloon to prevent it from disengaging with the catheter. Attachment is made by means of adhesive or thermal bonding or other method known in the art.
[0018] The constraining structure comprises an array of sinusoidal constraining rings spaced apart along the balloon working length. Each ring has a sinus curve length defined by the length of the ring when fully straitened. For each ring the sinus curve length is smaller than the balloon expanded circumference. When expanded the rings expand to its maximal expansion resulting in a substantially circular ring shape that is smaller in diameter than the balloon diameter and force a substantially circular channel around the balloon outer surface.
[0019] Expansion of the constraining rings results in an array of channels along the balloon length and also results in shortening of the balloon. It is easier to understand the shortening caused by the rings as it is obvious that if the rings were removed from an inflated balloon the balloon would elongate.
[0020] The maximum expanded diameter of the constraining structure is mainly controlled by the length of the sinus curve rings. The maximum expanded diameter could be 0.15 mm-0.3 mm smaller than the balloon free inflated diameter but it could also be in the range of 0.1 mm to 0.5 mm or exceed this range depending on the material of choice and the specifics of the design. For example for 3 mm balloon the maximum expanded diameter of the structure made of nitinol is in the range of 2.6 mm-2.85 mm. If the maximum expanded diameter is out of the desirable range the device will fail to perform. For example, if the maximum expanded diameter is similar or larger than the balloon free expanded diameter, the constraining structure would not be able to restrict the free expansion of the balloon and pillows will not form. If the structure is too small, the forces applied by the balloon would cause the structure to break and the device will fail, risking patient's safety.
[0021] The constraining rings are interconnected by a circumferential array of interlacing longitudinal waved struts. The number of struts is usually twice the number of the sine waves in the constraining ring. For example the structure scheme shows a two waves sine ring and therefore four longitudinal waved struts. Each strut begins near one end of the constraining structure and ends at the last constraining ring near the opposite end. It does not continue all the way to the opposite end in order to allow proper functionality and expansion. The following strut begins near the opposite end of the constraining structure and ends at the last constraining rings near the first end of the balloon, such that the opposing ends are not interconnected by the longitudinal waved struts.
[0022] This construction result in the last ring being connected to the ends with half the number of struts only. If the struts were to continue all the way to the opposing end it would restrict the first ring from expanding homogeneously over the balloon as the intermediate rings expand.
[0023] The struts connect to the first constraining rings at the external peaks of the ring and thus forming a structure that shortens when expanded. If the struts were connected to the first constraining rings at the internal peaks of the ring than the structure would elongate when expanded.
[0024] It is particularly important not to have “spine” or struts that are connected to both proximal and distal end of the balloon. The current structure in FIG. 1 in which two (or more) longitudinal struts are connected to the distal end of the balloon and two (or more) other interlacing struts connected to the proximal end of the balloon create “push/pull” forces during inflation and longitudinal struts are moving in opposing directions during inflation in order to apply compressive forces on the balloon and allow it to shorten. This “tilt” function supports expansion of the pillows at lower pressure. The longitudinal waved struts form longitudinal channels over the balloon outer surface and together with the circular channels formed by the rings it results in substantially square pattern of channels (“windows”) and balloon pillows protruding in the windows.
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A constraining structure for use with a balloon catheter can include multiple longitudinal struts and multiple, sinusoidal shaped radial rings. The constraining structure can expand to form a pattern of channels including substantially square windows. The constraining structure can modify, restrict, and control a shape and/or size of the balloon when inflated. Inflating the balloon catheter within the constraining structure can provide nonuniform pressure on a vessel wall adjacent the balloon.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a battery charger and more particularly, to a battery charger for charging two or more rechargeable battery cells using a parallel battery charger topology, which, as a result uses a reduced number of active components resulting in a relatively less expensive battery charger and at the same time provides the ability to independently control the charging of each of the battery cells.
2. Description of the Prior Art
Various portable devices and appliances are known to use multiple rechargeable battery cells, such as AA and AAA battery cells. In order to facilitate charging of the battery cells for such multiple cell appliances, multiple cell battery chargers have been developed. Both parallel and series topologies are known for such multiple cell battery chargers. For example, U.S. Pat. Nos. 5,821,733 and 6,580,249, as well as published U.S. Patent Application U.S. 2003/0160593, disclose multiple cell battery chargers configured in a series topology. U.S. Pat. Nos. 6,034,506 and 6,586,909 as well as published U.S. Patent Application U.S. 2003/0117109 A1 disclose battery chargers configured in a parallel topology.
In such multiple cell battery chargers configured in a series topology, a series charging current is applied to a plurality of serially coupled battery cells. Because the internal resistance and charge on the individual cells may vary during charging, it is necessary with such battery chargers to monitor the voltage across and/or temperature of each cell in order to avoid overcharging any of the serially connected cells. In the event that an over-voltage condition is sensed, it is necessary to shunt charging current around the cell to prevent overcharging of any of the individual serially connected cells. Thus, such multiple cell battery chargers normally include a parallel shunt around each of the serially connected cells. As such, when a battery cell becomes fully charged, additional charging current is thus shunted around the cell to prevent overcharging and possible damage to the cell. In addition, it is necessary to prevent discharge of such serially connected battery cells when such cells are not being charged.
Various embodiments of a multiple cell battery charger configured with a serial charging topography are disclosed in the '733 patent. In one embodiment, a Zener diode is connected in parallel across each of the serially connected battery cells. The Zener diode is selected so that its breakdown voltage is essentially equivalent to the fully-charged voltage of the battery cell. Thus, when any of the cells become fully charged, the Zener diode conducts and shunts current around that cell to prevent further charging of the battery cell. Unfortunately, the Zener diode does not provide relatively accurate control of the switching voltage.
In an alternate embodiment of the battery charger disclosed in the '733 patent, a multiple cell battery charger with a series topology is disclosed in which a field effect transistors (FET) are used in place of the Zener diodes to shunt current around the battery cells. In that embodiment, the voltage across each of the serially connected cells is monitored. When the voltage measurements indicate that the cell is fully charged, the FET is turned on to shunt additional charging current around the fully charged cell. In order to prevent discharge of battery cells, isolation switches, formed from additional FETs, are used. These isolation switches simply disconnect the charging circuit from the individual battery cells during a condition when the cells are not being charged.
U.S. Pat. No. 6,580,249 and published U.S. Patent Application No. U.S. 2003/01605393 A1 also disclosed multiple cell battery chargers configured in a serial topology. The multiple cell battery chargers disclosed in these publications also include a shunt device, connected in parallel around each of the serially coupled battery cells. In these embodiments, FETs are used for the shunts. The FETs are under the control of a microprocessor. Essentially, the microprocessor monitors the voltage and temperature of each of the serially connected cells. When the microprocessor senses that the cell voltage or temperature of any cell is above a predetermined theshold indicative that the the cell is fully charged, the microprocessor turns on the FET, thus shunting charging current around that particular battery cell. In order to prevent discharge of the serially connected cells when no power is applied to the battery charger, blocking devices, such as diodes, are used.
Although such multiple cell battery chargers configured in a series topology are able to simultaneously charge multiple battery cells without damage, such battery chargers are as discussed above, not without problems. For example, such multiple cell battery chargers require at least two active components, namely, either a Zener diode or a FET as a shunt and either a FET or diode for isolation to prevent discharge. The need for at least two active devices drives up the cost of such multiple battery cell chargers.
As mentioned above, U.S. Pat. Nos. 6,034,506 and 6,586,909, as well as U.S. Published Patent Application No. U.S. 2003/0117109, disclose multiple cell battery chargers configured in a parallel topology. U.S. Pat. No. 6,586,909 and published U.S. Application No. U.S. 2003/0117109 disclose a multiple cell battery charger for use in charging industrial high capacity electrochemical batteries. These publications disclose the use of a transformer having a single primary and multiple balanced secondary windings that are magnetically coupled together by way of an induction core. Each battery cell is charged by way of a regulator, coupled to one of the multiple secondary windings. While such a configuration may be suitable for large industrial applications, it is practically not suitable for use in charging appliance size batteries, such as, AA and AM batteries.
Finally, U.S. Pat. No. 6,034,506 discloses a multiple cell battery charger for charging multiple lithium ion cells in parallel. In particular, as shown best in FIG. 3 of the '506 patent, a plurality of serially connected lithium ion battery cells are connected together forming a module. Multiple modules are connected in series and in parallel as shown in FIG. 2 of the '506 patent. Three isolation devices are required for each cell making the topology disclosed in the '506 patent even more expensive to manufacture than the series battery chargers discussed above. Thus, there is a need for a battery charger which requires fewer active components than known battery chargers and is thus less expensive to manufacture.
SUMMARY OF THE INVENTION
Briefly, the present invention relates to a multiple cell battery charger configured in a parallel topology. In accordance with an important aspect of the invention, the multiple cell battery charger requires fewer active components than known battery chargers, while at the same time preventing overcharge and discharge of the battery cells. The multiple cell battery charger in accordance with the present invention is a constant voltage battery charger that includes a regulator for providing a regulated source of direct current (DC) voltage to the battery cells to be charged. In accordance with the present invention, the battery charger includes a pair of battery terminals that are coupled in series with a switching device, such as a field effect transistor (FET) and optionally a battery cell charging current sensing element, forming a charging circuit. In a charging mode, the serially connected FET conducts, thus enabling the battery cell to be charged. The FETs are controlled by a microprocessor that also monitors the battery cell voltage and optionally the cell temperature. When the microprocessor senses a voltage or temperature indicative that the battery cell is fully charged, the FET is turned off, thus disconnecting the battery cell from the circuit. Once the battery cell is disconnected from the charger by the FET, additional active devices are not required to isolate the battery cell to prevent the battery charger circuit from discharging the battery cell. As such, a single active device such as the FET, provides multiple functions without requiring additional active devices. Accordingly, the battery charger in accordance with the present invention utilizes fewer active components and is thus less expensive to manufacture than known battery chargers configured with a serial topography.
DESCRIPTION OF THE DRAWING
These and other advantages of the present invention will be readily understood with reference to the following specification and attached drawing wherein:
FIG. 1 is a schematic diagram of the battery charger in accordance with the present invention.
FIG. 2 is a graphical illustration of the voltage, pressure, and/or temperature charging characteristics as a function of time as an exemplary NiMH battery.
FIGS. 3A-3E illustrate exemplary flow-charts for the battery charger for the present invention.
DETAILED DESCRIPTION
The present invention relates to a constant voltage multiple cell battery charger configured to charge multiple battery cells connected in parallel defining a parallel topology. The battery charger, generally identified with the reference 20 , includes a power supply 22 and a regulator 24 . In an AC application, the power supply 22 is configured to receive a source of AC power, such as 120 volts AC, and convert it to a non-regulated source of DC power by way of a bridge rectifier (not shown), for example. or other device, such as a switched mode power supply. In DC applications, the power supply 22 may simply be a unregulated source of DC, for example in the range of 10 to 16 volts DC, such as a vehicular power adapter from an automobile. The unregulated source of DC power from the power supply 22 may be applied to, for example, to a regulator, such as, a DC buck regulator 24 , which generates a regulated source of DC power, which, in turn, is applied to the battery cells to be charged.
The regulator 24 may be an integrated circuit (IC) or formed from discrete components. The regulator 24 may be, for example, a switching type regulator which generates a pulse width modulated (PWM) signal at its output. The regulator 24 may be a synchronous buck regulator 24 , for example, a Linear Technology Model No. LTC 1736, a Fairchild Semiconductor Model No. RC5057; a Fairchild Semiconductor Model No. FAN5234; or a Lihear Technology Model No. LTC1709-85 or others.
The output of the regulator 24 may optionally be controlled by way of a feedback loop. In particular, a total charging current sensing device, such as a sensing resistor R 11 , may be serially coupled to the output of the regulator 24 . The sensing resistor R 11 may be used to measure the total charging current supplied by the regulator 24 . The value of the total charging current may be dropped across the sensing resistor R 11 and sensed by a microprocessor 26 . The microprocessor 26 may be programmed to control the regulator 24 , as will be discussed in more detail below, to control the regulator 24 based on the state of charge of the battery cells being charged.
As shown in FIG. 1 , the battery charger 20 may optionally be configured to charge four battery cells 28 , 30 , 32 , and 34 . As shown, these battery cells 28 , 30 , 32 and 34 are electrically coupled to corresponding pairs of battery terminals: T 1 and T 2 ; T 3 and T 4 ; T 5 and T 6 ; and T 7 and T 8 , respectively. However, the principles of the present invention are applicable to two or more battery cells.
Each battery cell 28 , 30 , 32 and 34 is serially connected to a switching device, such as a field effect transistor (FET) Q 12 , Q 13 , Q 14 and Q 15 . More particularly, the source and drain terminals of each of the FETs Q 12 , Q 13 , Q 14 and Q 15 are serially connected to the battery cells 28 , 30 , 32 and 34 . In order to sense the charging current supplied to each of the battery cells 28 , 30 , 32 and 34 , a current sensing devices, such as the sensing resistors R 37 , R 45 , R 53 , R 60 , may be serially coupled to the serial combination of the FETs Q 12 , Q 13 , Q 14 and Q 15 ; and the pairs of battery terminals, T 1 and T 2 ; T 3 and T 4 ; T 5 and T 6 ; and T 7 and T 8 , The serial combination of the battery terminals T 1 and T 2 ; T 3 and T 4 ; T 5 and T 6 ; and T 7 and T 8 ; FETs Q 12 , Q 12 , Q 14 and Q 15 ; and the optional charging current sensing devices R 37 , R 45 , R 53 and R 60 , respectively, form a charging circuit for each battery cell 28 , 30 , 32 and 34 . These charging circuits, in turn, are connected together in parallel.
The charging current supplied to each of the battery cells 28 , 30 , 32 and 34 can vary due to the differences in charge, as well as the internal resistance of the circuit and the various battery cells 28 , 30 , 32 and 34 . This charging current as well as the cell voltage and optionally the cell temperature may be sensed by the microprocessor 26 . In accordance with an important aspect of the present invention, the multiple cell battery charger 20 may be configured to optionally sense the charging current and cell voltage of each of the battery cells 28 , 30 , 32 and 34 , separately. This may be done by control of the serially connected FETS Q 12 , Q 13 , Q 14 and Q 15 . For example, in order to measure the cell voltage of an individual cell, such as the cell 28 , the FET Q 12 is turned on while the FETs Q 13 , Q 14 and Q 15 are turned off. When the FET 12 is turned on, the anode of the cell 28 is connected to system ground. The cathode of the cell is connected to the V sen terminal of the microprocessor 26 . The cell voltage is thus sensed at the terminal V sen .
As discussed above, the regulator 24 may be controlled by the microprocessor 26 . In particular, the magnitude of the total charging current supplied to the battery cells 28 , 30 , 32 and 34 may be used to determine the pulse width of the switched regulator circuit 24 . More particularly, as mentioned above, the sensing resistor R 11 may be used to sense the total charging current from the regulator 24 . In particular, the charging current is dropped across the sensing resistor R 11 to generate a voltage that is read by the microprocessor 26 . This charging current may be used to control the regulator 24 and specifically the pulse width of the output pulse of the pulse width modulated signal forming a closed feedback loop. In another embodiment of the invention, the amount of charging current applied to the individual cells Q 12 , Q 13 , Q 14 and Q 15 may be sensed by way of the respective sensing resistors R 37 , R 45 , R 53 and R 60 and used for control of the regulator 24 either by itself or in combination with the total output current from the regulator 24 . In other embodiments of the invention, the charging current to one or more of the battery cells 28 , 30 , 32 and 34 may be used for control.
In operation, during a charging mode, the pulse width of the regulator 24 is set to an initial value. Due to the differences in internal resistance and state of charge of each of the battery cells 28 , 30 , 32 and 34 at any given time, any individual cells which reach their fully charged state, as indicated by its respective cell voltage, as measured by the microprocessor 26 . More particularly, when the microprocessor 26 senses that any of the battery cells 28 , 30 , 32 or 34 are fully charged, the microprocessor 26 drives the respective FETs Q 12 , Q 13 , Q 14 , or Q 15 open in order to disconnect the respective battery cell 28 , 30 , 32 and 34 from the circuit. Since the battery cells are actually disconnected from the circuit, no additional active devices are required to protect the cells 28 , 30 , 32 and 34 from discharge. Thus, a single active device per cell (i.e., FETs Q 12 , Q 13 , Q 14 and Q 15 ) are used in place of two active devices normally used in multiple cell battery chargers configured with a serial topology to provide the dual function of preventing overcharge to individual cells and at the same time protecting those cells from discharge.
As mentioned above, the charging current of each of the battery cells 28 , 30 , 32 and 34 is dropped across a sensing resistor R 37 , R 45 , R 53 and R 60 . This voltage may be scaled by way of a voltage divider circuit, which may include a plurality of resistors R 30 , R 31 , R 33 and R 34 , R 35 , R 38 , R 39 , R 41 , R 43 , R 44 , R 46 , R 48 , R 49 , R 51 , R 52 , R 54 , R 57 , R 58 , R 59 , R 61 , as well as a plurality of operational amplifiers U 4 A, U 4 B, U 4 C and U 4 D. For brevity, only the amplifier circuit for the battery cell 28 is described. The other amplifier circuits operate in a similar manner. In particular, for the battery cell 28 , the charging current through the battery cell 28 is dropped across the resistor R 37 . That voltage drop is applied across a non-inverting input and inverting input of the operational amplifier U 4 D.
The resistors R 31 , R 33 , R 34 , and R 35 and the operational amplifier U 4 D form a current amplifier. In order to eliminate the off-set voltage, the value of the resistors R 33 and R 31 value are selected to be the same and the values of the resistors R 34 and R 35 value are also selected to be the same. The output voltage of the operational amplifier U 4 D=voltage drop across the resistor R 37 multiplied by the quotient of the resistor value R 31 resistance value divided by the resistor value R 34 . The amplified signal at the output of the operational amplifier U 4 D is applied to the microprocessor 26 by way of the resistor R 30 . The amplifier circuits for the other battery cells 30 , 32 , and 34 operate in a similar manner.
Charge Termination Techniques
The battery charger in accordance with the present invention can implement various charge termination techniques, such as temperature, pressure, negative delta, and peak cut-out techniques. These techniques can be implemented relatively easily by program control and are best understood with reference to FIG. 2 . For example, as shown, three different characteristics as a function of time are shown for an exemplary nickel metal hydride (NiMH) battery cell during charging. In particular, the curve 40 illustrates the cell voltage as a function of time. The curves 42 and 44 illustrate the pressure and temperature characteristics, respectively, of a NiMH battery cell under charge as a function of time.
In addition to the charge termination techniques mentioned above, various other charge termination techniques the principles of the invention are applicable to other charge termination techniques as well. For example, a peak cut-out charge termination technique, for example, as described and illustrated in U.S. Pat. No. 5,519,302, hereby incorporated by reference, can also be implemented. Other charge termination techniques are also suitable.
FIG. 2 illustrates an exemplary characteristic curve 40 for an exemplary NiMH or NiCd battery showing the relationship among current, voltage and temperature during charge. More particularly, the curve 40 illustrates the cell voltage of an exemplary battery cell under charge. In response to a constant voltage charge, the battery cell voltage, as indicated by the curve 40 , steadily increases over time until a peak voltage value Vpeak is reached as shown. As illustrated by the curve 44 , the temperature of the battery cell under charge also increases as a function of time. After the battery cell reaches its peak voltage V peak , continued charging at the increased temperature causes the battery cell voltage to drop. This drop in cell voltage can be detected and used as an indication that the battery's cell is fully charged. This charge termination technique is known as the negative delta V technique.
As discussed above, other known charge termination techniques are based on pressure and temperature. These charge termination techniques rely upon physical characteristics of the battery cell during charging. These charge termination techniques are best understood with respect to FIG. 2 . In particular, the characteristic curve 42 illustrates the internal pressure of a NiMH battery cell during charging while the curve 44 indicates the temperature of a NiMH battery cell during testing. The pressure-based charge termination technique is adapted to be used with battery cells with internal pressure switches, such as the Rayovac in-cell charge control (I-C 3 ) 1 , NiMH battery cells, which have an internal pressure switch coupled to one or the other anode or cathode of the battery cell. With such a battery cell, as the pressure of the cell builds up due to continued charging, the internal pressure switch opens, thus disconnecting the battery cell from the charger.
Temperature can also be used as a charge termination technique. As illustrated by the characteristic curve 44 , the temperature increases rather gradually. After a predetermined time period, the slope of the temperature curve becomes relatively steep. This slope, dT/dt may be used as a method for terminating battery charge.
The battery charge in accordance with the present invention can also utilize other known charge termination techniques. For example, in U.S. Pat. No. 5,519,302 discloses a peak cut-out charge termination technique in which the battery voltage and temperature is sensed. With this technique, a load is attached to the battery during charging. The battery charging is terminated when the peak voltage is reached and reactivated as a function of the temperature.
Software Control
FIGS. 3A-3E illustrate exemplary flow-charts for controlling the battery charger in accordance with the present invention. Referring to the main program, as illustrated in FIG. 3A , the main program is started upon power-up of the microprocessor 26 in step 50 . Upon power-up, the microprocessor 26 initializes various registers and closes all of the FETs Q 12 , Q 13 , Q 14 , and Q 15 in step 52 . The microprocessor 26 also sets the pulse-width of the PWM output of the regulated 24 to a nominal value. After the system is initialized in step 52 , the voltages across the current sensing resistors R 37 , R 45 , R 53 , and R 60 are sensed to determine if any battery cells are currently in any of the pockets in step 54 . If the battery cell is detected in one of the pockets, the system control proceeds to step 56 in which the duty cycle of the PWM out-put of the regulator 24 is set. In step 58 , a charging mode is determined. After the charging mode is determined, the microprocessor 26 takes control of the various pockets in step 60 and loops back to step 54 .
A more detailed flow-chart is illustrated in FIG. 3B . Initially, in step 50 , the system is started upon power-up of the microprocessor 26 . On start-up, the system is initialized in step 52 , as discussed above. As mentioned above, the battery charger in accordance with the present invention includes two or more parallel connected charging circuits. Each of the charging circuits includes a switching device, such as a MOSFETs Q 12 , Q 13 , Q 14 , or Q 15 , serially coupled to the battery terminals. As such, each charging circuit may be controlled by turning the MOSFETs on or off, as indicated in step 66 and discussed in more detail below. In step 68 , the output voltage and current of the regulator 24 is adjusted to a nominal value by the microprocessor 26 . After the regulator output is adjusted, a state of the battery cell is checked in step 70 . As mentioned above, various charge termination techniques can be used with the present invention. Subsequent to step 70 , the charging current is detected in step 72 by measuring the charging current dropped across the current sensing resistors R 37 , R 45 , R 53 , or R 60 .
One or more temperature based charge termination techniques may be implemented. If so, a thermistor may be provided to measure the external temperature of the battery cell. One such technique is based on dT/dt. Another technique relates to temperature cutoff. If one or more of the temperature based techniques are implemented, the temperature is measured in step 74 . If a dT/dt charge termination technique is utilized, the temperature is taken along various points along the curve 44 ( FIG. 2 ) to determine the slope of the curve. When the slope is greater than a predetermined threshold, the FET for that cell is turned off in step 76 .
As mentioned above, the system may optionally be provided with negative delta V charge termination. Thus, in step 78 , the system may constantly monitor the cell voltage by turning off all but one of the switching devices Q 12 , Q 13 , Q 14 , and Q 15 and measuring the cell voltage along the curve 40 ( FIG. 2 ). When the system detects a drop in cell voltage relative to the peak voltage V sen , the system loops back to step 66 to turn off the switching device Q 12 , Q 13 , Q 14 , and Q 15 for that battery cell.
As mentioned above, a temperature cut-out charge termination technique may be implemented. This charge termination technique requires that the temperature of the cells 28 , 30 , 32 and 34 to be periodically monitored. Should the temperature of any the cells 28 , 30 , 32 and 34 exceed a predetermined value, the FET for that cell is turned off in step 80 . In step 82 , the charging time of the cells 28 , 30 , 32 , and 34 is individually monitored. When the charging time exceeds a predetermined value, the FET for that cell is turned off in step 82 . A LED indication may be provided in step 84 indicating that the battery is being charged.
FIG. 3C illustrates a subroutine for charging mode detection. This subroutine may be used to optionally indicate whether the battery charger 20 is in a “no-cell” mode; “main-charge” mode; “maintenance-charge” mode; an “active” mode; or a “fault” mode. This subroutine corresponds to the block 58 in FIG. 3A . The system executes the charging mode detection subroutine for each cell being charged. Initially, the system checks in step 86 the open-circuit voltage of the battery cell by checking the voltage at terminal Vsen of the microprocessor 26 . If the open-circuit voltage is greater than or equal to a predetermined voltage, for example, 2.50 volts, the system assumes that no battery cell is in the pocket, as indicated in step 88 . If the open-circuit voltage is not greater than 2.50 volts, the system proceeds to step 90 and checks whether the open-circuit voltage is less than, for example, 1.90 volts. If the open circuit voltage is not less than 1.90 volts, the system indicates a fault mode in step 92 . If the open-circuit voltage is less than 1.90 volts, the system proceeds to step 94 and checks whether the open-circuit voltage is less than, for example, 0.25 volts. If so, the system returns an indication that the battery charger is in inactive mode in step 96 . If the open-circuit voltage is not less than, for example, 0.25 volts, the system proceeds to step 98 and checks whether a back-up timer, is greater than or equal to, for example, two minutes. If not, the system returns an indication that battery charger 20 is in the active mode in step 96 . If the more than, for example, two minutes has elapsed, the system checks in step 100 whether the battery cell voltage has decreased more than a predetermined value, for example, 6.2 millivolts. If so, the system returns an indication in step 102 of a maintenance mode. If not, the system proceeds to step 104 and determines whether the back-up timer is greater or equal to a maintenance time period, such as two hours. If not, the system returns an indication in step 106 of a main charge mode. If more than two hours, for example has elapsed, the system returns an indication in step 102 of a maintenance mode.
FIG. 3D illustrates a subroutine for the PWM duty cycle control. This subroutine corresponds to block 56 in FIG. 3A . This subroutine initially checks whether or not a cell is present in the pocket in step 108 as indicated above. If there is no cell in the pocket, the duty cycle of the PWM is set to zero in step 110 . When there is a battery cell being charged, the PWM output current of the regulator 24 is sensed by the microprocessor 26 by way of sensing resistor R 11 . The microprocessor 26 uses the output current of the regulator 24 to control the PWM duty cycle of the regulator 24 . Since the total output current from the regulator 24 is dropped across the resistor R 11 , the system checks in step 111 whether the voltage Vsen is greater than a predetermined value, for example, 2.50 volts in step 111 . If so, the PWM duty cycle is decreased in step 115 . If not, the system checks whether the total charging current for four pockets equal a predetermined value. If so, the system returns to the main program. If not, the system checks in step 114 whether the charging current is less than a preset value. If not, the PWM duty cycle is decreased in step 115 . If so, the PWM duty cycle is increased in step 116 .
The pocket on-off subroutine is illustrated in FIG. 3E . This subroutine corresponds to the block 60 in FIG. 3A . Initially, the system checks in step 118 whether the battery cell in the first pocket (i.e. channel 1 ) has been fully charged. If not, the system continues in the main program in FIG. 3 A., as discussed above. If so, the system checks in step 120 which channels (i.e pockets) are charging in order to take appropriate action. For example, if channel 1 and channel 2 are charging and channel 3 and channel 4 are not charging, the system moves to step 122 and turns off channel 3 and channel 4 , by turning off the switching devices Q 14 and Q 15 . and moves to step 124 and turns on channel 1 and channel 2 , by turning on the switching device Q 12 and Q 13 .
The channels refer to the individual charging circuits which include the switching devices Q 12 , Q 13 , Q 14 , and Q 15 . The channels are controlled by way of the switching devices Q 12 , Q 13 , Q 14 or Q 14 being turned on or off by the microprocessor 26 .
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. Thus, it is to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described above.
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A multiple cell battery charger configured with a parallel topography is disclosed. In accordance with an important aspect of the invention, the multiple cell battery charger requires fewer active components than known battery chargers while at the same time protecting multiple battery cells from overcharge and discharge. The multiple cell battery charger in accordance with the present invention is a constant voltage battery charger that includes a regulator for providing a regulated source of direct current (DC) voltage to the battery cells to be charged. In accordance with the present invention, each battery cell is connected in series with a switching device, such as a field effect transistor (FET) and optionally a current sensing device. In a charging mode, the serially connected FET conducts, thus enabling the battery cell to be charged. The battery voltage is sensed by a microprocessor. When the microprocessor senses that the battery cell is fully charged, the FET is turned off, thus disconnecting the battery cell from the circuit. Since the battery cell is disconnected from the circuit, no additional active devices are required to protect the battery cell from discharge. As such, a single active device per cell, such as the FET, provides multiple functions without requiring additional devices. Accordingly, the battery charger in accordance with the present invention utilizes fewer active components than known battery chargers and is thus much less be expensive to manufacture.
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BACKGROUND
[0001] Sound transmission through windows is one of the major noise sources in rooms. The challenge for noise transmission control through a window is in the implementation of any noise control techniques that do not sacrify the vision quality of the window, and are economical enough for mass production. In order to reduce noise transmission, grid-stiffened single-leaf windows are used, however, the use of grid-stiffeners will affect the vision quality of the windows. Some other techniques associating with noise reduction using acoustic resonators are also developed.
[0002] European patent to Serge and Eric (E. P. Pat No. 698753), discloses a sliding casement window which has a frame with inner and outer peripheral walls delimiting an inner free space and a peripheral opening. An acoustic resonator unit is disposed in this space. In this patent, the acoustic resonator unit is used to absorb the random impinging sound from outside environment and the transmitting sound in the room. However, since the acoustic resonator is only a narrow band noise control device, it cannot be guaranteed to always work at its resonance in this design, resulting in a low efficiency of noise absorption.
[0003] As known in the art, double-glazed windows have been also used for reducing noise transmission. Such windows generally comprise a pair of spaced glass sheets which a hermetically sealed together around their peripheral edges to form a dead-air space of chamber therebetween. Through introducing more mechanical filters, the sound insulation property of the double-glazed windows is significantly improved when compared with a normal single-leaf window. However, double-glazed windows are tied with an unacceptable noise transmission in low-frequencies.
[0004] Attempts have been also made in the past to overcome this problem. For example, United States patent to Eric et al. (U.S. Pat. No. 6,231,710) discloses a sandwiched cylindrical structure having a noise attenuation property, in which a Helmholtz resonator network is integrated into the sandwiched cylindrical shell to reduce the sound transmission. However, its potential of the Helmholtz resonator network using for noise transmission control in small enclosures like such a small air chamber inside the double-glazed window is limited because the bulb-like Helmholtz resonator will occupy more space and it is difficult to integrate into the windows without affecting the vision quality.
[0005] German patent to Jacobus (D.E. Pat. No. 3401996) discloses a sound-insulating double-glazed window having a circumferential acoustic resonator to control noise in low frequencies. The framework of the window consists of two pieces of frames having a U-shaped space in each, which will form the acoustic resonator body when they are connected, and the gap between the two connected frames forms the opening of the resonator. However, assembling such a window is labor-consuming since the framework includes more components than that of a regular double-glazed window, and in fabrication, more attenuation has to be paid on sealing treatments of the two connected frames, which form the acoustic resonator body and any leakage from it can disable the resonator. Moreover, the resonator used in this double-glazed window is actually a circumferential channel having a small gap, thus, the resonance frequencies of this resonator is difficult to design to target to the air-chamber resonances of interest.
[0006] It is an object of the present system to overcome the disadvantages and problems in the prior art.
DESCRIPTION
[0007] The present system proposes a window having a T-shaped acoustic resonator array structurally integrated in a window-spacer. The window provides a compact, economical, practical, and effective noise-reducing window system for noise insulation in broad or specific frequency band.
[0008] These and other features, aspects, and advantages of the apparatus and methods of the present invention will become better understood from the following description, appended claims, and accompanying drawings where:
[0009] FIG. 1 shows a perspective view of the window of the present invention;
[0010] FIG. 2 shows embodiments of typical T-shaped resonators;
[0011] FIG. 3 shows a sectional view of the window;
[0012] FIG. 4 shows half a spacer, integrating T-shaped acoustic resonators;
[0013] FIG. 5 shows the assembly method of the spacer component;
[0014] FIG. 6 shows the assembled spacer;
[0015] FIG. 7 , exhibits the measured noise reduction of the window integrated with one T-Shaped acoustic resonator.
[0016] The following description of certain exemplary embodiment(s) is merely exemplary in nature and is in no way intended to limit the invention, its application, or uses.
[0017] Now, to FIGS. 1-7 ,
[0018] The window of the present invention includes two separated panes of glass arranged in parallel relationship, such panes being separated by a rectangular cross-sectional spacer extending around the peripheral edges of the panes, defining an interior air chamber therebetween, substantially impervious to the ambient atmosphere. When noise impinges to the external pane, the pane vibration can induce the resonance of the air chamber inside the window, which traps a large quantity of acoustic energy at the resonance frequencies. This energy can be effectively dissipated by using T-shaped acoustic resonators incorporated within the spacer.
[0019] The window is suitable for use in civil and industrial structures, wherever noise interferes with comfortable living and working environment. For example, buildings or offices near heavy traffic zones or airports can use the window to effectively reduce noise transmission into rooms.
[0020] FIG. 1 shows a window 100 of the present invention, utilizing a rectangular cross-sectioned spacer tube integrated with a T-shaped acoustic resonator (TAR) array.
[0021] The window 100 generally includes two sheets of glass 101 / 103 , arranged in spaced parallel facing relationship by a prefabricated hollow end cap 105 which extends around the peripheral margined facing edges of the glass 101 / 103 , and each outer surface of the end cap 105 . The adhesive also fills an outwardly facing channel enclosed by the outer surface of the end cap 105 , the web 106 of the H-shaped frame 107 , and the inner surfaces of the sheets 101 / 103 . The end cap 105 , together with the adhesive materials, defines a closed interior chamber between the facing surfaces of the glass 101 / 103 .
[0022] The window 100 also includes end caps 109 , formed using rubber, plastic, or cork plug fixed in with adhesive and curing. Before assembling end cap 105 , resonators should be acoustically tuned and be located away from the nodes of the targeted modes. Therefore, the T-shaped acoustic resonators are integrated into the end cap 105 .
[0023] Although components of the window 100 will be described as being compressibly held in assembly, it should be understood that window components can be held in assembled relationship by a series of clips or like devices (not shown) for being mounted as a unit in a structural building opening. As illustrated in the drawings, the frame is adopted to be mounted in an opening defined by wood sashes 111 of a building structure (not shown). More specifically, the marginal edges of the window 100 are positioned adjacent to a web 106 interconnecting the legs 113 , 115 , 117 of the H-shaped frame. The legs 115 compress glass sheets 101 / 103 against the end cap 105 through the adhesive, while the legs 113 / 117 supporting the window 100 in the sashes 111 mount the window 100 in the spaced relation thereto.
[0024] Although the invention will be described in conjunction with a rectangular window, it should be understood that the invention is equally adoptable to window units having other shapes, for example square, circular, triangular, etc.
[0025] FIG. 2 is an illustration of embodiments of T-shaped acoustic resonators used in the present invention, having a rectangular body and circular neck perpendicular to the body. FIG. 2A , a specific neck is installed; FIG. 2B requires no specific neck.
[0026] Not to be bound theoretically, it is the basic concept of the present invention to use T-shaped acoustic resonators (TAR) 201 and 203 to control the modes of the air chamber (not shown) and thus alleviate noise corresponding to these modes. To this end, specifically designed TARs, either targeting a single mode for a narrow band noise control or multiple-modes with different resonance frequencies for a broadband noise control, are fabricated and integrated into end cap component (not shown). The body tube 205 of the resonator 201 and 203 is fabricated based on the tube; the neck tube 207 of the resonator 203 is formed by drilling a hole on the surface of the spacer tube, having the same physical thickness as the walls of the tube.
[0027] FIG. 3 is an embodiment of the H-shaped frame 300 used with the window of the present invention.
[0028] The frame 300 is adopted for attachment to a sash 301 of the building structure. Attachment is brought about by legs 303 , 305 , 307 and 309 , and a web 311 . The H-shaped frame 300 can take a variety of shapes for example legs longer than other legs, without deviating from the scope of this present invention, in order to adopt to the form of the sash 301 .
[0029] The bottom half of the frame 300 incorporates a end cap having outer surfaces 313 between which is held glass sheets 315 / 317 with a adhesive 319 , which is disposed between the glazing sheets 315 / 317 and each outer surface 313 of the spacer.
[0030] An H-shaped frame is also used for the bottomside of the window, 321 . The bottomside H-shaped frame 321 possesses the same elements as the topside H-shaped frame.
[0031] FIG. 4 shows an extended end cap component 400 present invention. The end cap component 400 is utilized to separate glass on either side of the window. As will be discussed, the end cap component is designed to effectively raise reducing qualities. The end cap 400 is preferably fabricated from a substantially rigid material, for example metal, plastic, glass, or composites. Plastics have a desired heat transfer characteristic, but metal may be less expensive and easier to form during automated manufacturing. The length of the end cap 400 should be slightly smaller than the summation of the width and height of the glass.
[0032] T-shaped resonators 401 , either targeting a single mode for a narrowband noise control or multiple-modes with different resonance frequencies for a broadband noise control, are fabricated and integrated into the end cap 400 . The neck 403 of the resonator 401 is fabricated by drilling a hole on the surface of the end cap 400 . Before assembly of the end cap 400 , resonators 401 should be acoustically tuned and be located away from the nodes of the targeted modes.
[0033] The resonators 401 include end caps 405 formed from rubber, plastic, or cork fixed into the resonator 401 with adhesive and curing. The end cap 400 includes a cutout 407 for forming the frame of the end cap 400 . Also included for forming the frame are connectors 409 on either side of the extended end cap 400 . The connectors are used for connecting to other sides of a end cap, thus forming the complete end cap frame.
[0034] FIG. 5 shows a schematic side view of the assembly method of the end cap 500 . The assembly method includes two end cap components 501 bent at the cutout 503 to a “L” formation. The end cap components 501 are made of resonators 507 , wherein the resonators 507 possess necks 505 .
[0035] The two end cap components 501 are attached at their connector ends 509 , which can be held together by a variety of means, such as adhesion, welding, clamping, etc.
[0036] FIG. 6 shows the end cap 600 fully assembled.
[0037] A double-glazed window consisting of two 3 mm glass panels was fabricated to demonstrate the noise transmission control in the first resonance of the air chamber. The geometric dimensions of the air chamber enclosed between the two glass panels are 830×830×19 mm. One small T-shaped acoustic resonator, having Helmholtz frequency 204 Hz, was designed to target to the first acoustic chamber resonance peak with measured resonance frequency of 204 Hz. The body of the resonator was fabricated by a square cross-sectional aluminum tube with width×height=14.2×14.2 mm and the neck of the resonator was fabricated by a circular cross-sectional aluminum tube having inner diameter 7.7 mm and length 20 mm. The resonator was located at (x,y)=(494, 10) mm. The measured noise reduction (NR) are shown in FIG. 7 . Measurements show a minimum 6.3 dB NR improvement around the targeted resonance peak.
[0038] Having described embodiments of the present system with reference to the accompanying drawings, it is to be understood that the present system is not limited to the precise embodiments, and that various changes and modifications may be effected therein by one having ordinary skill in the art without departing from the scope or spirit as defined in the appended claims.
[0039] In interpreting the appended claims, it should be understood that:
[0040] a) the word “comprising” does not exclude the presence of other elements or acts than those listed in the given claim;
[0041] b) the word “a” or “an” preceding an element does not exclude the presence of a plurality of such elements;
[0042] c) any reference signs in the claims do not limit their scope;
[0043] d) any of the disclosed devices or portions thereof may be combined together or separated into further portions unless specifically stated otherwise; and
[0044] e) no specific sequence of acts or steps is intended to be required unless specifically indicated.
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The present invention relates to a noise attenuating window comprised of two panes of glass separated by a spacer tube. The spacer tube contains T-shaped acoustic resonator capable of targeting a single mode or multiple-mode to be attenuated.
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TECHNICAL FIELD
The following relates to a dynamic environment manager to test binary files (binaries) locally, deploy to distributed clusters, and deploy to production.
BACKGROUND
A production environment having a large number of servers and data centers distributed geographically would benefit from a capability of testing groups of components or systems in various environments. Types of testing can include system testing, integration testing, and end-to-end testing. Integration testing is a type of testing in which two or more sub-components are combined and tested as a group. Integration testing includes validating the interface, data contract and functionality between sub-components. Integration testing typically occurs after unit testing of the sub-components. End-to-end testing is performed by applying tests to a group of various systems, from start of a given process to finish and validation at both points, including intermediate validation at given steps.
The testing process may range from deployment of binaries locally against code built from a mainline system, to clusters for load or integration testing, and to production for larger system testing or data validation.
Much manual overhead is involved in maintaining large, production-like systems. The production-like systems are manually deployed, maintained, refreshed, and typically become stale. Engineering organizations may also deploy system tests by pointing to production binaries. This limits the ability to simulate test data or scenarios or point to mainline-built binaries.
BRIEF SUMMARY
A system, method and computer-readable storage medium are described. An input receives a test specification that includes a list of imports, the list of imports includes an environment manager. The environment manager, being created upon processing of the test specification, delegates management functions to one or more specialized manager objects. The environment manager includes config data that describes paths to one or more binary files, and token settings specifying resources to be created in a test environment for the binary files. A test platform can be either of a local machine and a distributed computing system. The environment manager selects the local machine or distributed computing system as the test platform to be used in testing the one or more binary files. The environment manager by way of the specialized manager objects performs testing, including loading and starting the one or more binary files in the selected test platform based on the paths to the binary files, creating the data resources in the selected platform based on the token settings, and performing the testing using the test environment.
The disclosed system, method, and computer-readable storage medium enables a simple configuration interface for specifying testing of various stages of binaries in various deployment environments with automatic creation and break-down of resources, and without conflicts between test environments using common servers.
These and other aspects are described in detail with respect to the drawings. Other features, aspects, and advantages of the subject matter will become apparent from the description, the drawings, and the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings constitute part of this specification. In the drawings,
FIG. 1 is a system block diagram for testing in an example continuous build and test system;
FIG. 2 is a block diagram for an example Dynamic Environment Manager;
FIGS. 3A , 3 B show a specification of a binary config;
FIG. 4 shows an example binary config file;
FIG. 5 shows an alternative example binary config file;
FIG. 6 is a workflow diagram for the example Dynamic Environment Manager;
FIG. 7 is a flowchart of an example test using the Dynamic Environment Manager; and
FIG. 8 shows a block diagram for a computer that can be used to implement a computer in the system of FIG. 1 .
DETAILED DESCRIPTION
A continuous build and test system provides a capability to deploy binaries to test locally (on a single machine), and deploy to distributed clusters (e.g., in a cloud). Deployment of the binaries is based on tokens and flags to the binaries, and is performed from an abstraction layer that is wrapped in a system integration test. The tokens and flags for the binaries can be specified through a simple mechanism in the form of binary configuration files or at runtime. The abstraction layer enables simplified calls for complex processes performed by a dynamic environment manager (DEM). The dynamic environment manager gathers information from binary config files. The binary config files provide a simple interface for the dynamic environment manager. Provided information specified in binary config files, the dynamic environment manager automates the creation of resources, thus reducing the complexity of client code. Binary config files can be constructed to enable system and integration tests to be deployed at a runtime mainline, at a release branch or at production binaries to a production-like cluster or a local machine, and utilize mocks, point to prior-built binaries, and/or create data stores.
FIG. 1 is a system block diagram for an example continuous build and test system. The build and test system is continuous in the sense that it can be run each time a developer makes a change to binaries. In addition, a binary file can bring up multiple jobs (servers). A test specification 110 includes the test environment 140 where the testing will be performed. In addition, the continuous build and test system can also link to one or more already existing binaries. The continuous build system can include a dynamic environment manager object 120 as an object that can be imported in the test specification. The dynamic environment manager object is threaded so that its methods can be run in parallel. Depending on the set of binaries, the testing may be a system, integration, or end-to-end test. During testing, binaries can be brought up in parallel or sequentially. The order of bringing up binaries (loading and starting each binary file) as sequential jobs can be specified in a binary config file.
The dynamic environment manager 120 can receive as input one or more binary configuration files 134 (binary configs). The Environment Manager 120 refers to the binary configs to obtain information about binaries to be brought up during a test. In the case of a server brought up by a binary, information that can be provided to the environment manager includes location of a distributed system config file, a special health string to check for, arguments with default values, information for automated creation of directories and database tables.
The distributed system config file is a configuration file that can be used in the case of deployment to a distributed system, in order to provide information about the data center to deploy to, what resources are required for the job (e.g., memory, CPU), what flags to pass to a running binary, and any system dependencies.
The binary configs use flags to point to binaries and dependencies and tokens to point to resources including data stores. Tokens are used in creation of resources. The binary configs can contain flags for one or more binaries and for data dependencies between binaries. The binary configs can contain tokens for resources to be created and for specifying where the resources will be created. The config file can also contain config tokens that specify attributes for the creation of data stores.
The dynamic environment manager 120 further includes an abstraction layer that utilizes the config flags and tokens set in the config file and performs flag-based deployment of binaries for testing.
As shown in FIG. 1 , the DEM abstraction layer 122 is a layer above services, such as database creation, that allows actions to be carried out without the client having to directly call the services. Among the services that the abstraction layer 122 interacts with include a local file system interface 124 , a distributed system API 126 , a database creation mechanism 128 , binary validation/health system 130 , and dashboarding/monitoring API 132 .
Also as shown in FIG. 1 , the dynamic environment manager 120 can deploy a test in an environment 140 , such as a local machine 144 , a distributed cluster/datacenter cell 142 (for example as a cloud), or to a production-like environment that uses existing production or pre-built binaries 146 .
The dynamic environment manager 120 can perform job health validation, automatic retry and failure logic, in order to make testing reliable.
When testing is completed, the dynamic environment manager 120 can perform a clean-up operation for servers that are involved during the testing, for all actions performed during testing, as well as clean-up of any resources and data stores that were created for the testing.
FIG. 2 is a diagram showing details of an example implementation of the environment manager 120 . The environment manager 120 can be implemented using an Environment Manager object 202 . In the example implementation, the Environment Manager object 202 is a wrapper for other manager objects to delegate tasks to. The Environment Manager object 202 contains methods defined in the delegate managers. A Reversable actions object 204 keeps track of all actions taken by the DEM. At the end of testing, all actions can be undone (i.e., reversed). The Reversable actions object can also support persisting actions at a location in a distributed file system. This enables cleaning the environment with respect to a previous run before starting new tests.
A Access Control List (ACL) Manager object 206 , Table Manager object 208 , Binary Manager object 210 , Directory Manager object 212 , and Megastore Manager object 214 are manager objects that the environment manager object 202 can delegate tasks to.
The ACL Manager object 206 manages permissions and access to a particular job.
The Table Manager object 208 manages table creation and table deletion. Table creation is performed by a table creator. The Table Manager object 208 includes methods for obtaining a table path and obtaining a table by a table name.
The Binary Manager object 210 manages both local and specialized binaries by using binary executors (Binary Executor 218 , Local Binary Executor 222 and Specialized Binary Executor 220 ), which in turn use a configuration utility. The Binary Manager supports both parallel and sequential execution of binaries. The Binary Manager object 210 contains methods for starting and stopping binaries, as well as for starting queued binaries. The Binary Manager 210 includes a method to check a job health, and for getting information about binaries and jobs. The Binary Manager object 210 can obtain information from a system log.
The Directory Manager object 212 manages creation and deletion of namespace directories using gfile. The Directory Manager object includes methods for creating and deleting directories, and creating a path.
The Megastore Manager object 214 manages creation and deletion of Megastore. The Megastore Manager object 214 includes a method for setting up the Megastore, and can change a version of a Megastore.
Binary Configs
Binary configs include an info section, which can be designated by “[info], and arguments section, which can be designated by “[args],” and a database definitions section, which may be designated by “[Table-insertions].” The info section specifies whether the test environment will be a server, as well as specifies other input sources, such as a distributed system configuration file, and output sources, such as a log file. The arguments section specifies resources to be created and paths for resources. The database definitions section specifies database schemas. Although the binary configs are typically files, it is understood that other means of storage and/or for providing configuration information can be used. For example, it is possible for configuration information to be obtained from an external source, either all at once, or on an as needed basis.
FIGS. 3A , 3 B show examples of tokens supported in binary configs. Although the tokens are shown as specific format and naming, naming and format can be varied as long as they are consistent with the Environment Manager API, and are comprehendable by the user. It is noted that paths specified in a config file are typically relative paths, to for example a base path. Although directory paths are used in the provided examples, paths may also be virtual paths, or be specified using URL's.
The $RESOURCE.$TABLE.$(TABLE_NAME) informs the DEM that it needs to create the specified table before bringing up the job. A [TABLE-table_name] in the config is used to specify the location of the schema, and if the ACL running the test should own the schema.
The $RESOURCE.$GFS.$(dir_path) informs the DEM that it needs to create the specified dir_path before bringing up the job. The dir_path is created relative to the basepath, that is specified in the DEM constructor.
The $RESOURCE.$LS.$(ls_path) informs the DEM that it needs to create the specified ls_path before bringing up the job. The ls_path will be created relative to the is basepath used in the DEM.
The $RUNTIME.$UNIQUE is used to specify a unique job within the environment. It allows clients to use the unique_id specified in the DEM constructor.
The $FLAGS.flag_name allows clients to use a flag to point to binaries and dependencies, and can be used to specifiy a value for a vars key (a vars page for health checking).
FIG. 4 shows an example binary config file. The example config file includes an “info” section 410 , “args” section 420 , and data store definition section 430 . The “info” section 410 contains information that is to be used by a server. In the example, the attribute “healthz_msg” indicates a string to be returned by the server. The attribute “job_name” indicates a template having a position to insert a unique id into a server name. The unique id is used in naming servers and resources in order to prevent conflicts with other automated tests using the same test environment. The continuous build and test system can also use the unique name to preempt the test job in a distributed cell.
The “args” section 420 contains the tokens that are to be passed to the local machine or to the server. Tokens include, for example, pointers to resources and data stores that are to be created and used during a test. In the example, the token “snapshotBasePath” indicates a resource key that denotes a resource that the Environment Manager 120 will create before bringing up the server. The tokens “insertions_table” and “scheduledEventstableName” reference a data store to be created by the Environment Manager 120 . The data store definition section 430 contains a reference to a schema for the data store to be created.
FIG. 5 shows another example of a binary config file. This binary config file includes an info section ([info] 502 ), an arguments section ([args] 504 ), and a table insertions section ([TABLE-insertions] 518 ). The info section specifies that the environment will be a server and that a log of binaries will be saved with the name “severlog.” The info section also indicates the location of a distributed system config file.
The arguments section specifies locations of resources and resources that need to be created. FIG. 5 shows that a database 506 is a resource to be created, and shows the relative location of the database. The arguments section specifies a unique name 508 to be used in identifying the job associated with the binary config. The unique name enables the server to keep the job and its resources separate from other jobs. The arguments section also specifies a user 510 . In addition to specifying creation of a database at a location, the arguments section specifies the location of other resources: including a table 512 , and the files “minCpm.xml” 514 and “scheduleAttempt.data” 516 . The table insertions section specifies a location of a schema for the database, as “insertions.schema” 520 .
Dynamic Environment Manager—Operation
FIG. 6 shows a workflow diagram for operation of the DEM. As can be seen in the diagram, a user defines the destination environment 602 (which may be defined in a distributed system config file) and creates a binary config file 604 that specifies the set of binaries to be tested. The DEM reads from the binary config file to set up the environment 606 . A call is made to lower-level DEM objects to build and deploy the binaries 608 . The call out to lower level objects include calls to dependency abstraction layers 610 , which create the dependencies 612 . The call out to lower level objects also includes calls to build abstraction layers 620 . The build abstraction layers start up binaries 622 .
In the test environment, the DEM provides an API interface to binaries and dependencies as they are used in system tests 630 . Tests can be run in an external continuous build test infrastructure 634 . System tests interface with the DEM and control, use, setup, tear-down binaries and dependencies as needed 632 . Tests are completed as pass/fail status 636 . After completion of the tests, the environment is torn down based on binary config file parameters 638 .
FIG. 7 is a flowchart for an example operation of a continuous build and test system using the Dynamic Environment Manager 120 . To incorporate a Environment Manager, at step 702 a test specification can include a Dynamic Environment Manager object in a list of imports. At step 704 , the DEM object is instantiated.
A developer can specify a destination test environment in a test specification. The destination test environment can be specified as local on a single machine or in a particular distributed cell. The resources that are required for a job (e.g., memory, CPU), flags to pass to the running binary, and system dependencies can be specified in the distributed system config file. Also, dependencies between binaries are specified in the config file. At step 706 , a set of binaries to be included in the test environment are queued up. At step 708 , a unique id for the test environment is generated. At step 710 , dependencies between binaries are established and the set of binaries are started.
At step 712 , the DEM reads respective binary configs for the binaries. As in the example shown in FIG. 4 , a binary config can contain all necessary token and flag information with key values for data stores and resources and the string that the server will return when it is ready to accept test calls. At step 714 , the DEM creates resources specified by key values in the configs. At step 716 , the DEM makes a command line call using the tokens and flags and path to the resources to the specified environment. At step 718 , the continuous build system may call the DEM to add data to created data stores, communicate directly to servers and their associated APIs through exposed method calls. At step 720 , after test execution is completed, the continuous build system calls the DEM to tear down all servers and created resources as identified by the unique id.
Computing Device
FIG. 8 is a block diagram illustrating an example computing device 800 that is arranged for a continuous build and test system in accordance with the present disclosure. In a very basic configuration 801 , computing device 800 typically includes one or more processors 810 and system memory 820 . A memory bus 830 can be used for communicating between the processor 810 and the system memory 820 .
Depending on the desired configuration, processor 810 can be of any type including but not limited to a microprocessor (μP), a microcontroller (μC), a digital signal processor (DSP), or any combination thereof. Processor 810 can include one more levels of caching, such as a level one cache 811 and a level two cache 812 , a processor core 813 , and registers 814 . The processor core 813 can include an arithmetic logic unit (ALU), a floating point unit (FPU), a digital signal processing core (DSP Core), or any combination thereof. A memory controller 815 can also be used with the processor 810 , or in some implementations the memory controller 815 can be an internal part of the processor 810 .
Depending on the desired configuration, the system memory 820 can be of any type including but not limited to volatile memory (such as RAM), non-volatile memory (such as ROM, flash memory, etc.) or any combination thereof. System memory 820 typically includes an operating system 821 , one or more applications 822 , and program data 824 . Application 822 includes a Dynamic Environment Manager 823 . Program Data 824 includes configuration data 825 that is useful for specifying tokens and flags for binaries, as described above. This described basic configuration is illustrated in FIG. 8 by those components within dashed line 801 .
Computing device 800 can have additional features or functionality, and additional interfaces to facilitate communications between the basic configuration 801 and any required devices and interfaces. For example, a bus/interface controller 840 can be used to facilitate communications between the basic configuration 801 and one or more data storage devices 850 via a storage interface bus 841 . The data storage devices 850 can be removable storage devices 851 , non-removable storage devices 852 , or a combination thereof. Examples of removable storage and non-removable storage devices include magnetic disk devices such as flexible disk drives and hard-disk drives (HDD), optical disk drives such as compact disk (CD) drives or digital versatile disk (DVD) drives, solid state drives (SSD), and tape drives to name a few. Example computer storage media can include volatile and nonvolatile, removable and non-removable media implemented in any method or technology for storage of information, such as computer readable instructions, data structures, program modules, or other data.
System memory 820 , removable storage 851 and non-removable storage 852 are all examples of computer storage media. Computer storage media includes, but is not limited to, RAM, ROM, EEPROM, flash memory or other memory technology, CD-ROM, digital versatile disks (DVD) or other optical storage, magnetic cassettes, magnetic tape, magnetic disk storage or other magnetic storage devices, or any other medium which can be used to store the desired information and which can be accessed by computing device 800 . Any such computer storage media can be part of device 800 .
Computing device 800 can also include an interface bus 842 for facilitating communication from various interface devices (e.g., output interfaces, peripheral interfaces, and communication interfaces) to the basic configuration 801 via the bus/interface controller 840 . Example output devices 860 include a graphics processing unit 861 and an audio processing unit 862 , which can be configured to communicate to various external devices such as a display or speakers via one or more A/V ports 863 . Example peripheral interfaces 870 include a serial interface controller 871 or a parallel interface controller 872 , which can be configured to communicate with external devices such as input devices (e.g., keyboard, mouse, pen, voice input device, touch input device, etc.) or other peripheral devices (e.g., printer, scanner, etc.) via one or more I/O ports 873 . An example communication device 880 includes a network controller 881 , which can be arranged to facilitate communications with one or more other computing devices 890 over a network communication via one or more communication ports 882 . The communication connection is one example of a communication media. Communication media may typically be embodied by computer readable instructions, data structures, program modules, or other data in a modulated data signal, such as a carrier wave or other transport mechanism, and includes any information delivery media. A “modulated data signal” can be a signal that has one or more of its characteristics set or changed in such a manner as to encode information in the signal. By way of example, and not limitation, communication media can include wired media such as a wired network or direct-wired connection, and wireless media such as acoustic, radio frequency (RF), infrared (IR) and other wireless media. The term computer readable media as used herein can include both storage media and communication media.
Computing device 800 can be implemented as a portion of a small-form factor portable (or mobile) electronic device such as a cell phone, a personal data assistant (PDA), a personal media player device, a wireless web-watch device, a personal headset device, an application specific device, or a hybrid device that include any of the above functions. Computing device 800 can also be implemented as a personal computer including both laptop computer and non-laptop computer configurations.
There is little distinction left between hardware and software implementations of aspects of systems; the use of hardware or software is generally (but not always, in that in certain contexts the choice between hardware and software can become significant) a design choice representing cost vs. efficiency tradeoffs. There are various vehicles by which processes and/or systems and/or other technologies described herein can be effected (e.g., hardware, software, and/or firmware), and that the preferred vehicle will vary with the context in which the processes and/or systems and/or other technologies are deployed. For example, if an implementer determines that speed and accuracy are paramount, the implementer may opt for a mainly hardware and/or firmware vehicle; if flexibility is paramount, the implementer may opt for a mainly software implementation; or, yet again alternatively, the implementer may opt for some combination of hardware, software, and/or firmware.
The foregoing detailed description has set forth various embodiments of the devices and/or processes via the use of block diagrams, flowcharts, and/or examples. Insofar as such block diagrams, flowcharts, and/or examples contain one or more functions and/or operations, it will be understood by those within the art that each function and/or operation within such block diagrams, flowcharts, or examples can be implemented, individually and/or collectively, by a wide range of hardware, software, firmware, or virtually any combination thereof. In one embodiment, several portions of the subject matter described herein may be implemented via Application Specific Integrated Circuits (ASICs), Field Programmable Gate Arrays (FPGAs), digital signal processors (DSPs), or other integrated formats. However, those skilled in the art will recognize that some aspects of the embodiments disclosed herein, in whole or in part, can be equivalently implemented in integrated circuits, as one or more computer programs running on one or more computers (e.g., as one or more programs running on one or more computer systems), as one or more programs running on one or more processors (e.g., as one or more programs running on one or more microprocessors), as firmware, or as virtually any combination thereof, and that designing the circuitry and/or writing the code for the software and or firmware would be well within the skill of one of skill in the art in light of this disclosure. In addition, those skilled in the art will appreciate that the mechanisms of the subject matter described herein are capable of being distributed as a program product in a variety of forms, and that an illustrative embodiment of the subject matter described herein applies regardless of the particular type of signal bearing medium used to actually carry out the distribution. Examples of a signal bearing medium include, but are not limited to, the following: a recordable type medium such as a floppy disk, a hard disk drive, a Compact Disc (CD), a Digital Video Disk (DVD), a digital tape, a computer memory, etc.; and a transmission type medium such as a digital and/or an analog communication medium (e.g., a fiber optic cable, a waveguide, a wired communications link, a wireless communication link, etc.).
Those skilled in the art will recognize that it is common within the art to describe devices and/or processes in the fashion set forth herein, and thereafter use engineering practices to integrate such described devices and/or processes into data processing systems. That is, at least a portion of the devices and/or processes described herein can be integrated into a data processing system via a reasonable amount of experimentation. Those having skill in the art will recognize that a typical data processing system generally includes one or more of a system unit housing, a video display device, a memory such as volatile and non-volatile memory, processors such as microprocessors and digital signal processors, computational entities such as operating systems, drivers, graphical user interfaces, and applications programs, one or more interaction devices, such as a touch pad or screen, and/or control systems including feedback loops and control motors (e.g., feedback for sensing position and/or velocity; control motors for moving and/or adjusting components and/or quantities). A typical data processing system may be implemented utilizing any suitable commercially available components, such as those typically found in data computing/communication and/or network computing/communication systems.
With respect to the use of substantially any plural and/or singular terms herein, those having skill in the art can translate from the plural to the singular and/or from the singular to the plural as is appropriate to the context and/or application. The various singular/plural permutations may be expressly set forth herein for sake of clarity.
While various aspects and embodiments have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the following claims.
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A continuous build and test system, method, and computer-readable medium, performed by one or more processors is described. The system includes an input for inputting a test specification that imports an environment manager. An environment manager object is created upon processing of the test specification, and delegates management functions to one or more specialized manager objects. The environment manager includes config data that designate paths to one or more binary files, and token settings specifying resources to be used during testing of the binary files. The environment manager selects a test platform to be used in testing the one or more binary files. The specialized manager objects perform testing, including bringing up the one or more binary files in the selected test platform, creating the data resources based on the token settings, performing the instructed tests, and cleaning up created data resources.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to mechanical drivers in general and, more particularly, to a tilt head driver in which squeeze type motion is converted to rotary motion with a novel cable drive mechanism.
2. Description of the Prior Art
In the prior art, all sorts of tools have been devised for driving screws and bolts. Many of these have rather novel arrangements for converting one kind of motion to another but none of them, to applicants' knowledge, are able to convert squeeze type motion into rotary motion on a head which can be tilted to a plurality of positions so as to provide access into difficult areas.
For example, U.S. Pat. No. 3,948,120 discloses a wrench head with a fixed jaw and a sliding jaw. The handle is separate and is attached to the head through a square hole. The handle may be ratcheted. U.S. Pat. No. 4,296,654 discloses a wrench in which a gear drive is used to transmit power to the output. The input handle may be rotated or pumped in a plane parallel to or perpendicular to the output axis to impart the desired rotation at the output. U.S. Pat. No. 4,327,611 discloses a double ended wrench with pivoted ends and a sleeve which moves to i) leave both heads free or ii) lock either end. U.S. Pat. No. 4,463,632 discloses a device for temporarily holding a tool at a particular angle and then, when desired, locking it in that position. U.S. Pat. No. 4,488,461 discloses a continuously adjustable wrench. U.S. Pat. No. 4,513,642 discloses a wrench with a head rotatable with respect to the handle so that the angular relationship is variable. Retaining means hold the angle during application of force. Wiggling the handle allows the head to turn.
None of the prior art allows squeezing motion to be converted into rotary motion and where the head itself must be adjustable to various positions to accommodate reading difficult access areas.
SUMMARY OF THE INVENTION
The present invention provides a tool which converts squeeze motion to rotary motion and with a head tiltable to various anges to accommodate access to sites. A novel cable drive mechanism is employed and one-way turning is provided so that continuous resetting of the tool in the socket to be driven is not required. Such action is particularly desirable in situations where many rotations of the head may be required, and removal and reinsertion of the head into the screw slot on each turn is undesirable.
While the present invention has utility in many fields, it finds specific utility in surgical fieds where, for example, it is desired to fasten a prosthetic implant into or onto adjacent bones.
For example, in out U.S. Pat. No. 4,636,217, assigned to the assignee of the present invention, a spinal implant prosthetic insert for implementation into a void in the spinal column in place of a diseased or injured vertabra is disclosed. The insert is rigidly fixed in place with bone screws that will screw into the adjacent upper and lower vertabrae after the insert has been positioned in place. The driving shafts which cause the screws to move into the upper and lower bones are often awkward to reach with standard driving tools. Furthermore, the drive mechanism between the driving shafts and the screws requires a large number of turns before the screws are fully in place. With standard tools, this can be difficult and rather exhausting.
With the present invention, the screws or other rotatable fasteners can be accessed quite easily by tilting the head of the present invention to the proper position and inserting the driver into or around the fastener. After the driver has been properly connected to the fastener, it only takes further squeezing motions of the handles to provide one-way rotary motion of the driver. Thus, in the surgical use discussed above, the screws may be set in the upper and lower bones with simple squeezing motions much more easily than has been permitted with the prior art devices. It should be understood that while the present invention finds particular applicability to the surgical procedures outlined above, the invention is not to be limited to surgical applications since, as will be seen by those skilled in the art, many other applications of the tool are possible.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top view of the driver of the present invention;
FIG. 2 is a side view of the driver of FIG. 1;
FIG. 3 is a partial side view of the driver cut away to show the cable driving mechanism;
FIG. 4 is a cutaway view of the drive head; and
FIG. 5 is a side view of FIG. 4 showing the tilt head locking arrangement of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 and 2 show a top view and side view of the overall appearance of the driver 10 of the present invention. It is seen that the driver comprises a head portion 12 and a handle portion 14. The head portion 12 includes a drive member 16 at the far end thereof which drive member may have an end configured so as to fit the screw or other fastener configuration with which it is desired to be used. Drive member 16 may be screw-threaded onto the shaft 18 to which it is attached by a screw thread of opposite inclination to the direction of drive so as to prevent loosening of drive member 16 during use. Drive member 16 may be replaced with other forms of heads such as Philips head, flat or Allen wrench type heads to accommodate various drive configurations.
Head 12 also includes a spring biased member 20 which may be pushed upwardly in FIG. 1 so as to allow the steering of a shaft housing 18 and drive member 16 to any of a plurality of desired angles and thereafter the spring will bias the member 20 back to a locking position. This mechanism will be described more completely in connection with FIG. 5.
Drive member 16, shaft housing 18 and bias member 20 are preferably made of metal and, for surgical applications, are preferably made of 316 L low carbon stainless steel, as are the other metal parts described hereinafter.
Handle 14, which may be made of thick white nylon or other suitable material, is seen in FIGS. 1 and 2 to comprise three separate parts. In FIG. 1, an upper handle member 24 and a lower handle member 26 are shaped so as to provide a central opening 28 into which a movable handle member 30 is positioned. It is seen that both upper and lower handle members 24 and 26 are shaped at the left end in fluted fashion, as at 32, so as to provide hand grips for the operator.
Movable member 30 is joined into the opening 28 of the upper and lower housing members 24 and 26 by a suitable connector such as a bolt 36, as will be better described in connection with FIG. 3. Movable handle member 30 will rotate about the axis of bolt 36 is scissor-like fashion with respect to the upper and lower housing member 24 and 26 and into and out of the aperture 28. Member 30 is spring biased by apparatus best shown in FIG. 3 so as to automatically return to the position shown in FIG. 2 after each time it is squeezed together.
By a novel drive mechanism, to be described in connection with FIGS. 3 and 4, squeezing motion of movable member 30 with respect to upper and lower housing members 24 and 26 operates to cause clockwise driving motion to the member 16 and thus enable the rotation of the screws of the above described prosthetic insert to drive them into the upper and lower bones as desired.
Turning now to FIG. 3, a cutaway section of a portion of the handle 14 and the head 12 is shown. As seen in FIG. 3, the movable handle 30, shown in cross section, is attached to a cam shaped member 40 which may also be made of stainless steel.
A cable 44 is shown attached to member 40 at a position 46 and then winds around the cam shaped surface of member 40 and through the handle 14 where it is wrapped around a central drum 50 in head 12, as will be better seen in connection with FIG. 4.
After being wound around drum 50, cable 44 reenters handle 14 into an aperture 54 where its opposite end is connected to a tension spring 56 stretched out in cavity 54 and connected at the other end thereof by a pinion or bolt 58.
Drum 50 is connected, as will be better seen in connection with FIG. 4, to a gear 60 which is fastened to a rotatable shaft 62 extending down the interior of shaft housing 18 and is fastened to the drive member 16.
It will be understood that squeezing of movable member 30 with respect to handle members 24 and 26 will cause clockwise rotation of member 40 thus pulling cable 44 to the left, in FIG. 3, so as to rotate drum 50 in a clockwise direction and pull tension spring 56 further to the right in so doing. Rotation of drum 50 will cause rotation of pinion 60 and thus shaft 62 and driving member 16 so as to cause the desired motion for turning the screw members. Upon releasing the squeezing force, spring 56 will pull cable 44 and drum 50 in a counterclockwise direction thus bringing the apparatus back to the position shown in FIG. 3. By a clutch arrangement, described in connection with FIG. 4, releasing of the squeezing force, while rotating drum 50 in the counterclockwise direction, will not result in rotation of pinion 60 or driving member 16 thus eliminating the need to disengage the driving member 16. Further driving of the screw is accomplished by additional squeezings of handle 14 and a large number of rotations are possible without undue fatigue.
Referring to FIG. 4, an interior view of the driving head 12 is shown. As can be seen in FIG. 4, cable 44 on exiting handle 14 is wrapped several times around drum 50 which has on its outer surface grooves such as 70 sized to fit the cable 44.
Drum 50 is connected through a clutch mechanism 74, which may be an RL 040708 overrunning clutch manufactured by the Torrington Co., to central bolt 75 connected to a gear 76 which is adapted to cooperate with pinion 60 which is shown attached to shaft 62 as by a set screw 78. As drum 50 rotates in the driving direction, clutch 74 rotates central bolt 75 and gear 76 so as to drive pinion 60, shaft 62 and driver member 16. When drum 50 turns in the opposite direction, clutch 74 prevents bolt 75, gear 76, pinion 60, shaft 62 and member 16 from turning.
Driving member 16 is shown attachable to shaft housing 18 as by screw threads 86 so that member 16 may be removed and replaced for various applications. Screw threads 86 should be oppositely threaded to prevent unwinding during use.
It is thus seen that squeezing of the movable member 30 results in linear motion of cable 44, pulling drum 50 in the driving direction so that through clutch mechanism 74, driving gear 76, pinion 60, shaft 62 and driving member 16 are rotated in the desired direction. Release of the squeezing force results only in rotation of drum 50 since clutch 74 does not transfer this rotation to the member 16.
Spring biased member 20 is also shown in FIG. 4 having a cup-shaped portion 90 into which a compression spring 92 is positioned. Lower handle member 26 of handle 14 also has a cup-shaped portion 94 into which the other end of spring 92 is positioned. Spring 92 is held in place by a bolt 96 extending from a cup-shaped portion 98 in upper handle member 24 through handle 14 and the center of spring 92. Member 20 has a vertical shaft 100 extending through an aperture 101 in the head 12. The upper end of shaft 100 has an enlarged section 102 which cooperates with a member 104, better seen in FIG. 5, to allow rotation of the shaft housing 18 to various tilt angles. Member 104 has a plurality of crescent-shaped apertures 110 into which the enlarged end portion 102 may fit and lock. By pushing member 20 upwardly against the compression of spring 92, enlarged portion 102 will move out of contact with member 104 to allow rotation of the shaft housing 18 about the axis of bolt 80 so as to bring other crescent shaped apertures 110 into alignment with the enlarged portion 102. When the desired position is reached, member 20 is released and under the action of spring 92 enlarged portion 102 moves into the desired crescent cutout, thus locking it in the desired position. While three such positions have been shown in FIG. 5, it is clear that any number of desired positions may be utilized.
It is therefor seen that I have provided a novel tiltable head driver mechanism in which rotary motion is obtained through squeezing action of the handle through a one-way clutch mechanism that allows rotary motion of the driving member 16 without withdrawing it from the screw it is driving.
If desired, the cable 44 can be wound around drum 50 in the opposite direction so as to create a similar device but with unscrewing capabilities.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention.
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A driving tool having a tiltable head lockable into a plurality of positions for imparting rotating motion to an output device as the result of squeezing two handle members.
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FIELD OF THE INVENTION
This invention relates to novel physiologically active substances PF1092A, PF1092B and PF1092C, or salts thereof, which are useful as contraceptives or therapeutic drugs for certain forms of hormone dependent cancer of the breast, ovaries, uterus and endometrium, and to a process for the production thereof.
BACKGROUND OF THE INVENTION
Progesterone, which is a sex hormone, is an effective gestagen biologically synthesized in endocrine organs. It is an intermediate of various steroid hormones biologically synthesized from cholesterol, and its main secretion sources are corpus luteum and placenta. In the uterus and mammary gland, progesterone receptors are induced by pretreatment of estrogen, and progesterone is secreted from corpus luteum appeared after ovulation and renders possible implantation of fertilized egg in the uterus. Because of such a function, inhibiting substances of the progesterone-progesterone receptor binding (progesterone receptor antagonist) are used as contraceptives.
In the treatment for breast cancer, the ablative surgery such as oophorectomy and adrenalectomy have been carried out actively since the late nineteenth century. Thereafter, based on the progress in studies on the structures and physiological functions of sex hormones such as estrogen and progesterone, and their receptors, the antiestrogen tamoxifen was found (Wiseman, Tamoxifen, published by John Wiley & Sons, England, 1994), and the endocrine therapy of breast cancer was drastically changed by this discovery from the ablative surgery to internal endocrine therapy. In addition, a synthetic gestagen MPA (medroxyprogesterone acetate) (Y. Iino etaI., Jpn. J. Breast Cancer, vol. 1, pp. 201-213, 1986) has been put into practical use, and LH-RH (luteinizing hormone releasing hormone) agonist and aromatase inhibitor have been newly developed, so that the endocrine therapy of breast cancer is now taking a new turn.
As progesterone receptor antagonist to be used as oral contraceptives or breast cancer treating drugs, RU38486 (Cancer Res., vol. 49, pp. 2851-2856, 1989) and ZK98299 and ZK112993 (J. Sterold Biochem. Molec. Biol., vol. 41, pp. 339-348, 1992) are now under development. Since these agents still have problems in terms of side effect or production cost and their effects are not satisfied, the development of a new progesterone receptor antagonist has been desired in accordance with the increase in incidence of drug-resistant breast cancers.
SUMMARY OF THE INVENTION
In view of the above, the present inventors have continued screening of substances which inhibit binding of progesterone to progesterone receptor and have found that substances, which inhibit binding of progesterone to progesterone receptor, are produced in a cultured mixture of a strain belonging to the genus Penicillium. And the present inventors have isolated a substance PF1092A, a substance PF1092B and a substance PF1092C as active ingredients from the cultured mixture, and thereby completed the present invention.
The object of the present invention is to provide novel physiologically active substances PF1092A, PF1092B and PF1092C, or salts thereof, and a process for their production.
The first aspect of the present invention relates to a substance PF1092A which has the following physico-chemical properties:
(1) color and shape: colorless needle crystals;
(2) molecular formula: C 17 H 20 O 5 ;
(3) mass spectrum (FD-MS): m/z 304 (M) + ;
(4) specific rotation: α! D =-10.86° (c 0.5, CHCl 5 );
(5) ultraviolet ray absorption spectrum λmax: 322 (17,500) nm(ε) (in methanol);
(6) infrared absorption spectrum: measured in KBr tablet, as Shown in FIG. 1;
(7) 1 H NMR spectrum: measured in CDCl 3 solution, as shown in FIG. 2
δ (ppm): 5.97 (1H), 5.66 (1H), 5.28 (1H), 4.53 (1H), 2.83 (1H), 2.19 (3H), 2.18 (1H), 2.05 (0H), 1.97 (1H), 1.91 (3H), 1.15 (3H), 1.10 (3H);
(8) 13 C NMR spectrum: measured in CDCl 3 solution, as shown in FIG. 3
δ (ppm): 171.8 (s), 170,9 (s), 149.3 (s), 146.3 (s), 140.4 (s), 128.7 (d), 122,3 (s), 107.7 (d), 73.6 (d), 68.2 (d), 40.2 (d), 37.8 (s), 35.6 (t), 21.0 (q), 20,9 (q), 12.7 (q), 8.6 (q);
(9) solubility: soluble in chloroform, acetone, ethyl acetate, methanol and dimethyl sulfoxide, and insoluble in water and hexane;
(10) basic, acidic or neutral: neutral substance; and
(11) Rf value by silica gel thin layer chromatography (TLC): 0.25 in hexane-ethyl acetate (1:1) developing solvent.
The second aspect of the present invention relates to a substance PF1092B which has the following physico-chemical properties:
(1) color and shape: colorless needle crystals;
(2) molecular formula: C 17 H 20 O 5 ;
(3) mass spectrum (FD-MS): m/z 304 (M) + ;
(4) specific rotation: α! D =-110.22° (c 0.5, CHCl 3 );
(5) ultraviolet ray absorption spectrum λmax: 320 (15,100) nm(ε) (in methanol);
(6) infrared absorption spectrum: measured in KBr tablet, as shown in FIG. 4;
(7) 1 H NMR spectrum: measured in CDCl 3 solution, as shown in FIG. 5
δ (ppm): 5.95 (1H), 5.57 (1H), 5.46 (1H), 4.05 (1H), 2.84 (1H), 2.18 (1H), 2.15 (3H), 1.97 (0H), 1.91 (3H), 1.83 (1H), 1.23 (3H), 1.22 (3H);
(8) 13 C NMR spectrum: measured in CDCl 3 solution, as shown in FIG. 6
δ (ppm): 170.9 (s), 170.2 (s), 149.5 (s), 146.7 (s), 142.4 (s), 124.5 (d), 122.4 (s), 107.4 (d), 72.5 (d), 70.5 (d), 41.0 (d), 38.1 (s), 35.8 (t), 21.4 (q), 21.2 (q), 12.8 (q), 8.6 (q);
(9) solubility: soluble in chloroform, acetone, ethyl acetate, methanol and dimethyl sulfoxide, and insoluble in water and hexane;
(10) basic, acidic or neutral: neutral substance; and
(11) Rf value by silica gel thin layer chromatography (TLC): 0.42 in hexane-ethyl acetate (1:1) developing solvent.
The third aspect of the present invention relates to a substance PF1092C which has the following physico-chemical properties:
(1) color and shape: colorless needle crystals;
(2) molecular formula: C 15 H 18 O 4 ;
(3) mass spectrum (FD-MS): m/z 262 (M) + ;
(4) specific rotation: α! D =-96.36° (c 0.5, CHCl 3 );
(5) ultraviolet ray absorption spectrum λmax: 324 (14,900) nm(ε) (in methanol);
(6) infrared absorption spectrum: measured in KBr tablet, as shown in FIG. 7;
(7) 1 H NMR spectrum: measured in CDCl 3 solution, as shown in FIG. 8
δ (ppm): 5.96 (1H), 5.64 (1H), 4.37 (1H), 3.93 (1H), 2.83 (1H), 2.22 (0H), 2.20 (0H), 2.17 (1H), 1.91 (3H), 1.24 (3H), 1.20 (3H);
(8) PC NMR spectrum: measured in CDCl 3 solution, as shown in FIG. 9
δ (ppm): 171.0 (s), 149.3 (s), 146.7 (s), 141.0 (s), 129.1 (d), 122.1 (s), 107.8 (d), 72.4 (d), 69.0 (d), 40.3 (d), 37.9 (s), 35.9 (t), 21.5 (q), 13.0 (q), 8.5 (q);
(9) solubility: soluble in chloroform, acetone, ethyl acetate, methanol and dimethyl sulfoxide, and insoluble in water and hexane;
(10) basic, acidic or neutral: neutral substance; and
(11) Rf value by silica gel thin layer chromatography (TLC): 0.20 in hexane-ethyl acetate (1:1) developing solvent.
The fourth aspect of the present invention relates to a process for producing a physiologically active substance PF1092 which comprises culturing a fungal microorganism capable of producing the physiologically active substances PF1092 and collecting the physiologically active substances PF1092 from the cultured mixture. Strain PF1092 to be used in the present invention is a fungus isolated from a soil sample collected in 1991.
Other objects and advantages of the present invention will be made apparent as the description progresses.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a graph showing infrared absorption spectrum of substance PF1092A in KBr tablet.
FIG. 2 is a graph showing 400 MHz 1 H NMR spectrum of substance PF1092A in CDCl 3 solution.
FIG. 3 is a graph showing 100 MHz 13 C NMK spectrum of substance PF1092A in CDCl 3 solution.
FIG. 4 is a graph showing infrared absorption spectrum of substance PF1092B in KBr tablet.
FIG. 5 is a graph showing 400 MHz 1 H NMR spectrum of substance PF1092B in CDCl 3 solution.
FIG. 6 is a graph showing 100 MHz 13 C NMR spectrum of substance PF1092B in CDCl 3 solution.
FIG. 7 is a graph showing infrared absorption spectrum of substance PF1092C in KBr tablet.
FIG. 8 is a graph showing 400 MHz 1 H NMR spectrum of substance PP1092C in CDCl 3 solution.
FIG. 9 is a graph showing 100 MHz 13 C NMR spectrum of substance PF1092C in CDCl 3 solution.
DETAILED DESCRIPTION OF THE INVENTION
1. Mycological properties of strain PF1092
(1) Cultural characteristics:
It forms a colony of 30 to 40 mm diameter on Czapek yeast extract agar medium after culturing at 25° C. for 7 days. The colony is white and funiculose, and forms conidia scatteringly. Backside of the colony becomes light brown. It grows well on malt extract agar medium, and diameter of its colony reaches 40 to 45 mm after culturing at 25° C. for 7 days. The colony is white and funiculose, forms conidia slightly and produces light brown extract. Backside of the colony becomes light mud yellow. At 37° C., its growth and formation of conidia are superior to those at 25° C. on all media.
(2) Morphological characteristics:
Conidiophore stands straight almost vertically from aerial mycelium, is rough-surfaced and has a size of 30-70×2.5-3.5 μm. Penicilli are monoverticillate. Four to eight phialides are formed on conidiophore, each being needle-like and having smooth to slightly rough surface and a size of 8-10×2.5-3.0 μm. Conidium is globose to subglobose, flat with slightly depressed sides, and has smooth surface and a size of 2.0-2.5μm.
On the basis of the above mycological characteristics, this strain was identified as the genus Penicillium.
This strain has been deposited in National Institute of Bioscience and Human Technology, Agency of Industrial Science and Technology, as FERM P-14724 (international deposition number under Budapest Treaty, FERM BP-5350).
As can be found in other fungi, strain PF1092 is apt to change its properties. For example, not only strain PF1092 but also all of its mutant strains (spontaneous or induced mutants), zygotes and genetic recombinants can be used in the present invention, provided that they can produce substances PF1092.
2. A method of culturing substance PF1092 producing strain
The substance PF1092 producing strain is cultured using a medium containing nutrients which can be utilized by ordinary microorganisms. As the nutrient sources, known materials conventionally used for the culturing of fungi can be used. Examples of usable carbon sources include glucose, sucrose, starch syrup, dextrin, starch, glycerol, molasses, animal and plant oils and the like. Examples of usable nitrogen sources include soybean meal, wheat germ, corn steep liquor, cotton seed meal, meat extract, peptone, yeast extract, ammonium sulfate, sodium nitrate, urea and the like. In addition to these nutrients, it is effective to add inorganic salts which can release sodium, potassium, calcium, magnesium, cobalt, chlorine, phosphate, sulfate and the like ions as occasion demands. Also, certain organic and inorganic substances which can assist the fungal growth and enhance the production of substances PF1092 may be added properly.
Preferably, the culturing may be carried out under aerobic Conditions, particularly by static culturing using a rice medium or by submerged culturing. Suitable culturing temperature is 15° to 40° C., but the culturing is carried out at about 26° to 37° C. in most cases. Though it varies depending on the medium and culturing conditions employed, accumulation of produced substances PF1092 reaches its maximum generally after 10 to 20 days of culturing in the case of static culturing using a rice medium or generally after 2 to 10 days of shaking or fermentor culturing. The culturing is completed when maximum accumulation of substances PF1092 is obtained, and the desired substance is isolated and purified from the culture broth.
3. Purification of substances PF1092
Substances PF1092 thus obtained by the present invention can be extracted and purified from the cultured mixture making use of its properties by usual separation means such as solvent extraction, ion exchange resin method, absorption or partition chromatography, gel filtration, dialysis, precipitation and the like, alone or in an appropriate combination. For example, substances PF1092 can be extracted with acetone-water or ethyl acetate after culturing using a rice medium. In order to further purify substances PF1092, a chromatography may be carried out using an adsorbent such as silica gel (for example, Wakogel C-200 manufactured by Wako Pure Chemical Industries), alumina or the like or Sephadex LH-20 (manufactured by Pharmacia), Toyo Pearl HW-40SF (manufactured by Tosoh) or the like.
By carrying out such techniques alone or in an optional combination, highly purified substance PF1092A, substance PF1092B and substance PF1092C are obtained. Physico-chemical properties and chemical structures of the thus obtained substances PF1092A, PF1092B and PF1092C are as follows.
1. Physico-chemical properties and chemical structure of substance PF1092A:
(1) Color and shape: colorless needle crystals
(2) Molecular formula: C 17 H 20 O 5
(3) Mass spectrum (FD-MS): m/z 304 (M) +
(4) Specific rotation: α! D =-10.86° (c 0.5, CHCl 3 )
(5) Ultraviolet ray absorption spectrum λmax: 322 (17,500) ran(e) (in methanol)
(6) Infrared absorption spectrum: measured in KBr tablet (see FIG. 1)
(7) 1 H NMR Spectrum: measured in CDCl 3 solution (see FIG. 2)
δ (ppm): 5.97 (1H), 5.66 (1H), 5.28 (1H), 4.53 (1H), 2.83 (1H), 2.19 (3H), 2.18 (1H), 2.05 (0H), 1.97 (1H), 1-91 (3H), 1.15 (3H), 1.10 (3H)
(8) 13 C NMR Spectrum: measured in CDCl 3 solution (see FIG. 3)
δ (ppm): 171.8 (s), 170.9 (s), 149.3 (s), 146.3 (s), 140.4 (s), 128.7 (d), 122.3 (s), 107.7 (d), 73.6 (d)r 68.2 (d), 40.2 (d), 37.8 (s), 25.6 (t), 21.0 (q), 20.9 (q), 12.7 (q), 8.6 (q)
(9) Solubility; soluble in chloroform, acetone, ethyl acetate, methanol and dimethyl sulfoxide, and insoluble in water and hexane
(10) Basic, acidic or neutral: neutral substance
(11) Rf Value by silica gel thin layer chromatography (TLC): 0.25 in hexane-ethyl acetate (1:1) developing solvent
Based on the above physico-chemical properties and X-ray crystallographic analysis, the following chemical structure was determined. ##STR1## 2. Physico-chemical properties and chemical structure of substance PF1092B:
(1) Color and shape: colorless needle crystals
(2) Molecular formula: C 17 H 20 O 5
(3) Mass spectrum (FD-MS): m/z 304 (M) +
(4) Specific rotation: α! D 24 =-110.22° (c 0.5, CHCl 3 )
(5) Ultraviolet ray absorption spectrum λmax: 320 (15,100) nm(e) (in methanol)
(6) Infrared absorption spectrum: measured in KBr tablet (see FIG. 4)
(7) 1 H NMR Spectrum: measured in CDCl 3 solution (see FIG. 5)
δ (ppm): 5.95 (1H), 5.57 (1H), 5.46 (1H), 4.05 (1H), 2.84 (1H), 2.18 (1H), 2,15 (3H), 1.97 (0H), 1.91 (3H), 1.83 (1H), 1.23 (3H), 1.22 (3H)
(8) 13 C NMR Spectrum: measured in CDCl 3 solution (see FIG. 6)
δ (ppm): 170.9 (e), 170.2 (G), 149.5 (s), 146.7 (s), 142.4 (s), 124.5 (d), 122.4 (s), 107.4 (d), 72.5 (d), 70.5 (d), 41.0 (d), 38.1 (s), 35.8 (t), 21.4 (q), 21.2 (q), 12.8 (q), 8.6 (q)
(9) Solubility: soluble in chloroform, acetone, ethyl acetate, methanol and dimethyl sulfoxide, and insoluble in water and hexane
(10) Basic, acidic or neutral: neutral substance
(11) Rf Value by silica gel thin layer chromatography (TLC): 0.42 in hexane-ethyl acetate (1:1) developing solvent
Based on the above physico-chemical properties and X-ray crystallographic analysis, the following chemical structure was determined. ##STR2## 3. Physico-chemical properties and chemical structure of substance PF1092C:
(1) Color and shape: colorless needle crystals
(2) Molecular formula: C 15 H 18 O 4
(3) Mass spectrum (FD-MS): m/z 262 (M) +
(4) Specific rotation: α! D 24 =-96.3° (c 0.5, CHCl 3 )
(5) Ultraviolet ray absorption spectrum λmax, 324 (14,900) nm(e) (in methanol)
(6) Infrared absorption spectrum: measured in KBr tablet (see FIG. 7)
(7) 1 H NMR Spectrum: measured in CDCls solution (see-FIG. 8)
δ (ppm): 5.96 (1H), 5.64 (1M), 4.37 (1H), 3.93 (1M), 2.83 (1H), 2.22 (0H), 2.20 (0H), 2.17 (1H), 1.91 (3H), 1.24 (3H), 1.20 (3H).
(8) 13 C NMR Spectrum: measured in CDCl 3 solution (see FIG. 9)
δ (ppm): 171.0 (s), 149.3 (s), 146.7 (s), 141.0 (s), 129.1 (d), 122.1 (s), 107.8 (d), 72.4 (d), 69.0 (d), 40.3 (d), 37.9 (s), 35.8 (t), 21.5 (q), 13.0 (q), 8.5 (q).
(9) Solubility: soluble in chloroform, acetone, ethyl acetate, methanol and dimethyl sulfoxide, and insoluble in water and hexane,
(10) Basic, acidic or neutral: neutral substance
(11) Rf Value by silica gel thin layer chromatography (TLC): 0.20 in hexane-ethyl acetate (1:1) developing solvent.
Based on the above physico-chemical properties and X-ray crystallographic analysis, the following chemical structure was determined. ##STR3##
Examples of the salts of substances PP1092 include metal salts, particularly alkali metal salts such as sodium salt and alkaline earth metal salts such as calcium salt, as well as acid addition salts with pharmaceutically acceptable inorganic or organic acids.
As described below, the substance PF1092A, substance PF1092B and substance PF1092C or salts thereof in the present invention are Useful as contraceptives or anticancer drugs. When used as pharmaceutical preparations, various known formulation and administration methods can be employed. The drug compositions of the present invention are prepared by using substance PF1092A, substance PF1092B and substance PF1092C or salts thereof as active ingredients, mixing them with usually used inorganic or organic carriers and then making the mixture into solid, semi-solid or liquid form to give oral preparations or parenteral preparations such as external preparations.
Examples of the dosage form for use in oral administration include tablets, pills, granules, soft or hard capsules, powders, fine subtilaes, dusts, emulsions, suspensions, syrups, pellets, elixirs and the like. Examples of the dosage form for use in parenteral administration include injections, drip infusion, transfusion, ointments, lotions, tonic preparations, sprays, suspensions, oils, emulsions, suppositories and the like. Formulation of the active ingredients of the present invention can be effected in accordance with an ordinary method by optionally using surface active agents, fillers, coloring agents, flavors, preservatives, stabilizers, buffers, suspending agents, tonicity agent's and other usually used adjuvants.
Dose of the drug composition of the present invention varies depending on its type, diseases to be treated or prevented, its administration method, age and symptoms of each patient, treating period and the like, but, in general, the active ingredient may be administered in a dose per day per adult of from 0.01 to 1,000 mg/kg, preferably from 0.1 to 100 mg/kg in the case of intravenous injection, from 0,01 to 1,000 mg/kg, preferably from 0.1 to 100 mg/kg in the case of intramuscular injection or from 0.5 to 2,000 mg/kg, preferably from 1 to 1,000 mg/kg in the case one oral administration.
The following examples are provided to further illustrate the present invention. However, since various methods for the production of substances PF1092 can be devised based on its properties revealed by the present invention, it is to be expressly understood that the examples are not intended as a definition of the limits of the invention and therefore that not only modification means of the examples but also all methods for the production, concentration, extraction and purification of substances PF1092 carried out by known means based on its properties revealed by the present invention are included in the present invention. In these examples, all the percente are given by weight unless otherwise indicated.
INVENTIVE EXAMPLE 1
A medium composed of 2.0% of starch, 1.0% of glucose, 0.5% of polypeptone, 0.6% of wheat germ, 0.3% of yeast extract, 0.2% of soybean meal and 0.2% of calcium carbonate (pH 7,0 before sterilization) was used as a seed culture medium. Another medium prepared by adding 0.3% of soybean meal to sufficiently water-absorbed rice was used as a production medium.
A 20 ml portion of the seed culture medium dispensed in a 100 ml capacity conical flask was sterilized at 120° C. for 15 minutes, and one loopful of Penicillium sp. PF1092 (FERM P-14724) cells grown on a slant agar medium were inoculated into the medium and cultured at 25° C. for 3 days on a shaker to obtain a seed culture. Next, a 100 g portion of the aforementioned production medium dispensed in a 500 ml capacity conical flask was sterilized at 120° C. for 15 minutes, and 5 ml of the just obtained seed culture was inoculated into the medium, mixed thoroughly and then subjected to 10 days of static culturing at 28° C.
INVENTIVE EXAMPLE 2
A 6 kg portion of the thus obtained culture mixture was extracted with 12 liters of ethyl acetate, and the resulting ethyl acetate layer containing active components was evaporated to obtain 15.3 g of oily material. The thus obtained oily material was applied to a column packed with 400 g of silica gel (Wakogel C-200, manufactured by Wako Pure Chemical Industries), washed with chloroform and then chromatographed using chloroform-methanol (100:1 to 100:3) as a developing solvent, and the resulting active fraction was evaporated to obtain 4.6 g of crude powder. Next, the crude powder was applied to a column packed with 150 g of silica gel (Wakogel C-200, manufactured by Wako Pure Chemical Industries), washed with hexane-ethyl acetate (8:1 to 5:1) and then chromatographed using hexane-ethyl acetate (4:1 to 3:1) as a developing solvent to effect elution of substance PF1092B, and the resulting active fraction was evaporated to obtain 282 mg of crude powder containing substance PF1092B. The chromatography was continued using hexane-ethyl acetate (2:1 to 1:1) as a developing solvent to effect elution of substance PF1092A and substance PF1092C, and the resulting active fraction was evaporated to obtain 763 mg of crude powder containing substance PF1092A and substance PF1092C. Next, the crude powder containing substance PF1092B was purified by Sephadex LH-20 (700 ml, manufactured by Pharmacia) column chromatography using chloroform-methanol (1:1) as a developing solvent, and the active fraction containing substance PF1092B was evaporated to obtain 157.0 mg of substance PF1092B as colorless powder. The colorless powder of substance PF1092B was then dissolved in a chloroform-methanol mixture and allowed to stand to obtain 49.1 mg of substance PF1092B as colorless needle crystals.
On the other hand, the crude powder containing substance PF1092A and substance PF1092C obtained by the silica gel column chromatography using hexane-ethyl acetate (2:1 to 1:1) as a developing solvent was purified by Sephadex LH-20 (700 ml) column chromatography using chloroform-methanol (1:1) as a developing solvent to obtain 298 mg of substance PF1092A as colorless powder and then 159 mg of substance PF1092C as colorless powder. Thereafter, the colorless powder of substance PF1092A was dissolved in a chloroform-methanol mixture and allowed to stand to obtain 60.0 mg of substance PF1092A as colorless needle crystals, and the Colorless powder of substance PF1092C was dissolved in ethyl acetate and allowed to stand to obtain 30.1 mg of substance PF1092C as colorless needle crystals.
These substances have the aforementioned physico-chemical properties.
TEST EXAMPLE
The progesterone receptor binding activity of substance PF1092A, substance PF1092B and substance PF1092C of the present invention was measured in the following manner in accordance with the method of H. Kondo et al. (J. Antibiotics, vol. 43, pp. 1533-1542, 1990). That is, uteri taken from hogs in 5 mM phosphate buffer were disrupted using Polytron homogenizer, and the resulting solution was subjected to centrifugation (100,000 ×g, 30 minutes) to separate the supernatant fluid which was used as the cytosol containing progesterone receptor.
In the assay of progesterone receptor binding activity, 40 μl of a solution of 3 H-progesterone as a ligand of the receptor (3.84 TBq/mmol, 18.5 kBq/ml), 50 μl of the Just obtained cytosol (2-3 mg protein/ml), 30 μM of substance PF1092A, substance PF1092B and substance PF1092C and 30 μM of medroxyprogesterone acetate (MPA) were put into a test tube and incubated at 4° C. for 60 minutes to effect the reaction and then mixed with 100 μl of 0.5% activated carbon solution. After 10 minutes of standing, this was subjected to centrifugation (2,000×g, 10 minutes), and radioactivity of the thus obtained supernatant fluid was measured using a liquid scintillation counter. Inhibition ratio was calculated based on the following formula in which radioactivity with no addition of the test drug was defined as the amount of total binding to the cytosol and radioactivity with the addition of MPA was defined as the amount of non-specific binding. ##EQU1##
As the results, 30 μM of each of substance PF1092A and substance PF1092B inhibited 90% or more of the binding of 3 H-progesterone to the progesterone receptor. At the same concentration, substance PF1D92C inhibited about 70% of the binding. On the basis of the above results, it was confirmed that substance PF1092A, substance PF1092B and substance PF1092C are capable of binding to the progesterone receptor.
Thus, the substance PF2092A, substance PF1092B and substance PF1092C of the present invention can inhibit binding of progesterone to the progesterone receptor. On the basis of this property, the substance PF1092A, substance PF1092B and substance PF1092C of the present invention can be used as contraceptives or anticancer drugs, or lead compounds from which more effective derivatives will be synthesized.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
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This invention provides novel physiologically active substances PF1092A, PF1092B and PF1092C, which can inhibit binding of progesterone to progesterone receptor.
These substances were obtained by culturing a fungal microorganism belonging to the genus Penicillium using a medium containing ordinary nutrients for microorganisms and isolating the physiologically active substances PF1092A, PF1092B and PF1092C from the resulting culture mixture by means of solvent extraction, silica gel column chromatography, and the like. Molecular formulae of the novel physiologically active substances PF1092A, PF1092B and PF1092C are C 17 H 20 O 5 , C 17 H 20 O 5 and C 15 H 18 O 4 , respectively.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 14/468,303, filed Aug. 25, 2014, which claims priority to U.S. patent application Ser. No. 13/765,340, filed Feb. 12, 2013, now U.S. Pat. No. 8,815,320, issued on Aug. 26, 2014, which claims priority from EP 12171561.9, filed on Jun. 11, 2012 at the European Patent Office, the disclosures of which are incorporated herein by reference in their entireties as if fully set forth herein.
BACKGROUND
[0002] Field of the Invention
[0003] Embodiments of the present invention related to a method for producing a composition for increasing muscle mass.
[0004] Related Art
[0005] Whereas the pasteurization of liquid egg yolk is shown to inactivate the biological activity of follistatin contained therein, it is described that freeze-dried emulsified egg yolk can be irradiated, e.g. by gamma radiation or by an electron beam for preservation.
SUMMARY
[0006] Embodiments of the present invention relates to a process for producing a composition for increasing muscle mass from a biological source, wherein the composition is preserved, storage stable at room temperature, and pathogen free. Upon ingestion, the composition has activity to support, induce and/or positively regulate the increase of muscle in humans and animals. The composition is therefore suitable for use as a food ingredient or nutrition additive for humans and animals, e.g. for use as a compound for improving muscle increase and/or muscle regeneration.
[0007] Preferably, the process for producing the composition, and the composition itself, are free from added chemical preservatives, most preferably, the process for producing the composition, and the composition, respectively, essentially consist of the natural components of the starting material, egg and its components, only subject to the physical treatment steps of the process.
DETAILED DESCRIPTION
[0008] Embodiments of the invention are directed to a process for producing a composition from avian eggs or its components, especially from egg yolk, egg white or whole egg, the process comprising the preservation while maintaining a temperature below 38° C., preferably below 20° C., more preferably below 10° C., which step of preservation comprises or consists of subjecting the liquid egg yolk to a pressure of at least 4000 bar, for at least 1 minute, preferably to 5500-6500 bar, more preferably to 6000 bar for at least 1 minute, preferably for 3 minutes, more preferably for at least 5 minutes, preferably using an adiabatic compression and pressure release, and/or pulsed electric field treatment, preferably in a continuous process while pumping the liquid egg or its components, especially egg yolk, egg white or whole egg, through the space limited by at least 2 discharge electrodes, e.g. generating an electric field strength of 5 to 40 kV/cm, e.g. at 12 kV/cm at a flow rate of the liquid egg yolk of 30 L/h at a temperature of 30° C., preferably using unipolar pulses having a pulse duration of 5 to 20 μs, preferably of 10 μs, at a repetition rate of 70 to 200 Hz, especially positive, rectangular pulses. At an energy input of 50 to 140 kJ/kg, the decrease in bacterial contamination, determined as CFU, was by a factor of 10 to 630, respectively.
[0009] The embodiments of the step of preservation are non-thermal process steps, i.e. an increase in temperature that may occur during the high pressure treatment and/or pulsed electric field treatment is not causative for the reduction in micro-organisms, especially of bacteria to achieve preservation. In addition, the embodiments of the step of preservation are physical treatment methods, i.e. without addition of antimicrobial chemical compounds. Accordingly, the embodiments of the step of preservation are non-thermal process steps consisting of physical treatment steps, which do not generate radicals and therefore maintain the chemical structure of the ingredients, especially of unsaturated fatty acids and vitamins of the composition.
[0010] It was found that the high pressure treatment and/or the pulsed electric field treatment of liquid whole egg, liquid egg white, or liquid egg yolk effectively reduces the bacterial contamination by a factor of at least 10, preferably by a factor of at least 100, more preferably of at least 1000. For example, for high pressure treatment, a reduction of the bacterial contamination to about 50 CFU/g, corresponding to a reduction by a factor of 3000 was found when starting from raw liquid egg yolk having a natural bacterial content of 1.5×10 5 CFU/g. For pulsed electric field treatment, a reduction by a factor of 10 to a factor of 1000 was found. The reduction of the natural microbiological contamination by the high pressure treatment and/or the pulsed electric field treatment is sufficient for preserving the egg white, whole egg or egg yolk.
[0011] Preferably, the process subsequent to the preservation step comprises drying, for example freeze-drying of the liquid egg preparation, especially egg yolk, egg white or whole egg, resulting in an egg containing powder, especially an egg yolk, egg white or whole egg containing powder, preferably in a powder consisting essentially of the high pressure treated and/or pulsed electric field treated egg or egg constituents, e.g. egg yolk, egg white or whole egg. In the alternative to freeze-drying, other suitable types of drying may be utilized. For example, the drying can be fluidized bed drying, preferably at a temperature at or below 42° C., preferably at or below 40° C., more preferably at or below 38° C. or at or below 35° C.
[0012] The process for producing the composition comprising a preservation step comprising or consisting of high pressure treatment and/or pulsed electric field treatment, preferably with subsequent drying, especially but not limited to freeze-drying, leads both to an efficient reduction of bacterial contamination as determined e.g. as viable bacteria, and to follistatin maintaining its biological activity, e.g. to at least 50%, preferably to at least 70%, more preferably to at least 80%, more preferably to at least 85%, at least 90% or to at least 95%.
[0013] Especially in view of preservation processes using irradiation, it is an advantage of the process of the invention that no radicals are generated by the step of preservation, and therefore the resulting preserved liquid egg yolk, egg white or whole egg, which preferably is subsequently dried, preferably freeze-dried, contains less or no radicals and reaction products of radicals. E.g. the preserved liquid egg yolk, egg white or whole egg, as well as the dried, preferably freeze-dried, preserved egg yolk, egg white or whole egg, contains unsaturated fatty acids of the egg yolk essentially in their natural state and composition, e.g. without changes to their double bonds. Accordingly, the composition obtainable by the process of the invention preferably contains the unsaturated fatty acids of egg yolk without changes of their double bonds, i.e. in their natural biological constitution.
[0014] In the alternative to whole egg or egg yolk, the white of egg can be used in the process.
[0015] Preferably, in the process, no chemical preservative is added, e.g. no antimicrobial agent is added. Optionally, an antioxidant is added, e.g. ascorbic acid or a neutral salt thereof. Preferably, the whole egg, egg white, more preferably egg yolk only is free from added ingredients, e.g. the whole egg, egg white, or more preferably the egg yolk, is subjected to the physical process steps only, which comprise, preferably consist of subjecting liquid whole egg, egg white or liquid egg yolk to high pressure treatment and/or to pulsed electric field treatment, preferably followed by drying, e.g. freeze-drying or fluidized bed drying.
[0016] For high pressure treatment, it is preferred that the liquid whole egg, white of egg or liquid egg yolk is contained in sealed containers having an elastic wait e.g. in plastic bags, more preferably free from gas, more preferably degassed. For a gas-free whole egg, egg white or liquid egg yolk in a container, gas bubbles can be expelled before sealing the container. For degassing, a reduced pressure can be applied prior to high pressure treatment, preferably also prior to pulsed electric field treatment.
[0017] High pressure treatment is generally carried out using water as a compression medium that is pumped into a sealed chamber containing the liquid whole egg, egg white or liquid egg yolk until the high pressure is reached, maintaining the high pressure, and then releasing the pressure, e.g. by opening the high pressure container.
[0018] It was found that after high pressure treatment within sealed containers, e.g. in sealed polyethylene bags, the liquid whole egg, egg white or liquid egg yolk preparation is stable, e.g. for 12 to 24 hours, preferably for 2 to 5 days, e.g. at 5 to 10° C., without a drastic increase in bacterial contamination, and especially without a significant loss of follistatin activity.
[0019] For high pressure treatment, the adiabatic increase in temperature due to the high pressure preferably is counteracted by cooling the liquid whole egg, egg white or liquid egg yolk to a temperature which is at least 5° C., preferably about 10° C. below the maximum temperature, e.g. below 38° C. prior to the treatment. Preferably, prior to high pressure treatment and/or prior to the pulsed electric field treatment, the liquid whole egg, egg white or liquid egg yolk is cooled to a temperature of between 0 and 28° C., preferably to 5 to 20° C., more preferably to a maximum of 10° C.
[0020] For pulsed electric field treatment, it was found that a short rise in temperature, e.g. to a maximum of 45° C., preferably to a maximum of 42° C. or to 40° C., for maximally 10 s, preferably for maximally 5 or maximally 2 s results in a low loss of active follistatin. Accordingly, for the pulsed electric field treatment, the aforementioned short rise in temperature is acceptable, although less preferred.
[0021] Active follistatin was determined by size separation, e.g. by size-exclusion HPLC or by SDS-polyacrylamide gel electrophoresis (SDS-PAGE), optionally followed by Western blotting and immunospecific detection using an anti-follistatin antibody. A reduction of the size-specific signal identified for follistatin in eggs was used as an indicator for the reduction of follistatin activity, because an inactivation of follistatin results in the change, e.g. reduction of the molecule size.
[0022] The process may comprise a step of concentrating the whole egg, egg white or egg yolk of eggs. For concentrating, the fraction of whole egg, of egg white or of egg yolk having the higher proportion of follistatin is used, the fraction being obtained e.g. by size separation or by density separation. The preferred fraction is the fraction containing the egg yolk membrane, e.g. obtained from separating egg yolk or whole egg, and the fraction containing chalazae, e.g. obtained from separating the white of egg or whole egg. Preferably, the preferred fraction contains the major portion of the egg yolk membranes and/or of the chalazae of the whole egg, egg white or egg yolk subjected to the concentrating or separating step. For separating by size separation, sieving can be used, e.g. of a mesh size of 0.5 mm to 2 mm, preferably approx. 0.5 to 1 mm. Using size separation, the preferred fraction is the egg yolk membrane and/or chalazae containing fraction, which is the particulate or large fraction. For separating by density separation, centrifugation, e.g. using a centrifugal separator. Using density separation of whole egg, egg white or egg yolk, the higher density fraction is the preferred fraction.
[0023] Optionally, prior to the step of concentrating the whole egg, egg white or egg yolk of the eggs by separating the fraction containing the egg yolk membrane and/or chalazae, the whole egg, egg white or egg yolk can be diluted to facilitate the separating step, e.g. using water as a diluent, the water optionally containing salt.
[0024] In the alternative or in addition to whole egg, egg white or egg yolk of eggs, the process can be performed using blood serum from slaughtered animals as the starting material. Accordingly, the blood serum can replace the whole egg, egg white or egg yolk in the process, and therefore the description relating to whole egg, egg white or egg yolk also refers to blood serum.
[0025] Optionally, the process can comprise the further step of mixing or encapsulating the dried preserved egg or egg constituent. Preferably, for mixing or encapsulating, the dried egg yolk, whole egg or egg white, or alternatively the dried blood serum, is admixed with a solution, preferably an aqueous solution of an encapsulating agent. The encapsulating agent can e.g. be a sugar, sugar alcohol and/or sugar polymer, a solution of which in the process is admixed with the preserved and dried egg yolk, whole egg or egg white, or alternatively the dried blood serum, and dried to produce encapsulated dried egg yolk, whole egg or egg white, or alternatively the dried blood serum. The sugar can e.g. be sucrose, fructose, glucose, and/or corn syrup. The sugar alcohol can e.g. be maltitol, isomalt etc. The sugar polymer can e.g. be starch, modified starch and/or cellulose and/or methylcellulose, which preferably also serves as an anti-caking agent.
[0026] As a specific advantage of the high pressure treatment of liquid egg yolk, whole egg or egg white, it has been found that the bioavailability and digestibility of the protein, preferably of the total protein, is enhanced. Therefore, the process comprising the step of high pressure treatment of liquid egg yolk, whole egg or egg white is preferred for producing a preserved composition containing biologically active follistatin, in which composition the protein has increased bioavailability, e.g. increased digestibility, for example in relation to the non-treated liquid egg yolk, whole egg or egg white.
[0027] Several embodiments of the invention are now illustrated non-limiting experimental examples.
Example 1
Production of Preserved Egg Yolk Containing Active Follistatin
[0028] Hen eggs contained from a certified breeding station were used, which eggs were not brooded. The eggs were cracked and separated into egg yolk and the white of egg automatically. As raw liquid egg yolk, 3000 L egg yolk were used that were preferably homogenized by stirring were maintained at 5 to 10° C. and filled under sterile conditions into polyethylene bags and sealed after expulsion of entrapped air bubbles. These polyethylene bags could have a volume of between 1 L and 50 L, preferably of 5 to 20 L each. The bags were arranged in a high pressure chamber (NC-Hyperbaric, Spain). Using water as a pressurizing medium, the pressure was increased to 6000 bar within 10 to 20 minutes. After a holding time of 3 or 5 minutes, respectively, the pressure was released by opening a release valve.
[0029] The bacterial contamination was determined by standard dilution plating on complete medium and counting following cultivation in an incubator at 37° C. for 48 h.
[0030] Aliquots from the high pressure treated egg yolk were kept at about 5° C. for a few hours and subsequently freeze-dried by freezing the egg yolk and applying vacuum to withdraw water, while controlling the temperature of the egg yolk to preferably not exceed 10° C., preferably 5° C., preferably keeping the egg yolk in a frozen state.
[0031] The microbiological analysis showed that the high pressure treatment both for 3 minutes and 5 minutes resulted in a drastic reduction of bacterial contamination, and also the subsequent step of freeze-drying further reduced the bacterial contamination.
[0000]
TABLE 1
bacterial contamination, measured as CFU/g
Total cell
sample
Salmonella in 25 g sample
count (CFU/g)
raw liquid egg yolk
Negative
1.5 × 10 5
liquid egg yolk after
Negative
50
6000 bar, 3 min
liquid egg yolk after
Negative
50
6000 bar, 5 min
freeze-dried egg yolk after
Negative
40
6000 bar, 3 min
freeze-dried egg yolk after
Negative
<10
6000 bar, 5 min
CFU = colony forming units (viable micro-organisms)
[0032] Follistatin activity in the liquid egg yolk as determined by SDS-PAGE showed a reduction by approx. 15%, or a content of 85% active follistatin, on the basis of the content of active follistatin as determined by SDS-PAGE in the raw liquid yolk.
[0033] In the freeze-dried egg yolk, the content of active follistatin in relation to the total protein concentration was the same as in the liquid egg yolk after high pressure treatment. This shows that the step of freeze-drying does not substantially affect the activity of follistatin, e.g. freeze-drying does not substantially reduce the concentration of active follistatin per total protein content.
Example 2
Fraction of Freeze-Dried Egg Yolk Containing Active Follistatin Using Pulsed Electric Field Treatment
[0034] An aliquot of the raw liquid egg yolk used in Example 1 was treated at a flow rate of 30 L/h at 30° C. by pulsed electric field of a field strength of 12 kV/cm using unipolar positive pulses having a pulse duration of 10 μs at a repetition rate of 200 Hz. At an energy input of 50 to 140 kJ/kg, the viable bacterial contamination was reduced by a factor of 10 and 630 CFU, respectively, as determined by dilution plating.
[0035] Using SDS-PAGE, a reduction of active follistatin by approx. 15%, or a residual activity of follistatin of 85% based on the raw egg yolk was found. No thermal denaturation of the liquid egg yolk was observed in SDS-PAGE.
Example 3
Concentrating Whole Egg, White of Egg or Egg Yolk by Separation
[0036] The process of Example 1 was repeated with the alteration that before the high pressure treatment the egg yolk was separated by centrifugation at 3343×g for 20 min into a high density fraction that was collected as a pellet and a low density supernatant fraction. The high density was found the high follistatin fraction.
[0037] In the alternative, whole egg or white of egg was separated by centrifugation at 3343×g for 20 min into a high density fraction that was collected as a pellet and a low density supernatant fraction. Again, the high density was found the high follistatin fraction.
[0000] The analysis of the follistatin content is shown below:
[0000]
fraction
Follistatin [μg/kg]
white of egg, prior to centrifugation
15
white of egg, pellet
33
whole egg, prior to centrifugation
23
whole egg, pellet
41
egg yolk, prior to centrifugation
4
egg yolk, pellet
36
[0038] These results show that the separation of egg yolk, whole egg or egg white to a higher density fraction, corresponding to egg yolk membranes and chalazae, results in an increased concentration of follistatin, which fraction after the step of preservation, preferably with subsequent drying, yields a composition having an increased follistatin concentration.
[0039] Preferably, the egg yolk, whole egg or egg white prior to the separation was not homogenized, e.g. the egg yolk, whole egg or egg white was passed through a wide sieve or was stirred to only crack the egg yolk membrane to allow egg yolk to exit, preferably without breaking the egg yolk membrane or chalazae into small pieces.
[0040] Various features of the invention are set forth in the appended claims. While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof. It is also understood that various embodiments described herein may be utilized in combination with any other embodiment described, without departing from the scope contained herein.
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A process for producing a composition from a biological source, which composition is preserved and, especially pathogen free and is storage stable, preferably at room temperature. Embodiments of the invention provide a process for producing a composition from eggs.
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FIELD OF THE INVENTION
[0001] The present invention relates to a magnetic position device, and more particularly to a magnetic position device for using in a driver having a more precise position.
BACKGROUND OF THE INVENTION
[0002] Generally, data storage media for accessing and recording the data are supported by drivers. The magnetic storage devices, for example, FDD (floppy disk drive) or HDD (hard disk drive), have drivers for magnetic read/write heads. The optical storage devices, for example, Compact Disc (CD), Video CD (VCD) and Digital Video Disk (DVD), have corresponding drivers for optical read/write heads. In addition, Magneto Optical (MO) or Mini Disc (MD) has corresponding drivers for read/write heads. The drivers are used for precisely directing the read/write heads to the working positions.
[0003] The position device of the conventional drivers is implemented by using the characteristic of magnetism. FIGS. 1 to 4 are schematic views showing the conventional magnetic position devices for being used in the optical lens driver for an optical read/write head. Based on the structure of the movable element V of the magnetic position device for the optical lens (O.L.) driver, the magnetic position devices are divided into two types as follows.
[0004] a) moving coils: the movable element V has a focusing coil F 1 and perpendicular tracking coils T 1 , T 2 , T 3 and T 4 thereon as shown in FIGS. 1 to 3 .
[0005] b) moving magnets: the movable element V has permanent magnets M 1 and M 2 thereon as shown in FIG. 4.
[0006] However, the operation theories applied in the drivers are similar.
[0007] The magnetic field is generated by the permanent magnets M 1 and M 2 and the fixed yokes Y 1 , Y 2 and Y 3 . When electric current passes through the focusing coils F 1 and F 2 or the tracking coils T 1 , T 2 , T 3 and T 4 , another variable magnetic field is generated owing to electromagnetic induction, and then the relative displacement between the coils and the magnets are generated. The variable relative displacement is regulated by the electric current.
[0008] The conventional drivers have several drawbacks. For the moving coils type drivers, the magnetic force is enhanced by applying additional number of the coils wound on the movable element V. Moreover, the additional number of coils results in the heavier movable element V so that the sensitivity of the drivers is decreased. Furthermore, the movable element V for carrying the optical lens O.L. and the coils wound thereon should be produced in advance in the fabricating process. The fabricating process is complicated, and the coils are wounded on the movable element V with difficulty. It is more complicated that the coils are wound in advance, and then fixed to the movable element V. For example, the wound coils mounted on the movable element V in advance is more difficult to accomplish, as shown in FIG. 3.
[0009] For the moving magnets type drivers, the permanent magnets M 1 and M 2 are connected with the movable element V shown in FIG. 4. However, the magnets are much heavier than the coils, so that the sensitivity and the precision of the driver are reduced due to the heavy weight.
[0010] It is therefore tried by the applicant to deal with the above situation encountered in the prior art.
SUMMARY OF THE INVENTION
[0011] It is therefore an object of the present invention to provide a magnetic position device for using in a driver, which is capable of enhancing the sensitivity and the precision of the driver.
[0012] According to an aspect of the present invention, the magnetic position device for using in a driver includes a movable element having a first yoke assembly, and a fixed element adjacent to the movable element for generating a magnetic field to control the movable element to be moved toward a predetermined position.
[0013] Preferably, the fixed element includes a second yoke assembly, a magnet assembly connected to the second yoke assembly for generating the magnetic field, a first coil for generating a first motive force in a first direction in response to the magnetic flux of the magnetic field, and a second coil for generating a second motive force in a second direction in response to the magnetic flux of the magnetic field.
[0014] Preferably, the second coil is perpendicular to the first coil and the second direction is perpendicular to the first direction.
[0015] Preferably, the first coil and said second coil are winded around the second yoke assembly.
[0016] Preferably, the magnet assembly includes a plurality of permanent magnets.
[0017] Preferably, the movable element is capable of being moved along the first direction by the first motive force acted on the first yoke assembly.
[0018] Preferably, the movable element is capable of being moved along the second direction by the second motive force acted on the first yoke assembly.
[0019] The first coil is preferably a tracking coil and the second coil is preferably a focusing coil.
[0020] The first yoke assembly preferably includes two yokes being mounted on two opposite sides of the movable element, respectively.
[0021] Preferably, the driver is a read/write head of an optical read device
[0022] Preferably, the movable includes an optical lens.
[0023] According to another aspect of the present invention, the magnetic position device for using in a driver includes a movable element having a first yoke assembly, and a fixed element adjacent to the movable element for generating a magnetic field and having a coil assembly, wherein the coil assembly generates a motive force in response to the magnetic flux of the magnetic field to control the movable element to moved toward a predetermined position.
[0024] Preferably, the coil assembly includes a focusing coil and a tracking coil.
[0025] Preferably, the fixed element further includes a second yoke assembly and a magnet assembly connected with the second yoke to generate the magnetic field.
[0026] According to another aspect of the present invention, the position device is capable of controlling the position of an optical lens for using in a driver. The position device includes a movable element having a first yoke assembly, and a fixed element adjacent to the movable element for generating a magnetic field and having a coil assembly, wherein the coil assembly generates a motive force in response to the magnetic flux of the magnetic field, thereby controlling the optical lens to moved toward a predetermined position.
[0027] Preferably, the optical lens is mounted on the movable element.
[0028] The present invention may best be understood through the following descriptions with reference to the accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIGS. 1 to 4 are schematic views showing position devices for using in a driver according to the prior art;
[0030] [0030]FIG. 5 is a schematic view showing a magnetic position device for being used in a driver according to a preferred embodiment of the present invention;
[0031] FIGS. 6 is a schematic view showing a magnetic position device by varying the focusing coils location in FIG. 5;
[0032] [0032]FIG. 7 is a schematic view showing a magnetic position device having a half of FIG. 5;
[0033] [0033]FIG. 8 is a schematic view showing a magnetic position device for changing the tracking direction and the focusing direction in FIG. 5;
[0034] [0034]FIG. 9 is a schematic view showing a magnetic position device having a half of FIG. 8;
[0035] FIGS. 10 to 12 are schematic views showing a magnetic position devices according to the modified preferred embodiments of the present invention; and
[0036] FIGS. 13 to 18 are schematic views showing other modified preferred embodiments of the magnetic position devices of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0037] The present invention provides a magnetic position device for being used in a driver and enhances the efficiency and precision of the drivers for working position.
[0038] The operation principle of the present invention is similar to the prior art. The magnetic position device present invention is moving yokes type, which changes partial portions named Yoke 1 and Yoke 2 of the yokes to mount on the movable element V, yokes Y 1 to Y 4 and the permanent magnets M 1 and M 2 and the focusing coils F 1 to F 4 , and the tracking coils T 1 to T 4 are mounted on the fixed element. The present invention has the advantages as follows.
[0039] (a) The weight of the movable element V would not be increased by adding the coils number or enlarging the magnets for enhancing the magnetic force; and
[0040] (b) The movable element V and the coils are produced separately, which is easy to be manufactured.
[0041] [0041]FIG. 5 shows the magnetic position device according the preferred embodiment of the present invention. A plurality of movable yokes (Yoke 1 and Yoke 2 ) are mounted on the movable element V. The magnetic field is generated by the permanent magnets M 1 and M 2 and the fixed yokes Y 1 to Y 4 . The displacement and direction of the movable element V could be regulated by the magnetic force, e.g., Y-axis direction, generated by the tracking coils T 1 to T 4 in response to the magnetic flux of the magnetic field thereof and the magnetic force, e.g. Z-axis direction, generated by the focusing coils F 1 to F 4 in response to the magnetic flux of the magnetic field thereof. The focusing coils F 1 to F 4 are perpendicular to the tracking coils T 1 to T 4 .
[0042] [0042]FIG. 6 shows a magnetic position device by varying the focusing coils location in to FIG. 5. FIG. 7 shows a magnetic position device having a half of FIG. 5. FIG. 8 shows the magnetic position device by varying the focusing direction in Y-axis and the tracking direction in Z-axis in to FIG. 5. Moreover, FIG. 9 shows the magnetic position device having a half of FIG. 8.
[0043] In addition, the magnetic position devices in accordance with FIGS. 10 to 12 are modified by varying the related location or the shape of yokes, magnets and coils. Furthermore, the operation principle is similar to the foregoing statements. The present invention further includes a half magnetic position device according to FIG. 7. The present invention also discloses the magnetic position device for varying the focusing direction in Y axis according to FIG. 8 and FIG. 9. FIGS. 13 to 18 show the magnetic position device to regular the location and the shape for yokes, magnets and coils according to the present invention. The operation principle is still similar to the above-mentioned description.
[0044] It is understood that the magnetic position device could flexibly be applied to different operation conditions. Moreover, the manufacturing cost will be decreased and manufacturing process is less time-consuming. Also, the reliability for the magnetic position device could be enhanced according to the present invention.
[0045] While the invention has been described in terms of what are presently considered to be the most practical and preferred embodiments, it is to be understood that the invention need not be limited to the disclosed embodiment. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures. Therefore, the above description and illustration should not be taken as limiting the scope of the present invention which is defined by the appended claims.
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A magnetic position device for using in a driver is provided. The magnetic position device includes a movable element having a first yoke assembly, and a fixed element adjacent to the movable element for generating a magnetic field to control the movable element to be moved toward a predetermined position.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This is a Continuation Application of prior application Ser. No. 10/757,475 filed Jan. 15, 2004 now U.S. Pat. No. 7,109,951 whose entire disclosure is incorporated herein by reference. Further, this application claims the benefit of the Korean Application No. P2003-2856 filed on Jan. 16, 2003, which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a plasma display panel, and more particularly to a method and apparatus for driving a plasma display panel that is adaptive for preventing a spot misfire and a miswriting.
2. Description of the Related Art
Generally, a plasma display panel (PDP) excites and radiates a phosphorus material using an ultraviolet ray generated upon discharge of an inactive mixture gas such as He+Xe, Ne+Xe or He+Ne+Xe, to thereby display a picture. Such a PDP is easy to be made into a thin-film and large-dimension type. Moreover, the PDP provides a very improved picture quality owing to a recent technical development.
Referring to FIG. 1 , a discharge cell of a conventional three-electrode, AC surface-discharge PDP includes a scan electrode 30 Y and a sustain electrode 30 Z provided on an upper substrate 10 , and an address electrode 20 X provided on a lower substrate 18 . Each of the scan electrode 30 Y and the sustain electrode 30 Z includes transparent electrodes 12 Y and 12 Z, and metal bus electrodes 13 Y and 13 Z having smaller line widths than the transparent electrodes 12 Y and 12 Z and provided at one edge of the transparent electrodes 12 Y and 12 Z.
The transparent electrodes 12 Y and 12 Z are usually formed from indium-tin-oxide (ITO) on the upper substrate 10 . The metal bus electrodes 13 Y and 13 Z are usually formed from a metal such as chrome (Cr), etc. on the transparent electrodes 12 Y and 12 Z to thereby reduce a voltage drop caused by the transparent electrodes 12 Y and 12 Z having a high resistance.
On the upper substrate 10 provided, in parallel, with the scan electrode 30 Y and the common sustain electrode 30 Z, an upper dielectric layer 14 and a protective film 16 are disposed. Wall charges generated upon plasma discharge are accumulated onto the upper dielectric layer 14 . The protective film 16 prevents a damage of the upper dielectric layer 14 caused by a sputtering during the plasma discharge and improves the emission efficiency of secondary electrons. This protective film 16 is usually made from magnesium oxide (MgO).
A lower dielectric layer 22 and barrier ribs 24 are formed on the lower substrate 18 provided with the address electrode 20 X. The surfaces of the lower dielectric layer 22 and the barrier ribs 24 are coated with a phosphorous material 26 . The address electrode 20 X is formed in a direction crossing the scan electrode 30 Y and the sustain electrode 30 Z. The barrier rib 24 is formed in parallel to the address electrode 20 X to thereby prevent an ultraviolet ray and a visible light generated by a discharge from being leaked to the adjacent discharge cells. The phosphorous material 26 is excited by an ultraviolet ray generated during the plasma discharge to generate any one of red, green and blue visible light rays. An inactive mixture gas for a gas discharge is injected into a discharge space defined between the upper and lower substrate 10 and 18 and the barrier rib 24 .
Such a PDP makes a time-divisional driving of one frame, which is divided into various sub-fields having a different emission frequency, so as to realize gray levels of a picture. Each sub-field is again divided into an initialization period for initializing the entire field, an address period for selecting a scan line and selecting the cell from the selected scan line and a sustain period for expressing gray levels depending on the discharge frequency. Herein, the initialization period is again divided into a set-up interval supplied with a rising ramp waveform and a set-down interval supplied with a falling ramp waveform.
For instance, when it is intended to display a picture of 256 gray levels, a frame interval equal to 1/60 second (i.e. 16.67 msec) is divided into 8 sub-fields SF 1 to SF 8 as shown in FIG. 2 . Each of the 8 sub-field SF 1 to SF 8 is divided into an initialization period, an address period and a sustain period as mentioned above. Herein, the initialization period and the address period of each sub-field are equal for each sub-field, whereas the sustain period and the number of sustain pulses assigned thereto are increased at a ratio of 2n (wherein n=0, 1, 2, 3, 4, 5, 6 and 7) at each sub-field.
FIG. 3 shows a driving waveform of the PDP applied to two sub-fields. In FIG. 3 , Y represents the scan electrode; Z denotes the sustain electrode; and X denotes the address electrode.
Referring to FIG. 3 , the PDP is divided into an initialization period for initializing the full field, an address period for selecting a cell, and a sustain period for sustaining a discharge of the selected cell for its driving.
In the initialization period, a rising ramp waveform Ramp-up is simultaneously applied to the entire scan electrodes Y in a set-up interval. This rising ramp waveform Ramp-up causes a weak discharge within cells at the full field to generate wall charges within the cells. The rising ramp waveform Ramp-up rises from a sustain voltage Vs until a sum value of a set-up voltage Vsetup with the sustain voltage Vs.
In the set-down interval, after the rising ramp waveform Ramp-up was supplied, a falling ramp waveform Ramp-down falling from a positive voltage lower than a peak voltage of the rising ramp waveform Ramp-up is simultaneously applied to the scan electrodes Y. The falling ramp waveform Ramp-down causes a weak erasure discharge within the cells, to thereby erase spurious charges of wall charges and space charges generated by the set-up discharge and uniformly leave wall charges required for the address discharge within the cells of the full field. In real, the falling ramp waveform Ramp-down falls from the sustain voltage Vs until a negative voltage −Vy so that desired wall charges can be left during the set-down interval.
In the address period, a negative scanning pulse scan is sequentially applied to the scan electrodes Y and, at the same time, a positive data pulse data is applied to the address electrodes X. A voltage difference between the scanning pulse scan and the data pulse data is added to a wall voltage generated in the initialization period to thereby generate an address discharge within the cells supplied with the data pulse data. Wall charges are formed within the cells selected by the address discharge.
Meanwhile, a positive direct current voltage having a sustain voltage level Vs is applied to the sustain electrodes Z during the set-down interval and the address period.
In the sustain period, a sustaining pulse sus is alternately applied to the scan electrodes Y and the sustain electrodes Z. Then, a wall voltage within the cell selected by the address discharge is added to the sustain pulse sus to thereby generate a sustain discharge taking a surface-discharge type between the scan electrode Y and the common sustain electrode Z whenever each sustain pulse sus is applied. Finally, after the sustain discharge was finished, a erasing ramp waveform erase having a small pulse width is applied to the sustain electrode Z to thereby erase wall charges left within the cells.
In the set-up interval of such a convention PDP, the scan electrode Y is supplied with a positive voltage while the sustain electrode Z is supplied with a negative voltage (or a ground voltage). Accordingly, in the set-up interval, negative wall charges are formed at the scan electrode Y while positive wall charges are formed at the sustain electrode Z as shown in FIG. 4 . The falling ramp waveform Ramp-down falling from a positive voltage lower than a peak voltage of the rising ramp waveform Ramp-up are supplied in the set-down interval. Thus, spurious wall charges formed excessively and non-uniformly are erased to thereby reduce the wall charges within the cell into a predetermined amount.
Subsequently, in the address period, the scan electrode Y is supplied with a negative voltage while the sustain electrode Z is supplied with a positive voltage. At this time, a voltage value (having a negative polarity) of wall charges formed in the set-down interval is added to a negative voltage value applied to the scan electrode Y, to thereby cause an address discharge.
The conventional PDP driven as mentioned above does not make a stable address discharge until desired wall charges are formed in the initialization period. However, in the conventional PDP, desired wall charges are not formed in the initialization period depending upon a property of the panel, and thus a spot misfire or a miswriting occurs.
More specifically, when wall charges are normally formed in the initialization period, negative wall charges are formed at the scan electrode Y while positive wall charges are formed at the sustain electrode Z as shown in FIG. 4 . However, due to problems of the panel property, etc., positive wall charges are formed at the scan electrode Y of a portion of discharge cells during the set-down interval as shown in FIG. 5 . In other words, the falling ramp waveform Ramp-down falls until a negative voltage −Vy in the set-down interval. At this time, positive wall charges are formed at the scan electrode Y provided at the portion of discharge cells. If positive wall charges are formed at the scan electrode Y as mentioned above, then a spot misfire or a miswriting is generated to thereby cause a deterioration of picture quality in the PDP.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a method and apparatus for driving a plasma display panel that is adaptive for preventing a spot misfire and a miswriting.
In order to achieve these and other objects of the invention, a method of driving a plasma display panel according to one aspect of the present invention includes an initial period for forming wall charges at a discharge cell; an address period for selecting the discharge cell; a wall charge control period, being arranged between said initialization period and said address period, for controlling a wall charge distribution at the discharge cell; and a sustain period for causing a sustain discharge at discharge cells selected in said address period.
In the method, said initialization period is divided into a set-up interval and a set-down interval; a rising ramp waveform rising at a first slope from a sustain voltage until a sum value of said sustain voltage and a set-up voltage; and a falling ramp waveform falling at a second slope from said sustain voltage until a negative voltage.
A control pulse having a voltage rising at said first slope from a ground voltage is applied to the scan electrode during said wall charge control period.
Herein, a voltage of said control pulse is a voltage less than said set-up voltage.
An application time of said control pulse is differentiated depending upon sub-fields.
Herein, an application time of said control pulse is set more shortly as it goes from a sub-field arranged in an initial time of a frame into the last sub-field of the frame.
Alternatively, an application time of said control pulse is set longer as it goes from a sub-field arranged in an initial time of a frame into the last sub-field of the frame.
Application time of said control pulse is equal to each other at the entire sub-fields included in one frame.
A ground voltage is applied to a sustain electrode arranged in parallel to the scan electrode during said wall charge control period.
A control pulse rising at a slope different from said first slope from a ground voltage is applied to the scan electrode during wall charge control period.
Alternatively, a rectangular control pulse having said sustain voltage is applied to the scan electrode during said wall charge control period.
Herein, said control pulse is applied during a time less than 1 μs.
An application time of said control pulse is differentiated depending upon sub-fields.
Application time of said control pulse is equal to each other at the entire sub-fields included in one frame.
A ground voltage is applied to a sustain electrode arranged in parallel to the scan electrode during said wall charge control period.
A driving apparatus for a plasma display panel according to another aspect of the present invention includes a set-up supplier for supplying a rising ramp waveform to scan electrodes during an initialization period; and a scan voltage supplier for sequentially supplying a scanning pulse to the scan electrodes during an address period, wherein the set-up supplier applies a control pulse rising at the same slope as said rising ramp waveform to the scan electrodes between said initialization period and said address period.
Herein, after said control pulse was supplied, a ground voltage is applied to the scan electrodes.
A driving apparatus for a plasma display panel according to still another aspect of the present invention includes a set-up supplier for supplying a rising ramp waveform to scan electrodes during an initialization period; a scan voltage supplier for sequentially supplying a scanning pulse to the scan electrodes during an address period; an energy recovering circuit for supplying a sustaining pulse having a sustain voltage during a sustain period; and a scan reference voltage supplier for supplying a scan reference voltage to the remaining scan electrodes other than said scan electrodes to which said scanning pulse is applied during said address period, wherein said energy recovering circuit applies a rectangular control pulse having said sustain voltage to the scan electrodes between said initialization period and said address period.
In the driving apparatus, prior to said control pulse was supplied, said scan reference voltage is applied to the scan electrodes.
Said control pulse is applied during a time less than 1 μs.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other objects of the invention will be apparent from the following detailed description of the embodiments of the present invention with reference to the accompanying drawings, in which:
FIG. 1 is a perspective view showing a discharge cell structure of a conventional three-electrode, AC surface-discharge plasma display panel;
FIG. 2 illustrates sub-fields included in one frame of the conventional plasma display panel;
FIG. 3 is a waveform diagram of driving signals supplied to the electrodes during the sub-fields shown in FIG. 2 ;
FIG. 4 depicts wall charges formed at the electrodes in the initialization period shown in FIG. 2 ;
FIG. 5 depicts wall charges formed at a portion of discharge cells in the initialization period shown in FIG. 2 ;
FIG. 6 is a waveform diagram for explaining a method of driving a plasma display panel according to a first embodiment of the present invention;
FIG. 7 is a circuit diagram of a driving apparatus for the plasma display panel according to an embodiment of the present invention; and
FIG. 8 is a waveform diagram for explaining a method of driving a plasma display panel according to a first embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 6 shows a method of driving a plasma display panel (PDP) according to a first embodiment of the present invention.
Referring to FIG. 6 , the PDP according to the first embodiment of the present invention is divided into an initialization period for initializing the entire field, a wall charge control period for preventing an inversion of wall charges, an address period for selecting a cell and a sustain period for sustaining a discharge of the selected cell for its driving.
In the initialization period, a rising ramp waveform Ramp-up is simultaneously applied to all of scan electrodes Y in a set-up interval. This rising ramp waveform Ramp-up causes a weak discharge within cells at the full field to generate wall charges within the cells. The rising ramp waveform Ramp-up rises from a sustain voltage Vs until a sum value of a set-up voltage Vsetup with the sustain voltage Vs.
In the set-down interval, after the rising ramp waveform Ramp-up was supplied, a falling ramp waveform Ramp-down falling from a positive voltage lower than a peak voltage of the rising ramp waveform Ramp-up is simultaneously applied to the scan electrodes Y. The falling ramp waveform Ramp-down causes a weak erasure discharge within the cells, to thereby erase spurious charges of wall charges and space charges generated by the set-up discharge and uniformly leave wall charges required for the address discharge within the cells of the full field. In real, the falling ramp waveform Ramp-down falls from the sustain voltage Vs until a negative voltage −Vy so that desired wall charges can be left during the set-down interval.
In the wall charge control period, the scan electrodes Y are supplied with a positive control pulse Ramp-p rising from a ground voltage GND until a set-up voltage Vsetup. If the positive control pulse Ramp-p is applied to the scan electrodes Y, then a fine discharge is generated at the discharge cells to thereby control the polarities of the discharge cells into desired types.
More specifically, in the set-down interval, wall charges having an undesired type of polarities are formed at a portion of discharge cells as shown in FIG. 5 . Thereafter, if the positive control pulse Ramp-p is applied to the scan electrodes Y, then a fine discharge is generated at the discharge cells to thereby form negative wall charges at the scan electrodes Y while forming positive wall charges at the sustain electrodes Z. In other words, in the embodiment of the present invention, the polarities of wall charges of the entire discharge cells can be controlled into desired polarities during the wall charge control period.
Meanwhile, an application time of the control pulse Ramp-p can be set in various methods. For instance, an application time of the control pulse Ramp-p may be set equally or differently for each sub-field. Herein, if an application time of the control pulse Ramp-p is set differently for each sub-field, then a voltage value of the control pulse Ramp-p also is set differently for each sub-field. In other words, an application time of the control pulse Ramp-p rising at the same slope is controlled, so that the control pulse Ramp-p having a different voltage value can be applied to each sub-field. Herein, an application time of the control pulse may be set to be shorter as it goes from the initial sub-field into the later sub-fields. Then, as it goes from the initial sub-field into the later sub-fields, a voltage value of the control pulse becomes lower. Alternatively, an application of the control pulse may be set to be longer as it goes from the initial sub-field into the later sub-fields. In real, an application time of the control pulse is experimentally determined in consideration of a length (i.e., inch) of the panel, a resolution of the panel and a process state, etc. Otherwise, the control pulse Ramp-p having different slope and/or voltage for each sub-field may be supplied.
In the address period, a negative scanning pulse scan is sequentially applied to the scan electrodes Y and, at the same time, a positive data pulse data is applied to the address electrodes X. A voltage difference between the scanning pulse scan and the data pulse data is added to a wall voltage generated in the initialization period to thereby generate an address discharge within the cells supplied with the data pulse data. Wall charges are formed within the cells selected by the address discharge. In the above-mentioned embodiment of the present invention, negative wall charges are formed at the scan electrodes of the entire discharge cells during the wall charge control period to thereby cause a stable address discharge. Accordingly, it becomes possible to prevent a miswriting and/or a spot misfire.
Meanwhile, a positive direct current voltage having a sustain voltage level Vs is applied to the sustain electrodes Z during the set-down interval and the address period. Further, in the wall charge control period, the sustain electrodes Z are supplied with a ground voltage GND. The sustain electrodes Z are supplied with the ground voltage GND during the wall charge control period to thereby cause a stable intensified discharge.
In the sustain period, a sustaining pulse sus is alternately applied to the scan electrodes Y and the sustain electrodes Z. Then, a wall voltage within the cell selected by the address discharge is added to the sustain pulse sus to thereby generate a sustain discharge taking a surface-discharge type between the scan electrode Y and the common sustain electrode Z whenever each sustain pulse sus is applied. Finally, after the sustain discharge was finished, an erasing ramp waveform erase having a small pulse width is applied to the sustain electrode Z to thereby erase wall charges left within the cells.
FIG. 7 shows a scan electrode driver according to an embodiment of the present invention.
Referring to FIG. 7 , the scan electrode driver includes an energy recovering circuit 41 , a fourth switch Q 4 connected between the energy recovering circuit 41 and a driving integrated circuit (IC) 42 , a negative scan voltage supplier 43 and a scan reference voltage supplier 44 connected between the fourth switch Q 4 and the driving IC 42 to apply a scanning pulse Scan, and a set-up supplier 45 connected among the fourth switch Q 4 , the negative scan voltage supplier 43 and the scan reference voltage supplier 44 to generate a rising ramp waveform Ramp-up.
The driving IC 42 is connected in a push-pull shape, and consists of tenth and eleventh switches Q 10 and Q 11 to which voltage signals from the energy recovering circuit 41 , the scan voltage supplier 43 and the scan reference voltage supplier 44 are inputted. An output line between the tenth and eleventh switches Q 10 and Q 11 are connected to any one of scan electrode lines Y 1 to Ym.
The energy recovering circuit 41 includes an external capacitor CexY for charging an energy recovered from the scan electrode lines Y 1 to Ym, switches Q 14 and Q 15 connected, in parallel, to the external capacitor CexY, an inductor Ly connected between a first node n 1 and a second node n 2 , a first switch Q 1 connected between a sustain voltage supply Vs and the second node n 2 , and a second switch Q 2 connected between the second node n 2 and a ground voltage terminal GND.
An operation of the energy recovering circuit 41 will be described below.
First, it is assumed that a Vs/2 voltage has been charged in the external capacitor CexY. If the fourteenth switch Q 14 is turned on, then a voltage charged in the external capacitor CexY is applied, via the fourth switch Q 14 , a first diode D 1 , the inductor Ly and the fourth switch Q 4 , to the driving IC 42 and, at the same time, is applied, via an internal diode (not shown), to the scan electrode lines Y 1 to Ym. At this time, the inductor Ly configures a serial LC resonance circuit along with a capacitance C of the cell of the PDP to thereby apply a resonating waveform to the scan electrode lines Y 1 to Ym.
The first switch Q 1 is turned on at a resonance point of the resonating waveform. If the first switch Q 1 is turned on, then the sustain voltage Vs is applied, via the first switch Q 1 and the driving IC 42 , to the scan electrode lines Y 1 to Ym. During the time interval when voltages on the scan electrode lines Y 1 to Ym are charged and discharged by such an operation of the energy recovering circuit 41 , the fourth switch Q 4 keeps an ON state so as to form a current path between the energy recovering circuit 41 and the driving IC 42 .
The energy recovering circuit 41 recovers an energy from the PDP and then applies a voltage to the scan electrode lines Y 1 to Ym using the recovered energy, thereby reducing an excessive power consumption upon discharging in the set-up interval and in the sustain period.
The negative scan voltage supplier 43 consists of a sixth switch Q 6 connected between a third node n 3 and a scan voltage source −Vy. The sixth switches Q 6 is switched in response to a control signal yw from a timing controller (not shown) during the address period to thereby apply a scan voltage −Vy to the driving IC n 4 .
The scan reference voltage supplier 44 consists of an eighth switch Q 8 connected between a scan reference voltage source Vsc and a fourth node n 4 . The eighth switch Q 8 is switched in response to a control signal SCW from the timing controller (not shown) to thereby apply the scan reference voltage Vsc to the driving IC 42 .
The set-up supplier 45 consists of a fourth diode D 4 and a third switch Q 3 connected between a set-up voltage source Vsetup and a third node n 3 . The fourth diode D 4 shuts off a backward current flowing from the third node n 3 into the set-up voltage source Vsetup. The third switch Q 3 is switched in response to a control signal setup from the timing controller (not shown) to thereby apply a rising ramp waveform Ramp-up having a slope determined by a RC time constant value to the third node n 3 .
A procedure in which a control pulse Ramp-p is supplied from the scan electrode driver of the present invention will be described below.
First, since a control signal set-up is applied via a first variable resistor R 1 , a channel width of the third switch Q 3 is controlled by a resistance value of the first variable resistor R 1 . In real, a channel width of the third switch Q 3 is controlled by a capacitance value of a capacitor or a parasitic capacitor (not shown) and a RC time constant of the first variable resistor R 1 .
Accordingly, a control pulse Ramp-p supplied via the third switch Q 3 at a predetermined slope (i.e., the same slope as the rising ramp waveform) is applied, via the third node n 3 , to the driving IC 42 . The control pulse Ramp-p applied to the driving IC 42 is applied, via the driving IC 42 , to the scan electrode Y. If the control pulse Ramp-p is applied to the scan electrode Y, then an intensified discharge is generated at the discharge cells to thereby form negative wall charges at the entire scan electrodes Y. After the control pulse Ramp-p was applied to the scan electrodes Y, the second switch Q 2 is turned on. If the second switch Q 2 is turned on, then a ground voltage GND is applied to the scan electrodes Y.
Such an embodiment of the present invention can apply the control pulse Ramp-p with the aid of the set-up supplier 45 for supplying the rising ramp waveform without any additional circuit for supplying the control pulse Ramp-p.
FIG. 8 shows a method of driving a plasma display panel (PDP) according to a second embodiment of the present invention.
Referring to FIG. 8 , the PDP according to the second embodiment of the present invention is divided into an initialization period for initializing the entire field, a wall charge control period for preventing an inversion of wall charges, an address period for selecting a cell and a sustain period for sustaining a discharge of the selected cell for its driving.
In the initialization period, a rising ramp waveform Ramp-up is simultaneously applied to all of scan electrodes Y in a set-up interval. This rising ramp waveform Ramp-up causes a weak discharge within cells at the full field to generate wall charges within the cells. The rising ramp waveform Ramp-up rises from a sustain voltage Vs until a sum value of a set-up voltage Vsetup with the sustain voltage Vs.
In the set-down interval, after the rising ramp waveform Ramp-up was supplied, a falling ramp waveform Ramp-down falling from a positive voltage lower than a peak voltage of the rising ramp waveform Ramp-up is simultaneously applied to the scan electrodes Y. The falling ramp waveform Ramp-down causes a weak erasure discharge within the cells, to thereby erase spurious charges of wall charges and space charges generated by the set-up discharge and uniformly leave wall charges required for the address discharge within the cells of the full field. In real, the falling ramp waveform Ramp-down falls from the sustain voltage Vs until a negative voltage −Vy so that desired wall charges can be left during the set-down interval.
In the wall charge control period, the scan electrodes Y are supplied with a rectangular control pulse pp rising from a ground voltage GND until a sustain voltage Vs. If the rectangular control pulse pp is applied to the scan electrodes Y, then a discharge is generated at the discharge cells to thereby control the polarities of the discharge cells into desired types.
More specifically, in the set-down interval, wall charges having an undesired type of polarities are formed at a portion of discharge cells as shown in FIG. 5 . Thereafter, if the rectangular control pulse pp is applied to the scan electrodes Y, then a discharge is generated at the discharge cells to thereby form negative wall charges at the scan electrodes Y while forming positive wall charges at the sustain electrodes Z. In other words, in the embodiment of the present invention, the polarities of wall charges of the entire discharge cells can be controlled into desired polarities during the wall charge control period.
Meanwhile, an application time of the control pulse pp is set within 1 μs. For instance, an application time of the control pulse pp may be set more shortly as it goes from the initial sub-field into the later sub-fields. Alternatively, an application time of the control pulse pp may be set longer as it goes from the initial sub-field into the later sub-fields. In real, an application time of the control pulse pp is experimentally determined in consideration of a length (i.e., inch) of the panel, a resolution of the panel and a process state, etc. Further, a scan reference voltage Vsc is applied to the scan electrode Y prior to an application of the control pulse pp. FIG. 8 shows a pulse having the scan reference voltage Vsc applied in the wall charge control period prior to the control pulse pp.
In the address period, a negative scanning pulse scan is sequentially applied to the scan electrodes Y and, at the same time, a positive data pulse data is applied to the address electrodes X. A voltage difference between the scanning pulse scan and the data pulse data is added to a wall voltage generated in the initialization period to thereby generate an address discharge within the cells supplied with the data pulse data. Wall charges are formed within the cells selected by the address discharge. In the above-mentioned embodiment of the present invention, negative wall charges are formed at the scan electrodes Y of the entire discharge cells during the wall charge control period to thereby cause a stable address discharge. Accordingly, it becomes possible to prevent a miswriting and/or a spot misfire.
Meanwhile, a positive direct current voltage having a sustain voltage level Vs is applied to the sustain electrodes Z during the set-down interval and the address period. Further, in the wall charge control period, the sustain electrodes Z are supplied with a ground voltage GND. The sustain electrodes Z are supplied with the ground voltage GND during the wall charge control period to thereby cause a stable intensified discharge.
In the sustain period, a sustaining pulse sus is alternately applied to the scan electrodes Y and the sustain electrodes Z. Then, a wall voltage within the cell selected by the address discharge is added to the sustain pulse sus to thereby generate a sustain discharge taking a surface-discharge type between the scan electrode Y and the common sustain electrode Z whenever each sustain pulse sus is applied. Finally, after the sustain discharge was finished, an erasing ramp waveform erase having a small pulse width is applied to the sustain electrode Z to thereby erase wall charges left within the cells.
In the mean time, in FIG. 8 , the control pulse pp can be supplied by means of the scan electrode driver shown in FIG. 7 . This will be described with reference to FIG. 7 below.
First, an eighth switch Q 8 is turned on during the wall charge control period to thereby apply a scan reference voltage Vsc to the scan electrodes Y. Thereafter, a second switch Q 2 is turned on, to thereby apply a ground voltage GND to the scan electrodes Y. After the ground voltage GND was applied to the scan electrodes Y, a first switch Q 1 is switched (e.g., during a time less than 1 μs), to thereby apply a control pulse pp having a sustain voltage level Vs to the scan electrodes Y. Thereafter, the ground voltage GND, the scan reference voltage Vs and a scan voltage −Vr are applied to the scan electrodes Y, to thereby cause an address discharge.
As described above, according to the present invention, a control pulse is applied after the reset period to thereby prevent an inversion phenomenon of wall charges. In other words, a positive control pulse is applied to the scan electrodes after the reset period to thereby form negative wall charges at the entire scan electrodes. Accordingly, it becomes possible to generate a stable address discharge and thus to prevent a miswriting and a spot misfire.
Although the present invention has been explained by the embodiments shown in the drawings described above, it should be understood to the ordinary skilled person in the art that the invention is not limited to the embodiments, but rather that various changes or modifications thereof are possible without departing from the spirit of the invention. Accordingly, the scope of the invention shall be determined only by the appended claims and their equivalents.
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A method and apparatus for driving a plasma display panel for preventing and a spot misfire and a miswriting is disclosed. In the method, wall charges are formed at a discharge cell in an initial period. The discharge cell selects discharge cells in an address period. A wall charge control period is arranged between said initialization period and said address period. A wall charge distribution at the discharge cell is controlled in the wall charge control period. A sustain discharge is caused at discharge cells selected in said address period in the sustain period.
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BACKGROUND OF THE INVENTION
[0001] The present invention relates to a novel method of competitive marksmanship and, preferably, simulated combat marksmanship. An aspect of the present novel method of marksmanship lies in its use of novel types of targets, elements therein and novel rules for the use of the targets.
[0002] Historically, shooting targets have always been identical for each competitor as, for example, is shown in FIG. 1 , labeled “Prior Art.”
[0003] Further, within the art of targets, numerous forms and types of single competitor targets, or like targets for use by multiple competitors, are known in the art. These for example are reflected in U.S. Pat. No. 6,213,470 (2001) to Miller, entitled Precise Aim Sighting Target; and U.S. Pat. No. 7,175,181 (2007) to Bateman, entitled Portable Shooting Target.
[0004] Also known in the art are targets of numerous different individual appearances as, for example, may be seen in The Glock FAQ target gallery website glockfaq.com/targets.htm. Therein are shown dozens of targets having almost every conceivable appearance and image thereupon. Various targets of other forms may be seen at www.lyndenhuggins.com/Hunting/Targets, www.tjtarget.com and site for “My Real Picture Targets” in which the targets consist of photographs of typical hunted animals, such as rabbits, deer and elk
[0005] There, as well, exist many dozens of United States design patents directed to the ornamental appearance of marksmanship targets. Some of these, for example, U.S. Des. Pat. No. 392,687 (1998) to Wilson, entitled Target Game and U.S. Des. Pat. No. 381,732 (1997) to Tenor, entitled Indicia for a Target are directed to a design portion of a target game, the rules of which however are not disclosed in said design patents. The same is similarly in the case in several other design patents, that is, the rules or protocols associated with a given ornamental target are not disclosed in any fashion in the design patent itself.
[0006] There also exists in the art psychedelic targets, as are reflected in U.S. Design Pat. No. 269,631 (1983) to Dulude, entitled Gun Target, again without any rules or protocol associated therewith. There also exists in the art actual battlefield or combat training target as is reflected in U.S. Pat. No. 5,326,265 (1994) to Prevou, entitled Battlefield Reference Marking System Signal Device.
[0007] Finally, there is shown in the prior art a system which simulates a complete hunting environment, that is, a virtual hunting range within an environment projected onto a hemispherical enclosure of the system. See United States Patent Application Publication US 2007/0015116 (2007) to Coleman, entitled Method of and Apparatus for Virtual Shooting Practice. The concept of a target projected by cinematic means has been known in the art since 1935, as is reflected in United Kingdom Patent No. 459,313 (1935) to Chollat, entitled Shooting Target with Cinematographic or Animated Pictures.
[0008] The concept of mechanically moveable or physically variable targets is also known as is reflected in published German Patent Specification DE 195 43 492 A1 (1997) to Stechemesser.
[0009] In distinction, the instant invention differs from those targets and target systems, above described, not only in its differences of appearance but, more particularly, in the manner and concept of use thereof. The invention also differs from all art of record in that it provides a unique platform for competitive marksmanship between two or more competitors of a type unlike that heretofore known in the art.
[0010] Yet further, the platform of a present game, as described below, is one having a potential for numerous variations thereof, as may suit the needs and preferences of particular competitors.
SUMMARY OF THE INVENTION
[0011] The present invention relates to a method of competitive marksmanship relative to specific target types, as is more fully set forth below. The method includes the steps of providing a first shooter with a first designated target system having a first target composition, the composition comprising a plurality of graphic elements. Therein, respective selectable rule-based values are, in accordance with rules, assigned for respective graphic elements of the first target composition. Thereafter, a second shooter is provided with a second designated target system, said system having a second target composition, visually different from said first composition, and said target composition also comprising a plurality of graphic elements. Thereafter, each respective graphic element of said second target composition is assigned a rule-based respective value. As the game progresses, and in accordance with variations of the game, there is calculated a progressive accumulation of values resultant of a successful scoring of hits upon elements of said target composition of each shooter's respective designated target system, until a winner is declared.
[0012] In broad concept, there exist three categories of targets, namely, full Force targets, split targets in which the players share the same firing lane or position, and mixed targets, also used when players share the same firing position or lane. In each of these three such categories, there exists in turn three bases upon which the competitive marksmanship may proceed, namely, unlimited time rules and slot limited time rules, and limited shot rules.
[0013] As may be more fully appreciated with respect to the following, the inventive method of competitive marksmanship has as object the provision of completely new and different kind of competitive shooting, namely, one in which each competitor shoots at a dissimilar target.
[0014] It is accordingly an object of the present invention to provide a novel method of marksmanship in which, within the context of shooting by each competitor at a dissimilar target, there exist a multiplicity of combinations and sub-combinations of target selection and therein distinct rules of time and shot selection. Each option thereof is yet subject to numerous refinements in order to add interest to the shooting experience and competitive stimulation thereof.
[0015] The above and yet other objects and advantages of the present invention will become apparent from the hereinafter set forth Brief Description of the Drawings, Detailed Description of the Invention and Claims appended herewith.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] FIG. 1 is a schematic view of the prior art method of competitive marksmanship in which two competitors are shooting at separate like targets.
[0017] FIG. 2 is a flow diagram showing the basic target and rule variations applicable to the present method, as well as the variations which are available within each target/rule sub-rule.
[0018] FIGS. 3A and 3B are examples showing the use of dissimilar targets comprising different elements within the target composition of each respective competitor.
[0019] FIG. 4 is a schematic view of a target in accordance with the present invention showing the split field type target.
[0020] FIG. 5 is a view of the target used with the present method, employing so-called mixed targets.
[0021] FIG. 6 corresponds to FIG. 3A in which however a graphic expression of the elements of the first target composition of the first designated target system of the first shooter is shown.
[0022] FIG. 7 corresponds to FIG. 3B in which however a graphic expression of the elements of the second target composition comprising the second designated target system used by the second shooter is shown,
[0023] FIG. 8 corresponds to FIG. 4 in that it shows a graphic expression of a target of the split target type.
[0024] FIG. 9 corresponds to the schematic of FIG. 5 however showing a graphic expression of the respective elements of each of the respective target compositions and elements of a mixed target system.
DETAILED DESCRIPTION OF THE INVENTION
[0025] With reference to FIG. 1 (Prior Art), there is shown a representative shooting and target format for competitive marksmanship as it is generally known in the art. Therein, as may be noted, each competitor, noted in FIG. 1 as Competitor 1 and Competitor 2 shoots at identical targets 10 and 12 having thereon identical graphics 14 which, in the classical type of target, is simply that of a series of concentric circles, although enumerable other target configurations are known, as is set forth in the Background of the Invention. Therein, competitors fire a given number of shots and the shooter having the most closest to the center of their respective targets thereby score the highest number of points and win the competition.
[0026] In the instant inventive method, there is offered an entirely new and different format of competitive marksmanship in which, at essence, each competitor shoots at a dissimilar target. As such, the experience of competitive shooting may be expressed not only with traditional guns, pistols, rifles or arrows but, alternatively, in electronic form or in a children's analog in which non-lethal bullets are used in the shooting device. Paramount in the instant method is that each competitor shoots at a dissimilar target and that each dissimilar target is defined by a particular target composition comprising a multiplicity of graphic elements that provide to the target composition in distinctive character or connotation.
[0027] An overview of the rules which govern the method of competitive marksmanship, also termed herein the “rules of engagement,” begin (see FIG. 2 ) with a target type selection, that is, a selection between three different types of respectively dissimilar targets. In the so-called full Force target selection, each competitor is provided with an entirely separate target 16 and 18 (see FIGS. 3A and 3B ), thereby completely isolating Force elements 20 of Force A from Force elements 30 of Force B that appear in target 18 (also target B). Simply stated, competitor one will shoot at target A/ 16 while competitor two will shoot at target B/ 18 . Therein, all of the shown elements 20 will, as a group, comprise a first target composition 24 of a first designated target system 16 . Similarly, a second shooter (competitor 2 ) is provided with a second designated target B/ 18 having a second target composition 26 and therein a multiplicity of graphics which are common in theme or connotation with all other graphic elements 30 (Force B) of target B/ 18 . The same is conversely true with target A. Elements 30 will exhibit an opposite or opposing connotation of these of elements 20 . This form of practice of the inventive method is reflected in the left hand one third of the flow diagram of FIG. 2 . It is to be appreciated that elements 20 are expressed as a plurality thereof, namely, elements 20 . 1 to 20 . 5 . The same is true of elements 30 , shown as elements 30 . 1 to 30 . 5 .
[0028] In the next general mode in which the inventive method may be practiced, there are provided so-called split targets 100 and 102 (see FIG. 4 ) upon a single physical target 104 which is used when the respective shooters or competitors wish to share the same firing position or lane. However, within the respective upper and lower portions 100 and 102 of the split target 104 are provided the same respective designated target systems, namely, first designated target system 116 and second designated target system 118 as are correspondingly employed in the separate so-called individual full Force targets shown in FIGS. 3A and 3B . Similarly, within each respective split target 100 and 102 is shown a similar or comparable first target composition 124 and second target composition 126 . Therein, in similar to that fashion above described with respect to separate targets A and B shown in FIGS. 3A and 3B respectively are a multiplicity of graphic elements 120 of first target composition 124 of split target 104 and second graphic elements, visually different from those first composition 124 . These would take the form of elements 130 , which, in aggregate, correspond to Force B, related in subject matter or connotation to that of Force B elements 30 of target composition 26 target B/ 18 shown in FIG. 3B .
[0029] In summary, split targets 100 and 102 , which, in combination, comprises physical target 104 , each exhibiting a correspondence, but typically having fewer elements therein, to Force A/element 20 of FIG. 3A and Force B/elements 30 of target B, above described, of FIG. 3B .
[0030] The instant method of competitive marksmanship may be executed in a yet further physical format, namely, that of so-called mixed target 200 (see FIG. 5 ). Therein, as is the case in FIGS. 3 and 4 , all Force A elements are indicated by a square and all Force B elements by a circle or oval, Force A elements being denoted by reference numerals 220 in FIG. 4 , and Force B elements by reference numerals 230 in FIG. 5 . Accordingly, as may be appreciated with regard to said figure, graphic elements 220 . 1 to 220 . 6 and 230 . 1 to 230 . 6 , of the respective Forces are mixed, or interspersed with each other in the mixed target 200 of the invention. Therein, the first and second target compositions 224 and 226 are intermixed although the elements 220 and 230 thereof retain their particular opposing appearance or identity.
[0031] With reference to FIG. 6 , there is shown the appearance, in graphic expression, of target A of Competitor 1 in FIG. 3A . Therein, the graphic expression of Force A element 20 . 1 is shown as a Zero aircraft of design element 20 A. 1 . The target A/ 16 Force A element 20 . 2 is expressed as elements 20 A. 2 which is a rendering of a Kate aircraft. The same correspondence proceeds throughout FIG. 6 , that is, target A/ 16 design element 20 A. 3 comprising a graphic expression of element 20 . 3 of Force A; design element 20 A. 4 comprising a design element expression of Force A element 20 . 4 , the aircraft carrier element 28 A. 5 in FIG. 6 comprising a graphic expression of element 20 . 5 of Force A of target A/ 16 , and the aircraft carrier 20 A. 6 of FIG. 6 comprising a graphic element corresponding to Force A element 20 . 6 of target A/ 16 .
[0032] In FIG. 6 is shown a similar correspondence relative to the conceptual view of FIG. 3B showing target B/ 18 . That is, graphic element 30 A. 1 of FIG. B corresponds to element 30 . 1 of FIG. 3B ; 30 A. 2 to element 30 . 2 ; 30 A. 3 to element 30 . 3 ; 30 A. 4 to element 30 . 4 ; 30 A. 5 to element 30 . 5 , and 30 . 6 to aircraft carrier 30 A. 6 of FIG. 6 .
[0033] With respect to the split target protocol 104 shown in FIG. 4 and described above, the graphic expression thereof is shown in FIG. 8 as a single target 104 A. Therein the upper field 100 A of split target of FIG. 8 is seen to represent a graphic expression of the conceptual target 100 shown in FIG. 4 . More particularly, element 120 . 1 is expressed in target 100 A as a Sherman tank 120 A. 1 ; element 120 . 2 of target 100 is expressed as personnel and machine gun carrier 120 A. 2 in target 100 A of FIG. 8 . The same form of graphic expression corresponds throughout target 100 A, that is, element 120 . 3 of FIG. 4 corresponding to graphic element 120 A. 3 ; element 120 . 4 corresponding to the tank of element 120 A. 4 of FIG. 4 ; element 120 . 5 corresponding to the Sheffield tank of element 120 A. 5 ; and element 120 . 6 of FIG. 4 corresponding to element 120 A. 6 expressed as artillery piece on target 100 A of FIG. 8 .
[0034] As may be noted, lower field composition 118 of lower target 102 corresponds to the lower target 102 A shown in FIG. 8 in which each of the graphic elements thereof represents graphic expressions of the elements 130 of Force B shown in FIG. 4 . Therein, element 130 . 1 corresponds to the Mark 4 Panzer tank of element 130 A. 1 ; element 130 . 2 corresponds to the armored personnel half track of element 130 A. 2 of FIG. 8 ; element 130 . 3 corresponds to the armored personnel carrier and mobile machine gun of element 130 A. 3 ; element 130 . 4 of target field 118 of target B of FIG. 4 is expressed as element 130 A. 4 upon target 102 A of FIG. 8 ; element 130 . 5 is expressed as element 130 A. 5 ; and element 130 . 6 is expressed as element as 130 A. 6 on lower target 102 A of split target 104 A in FIG. 8 .
[0035] With reference to the mixed target embodiment of the present invention, the graphic expression of the mixed target, target 200 , of FIG. 4 is shown as target 200 A in FIG. 9 . Therein it may be appreciated that, within the interdispersal of Force A elements with Force B elements upon field 224 (field 224 A in FIG. 9 ) is a mix of the forces of the respective shooters. In FIG. 9 , aircraft of World War II vintage Royal Air Force are shown interspersed between “enemy” German aircraft of the same period. All Force A elements begin with the digits 220 while all element of the opposing Force begin with the digits 230 . Therefrom, it may be seen that Force A element 220 . 1 of FIG. 4 is expressed as Force A element 220 A. 1 in FIG. 9 ; Force A element 220 . 2 is expressed as element 220 A. 2 ; Force A element 220 . 3 as element 220 A. 3 ; and Force A element 220 . 5 as Force A element 220 A. 5 in FIG. 9 . Correspondingly, with respect to Force B, element 230 . 1 . of FIG. 4 as expressed as Force B element 230 A. 1 in FIG. 9 ; element 230 . 2 as element 230 A. 2 ; element 230 . 3 as element 230 A. 3 ; element 230 . 4 of FIG. 4 is element 230 A. 4 of FIG. 9 ; element 230 . 5 as element 230 A. 5 , and element 230 . 6 as element 230 A. 6 of FIG. 9 . Therein, opposing “allied” and “enemy” forces, that is, Forces A and B are shown interspaced with each other in the target 200 A of FIG. 9 at which both competitors/shooters attempt to score in accordance with the rules of engagement set forth herein.
[0036] With reference to the flow chart of FIG. 2 , there is shown the above set forth methods of target selection, namely, full Force ( FIGS. 3A and B), split target ( FIG. 4 ), and mixed target ( FIG. 5 ). However, with respect to further terms, conditions or limitations with which each of said forms of target may be employed, these areas relate to the basic rules of engagement, i.e., unlimited time for shooting, shooting within a limited time, and limited shot rules. As noted in FIG. 2 , these are defined as follows:
[0037] Unlimited time: each side fires at respective targets, whether at the full Force, split, or mixed type, until one side eliminates all of the targets in a designated target system.
[0038] Limited time: a predetermined total amount of time, as stipulated, within which each shooter is permitted to attempt to score. Within that limited time, each shooter is permitted an unlimited number of shots at his designated target system, namely, Force A or Force B.
[0039] Limited shot rules: each shooter/player is permitted a pre-determined number of shots at his selected first or second target composition.
[0040] Within any of the above nine target/rule selections, shown in FIG. 2 , various additional limitations or rules may be agreed upon by the parties in each of the target/variations, these as follows:
[0041] 1. Kill ratio basis of scoring. In either of the ‘limited’ versions of the game, at the end of the game, scores are determined by adding the “kill ratios” of all individual components of a “force” that has been completely eliminated. For example, if there five are individual elements 20 / 30 , each with a “kill ratio” of 3, and they have each been hit three times, they would represent a score of 15. However, if one of those components had only been hit twice, that element would not score any points.
[0042] 2. Qualifying shots. Contestants determine what constitutes a ‘hit’ on target, for example, whether flags, masts and/or antennae on ships constitute a hit (see Handicapping below).
[0043] 3. Target order/Contestants may determine the order in which the targets are to be engaged, for example, all fighter aircraft must be eliminated before bombers may be targeted. Other forms of “Target Order” may be: order of target value (i.e., targets are to be destroyed in ascending/descending order or value), or row order (i.e., front rank first, and the like).
[0044] 4. Target elimination. Contestants may determine that once a target with a “kill ratio” of two or more has been hit once, then that target must be completely, eliminated before any other target may be acquired.
[0045] 5. Order of firing. Contestants may decide, particularly when sharing a firing position, to alternate either single or a specified number of shots, or elect an independent ‘fire at will.’
[0046] 6. Penalties for infraction: A penalty may be applied to any infraction of the agreed upon “rules of engagement.” Examples of infractions may include: exceeding the time allowed (if applied to the limited time variant of the game), exceeding the agreed number of shots (if applying the limited shot version of the game), requiring eliminating individual components of Force A or B before acquiring another element of the target composition, and hitting elements out-of-order. Such penalties are of course agreed upon before the commencement of the game and, penalties for such infraction may include the following:
[0047] 1. Point reduction: a competitor's score may be reduced if one of the agreed rules of engagement are breached.
[0048] 2. Shot deduction: if playing the limited shot version of the game, infractions may call for a reduction of total number of shots allowed.
[0049] 3. Time deduction: if using the limited time variant of the game, points may be deducted for a time infraction or, in the case of individual time shots, the player's next shot time allocation may be reduced.
[0050] 4. Handicapping: Handicapping may be applied either as another form of penalty, or as a means of equalizing any unfair advantage due to differing skill levels or experience. Handicapping may include:
[0051] “kill Ratios”—Higher “kill ratios” may be applied to one player/team to equalize skill levels or as a penalty. When using any of the scoring versions of the game, then the original score value of each component will apply to both sides, irrespective of the number of hits required for that component to be eligible to score.
[0052] “Target Zones”—Specific target zones may be applied to individual components to make it more difficult to eliminate/score. For example, it may be determined that for one player/team, only shots to aircraft from the cockpit to the propeller—or only shots on ships above the hull—or only shots to tanks above the tracks—constitute a hit.
[0053] “Target Range”—Particularly with “Full Force” targets, distance to target is adjusted to allow for differences in skill levels.
[0054] While there has been shown and described the preferred embodiment of the instant invention it is to be appreciated that the invention may be embodied otherwise than is herein specifically shown and described and that, within said embodiment, certain changes may be made in the form and arrangement of the parts without departing from the underlying ideas or principles of this invention as set forth in the Claims appended herewith.
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The method of competitive marksmanship includes the steps of providing a first shooter with a first designated target system having a first target composition, the composition including various graphic elements. Respective selectable rule-based values are, in accordance with rules, assigned for respective graphic elements of the first target composition. A second shooter is provided with a second designated target system, the system having a second target composition, visually different from the first composition, and the target composition also including various graphic elements. Each respective graphic element of the second target composition is then assigned a rule-based respective value. As the game progresses, and in accordance with variations of the game, there is calculated a progressive accumulation of values resultant of a successful scoring of hits upon elements of the target composition of each shooter's respective designated target system, until a winner is declared.
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FIELD OF THE INVENTION
This invention relates to a heat-exchanger.
BACKGROUND TO THE INVENTION
Our U.S. patent application Ser. No. 523,891 now U.S. Pat. No. 3,989,105, describes a multiple-tube heat exchanger which is particularly suitable for use as a steam generator and in which the primary heat-carrying fluid is formed by the cooling fluid (pressurized water or liquid sodium) of a nuclear reactor. The exchanger described in the parent patent comprises, in combination, an outer heavy structure in the form of an outer cylindrical shell fixed at its upper end to an annular intake head and an annular outlet head for one of the fluids, of which the inner bases are perforated, and an inner lightweight structure subsequently mounted in the heavy structure and formed by an annular nest of tubes inserted and welded at their ends into the perforations in said bases and arranged in the form of concentric layers forming a large central passage which is accessible for installation of the tubes, beginning with the peripheral layer adjacent the outer shell, the concentric layers of tubes being held in several transverse planes by discs formed by concentric rows of rings arranged between these layers and joined together by radial stays, a wide central shaft subsequently being fixed for internally defining the annular exchange chamber.
In one embodiment described in earlier Specification, the tubes of the exchanger are all identical and comprise arcuate bends situated successively on either side of the longitudinal axis of the tubes, which provides them with a quasi-sinusoidal form, the retaining planes, in the form of concentric rings joined together by connecting elements allowing through the fluid circulating along and around the tubes, being situated level with the crests of the sinusoids or level with the inflexion points and being joined by welding to the outer cyclindrical shell and to the central shaft.
It will be appreciated that it is possible, by using tubes shaped in this way, to compensate by elastic flexural deformation the differential expansion which can occur between the tubes and the outer shell in view of the fairly significant differences in temperature, which may amount to as much as 200° C, between the tubes and the shell, which would obviously not be the case if the tubes were straight. As indicated in the earlier Specification, the result obtained in this way is a considerable reduction in the stressing which the tubes undergo. However, this method of fixing the tubes has to satisfy two opposing requirements to enable maximum benefit to be derived from the flexibility of the tubes. On the one hand, the manner in which the tubes are fixed should leave them with maximum freedom of expansion, whilst on the other hand the tubes have to be fixed fairly rigidly in order to prevent them from vibrating. In the arrangement described in the earlier Specification, this result was obtained by varying the distance between the rigid retaining planes of the tubes because the tubes can expand more freely, the longer the curve along which their free expansion occurs, whilst widening the intervals between the fixing points involves the danger of vibration of the tubes. Thus, it is extremely difficult to establish a satisfactory compromise between these two opposing requirements. The present invention enables this result to be obtained by simple and effective means.
BRIEF SUMMARY OF THE INVENTION
The improvement which is the subject of the present invention is distinguished by the fact that the discs by which the tubes are held in position and which are formed by the above-mentioned concentric rings are in some cases, free to rotate about the axis of the apparatus under the effect of the flexural deformation of the tubes attributable to their expansion and in other cases, are fixed and joined to the outer shell and, optionally, to the central shaft which internally closes the annular exchange chamber occupied by the nest of tubes.
FURTHER FEATURES OF THE INVENTION
The fixed retaining discs and the retaining discs which are free to rotate about the axis of the apparatus are preferably arranged equidistant from one another in an alternating sequence, the distance between them being selected in such a way that, individually, each tube is perfectly stable, this distance generally being of the order of 1 meter.
In order, on the other hand, to ensure that the undulating tubes are not in any danger of being displaced or of vibrating outside the planes containing the undulations, the tubes may comprise asymmetrical undulations on either side of their general longitudinal axis so that the fixing points of the tubes situated on either side of that axis are situated at different distances therefrom. In one preferred embodiment, however, the fixing points of the tubes which are held in the fixed retaining discs are situated on the general axis of the tubes, whilst the freely rotatable retaining discs are situated at the level of the crests of the undulations situated on one side of this general axis.
The tubes may compise straight sections between undulations situated on one and the same side, in which case the fixed retaining discs are arranged substantially level with the centres of these straight sections.
In another embodiment, the tubes comprise, between two successive unilateral undulations, two very slight, oppositely directed undulations, whilst the fixed retaining discs are situated level with the connecting points of these slight undulations so that the tubes are rigidly held at points situated along their longitudinal axes.
In order, in addition, to improve heat exchange at the point where the water to be vaporized enters the lower part of the exchanger and in its upper part, in which the vapor produced is superheated, means are provided for imparting both to the water and to the steam a transverse flow relative to the tubes through which the heat-carrying fluid passes. To this end, the exchanger comprises, in the lower part and in the upper part of the annular exchange chamber, at least one baffle plate of which the central and marginal zones are respectively formed by retaining rings joined by tubular radial stays separating the tubes from one another and allowing through the fluid circulating around the tubes, and by rings comprising, in their opposite lateral faces, semi-circular recesses for receiving the tubes and for preventing axial circulation of the fluid so as to impart to it a transverse flow relative to the tubes, or vice versa.
One embodiment of the heat exchanger according to the present invention is described by way of example in the following with reference to the accompanying drawings, wherein:
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is an axial section through the exchanger according to the invention;
FIG. 2 is an elevation of one tube of this exchanger;
FIG. 2a is an elevation of a variant of the tube shown in FIG. 2;
FIG. 3 is a partial plan view of a retaining disc, of which FIG. 3a shows a variant;
FIG. 4 shows on a larger scale that part of this tube situated between two fixed retaining discs, and the deformation which this tube undergoes at the level of the freely rotatable retaining disc according to whether it is situated at the outer or inner periphery of or inside the nest of tubes;
FIG. 5 is a partial cross-section through a nest of tubes showing the displacements of the crests of the undulations of these tubes for a given rotation of the free retaining discs; and
FIGS. 6 and 7 are partial plan views of two baffle plates.
DESCRIPTION OF EMBODIMENTS
As mentioned earlier on, the heat exchanger shown in FIG. 1 comprises an outer heavy structure in the form of a cylindrical shell 1 fixed by welding at its two ends to perforated, annular terminal plates 2, 3 and to two annular heads 4, 5 comprising an outer dome-shaped wall and an inner cylindrical wall forming a wide central passage. The heads 4, 5 which are used respectively for the admission and removal of the heat-carrying fluid circulating through the tubes of the nest (in the embodiment illustrated hot pressurised water coming from the cooling circuit of a nuclear reactor), respectively comprise an intake opening 6 and an outlet opening 7 for that fluid, and manholes 8, 8' closed by fluid-tight doors 9, 9'.
The central passage 10 of the lower head 5 are used to admit the water to be vaporized, whilst the superheated steam produced in the exchanger leaves the exchanger through the central passage 10' of the upper head 4.
Flexible tubes, all of which have the shape illustrated in FIG. 2, are introduced and welded at their straight ends into perforations in the perforated terminal plates 2, 3.
In the interests of clarity, FIG. 1 shows only two tubes 11, 11' belonging to the outer, circular peripheral layer, two tubes 12, 12' belonging to a layer situated inside the nest of tubes, and two tubes 13, 13' belonging to the inner peripheral layer.
A wide central shaft 20 of thin sheet metal internally closes the annular exchange chamber containing the nest of tubes over the greater part of the height of the apparatus.
As shown in FIG. 2a, each tube comprises undulations, such as 14, 14', 14" , situated along one side of the general longitudinal axis X' X of the tube, along which are situated its straight ends 15, 15' which are inserted into the perforated terminal plates. These undulations are in the form of arcuate bends extending over 60° which are joined at their two ends to undulations 16, 16', 17, 17' with a camber 5 to 10 shallower than the preceding undulations, these small undulations extending over 35° and being arranged in pairs, returning to the axis X' X at the points 18, 18'.
These tubes are held in position by means of rows of concentric rings 19, 19', 19" as shown in FIG. 3 joined together by tubular stays 21, 21', 21" with concave lateral walls arranged head-to-tail and separating the tubes from one another whilst, at the same time, holding them firmly in position and leaving a free passage of considerable width for the fluid circulating along the tubes.
These stays are welded through their convex, cylindrical radial surfaces to the inner face of a ring situated outside a layer of tubes and to the outer face of the ring situated inside that layer so that all the rings are held firmly together and form a rigid plate or disc.
These retaining plates or discs are arranged at equal distances from one another on the one hand level with the connecting points 18,18' of the small undulations of the tubes, which are thus held at points situated along their longitudinal axes, and on the other hand level with the crests 22,22',22" of the major undulations situated on the opposite side to the minor undulations relative to the axis X'X.
The retaining discs arranged level with the points 18,18' are fixed and, to this end, their outer peripheral rings are welded to the inner surface of the cylindrical shell 1. By contrast, the retaining discs situated level with the crests 22,22',22" of the undulations are not joined to the outer shell 1 and, accordingly, are free to rotate about the longitudinal axis of the apparatus under the effect of the expansions of the tubes which produce an increase in their camber at the crest. Theoretically, the retaining rings forming the mobile plates or discs could have been designed to slide relative to one another which would have enabled all the tubes, irrespective of their position in the nest, to be deformed in the same way. However, this method of retaining the tubes in rings sliding relative to one another would considerably complicate the construction and would involve the danger of reducing the inertia of the assembly, thereby promoting vibration. Accordingly, it is preferable to render these discs rigid and to allow the tubes situated in different layers to undergo equally different deformation, thereby giving rise to different stresses. However, as will be shown hereinafter, these differences in stressing are by no means significant and, in any event, are very much smaller than those to which straight tubes would be subjected.
These deformations are illustrated in FIGS. 4 and 5 for three tubes situated in the same radial plane, one (11) on the outer periphery of the nest, the second (12) substantially on the middle ring of the nest and the third (13) on the inner periphery. Under the effect of expansion, the cambers of the undulations of the tubes at their crests 22 increase and, hence, tend to cause the retaining disc to turn through an angle Δθ (FIG. 5). Since the disc is rigid, the displacements which the crests 22 of the sinusoids undergo are of necessity different in the different concentric layers. Assuming that the tubes 12 of the middle layer are displaced in a completely free manner, the displacement of the outer peripheral layer will extend over a wider arc, whilst the displacement of the tubes of the inner layer will, by contrast, be restrained, the angle of rotation Δθ of the disc ultimately being determined by the equilibrium of the oppositely directed forces applied to that disc by the tubes situated on either side of the middle layer.
In FIG. 4, the initial form of all the tubes before any expansion is denoted by the reference 24. When, at a given temperature, the mobile retaining disc is turned through the angle Δθ, thereby establishing equilibrium, the tubes such as 11 of the outer layer will be deformed into position 11 1 , the tubes such as 12 of the middle layer will be deformed into position 12 1 and the tubes such as 13 of the inner peripheral layer will be deformed into position 13 1 . By contrast, the camber of the minor undulations, such as 16 and 16', will be reduced during this deformation to compensate for the increase in length of the tubes due to their expansion.
Stress calculations for tubes made of Inconel 14/16 forming an annular nest with an external diameter of 3.80 meters and an internal diameter of 1.50 meters, produced the following results for a temperature of 280° C of the outer shell, a temperature of 326° C for the tubes and a pressure of 172 bars prevailing inside the tubes:
for the tubes of the middle layer 12, the displacement of the crests of the undulations amounts to 5.62 mm and the total stressing to 15.76 kg/mm 2 ,
for the tubes of the outer peripheral layer 11, the displacement of the crests of the undulations amounts to 7.31 mm and the total stressing to 15.9 kg/mm 2 , and
for the tubes of the inner peripheral layer 13, the displacement of the crests of the undulations amounts to 2.81 mm and the total stressing to 15.53 kg/mm 2 .
It can be seen that the total stressing varies relatively little from one layer to the other of the nest of tubes, which fully justifies the use of rigid mobile retaining discs, turning in a single piece, at the level of the crests of the undulations of the tubes.
The stresses indicated above are very much lower than the permitted values normally specified. A comparable result could also be obtained, if necessary, for greater temperature differences between the tubes and the outer shell.
It is pointed out that, in certain cases, the shape of the tubes could be simplified. Instead of shallow undulations directed oppositely to the major undulations, the major undulations could be joined together by straight sections disposed along the general longitudinal axis X'X of the tubes, the fixed retaining discs being disposed substantially at the centre of these straight sections. In this case, the differential deformations at the crests of the undulations would be compensated by more or less considerable deflection of the straight sections (it is pointed out that the shallow curves 16, 17 are designed to prevent possible deformation of the straight section which could be slightly curved in the wrong direction.)
FIG. 2a shows by way of modification a tube comprising, as indicated above, straight sections 116, 116', 116" between the unilateral undulations 14, 14'. In this case, it would be possible, for example, to provide three mobile retaining rings disposed at the crests 22, 22' of the undulations 14, 14' and at the centre 118' of the straight section which separates them between two fixed retaining rings disposed at the middle points 118 and 118" of the two straight sections situated outside the undulations 14, 14'. This arrangement enables the flexibility of the tubes to be increased in the event of very considerable differences in temperature.
As indicated in the earlier specification, the undulating form of the tubes enables the heat transfer coefficient to be improved, without increasing the overall height of the apparatus, in order to obtain superheated steam in the upper part of the apparatus. In addition, the transfer of heat is considerably increased at the same time as the rate of circulation around the tubes.
In order further to improve heat transfer, the invention provides means which enable a transverse flow relative to the tubes as close as possible to the perpendicular direction thereof to be established both in the heating zone and in the superheating zone. These means are in the form of baffle plates which are made similarly to the retaining discs described above, except that they are solid over at least part of their surface. In this way, it is possible to control the direction of the superheated steam and its rate of flow which has to be very high on account of the low thermal conductivity of superheated steam.
As shown in FIG. 1, a baffle plate 25 of the kind referred to above is arranged in the lower part of the exchanger above the central inlet 10 for the water to be vaporised, this baffle plate being solid over the greater part of its surface and only allowing water to flow through around its outer peripheral section so as to induce below the plate a transverse flow relative to the tubes indicated by the arrows.
A plan view of this plate 25 is shown in FIG. 6 which shows that, around its outer peripheral section, the plate is similar to the retaining plates or discs shown in FIG. 3 in the form of concentric rings 25, 26', 26" joined together by welded tubular stays 27, 27', 27" separating the tubes of the concentric layers 28,28' from one another. By contrast, the rest of the surface of the plate is formed by thicker rings 29, 29', 29" welded directly together and comprising in their opposite surfaces semicylindrical recesses 30, 30', 30" in which the tubes of the concentric layers 28", 28'" are accommodated with minimum play.
In one modification, the retaining rings forming the solid zone of the baffle plate 31 or 32 are identical with those 26 of the open zone, the flow of steam being blocked in this zone by flat sections, for example in the form of flat circular segments which are formed with circular holes for the passages of the tubes and which are placed on or, optionally, welded to the rings 26.
In its upper part, i.e., in the superheating zone, the apparatus comprises two baffle plates 31, 32, of which the first, shown in FIG. 7, is arranged oppositely to that illustrated in FIG. 6 in such a way that it allows steam through in its zone adjacent the central shaft, whilst the second is arranged in the same way as that shown in FIG. 6 in such a way that it allows the steam through in its outer peripheral zone. As a result, the steam flows transversely of the tubes from inside to outside between the two plates 31 and 32 and from outside to inside between the plate 32 and the steam outlet 10'.
These baffle plates, of which the number may be different from those quoted by way of example above, contribute towards retaining the tubes and, like the retaining discs, may be fixed by connection to the outer shell of the exchanger, or free to rotate about the axis of the apparatus, according to whether they are situated at the level of the crests of the major undulations of the tubes or at the level of those points of these tubes which are situated on the longitudinal axis of the tubes between these undulations.
These baffle plates, in the form of concentric rings of two different types, are assembled in the same way as the retaining discs by introduction through the central passages in the heads of the outer structure and by positioning them from the periphery towards the outside as the tubes of the nest are installed.
In order not to reduce the throughflow cross-section of the steam in the zone of the baffle plates 31, 32 to any significant extent, the diameter of the corresponding part 38 of the central shaft 20 is reduced which provides for transverse circulation of the steam without substantially increasing its rate of flow and, hence, without reducing the exchange coefficient.
The fixed and mobile retaining discs and those parts of the baffle plates which allow the fluid to flow through, may have the modified configuration illustrated in FIG. 3a. In this variant, all the tubular stays, such as 33, 33', 33" . . . have the same form as those shown in FIGS. 3, 6 and 7, but are all arranged in the same direction rather than head-to-tail, and are welded in advance by their major convex surfaces to the points 34, 34', 34" . . . only on the inner face of the outer ring 35 of the row of tubes 36, 36', 36" . . . This arrangement has several advantages:
the distance between two consecutive stays is clearly defined so that the play between the tubes and their mountings may be defined,
for installation, each tube has a clearly defined recess so that it is easier to position,
the stays are welded in advance to the elements forming the retaining rings.
In order, in this modification, to improve the stability of the tubes, optionally tubular shims 37, 37', 37" are inserted between two adjacent tubular stays, the tube arranged between these two shims and the inner retaining ring, as shown in FIG. 3a.
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A heat exchanger comprising an outer heavy structure in the form of an outer cylindrical shell fixed at its upper end to an annular intake head and an annular outlet head for one of the fluids, of which the outer bases are perforated, and an inner lightweight structure subsequently mounted in the heavy structure and formed by an annular nest of tubes inserted and welded at their ends into the perforations in said bases and arranged in the form of concentric layers forming a large central passage which is accessible for installation of the tubes, beginning with the peripheral layer adjacent the outer shell, the concentric layers of tubes being held in several transverse planes by discs formed by concentric rows of rings arranged between these layers and joined together by connecting elements, a wide central shaft subsequently being fixed for internally defining the annular exchange chamber, wherein the discs by which the tubes are held in position and which are formed by the concentric rings are in some cases, free to rotate about the axis of the apparatus under the effect of the flexural deformation of the tubes attributable to their expansion and in other cases, are fixed and joined to the outer shell and, optionally, to the central shaft which internally closes the annular exchange chamber occupied by the nest of tubes.
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BACKGROUND OF THE INVENTION
I. Field of the Invention
The present invention relates generally to a valve for controlling the passage of fluids. In particular, the present invention relates to an elastomer body which is installed in a main valve body and which can be stretched to control the fluid flow between two points.
II. Background and Description of Related Art
In biochemistry and biotechnology research, the precise metering of fluids is critical to the success or failure of experiments and/or the production of bioengineered products. Many existing valve designs are simply inappropriate for such use. Valves which are suited for such use, however, are those having designs which use elastomeric components, because of their resilient spring qualities. Elastomeric elements are especially well suited for the design of valves which are to be used to precisely control the flow rate of a fluid or to dispense a precise volume of fluid. Some valves, however, are designed to merely open or close an opening, without regard to the flow rate or output volume of fluid allowed by the valve. Such designs do not take into account precision fluid flow control. For example, U.S. Pat. No. 3,584,834 to Reid et al. discloses a valve assembly that features a rubber element that acts as both a stopper for the valve and as a spring. When a button is depressed, the stopper moves and the valve opens. When pressure on the button is released, the spring properties of the rubber element draw the stopper back into place. The stopper valve design is not directed to the precision control of fluid flow.
Other valves are designed to select among influents to be passed to an output port. For example, U.S. Pat. No. 4,275,765 to Dugas discloses a valve assembly utilizing an elastomeric member that is designed to enable a fast flush of body fluids from either of two catheters to a pressure transducer. The elastomer member has a cylindrical cavity into which a plunger is inserted. Pushing the plunger distorts the elastomeric member, allowing the fast flush of fluids. Again, the valve is not suitable for precise fluid flow control between ports, and fluid remains in the valve cavity even when the valve is closed. Thus, the valve itself must be flushed out if different ports are connected to it between uses and precision of flow is limited by the amount of fluid left in the is valve cavity when the valve is closed. In a precision valve, this unswept or dead volume must be minimized.
When the influent to a device is not pressurized, a valve is sometimes needed so that the influent may be drawn into a container and then passed along to an output port. For example, U.S. Pat. No. 2,888,034 to Clegg discloses a valve assembly utilizing a high density rubber piece as a valve element. The valve assembly includes an inlet port, an outlet port, and an intermediate chamber. A piston plunger causes a vacuum condition in the intermediate chamber, and the valve element allows fluid to flow from the inlet port into the intermediate chamber. The piston plunger then applies a pressure stroke and the valve allows fluid in the intermediate chamber to flow to the outlet port. Precision control of fluid flow from inlet port to outlet port is not provided by this two stroke valve.
In some applications, however, precise control of the flow of a pressurized fluid from an input port to an output port is necessary. For example, in chemical applications, minute quantities of particular fluids are frequently needed in forming compounds. In other cases, while the quantity required is not minute, the quantity that is provided must be precisely dispensed. In pharmaceutical applications, drug manufacturers require precise control of the volume of components making up the drug. In other medical applications, for example surgery, control of bodily fluid flow or of anesthetics is critical. Precise control of fluid flow rates is desirable in agricultural, aerospace, and other commercial applications as well.
Other known valves also use elastomer members. For example, U.S. Pat. No. 3,548,878 to Brigandi discloses a valve assembly utilizing a bellows type expansion plug formed out of a resilient material such as rubber. The pleats of the bellows provide resilient sealing points along the internal walls of the valve housing when the bellows is compressed. When a plunger causes the bellows to expand, fluid is allowed through the valve from an inlet port to an outlet port. A clear path is never made for fluid flow; fluid pressure must overcome the sealing force of the pleats for the fluid to flow. As the bellows expands, the sealing force of the pleats becomes weaker and easier to overcome by the fluid force. Fluid flow therefore becomes greater as the bellows is expanded.
For truly precise control of fluid flow, however, the pressure of the influent should not be relied upon to overcome the sealing force of the valve. A clear path for the fluid should be provided when the valve is in the open position. The elastomeric qualities of the valve element should not be solely relied upon to return the valve to the closed position. Such reliance can cause the valve element to wear out prematurely, and would certainly make the element less reliable over the lifetime of the valve. Rather, the valve should be equipped with a spring which returns the valve to the closed position and which counteracts fluid pressure forces which would otherwise tend to open the valve.
Some valves are known to use springs to close the valve. For example, U.S. Pat. No. 2,095,770 to Sorensen discloses a valve assembly that utilizes a coil spring. The force of the spring must be overcome in order to open the valve. However, the spring is the valve element itself; it is not used to return an elastomeric valve element.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a valve that can be used to precisely control the flow rate of a fluid passing from an inlet port to an outlet port.
It is a further object of the present invention to provide a valve that completely prevents the flow of fluid from the input port to the output port when he valve is in a closed position.
It is another object of the present invention to provide a valve that does not allow any residual fluid to remain in the flow path when the valve is in a closed position, that is, allows only minimum unswept or dead volume.
It is also an object of the present invention to provide a valve that is able to reliably seal with a minimum amount of pumping when activated and deactivated.
These and other objects and advantages of the present invention will be apparent to persons of skill in the art upon inspection of the specification, drawing figures, and appended claims.
The present invention achieves precise control of fluid flow rates through the use of a cylindrical elastomeric valve element. This elastomer element is installed within the cylindrical flow path of a valve body. The flow path has a diameter that is slightly smaller than that of the elastomer element, which is therefore constrained within the flow path. Longitudinal stretching of the elastomer element causes the diameter of the elastomer element to decrease. As a result, a flow path is opened. The further the elastomer element is stretched, the larger is the fluid path that is created. Therefore, precise control of the fluid flow rate is made possible.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cut-away view of the valve in the closed position.
FIG. 2 is a cut-away view of the valve in the open position.
FIG. 3 is a cut-away exploded view of the complete valve assembly.
FIG. 4 is a detail cut-away view of the elastomer/pull handle junction.
FIG. 5 shows a step in the installation of the elastomer within the valve body.
DETAILED DESCRIPTION
FIG. 1 shows a cut-away view of the valve of the present invention. Valve body 1 is the main housing for the valve. It has an inlet port 5 and an outlet port 6 connected by and in communication with a bore 20 in the valve body 1. The valve body 1 supports fluids under pressure or vacuum which are to be passed from the inlet port 5 to the outlet port 6. It is shaped specifically to allow the notion of the other mechanical components of the valve.
An elastomer body, the cylindrical elastomer 2, is the active seal component of the valve. The cylindrical elastomer 2 is placed within the bore 20 such that it protrudes from the distal end of the bore 20. The cylindrical elastomer 2 is then secured at the distal end, preferably by a distal elastomer retainer barb 3. A pull handle 4, having a cylindrical diameter larger than that of the cylindrical elastomer 2, is attached to the cylindrical elastomer 2 at its proximate end. The diameter of the cylindrical elastomer 2 is slightly larger than that of the bore 20, thereby creating a fluid tight seal when compressed and placed within the bore 20. The fluid tight seal prevents any fluid leakage from the inlet port 5 to the outlet port 6 when the valve is closed, and completely evacuates the bore 20 of fluid when the valve moves from the open position to the closed position. When the distal elastomer retainer barb 3 is inserted into the distal end of cylindrical elastomer 2, the elastomer diameter is stretched so that even when compressed it is greater than the diameter of the bore 20. Thus, if the pull handle 4 is pulled, the cylindrical elastomer 2 remains secure at the distal end. The distal elastomer retainer barb 3 also seals the bore 20 at the distal end, preventing any gasses or other fluids from entering or leaving the bore 20 at this end. The pull handle cylinder 7 is a section at the proximal end of the bore 20 having a larger diameter to accommodate the pull handle 4. A pull handle O-ring 12 seals any space between the valve body and the pull handle to prevent all fluids and gasses from escaping or entering the fluid passage.
FIG. 1 shows the valve in the closed position. It is closed because the cylindrical elastomer 2 seals off the bore 20 between the inlet port 5 and the outlet port 6, preventing fluid flow between them. When the pull handle 4 is pulled, as shown in FIG. 2, the cylindrical elastomer 2 stretches. Secured at the distal end by the distal elastomer retainer barb 3 and pulled at the proximal end by the pull handle 4, the cylindrical elastomer 2 stretches and its diameter decreases. When the diameter decreases, a fluid flow path is created between the inlet port 5 and the outlet port 6 along the length of the cylindrical elastomer 2. As the pull handle 4 is pulled a greater distance, the cylindrical elastomer 2 is stretched further and its diameter further decreases accordingly. As the diameter decreases, a larger fluid flow path is created, and therefore the fluid flow rate from the inlet port 5 to the outlet port 6 increases. Thus, the fluid flow rate can be precisely controlled using the valve of the present invention by regulating the distance that the pull handle 4 is pulled. The pull handle 4 may be connected to a mechanical device which causes the pull handle 4 to be pulled particular precise distances, depending on the application with which the valve is used.
FIGS. 1 and 2 show the inlet and outlet ports 5 and 6 positioned in a parallel relationship to one another within the valve body 1. In this preferred embodiment, the fluid flow path between the ports is created along the length of the cylindrical elastomer 2. However, the ports can be positioned within the valve body 1 such that they are facing each other across the cylindrical elastomer 2. In this case, the fluid flow path created by the valve would occur around the circumference of the cylindrical elastomer 2. As the pull handle 4 is pulled and the diameter of cylindrical elastomer 2 decreases, the circumference of cylindrical elastomer 2 decreases proportionately. Thus, the fluid flow rate can be regulated just as well with the inlet and outlet ports 5 and 6 in this configuration as it can in the configuration shown in FIGS. 1 and 2. In fact, the present invention will work if the ports are oriented anywhere in the valve body 1 along the unstretched length of cylindrical elastomer 2. When the pull handle 4 is pulled, a fluid flow path will be created along the length and circumference of cylindrical elastomer 2, and the fluid or gas will flow from the inlet port 5 to the outlet port 6.
FIG. 3 shows the complete valve assembly. As in FIGS. 1 and 2, the cylindrical elastomer 2 is shown attached to the pull handle 4 and is ready to be inserted into the valve body 1. The distal elastomer retainer barb 3 is shown positioned at the distal end of bore 20. This will be used to retain the cylindrical elastomer 2 at the distal end once it is inserted into the valve body 1. The valve body 1 as shown in this figure has a chamfer 18 at the distal end of the bore 20. The chamfer 18 is present in the preferred embodiment to prevent chafing to the cylindrical elastomer 2 where it is pinched between the valve body 1 and the distal elastomer retainer barb 3. The bevel angle of the chamfer 18 may vary, but is preferably about 60 degrees from a line normal to the longitudinal axis of the bore 20.
FIG. 4 shows the connection of the cylindrical elastomer 2 and the pull handle 4 in more detail. The pull handle 4 is basically cylindrical in shape and has an outside diameter that is larger than that of the cylindrical elastomer 2. The pull handle 4 has a hollow channel along its longitudinal axis, the pull handle counterbore 14. The diameter of the pull handle counterbore 14 at the fixed end of the pull handle 4 is slightly larger than that of the cylindrical elastomer 2. The proximal end of the cylindrical elastomer 2 is placed partially inside the pull handle counterbore 14. The proximal elastomer retainer barb 22 is inserted into the proximal end of the cylindrical elastomer 2 to hold the cylindrical elastomer 2 in place and to prevent fluid from entering or leaving the bore 20 through the pull handle counterbore 14. The pull handle counterbore 14 fans outward at pull handle chamfer 23. As with the chamfer 18, the pull handle chamfer 23 is present in the preferred embodiment to prevent chafing to the cylindrical elastomer 2 where it is pinched between the pull handle 4 and the proximal elastomer retainer barb 22. The bevel angle of the pull handle chamfer 23 may vary, but is preferably about 60 degrees from a line normal to the longitudinal axis of the pull handle counterbore 14.
Beyond the point at which the pull handle chamfer 23 fans outward within the pull handle counterbore 14, the diameter of the pull handle counterbore 14 becomes a uniform larger size, in order to accommodate the proximal elastomer retainer barb 22. Therefore, for assembly of the valve, the proximal elastomer retainer barb 22 is first inserted into the proximal end of the cylindrical elastomer 2. The distal end of the cylindrical elastomer 2 is then inserted into the free end of the pull handle counterbore 14, and the cylindrical elastomer 2 slides through the pull handle counterbore toward the fixed end of the pull handle 4 until the proximal elastomer retainer barb 22 causes the cylindrical elastomer 2 to catch at the pull handle chamfer 23.
Now that the cylindrical elastomer 2 is secured to the pull handle 4, the pull handle 4 and the cylindrical elastomer 2 are inserted into the valve body 1. The proximal end of the bore 20 has a diameter that is larger than the diameter at the distal end in order to accommodate the pull handle 4. This section of the bore 20 is the pull handle cylinder 7. The pull handle is adapted around the outside of its distal end with a sealing means, preferably a pull handle O-ring 12, to create a fluid tight seal between the pull handle 4 and the valve body 1. The pull handle O-ring 12 ensures that no fluids will escape via the interface between the pull handle 4 and the valve body 1 while the valve is in use. Once the cylindrical elastomer 2 is installed within the valve body 1, the distal elastomer retainer barb 3 is inserted into the distal end of the cylindrical elastomer 2 as previously described in order to hold the cylindrical elastomer 2 in place within the valve body 1.
Because the diameter of the cylindrical elastomer 2 is slightly larger than that of the bore 20, a sleeve 21 is used to aid the installation. The sleeve 21 is made of braided mylar filament which is placed over the cylindrical elastomer 2 and which compresses the cylindrical elastomer 2 slightly. The sleeve 21 also offers less friction with the inside surface of the bore 20 than does the cylindrical elastomer 2, further aiding the installation. The sleeve 21 and the cylindrical elastomer 2 are pulled through the bore 20, as shown in FIG. 5. After the cylindrical elastomer 2 is fully inserted in the bore 20, the sleeve 21 is stripped off by pulling the sleeve 21 at the distal end.
Once the cylindrical elastomer 2 and the pull handle 4 are installed within the valve body 1, the base 9 and through-hole cap 16 are secured to the valve body 1. The valve body 1 rests its distal face on the base 9. The base 9 includes a counterbase 10 region which is countersunk from the face of the base 9 in order to accommodate whatever portions of the distal elastomer retainer barb 3 and cylindrical elastomer 2 extend beyond the distal face of the valve body 1. The through-hole cap 16 is placed over the free end of the pull handle 4 and rests on the proximal face of the valve body 1. The through-hole cap 16 has a cap counterbore 15 to accommodate the free end of the pull handle 4. A pull handle spring 11 is placed over the pull handle 4 and rests on a pull handle shoulder 19. The pull handle shoulder 19 is an annular portion of the pull handle 4, at the fixed end, which has an outer diameter that is larger than that at the free end, forming a shoulder which supports the pull handle spring 11. The pull handle spring 11 ensures that when the pull handle 4 is released after having been pulled, the pull handle will return to a fully retracted position, closing any fluid flow path within the valve. Because it is important to the long life and reliable operation of the cylindrical elastomer 2 that its elasticity is not completely relied upon to return the pull handle 4, use of the pull handle spring 11 in the preferred embodiment will extend the reliable life of the valve. The pull handle spring 11 also helps the cylindrical elastomer 2 to overcome any fluid pressure built up within the valve body 1 that would otherwise cause the pull handle 4 to be pushed out of the pull handle cylinder 7.
The through hole cap 16, valve body 1, and base 9 are secured together by screws 17. These screws 17 are mated to screw holes 24 that pass through the length of the through hole cap 16, valve body 1, and base 9.
Preferred and alternate embodiments of the present invention have now been described in detail. It is to be noted, however, that this description of these embodiments is merely illustrative of the principles underlying the inventive concept. It is therefore contemplated that various modifications of the disclosed embodiments will, without departing from the spirit and scope of the invention, be apparent to persons skilled in the art.
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A stretch valve which achieves precise control of fluid flow rates through the use of a cylindrical elastomeric valve element. This elastomer element is installed within the cylindrical flow path of a valve body. The flow path has a diameter that is slightly smaller than that of the elastomer element, which is therefore constrained within the flow path. Longitudinal stretching of the elastomer element causes the diameter of the elastomer element to decrease. As a result, a flow path is opened. The further the elastomer element is stretched, the larger is the fluid path that is created. Therefore, precise control of the fluid flow rate is made possible.
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RELATED APPLICATION
The present application is a continuation-in-part of U.S. patent application Ser. No. 09/640,815 filed Aug. 16, 2000, now U.S. Pat. No. 6,419,788, entitled CELLULOSE PRODUCTION FROM LIGNOCELLULOSIC BIOMASS, which is assigned to the assignee of the present case.
FIELD OF THE INVENTION
This invention relates to the production of cellulose from lignocellulosic biomass, and in particular to process whereby cellulose is separated from other constituents of lignocellulosic biomass so as to make the cellulose available as a chemical feedstock and/or accessible to enzymatic hydrolysis for conversion to sugar.
BACKGROUND OF THE INVENTION
The possibility of producing sugar and other products from cellulose has received much attention. This attention is due to the availability of large amounts of cellulosic feedstock, the need to minimize burning or landfilling of waste cellulosic materials, and the usefulness of sugar and cellulose as raw materials substituting for oil-based products.
Natural cellulosic feedstocks typically are referred to as “biomass”. Many types of biomass, including wood, paper, agricultural residues, herbaceous crops, and municipal and industrial solid wastes, have been considered as feedstocks. These biomass materials primarily consist of cellulose, hemicellulose, and lignin bound together in a complex gel structure along with small quantities of extractives, pectins, proteins, and ash. Due to the complex chemical structure of the biomass material, microorganisms and enzymes cannot effectively attack the cellulose without prior treatment because the cellulose is highly inaccessible to enzymes or bacteria. This inaccessibility is illustrated by the inability of cattle to digest wood with its high lignin content even though they can digest cellulose from such material as grass. Successful commercial use of biomass as a chemical feedstock depends on the separation of cellulose from other constituents.
The separation of cellulose from other biomass constituents remains problematic, in part because the chemical structure of lignocellulosic biomass is not yet well understood. See, e.g., ACS Symposium Series 397, “Lignin, Properties and Materials”, edited by W. G. Glasser and S Sarkanen, published by the American Chemical Society, 1989, which includes the statement that “[l]ignin in the true middle lamella of wood is a random three-dimensional network polymer comprised of phenylpropane monomers linked together in different ways. Lignin in the secondary wall is a nonrandom two-dimensional network polymer. The chemical structure of the monomers and linkages which constitute these networks differ in different morphological regions (middle lamella vs. secondary wall), different types of cell (vessels vs. fibers), and different types of wood (softwoods vs. hardwoods). When wood is delignified, the properties of the macromolecules made soluble reflect the properties of the network from which they are derived.”
The separation of cellulose from other biomass constituents is further complicated by the fact that lignin is intertwined and linked in various ways with cellulose and hemicellulose. In this complex system, it is not surprising that the “severity index” commonly used in data correlation and briefly described below, can be misleading. This index has a theoretical basis for chemical reactions (such as hydrolysis) involving covalent linkages. In lignocellulose, however, there are believed to be four different mechanisms of non-covalent molecular association contributing to the structure: hydrogen bonding, stereoregular association, lyophobic bonding, and charge transfer bonding. Bonding occurs both within and between components. As temperature is increased, bonds of different types and at different locations in the polymeric structure will progressively “melt”, thereby disrupting the structure and mobilizing the monomers and macro-molecules.
Many of these reactions are reversible, and on cooling, re-polymerization can occur with deposits in different forms and in different locations from their origins. This deposition is a common feature of various conventional high temperature cellulosic biomass separation techniques. Furthermore, at higher temperatures in acid environments, mobilization of lignin is in competition with polymer degradation through hydrolysis and decomposition impacting all lignocellulosic components. As a result, much effort has been expended to devise “optimum” conditions of time and temperature that maximize the yield of particular desired products. These efforts have met with only limited success.
Known techniques for the conversion of biomass directly to sugar or other chemicals include concentrated acid hydrolysis, weak acid hydrolysis and pyrolysis processes. These processes are not known to have been demonstrated as feasible at commercial scale under current economic conditions or produce cellulose as either a final or intermediate product.
Conventional processes for separation of cellulose from other biomass components include processes used in papermaking such as the alkaline kraft process most commonly used in the United States and the sulphite pulping process most commonly used in central Europe. There are additional processes to remove the last traces of lignin from the cellulose pulp. This is referred to as “bleaching” and a common treatment uses a mixture of hot lye and hydrogen peroxide. These technologies are well established and economic for paper making purposes, but have come under criticism recently because of environmental concerns over noxious and toxic wastes. These technologies are also believed to be too expensive for use in production of cellulose for use as chemical raw material for low value products.
The use of organic solvents in cellulose production has recently been commercialized. These processes also are expensive and intended for production of paper pulp.
Many treatments have been investigated which involve preparating crude cellulose at elevated temperature for enzymatic hydrolysis to sugar. Investigators have distinguished particular process variations by such names as “steam explosion”, “steam cooking”, “pressure cooking in water”, “weak acid hydrolysis”, “liquid hot water pretreatment”, and “hydrothermal treatment”. The common feature of these processes is wet cooking at elevated temperature and pressure in order to render the cellulosic component of the biomass more accessible to enzymatic attack. In recent research, the importance of lignin and hemicellulose to accessibility has been recognized.
Steam cooking procedures typically involve the use of pressure of saturated steam in a reactor vessel in a well-defined relationship with temperature. Because an inverse relationship generally exists between cooking time and temperature, when a pressure range is stated in conjunction with a range of cooking times, the shorter times are associated with the higher pressures (and temperatures), and the longer times with the lower pressures. As an aid in interpreting and presenting data from steam cooking, a “severity index” has been widely adopted and is defined as the product of treatment time and an exponential function of temperature that doubles for every 10° C. rise in temperature. This function has a value of 1 at 100° C.
It is known that steam cooking changes the properties of lignocellulosic materials. Work on steam cooking of hardwoods by Mason is described in U.S. Pat. Nos. 1,824,221; 2,645,633; 2,294,545; 2,379,899; 2,379,890; and 2,759,856. These patents disclose an initial slow cooking at low temperatures to glassify the lignin, followed by a very rapid pressure rise and quick release. Pressurized material is blown from a reactor through a die (hence “steam explosion”), causing defibration of the wood. This results in the “fluffy”, fibrous material commonly used in the manufacture of Masonite™ boards and Cellotex™ insulation.
More recent research in steam cooking under various conditions has centered on breaking down the fiber structure so as to increase the cellulose accessibility. One such pretreatment involves an acidified “steam explosion” followed by chemical washing. This treatment may be characterized as a variant of the weak acid hydrolysis process in which partial hydrolysis occurs during pretreatment and the hydrolysis is completed enzymatically downstream. One criticism of this technique is that the separation of cellulose from lignin is incomplete. This makes the process only partially effective in improving the accessibility of the cellulose to enzymatic attack. Incomplete separation of cellulose from lignin is believed to characterize all steam cooking processes disclosed in prior art.
Advanced work with steam cooking in the United States has been carried out at the National Renewable Energy Laboratory in Golden, Colo. U.S. Pat. Nos. 5,125,977; 5,424,417; 5,503,996; 5,705,369; and 6,022,419 to Torget, et al. incorporated herein by reference, involve the minimization of acid required in the production of sugar from cellulose by acid hydrolysis in processes that may also include the use of cellulase enzymes. These patents teach the use of an acid wash of solids in the reaction chamber at the elevated temperature and pressure conditions where hemicellulose and lignin are better decomposed and mobilized. The use of acid is tied to the goal of sugar production by hydrolysis. The focus of Torget's work appears to be acid treatments and hydrolysis and does not claim to produce high purity cellulose that is a principal objective of the present invention.
A common feature of acid hydrolysis, acid pretreatment, and chemical paper pulping is the generation of large quantities of waste chemicals that require environmentally acceptable disposal. One proposed means of waste disposal is as a marketable byproduct. Thus wallboard has been suggested as a potential use for the large quantities of gypsum produced in acid hydrolysis and acid pretreatment. This potential market is believed illusory since the market for cheap sugar is so vast that any significant byproduct will quickly saturate its more limited market.
There remains a pressing need for a process to provide low cost cellulose for subsequent conversion to glucose sugar by enzymatic hydrolysis. However, the presence of lignin in cellulosic biomass increases dramatically the amount of enzyme needed, thereby imposing unacceptably high conversion costs. Economics demand a process by which substantially pure cellulose can be produced for only a few cents per pound. Mainstream scientific and engineering efforts to utilize lignocellulosic biomass have been unable to achieve this goal over several decades. The challenge is to find a process that solves or avoids the problems of cost, chemical wastes, the clean separation of lignocellulosic components, and the unwanted degradation of said components.
Ignored by the mainstream effort is a process referred to as “wet oxidation”. This is a mature technology used for the disposal of liquid and toxic organic wastes. The process involves exposing a slurry of organic material to oxygen at elevated temperature and pressure even higher than that used in steam cooking. The result is destruction of the organic material and its conversion to carbon dioxide and water. While the effectiveness of wet oxidation in the chemical modification of organic matter has been demonstrated at commercial scale, the severity of chemical breakdown in waste disposal applications leaves few useful products.
The use of wet oxidation in the pretreatment of lignocellulosic biomass is known. In one described process, wet oxidation occurs at relatively low temperatures (40° C.) and extends over 2 days. In other uses of wet oxidation in the pretreatment of lignocellulosic biomass, there is no control of pH, so acids formed in the process essentially create a variant of the mild acid pretreatment process.
In other wet oxidation work with wheat straw to recover hydrolyzed hemicellulose, process temperatures were maintained from 150° to 200° C. and pH was maintained at above 5 with sodium carbonate. Lower pHs were avoided to minimize decomposition and the formation of chemicals toxic in downstream processes. The separation of cellulose from lignin was not a stated goal in this work, and it is believed that the chemical conditions were not appropriate for such a separation. Perhaps the greatest deficiency of this work is that the entire biomass was subjected to the same treatment for the entire processing time. Thus a compromise was needed with consideration given to both the most reactive and the least reactive components. The resulting “optimized” procedure fails to satisfy the requirements for commercialization because of component degradation and low yields.
Thus it can be seen that neither technologies for paper making, for acidified steam cooking, nor for wet oxidation as presently practiced can fill the need for commercially economical techniques for preparation of high purity cellulose from cellulosic biomass which do not produce objectionable waste streams.
OBJECTS OF THE PRESENT INVENTION
Accordingly, one object of the present invention is to provide a lower cost and environmentally benign process for the separation of cellulose from other constituents of cellulosic biomass.
Another object of this invention is to produce at high yield and in a chemically active state cellulose that is substantially free of lignin, hemicellulose, and extractives that are other constituents of biomass.
SUMMARY OF THE INVENTION
According to the present invention, it has been found that relatively pure cellulose can be produced if lignocellulosic materials first are treated with steam to partially hydrolyze the hemicellulose to soluble oligomers and then are washed with alkaline hot water containing dissolved oxygen to remove these hydrolysis products and to decompose, mobilize and remove lignin, extractives, and residual hemicellulose.
A preferred method of the present invention involves the production of purified cellulose containing less than 20% lignin by chemical alteration and washing of lignocellulosic biomass material under elevated pressure and temperature. The method includes the steps of providing a lignocellulosic feedstock having an average constituent thickness of at most 1″, (most preferably up to ⅛″ thick), introducing the feedstock into a pressure vessel having at least two reaction zones, heating the feedstock in a first reaction zone to a temperature of from about 180° C. to about 240° C., transferring said heated feedstock from said first reaction zone to said second reaction zone while subjecting said feedstock to an oxidizing counterflow of hot wash water of pH from about 8 pH to about 13 pH to create a residual solid containing cellulose and a filtered wash water containing dissolved materials.
Optimum operating conditions depend somewhat on the type of biomass being treated, with process times being about 1 to 10 minutes and the weight of wash water used being about 2 to 20 times the dry weight of feedstock. In addition to an oxidizer, chemicals must be introduced as necessary to maintain a pH between about 8 and 13 in various reaction zones.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustrating a continuous system incorporating the techniques of the present invention in the production of cellulose from lignocellulosic biomass.
FIG. 2 is a schematic illustrating details of the operation of the hydrothermal wash chamber of FIG. 1 .
FIG. 3 is a schematic illustrating portions of a heat recuperation subsystem of FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention relates to a technique in which relatively pure cellulose is produced from lignocellulosic materials which are treated with steam to partially hydrolyze the hemicellulose to soluble oligomers and then washed with a counter current flow of alkaline hot water containing dissolved oxygen to remove these hydrolysis products and to decompose, mobilize and remove lignin, extractives, and residual hemicellulose. In a preferred embodiment, a method of the present invention involves the production of purified cellulose containing less than 20% lignin by chemical alteration and washing of lignocellulosic biomass material under elevated pressure and temperature. The method includes the steps of providing a lignocellulosic feedstock having an average constituent thickness of at most 1″, (most preferably up to ⅛″ thick), introducing said feedstock into a pressure vessel having at least two reaction zones, heating said feedstock in said first reaction zone to a temperature of from about 180° C. to about 240° C., transferring said heated feedstock from said first reaction zone to said second reaction zone while subjecting said feedstock to a counterflow of hot, alkaline wash water from about 8 pH to about 13 pH to create a residual solid containing cellulose and a filtered wash water containing dissolved materials.
More particularly, the preferred feedstock is sawmill waste in the Pacific Northwest consisting of sawdust, bark, chips, hog material, and the like. It should be understood, however, that the techniques of the present invention are effective on a broad range of lignocellulosic materials including but not limited to wood, grass, herbacious crops, agricultural waste, waste paper, high cellulosic industrial solid waste and municipal solid waste.
The operation of a system in which the present invention may be practiced is shown in FIG. 1 . Lignocellulosic biomass feedstock ( 1 ) is subjected to a preliminary preparation ( 2 ) as required by the particular nature of the feedstock. In the case of moist sawdust, for example, no preparation of any kind might be needed. In the case of municipal solid waste, a materials recycling facility may be the source of a feedstock stream substantially free of extraneous materials. The preferred average constituent thickness of the feedstock material is at most 1″ in thickness. Constituent size is controlled by mechanical treatment of the feedstock material by chipping, grinding, milling, shredding or other means. The most preferred average constituent size is not greater than about ⅛″ thick by 1″ in other dimensions. For sawmill waste, a conventional chipper provides adequate size reduction.
The prepared feedstock is next preheated ( 3 ) by steam and forced mechanically ( 4 ) into the hydrothermal wash chamber ( 5 ) where it is further heated by steam injection ( 6 ) to a temperature of about 220° C. and a pressure of about 340 psia. As solids pass through the wash chamber, lignin and hemicellulose are mobilized and separated from the cellulose. The cellulose is discharged from the wash chamber at ( 7 ) into the flash tank ( 8 ) and delivered as product ( 9 ). Steam generated in the flash cooling ( 10 ) is recycled to preheat the solids feed.
Wash water from a reservoir ( 11 ) is pumped ( 12 ) into the heat recovery system ( 14 ) where it is preheated before entering the heater ( 16 ) where alkali ( 22 ) and steam ( 17 ) are injected to raise the temperature to about 220° C. for injection into the hydrothermal wash chamber ( 5 ) at ( 18 ). This hot, pressurized wash water flows counter to the movement of solids, collecting lignin and hemicellulose and leaving the wash chamber at ( 19 ) where it passes through the heat recovery system to provide preheat for the wash water. The weight of wash water used typically will be about 5 times the dry weight of feedstock.
The process of this invention requires that the wash water be alkaline. This is accomplished by adding lime at ( 22 ) in sufficient quantity to provide near saturation. This will require about 0.3 kgm of lime per metric ton of wash water. In addition, lime will be consumed in neutralizing acids that may be formed by oxidation. An additional kgm or more of lime per dry metric ton of feed may need to be introduced as a slurry at ( 23 ). The auger action mixes the lime with the feed to be consumed as needed in the process. The precise amount to be added will depend, in part, on the nature of the feedstock. The cellulose product must be monitored to insure that little or no lime carries through the process, and the wash liquor must be monitored to insure that a pH of at least 11 is maintained. The flow of lime slurry is then adjusted to meet these two requirements.
FIG. 2 illustrates operation of the hydrothermal wash chamber in more detail. This apparatus consists of a cylindrical pressure vessel ( 24 ) containing a rotal auger ( 25 ) driven by a motor ( 26 ). Provision is made for forced insertion of solid material ( 4 ) at ( 27 ) and for intermittent discharge of solids (7) through a ball valve ( 28 ). The insertion and release of solids is accomplished without significant loss of chamber pressure. This entire apparatus, known as STAKE II, is commercially available from Stake Technology, Ltd., a Canadian corporation, and can be sized for any application. Functionally equivalent apparatus is available elsewhere and is in common use in the paper industry. Some such apparatus may employ twin screws either co-rotating or counter-rotating. For the present application, the standard STAKE II design is modified by the manufacturer to include a screw having interruptions and/or different pitch on the two ends (to accommodate the dissolving of a portion of the feed) and having ports for the injection and discharge of pressurized liquid. Auger action compacts solids at the discharge end to minimize loss of wash water during solids release. The auger action also subjects solids to shearing forces. As material dissolves, the remaining solid is weakened, and the shear forces break up the larger pieces, expose more surface area, and so facilitate further dissolution.
In the preferred implementation, pressurized wash water is injected at ( 17 ) and exits at ( 29 ) to a gas trap ( 30 ) where air trapped in the feed and gasses introduced or released in the processing can be vented ( 31 ). The wash liquor containing dissolved lignin and hemicellulose then continues its flow under pressure at ( 19 ). It is necessary that the drain ( 29 ) be equipped with a filter in the wall of the wash chamber to prevent solids from escaping. The fresh solids are driven by the auger at close spacing to scour the filter and prevent the buildup of fines that could cause clogging.
An important feature of the process of the present invention is the control of pH. Either acid or base can catalyze hydrolysis and other irreversible chemical reactions. As steam ( 6 ) heats the fresh solids, acetic acid is released from degradation of the hemicellulose and can reduce the pH to as low as 3. In the preferred implementation, this acidity auto-catalyzes the hydrolysis of some hemicellulose to soluble oligomers. The goal is to hydrolyze the hemicellulose and then quickly to raise the pH and wash the resulting oligomers out of the chamber at ( 29 ) in order to prevent further degradation. The hemicellulose spends not more than about 30 to 60 seconds in the wash chamber, and during this brief time, the steam has little effect on the lignin and cellulose. As a variation on this procedure, steam injected at ( 6 ) might raise the temperature to as little as 180° C. for a more extended time to hydrolyze hemicellulose after which additional steam injected at ( 35 ) could further increase the temperature to dissolve lignin.
In the wash zone between ( 17 ) and ( 29 ), the goals are first to maintain alkaline conditions in order to prevent hydrolysis of cellulose, prevent condensation of lignin, and promote dissolution of the lignin and wash it away. To maintain a proper pH, lime or other base is injected with the wash water ( 18 ) and in a slurry at ( 29 ). At ( 29 ) the lime is injected both before and after the liquid discharge at ( 29 ) in order to avoid waste. The flow just before ( 29 ) is adjusted to the minimum required to neutralize acids formed in zone one and to raise the pH to about 11 or 12. The flow ( 23 ) just after ( 29 ) should be sufficient to neutralize all acids formed in the following zone(s).
In other implementations, more complex wash patterns may be employed such as feeding wash water at ( 17 ) with an exit at ( 36 ) to remove lignin while providing a second feed of wash water at ( 35 ) with exit at ( 29 ) to remove hemicellulose. Interruption of the screw between ( 36 ) and ( 29 ) and perhaps modifying the cross section of the wash chamber wall could then provide a moving barrier of compacted solids to minimize mixing of liquids. The common innovation in all implementations of the present invention is the washing of cellulose solids at high temperature and pressure under alkaline conditions that minimize undesirable chemical degradation.
Oxygen is injected in controlled amounts and at controlled pressure at positions ( 32 ) and ( 34 ) and at intervening position (not shown) as required, depending on apparatus size and other factors. In the preferred implementation, at least 3 kgm of oxygen may be required for each dry metric ton of feed. The total reaction time depends on the speed of the auger drive motor ( 26 ) and will be between 2 and 4 minutes in the preferred implementation. Motor speed, temperature, water wash, and oxygen flow rate can be adjusted to optimize cellulose production.
Heating large volumes of wash water to high temperatures is energy intensive. FIG. 3 illustrates an energy conservation feature. Wash liquor carrying dissolved solids from the wash chamber is discharged ( 19 ) to a chain of flash tanks ( 57 ), ( 53 ), ( 45 ) for stepwise reduction of pressure to atmospheric. Each flash tank is paired with a condensing heat exchanger ( 55 ), ( 49 ), ( 42 ) that is part of a chain to preheat the wash water to the wash chamber. Flash cooling of liquid ( 19 ), ( 54 ), ( 48 ) entering each flash tank generates steam ( 56 ), ( 52 ), ( 44 ) that flows to the heat exchangers where it condenses. This condensed liquid ( 51 ), ( 47 ) is then flashed to the next heat exchanger in the chain. Thus the total wash liquor plus flash liquor being flash cooled at each stage remains constant. Flash tanks are of a standard design, and heat exchangers are of standard design—all apparatus sized for the particular application and rated for the required pressure.
The heat of the final condensed flash liquor ( 41 ) at about 100° C. is used entirely or in part to preheat wash water in the liquid—liquid heat exchanger ( 39 ). This flash condensate may contain some volatile chemicals but is not particularly corrosive.
To insure proper operation, pressure in the flash tanks is controlled with a control system in which the measured pressure and/or temperatures in the various flash tanks and heat exchangers are used to regulate variable nozzles that admit liquid continuously to the tanks.
Wash water ( 13 ) from the feed pump ( 12 ) flows through heat exchangers ( 39 ) and ( 42 ) that operate near atmospheric pressure at temperatures below 100 degrees C. Pressure pump ( 46 ) then increases pressure to that required for the hydrothermal wash—about 450 psia in the preferred embodiment. The wash water continues its flow through heat exchangers ( 49 ) and ( 55 ) to the final heater ( 16 ) where it is brought to final temperature by steam injection ( 17 ). When three stages of flash cooling are used as shown, the wash water heating requirement is reduced by over 75%. If an additional stage of flash cooling with heat exchanger is added between ( 53 ) and ( 57 ) the wash water heating requirement is reduced by over 80%. The choice of the number of flash cooling stages to be used in any application involves the balancing of capital and operating costs.
More particularly, optimal energy recycle depends on a number of factors that translate ultimately to a sequence of operating pressures for the flash tanks. Factors that must be considered include: composition of the solid feed material to the cellulose recovery process including moisture content, temperature of this feed, processing temperature, dilution of dissolved solids, moisture content of discharged cellulose, and temperature drop across the heat exchangers. In the course of computation it is generally found that the flow of effluent wash water is not the same as the input of fresh wash water since moisture from the solids feed and from steam condensate has been added and moisture in the cellulose output has been subtracted. In addition, there are the dissolved solids to consider. Because of all these dependencies, an automated system is needed for minute by minute heat exchanger control, but set points need first to be calculated in setting up the system.
Calculation begins with mass balances for the hydrothermal wash chamber. With reference to FIG. 3, let the flow of fresh wash water into the reaction chamber at ( 18 ) be Wr and the flow of wash liquor with dissolved solids out of the reaction chamber at ( 19 ) be Lr. The ratio of these two flows is an important determinant of the flash tank pressures, so define R=Wr/Lr. Values for Wr, Lr, and R must be calculated from the operational requirements of the process application. Thus start with the feed rate of solid material, its temperature, and its composition, consider the steam flow required to heat to operating temperature, consider the portion of the feed that will be dissolved, consider the moisture content of the solids to be discharged, and consider the allowable concentration of dissolved solids in the effluent wash liquor. With knowledge of the heat capacities of the various materials and by use of a set of steam tables the necessary calculations can be performed. For fresh sawmill waste in the Pacific Northwest the result will be R=0.8 more or less.
For initial process design purposes, an approximate calculation can be done to determine stage temperatures and mass flows. Consider the liquid flow, Lr, at temperature, Tr, with enthalpy Hr at ( 19 ) in FIG. 3 . This liquid is to be cooled to temperature, T3, and enthalpy H3 in flash tank FT3 ( 57 ). The enthalpy change will be Lr*(Hr−H3). This excess heat will flash part of the liquid to steam with an enthalpy change from liquid to vapor given by F3*HIv3=Lr*(Hr−H3) where F3 is the rate of steam flow at ( 56 ). This flash steam will pass to the heat exchanger HE3 ( 55 ) where it will be condensed and give up its heat to the fresh wash water Wo ( 13 ): Wo*(H3−H2)=F3*HIv3. Similar relationships can be written for all stages. For ease of calculation, liquid enthalpies in Btu/pound can be expressed approximately as H=1.8*T degrees C. It is also convenient to normalize mass flows with respect to the fresh wash water feed, Wo, so that L=Lr/Wo, S=Sr/Wo, W=Wr/Wo, fs=Fs/Wo where “s” is stage number. Thus a set of equations can be written to describe the heat exchange process:
Steam Input:
W = 1 + S
(50)
S*HIvr 18*(Tr − T3 + D)
(51)
where “D” is the temperature drop across any heat exchanger.
Stage 1:
T2 − T1 = (T1 − To)/L
(52)
f1*HIv1 = L*1.8*(T2 − T1)
(53)
Stage 2:
T3 − T2 = (T2 − T1)/L
(54)
f2*HIv2 = L*1.8*(T3 − T2)
(55)
Stage 3:
Tr − T3 = (T3 − T2)/L
(56)
f3*HIv3 = L*1.8*(Tr − T3)
(57)
The pattern can be extended to any number of stages, from which:
S=W− 1 =L*R− 1 (58)
D =( HIvr*S )/1.8−( Tr−T 1)*( L− 1)/( L n −1) (59)
T 1 −To =( Tr−T 1)*( L− 1)/(1− L −n ) (60)
Where: n=3 is the number of stages in the preferred implementation.
Computation is facilitated if a certain sequence is followed: First, set the reactor temperature, Tr, and the temperature of the first stage, T1=100. With Tr, T1, and R specified pick a trial value for L>1 from which get S ( 58 ) and D ( 59 ). Adjust L until the value for D is acceptable—usually about 10. Then calculate (T1−To) ( 60 ), (T2−T1) ( 52 ), (T3−T2) ( 54 ), etc. through all stages. Obtain values for the liquid-to-vapor enthalpy changes, HIv, from steam tables and calculate f1, f2, f3, etc. through all stages and sum for the total flash liquor fo. From the mass balance on the wash chamber, Lr will be known, so use Wo=Lr/L to remove the normalization from mass flows for steam and liquids. With T1 known, calculate To, T2, T3, etc. and determine corresponding flash tank pressures (Ps in pounds per square inch) from the steam tables. For example, with Tr=220 C: T3=192, P3=188, T2=153, P2=74, more or less.
Although optimization of the operating parameters in the practice of the present invention provides additional economic and other benefits, the techniques of the present invention provide more fundamental benefits which can be readily appreciated. Because little use is made of chemical additives in the processes of the present invention, waste disposal problems are minimized. Furthermore, the effluent wash water liquor includes lignin, oligomers and monomers from hemicellulose and extractives that are relatively free of toxic degradation products and may be further processed for their economic values. In addition, energy recuperation is achieved through use of heat transfer between output and input streams to minimize the cost of heating wash water.
Batch type experiments utilizing corn stover (stems, leaves, cobs, shucks, etc.) were conducted in the laboratory to simulate a continuous process for commercial production of purified cellulase from common waste biomass. In the continuous process, a single elongated reaction vessel may be used in which liquid and solids move in opposite directions in some zones and in the same direction in others with the solids passing through as sequence of reactive conditions.
For the laboratory experiments, two reaction vessels were used. In the first reaction vessel, granular solid feedstock prepared in a hammer mill were loaded as a fixed bed adapted for soaking and/or washing at elevated temperature and pressure using one or more liquid preparations. Conducted in the first reaction vessel are the steps of the process in which hemicellulose and extractives are mobilized and eluted and in which, under changed conditions, most of the lignin is eluted.
In the second reaction vessel, residual lignin was eliminated with a “polishing” step. This second reaction vessel used in the laboratory experiments was a simple “bomb” into which solids from the first reaction vessel were loaded along with water, alkali, and pressurized oxygen. The “bomb” was then heated to initiate oxygenation and quenched to end the run.
EXAMPLE I
PVT-12
13.2 grams (dry weight) feedstock of feedstock were placed in the first reaction vessel. Water was added, the slurry heated and the heated slurry maintained at a peak temperature of 170° C. for 5 minutes. The slurry was then washed with 900 grams of heated water previously treated with NaOH to pH 12.8. Maximum temperature of the wash water was measured at 224° C. Log severity=4.5 Product results were measured without transfer to and treatment in the second reaction vessel. Recovery results are summarized as follows:
Solid product: Recovery=44.2% by wt. of feed material
Recovery of original cellulose with composition>98%
92.4% 6-carbon components (mostly cellulose)
0.3% 5-carbon components
3.3% Klason lignin
0.2% acid soluble lignin
3.8% ash.
EXAMPLE II
PVT-Combo
First Vessel:
53.1 grams (dry weight) feedstock distributed in 4 runs in the first vessel. As much as possible, conditions of the PVT-12 run were duplicated for each run, and the products were combined to provide material for studies of oxidation in the second vessel.
Combined product recovery=37.9% by wt of feed material
1.9% Klason lignin
3.2% ash.
Second Vessel:
Two samples of combo product of about 1 gram each were treated with oxygen as described above at a peak temperature of 217° C. and a log severity of 4. Oxygen pressure in one sample was 50 psig and in the other was 60 psig. Results from these two runs were indistinguishable, so only averages follow.
Solid product: Recovery=31.9% by wt. of feed material
Recovery of original cellulose with composition≈82%
96.4% 6-carbon components (mostly cellulose)
5-carbon components not detectable
0.7% Klason lignin
acid soluble lignin not detectable
2.9% ash.
EXAMPLE II
PVT-19
First Vessel:
12.0 grams (dry weight) feedstock. Initial Water Soak: 5 minutes at peak temperature of 200° C. Washed with 370 grams of distilled water at 200° C. followed by 865 grams of water at pH 12.8 with NaOH. Maximum temperature=218 C. Log severity=4.1.
Second Vessel:
All solid material from first vessel transferred to second vessel and soaked in a pH 12.8 solution with 150 cc of oxygen at STP and oxygen pressure of 45 psig. Maximum temperature=215° C. Log severity=3.8.
Solid product: Recovery=31.4% by wt. of feed material
Recovery of original cellulose with composition≈82%
97.5% 6-carbon components (mostly cellulose)
5-carbon components not detectable
Klason lignin not detectable
acid soluble lignin not detectable
2.5% ash.
As can be seen, using the process of the present invention, the recovered cellulose consistently contains less then 20% lignin, as predicted, with the two reaction zone technique of the present invention consistently yielding recovered cellulose containing less than 10% to 5% lignin. Indeed, the two reaction zone technique of the present invention is shown above to yield recovered cellulose containing less than 2% lignin and less than 1%, which is most preferred.
While the processes herein described and the forms of apparatus for carrying these processes into effect constitute preferred embodiments of this invention, it is to be understood that the invention is not limited to these precise processes and forms of apparatus and that changes may be made in either without departing from the scope of the invention which is defined in the appended claims.
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A multi-function process is described for the separation of cellulose fibers from the other constituents of lignocellulosic biomass such as found in trees, grasses, agricultural waste, and waste paper with application in the preparation of feedstocks for use in the manufacture of paper, plastics, ethanol, and other chemicals. This process minimizes waste disposal problems since it uses only steam, water, and oxygen at elevated temperature in the range of 180° C. to 240° C. for 1 to 10 minutes plus a small amount of chemical reagents to maintain pH in the range 8 to 13. An energy recuperation function is important to the economic viability of the process.
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BACKGROUND OF THE INVENTION
[0001] Field of the Invention
[0002] This invention relates to patient interfaces particularly though not solely for use in delivering CPAP therapy to patients suffering from obstructive sleep apnoea (OSA).
[0003] Description of the Related Art
[0004] In the art of respiration devices, there are well known variety of respiratory masks which cover the nose and/or mouth of a human user in order to provide a continuous seal around the nasal and/or oral areas of the face such that gas may be provided at positive pressure within the mask for consumption by the user. The uses for such masks range from high altitude breathing (i.e., aviation applications) to mining and fire fighting applications, to various medical diagnostic and therapeutic applications.
[0005] One requisite of such respiratory masks has been that they provide an effective seal against the user's face to prevent leakage of the gas being supplied. Commonly, in prior mask configurations, a good mask-to-face seal has been attained in many instances only with considerable discomfort for the user. This problem is most crucial in those applications, especially medical applications, which require the user to wear such a mask continuously for hours or perhaps even days. In such situations, the user will not tolerate the mask for long durations and optimum therapeutic or diagnostic objectives thus will not be achieved, or will be achieved with great difficulty and considerable user discomfort.
[0006] U.S. Pat. No. 5,243,971 and U.S. Pat. No. 6,112,746 are examples of prior art attempts to improve the mask system U.S. Pat. No. 5,570,689 and PCT publication No. WO 00/78384 are examples of attempts to improve the forehead rest.
[0007] Where such masks are used in respiratory therapy, in particular treatment of obstructive sleep apnea (OSA) using continuance positive airway pressure (CPAP) therapy, there is generally provided in the art a vent for washout of the bias flow or expired gases to the atmosphere. Such a vent may be provided for example, as part of the mask, or in the case of some respirators where a further conduit carries the expiratory gases, at the respirator. A further requisite of such masks is the washout of gas from the mask to ensure that carbon dioxide build up does not occur over the range of flow rates. In the typical flow rates in CP AP treatment, usually between 4 cm H 2 O to 20 cm H 2 O, prior art attempts at such vents have resulted in excessive noise causing irritation to the user and any bed partners.
[0008] In common with all attempts to improve the fit, sealing and user comfort is the need to avoid a concentrated flow of air at any portion of the respiratory tracts. In particular with oral masks or mouthpieces it is a disadvantage of prior art devices that the oral cavity may become overly dehydrated by use of the device, causing irritation and possible later complications. Furthermore, a common complaint of a user of CPAP therapy is pressure sores caused by the mask about the nose and face and in particular in the nasal bridge region of the user.
SUMMARY OF THE INVENTION
[0009] It is an object of the present invention to attempt to provide a patient interface which goes some way to overcoming the abovementioned disadvantages in the prior art or which will at least provide the industry with a useful choice.
[0010] Accordingly in a first aspect the present invention consists in a breathing assistance apparatus, for use with delivery of respiratory gases to a patient comprising: a patient interface, having a body section adapted to cover the nose, or nose and mouth of said patient, a sealing interface, including at least an outer sealing member, said outer sealing member adapted to attach to said body section in a sealing manner, said outer sealing member having a substantially thin section in at least its nasal bridge region, said thin section being substantially thinner than the rest of said outer sealing member, wherein said outer sealing member is adapted to seal around the facial contours of said patient thereby providing a sealed fluid communication to the respiratory tract of said patient.
[0011] The invention consists in the foregoing and also envisages constructions of which the following gives examples.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] Preferred forms of the present invention will now be described with reference to the accompanying drawings.
[0013] FIG. 1 is a block diagram of a humidified continuous positive airway pressure (system) as might be used in conjunction with the sealing interface of the present invention.
[0014] FIG. 2 is an illustration of the nasal mask including a sealing interface in use according to the preferred embodiment of the present invention.
[0015] FIG. 3 shows a perspective view of a mask with a sealing interface that is a cushion.
[0016] FIG. 4 is a cutaway view of the mask showing the sealing interface cushion that has an inner sealing member and an outer sealing member.
[0017] FIG. 5 is a cutaway view of the periphery of the outer sealing member or membrane.
[0018] FIG. 6 is a cutaway view of the periphery of the mask body portion.
[0019] FIG. 7 shows a mask and sealing interface as used with a forehead rest on a patient.
[0020] FIG. 8 shows a cross section of a second preferred embodiment of the sealing interface.
[0021] FIG. 9 shows perspective view of an inner sealing member of the second preferred embodiment of the sealing interface.
[0022] FIG. 10 shows a cross section of a third preferred embodiment of the inner and outer sealing members of the present invention.
[0023] FIG. 11 shows a perspective view of the inner sealing member of the third preferred embodiment of the sealing interface.
[0024] FIG. 12 shows a plan view of the inner sealing member of the third preferred embodiment of the mask cushion.
[0025] FIG. 13 shows a cross section of a fourth preferred embodiment of the sealing interface of the present invention.
[0026] FIG. 14 shows a perspective view of the inner sealing member according to a fifth preferred embodiment of the sealing interface of the present invention.
[0027] FIG. 15 shows a cross section of a sixth preferred embodiment of the sealing interface of the present invention.
[0028] FIG. 16 shows a perspective view of the inner sealing member according to a seventh preferred embodiment of the sealing interface of the present invention.
[0029] FIG. 17 shows a perspective view of the inner sealing member according to an eighth preferred embodiment of the sealing interface of the present invention.
[0030] FIG. 18 shows a perspective view of the inner sealing member according to a ninth preferred embodiment of the sealing interface of the present invention.
[0031] FIG. 19 shows a perspective view of the inner sealing member according to a tenth preferred embodiment of the sealing interface of the present invention.
[0032] FIG. 20 shows a cross section of a further embodiment of the sealing interface of the present invention where the inner sealing foam member touches the outer sealing member at all times.
[0033] FIG. 21 is a side view of a nasal mask of the present invention where the outer sealing member is substantially thinner in width in the nasal bridge region than the rest of the outer sealing member.
[0034] FIG. 22 is a close-up view of detail A in FIG. 21 .
[0035] FIG. 23 is a perspective view of the nasal mask of FIG. 21 .
[0036] FIG. 24 is a cross-section of the outer sealing member of FIG. 21 .
[0037] FIG. 25 is a front perspective view of a full face mask of the present invention, where the outer sealing member is substantially thinner in width in the nasal bridge region than the rest of the outer sealing member.
[0038] FIG. 26 is a back perspective view of a full face mask of FIG. 25 .
[0039] FIG. 27 is a cross-section through BB of the full face mask of FIG. 25 .
[0040] FIG. 28 is a perspective view of the outer sealing member of the full face mask of FIG. 25 in isolation, where the thin nasal bridge region is particularly shown.
[0041] FIG. 29 is a cross-section through CC of the outer sealing member of FIG. 28 .
[0042] FIG. 30 is a front view of the outer sealing member of FIG. 28 .
[0043] FIG. 31 is a front view of a first alternative outer sealing member.
[0044] FIG. 32 is a front view of a second alternative outer sealing member.
[0045] FIG. 33 is a front view of a third alternative outer sealing member.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0046] The sealing interface of the present invention provides improvements in the delivery of CP AP therapy. In particular a patient interface is described which reduces the pressure of the mask on the patient's face and may be quieter for the patient to wear and reduces the side leakage as compared with the prior art. It will be appreciated that the patient interface as described in the preferred embodiment of the present invention can be used in respiratory care generally or with a ventilator, but will now be described below with reference to use in a humidified CP AP system. It will also be appreciated that the present invention can be applied to any form of patient interface including, but not limited to, nasal masks, oral masks and mouthpieces.
[0047] With reference to FIG. 1 a humidified Continuous Positive Airway Pressure (CP AP) system is shown in which a patient 1 is receiving humidified and pressurized gases through a patient interface 2 connected to a humidified gases transportation pathway or inspiratory conduit 3 . It should be understood that delivery systems could also be VPAP (Variable Positive Airway Pressure) and BiPAP (Bi-level Positive Airway Pressure) or numerous other forms of respiratory therapy. Respiratory conduit 3 is connected to the outlet 4 of a humidification chamber 5 that contains a volume of water 6 . Inspiratory conduit 3 may contain heating means or heater wires (not shown) which heat the walls of the conduit to reduce condensation of humidified gases within the conduit. Humidification chamber 6 is preferably formed from a plastics material and may have a highly heat conductive base (for example an aluminium base) which is in direct contact with a heater plate 7 of humidifier 8 . Humidifier 8 is provided with control means or electronic controller 9 which may comprise a microprocessor based controller executing computer software commands stored in associated memory.
[0048] Controller 9 receives input from sources such as user input means or dial 10 through which a user of the device may, for example, set a predetermined required value (preset value) of humidity or temperature of the gases supplied to patient I. The controller may also receive input from other sources; for example temperature and/or flow velocity sensors 11 and 12 through connector 13 and heater plate temperature sensor 14 . In response to the user set humidity or temperature value input via dial 10 and the other inputs, controller 9 determines when (or to what level) to energize heater plate 7 to heat the water 6 within humidification chamber 5 . As the volume of water 6 within humidification chamber 5 is heated, water vapour begins to fill the volume of the chamber above the water's surface and is passed out of the humidification chamber 5 outlet 4 with the flow of gases (for example air) provided from a gases supply means or blower 15 which enters the chamber through inlet 16 . Exhaled gases from the patient's mouth are passed directly to ambient surroundings in FIG. 1 .
[0049] Blower 15 is provided with variable pressure regulating means or variable speed fan 21 which draws air or other gases through blower inlet 17 . The speed of variable speed fan 21 is controlled by electronic controller 18 (or alternatively the function of controller 18 could carried out by controller 9 ) in response to inputs from controller 9 and a user set predetermined required value (preset value) of pressure or fan speed via dial 19 .
Nasal Mask
[0050] According to a first embodiment of the present invention the patient interface is shown in FIG. 2 as a nasal mask. The mask includes a hollow body 102 with an inlet 103 connected to the inspiratory conduit 3 . The mask 2 is positioned around the nose of the patient 1 with the headgear 108 secured around the back of the head of the patient 1 . The restraining force from the headgear 108 on the hollow body 102 and the forehead rest 106 ensures enough compressive force on the mask cushion 104 , to provide an effective seal against the patient's face.
[0051] The hollow body 102 is constructed of a relatively inflexible material for example, polycarbonate plastic. Such a material would provide the requisite rigidity as well as being transparent and a relatively good insulator. The expiratory gases can be expelled through a valve (not shown) in the mask, a further expiratory conduit (not shown), or any other such method as is known in the art.
Mask Cushion
[0052] Referring now to FIGS. 3 and 4 in particular, the mask cushion 1104 is provided around the periphery of the nasal mask 1102 to provide an effective seal onto the face of the patient to prevent leakage. The mask cushion 1104 is shaped to approximately follow the contours of a patient's face. The mask cushion 1104 will deform when pressure is applied by the headgear 2108 (see FIG. 7 ) to adapt to the individual contours of any particular patient. In particular, there is an indented section 1150 intended to fit over the bridge of the patient's nose as well as an indented section 1152 to seal around the section beneath the nose and above the upper lip.
[0053] In FIG. 4 we see that the mask cushion 1104 is composed of an inner sealing member that is an inner cushion 1110 covered by an outer sealing sheath or member 1112 . The inner cushion 1110 is constructed of a resilient material for example polyurethane foam, to distribute the pressure evenly along the seal around the patient's face. In other forms the inner cushion 1110 may be formed of other appropriate material, such as silicone or other composite materials. The inner cushion 1110 is located around the outer periphery 1114 of the open face 1116 of the hollow body 1102 . Similarly the outer sheath 1112 may be commonly attached at its base 1113 to the periphery 1114 and loosely covers over the top of the inner cushion 1110 .
[0054] In the preferred embodiment of the present invention as shown in FIGS. 4 to 6 the bottom of the inner cushion 1110 fits into a generally triangular cavity 1154 in the hollow body 1102 . The cavity 1154 is formed from a flange 1156 running mid-way around the interior of the hollow body.
[0055] The outer sheath 1112 fits in place over the cushion 1110 , holding it in place. The sheath 1112 is secured by a snap-fit to the periphery 1114 of the hollow body. In FIGS. 5 to 6 the periphery 1114 is shown including an outer bead 1158 . The sheath 1112 includes a matching bead 1159 , whereby once stretched around the periphery; the two beads engage to hold the sheath in place.
[0056] A second preferred embodiment to the mask cushion is depicted in FIGS. 9 and 10 . In the second embodiment the inner cushion 2000 includes a raised bridge 2002 in the nasal bridge region. The raised bridge 2002 can also be described as a cut out section made in the cushion. Also, the notch in the contacting portion (between the inner cushion and outer sheath) is less pronounced than proceeding embodiments. However, as the raised bridge 2002 is unsupported it is much more flexible and results in less pressure on the nasal bridge of the patient. The outer sheath 2004 contacts the inner cushion 2000 throughout the raised bridge 2002 . The peaks 2005 , 2007 , 2009 , 2011 in the inner cushion 2000 between each of the indented sections 2006 , 2008 and the raised bridge 2002 contact the outer sheath 2004 and when in use the sheath 2004 contacts the facial contours of the patient in the regions of these peaks.
[0057] Referring particularly to FIG. 10 the inner cushion 2000 includes a cheek contour 2006 to follow the cartilage extending from the middle of the nose, and a contoured lip sealing portion 2008 to seal between the base of the nose and the upper lip.
[0058] Referring now to FIGS. 11 and 12 a third preferred embodiment of the mask cushion is depicted, in this case, the inner cushion 2010 tapers down 2012 towards the nasal bridge region 2014 . For a short portion either side of the nasal bridge region 2014 the inner cushion 2010 is absent, forming a semi annular form in plan view as seen in FIG. 12 .
[0059] Referring to FIG. 13 , a fourth preferred embodiment of the mask cushion is depicted. The outer sheath 2020 is adapted to contact the inner cushion 2022 completely about the inner cushion, including in the nasal bridge region 2024 and the check contour 2026 . FIG. 18 shows the inner cushion 2022 where the upper edge 2050 of the cushion does not have any contours and thus will contact the outer sheath all around the edge of the inner cushion. FIG. 20 shows a sealing interface similar to that of FIG. 13 where the inner cushion also follows and touches the outer sheath all around its edge.
[0060] FIG. 14 illustrates a fifth preferred embodiment of the inner cushion 2030 . In the nasal bridge region 2032 the inner cushion includes a lower bridge 2034 and upper bridge 2036 . Due to the gap the upper bridge 2036 is unsupported to reduce pressure on the patient's nasal bridge, but the lower rim 2034 of the inner cushion 2030 is continuous, which aids installation.
[0061] In yet other forms of the sealing interface of the present invention the inner cushion may be provided with other contours on the front side of the inner cushion or cut outs on the back side of the inner cushion, so that in the areas where there are regions cut out of the back side of the cushion the cushion is more flexible. In particular, cut outs in the nasal bridge, cheek and upper lip regions provide the patient with a mask cushion that is more flexible and thus more comfortable. FIG. 15 shows an embodiment of an inner cushion 2024 that has a curved cut out or dead space 2044 in the cheek region. FIGS. 16 and 17 show embodiments of an inner cushion 2000 that has a cut out or dead space 2046 in the area where the patient's upper lip rests in the foam.
[0062] A final form of a sealing interface is shown in FIG. 19 , here the inner foam member has an annular shape but has a thin bridge or membrane 2048 that extends across and provides flexibility to the nasal bridge region.
[0063] Referring now to FIG. 21 , to improve the comfort to the patient the nasal mask 200 includes a thin bridge section 203 in the nasal bridge region of the outer sealing member 201 , that is, that part extending over the bridge of a patient's nose.
[0064] Similar to described above the outer sealing member or outer sheath 201 fits in place over the inner sealing member (inner cushion) 202 , holding it in place. The outer sheath 201 is secured by a snap-fit to the periphery 205 of the mask hollow body 204 . The periphery 205 is shown including an outer bead 206 . The outer sheath 201 includes a matching bead 207 , whereby once stretched around the periphery 205 ; the two beads engage to hold the outer sheath 201 in place.
[0065] The outer sealing member or sheath 201 is shown in more detail in FIGS. 22 to 24 . The outer sheath 201 has formed in it a region 203 that is thinner than the remainder of the cross-sectional thickness 210 of the sheath. In particular, the side walls 211 , 212 (see FIG. 23 ) must be thicker than in the region 203 so as to provide structural support for the sheath and ensure the sheath does not collapse in use, or when being assembled with the mask body. As an example only, for a nasal mask, if the thin bridge region was 0.2 mm thick, the side walls may be 0.3 to 0.6 mm thick. Therefore, the thin bridge region 203 is approximately half the thickness of the rest of the sheath 201 and so can provide a significant effect, such that the pressure to the patient's nose in the nasal bridge region is reduced compared to when a sheath does not have any reduced thickness section. Furthermore, a thin bridge region 203 in the outer sheath 201 allows for different sized patient's to comfortably use the mask and outer sheath of the present invention.
[0066] In use, when a force is placed against the outer sheath 201 the thin bridge region 203 will collapse more than the rest of the outer sheath 201 . Therefore, this section 203 is more flexible and allows for added patient comfort.
[0067] Referring particularly to FIG. 22 , the thin bridge region 203 on the outer sheath 201 preferably does not extend completely to the outer edge 211 of the outer sheath 201 , but grows thicker in thickness. This is because the outer edges of the outer sheath 201 when thicker are less prone to tearing.
[0068] In particular, in FIG. 23 , that outer sheath 201 is substantially heart shaped and the thin bridge region 203 is shown to extend more than halfway down the sides of the sheath from the apex 213 . As shown in FIG. 23 , the thin bridge region 203 does not extend fully down the edges 211 and 212 of the outer sheath 201 . This is because support is required in the edges of the sheath 201 , to provide structural stability of the sheath.
[0069] In other forms of the nasal mask of the present invention, the thin bridge region may not extend as far as that shown in FIG. 23 , but be restricted merely to the nasal bridge region (similar in manner to the mask cushion shown in FIG. 30 , in relation to a full face mask).
Full Face Mask
[0070] A further embodiment of the present invention is shown in FIGS. 25 to 31 where the patient interface is a full face mask similar to that described in co-pending New Zealand patent application number 528029. The full face mask 300 includes a hollow body 302 and outer sealing member or mask cushion 301 . The cushion 301 is attached to the body 302 in a similar manner as described with reference to the nasal mask, but here no inner cushion is provided. Thus, the cushion 301 periphery extends over a flange on the mask body.
[0071] The hollow body 302 has an integrally formed recess (not shown) in which an insert 304 is fitted into. The recess and insert 304 each have complimentary circular apertures (generally indicated as 305 ) that form an inspiratory inlet when the insert 304 is placed in the recess. The inlet 304 is capable of being connected to the tubing that forms the inspiratory conduit 3 (as shown on FIG. 1 ). Gases, supplied to the inspiratory conduit 3 from the CP AP device and humidifier, enter the mask through the apertures 305 and the patient is able to breathe these gases. The mask 300 is positioned around the nose and mouth of the patient and headgear (not shown) may be secured around the back of the head of the patient to assist in the maintaining of the mask on the patient's face. The restraining force from the headgear on the hollow body 302 ensures enough compressive force on the mask cushion 301 to provide an effective seal against the patient's face.
[0072] The hollow body 302 and insert 304 are injection moulded in a relatively inflexible material, for example, polycarbonate plastic. Such a material would provide the requisite rigidity for the mask as well as being transparent and a relatively good insulator. The mask cushion 301 is preferably made of a soft plastics material, such as silicone, KRATON™ or similar materials.
[0073] The cushion 301 of the mask 300 includes a thin bridge section 305 in the nasal bridge region of the cushion 301 , that is, that part extending over the bridge of a patient's nose. As an example, in the region of the thin bridge section 305 the walls of the cushion may be 0.2 to 0.3 mm thick and the rest of the cushion may have a thickness of 1 mm. In particular, the side walls need to be thicker to provide support in the cushion, so that it does not collapse during use or assembly with the mask body. In FIG. 29 , this is particularly illustrated, as the section 305 in the nasal bridge region is shown as being much thinner than the rest of the cushion (in particular the bottom side wall region 306 , which are much thicker in cross-section).
[0074] Note must be made that the inner flange 307 of the cushion 301 that rests against the patient's face is also thinner in section than the side walls of the cushion 301 to provide flexibility to the cushion and thus comfort to the patient. In use, the inner flange 307 is the area of the cushion that seals against the patient's face and the side walls of the cushion provide stability to the cushion 301 .
[0075] In use, when a force is placed against the cushion 301 the thin bridge section 305 will collapse more than the rest of the cushion 301 . Therefore, this section 305 is more flexible and allows for added patient comfort.
[0076] Other forms of the cushion that may be used with the full face mask of the present invention are shown in FIGS. 31 to 33 and each show alternative thin sections that may be provided for patient comfort, and to allow for fitting to different sized patients.
[0077] Referring first to FIG. 31 , cushion 310 may have a thin bridge section 311 that is narrower than that shown in FIG. 30 .
[0078] In FIG. 32 the cushion 312 has a thin bridge section 313 only near the outer edge 317 of the cushion 312 . This cushion 312 also had a thin section 314 in the region of the cushion that would rest against the patient's chin.
[0079] Finally, in FIG. 33 , the thin section 316 of the cushion 315 may extend down the sides 318 , 319 of the cushion.
Forehead Rest
[0080] The nasal mask and/or full face mask of the present invention is preferably provided with a fixed forehead rest ( 208 , as shown in relation to the nasal mask in FIGS. 21 and 23 or 303 , as shown in relation to the full face mask in FIG. 25 ). The forehead rest is not required to be adjustable as the cut out in the nasal bridge region of the inner foam (for the nasal mask) and the thin section in the outer sheath (for both the nasal and full face masks) provides enough flexibility of the mask cushion to provide fitting to a number of different patients.
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A breathing assistance apparatus is designed for use with delivery of respiratory gases to a patient. The breathing assistance apparatus includes a patient interface, having a body section adapted to cover the nose, or nose and mouth of a patient and a sealing interface. The sealing interface includes at least an outer sealing member. The outer sealing member ( 201 ) is adapted to attach to the body section in a sealing manner and has a substantially thin section ( 203 ) in at least its nasal bridge region. The thin section is substantially thinner than the rest of the outer sealing member.
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This is a continuation-in-part of Ser. No. 004,117 filed Jan. 17, 1979, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a bobbin case adjustment mechanism, referred to in the sewing machine industry as a cushion spring assembly, for use in a sewing machine having a vertical axis rotary hook.
2. Description of the Prior Art
In a sewing machine that has a vertical axis hook, the bobbin case must be restrained from rotation within the hook while still leaving enough space between the bobbin case and the rotation restraining mechanism to allow a loop of needle thread to pass between the restraining mechanism and the hook during the process of forming stitches.
Some prior bobbin case rotation restraining mechanisms were fastened to the sewing machine bed by screws or similar fasteners that precluded adjusting their positions to correct for errors due to construction and assembly tolerances incurred during the manufacture of the restraining mechanism.
Another prior bobbin case rotation restraining mechanism shown in Japanese Utility Model Application No. 52-74864 incorporated, at one extremity thereof, a stud with an eccentric portion that permitted the mechanism to be pivotally moved toward or away from the bobbin case to effect limited control over the width of a slot located between the bobbin case rotation restraining member and the bobbin case and through which the needle thread must pass during its concatenation with the bobbin thread. While the means for pivotal adjustment incorporated in that mechanism made the machine less prone to thread jamming than rotation restraining mechamisms that did not incorporate adjustment means, the adjustable means can only be adjusted along a limited line, or arc, but cannot be adjusted to all of the points around a closed loop. Such freedom of movement is necessary to allow the cushion spring to be moved in two dimensions relative to the position of the bobbin case to permit accurate setting of the dimensions of more than one part of the slot.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of this invention to provide a bobbin case rotation restraining mechanism that will permit adjustment of the distance between the bobbin case and the cushion spring by allowing a critical part of the cushion spring assembly to be moved around a closed loop path.
Another object of this invention is to produce a cushion spring assembly that may be easily adjusted in two dimensions after assembly of the sewing machine.
Still another object is to provide a cushion spring assembly that may be easily released to permit the removal of the bobbin case from the loop taker without disturbing the adjustment of the assembly.
Further objects will be apparent from the following description and the accompanying drawings.
The above and other objects are achieved by fastening a cushion spring to a movable bobbin case retainer mechanism that permits adjustments to be made such that a given point on the cushion spring assembly can be moved to any point along a closed loop path relative to the bobbin case. The cushion spring is mounted on a base plate that contains a pair of slots, the directions of elongation of which are substantially orthogonal to each other. One of the slots permits the bobbin case to be moved in a front-or-rear direction relative to the hook, or loop taker. The second elongated slot permits side-to-side arcuate movement toward or away from the hook. The combined effects of the front-rear and arcuate movements constrains any given point on the cushion spring to be placed at any point along a closed loop. A spring biased slide lock engages an eccentric portion of a round, cylindrical stud received by one of the slots to help constrain movement of the cushion spring assembly so that a specific part of the cushion spring can be placed only at any point on a closed loop. The lock also allows the rotation restraining member to be swung away from the bobbin case to simplify removal of the bobbin case from the hook.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of a fragment of a sewing machine bed showing a bobbin case within a vertical axis hook and a cushion spring assembly constructed according to this invention;
FIG. 2 is an enlarged view of a stud as used in the embodiment in FIG. 1, with, however, a modified eccentric stud applied thereto;
FIG. 3 is a cross-sectional side view taken along the line 3--3 of FIG. 1;
FIG. 4 is a perspective view of the bobbin case and cushion spring assembly of FIG. 1 in operating position; and
FIG. 5 shows the apparatus in FIG. 4 with the cushion spring assembly moved away form the bobbin case.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows a portion of a sewing machine bed 10 that includes a recess 12 in which there is a loop taker, or hook, 14 that has a vertical axis. The recess 12 is partly covered during the sewing process by a standard throat plate (not shown) located relative to the bed 10 by a pair of pins 16. The remainder of the recess is covered by a slide plate 18. The hook 14 is rotatably driven in timed relation to reciprocation of a needle, which is not shown, to produce stitches in a well known manner. A more complete description of one type of sewing machine in which the component parts of the present invention may be used is contained in U.S. Pat. No. 3,115,855 issued to S. J. Ketterer. The teachings of the Ketterer patent are incorporated herein by reference.
FIG. 1 also shows that the hook 14 includes a beak 20 that seizes a loop of needle thread from the needle and draws it around a bobbin 22 that contains a supply of bobbin thread, thereby causing the concatenation of the needle thread with the bobbin thread to produce a lockstitch in a well known manner. The bobbin 22 is in a recess within a bobbin case 24 that has a raised wall 26 and is held in that recess by a pivotally movable, spring-biased arm 28, one end of which is fastened to the wall 26 holding the bobbin 22 within the case 24. The arm is shown in its bobbin-retaining position in which it holds the bobbin 22 in the recess in the case 24 but with sufficient freedom to allow the bobbin to rotate freely within the case 24 as bobbin thread is removed to form stitches.
The bobbin case 24 is, in part, restrained from rotating with the hook 14 by a fixed bobbin case rotation restraining member 30, one end of which is fastened to the sewing machine bed 10 by a screw 32 or other suitable fastener. The other end of the fixed rotation restraining member +is contoured to allow thread passage between it and a restraining depression 34 implemented by a substantially radial surface portion in the wall 26 of the bobbin case 24.
The bobbin case 24 is further prevented from rotating with the hook 14 by an adjustable bobbin case retainer, or cushion spring assembly, 36. The assembly 36 includes an elongated base plate 38 to which is fastened a cushion spring 40 constructed of a resilient material, such as spring steel and comprising an arcuate section 42. The cushion spring 40 is secured to the base plate 38 by fasteners, such as a pair of rivets 44. Preferably, the free end 46 of the cushion spring 40 is substantially straight and extends approximately radially with respect to the center of the case 24 and forms an elbow 48 at the point where the free end is bent outwardly from the arcuate section 42. The cushion spring 40 is aligned with, and properly spaced from, a generally radial abutment surface portion 50 in the wall 26 of the bobbin case 24 distant from the depression 34. Preferably the radius of curvature of arcuate section 42 of the cushion spring 40 is large enough to produce a slot 52 of increasing width between the cushion spring and the bobbin case wall 26 so that the cushion spring only contacts the bobbin case 24, if at all, at the interface between the elbow 48 and the abutment surface portion 50 on the bobbin case wall 26. Furthermore, it is essential that free end 46 extend far enough forward (i.e., away from the center of the bobbin case 24) to be sure that each loop of needle thread cannot get past the free end but is forced to move between the free end and the abutment surface portion 50 and on into the slot 52.
The base plate 38 of the cushion spring assembly 36 contains means for adjusting the distances A and B between the bobbin case 24 and the free end 46 and elbow 48, which are key parts of the spring 40. In a typical sewing machine in which the cushion spring assembly 36 can be used, the Singer Model 930, the distance A should be in the range of approximately 0.010" to about 0.014" and the distance B should be in the range from about 0.020" to about 0.060". The adjustment means includes a first slot 54, which is elongated in a direction substantially parallel to a radial line from the abutment surface portion 50 to the center of the case 24, and a second slot 56 elongated in a direction substantially perpendicular in this case to the direction of elongation of the slot 54 and located near the opposite end of the plate 38.
A shouldered screw 58, which constitutes means for fastening the base plate 38 to the bed 10, has the shoulder thereof of such a diameter to just pass through the first elongated slot 54, and is screwed into a threaded hole 60 in the sewing machine bed 10. The bed 10 also has a smooth bore that receives one end of a round cylindrical stud 64, as will be described hereinafter.
The base plate 38 also has a pair of parallel guides 66 that overlap opposite, parallel edges of a spring-loaded slide lock 68, one end of which slides under the head 70 of the stud 64 to lock the cushion spring assembly 36 relative to the bobbin case 24. The slide lock is preferrably made of sheet metal and has a central tunnel portion 72 within which is located a coil spring 74 that presses the lock 68 against the stud 64.
FIG. 2 shows the stud 64 more clearly. The stud includes a main body 76 that is cylindrical, has a circular cross-section, and is concentric with the head 70. An eccentric part 78 in the form of a round cylinder is located between the head 70 and the closer end of the body 76. In this embodiment, the diameter of the eccentric part 78 is smaller than that of the body.
FIG. 3 is a cross-sectional view of the plate 38 held on the bed 10 by the shouldered screw 58 and a modified stud 64a. The stud 64a differs from the stud 64 in FIG. 2 by having a body portion 76a that has a diameter no greater than the diameter of the eccentric portion 78. The latter portion and the head 70 are identical with correspondingly numbered parts in the embodiment in FIG. 2. The body portion 76a fits rotatably but not loosely in the smooth bore 79 in the bed 10.
The tunnel portion 72 of the lock 68 in FIG. 3 is produced by deforming the central part of the sheet metal slide lock 68 between one end 80 and a region 82. The spring 74 is located within a slot 84 in the base plate 38 in line with the slot 54 and bounded by two ends 86 and 88. The spring 74 exerts pressure on the end 86 and on the region 82 to urge the lock toward the eccentric portion 78. The eccentric portion 78 fits snugly within the slot 56 so that turning the head 70 of the stud 64 about its axis, which is common to the axis of the body 76a, moves the offset axis of the eccentric portion 78 in a circle and thus moves the plate 38 left and right relative to the position shown in FIG. 3. The plate 38 is shown approximately in its leftmost position (from the point of view of this figure), and so rotation of the head 70 would move the plate 38 to the right, but continued rotation would move it back to the left. A set screw 90 in a threaded hole 92 in the bed 10 can be tightened against the body 76a to hold the stud 64a, and therefore the plate 38, fixed in any position within the range of physically possible positions determined by the crank arm offset between the axis of the body 76a and the axis of the eccentric portion 78.
FIG. 4 shows the cushion spring assembly 36 in its operating position adjacent the bobbin case 24 but does not show the bed 10. In the operating position of the cushion spring assembly 36, the eccentric portion 78 of the stud 64 fits within the controlling part of the second slot 56, as shown in FIG. 4, to effect limited movement of the cushion spring assembly along the length of the first slot 54 as well as movement of the second slot 56 and cushion spring 40 towards and away from the abutment surface portion 50. A loop of thread 94 that has been cast off from the hook 14 during the formation of a stitch is shown passing through the slot 52 as the loop is being drawn about the bobbin case 24. The free end 46 of the cushion spring 40 insures that the thread is smoothly guided into the slot 52. It will best be appreciated from a review of FIG. 1 that, when the free end 46 of the cushion spring 40 is in position against the abutment surface portion 50, the bobbin case 24 will be restrained from rotating with the hook 14 by the combined effects of the fixed bobbin case rotation restraining member 30 and the free end 46 of the cushion spring 40 carried on the adjustable bobbin case retainer 36.
In order to adjust the spacing of the cushion spring 40 from the bobbin case 24, the set screw 90 is loosened to allow the stud 64 to be rotated. As indicated in FIG. 3, the main body portion 76 of the stud fits rotatably but not loosely in a smooth bore that holds the axis of the main body portion virtually fixed as the stud 64a rotates. The smooth bore 79 is not shown in FIG. 4, but it is to be understood that the body portion 76 of the stud 64 is located in such a bore. As a result, rotation of the stud 64 causes the eccentric portion 78 to move in a circular path centered on the axis of the main body portion 76 therein.
As the eccentric portion 78 is caused to follow a circular path of rotation of the stud 64, the plate 38 is moved back and forth in the direction of elongation of the slot 54, guided by the shouldered screw 58. This tends to move the end 46 of the cushion spring 40 more or less parallel to the abutment surface portion 50 on the wall of the bobbin case 24.
The end of the slide lock 68 that engages the eccentric portion 78 is shown to be bifurcated so that it has two points 96 and 98 separated by a distance substantially equal to the diameter of the eccentric portion 78. The slide lock 68 is constrained by the parallel guide 66 so that it can only move back and forth in the direction of the guides 66, which corresponds to the direction of elongation of the slot 54. This means that, as the stud 64 is rotated, not only does the base plate 38 have to move back and forth in the direction of the slot 54 but it also has to occupy a position such that the two points 96 and 98 at the end of the spring lock 68 can fit on opposite sides of the eccentric portion 78 to maintain the eccentric portion in the controlling part of the slot 56. Thus, although the cushion spring assembly 36 can be adjusted to move the elbow 48 parallel to the wall portion 50 to a point as close to the wall 26 as may be desired by moving the base plate 38 in the direction of elongation of the slot 54, engagement of the slide lock 68 with the eccentric portion 78 allows end portion 46 to be held in only certain positions. The net result is that the point within the base plate 38 that is midway between the two side walls of the slot 56 and is also midway between the two points 96 and 98 of the slide lock 68 is constrained so that it must move in a circle as the stud 64 rotates.
At the same time, the portion of the base plate 38 that defines the slot 54 undergoes a different motion, moving back and forth in the direction of elongation of the slot 54 and pivoting slightly from side to side. Other points of the cushion spring assembly 36 not aligned with the slot 54, for example the elbow 48 of the cushion spring, itself, move in a closed loop, which is essentially an ellipse. This gives the elbow 48 greater freedom of motion than if it were limited to just a straight line or an open arc and facilitates placing the elbow within the desired ranges of both A and B in FIG. 1.
FIG. 5 shows the apparatus of FIG. 4 with the cushion spring assembly 36 pivoted aside in order to allow the bobbin case 24 to be removed. In order to move the cushion spring assembly to the position shown in FIG. 5 without disturbing the eccentric adjustment means, the slide lock 68 is simply pushed toward the shouldered screw 58 so as to allow the point 98 to clear the eccentric portion 78 of the stud 64. An extension 100 on the cushion spring 40 serves as a handle to permit the entire cushion spring assembly 36 to be moved away from the bobbin case 24. As will be noticed, the cushion spring assembly 36 has been moved so that the eccentric portion 78 of the stud 64 no longer passes through the narrow part of the slot 56 but through an enlarged part 102 at one end of the slot. The purpose of this enlarged part is to allow the main body 76 of the stud to be inserted through it during assembly of the components. Since both the body 76 and the head 70 (FIG. 2) are larger in diameter than the eccentric portion 78, and yet the eccentric portion must fit relatively snuggly in the slot 56, an enlarged opening must be provided, and it is convenient that this opening be the part 102 at the end of the slot 56.
The whole purpose of the slot 56 is to make it possible to adjust the position of the cushion spring 40 but by only a relatively small distance. Thus, the slot 56 need not be very long. In order to keep the sliding lock 68 from slipping forward and out of position when the cushion spring assembly is pivoted to the position shown in FIG. 5, it is desirable that the point 98 engage the eccentric portion 78 when the components are placed as shown in FIG. 5. By limiting the slot 56 so that this contact between the point 98 and the eccentric portion 78 will take place even in the most extreme position of the cushion spring assembly 36, the sliding lock 68 will be held safely in position at all times.
While this invention has been described in terms of specific embodiments, it will be understood by those skilled in the art that modifications may be made therein within the scope of the following claims.
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A mechanism for allowing adjustment of a cushion spring assembly to vary the distance between the wall of the bobbin case and the cushion spring in two directions. Means are incorporated to permit movement of the cushion spring assembly to facilitate removal of the bobbin case from the loop taker, without affecting the adjustment of the mechanism.
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BACKGROUND OF THE INVENTION
This invention relates to vehicles, and in particular, to a vehicle adapted for use in maintaining streets and roads regardless of weather conditions.
One of the greatest challenges for municipalities in maintaining their physical services is countering the effects of adverse weather conditions. Snow hinders roads and covers fire hydrants. Snow, rain and wind adversely affect the ability of municipalities to respond to and take action at accident scenes and other disaster locations. Conversely, high air temperatures make it difficult for workmen and the like to accomplish tasks at a given location for an extended period of time.
SUMMARY OF THE INVENTION
The present invention addresses the above problems by providing a vehicle with the capability of off-setting the weather conditions at a given location. Although the primary purpose of the present invention is to provide snow melting capability to selected areas, it also has the ability to provide cooling to an enclosed area. The above tasks are accomplished by providing a vehicle with a self-contained cooling and heating capability and a tenting feature for sheltering and controlling the temperature at a given location. Warm air is directed out of a heat chamber through a telescopic tube arrangement which may be horizontally pivoted for improved heat direction. The tube arrangement may also be vertically tipped upwardly and downwardly to maximize directional control of heat output. Heat for melting snow may thereby be directed to specific locations. The tenting arrangement provides elevated and focused heating and little heat waste.
These together with other objects of the invention, along with various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed hereto and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated a preferred embodiment of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a vehicle constructed according to the invention.
FIG. 2 is a top view thereof.
FIG. 3 is a front view thereof.
FIG. 4 is a rear view thereof.
FIG. 5 is a top diagrammic view of the invention air path.
FIG. 6 is a side diagrammic view of the invention air path.
FIG. 7 is a close up side view of the tube distal end with canopy.
FIG. 8 is a side view of the pivot bar arrangement.
FIG. 9 is a close up view of the pivot bar tent end.
FIG. 10 is a side view of the pivot bar arrangement with tent.
FIG. 11 is a side view of a warm weather embodiment of the invention.
FIG. 12 is a top view thereof with tent deployed.
FIG. 13 is a front view thereof.
FIG. 14 is a rear view thereof.
FIG. 15 is a top diagrammic view of the air path for this embodiment.
FIG. 16 is a side diagrammic view thereof.
FIG. 17 is a top diagrammic view of the tube and heat chamber connection.
FIG. 18 is a side diagrammic view of the tube and heat chamber connection.
DETAILED DESCRIPTION OF INVENTION
Referring to the drawings in detail wherein like elements are indicated by like numerals, there is shown an equipment and control cab 40 and an air outlet unit 60 constructed according to the principles of the present invention. The cab 40 and outlet unit 60 may be mounted on a trailer or a vehicle 1 . In the present example shown, the invention is mounted on a vehicle.
There is shown a vehicle 1 constructed according to the principles of the present invention. The vehicle 1 includes a chassis 10 mounted upon front and rear axles 11 supporting front and rear road wheels 13 and 14 , respectively. The chassis 10 has a front 15 , a rear 16 , and two opposing sides 12 , said front and rear defining a vehicle longitudinal axis, said opposing sides 12 defining a transverse axis. The chassis 10 includes longitudinally extending beams 17 coincident with the longitudinal axis of the chassis supported on the axles, and cross members 18 coincident with the transverse axis of the chassis connecting the beams 17 . The foremost cross member is the front bumper 19 and the rearmost cross member is the rear bumper 20 .
The vehicle 1 may be longitudinally divided into three sections, a front driver's cab 30 , a middle equipment and control cab 40 , and an air outlet unit 60 . There is a first longitudinal gap 31 between the driver's cab 30 and the control cab 40 . There is a second longitudinal gap 48 between the control cab 40 and the air outlet unit 60 . The front driver's cab 30 is a conventional driving cab with normal ignition, steering, throttle, and braking controls.
The equipment and control cab 40 has a front wall 41 , a rear wall 42 , opposing sides 43 interconnecting the front and rear walls, a roof 44 and floor 45 , said walls, sides, roof and floor defining an equipment and control cab interior 46 . One or both opposing sides 43 contain a door 47 for access into the cab interior 46 . The vertical height of the walls and sides exceed the vertical height of the driver's cab 30 .
The equipment and control cab 40 contains a fiberglass air tunnel 50 with a forward end terminating in an open air scoop 51 formed in the equipment and control cab front wall 41 adjacent the control cab roof 44 and positioned above the driver's cab 30 . The fiberglass air tunnel 50 contains screening 53 adjacent to the air scoop 51 for preventing airborne objects and other debris from entering into the tunnel 50 . The tunnel 50 contains one or more intake fans 54 within the tunnel interior 55 immediately rearward of the screening 53 . The tunnel 50 extends through the control cab interior 46 adjacent the control cab roof 44 and terminates in an open outlet 52 in the control cab rear wall 42 . The open outlet 52 is interconnected to the air outlet unit 60 .
The control cab 40 contains a diesel-powered electric turbine 56 rated at 330 amps along with three 10 gallon hot water heaters 57 producing a hot fluid mixture of anti-freeze and water circulating through three hot water circulators 58 which in turn pump the heated fluid through a plurality of one inch radiator pipes 59 installed in the tunnel open outlet 52 . An exhaust fan 61 may be installed as well at the tunnel open outlet 52 to blow the heated air into the air outlet unit 60 .
The air outlet unit 60 is comprised of a heat chamber 62 and a telescopic ejection tube apparatus 80 attached thereto. The heat chamber 62 has a forward wall 63 , rearward wall 64 , two opposing side walls 65 interconnecting the forward and rear walls, a top 66 and a bottom 67 , said walls, top and bottom defining a heat chamber interior 68 . The heat chamber forward wall 63 has an opening 69 formed therein and adapted to be interconnected by ducting 70 with the central cab outlet 52 . The heat chamber top 66 has an opening 71 formed therein. A fan 73 is mounted within the heat chamber interior 68 and is positioned to blow heated air out through the top opening 71 .
The ejection tube apparatus 80 includes a caster bearing 81 , with a central opening 83 , fixedly attached on the heat chamber exterior 72 about the top opening 71 , said caster bearing central opening 83 being coincident with the heat chamber top opening 71 . In one embodiment of the invention a spring collar 82 is mounted onto the caster bearing 81 over the caster bearing central opening 83 . The ejection tube apparatus includes a telescoping tube 85 mounted on and pivotally attached to said caster bearing spring collar 82 . The caster bearing 81 is adapted to horizontally pivot plus or minus one hundred and eighty degrees thereby pivoting the tube 85 . The caster bearing 81 is driven by an electric motor 94 mounted on the heat chamber top 66 and electronically connected to and controlled within the equipment and control cab 40 .
The tube 85 is adapted to telescopically extend from eight to fifteen feet. This may be done manually or be powered by the electric motor 94 . The tube 85 has a proximal end 86 , a distal end 87 , and a cylindrical side wall 88 defining a tube interior 89 . The cylindrical side wall 88 has an opening 90 formed therein near to the tube proximal end 86 , said opening 90 providing direct access to the tube interior 89 . The tube opening 90 is coincident with the heat chamber top opening 71 . The tube distal end 87 may have a variable speed blower fan 91 contained therein to increase the heated air exhaust pressure.
In other embodiments of the invention, one or more lights 92 may be attached to the tube distal end 87 , said lights adapted for illumination of the exhaust air output target. A video camera eye 93 could also be attached to the tube distal end 87 so that an operator could view the exhaust output without leaving the cabs 30 or 40 .
It may be desirable to elevate or lower the distal end 87 of the tube arrangement 85 . In one embodiment of the invention this is accomplished by the installation of two electric, hydraulic or pneumatic pistons 95 on the caster bearing 81 and interconnected to the tube arrangement 85 on each side of the top opening 71 . Although a single piston 95 is adequate, it would be preferable to use two pistons 95 which would provide greater control under harsh weather conditions.
The tube 85 has a deployable canopy section 100 attached thereto and deployable with the tube distal end 87 . The canopy 100 section is comprised of two elongated attachment elements 101 adapted for attachment to each side of the tube side wall 88 adjacent the tube distal end 87 . Each attachment element 101 has a plurality of plastic strips 102 extending therefrom, each plastic strip being preferably six inches wide and approximately four feet long. The plastic strips 102 are easily bundled and stowed on the vehicle when not in use. The canopy section 100 is adapted to focus heat exhaust from the tube 85 into a defined area, e.g., a snow covered hydrant.
The present invention may also be adapted for use in warm weather. The invention is adapted to set up a tent 130 on each side of the vehicle 1 . Two sets of four hydraulic tent pistons 22 are installed on each side of the vehicle chassis 10 , each set being comprised of one on the front bumper 19 , one on the rear bumper 20 , one in the first gap 31 and the last in the second gap 48 . Each hydraulic tent piston 22 is connected to a steel pivotal bar arrangement 110 , comprised of an elongated base element 111 fastened to a chassis cross member 18 , each base element having an inside end 112 and an outside end 113 , said ends defining a longitudinal axis which is parallel to the longitudinal axis of a cross member 18 . The base element outside end 113 is that end attached adjacent the chassis side 12 . The pivotal bar arrangement 110 is further comprised of an elongated pivot bar 114 having two ends, one a pivot end 115 and the other a tent end 116 . The pivot bar pivot end 115 is pivotally joined to the base element inside end 112 . Each hydraulic tent piston 22 is attached at one end to the base element 111 and at the other end to the pivot bar 114 . Elongated and hollow aluminum extender pipes 120 are attachable to the pivot bar tent ends 116 . Each pivot bar 114 has a radial flange stop element 117 formed therein a desired distance from the pivot bar tent end 116 .
Elongated and hollow aluminum extender pipes 120 are attachable to the pivot bar tent ends 116 up to the stop elements 117 . The extender pipes 120 have a diameter slightly greater than the pivot bars 114 and less than the stop elements 117 . For security several holes 121 are drilled through the diameter of the extender pipes 120 near to an extender pipe engagement end 122 . Corresponding holes 118 are drilled through the diameters of the pivot bar between the stop elements 117 and the pivot bar tent ends 116 . Engagement clasping pins 123 are adapted to be inserted through the holes 118 , 121 to secure the extender pipes 120 to the pivot bars 114 .
A tent 130 would be deployable on each side of the vehicle 1 . Each tent would have looping 131 about its external surface 132 for engagement with the extender pipes 120 . The tents 130 would be made from a lightweight, insulated and fireproof material.
In the warm weather embodiment of the present invention, the ejection tube 85 is removed. A fiber glass box 140 is installed over the air outlet unit top 66 . The box 140 has a forward wall 141 , a rear wall 142 , two opposing side walls 143 and a top 144 , the air outlet unit top 66 acting as a box floor. One or two air conditioning units 145 are installed in each side wall 143 . The air conditioning units 145 draw in outside air through the air tunnel 50 and air outlet unit top opening 71 . Each tent 130 is either partially draped over the box 140 or has openings fitted about the air conditioning units.
It is understood that the above-described embodiment is merely illustrative of the application. Other embodiments may be readily devised by those skilled in the art which will embody the principles of the invention and fall within the spirit and scope thereof.
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A vehicle with a self-contained cooling and heating capability and a tenting feature for sheltering and controlling the temperature at a given location. Warm air is directed out of a heat chamber through a telescopic tube arrangement which may be horizontally piovoted for improved heat direction. The tube arrangement may also be vertically tipped upwardly and downwardly to maximize directional control of heat output. Heat for melting snow may thereby be directed to specific locations. The tenting arrangement provides elevated and focused heating and little heat waste.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a tiller which is operable with a variable driving force and under variable tilling conditions, depending on the soil.
2. Description of the Related Art
A small tiller as disclosed in, for example, Japanese Utility Model Laid-Open Publication No. SHO-57-86502 is known as a controlled machine having tilling claws attached to a tilling shaft rotatably for cultivating the soil with the forward movement of the machine, as well as allowing it to run on a road. The machine has a plurality of appropriately spaced apart tilling claws attached to the tilling shaft extending transversely under its main body, a rearwardly extending operating handlebar, and a resistance bar extending rearwardly and downwardly from its main body.
As the tilling claws serve also as traveling wheels, however, the machine requires a great deal of labor and skill for its operation, since the nature of the soil may disable it to keep a good balance between its driving force and tillage, and call for a change of the tilling conditions. If the soil is hard, the machine suffers from a serious lowering of its operability due to a dashing phenomenon, since the tilling claws do not cut into the ground, but roll thereon and cause the machine to move forward uselessly. If the soil is soft, the machine has a lower working efficiency, as it is likely to work on the soil to an unnecessary extent and have a lower driving force.
A small tiller as disclosed in, for example, Japanese Utility Model Laid-Open Publication No. HEI-6-3002 is known as having been devised to solve those problems. The tiller has a connecting shaft connected to a tilling shaft, which is the output shaft of a transmission, and carrying tilling claws on its portion close to the transmission. The connecting shaft also carries thereon a planetary gear mechanism composed of a sun gear formed on its middle portion, a plurality of planet gears meshing with the sun gear and gear shafts each attached rotatably to the center of one of the planet gears. Traveling wheels are attached to the gear shafts of the planetary gear mechanism by bosses. A ring gear is rotatably fitted to the connecting shaft. The ring gear has a toothed inner periphery meshing with the planet gears. The ring gear is secured to a fender fixed to the transmission. The rotation of the tilling shaft is transmitted to the traveling wheels by the planetary gear mechanism, so that the traveling wheels may be rotated at a reduced speed relative to the tilling claws rotating with the tilling shaft. As the wheels have a fixed reduction ratio relative to the tilling shaft, however, the wheels have a fixed driving force for moving the machine forward, and under certain soil conditions, therefore, it is impossible to obtain the desired driving force for achieving any adequate tilling work. The tiller is so designed that a part of the planetary gear mechanism may be altered in structure to reverse the rotation of the traveling wheels relative to the tilling claws, but its structural alteration is a large-scaled and complicated job.
SUMMARY OF THE INVENTION
It is, therefore, an object of this invention to provide a tiller which can always maintain stability in operation to achieve an improved finish of tilling, a reduction of dashing and an improved ability to move forward irrespective of the conditions of the soil.
According to an aspect of this invention, there is provided a tiller for cultivating the soil, having a power source, a tilling shaft rotatable by a driving force supplied to it from the power source through a power transmission, and a plurality of tilling claws carried on the tilling shaft, the tilling shaft being a concentric dual-shaft structure having a hollow outer shaft and an inner shaft extending through the outer shaft, the inner shaft having its rotating speed and/or its direction of rotation variable relative to the outer shaft.
If the rotating speed of the inner shaft or its direction of rotation is altered relative to the outer shaft, it is easily possible to alter the tilling conditions as required to suit the nature of the soil of a field and thereby obtain the desired tillage and tilling speed, so that the tiller of this invention can maintain stability in operation despite any change in the nature of the soil. The alteration of the rotating speed of the inner shaft is particularly useful, as it makes it possible to select any tillage and tilling speed from a finely divided range to thereby obtain the soil which is suitable for growing any of various kinds of crops.
The power transmission may be composed of a first power transmission system for transmitting a driving force from the power source to the outer shaft and a second power transmission system for transmitting a driving force from the power source to the inner shaft, the second power transmission system including a hydrostatic transmission composed of a hydraulic pump and a hydraulic motor, as will be described more specifically. The hydrostatic transmission makes it possible to change the rotating speed of the inner shaft in a stepless way and control its direction of rotation selectively as desired.
In a preferred form, the outer and inner shafts are fitted with a plurality of tilling claws. The tiller can easily be moved backward on the ground if the inner shaft is rotated at an increased speed in the opposite direction to the outer shaft. The dashing of the tiller can be prevented during the tilling of hard soil by the rotation of the outer and inner shafts in the same direction if the inner shaft is rotated at a lower speed than the outer shaft, since the force for driving the tiller by the tilling claws fitted on the outer shaft is restrained by the claws on the inner shaft.
A side disk is fitted on each of the opposite ends of the inner shaft, and a plurality of tilling claws are fitted on the outer shaft. Each side disk is provided on its inner surface with a plurality of upstanding plates each lying at an angle to the radius of the disk for producing a greater amount of friction with the soil. The friction force produced in the soil by the upstanding plates on the side disks enables the tiller to remain stable on both sides throughout its operation to thereby achieve an improved straight drive. If the rotating speed of the side disks on the inner shaft or their direction of rotation is altered relative to the tilling claws on the outer shaft, it is possible to vary the driving force of the side disks as desired, so that the tilling conditions can easily be altered to suit the nature of the soil to realize any desired tillage and tilling speed. The alteration of the rotating speed of the side disks is particularly useful, since it makes it possible to select any tilling speed from a finely divided range and thereby control tillage as desired. Thus, this invention makes it possible to realize an adequate tilling speed for achieving an improved operating efficiency and the desired control of tillage for making the soil suitable for growing any of various kinds of crops.
BRIEF DESCRIPTION OF THE DRAWINGS
A preferred embodiment of this invention will now be described in detail, by way of example only, with reference to the accompanying drawings, in which:
FIG. 1 is a side elevational view of a small tiller embodying this invention;
FIG. 2 is a circuit diagram showing the transmission of power in the tiller shown in FIG. 1;
FIG. 3 is a front elevational view of a lower portion of the tiller;
FIG. 4 is a view similar to FIG. 3, but showing a different form of side disks;
FIG. 5 is an enlarged sectional view of the upper casing of the tiller shown in FIG. 3;
FIG. 6 is an enlarged sectional view of the lower casing of the tiller shown in FIG. 3;
FIG. 7 is a horizontal sectional view of the upper casing of the tiller shown in FIG. 3;
FIG. 8 is a horizontal sectional view of the hydrostatic transmission shown in FIG. 1;
FIG. 9 is a view showing an oil passage in the hydrostatic transmission shown in FIG. 8;
FIG. 10 is a front elevational view of one of the side disks shown in FIG. 3;
FIG. 11 is a sectional view taken along the line 11 — 11 of FIG. 10;
FIG. 12 is a view showing a mechanism for adjusting the hydrostatic transmission;
FIG. 13 is an enlarged sectional view taken along the line 13 — 13 of FIG. 12;
FIGS. 14A and 14B are a set of views illustrating the adjustment of inclination of an inclined plate by the lever shown in FIG. 12;
FIG. 15 is a view showing an arrangement of parts for power transmission;
FIG. 16 is a diagram showing a first pattern of operation for the power transmission circuit shown in FIG. 2;
FIGS. 17A to 17 C are a set of views showing the operation of the hydrostatic transmission;
FIG. 18 is a diagram similar to FIG. 16, but showing a second pattern of operation; and
FIGS. 19A to 19 C are a set of views for explaining the conditions which are suitable for the soil to be cultivated by the tiller embodying this invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following description is merely exemplary in nature and is in no way intended to limit the invention, its application or uses.
Referring to FIG. 1, a small tiller 10 has an engine 12 as a power source, a gear casing 15 mounted under the engine 12 for transmitting power from the engine 12 to a plurality of tilling claws 13 and 14 , a hydrostatic transmission 16 mounted in front of the gear casing 15 , a handle post 17 extending rearwardly and upwardly from the gear casing 15 , a handlebar 18 attached to the top of the handle post 17 and a clutch lever 19 attached to the handlebar 18 . A fuel tank is shown at 22 , an engine cover at 23 , an air strainer at 24 , and a pair of side disks at 26 (only one of which is shown), and a fan shown at 28 has a cover not shown.
FIG. 2 is a diagram showing the transmission of power in the tiller. A power transmission 29 for transmitting power from the engine 12 to a tilling shaft (to be described), to which the tilling claws 13 and 14 (FIG. 1) are attached, includes a crank gear 32 connected to the distal end of a crankshaft 31 extending from the engine 12 . A plurality of planet gears 33 mesh with the crank gear 32 . The planet gears 33 are rotatably supported by a planet carrier 34 . The planet gears 33 mesh with a ring gear 35 . A plurality of brake shoes 36 are engageable with the inner periphery of the ring gear 35 . A first bevel gear 37 is attached to the planet carrier 34 . A second bevel gear 38 meshes with the first bevel gear 37 . The second bevel gear 38 has a first supporting shaft 41 .
The first supporting shaft 41 carries an outer drive sprocket 42 thereon. An outer driven sprocket 44 is connected to the outer drive sprocket 42 by an outer drive chain 43 . The outer driven sprocket 44 has a second supporting shaft 45 . A pair of transversely spaced apart outer drive gears 46 are carried on the second supporting shaft 45 . A pair of transversely spaced apart outer driven gears 48 mesh with the outer drive gears 46 , respectively. The outer driven gears 48 have outer shafts 47 which are rotatable with the tilling claws 13 and 14 . A system for transmitting power from the engine 12 to the outer shafts 47 is a first power transmission system 49 (which excludes the engine 12 and the outer shafts 47 ).
A third bevel gear 51 is carried on the first supporting shaft 41 . A fourth bevel gear 52 meshes with the third bevel gear 51 . The fourth bevel gear 52 has a third supporting shaft 53 . A pump drive gear 54 is carried on the third supporting shaft 53 . A pump driven gear 55 meshes with the pump drive gear 54 . The pump driven gear 55 has a pump axle 56 . The pump axle 56 is connected to the hydrostatic transmission (HST) 16 . The HST 16 effects a stepless change of the rotating speed of the pump axle 56 and rotates a motor axle 57 by varying its direction of rotation as desired.
The motor axle 57 carries a motor drive gear 61 thereon. A motor driven gear 62 meshes with the motor drive gear 61 . The motor driven gear 62 has a fourth supporting shaft 63 . A fifth bevel gear 64 is carried on the fourth supporting shaft 63 . A sixth bevel gear 65 meshes with the fifth bevel gear 64 . The sixth bevel gear 65 has a fifth supporting shaft 66 . The fifth supporting shaft 66 is connected about the first supporting shaft 41 rotatably relative to it. An inner drive sprocket 67 is carried on the fifth supporting shaft 66 . An inner driven sprocket 72 is connected to the inner drive sprocket 67 by an inner drive chain 68 . The inner driven sprocket 72 is connected to an inner shaft 71 extending through the outer shafts 47 which are hollow. Ball bearings are shown at 74 a to 74 g , and needle bearings at 75 a and 75 b . A system for transmitting power from the engine 12 to the inner shaft 71 is a second power transmission system 76 (which excludes the engine 12 and the inner shaft 71 ).
FIG. 3 shows examples of tilling claws and side disks on the tiller 10 . The tiller 10 has the gear casing 15 situated in its central portion. The gear casing 15 has a lower casing portion 15 a from which the hollow outer shafts 47 project laterally in the opposite directions. A plurality of tilling claws 13 each curved inwardly at both ends and a plurality of tilling claws 14 each curved outwardly at both ends are attached to the outer shafts 47 by brackets 77 . The inner shaft 71 extends transversely through the gear casing 15 and the outer shafts 47 . Each side disk 26 has a boss 83 into which the inner shaft 71 is connected at one end. An upper portion of the gear casing 15 is shown at 15 b , and a clutch casing at 15 c . The construction of the side disks 26 will be described later with reference to FIGS. 10A and 10B.
FIG. 4 shows other examples of tilling claws and side disks on the tiller 10 , the side disks being of the same construction with known side disks. Two outermost tilling claws 14 are attached to the inner shaft 71 by two brackets 81 , respectively. In the other aspects of construction, the tiller 10 shown in FIG. 4 is equal to that shown in FIG. 3 .
FIG. 5 is a sectional view showing the arrangement of gears in the upper casing portion and clutch casing shown in FIG. 3 . Each of the two transversely spaced apart planet gears 33 in the clutch casing 15 c is attached to the planet carrier 34 by a rotary shaft 85 . The planet carrier 34 is composed of a disk portion 86 and a shaft portion 87 fitted to the center of the disk portion 86 and having an end splined to the first bevel gear 37 . The shaft portion 87 is supported rotatably by the ball bearing 74 b on the clutch casing 15 c . The ring gear 35 is composed of a disk portion 88 having an inner periphery engaging with the planet gears 33 and a cylindrical portion 91 extending from the outer periphery of the disk portion 88 . The brake shoes 36 are engageable with the inner peripheral surface of the cylindrical portion 91 of the ring gear 35 for holding the ring gear 35 against rotation in the clutch casing 15 c . The planet gears 33 , rotary shafts 85 , planet carrier 34 , ring gear 35 , and brake shoes 36 form a clutch mechanism 92 .
The clutch mechanism 92 is so operated that when the brake shoes 36 stay away from the cylindrical portion 91 of the ring gear 35 , the rotation of the crankshaft 31 is transmitted to the ring gear 35 by the planet gears 33 , but not to the planet carrier 34 . If the brake shoes 36 are held against the inner surface of the cylindrical portion 91 , the rotation of the ring gear 35 is stopped, and the rotation of the crankshaft 31 is transmitted to the planet carrier 34 by the planet gears 33 , whereby the first bevel gear 37 is rotated. A semiclutched situation occurs if the rotation of the ring gear 35 is not completely stopped by the brake shoes 36 .
Description will now be made of the arrangement of gears, etc. in the upper casing portion 15 b . The second bevel gear 38 , outer drive sprocket 42 , and third bevel gear 51 are splined to the large diameter portion 41 a of the first supporting shaft 41 . The first supporting shaft 41 has at both ends thereof small diameter portions 41 b supported rotatably by the ball bearings 74 c on the upper casing portion 15 b . The sixth bevel gear 65 is splined to the fifth supporting shaft 66 and has its opposite ends secured to the fifth supporting shaft 66 by retaining rings 93 . The fifth supporting shaft 66 is supported rotatably by the needle bearings 75 a on the medium diameter portion 41 c of the first supporting shaft 41 . The fifth supporting shaft 66 has the inner drive sprocket 67 as an integral part thereof. A thrust bearing is shown at 94 , and collars at 95 and 96 .
FIG. 6 is a vertical sectional view of the lower portion 15 a of the gear casing 15 shown in FIG. 3 . The outer driven sprocket 44 and the outer drive gears 46 are splined to the large diameter portion 45 a of the second supporting shaft 45 , as shown in FIG. 6. A collar for positioning the outer driven sprocket 44 is shown at 44 a . The second supporting shaft 45 has at both ends thereof small diameter portions 45 b at which it is supported rotatably by the ball bearings 74 d on the lower casing portion 15 a . The outer shafts 47 are mounted rotatably by the ball bearings 74 e on the lower casing portion 15 a . Each outer shaft 47 is a hollow shaft held against rotation in a bracket 77 by a key 97 (only the key for one of the shafts is shown), and held against axial displacement by a bolt 98 (only the bolt for one of the shafts is shown). Oil seals are shown at 47 a , and each bracket 77 has a key groove 101 for the insertion of the key 97 . Each bolt 98 is locked by a nut 102 (only the lock nut for one of the bolts is shown), and oil seals are shown at 103 . The inner shaft 71 is supported in the outer shafts 47 rotatably by the needle bearings 75 b provided on the inner surfaces of the outer shafts 47 . The inner driven sprocket 72 is splined to the middle portion of the inner shaft 71 . A stop ring 104 is provided at one end of the inner driven sprocket 72 for restraining its movement in one axial direction. A thrust bearing 105 is interposed between each outer shaft 47 and the middle portion of the inner shaft 71 . The outer shafts 47 , inner shaft 71 , and needle bearings 75 b form a tilling shaft 106 .
FIG. 7 is a top plan view, partly in section, of the upper portion of the gear casing 15 . The third supporting shaft 53 lies at right angles to the first supporting shaft 41 and is connected thereto by the third and fourth bevel gears 51 and 52 . The third supporting shaft 53 is supported by the ball bearings 74 f on the upper casing portion 15 b . The third supporting shaft 53 is splined at one end to the pump drive gear 54 . The fourth supporting shaft 63 lies at right angles to the fifth supporting shaft 66 fitted about the first supporting shaft 41 and is connected to the fifth supporting shaft by the fifth and sixth bevel gears 64 and 65 . The fourth supporting shaft 63 is supported rotatably by the ball bearings 74 g on the upper casing portion 15 b , and is splined at one end to the motor driven gear 62 .
FIG. 8 is an enlarged top plan view, partly in section, of the HST 16 in the tiller. The HST 16 has a base 107 mounted to the gear casing 15 (see FIG. 7 ), a casing 108 attached to the base 107 , and a hydraulic pump 110 and a hydraulic motor 120 having their principal parts located within the base 107 and the casing 108 , as shown in FIG. 8 . The base 107 and the casing 108 support the pump axle 56 and the motor axle 57 rotatably. The hydraulic pump 110 is a device for generating a hydraulic pressure by the rotation of the pump axle 56 . The hydraulic pump 110 is composed of the pump axle 56 , a cylinder block 112 splined to the pump axle 56 and having a plurality of cylinders 111 , a plurality of plungers 113 each fitted slidably in one of the cylinders 111 , an inclined plate 114 contacting the ends of the plungers 113 , an inclined plate shaft 151 supporting the inclined plate 114 (as will be described), springs 116 urging the plungers 113 against the inclined plate 114 , and a handle 117 attached to the inclined plate shaft 151 for altering the inclination of the inclined plate 114 . Each cylinder 111 has a port 118 through which oil is allowed to flow between the cylinder and an oil passage formed in the base 107 , but not shown. The inclined plate 114 is a thrust bearing having one of its track disks secured to the inclined plate shaft 151 , while the other contacts the ends of the plungers 113 .
The hydraulic motor 120 is a device for rotating the motor axle 57 by the hydraulic pressure generated by the hydraulic pump 110 . The hydraulic motor 120 is composed of the motor axle 57 , a cylinder block 122 splined to the motor axle 57 and having a plurality of cylinders 121 , a plurality of plungers 123 each fitted slidably in one of the cylinders 121 , an inclined plate 124 contacting the ends of the plungers 123 , and springs 125 urging the plungers 123 against the inclined plate 124 . Each cylinder 121 has a port 128 through which oil is allowed to flow between the cylinder and an oil passage formed in the base 107 , but not shown. The inclined plate 124 is a thrust bearing having one of its track disks secured to the casing 108 , while the other contacts the ends of the plungers 123 .
FIG. 9 is a diagram showing the oil passages in the HST of the tiller. The hydraulic pump 110 has the cylinders 111 formed along the circumference of the cylinder block 112 . The base 107 (see FIG. 8) has a first arcuate groove 131 lying over some of the ports 118 of the cylinders 111 . The base 107 also has a second arcuate groove 132 lying over some of the remaining ports 118 . The hydraulic motor 120 has the cylinders 121 formed along the circumference of the cylinder block 122 . The base 107 (see FIG. 9 ) has a first arcuate groove 133 lying over some of the ports 128 of the cylinders 121 . The base 107 also has a second arcuate groove 134 lying over some of the remaining ports 128 . The first arcuate groove 131 above the pump and the first arcuate groove 133 above the motor are connected to each other by a first oil passage 135 . The second arcuate groove 132 above the pump and the second arcuate groove 134 above the motor are connected to each other by a second oil passage 136 .
FIGS. 10 and 11 show one of the two side disks 26 shown in FIG. 3 . Referring to FIG. 10, the side disk 26 is composed of a disk portion 141 curved outwardly of the tiller 10 (see FIG. 1 ), a plurality of upstanding plates or lugs 142 attached to the inner surface of the disk portion 141 close to its outer edge for producing a greater amount of friction with the soil, and a boss 83 extending inwardly from the center of the disk portion 141 . Each lug 142 has a base 143 attached to the disk portion 141 , and an upstanding portion 144 projecting from the base 143 . The upstanding portion 144 lies at an angle a of, for example, from 30° to 60° to a line RL extending along the radius of the disk. FIG. 10 also includes an arrow showing the direction of normal rotation of the side disk 26 in which the tiller 10 is moved forward. The upstanding portion 144 of each lug 142 is substantially rectangular, as shown in FIG. 11 . The other side disk 26 is similar to the side disk 26 shown in FIG. 10, but the upstanding portion 144 of each of its lugs 142 has an angle of −α to the line RL, so that the inclination of its upstanding portions 144 relative to the direction of its normal rotation may be equal to that of the side disk 26 shown in FIG. 10 . The inclination of the upstanding portions 144 of the lugs 142 on one side disk 26 at an angle of α to the lines RL and the inclination of the upstanding portions 144 of the lugs 142 on the other side disk 26 at an angle of −α to the lines RL as described enable each upstanding portion 144 to have a greater area of contact with the ground to thereby prevent the side disks 26 from sinking undesirably in the ground, while also striking against the ground more effectively to produce a greater traction, when the side disks 26 are rotated in the direction of their normal rotation, than in the event that 0°≦α<30°, or 60°<α≦90°.
FIG. 12 is a top plan view of the HST for the tiller embodying this invention and a mechanism for adjusting the inclination of the inclined plate shown in FIG. 8 . The inclined plate shaft 151 is rotatably mounted on the casing 108 of the HST 16 . A sectorial lever 152 has a base end 153 secured to the shaft 151 to which the handle 117 for adjusting the inclination of the inclined plate is also secured. The lever 152 has an arcuate end 154 having an arcuate guide hole 155 . The lever 152 has a side edge 157 to which a coiled tension spring 158 is fastened at one end. A wire 162 is connected at one end to the other side edge 161 of the lever 152 . The other end of the wire 162 is connected to a lever 163 attached to the handlebar 18 for adjusting the inclination of the inclined plate by pulling the wire. The lever 152 is shown in its position in which the inclined plate 114 is not inclined, so that the inner shaft 71 (see FIG. 3) may be out of rotation, as will be explained. The other end of the spring 158 is fastened to the casing 108 by a fitting 164 . The wire 162 has an outer tube 165 , and an inner wire 166 inserted slidably in the outer tube 165 . The outer tube 165 has one end secured to the casing 108 by a bracket 167 . A friction generator 168 extends through the guide hole 155 and contacts the lever 152 on both sides thereof to produce a friction (or resistance) force when the lever 152 is swung.
Referring to FIG. 13, the inclined plate shaft 151 is shaped like a crankshaft. It has a crank portion 171 to which the inclined plate 114 is mounted. The crank portion 171 is supported at both ends on the casing 108 by bearings 172 . Stop rings for the bearings 172 are shown at 173 , an oil seal at 174 , and a plug at 175 . A cylindrical member is shown at 176 for attaching the handle 117 for adjusting the inclination of the inclined plate and the lever 152 to the inclined plate shaft 151 .
As is obvious from the foregoing, the inclination of the inclined plate 114 can be adjusted by using either the handle 117 or the lever 163 (FIG. 12 ). Description will now be made with reference to FIGS. 14A and 14B of a method in which the lever 163 is used for adjusting the inclination of the inclined plate 114 .
If the lever 163 is turned counterclockwise from its position shown in FIG. 12 (as shown by phantom lines in FIG. 14A) to its position shown by solid lines, the wire 162 is loosened. The sectorial lever 152 is caused by the tensile force of the tension spring 158 to swing clockwise. The inclined plate shaft 151 secured to the base end of the lever 152 is rotated in the same direction with the lever 152 , and the handle 117 secured to the shaft 151 is inclined by rotating in the same direction, whereby the inclined plate 114 is inclined into its position in which the inner shaft is rotated in the direction of its normal rotation (as will be described in further detail). If the lever 163 is turned clockwise from its position shown in FIG. 12 (as shown by phantom lines in FIG. 14 B), the lever 152 is caused by the wire 162 to swing counterclockwise by overcoming the tensile force of the tension spring 158 , as shown in FIG. 14 B. The inclined plate shaft 151 is rotated in the same direction with the lever 152 , and the handle 117 is inclined by rotating in the same direction, whereby the inclined shaft 114 is inclined into its position in which the inner shaft is rotated in the reverse direction (as will be described in further detail).
FIG. 15 is a view showing the layout of parts for the power transmission in the tiller. The engine 12 in the tiller 10 is so mounted that its output shaft, or crankshaft 31 may be vertical. The shaft portion 87 of the planet carrier 34 and the first bevel gear 37 connected to the shaft portion 87 are positioned below the crankshaft 31 coaxially therewith. The pump and motor axles 56 and 57 extend horizontally toward the fan 28 . The third supporting shaft 53 is connected to the pump axle 56 by the pump drive and driven gears 54 and 55 , and extends horizontally toward the first supporting shaft 41 . The third supporting shaft 53 terminates in the fourth bevel gear 52 . The fourth supporting shaft 63 is connected to the motor axle 57 by the motor drive and driven gears 61 and 62 , and likewise extends horizontally toward the first supporting shaft 41 . The fourth supporting shaft 63 terminates in the fifth bevel gear 64 . The first, fourth and fifth bevel gears 37 , 52 and 64 are operationally connected to the first supporting shaft 41 . The rotation of the first supporting shaft 41 is transmitted to the outer shafts 47 by the outer drive chain 43 , and to the inner shaft 71 by the inner drive chain 68 .
As the crankshaft 31 and the third and fourth supporting shafts 53 and 63 are all so mounted as to terminate adjacent to the first supporting shaft 41 from which a driving force is transmitted to the outer and inner shafts 47 and 71 mounted therebelow, the power transmission 29 of the tiller 10 is simple in construction, and is operable without causing any substantial mechanical loss. As the power transmission 29 is compact, the tiller 10 is small and light in weight, and is operable with an improved efficiency and a low fuel consumption.
Description will now be made of the operation of the power transmission 29 of the tiller 10 with reference to FIGS. 16 to 18 .
(1) Description will first be made of the mode in which the outer and inner shafts 47 and 71 are both rotated in the normal direction. In FIG. 16, the direction of rotation of the crankshaft 31 of the engine 12 is shown as direction A, and the direction of normal rotation of the outer shafts 47 as direction B. The rotation of the crankshaft 31 in the direction A is transmitted by the crank gear 32 and the clutch mechanism 92 to rotate the shaft portion 87 of the planet carrier 34 in the direction A if the clutch mechanism 92 is in its engaged position. Its rotation is transmitted by the first and second bevel gears 37 and 38 to rotate the first supporting shaft 41 in direction RB (the reverse of direction B). Its rotation is transmitted by the outer drive sprocket 42 , outer drive chain 43 , and outer driven sprocket 44 to rotate the second supporting shaft 45 in the direction RB. Its rotation is transmitted by the outer drive and driven gears 46 and 48 to rotate the outer shafts 47 in the normal direction B. The rotation of the first supporting shaft 41 is also transmitted to the third supporting shaft 53 by the third and fourth bevel gears 51 and 52 to rotate it in direction RA (the reverse of direction A). Its rotation is transmitted by the pump drive and driven gears 54 and 55 to rotate the pump axle 56 in the direction A.
FIGS. 17A to 17 C show the operation of the HST 16 in the power transmission of the tiller. FIG. 17A shows the flow of oil, and FIGS. 17B and 17C show the movements of the plungers 113 and the inclined plate 114 in the hydraulic pump 110 and the corresponding movements of the plungers 123 and the inclined plate 124 in the hydraulic motor 120 . For the convenience of description, only four have been chosen from the cylinders 111 , plungers 113 , ports 118 , cylinders 121 , plungers 123 , or ports 128 shown in FIGS. 8 and 9, and are shown at 111 a to 111 d , 113 a to 113 d (including 113 c and 113 d not shown), 118 a to 118 d , 121 a to 121 d , 123 a to 123 d (including 123 c and 123 d not shown), or 128 a to 128 d.
The rotation of the pump axle 56 for the hydraulic pump 110 in the direction A as shown in FIG. 16 causes the cylinder block 112 to rotate therewith in the direction A as shown by a white arrow in FIG. 17 A. If the inclined plate 114 is inclined by the handle 117 , or lever 163 shown in FIGS. 14A and 14B by an angle θ to a line L extending at right angles to the direction of movement of the plungers 113 a and 113 B as shown in FIG. 17B, the plungers 113 a and 113 b in the cylinders 111 a and 111 b facing the first arcuate groove 131 (FIG. 17A) move from right to left as shown by an arrow M in FIG. 17B, and retract into the cylinders 111 a and 111 b , respectively, as shown by arrows P and Q, while remaining in contact with the inclined plate 114 . As a result, the oil in the cylinders 111 a and 111 b flows out through the ports 118 a and 118 b into the first arcuate groove 131 shown in FIG. 17A, and from the groove 131 into the first arcuate groove 133 above the motor through the first oil passage 135 , as shown by arrows each having a solid line.
The oil flows from the first arcuate groove 133 into the cylinders 121 a and 121 b of the hydraulic motor 120 through the ports 128 a and 128 b , as shown in FIG. 17 A. The plungers 123 a and 123 b project from the cylinders 121 a and 121 b , respectively, as shown by arrows R and S, and move from right to left as shown by an arrow T in FIG. 17B, while remaining in contact with the inclined plate 124 . As a result, the cylinder block 122 is rotated in the direction A as shown by a thick solid arrow in FIG. 17A to cause the motor axle 57 to rotate in the same direction.
On the other hand, the plungers 113 c and 113 d in the cylinders 111 c and 111 d facing the second arcuate groove 132 above the hydraulic pump 110 as shown in FIG. 17A move in the opposite direction to the arrow M and project from the cylinders 111 c and 111 d , while remaining in contact with the inclined plate 114 . The oil in the cylinders 121 c and 121 d of the hydraulic motor 120 flows out through the ports 128 c and 128 d , second arcuate groove 134 above the motor, second oil passage 136 , second arcuate groove 132 above the pump, and ports 118 c and 118 d , as shown by arrows having a solid line, and is drawn into the cylinders 111 c and 111 d . As a result, the plungers 123 c and 123 d retract into the cylinders 121 c and 121 d , respectively.
As shown in FIG. 17B, as the inclined plate 114 has a larger angle θ of inclination, the plungers 113 a to 113 d of the hydraulic pump 110 have a higher speed of axial movement, and oil flows into and out of the cylinders 121 a to 121 d of the hydraulic motor 120 at a higher speed, so that the motor axle 57 has a gradually increasing speed of rotation in the direction A. As the inclined plate 114 has a smaller angle θ of inclination (θ>0), the plungers 113 a to 113 d of the hydraulic pump 110 have a lower speed of axial movement, and oil flows into and out of the cylinders 121 a to 121 d of the hydraulic motor 120 at a lower speed, so that the motor axle 57 has a gradually decreasing speed of rotation in the direction A. If the angle θ of inclination of the inclined plate 114 is reduced to zero, the plungers 113 a to 113 d cease to move relative to the cylinders 111 a to 111 d , oil ceases to flow between the hydraulic pump and motor 110 and 120 , and the plungers 123 a to 123 d cease to move, so that the motor axle 57 stops its rotation.
Referring to FIG. 16, the rotation of the motor axle 57 in the direction A is transmitted by the motor drive and driven gears 61 and 62 to rotate the fourth supporting shaft 63 in the direction RA, and its rotation is transmitted by the fifth and sixth bevel gears 64 and 65 to rotate the fifth supporting shaft 66 in the direction B. Its rotation is transmitted by the inner drive sprocket 67 , inner drive chain 68 , and inner driven sprocket 72 to rotate the inner shaft 71 in the direction B of normal rotation.
Thus, as the inclination θ of the inclined plate 114 shown in FIG. 17B is increased by using the handle 117 shown in FIG. 8, the motor axle 57 of the HST 16 shown in FIG. 16 has a higher speed of rotation, and the inner shaft 71 has a gradually increasing speed of normal rotation. As the inclination θ of the inclined plate 114 is decreased (θ>0) by the handle 117 , the motor axle 57 has a lower speed of rotation, and the inner shaft 71 has a gradually decreasing speed of normal rotation. If the inclination θ of the inclined plate 114 is kept at an appropriate angle by the handle 117 , the outer and inner shafts 47 and 71 have an equal speed of normal rotation. Moreover, the inner shaft 71 stops its rotation if the inclination θ of the inclined plate 114 is reduced to zero by the handle 117 .
(2) Description will now be made of the mode in which the outer shafts 47 are rotated in the normal direction, while the inner shaft 71 is rotated in the reverse direction. The normal rotation of the outer shafts 47 has already been described at (1) above, and no repeated description thereof is made. With regard to the reverse rotation of the inner shaft 71 , the directions of rotation of the parts of the power transmission from the crankshaft 31 to the pump axle 56 have already been explained at (1) above with reference to FIG. 16, and no repeated description thereof is made, but description will be made of the directions of rotation of the parts after the motor axle 57 . Description will first be made of the operation of the HST 16 with reference to FIGS. 17A and 17B.
The rotation of the pump axle 56 of the hydraulic pump 110 in the direction A as shown in FIG. 17A causes the cylinder block 112 to rotate therewith in the same direction. If the inclined plate 114 is inclined by using the handle 117 , or lever 163 shown in FIGS. 14A and 14B by an angle of −θ to a line L as shown in FIG. 17C, the plungers 113 a and 113 b of the cylinders 111 a and 111 b facing the first arcuate groove 131 (FIG. 17A) above the pump move from right to left as shown by an arrow U in FIG. 17C, while remaining in contact with the inclined plate 114 . As a result, the plungers 113 a and 113 b project from the cylinders 111 a and 111 b , respectively, as shown by arrows V and W. As a result, oil flows from the cylinders 121 a and 121 b of the hydraulic motor 120 to the first arcuate groove 131 above the pump through the ports 128 a and 128 b , the first arcuate groove 133 above the motor, and the first oil passage 135 as shown by broken arrows in FIG. 17 A. The oil is drawn from the first arcuate groove 131 above the pump into the cylinders 111 a and 111 b of the hydraulic pump 110 through the ports 118 a and 118 b . As a result, the plungers 123 a and 123 b retract into the cylinders 121 a and 121 b , respectively, as shown by arrows X and Y, and are urged to move from left to right as shown by an arrow Z, while remaining in contact with the inclined plate 124 .
On the other hand, the plungers 113 c and 113 d move in the opposite direction to the arrow U (FIG. 17C) and retract into the cylinders 111 c and 111 d facing the second arcuate groove 132 above the hydraulic pump 110 as shown in FIG. 17A, while remaining in contact with the inclined plate 114 . As a result, oil flows from the cylinders 111 c and 111 d into the cylinders 121 c and 121 d through the ports 118 c and 118 d , the second arcuate groove 132 above the pump, the second oil passage 136 , the second arcuate groove 134 above the motor and the ports 128 c and 128 d , as shown by broken arrows. As a result, the plungers 123 c and 123 d project from the cylinders 121 c and 121 d , and move from right to left in the opposite direction to the arrow Z (FIG. 17 C), while remaining in contact with the inclined plate 124 . Thus, the cylinder block 122 is rotated in the direction RA as shown by a thick broken arrow to rotate the motor axle 57 in the same direction.
As the inclined plate 114 shown in FIG. 17C has a smaller angle of −θ (or a larger degree of inclination to the negative side), the plungers 113 a to 113 d of the hydraulic pump 110 have a higher speed of axial movement and oil flows into and out of the cylinders 121 a to 121 d of the hydraulic motor 120 at a higher speed, so that the motor axle 57 has a gradually increasing speed of rotation in the direction RA (FIG. 17 A). As the inclined plate 114 has a larger angle of −θ (θ>0) (or a smaller degree of inclination to the negative side), the plungers 113 a to 113 d of the hydraulic pump 110 have a lower speed of axial movement and oil flows into and out of the cylinders 121 a to 121 d of the hydraulic motor 120 at a lower speed, so that the motor axle 57 has a gradually decreasing speed of rotation in the direction RA.
Referring to FIG. 18, the rotation of the motor axle 57 in the direction RA is transmitted by the motor drive and driven gears 61 and 62 to rotate the fourth supporting shaft 63 in the direction A. Its rotation is transmitted by the fifth and sixth bevel gears 64 and 65 to rotate the fifth supporting shaft 66 in the direction RB. Its rotation is transmitted by the inner drive sprocket 67 , inner drive chain 68 , and inner driven sprocket 72 to rotate the inner shaft 71 in the direction RB opposite to the direction of rotation of the outer shafts 47 .
Thus, as the inclination −θ of the inclined plate 114 shown in FIG. 17C is decreased, the motor axle 57 of the HST 16 has a gradually increasing speed of reverse rotation, and the inner shaft 71 also has a gradually increasing speed of reverse rotation. As the inclination −θ of the inclined plate 114 is increased (−θ<0) the motor axle 57 has a gradually decreasing speed of reverse rotation, and the inner shaft 71 has, therefore, a gradually decreasing speed of reverse rotation.
Description will now be made with reference to FIGS. 19A to 19 C of the operating conditions which are suitable for the soil to be cultivated by the tiller 10 . If the soil is soft as shown in FIG. 19A, the outer and inner shafts are both rotated in the direction of normal rotation, and the inner shaft is rotated at a higher speed. This mode is obtained if the inclined plate is inclined by the handle, or lever over the angle at which the outer and inner shafts have an equal speed of rotation, as described before at (1) with reference to FIGS. 16, 17 A and 17 B. If the inner shaft has a higher speed of normal rotation, the tilling laws 13 and 14 attached to the outer shafts produce a smaller driving force on the soft soil. The side disks 26 attached to the inner shaft, however, produces a larger driving force, and the tilling claws 13 and 14 and the side disks 26 or 27 produce a larger total driving force F 1 (as shown by a white arrow), so that the tilling claws 13 and 14 are moved forward at a higher speed without working the soil to any undesirably large depth. Thus, the tiller 10 has a higher tilling rate and a higher working efficiency.
If the soil is hard as shown in FIG. 19B, the outer and inner shafts are both rotated in the direction of normal rotation, and the inner shaft is rotated at a lower speed. This mode is obtained if the inclined plate is inclined by an angle smaller than that at which the outer and inner shafts have an equal speed of rotation, as described before at (1) with reference to FIGS. 16, 17 A and 17 B. If the inner shaft has a lower speed of normal rotation, the tilling claws 13 and 14 produce a larger driving force on the hard soil. The side disks 26 , however, produce a smaller driving force and resist the driving force of the claws 13 and 14 . Thus, the claws 13 and 14 and the side disks 26 produce a smaller total driving force F 2 (as shown by a white arrow), so that no dashing of the tiller 10 may occur. When the soil is hard, it is alternatively possible to hold the inner shaft against rotation, or place it in reverse rotation, so that the side disks 26 or 27 may produce a still greater resistance, depending on the nature of the field to be cultivated. In either event, the tiller 10 can do an adequate tilling job with a higher efficiency without any fear of dashing.
The side disks 26 or 27 are also placed in reverse rotation for moving the tiller 10 backward. The tiller 10 can be moved backward if the inner shaft is rotated in reverse direction, and sometimes at a higher speed, while the outer shafts are rotated in normal direction. When the tiller 10 has reached an edge of a rectangular field after working the soil along one ridge, for example, the lever for adjusting the inclination of the inclined plate is operated to rotate the side disks 26 or 27 in reverse direction to move back the tiller 10 to a position in which the tiller 10 can make a turn, and the lever is operated again to rotate the side disks 26 or 27 in normal direction, so that the tiller can work the soil along a neighboring ridge. The backward movement of the tiller 10 by the reverse rotation of the inner shaft as described ensures an improved working efficiency, as it facilitates the cultivation of the soil even along any edge or corner of a field which has hitherto been difficult.
When the tiller 10 is, for example, transferred from one field to another as shown in FIG. 19C, the outer and inner shafts are both rotated in normal direction at a substantially equal speed. The tilling claws 13 and 14 and the side disks 26 or 27 are rotated at substantially the same speed to enable the tiller 10 to travel easily.
Although the foregoing description has been directed to the cases in which the soil is soft, or hard, and in which the tiller is transferred, it is not intended for limiting the scope of this invention, but it is alternatively possible to alter the rotating speed of the inner shaft and its direction of rotation in any other appropriate way depending on the nature of the soil to be cultivated. It is also possible to employ, for example, a throttle lever for varying the rotating speed of the outer shafts so that it may suit the nature of the soil. Although the hydrostatic transmission composed of a hydraulic pump and a hydraulic motor has been employed for changing the rotating speeds of the shafts, it is alternatively possible to employ a belt or traction drive type CVT for that purpose.
Obviously, various minor changes and modifications of the present invention are possible in the light of the above teaching. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.
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A tiller for cultivating soil has a power source and a tilling shaft mounted for undergoing rotation by a driving force supplied from the power source. The tilling shaft has a hollow outer shaft and an inner shaft extending through the outer shaft. The inner shaft has a variable rotating speed and/or direction of rotation relative to the outer shaft. A power transmission mechanism transmits a driving force from the power source to the tilling shaft. The power transmission mechanism has a first power transmission system for transmitting the driving force from the power source to the outer shaft and a second power transmission system transmitting the driving force from the power source to the inner shaft. The second power transmission system has a hydrostatic transmission comprised of a hydraulic pump and a hydraulic motor for effecting a stepless change of the rotating speed of the inner shaft as well as a selective change of its direction of rotation. Tilling claws are disposed on the tilling shaft for tilling soil.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention is broadly concerned with an improved method to aid in the diagnosis of autism, and a corresponding method of treating this condition in order to ameliorate the symptoms thereof. More particularly, the invention pertains to a diagnosis method wherein a body fluid sample (e.g., urine) is obtained and quantified for the presence of certain marker compounds such as tartaric acid; abnormally high quantities of one or more of the marker compounds is an indication of autism. In a treatment protocol, a patient suffering from autism is given an antifungal drug, which reduces the quantities of marker compounds and ameliorates the symptoms of autism.
2. Description of the Prior Art
Childhood autism is the most characteristic group of the broader persuasive developmental disorder category of childhood diseases. The cause of autism is unknown except for a small subgroup due to adenylosuccinic aciduria, a defect in purine metabolism. Autism is characterized by a behavioral syndrome often recognized between two and three years of age. The core of the syndrome is a deviant and/or retarded development of cognitive capacities and skills necessary for social relations, communication, fantasy, and symbolic thinking. Almost all autistic children do not reach independence as adults and 75% are deemed mentally retarded. Taurine aspartate, and glutonate are reported to be significantly elevated in the plasma of a significant fraction of autistic persons, and some have metabolic acidosis. Diagnosis of autism presents difficulties in its own right, and a number of modalities have been proposed primarily based upon psychiatric evaluations.
A number of different therapies have been attempted in an effort to cure autism or at least lessen the clinical symptoms thereof. Such have included drug therapies as well as psychiatric care and attempted counseling. In general, results of such treatments have been disappointing, and autism remains very difficult to effectively treat, particularly in severe cases.
SUMMARY OF THE INVENTION
The present invention provides a method of diagnosing the likelihood of autism in patients, and particularly children. Broadly speaking, the diagnostic method of the invention involves first obtaining from a patient a sample of a body fluid selected from the group consisting of urine, blood, saliva and cerebral spinal fluid. Such a sample is then analyzed to determine the quantity therein of at least one marker compound selected from the group consisting of citramalic acid, 5-hydroxy-methyl-2-furoic acid, 3-oxo-glutaric acid, furan-2,5-dicarboxylic acid, tartaric acid, furancarbonylglycine, arabinose, dihydroxyphenylpropionic acid, carboxycitric acid and phenylcarboxylic acid. Such marker compounds may inhibit normal Krebs cycle function.
In any case, once the quantities of one or more of the marker compounds are determined in the body fluid sample, these quantities are compared with normal quantities of the corresponding compounds found in the same type of body fluid sample in non-autistic individuals of approximately the same age as the patient in question. In this connection, a sufficient sampling of the respective body fluid type of normal individuals should be obtained so as to achieve statistical significance. Likewise, as used herein, a marker compound is generally deemed to be "abnormally high" when it is at least about two standard deviations greater than the mean of the statistically significant sampling of normal individuals for the marker compound in question. For example, if the body fluid being analyzed is urine, the mean of a given marker compound is determined from the analysis of urine samples from a statically significant sampling of non-autistic individuals. This is used as the standard or "normal" level for the given marker compound, and "abnormally high" amounts of the marker compound would generally be at least about two standard deviations greater than this mean value.
With particular reference to urine samples of children up to about 12 years in age, present data establishes that the respective marker compounds are abnormally high if present in at least one urine sample of a patient in the following amounts:
(a) at least about 10 mmol citramalic acid/mol creatinine in the urine sample;
(b) at least about 100 mmol 5-hydroxy-methyl-2-furoic acid/mol creatinine in the urine sample;
(c) at least about 300 mmol arabinose/mol creatinine in the urine sample;
(d) at least about 100 mmol furan-2,5-dicarboxylic acid/mol creatinine in the urine sample
(e) at least about 90 mmol tartaric acid/mol creatinine in the urine sample;
(f) at least about 100 mmol furancarbonylglycine/mol creatinine in the urine sample;
(g) at least about 1 mmol 3-oxo-glutaric acid/mol creatinine in the urine sample;
(h) at least about 250 mmol dihydroxyphenylpropionic acid/mol creatinine in the urine sample;
(i) at least about 50 mmol carboxycitric acid/mol creatinine in the urine sample; and
(j) at least about 100 mmol phenylcarboxylic acid/mol creatinine in the urine sample.
In actual practice, the diagnostic test of the invention is preferably carried out by analyzing urine samples of a patient for a plurality, and preferably all, of the marker compounds. It may be that in certain instances a given individual's urine will be abnormally high in a number of the compounds, but not all. Therefore, quantitation of all of the marker compounds and comparison with the mean normals is preferred. Likewise, the urine samples should be collected over a period of time, e.g., on a daily basis over a period of at least seven days.
The invention also relates to a method of treating an autistic patient in order to ameliorate certain symptoms of autism. Such method comprises the step of administering an antifungal drug to the patient. Although not essential, such drugs are generally administered orally. A preferred antifungal drug mycostatin may be employed, and is preferably given at a level of at least about 200,000 units per day for a period of at least seven days.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a gas chromatography-mass spectrometry (GC/MS) chromatogram obtained from an analysis of a urine sample of an autistic child and illustrating the concentrations of various trimethylsilyl (TMS) derivative compounds wherein the peaks are identified as follows: A, glycollic acid; B, oxalic acid; C, 3-hydroxyisobutyric acid; D, urea; E, phosphoric acid; F, succinic acid; G, deoxytetronic acid; H, citramalic acid; I, undecanoic acid (internal standard); J, unidentified; K, 3-hydroxyphenylacetic acid; L, 2-oxoglutaric acid; M, 4-hydroxyphenylacetic acid; N, furandicarboxylic acid; 0, furancarbonylglycine; P, tartaric acid; Q, arabinose; R, aconitic acid; S, hippuric acid; T, citric acid; U, dihydroxyphenylpropionic acid; V, vanillylmandelic acid; W, 3-indoleacetic acid; X, ascorbic acid; Y, citric acid analog; Z, uric acid; AA, unidentified; BB, 4-hydroxyhippuric acid;
FIG. 2 is a GC/MS chromatogram similar to that of FIG. 1 but illustrating the results using the urine sample of a normal child wherein the TMS derivative peaks are identified as follows: A, pyruvic; B, oxalic; C, urea; D, undecanoic; E, 3-hydroxyphenylacetic; F, 2-oxoglutaric; G, 4-hydroxyphenylacetic; H, aconitic; I,J, hippuric; K, citric; L, vanillylmandelic; and M, 3-hydroxyhippuric;
FIG. 3 is a GC/MS chromatogram giving the mass spectrum of a compound identified as the TMS derivative of 3-methyimalic acid found in the urine of an autistic patient, wherein the numbers within the graph represent the mass in Da of the ion fragments of the compound;
FIG. 4 is a GC/MS chromatogram giving the mass spectrum of the TMS derivative of authentic citramalic acid;
FIG. 5 is a GC/MS chromatogram giving the mass spectrum of a compound found in the urine of an autistic patient and which by comparison with the chromatogram of FIG. 4 is identified as citramalic acid TMS derivative;
FIG. 6 illustrates a possible mechanism for the formation of the ion fragments referred to in FIG. 3;
FIG. 7 is a comparative graph depicting the amounts of the TMS derivative of citramalic acid in normal patients and the autistic brothers described in Example 1;
FIG. 8 is a GC/MS chromatogram giving the mass spectrum of citric acid TMS derivative;
FIG. 9 is a GC/MS chromatogram giving the mass spectrum of isocitric acid TMS derivative;
FIG. 10 is a GC/MS chromatogram giving the mass spectrum of the perdeuterated TMS derivative of a citric acid analog;
FIG. 11 is a GC/MS chromatogram giving the mass spectrum of the non-perdeuterated TMS derivative referred to in FIG. 10;
FIG. 12 is a proposed fragmentation mechanism of citric acid, isocitric acid, and citric acid analog derivatives that yield 175 Da losses from the molecular ion;
FIG. 13 is a comparative graph depicting the amounts of the TMS derivative of the citric acid analog referred to in FIG. 11 in normal patients and the autistic brothers referred to in Example 1;
FIG. 14 is a GC/MS chromatogram giving the mass spectrum of 3-oxo-glutaric acid TMS derivative from the urine of an autistic child;
FIG. 15 is a GC/MS chromatogram giving the mass spectrum of the TMS derivative of authentic 3-oxoglutaric acid;
FIG. 16 is a GC/MS chromatogram giving the mass spectrum of the TMS derivative of 3-oxoglutaric acid;
FIG. 17 is a comparative graph depicting the amounts of the TMS derivative of tartaric acid in normal patients and the autistic brothers referred to in Example 1;
FIG. 18 is a GC/MS chromatogram giving the mass spectrum of the TMS derivative of a phenylcarboxylic acid found in high concentration in the urine samples of the brothers referred to in Example 1;
FIG. 19 is a comparative graph depicting the amounts of the TMS derivative of the phenylcarboxylic acid referred to in FIG. 16 in normal patients and the autistic brothers referred to in Example 1;
FIG. 20 is a GC/MS chromatogram giving the mass spectrum of the TMS derivative of arabinose found in the urine of the autistic brothers referred to in Example 1;
FIG. 21 is a GC/MS chromatogram giving the mass spectrum of the TMS derivative of authentic arabinose;
FIG. 22 is a comparative graph depicting the amounts of the TMS derivative of arabinose in normal patients and the autistic brothers referred to in Example 1;
FIG. 23 sets forth the structures of normal and abnormal Krebs cycle compounds found in the urine samples of the autistic brothers referred to in Example 1;
FIG. 24 is a comparative graph depicting the amounts of the TMS derivative of the 5-hydroxy-methyl-2-furoic acid in normal patients and in autistic patents referred to in Example 2;
FIG. 25 is a comparative graph depicting the amounts of the TMS derivative of the arabinose in normal patients and in autistic patents referred to in Example 2;
FIG. 26 is a comparative graph depicting the amounts of the TMS derivative of the dihydroxyphenylpropionic acid in normal patients and in autistic patents referred to in Example 2;
FIG. 27 is a comparative graph depicting the amounts of the TMS derivative of the tartaric acid in normal patients and in autistic patents referred to in Example 2;
FIG. 28 is a comparative graph depicting the amounts of the TMS derivative of the carboxy citric acid in normal patients and in autistic patents referred to in Example 2;
FIG. 29 is a comparative graph depicting the amounts of the TMS derivative of the citramalic acid in normal patients and in autistic patents referred to in Example 2;
FIG. 30 is a comparative graph depicting the amounts of the TMS derivative of the furandicarboxylic acid in normal patients and in autistic patents referred to in Example 2; and
FIG. 31 is a comparative graph depicting the amounts of the TMS derivative of the furancarbonylglycine acid in normal patients and in autistic patents referred to in Example 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The following examples describe the diagnosis and treatment techniques in accordance with the invention. It is be understood that these examples are set forth by way of illustration only, and nothing therein shall be taken as a limitation upon the overall scope of the invention. The attached list of references are referred to by number in the Examples and are incorporated by reference herein.
Example 1
Summary
In this example, the urine of two brothers (A and B) with autistic features were analyzed for the presence of elevated amounts of abnormal Krebs cycle metabolites. These metabolites included citramalic, tartaric (3-OH-malic), and 3-oxoglutaric acids, and compounds tentatively identified as a citric acid analog and partially identified as a phenylcarboxylic acid by the fragmentation pattern of the trimethylsilyl (TMS) derivatives of the compounds and mass shifts of the same compounds derivatized with perdeuterated N,O-bis (trimethylsilyl) trifiuoroacetamide. It was discovered that the urine of the autistic brothers exhibited elevated levels of these abnormal metabolites.
Materials and Methods
Gas Chromatography-Mass Spectrometry (GC/MS). Urinary organic acids were quantified as their trimethylsilyl (TMS) ethers or esters essentially as described by Tanaka et al (6). That is, organic acids in urine which are ketocompounds are first converted to ethoxylamine (EO) derivatives and then the urine is acidified to convert the organic acids to an uncharged form more readily extracted from urine into ethylacetate and ether. The solvents are evaporated under nitrogen and then the organic acid residues are reacted with N,O-bis(trimethylsilyl) acetamide (BSTFA) in combination with 1% trimethylchlorosilane. Alcohol, acid and sulfhydryl substituents on the organic acids form trimethylsilyl ethers and esters which are commonly termed TMS derivatives. The byproducts of the reaction, monotrimethyl-silyl trifluoroacetamide and trifiuoroacetamide, elute with the solvent front. The solution of TMS derivatives is injected into the GC/MS and the organic acids are identified by comparison to a GC/MS library of known compounds.
In each case, 1 mL of urine was incubated with 200 μL of ethoxylamine hydrochloride solution at a concentration of 75 g/L at 60° C. for 30 min. to convert ketoacids to their ethoxime derivatives (7). In order to identify unknown compounds, the same procedure was performed except that perdeuterated BSTFA was substituted for ordinary BSTFA. In one experiment methoxylamine at the same concentration as ethoxylamine was substituted in the standard procedure. After the EO conversion, 3 drops of 6 N HCI were added to each sample and the pH was checked to insure that it was 1.0 or below. One hundred μl of undecanoic acid was then added as an internal standard, followed by 3 ml of ethyl acetate. Each sample was then capped and mixed for 1 min., followed by centrifugation for 1 min. The supernatant from each sample was then transferred to another test tube, and 3 ml of ethyl ether was added to the urine residue in the lower layer of the original tube. This original tube was then capped, mixed for 1 min. and centrifuged for 1 min. The supernatant from the first tube after the second centrifugation was then combined with the first supernatant in the second tube. Approximately 2 g of sodium sulfate was then added to the combined supernatants, followed by capping, mixing for 1 min. and centrifugation for 1 min. The supernatant from this step was then decanted into a vial and put in a 37° C. heating block under nitrogen for complete evaporation.
After evaporation, the appropriate amount of BSTFA was added to the evaporated extract based upon urine creatinine concentration (determined from an original aliquot of the urine sample). The following sets forth the amount of BSTFA employed:
______________________________________Creatinine Conc. (mg/dL) μl of BSTFA______________________________________ 0-24.9 50 25.0-49.9 100 50.0-74.9 150 75.0-99.9 200100.0-124.9 250125.0-149.9 300150.0-174.9 350175+ 400______________________________________
After addition of the BSTFA, the heating block was set to 60-90° C. (average 75° C.) and the BSTFA-supplemented extract was placed in the block for 10 min. Thereafter, the urine vial was removed and allowed to cool. Using a transfer pipette, the patient's BSTFA-supplemented extract was placed into a GC/MS autosampler vial. Such vials were then used in conventional fashion for GC/MS analysis, using the manufacturer's directions and software.
All analytical standards were purchased from Sigma Chemical Co., St. Louis, Mo. Quantitation for compounds for which no analytical standards were available were performed by assigning the response of an average size ion chromatogram peak as 100 units and then calibrating all other peaks against these arbitrary standards. The GC/MS system used was from Hewlett Packard, Palo Alto, Calif. and consisted of an HP5970 mass selective detector, a 5890A gas chromatograph, a model 18593B autosampler, and an Apollo 400 series computer with a 664 MB hard disk drive. The operating software for both instrument control and data analysis was a UNIX-based Chemsystem which operated simultaneously with a Target 2 software system. For GC/MS analysis, 1 μL of sample was injected onto a 15-meter, DB-1 capillary column with a 0.25 mm internal diameter and an 0.25 micron film from J & W Scientific, Folsom, Calif., using purified helium as the carrier gas. All experiments were done using electron-impact (El) ionization with electron energy of 70 eV. The temperature program was started at 90° C., held for 4 min. after injection and then increased to 280° C. at a rate of 8° C./min. The electron-impact mass spectra of arabinose and arabitol were differentiated by the fact that the spectrum of the TMS derivative of arabitol has a significant ion at m/z 319 that is not present in the spectrum of the TMS derivative of arabinose.
Urine samples were randomly collected in plastic screw-cap containers and stored at -20° C. until tested. Normal urine samples were collected from children of laboratory employees. Urine creatinine tests were performed by a modification of the Jaffe method (8) on a Beckman CX-7 chemistry analyzer using standard Beckman creatinine reagents. The procedures followed were in accordance with the Helsinki Declaration of 1975, as revised in 1983.
Results
A typical total ion current (TIC) chromatogram of the TMS derivatives in the urine of brother A is shown in (FIG. 1). Significant peaks at 10.31 min., 14.36 min., 17.78 min., and 18.86 min. were present that were not prominent in normal urine samples (FIG. 2). The results of the urine samples of brother B were very similar to those of his sibling A. In addition, tartaric acid was frequently found in high concentrations in urine samples of these siblings. A much smaller peak at 12.1 min. was also detected in some of the urine samples of the siblings with autistic features. Since the concentration of these metabolites in urine samples of the siblings vary widely, it is important to show data demonstrating the variability of the concentration of these compounds and comparing these concentrations to those in normal children. Therefore, results for four of the metabolites are presented in an identification section and a quantitation section comparing them to normals. No identification section is given for tartaric acid since it is well-recognized in the field of metabolic diseases. No quantitation section is given for 3-oxoglutaric acid since it was only quantitated in some of the samples.
Tentative identification of 2-methylmalic(citramalic) and 3-methylmalic acids. The mass spectrum of the peak at 10.31 min. (FIG. 3) is very similar to that of authentic citramalic acid (2-hydroxy-2-methylbutanedioic or 2-methyl-malic acid (FIG. 4) and has an identical retention time (±0.1 min.). However, a very abundant ion at m/z 205 and a less abundant ion at m/z 220 were present in the spectrum of the peak in the urine of the child with autistic features. The abundance of the ions at m/z 205 and m/z 220 varied widely in different urine samples of the brothers with autistic features. For example, in a spectrum from a different urine extract the abundances of the ions at m/z 203 and 205 are approximately equal and the 220 ion is not detectable (FIG. 5). It is believed that the compound producing the 205 and 220 ions is 2-hydroxy-3-methyl-butanedioc (3-methylmalic). The abundant ion fragment at m/z 220 would be consistent with the loss of a CH 3 --C--CO 2 TMS fragment following a McLafferty rearrangement and cleavage of the bond between carbons 2 and 3; a loss of CH 3 from another TMS group from the m/z 220 ion fragment yields the ion fragment at m/z 205 (FIG. 6). Equivalent ion fragments cannot be formed by fragmentation of 2-methylmalic. 3-Methylmalic acid is not commercially available for confirmation studies.
Quantitation of Methylmalic Acids. For the quantitative studies, the ion signal peak at m/z 247 was used for quantitation. Since both 2- and 3-methylmalic acid isomers have abundant 247 ions and we used citramalic acid (2-methylmalic) as the calibration standard, the values we give for citramalic acid probably represent the total of these isomers. Concentrations of this compound are markedly higher in the brothers with autistic features than in normal children. Citramalic acid concentrations in 19 of the 20 urines from normal children are below 2 mmol/mol creatinine while citramalic acid concentrations in 14 of the 15 urines from the brothers with autistic features exceed 2 mmol/mol creatinine and in one of the urine samples from brother A is 62 mmol/mol creatinine (FIG. 7). The mean citramalic acid concentration in the brothers with autistic features is 14.4 mmol/mol creatinine and 1.5 mmol/mol creatinine in the normal children. The means are statistically different using the t-test at the 0.01 probability level.
Tentative Identification of new citric acid analog. The possibility that a new citric acid analog might be present in the urine of autistic children was considered when an analysis of the mass spectrum of the peak eluting at 7.78 min. (FIG. 11) following the computerized mass spectra library search revealed that the unknown shared several unique ions with the TMS derivatives of citric and isocitric acids (FIGS. 8 and 9) including those for m/z 273, 347, and 375. Selected ion chromatograms of multiple urine extracts revealed that all of these three ions were found only in peaks corresponding to the TMS derivatives of citric, isocitric, and the unknown peak. The unknown spectra had a significant ion at m/z 581. Since the largest detectable ion for TMS derivatives is frequently the M-15 ion due to the loss of a methyl group from one of the TMS groups, the tentative molecular weight of 596 could correspond to a citric acid TMS derivative (molecular weight=480 Da) with an additional COOTMS group (mass=117 Da)-H (mass=1 Da).
Additional evidence for a citric acid analog was obtained by making a perdeuterated TMS derivative of the compound. An aliquot of the same urine was extracted by the regular method and then derivatized with perdeuterated BSTFA to identify the fragments, mass losses from the molecular ion, TMS and/or dimethylsilyl (DMS) content of each mass fragment and the number of functional groups. The mass spectra of the compound formed with the perdeuterated BSTFA is given in FIG. 10 and an interpretation of the data from the spectra of both the perdeuterated and nondeuterated BSTFA derivatives are given in Table 1 below.
TABLE 1__________________________________________________________________________Mass lossMajor ions with Major ions TMSfrom 596plain TMS d.sub.2 TMS Λ Content Interpretation__________________________________________________________________________523 73 82 9 1 TMS TMS449 147 162 15 1 TMS TMS--O--DMS 1 DMS407 189 ? ? ? ?375 221 242 21 2 DMS ? 1 TMS323 273 291 18 2 TMS M--COOTMS--COOHTMS--TMSOH249 347 371 24 2 TMS M--CH.sub.3 --2COOTMS 1 DMS221 375 399 24 2 TMS M--CH.sub.3 --COOTMS--OTMS 1 DMS207 389 416 27 3 TMS M--COOTMS--TMSOH175 421 457 36 4 TMS M--CH.sub.2 COOTMS--CO133 463 496 33 3 TMS M--CH.sub.3 --COOHTMS 1 DMS105 491 524 33 3 TMS M--CH.sub.2 --TMSOH 1 DMS 15 581 623 42 4 TMS M--CH.sub.3 1 DMS__________________________________________________________________________
The largest mass fragment in the spectrum of the nondeuterated compound is m/z 581 Da; the largest mass fragment in the perdeuterated derivative is m/z 623, a shift of 42 Da. This mass shift is consistent with the 581 Da fragment ion containing five derivatized functional groups, four of which are TMS and one of which is DMS. These data also indicate that the m/z 581 ion is the M-15 ion, and that the molecular weight of the penta TMS derivative is 596 Da. The ion at m/z 491 in the spectrum of the nondeuterated compound corresponds to the ion at m/z 524 in the spectrum of the perdeuterated derivative, a shift of 33 Da, indicating that this ion contains three TMS and one DMS groups, and that one TMS group and a methyl group from one TMS group were lost from the molecular ion in the formation of this ion. This ion at m/z 491 results from a loss of 105 Da from the molecular ion; one TMS accounts for 73 Da and the methyl group accounts for 15 Da, leaving a mass of 17 Da unaccounted, This remaining mass of 17 Da is consistent with the loss of OH, as TMSOH, an extremely common loss in the literature of the mass spectra of TMS derivatives (9).
The ion at m/z 463 in the spectrum of the nondeuterated compound corresponds to the ion at m/z 496 in the spectrum of the perdeuterated derivative, a shift of 33 Da, indicating that this ion contains three TMS and one DMS groups and that one TMS group and a methyl group from another TMS group were lost in the formation of this ion. The ion at m/z 463 results from a loss of 133 Da from the molecular ion; one TMS accounts for 73 Da and the methyl group from another TMS accounts for 15 Da, leaving a mass of 45 Da unaccounted, which clearly is consistent with the loss of COOH, as TMSCOOH, an extremely common loss in the literature of the mass spectra of TMS derivatives (9).
The ion at m/z 421 in the spectrum of the nondeuterated compound corresponds to the ion at m/z 457 in the spectrum of the perdeuterated derivative, a shift of 36 Da, indicating that this ion contains four TMS groups and that one TMS group was lost in the formation of this ion. The ion at m/z 421 is unusual in that one COO is lost without an accompanying TMS group, a neutral loss of 175 from the molecular ion (FIG. 12 and Table 1). This ion (FIG. 12) is attributed to the loss of CH 2 COOTMS (-131) followed by a rearrangement of the COOTMS group attached to carbon-3 in which the silicon atom of this COOTMS group attacks carbon-3 and CO 2 is expelled (-44). Similar losses of 175, also found in the mass spectra of citric and isocitric acids, are consistent with the proposition that the structures (FIG. 6) for the three compounds are similar and result in similar fragmentation patterns. This loss of 175 can occur in two different ways in citric acid since structure a and structure b (FIG. 12) are equivalent. In isocitric acid, this loss of 175 can only involve structure b of the molecule. The molecular weight of the unknown compound is 596 Da. The fragmentation pattern and labeling prove the presence of at least one OTMS group and two COOTMS groups, accounting for 323 Da. Two additional TMS groups account for 146 Da. The results of the labeling experiments with the unknown and the similar fragmentation patterns of the unknown, citric acid, and isocitric acid are consistent with identical portions of these molecules labeled structure b in FIG. 12. The carbon atom at C-3 and the CH 2 group in structure b in FIG. 12 account for an additional 26 Da, leaving 101 Da unaccounted; the two additional functional groups remaining can only be COOTMS and TMSOH since there are no losses consistent with any other functional groups. Thus, the rest of the molecule contains two COOTMS groups, or two OTMS groups, or one OTMS group and one COOTMS group. The presence of two additional OTMS groups is unlikely because there are no ions that correspond to the loss of two OTMS groups. Thus, the unknown compound is likely a citric acid analog with an extra carboxylic acid group or a hydroxylcitric acid. Because the unknown is more unstable than citric acid, it is believed that a 2-carboxycitric acid structure is more likely. 2-carboxycarboxylic acids are relatively unstable.
Because this derivative was formed in the presence of ethoxylamine HCI, it was desired to rule out the possibility that the compound is an ethoxime derivative. Substitution of methoxylamine HCI in the procedure yielded a derivative with an identical spectrum indicating that no oxime was present in the molecule, and therefore no keto group was present in this compound. Curiously, when an identical urine aliquot was tested with the oxime derivatization step omitted, this compound was not detected. It was suspected that the failure to detect this compound was due to the salt effect of the methoxylamine HCI or ethoxylamine HCI which increased the efficiency of extracting an extremely water-soluble compound with five polar functional groups into the organic solvents.
An attempt was made to confirm this idea by substituting sodium chloride for the oxime reagent and then performing the normal extraction and derivatization procedure. Results of this experiment revealed that this compound was still not detected, indicating that the effect of the oxime is not a simple salting out effect but might be the result of ion pair formation between the positively charged oxime ions and the negatively charged citric acid analog. It was also noted that the size of the peak for citric acid was also markedly diminished when oxime reagents were omitted also strengthening the hypothesis that the oxime reagent acts as an ion pair extraction reagent for other highly water-soluble acids. However, 2- carboxycarboxylic acids are very unstable, especially in acidic solution and tend to decarboxylate and the oxime might also protect this molecule from decarboxylation.
Quantitation of tentatively identified citric acid analog. The tentatively identified citric acid analog is found in much higher values in the urine of the brothers with autistio features compared to normal children (FIG. 13). The mean value for the brothers with autistic features is 93 units/mol creatinine while the mean value for normal children is 18 units/mol creatinine. Brother A excreted the largest amount of (335 units/mol creatinine). If this compound has a response factor for total ion current equivalent to citric acid, the absolute concentration would be 137 mmol/mol creatinine. The presence of this compound in the urine of 18/20 normal children was confirmed by identification with complete mass spectra demonstrating that this compound is not a drug metabolite.
Identification of 3-oxoglutaric acid. 3-Oxoglutaric acid in the urine of these brothers was identified by the fact that the retention time of the peak at 12.1 min. by GC/MS and the spectrum of the ethoxylamine-TMS derivative were similar to that of authentic 3-oxoglutaric acid processed by the standard method. In addition, the ion ratio for masses 318/243 is characteristic of 3-oxoglutaric acid. The ion ratio for 2-oxoglutaric acid is markedly different. However, the concentration of this compound was too low to obtain a conclusive mass spectrum. The urine samples of the brothers were also unusual in that the concentration of 3-oxoglutaric acid was nearly as great as that of 2-oxoglutaric acid, a finding confirmed in other autistic children. The urine of another unrelated autistic child had a higher concentration of this compound which permitted unequivocal identification of this compound (FIG. 14). 3-Oxoglutaric acid elutes 0.3 min. before 2-oxoglutaric acid with our chromatographic conditions. The mass spectrum of this compound is consistent with the presence of a di-TMS ethoxylamine derivative. Mass spectra for the two compounds are very similar. Both contain significant ions at m/z 318 due to loss of a methyl group from the molecular ion and significant ions at m/z 103 and 318. The spectrum of the 2-oxoglutaric acid derivative has prominent ions at m/z 288 and 198 (FIG. 16) that are not significant in the spectrum of the 3-oxoglutaric acid derivative (FIG. 15). The fragment at m/z 243 is abundant in the spectrum of 3-oxoglutaric acid but very weak in the spectrum of 2-oxoglutaric. A weak molecular ion at m/z 333 was identified in the spectra of both compounds. 3-Oxoglutaric acid was variably present in the urine of these brothers and was present as a relatively small peak that might not be detected without the use of reconstructed ion chromatograms for m/z 243. The concentration in the child with the highest value was 26 mmol/mol creatinine.
Quantitation of tartaric acid. The distributions of tartaric acid concentrations are clearly different for the normal children and the brothers with autistic features (FIG. 17). Tartaric acid exceeds 20 mmol/mol creatinine in only 6 of 20 (30%) of the normal urines while tartaric acid is above this value in 15/17 (88%) of the urines from the brothers with autistic features. The mean value in the normal children is 26.6 mmol/mol creatinine (SD=26.6) while the mean value for the brothers with autistic features was 69.2 mmol/mol creatinine (SD=71.3). However, an inspection of the data clearly indicates a non-normal distribution of data for which median values provide a more meaningful comparison of the two groups. The median value of the normal urine group is 3 mmol/mol creatinine but is 36 mmol/mol creatinine in the brothers with autistic features.
Identification of a phenylcarboxylic acid. The large peak at 18.86 min. has been found in extremely high concentrations in urine samples of the brothers with autistic features and in urine samples of some other children with autism and as a much smaller peak in most normal children. The spectrum of this compound is shown in FIG. 18. Ions at both m/z 73 and 147 indicate that this compound has at least two TMS groups. Other prominent ions are m/z 155, 273, 299, 350, 375, and 390. The use of perdeuterated TMS derivatives of this compound provides additional information about this compound (Table 2). The prominent ion at m/z 91 is consistent with the presence of the tropylium ion. An ion at m/z 65 is consistent with the loss of CH 2 CH 2 from the tropylium ion. The ion at m/z 299 is due to the loss of a tropylium ion from the molecular ion at m/z 390. The ion at m/z 273 is consistent with a loss of COOTMS from the molecular ion, which clearly contains 2 TMS groups and, therefore, two functional groups. The additional functional group appears to be a hydroxyl group based on the ions at m/z 100 and 113. Thus, this compound is partially identified as a phenylcarboxylic acid.
TABLE 2__________________________________________________________________________Mass lossMajor ions with Major ions TMSfrom 390plain TMS d.sub.2 TMS Λ Content Interpretation__________________________________________________________________________325 65 65 0 0 C.sub.5 H.sub.5317 73 82 9 1 TMS299 919 91 0 0 C.sub.7 H.sub.7290 100 106 6 1 DMS DMS--O--CH═CH277 113 122 9 1 TMS TMS--O--CH.sub.2 --CH.sub.2243 147 162 15 1 TMS TMS--O--DMS235 155 164 9 1 DMS ?161 229 244 15 1 TMS ? 1 DMS117 273 282 9 1 TMS M--COOTMS 91 299 317 18 2 TMS M--C.sub.7 --H.sub.7 1 DMS 53 337 355 18 2 TMS M--CH.sub.2 CH═CHCH 40 350 368 18 2 TMS M--CH.sub.2 CH═CH 1 DMS 15 375 390 15 1 TMS M--CH.sub.3 1 DMS 0 390 408 18 2 TMS M__________________________________________________________________________
Quantitation of phenylcarboxylic acid compound. The concentra- tion of the phenylcarboxylic acid was found in much higher values in the urine of the autistic brothers than in normal urine (FIG. 19). The concentration of this compound in 13 of 20 normal children is less than 10 units/mol creatinine while the concentration was as high as 800 units/mol creatinine in brother A. This compound was confirmed by identification of complete mass spectra in all of the normal children demonstrating that this compound is not a drug metabolite.
Identification of arabinose. The peak at 14.36 min. was identified as the TMS derivative of the carbo-hydrate arabinose based on comparison of its mass spectrum and retention time to those of the TMS derivative of the authentic compound (FIGS. 20-21). Both D- and L-arabinose have identical retention times and mass spectra.
Quantitation of arabinose. The mean concentration of arabinose in urine samples of normal children was 60.4 mmol/mol creatinine but an examination of the data in FIG. 22 shows that the data are not normally distributed since data points are much more frequent at the lower concentrations. The median value in the urine samples of normal children is 31.0 mmol/mol creatinine. The median value for the urine samples of the brothers with autistic features is 179 mmol/mol creatinine, nearly six times greater than the median value for the urine samples of the normal children. The mean value for the urine samples from the brothers with autistic features is 305 mmol/mol creatinine, five times the mean for the urine samples from normal children. The highest concentration of urine arabinose, 1008 mmol/mol creatinine was obtained in a sample from brother B.
Concentration of metabolites in maternal urine. The urine of the mother of the autistic brothers also had a somewhat unusual organic acid pattern in that the concentration of 3-oxoglutaric acid (6.1 mmol/mol creatinine) exceeded that of 2-oxoglutaric acid (5.3 mmol/mol creatinine). This same abnormal ratio was also found in several of the urine samples of the two brothers. The concentrations of arabinose (239 mmol/mol creatinine), the citric acid analog (74 mmol/mol creatinine), and the phenylcarboxylic acid compound(117 mmol/mol creatinine) were all elevated compared to normal children. The mother had no symptoms of autism.
Discussion
The structures of a number of compounds evaluated in this study are given in FIG. 23. The citric acid analog, tartaric, citramalic, and 3-oxo- glutaric acid are all analogs of Krebs cycle intermediates. (The structure of the citric acid analog is represented as 2-carboxycitric although the position of the extra carboxyl group has not been established.)
Elevated concentrations of citramalic acid appear to be clearly different than those in normal children since only one of the control children had a value greater than 2 mmol/mol creatinine. Citramalic acid, (2-methylmalic acid) and 3-methylmalic acid are analogs of the Krebs cycle intermediate malic acid and might interfere in the further metabolism of malic acid, leading to depletion of oxalacetic, the product of the action of malate dehydrogenase on malic acid. Oxalacetic acid is needed for condensation with acetic acid to replenish the Krebs cycle. A significant decrease in Krebs cycle activity could significantly impair cellular energy production. Very little information is available in the literature on citramalic acid or 3-methylmalic acid in biological fluids of humans. Citramalic acid was found in increased concentration in cerebrospinal fluid (CSF) samples of patients with bacterial meningitis but not in normal samples of CSF, CSF samples from febrile patients or from patients with aseptic meningitis (10). Citramalic acid has not been reported as a mammalian metabolite but has been reported to accumulate in respiration- deficient mutants of brewer's, baker's, and wine yeasts (11). Furthermore, an enzyme which catalyzes the condensation of acetyl coenzyme A (CoA) and pyruvate to form citramalic acid has been isolated from Baker's yeast (11). In addition, we have found citramalic to be consistently produced by Propionobacteria acnes cultures from human stool samples. A very large number of culture media from a wide variety of anaerobic bacteria isolated from stool samples by us were negative for citramalic acid production. It should also be noted that, although citramalic acid has not been reported as a mammalian metabolite, the possibility that it is of human origin cannot be ruled out.
The citric acid analog is a tentatively identified new molecule which was not previously known. The biosynthesis of several citric acid analogs has been reported as an ability of several species of fungi although the citric add analog is not one of the analogs reported to be produced by these spedes (12). A citric acid analog methylcitric acid, is produced in the disease propionic aoidemia when propionyl CoA instead of acetyl CoA condenses with oxalacetio acid (13). Carboxycitric add could hypothetically be formed by condensation of malonyl CoA instead of acetyl CoA with oxalacetic acid, resulting in the production of 2-carboxyoitdc acid.
Tartaric acid is another compound that appears to be abnormally elevated. However, unlike citramalic, some normal children excreted significant amounts of tartaric acid. Tartaric acid is an analog of malic acid and is a known inhibitor of the citric acid cycle enzyme fumarase (14), which catalyzes the interconversion of malate and fumarate. Tartaric acid is not known as a mammalian metabolite. It is most widely known as a byproduct of the wine industry in which special procedures are used to remove tartaric acid sediment. Tartaric acid is known as a metabolic product of Saccharomyces. Since this species is endogenous to grapes, it is not clear whether all tartaric acid is a yeast metabolic product or whether some is due to endogenous grape metabolism (15). Tartaric acid is present in all grape products such as grape juice, wine, grape jelly, and is used as a food additive (16). However, grape products were not commonly ingested by either of the siblings with autistic features. It is classified as GRAS (generally recognized as safe) by the United States Food and Drug Administration (16). Evidence of toxicity is conflicting. It has been reported to cause muscle weakness and renal impairment (17) which is of interest since the two brothers with autistic features had these symptoms at times.
Unfortunately, tartaric acid was not measured at the time these symptoms were present. The oral ingestion of as little as 12 grams of tartaric acid has been reported to cause a human fatality (18) while other studies indicate a much greater amount can be tolerated without causing toxicity (19-21). The guinea pig and pig are much more susceptible to renal damage by tartaric acid than the rat upon which much toxicological data have been gathered (22).
A compound with the same retention time and mass spectrum as arabinose was detected as present in high concentrations in the urine. Arabinose is present in a number of fruits but was not found as a major component of 72 individuals with pentosuria (23). The carbohydrate alcohol arabitol is a carbohydrate produced by Candida albicans (24). Measurement of arabitol in human blood and in animal blood has been used as an indicator of the extent of Candida infection(25). These other studies employed GC or GC/MS of TMS derivatives as in this study. However, the retention time on GC and the electron impact mass spectra of these compounds are so similar that it is not clear whether arabitol and arabinose were differentiated in these other studies but they were definitely differentiated in our study.
Example 2
In this example, urine samples from a larger number of autistic patients were analyzed for the presence of the abnormal metabolites referred to in Example 1. In addition, the urine samples from these patients were tested for other abnormal metabolites, namely 5-hydroxy-methyl-2-furoic acid, dihydroxyphenylpropionic acid (DHPPA), furandicarboxylic acid and furancarbonylglycine. In particular, urine samples from a total of 97 autistic patients were collected, as well as urine samples from a total of 20 normal individuals. These samples were collected at various times over an approximate one-year period.
Quantitation for these additional compounds (except for dihydroxyphenylpropionic acid) was performed by assigning the response of an average size ion chromatogram peak as 100 units and then calibrating all other peaks against these standards. Dihydroxyphenylpropionic acid was quantitated by using 3,4-dihydroxyphenylpropionic acid as the analytical standard. The rest of the test was performed exactly as described in Example 1.
FIGS. 24-31 illustrate the results of these tests. In each instance, at least certain of the urine samples from the autistic patients exhibited levels of the abnormal metabolites greatly in excess of the normals. This further indicates that the presence of these metabolites is an indicator of autism.
Example 3
In this example, an antifungal drug was administered to a total of 19 autistic children (each was classified as an autistic according to the latest criteria proposed by the American Psychiatric Association) in order to determine whether such therapy would have an effect on the levels of abnormal metabolites in the patients' urine. Certain of the marker compounds are related to those produced by fungi or yeast in culture, and it was hypothesized that the abnormally high presence of one or more of the marker compounds in the urine of autistic patients could be explained on the basis of infection or colonization of the patients with fungi or yeast.
In initial or baseline testing for the presence of abnormal metabolites, all of the patients exhibited above normal levels of at least certain of the metabolites. Each child was then treated with mycostatin (Nystatin) at a level of 100,000 units four times per day (a total of 400,000 units/day) for 10 days. At this point, urine samples were obtained from each patient and analyzed for abnormal metabolites. The results of this study are set forth below, where all quantitative data are in mmol of compound/tool creatinine in urine:
TABLE 3__________________________________________________________________________Baseline NystatinCOMPOUNDS AVG. MEDIAN STDEV AVG MEDIAN STDEV TTEST__________________________________________________________________________Citramalic 3.95 1.70 5.52 2.52 1.40 3.57 0.155-OH-methyl-2-furoic 139.13 58.00 181.37 56.59 16.50 129.74 0.053-oxo-glutaric 16.50 0.00 69.31 0.22 0.00 0.94 0.16Furan-2,5-dicarboxylic 55.77 26.00 75.94 16.87 10.00 19.64 0.01Tartaric 27.51 4.20 72.80 15.31 1.80 45.81 0.06Furancarbonylglycine 58.88 41.00 77.53 45.54 12.00 88.73 0.31Arabinose 384.36 271.00 480.31 178.95 126.00 145.28 0.04DHPPA analog 147.00 99.00 158.52 131.87 131.00 85.16 0.34Carboxycitric 31.45 9.80 65.89 18.26 63.0 27.85 0.22Phenylcarboxylic 24.33 8.70 30.69 46.06 14.00 57.04 0.05__________________________________________________________________________
This data establishes that administration of the antifungal drug materially decreases the amounts of abnormal metabolites (save for phenylcarboxylic acid) in the urine of the autistic patients. This is indirect evidence that the abnormal levels may be due to fungal infection of these patients.
The parents of the autistic patients also reported some amelioration of the symptoms of autism in the treated patients including decreased hyperactivity, better sleep patterns, less stereotypical behavior, better eye contact, increased socialization, more and better vocalization, and increased concentration and focus.
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5. Moreno, H., Borjas, L., Arvieta, A., Saez, L., Prassada, Estevez J., Bonilla, E.; Clinical heterogeneity of the autistic syndrome: a study of 60 families. Invest. Clin., 1992; 33:13-31.
6. Tanaka, K.., Heine, DG., West-Dull, A., Lowe, T.; Gas-chromatographic method of analysis of urinary organic acids. Clin. Chem., 1980; 26:1839-46.
7. Chalmers, R. A,, Lawson, A. M.; Organic acids in man. New York: Chapman and Hall, 1982:123-5.
8. Larsen, K.; Creatinine assay by a reaction kinetic principle. Clin. Chim. Acta. 1972; 41:209-17.
9. Petersson, G.; Mass-spectrometry of hydroxydicarboxylic acids as trimethylsilyl derivatives. Rearrangement reactions. Organic Mass Spectrometry, 1972; 6:565-76.
10. Periman, S., Carr, S. A.; Citramalic acid in cerebrospinal fluid of patients with bacterial meningitis. Clin. Chem. 1984; 30:1209-12.
11. Amaha, M., Sai, T.; Some aspects of (-)- citramalic acid accumulation by respiration-deficient routants of yeast. Antonie van Leeuwenhoek, 1969; 35:G15-16 (Supplement Yeast Symposium)
12. Birkinshaw, J. H.; Special chemical products. In: Ainsworth GC, Sussman AS, eds. The fungi, an advanced treatise, vol. 1. New York: Academic Press, 1965:179-228.
13. Ando, T., Rasmussen, K., Wright, J., Nyhan, W.; Isolation and identification of methylcitrate, a major metabolic product of propionate in patients with propionic acidemia. J. Biol. Chem. 1972; 247:2200-4.
14. Mahler, H., Cordes, E.; Biological chemistry. New York: Harper and Row, 1966:525-53.
15. Budavari, S., O'Neil, M., Smith, A., Heckelman, P., eds. The merck index, 11 th edition. Rahway, N.J.: Merck, 1989: 1433.
16. Lewis, R. J.; Food additives handbook. New York: Van Nostrand Reinhold, 1989: 417-8.
17. Webster, R.; Legal medicine and toxicology. Philadelphia: WB Saunders, 1930: 413-4.
18. Gosselin, R. E., Smith, R. P., Hodge, H. C.; Clinical toxicology of commercial products, 5 th edition. Baltimore: Williams and Wilkins, 1984:200.
19. Chasseaud, L. F., Down, W. H., Kilpatrick, D.; Absorption and biotransformation of L (+)-tartaric acid in rats. Experentia 1977; 33:998-9.
20. Down, W. H., Sacharin, R. M., Chasseaud, W. F., Kirkpatrick, D., Franklin, E. R.; Renal and bone intake of tartaric acid in rats: comparison of L (+) and DL-forms. Toxicology 1977; 8:333-46.
21. Gold, H., Zahm, W.; A method for the evaluation of laxative agents in constipated human subjects with a study of the comparative laxative potency of fumarates, sodium tartrate, and magnesium acid citrate. J. Am. Pharm. Assoc., 1943; 32:173-8.
22. Ory, J., Larsen, J.; Metabolism of L (+)- and D (-)-tartaric acids in different animal species. Arch. Toxicol. Suppl., 1978; 1:351-3.
23. Hiatt, H., Pentosuria. In: Scriver C, Beaudet, A., Sly, W., Valle, D., eds. The metabolic basis of inherited disease, vol. 1, 6 th edition. New York: McGraw Hill, 1989: 481-91.
24. Kiehn, T. E., Bernard, E. M., Gold, J. W., Armstrong, D. Candidiasis: detection by gas-liquid chromatography of D-arabinitol, a fungal metabolite in human serum. Science 1979; 206:577-80.
25. Cook, E.; Autism: review of neurochemical investigation. Synapse 1990; 6:292-308.
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A method for diagnosing the likelihood of autism in patients is provided which comprises first obtaining from the patient a sample of body fluid such as urine and analyzing the sample to determine the quantity therein of at least one marker compound selected from the group consisting of citramalic acid, 5-hydroxy-methyl-2-furoic acid, 3-oxo-glutaric acid, furan-2,5-dicarboxylic acid, tartaric acid, furancarbonylglycine, arabinose, dihydroxyphenylpropionic acid, carboxycitric acid and phenylcarboxylic acid; if the quantities of one or more of the compounds are abnormally high, as compared with the urine of non-autistic individuals, an ultimate diagnosis of autism is likely. The invention also pertains to a method of treating autistic patients by administration of antifungal drugs, in order to ameliorate the clinical symptoms of autism.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] Embodiments of the present invention generally relate to an apparatus and a method for transferring a substrate during processing. More particularly, embodiments of the present invention provide apparatus and method for supporting a substrate during loading and unloading.
[0003] 2. Description of the Related Art
[0004] Sub-micron multi-level metallization is one of the key technologies for the next generation of ultra large-scale integration (ULSI). The multilevel interconnects that lie at the heart of this technology require planarization of interconnect features formed in high aspect ratio apertures, including contacts, vias, trenches and other features.
[0005] Planarization is generally performed using Chemical Mechanical Polishing (CMP) and/or Electro-Chemical Mechanical Deposition (ECMP). A planarization method typically requires that a substrate be mounted in a carrier head, with the surface to be polished exposed. The substrate supported by the carrier head is then placed against a rotating polishing pad. The carrier head holding the substrate may also rotate, to provide additional motion between the substrate and the polishing pad surface. A polishing solution is usually supplied to the rotating polishing surface to assist the planarization process.
[0006] During the planarization process, the substrate is generally secured on the carrier head from the backside of the substrate, for example by forming vacuum cups between a membrane on the carrier head and the backside of the substrate. Prior to or after the planarization process, a load cup is generally used for substrate transferring to and from a carrier head.
[0007] In the state of the art load cup may have a substrate supporting means, for example, support fingers, configured to hold a substrate and transfer the substrate to and from the carrier head. When unloading a substrate from a carrier head, the membrane is usually inflated to release the vacuum cups between the membrane and the backside of the substrate. The substrate will then fall off the carrier head to a load cup underneath under the effect of gravity. FIG. 1 schematically illustrates a substrate holder used in the state of the art load cup. A carrier head 10 having a membrane 11 configured to secure a substrate 12 thereon. The membrane 11 is inflated so that the substrate 12 is no longer drawn to the carrier head 10 by suction. A substrate holder 15 having a plurality of support fingers 14 is positioned underneath the carrier head 10 to catch the substrate 12 once the substrate 12 falls off the carrier head 10 under the effect of gravity. During this transferring process, a processed surface 13 of the substrate 12 is exposed to air or other process environment. The processed surface 13 is generally wet from polishing solutions on polishing stations. Structures, such as copper structures, easily corroded when exposing to air in a wet condition.
[0008] The state of the art load cup has several limitations. First, the time requires to load/unload a substrate from a carrier head is relatively long and unpredictable since the load cup passively waits for gravity to take effect. Second, a substrate to be loaded/unloaded is generally wet and exposed to atmosphere during unloading resulting in corrosion on the processed surface.
[0009] Therefore, there is a need for apparatus and method to transfer a substrate at an increased and predictable rate and with decreased corrosion.
SUMMARY OF THE INVENTION
[0010] The present invention generally relates to a substrate transferring system. Particularly, the present invention relates to a load cup for transferring a substrate with reduced corrosion and increased speed.
[0011] One embodiment of the present invention provides a substrate holder comprising a pedestal plate, a basin wall extending from a top surface of the pedestal plate, wherein the basin wall has a substantially leveled top surface, the basin wall and the pedestal plate define a basin configured to retain a liquid therein, and a liquid port opening to the basin, wherein the liquid port is configured to flow a liquid to the basin and allow the liquid to overflow from the basin wall, and a top surface of the overflow liquid in the basin is configured to support a substrate without contacting the basin wall or the pedestal plate.
[0012] Another embodiment of the present invention provides a method for transferring a substrate comprising holding the substrate using a first substrate holder, filling a basin in a second substrate holder with a liquid to form a liquid surface over a basin wall of the second substrate holder, maintaining a flow of the liquid to the basin to allow the liquid overflow from the basin wall without disturbing the liquid surface, and releasing the substrate from the first substrate holder to the liquid surface, wherein the substrate is supported on the liquid surface.
[0013] Yet another embodiment of the present invention relates to a method for transferring a substrate comprising maintaining a flow of the liquid to a basin of a load cup to form a liquid support surface for supporting a substrate and to allow the liquid overflow from walls of the basin without disturbing the liquid support surface, aligning a first substrate handler with the load cup, wherein the substrate is secured by the first substrate handler, releasing the substrate to the load cup, wherein the substrate is supported by the liquid support surface, aligning a second substrate handler with the load cup, loading the substrate to the second substrate handler, and draining the liquid from the basin of the load cup.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0015] FIG. 1 (prior art) schematically illustrates a substrate holder used in the state of the art load cup.
[0016] FIG. 2 schematically illustrates a planarization system in accordance with one embodiment of the present invention.
[0017] FIG. 3 schematically illustrates a substrate holder in accordance with one embodiment of the present invention.
[0018] FIGS. 4A-4F schematically illustrate substrate unloading/loading process in accordance with one embodiment of the present invention.
[0019] FIG. 5 is a flow chart showing a substrate loading method in accordance with one embodiment of the present invention.
[0020] FIG. 6 is a flow chart showing a substrate unloading method in accordance with one embodiment of the present invention.
[0021] FIGS. 7A-7E schematically illustrate a substrate holder in accordance with one embodiment of the present invention.
[0022] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements disclosed in one embodiment may be beneficially utilized on other embodiments without specific recitation.
DETAILED DESCRIPTION
[0023] The present invention generally relates to an apparatus and a method for transferring a substrate, particularly relates to supporting a substrate in a chemical mechanical polishing (CMP) system or electrochemical mechanical polishing (ECMP) system.
[0024] FIG. 2 illustrates a partial sectional view of a polishing system 100 . The polishing system 100 comprises a polishing station 102 , a carrier head 104 and a load cup 110 . The polishing station 102 comprises a rotatable platen 106 having a polishing material 116 disposed thereon. The carrier head 104 is supported above the polishing station 102 coupled to a base 126 by a transfer mechanism 118 .
[0025] The transfer mechanism 118 is adapted to position the carrier head 104 selectively over the polishing material 116 or over the load cup 110 (shown in dotted lines). The carrier head 104 comprises a membrane 150 configured to hold a substrate 146 thereon. A detailed description of the carrier head 104 may be found in U.S. Pat. No. 6,183,354, entitled “Carrier Head with a Flexible Membrane for a Chemical Mechanical Polishing”, and U.S. patent application Ser. No. 11/054,128 filed on Feb. 8, 2005 now U.S. Pat. No. 7,001,257, entitled “Multi-chamber Carrier Head with a Flexible Membrane”, which are herein incorporated as reference.
[0026] The load cup 110 generally includes a pedestal assembly 128 configured to support a substrate 146 on a liquid surface. The pedestal assembly 128 is supported by a shaft 136 which is coupled to an actuator 133 . When transferring a substrate between the load cup 110 and the carrier head 104 , the carrier head 104 is generally rotated to above the load cup 110 , as shown in the dotted lines. The membrane 150 may be inflated to release the substrate 150 which is then grabbed by the load cup 110 .
[0027] In one embodiment, the pedestal assembly 128 defines a shallow basin configured to retain liquid, such as deionized (DI) water, and to support the substrate 146 on a top surface of the retained liquid in the shallow basin.
[0028] FIG. 3 schematically illustrates a non-contact substrate holder 200 in accordance with one embodiment of the present invention. The non-contact substrate holder 200 is configured to support a substrate on a liquid support surface formed in a basin, wherein the substrate does not contact the non-contact substrate holder 200 other than the liquid support surface. The non-contact substrate holder 200 may be used as the pedestal assembly 128 of the polishing system 100 of FIG. 2 .
[0029] The non-contact substrate holder 200 comprises a pedestal 201 having a basin wall 202 extended thereon. The basin wall 202 and an inner surface 203 of the pedestal 201 form a basin 204 . The basin 204 is configured to retain a liquid and form a liquid support surface to support a substrate thereon.
[0030] A liquid port 209 is formed on the pedestal 201 near a center of the inner surface 203 . The liquid port 209 is in fluid communication with a liquid source 205 and is configured to fill the basin 204 and to provide a liquid flow to the basin 204 during operation. After the basin 204 has been filled, a liquid flow from the liquid port 209 will cause the liquid to over flow out of the basin wall 202 . The liquid flow is configured to provide a force to the liquid support surface for supporting a substrate thereon without disturbing the liquid support surface.
[0031] In one embodiment, the liquid port 209 is also connected to a collecting pen 206 to which liquid in the basin 204 may be drained. Shut off valves 207 , 210 may be used to switch the basin 204 between the liquid source 205 and the collecting pen 206 . In another embodiment, an output port may be formed on the pedestal 201 to drain the basin 202 .
[0032] The non-contact substrate holder 200 is configured to support a substrate on a liquid support surface over the basin 201 . The basin 201 may have a surface area smaller than a substrate. In one embodiment, at least three blocking pins 208 may extend from the pedestal 201 outside the basin wall 202 . The blocking pins 208 are higher than the basin wall 202 and are configured to keep a substrate supported on the liquid support surface from drifting away.
[0033] FIGS. 4A-4E schematically illustrate substrate unloading/loading process in accordance with one embodiment of the present invention using the non-contact substrate holder 200 of FIG. 3 .
[0034] FIG. 4A schematically illustrates the non-contact substrate holder 200 in a receiving state. A liquid flow 212 is provided continuously to the basin 204 through the liquid port 209 forming a liquid support surface 214 and causing liquid to over flow over the basin wall 202 . Flow rate of the liquid flow 212 is set such that the force of over flowing liquid is large enough to support a substrate over the liquid support surface 214 without generating disturbance, such as bubbles, on the liquid support surface 214 .
[0035] As shown in FIG. 4B , a substrate 213 may be lowered towards the liquid support surface 214 to be loaded on the non-contact substrate holder 200 . The substrate 213 may be lowered to the liquid support surface 214 by any a substrate handler, such as a robot or a polishing head. The liquid support surface 214 may have a slightly domed shape due to the liquid flow 212 entering near a center of the basin 202 . As a result of the domed shape of the liquid support surface 214 , center areas of a surface 211 of the substrate 213 usually contacts the liquid support surface 214 first. As the substrate 213 continue to lower, contact areas between the surface 211 the liquid support surface 214 gradually increase from center outwards to a complete contact.
[0036] As shown in FIG. 4C , the substrate 213 is held by the non-contact substrate holder 200 over the liquid support surface 214 . Gravity G of the substrate 213 is countered by upward force F from upward liquid flow 212 and surface tension of the liquid support surface 214 . In one embodiment, the liquid is DI water. In one embodiment, the liquid flow has a flow rate of about 2 liter/minute to about 6 liter/minute for supporting a substrate on the liquid support surface 214 .
[0037] The substrate 213 may be held in FIG. 4C waiting to be transferred to another substrate handler, for example a robot or a polishing head. A substrate handler, which secures a substrate by an edge of the substrate, may grab the substrate 213 by edge while the substrate 213 is supported by the liquid support surface 214 . Once, the substrate handler has a secure handle of the substrate 213 , the liquid flow 212 may be stopped and basin 202 drained for the substrate 213 to be lifted away.
[0038] Polishing heads used in chemical mechanical polishing generally hold substrates from backside by vacuum. FIGS. 4D-4E schematically illustrate transferring of the substrate 213 from the non-contact substrate holder 200 to a polishing head 250 .
[0039] The polishing head 250 comprises a support plate 252 surrounded by a membrane 251 configured to be in contact with a backside of a substrate. The support plate 252 has a planar surface 252 a and a plurality of recesses 253 are formed on the support plate 252 . A pumping system is generally connected to the space between the support plate 252 and the membrane 251 to inflate and deflate the membrane 251 . To load a substrate, the support plate 252 may be used to push the membrane 251 against a backside of the substrate. The membrane 251 is then deflated generating vacuum pouches between the membrane 251 and the substrate when portions of the membrane 251 retreat into the plurality of recesses 253 formed on the support plate 252 .
[0040] A detailed description of similar polishing head and method for loading/unloading substrates using such polishing head may be found in the U.S. patent application Ser. No. 11/757,069 (Attorney Docket No. 10782), filed Jun. 1, 2007, entitled “Fast Substrate Loading on Polishing Head without Membrane Inflation Step”, which is incorporated by reference.
[0041] As shown in FIG. 4D , the polishing head 250 approaches the non-contact substrate holder 200 and presses the membrane 251 against the substrate 213 supported on the liquid support surface 214 . The pressing allows the membrane 251 to make solid contact with the substrate 213 . The pressing force of the polishing head 250 and gravity of the substrate 213 is countered by upward force F from upward liquid flow 212 and surface tension of the liquid support surface 214 .
[0042] In one embodiment, the flow rate of the liquid flow 212 may be increased to support the substrate 213 while the polishing head 250 presses against the substrate 250 . In one embodiment, the liquid flow has a flow rate of about 2 liter/minute to about 6 liter/minute during pressing of the polishing head 250 .
[0043] As shown in FIG. 4E , after the membrane 251 makes full contact with the substrate 213 , the membrane 251 is then deflated to form a plurality of vacuum pouches 255 between the substrate 213 and the membrane 251 within the plurality of recesses 253 . The substrate 213 is now secured to the polishing head 250 .
[0044] Once the substrate 213 is secured attached to the polishing head 250 , the liquid flow 212 may be stopped and basin 202 drained for the substrate 213 to be transferred to the polishing head 250 , as shown in FIG. 4F . In another embodiment, the liquid flow 212 may be increased to push the substrate 213 towards the polishing head 250 .
[0045] FIG. 5 is a flow chart showing a method 300 for loading a substrate to a load cup in accordance with one embodiment of the present invention.
[0046] In step 310 , a liquid flow is provided to a load cup having a basin to fill the basin and maintain an overflow from the basin. The liquid flow is configured to form a liquid surface over the basin for supporting a substrate thereon. In one embodiment, the liquid flow may have a constant flow rate.
[0047] In step 320 , a substrate is lowered toward the liquid support surface by a substrate handler, such as a robot or a polishing head.
[0048] In step 330 , the substrate is released from the substrate handler to the load cup on the liquid support surface. The liquid flow allows the substrate stay afloat on the liquid support surface.
[0049] FIG. 6 is a flow chart showing a method 350 for unloading a substrate from a load cup in accordance with one embodiment of the present invention.
[0050] In step 360 , a substrate holder, such as a robot or a polishing head, is aligned with a substrate supported on a liquid surface of a load cup. The alignment may be completed using alignment pins disposed on the load cup.
[0051] In step 370 , the substrate holder pushes the substrate against the liquid support surface to load the substrate on the substrate holder.
[0052] In step 380 , the load cup is drained or the liquid flow rate is increased to release the substrate from the liquid surface of the load cup.
[0053] FIGS. 7A-7E schematically illustrate a substrate holder 400 in accordance with one embodiment of the present invention. FIG. 7A is a schematic top view of the substrate holder 400 and FIG. 7B is a schematic side view of the substrate holder 400 .
[0054] The substrate holder 400 comprises a pedestal body 401 . A basin wall 402 extends from the pedestal body 401 . The basin wall 402 and a top surface 403 of the pedestal body 401 form a basin 404 . In one embodiment, the basin 404 is substantially circular and configured to support a circular substrate.
[0055] A recess 405 is formed on the pedestal body 401 near a center of the basin 404 . A port 408 is formed within the recess 405 . The port 408 may be adapted to a liquid source or a drain. The port 408 is substantially smaller than the recess and has a side opening 409 opens to a buffering basin 410 . The recess 405 has a shoulder 405 a configured to support a cover 406 thereon. The cover 406 has a plurality of openings 407 between the buffering basin 410 and the basin 404 .
[0056] FIG. 7C schematically illustrates the substrate holder 400 supporting a substrate 418 thereon. A liquid flow 417 enters of the port 408 maintains an overflow off the basin wall 402 allowing the substrate 418 to be supported on a liquid surface 416 within the basin 404 .
[0057] The cover 406 covers the port 408 directing flow of a liquid along a path from the port 408 through the side opening 409 to the buffering basin 410 , then through the plurality of openings 407 to the basin 404 , as shown in FIG. 7C . This configuration reduces turbulence to a liquid surface 416 from the incoming liquid flow 417 from the port 408 to achieve a smooth liquid surface 416 . The smooth liquid surface of the present invention reduces air bubbles between the liquid surface 416 and the substrate supported thereon, thus reduces corrosion. The smooth liquid surface all so reduces damages to structures on the substrate from the liquid flow. During draining, the liquid flows a reversed direction as shown in FIG. 7C .
[0058] Returning to FIGS. 7A-7B , the substrate holder 400 further comprises a plurality of blocking pins 414 extending from the pedestal body 401 outside the basin wall 402 . Each of the plurality of blocking pins 414 is retractable. In an extended position, the blocking pin 414 is taller than the basin wall 402 thus prevents a substrate supported on the liquid surface 416 from drifting away. In one embodiment, the plurality of blocking pins 414 are evenly distributed alone a perimeter of the basin wall 402 . The blocking pins 414 may be pressed to retract during transferring of a substrate between a polishing head and the substrate holder 400 , as shown in FIG. 7D .
[0059] The substrate holder 400 further comprises one or more aligning pin 415 . As shown in FIG. 7B , the aligning pins 415 extend from the pedestal body 401 outside the basin wall 402 . Each aligning pin 415 has a coned shape to form an extended circle around the basin wall 402 . The aligning pins 415 are configured to gradually align with the substrate 418 during dropping off the substrate 418 . The coned shape of the aligning pins 415 gradually guides the substrate 418 towards the basin wall 402 as the substrate 418 moves vertically downward. The aligning pins 415 may be pressed to retract during transferring of a substrate between a polishing head and the substrate holder 400 , as shown in FIG. 7D .
[0060] The substrate holder 400 further comprises one or more head aligning pin 419 . As shown in FIG. 7B , the head aligning pins 419 extend from the pedestal body 401 outside the basin wall 402 . The head aligning pins 419 is configured to align the substrate holder 400 with the polishing head 450 when the polishing head 450 approaches the substrate holder 400 , as shown in FIG. 7D .
[0061] The substrate holder 400 further comprises a plurality of spraying nozzles 412 disposed in recesses 411 formed under the top surface 403 of the pedestal body 401 inside the basin 404 . The spraying nozzles 412 are configured to spray cleaning solution to a polishing head as shown in FIG. 7E . The spraying nozzles 412 may also be used to clean substrates prior to or after loading. The spraying nozzles 412 are formed in the recesses 411 to avoid contact with the substrate.
[0062] The substrate holders of the present invention use a smooth liquid surface to support a substrate. As a result, very small impact is applied to the substrate from the liquid during operation, thus, reduces damages to delicate features formed on the substrate. The liquid contact of the substrate holders of the present invention reduces contacts between the substrate surface and the air, thus reducing erosion and contamination.
[0063] Even though a planarization process is described with the non-contact substrate holder of the present invention, a person skilled in the art can apply the non-contact substrate holder for holding and transferring substrates in any suitable processes, such as wet cleaning, electroplating, and electroless plating.
[0064] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
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Embodiments of the present invention generally relate to a substrate transferring system. One embodiment of the present invention provides a substrate holder comprising a pedestal plate, a basin wall extending from a top surface of the pedestal plate, wherein the basin wall has a substantially leveled top surface, the basin wall and the pedestal plate define a basin configured to retain a liquid therein, and a liquid port opening to the basin, wherein the liquid port is configured to flow a liquid to the basin and allow the liquid to overflow from the basin wall, and a top surface of the overflow liquid in the basin is configured to support a substrate without contacting the basin wall or the pedestal plate.
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The United States Government has rights in this invention pursuant to Contract No. DAAB07-76-C-1357 awarded by the Department of the Army.
BACKGROUND OF THE INVENTION
The present invention relates generally to a connector and, more specifically, to an optical coupler for single optical fibers.
The employment of fiber optic cables or light guides, also sometimes referred to as optical communication fibers for the transmission of information-bearing light signals, is now an established art. Much development work has been devoted to the provision of practical low-loss glass materials and production techniques for producing glass fiber cables with protective outer claddings or jackets. The jackets make them resemble ordinary metallic-core electrical cable upon superficial external inspection. Obviously, if fiber optic cables are to be used in practical signal transmission and processing systems, practical connectors for their selective engagement and disengagement must be provided.
A reference for background in the state of the fiber optic art in general is an article entitled "Fiber Optics", by Narinder S. Kapany, published in Scientific American, Vol. 203, pages 72-81, November 1960. That article provides a useful background in respect to some theoretical and practical aspects of fiber optic transmission.
Of considerable relevance to the problem of developing practical fiber optic connectors is the question of transfer efficiency at the connector. Various factors, including separation at the point of abutment and lateral separation or axial misalignment, are among the factors effecting the light transfer efficiency at a connector. In this connection, attention is directed to the Bell System Technical Journal, Vol. 50, No. 10, December 1971, specifically to an article by D. L. Bisbee, entitled, "Measurement of Loss Due to Offset and End Separations of Optical Fibers". Another Bell System Technical Journal article of interest appeared in Vol 52, No. 8, October 1973, and was entitled, "Effect of Misalignments on Coupling Efficiency on Single-Mode Optical Fiber Butt Joints", by J. S. Cook, W. L. Mammel and R. J. Grow.
Fiber optic bundles are normally utilized for only short transmission distances in fiber optic communications networks. On the other hand, fibers are used individually as optical data channels to allow transmission over many kilometers. At present, most fiber optic cables are multi-fiber bundles due to the less stringent splicing requirements, greater inherent redundancy, and higher signal-to-noise ratio. The difficulty in achieving connection between single fibers which are relatively insensitive to axial misalignment problems but relatively sensitive to lateral misalignment has created an obstacle to the use of long-run single data transmission systems.
In accordance with the foregoing, a connector or coupler is required to essentially eliminate lateral tolerances if low-loss connections are to be obtained in the use of single fiber optical transmission arrangements. In the prior art, "V" groove and metal sleeve arrangements have been used to interconnect single fibers. Reference is made to U.S. Pat. No. 3,768,146 which discloses a metal sleeve interconnection for single fibers.
Another known device, as shown in U.S. Pat. No. 3,734,594, utilizes a deformable annular core having pressure plates at the ends. The fiber ends are inserted into the core and an axial force is applied to the plates to deform the core radially, thereby aligning and securing the fibers.
These prior devices, however, do not readily provide sufficient accuracy for joining and aligning optical fiber cores of small diameter.
Copending application of Charles K. Kao, entitled, "Precision Optical Fiber Connector", Ser. No. 613,390, filed Sept. 15, 1975 (now U.S. Pat. No. 4,047,796), assigned to the assignee of the present application, discloses a single optical fiber connector in which the ends of mating fibers are precisely aligned and coupled together in the interstice between three like-contacting cylindrical rods. The rods are mounted along and around the fibers within an adjustable connector assembly. Means is provided for expanding the interstice to insert the fiber ends and for clamping the rods in position around the fibers. Copending application of Charles K. Kao entitled, "Precision Surface Optical Fiber", Ser. No. 629,210 filed Nov. 5, 1975, assigned to the assignee of the present application, discloses an optical fiber in which the plastic cladding thereof is formed with three rounded indentations along its surface and a thin metal ferrule is formed around the classing at the mating end of the fiber. A pair of such fibers may be aligned in a three-rod arrangement of the type mentioned above.
A hermaphroditic connector for coupling a pair of single optical fibers is disclosed in the copending U.S. Patent application of Ronald L. McCartney entitled, "Single Optical Fiber Connector", Ser. No. 629,004, filed Nov. 5, 1975, abandoned in favor of Ser. No. 682,274 filed May 3, 1976, now U.S. Pat. No. 4,088,390 also assigned to the assignee of the present application. The connector comprises a pair of connector members each containing at least one single optical fiber terminated by a termination pin. The pin includes a metal eyelet crimped about the optical fiber in three places providing three, spaced, curved indentations which centrally position the fiber in the pin. When the connector members are mated, the mating termination pins are positioned so that the indentations therein are generally aligned. Three arcuate cam or spring members are forced into the indentations in the mating termination pins to accurately laterally align the pins and, thence, the optical fibers therein.
In copending application of Ronald L. McCartney entitled, "Single Optical Fiber Connector", Ser. No. 680,171, filed Apr. 26, 1976 (same assignee as above), there is disclosed a single optical fiber connector comprising a base plate having a V-groove in its upper surface which has the transverse cross-section of an equilateral triangle. Two sets of three equal diameter cylindrical rods lie in the groove, each defining an interstitital space therebetween which receives an optical fiber. The sets of rods have mating end faces which abut each other in the groove. A compression plate is mounted over the base plate to arrange the rods in the V-groove so that the centers of the rods are disposed at the vertices of the same equilateral triangle whereby the fibers in the interstitial spaces between the rods become precisely laterally aligned. Such a connector arrangement is particularly suited for a flat cable having single optical fibers.
In copending application of R. L. McCartney et al, entitled, "Single Optical Fiber Connector Utilizing Elastomeric Alignment Device", Ser. No. 680,170, filed Apr. 26, 1976, now abandoned (same assignee), there is disclosed a single optical fiber connector which incorporates a deformable elastomeric alignment element having a bore therethrough. A pair of contacts are mounted lengthwise in the bore. The contacts embody like sets of three equal diameter cylindrical rods. Preferably, the rods are formed of plastic and are integral with a plastic body of the contact. The adjacent cylindrical surfaces of the rods of each contact provide a tricuspid interstitial space for receiving an optical fiber. The sets of rods of the contacts have mating end faces which abut each other when the contacts are pushed into the opposite ends of the bore in the alignment element. The relative dimensions of the two sets of rods and the bore in the elastomeric alignment element are selected so that the region of the element surrounding the mating end faces of the rods is strained to exert a radially inwardly directed compressive force urging the rods of each set inwardly. Such inward compression of the rods causes the adjacent cylindrical surfaces thereof to engage each other and the fiber disposed therebetween so that the centers of the three rods of each contact are disposed at the vertices of an equilateral triangle, whereby the fibers in the contacts become precisely laterally aligned. Such coupling arrangement is suited for axially mated connectors.
The three-rod contact alignment approach discussed hereinabove has been found to suffer some problems. Normally, the optical fiber mounted in the interstitial space defined by the three rods of the contact is recessed slightly behind the mating end faces of the rods so that when two mating contacts are abutted under axial compression force, the fibers therein will not engage each other but will be slightly spaced apart. Since the alignment rods are formed of plastic, the rods experience axial creepage due to the axial compression force applied to the contacts to maintain them in mating engagement. The creepage of the rods causes the fibers mounted therebetween to be exposed at their ends with the result that the fibers in the mating contacts eventually touch each other, causing chipping at their end faces, which produces a loss in light transmission. Also, frequently the fibers will buckle and crack under the axial compressive loads produced.
Another prior art approach to the single fiber connector problem is described in the copending U.S. patent application of G. R. Deacon entitled, "Single Optical Fiber Connector Utilizing Spherical Alignment Elements", Ser. No. 780,259, filed Mar. 23, 1977, now U.S. Pat. No. 4,087,155 and also assigned to the assignee of the present application. In that invention, a set of equal diameter spheres arranged in closely adjacent but not necessarily engaging relationship, defining an interstitial space therebetween, are used. The centers of the spheres lie in a common plane normal to the axial length of the optical fiber. The spheres are dimensioned, to a close tolerance, to closely confine the fiber in the interstitial space. The spheres of one of a pair of mating contacts are abutted under an axial compression force against those of the other contact so that the sphere sets nest with respect to each other, whereby the optical fiber in the space of one such contact is brought into close lateral alignment with that of the mating contact. That particular arrangement is of direct interest in respect to the invention. It has been found that insertion of the optical fibers in the contacts is difficult, however, and tolerances, including the optical fiber diameter tolerance, often result in excessively loose or excessively tight fits.
The manner in which the invention deals with the prior art disadvantages, especially in respect to the disadvantages of the aforementioned invention described in U.S. patent application, Ser. No. 780,259, will be pointed out as this description proceeds.
SUMMARY OF THE INVENTION
In accordance with the hereinbefore outlined state of the prior art in single optical fiber connectors, it may be said to have been the general objective of the present invention to provide an improved connector arrangement effecting a very high order of lateral alignment accuracy at the interface of the optical fibers to be connected. At the same time, it was desired to provide a structure for such connectors which permitted relatively easy optical fiber insertion and which was self-adjusting to accommodate diameter tolerances encountered in typical commercially available single fiber optical cables.
The basic concept of the present invention involves employment of a plurality (preferably three) of alignment spheres in each contact as contemplated in the aforementioned U.S. patent application Ser. No. 780,259, filed Mar. 23, 1977, with the addition of a novel containment sleeve spring-loaded to exert a resilient force acting rearward at its outward aperture to tend to contain and consolidate the spheres of each contact with rearward force against the inwardmost support barrel end. That force is resolved into rearward and radially inward forces.
This support barrel is retained in place in the inner bore within each of the contact subassemblies of the connector, the optical fiber passing through a concentric axial bore within each of these support barrels to the innermost end (interface plane) thereof. Like the configuration described in Ser. No. 780,259, the three-sphere configuration acts as a bearing jewel gripping the optical fibers corresponding to each of the contact subassemblies in a three-point contact (for the preferred three-sphere configuration).
Resilient means (compression spring in the preferred embodiment) urges the containment sleeve rearward by applying its resilient force between the support barrel and the containment sleeve.
At the inward aperture of the aforementioned containment sleeve, a radially, inwardly-directed lip reduces the aperture diameter of the containment sleeve slightly at this end, this reduction being sufficient to prevent the loss of the spheres in the absence of an optical fiber in the interstitial space at the geometric center of the sphere configuration and, also, produces a radially inward sphere-compacting force as the aforementioned inwardly directed lip tends to ride on the surfaces of the spheres in a manner not unlike a cam action. Accordingly, the said interstitial space is automatically adjusted to accommodate the actual outer diameter of the optical fiber used without interfering with the nesting action of the spheres of a pair of mated contacts, producing the desired light-transmitting relationship between abutting optical fibers and also preserving the lateral alignment capability defined in the aforementioned Ser. No. 780,259.
Manual applied force overcoming the spring force operative between the support barrel end and containment sleeve, as aforementioned, allows the spheres of the corresponding contact to assume relatively loose positions within the unrestricted bore portion inward from the lip of the containment sleeve, thereby facilitating optical fiber installation and removal.
The details of a representative embodiment in accordance with the present invention will be presented as this description proceeds.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 depicts a pair of contacts according to the invention substantially fully mated in a connector configuration in a section view obtained in accordance with a sectioning plane containing the axial center line of the connector assembly.
FIG. 2 is a pictorial showing two contacts ready for mating according to FIG. 1, omitting only the coupling nut of FIG. 1 for clarity.
FIG. 3 is an inward end view of the left contact of FIGS. 1 or 2.
DETAILED DESCRIPTION
Referring now to FIG. 1, the two sets of nested spheres are depicted more or less at the axial and lateral center of the view, 17 being a typical sphere of the sphere set for the left contact member and 18 being a typical sphere for the right hand contact of the connector assembly. It will be seen that the spheres of the left contact have their centers all in a common plane, normal to the axial dimension of the assembly. Similarly, the spheres of the right contact have their centers in another plane parallel to the first-mentioned plane. The optical fiber is not illustrated in FIG. 1. However, its placement with respect to the respective spheres is evident from FIG. 2, the fibers 40 and 41 corresponding to the left and the right contacts, respectively, as illustrated.
It will be noted that the left contact subassembly comprises a body or housing 10 and the right contact subassembly comprises a similar body 11. It is presumed that the connector overall assembly is intended for the connection of only one pair of single optical fibers; however, it will be evident that the present invention is in no way limited to such an arrangement. Actually, there could be a number of left and corresponding right contact subassemblies inserted into suitable bores or cavities in a larger body block corresponding to the right and left-hand contact subassemblies.
In the left contact subassembly depicted in FIG. 1, a support barrel 42 has three concentric tandem bore sections 21, 22 and 23. The bore 23 has an enlarged frusto-conical aperture to facilitate insertion of the fiber optic cable therein, and the transitions to each of 22 and 21 include an additional frusto-conical section providing smooth transition from the largest of these diameters at 23 through the intermediate diameter section 22 to the smallest diameter 21. The bore 21 need be only as large as necessary to accommodate the nominal diameter of the optical fiber for which it is designed, with some allowance for tolerances, of course. The right contact subassembly includes the same bores 24, 25 and 26 with essentially the same transition sections, and in fact, support barrel 42 may advantageously be the identical part used at 44. When the housings 10 and 11 are axially joined by means of a coupling nut 12 having internal threads engaging the external threads of 10 along 13, the entire assembly is in the mated condition. A flat "C washer" or ring fits into an annular internal ring in 12 at 15 and engages a circumferential groove 16, making the coupling nut 12 loosely captive on the body 11.
It will be noted that the innermost part of the body 11 slipfits into the mating bore of 10, the latter being thereby appropriately referred to as a socket member. A keying arrangement 46 is provided for discrete rotational keying (positioning) of 11 in 7 to 10 in the mating operation. The degree of tolerance or freedom of fit of 11 into the socket bore of 10 is indicated by the two dashed lines at 14. A particularly close fit at 14 is not necessary, since the alignment of the fibers is basically determined by the nesting of the spheres associated with each contact subassembly as will be more fully explained hereinafter. Suffice it to say at this point that the fit along 14 is not determinative of the quality of the optical fiber alignment achieved in the connector assembly.
The support barrels 42 and 44 are held within split-yoke parts 47 and 48, respectively, and are headed by circular rings or containment sleeves 19 and 20. Compression springs 43 and 45 operate to position and retain support barrels 42 and 44 as indicated. O-rings seals 27 and 28 surround the barrels 42 and 44, respectively.
A tubular grommet 29 of resilient material such as silicone rubber fits within the leftmost extreme of body 11 and holds an alignment sleeve 30 in place, as shown. It may also be said that the alignment sleeve 30 holds the flexible walls of 29 in place over its own length.
As the part 11 is inserted within the socket end of 10, support barrel 42 headed by containment sleeve 19 enters alignment sleeve 30 and proceeds until the spheres associated with the left contact member and the right contact member are nested in much the same manner as described in U.S. patent application Ser. No. 780,259. However, it will be noted that each of the containment sleeves is resiliently anchored to its corresponding support barrel; i.e., by a spring 31 engaging support barrel 42 at 33 at one end and the rear inward-facing wall of 19 at 37 on the other spring end. This speing exerts a force tending to urge 19 to the left, as illustrated, in which case the inwardly directed lip 19a rides against a point of each of the spheres corresponding to the left contact so that they are urged radially inward as well as being compressed against the nose of 42. The same pertains to the right contact subassembly; i.e., the containment sleeve 20 with inwardly directed lip 20a exerts the same forces on the right optical fiber, passing through 24, in view of the action of spring 32 effective between the groove 34 in sleeve 20 and the rear inward wall 38 of the sleeve. Sliding fits at 35, 35a, 36 and 36a provide for manual application of axial force tending to further compress springs 31 and 32. That procedure releases the rearward and radially inward sphere consolidation forces, thereby facilitating insertion of an optical fiber passing through bores 21 on the left and 24 on the right.
Referring now to FIG. 3, the end of the contact 19 is depicted showing the arrangement of the spheres, vis-a-vis, the optical fiber in the situation of FIG. 1. It will be noted that the diameters of the spheres and the fibers are selected such that each of the spheres touches the inner wall of 19 and the optical fiber, but no one of the spheres touches any other of the spheres, when the spheres are nested with the spheres 18 of the opposite contact 20 in the fully mated condition of the connector. Thus, it will be evident that each sphere of each contact subassembly is in contact with a pair of spheres of the opposite contact subassembly.
Without the optical fiber in place, the spheres are relatively loose within the containment sleeves 19 and 20, in which case, they may be in a random-contact position, assuming that the connector contacts are not mated at the time. The radially inward extent of the lips 19a and 20a is sufficient, however, to prevent the spheres from falling out of the end of 19 or 20 in the unmated condition, even without the optical fiber in place.
The exact point of the tangency of 19a or 20a on the corresponding sphere set will vary according to diameter variations of the optic fiber 40 or 41. A nose-to-nose gap between 19 and 20 in the fully mated condition, as depicted in FIG. 1, assures that these parts will not physically abut to thwart the sphere nesting under any condition within the design limits. However, the nesting of opposite sphere sets is automatically self-adjusting, these acting much as bearing jewels might act.
For the spheres, of which 17 and 18 are typical, hardened steel ball bearings may be advantageously used. These are readily available and are commercially manufactured to very close tolerances. Accordingly, the nesting of opposite sphere sets very effectively controls the lateral alignment of the opposing and abutting optical fibers between which it is desired to establish a light-transmissive relationship with minimum loss.
Of course, the spheres might also be manufactured in hard plastic, glass, or like material. However, bearing balls of bearing grade steel are clearly preferred.
FIG. 2 is largely self-explanatory and is presented to provide a clear understanding of the connector overall assembly resulting when the two contact subassemblies are mated.
Except for the tubular grommet 29 and the springs (which may be satisfactorily provided in ordinary grades of spring steel), all other parts of the contact subassemblies may be fabricated from metals such as stainless steel or other commonly used metals for fiber optic connector structures, or even for electrical contact connector structures. Those skilled in this art will recognize the possibility of substituting certain suitable plastics for certain of the parts of the structure, and accordingly, it may be said that there are no critical material requirements extant in the combination.
Various other modifications in the structure disclosed and described will suggest themselves to those skilled in this art, once the principles of the present invention are well understood. Accordingly, it is not intended that the drawings and this description should be considered as defining the scope of the invention, these being intended to be typical and illustrative only.
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A connector for coupling a pair of single optical fibers is disclosed. Each contact of the connector utilizes three spheres of equal diameter defining a tricuspid interstitial space therebetween into which the end of a fiber is mounted. The spheres are embraced by a circular race and may engage each other but always engage the race. When a pair of contacts is mated in axial abutting relationship, the spheres in the mating abutting contacts nest with respect to each other, thereby precisely laterally aligning the optical fibers which are mounted in the interstitial spaces of the sets of spheres in the two contacts. Spring means are included to urge the spheres inwardly and are releasable to facilitate insertion of a single optical fiber extending axially and to compensate for alignment tolerances.
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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an information storage system having a high-efficiency information transfer function. The above information transfer function may be an information transfer function for transferring data from an information storage medium such as a magneto-optical disc to a mother information processing system. In particular, the present invention improves an advance reading function previously proposed by the inventor of the present invention so that the advance reading function may be used more effectively.
2. Related Art
An information storage system in the related art includes a control unit for reading data out from a information storage medium and writing data thereinto and a data buffer memory. The control unit, according to an amount of information to be transferred specified by a mother information processing system, transfers data previously stored in the information storage medium using the data buffer memory.
Such an information storage system may be a disc apparatus such as a magneto-optical disc apparatus and constitutes a filing system together with a mother information processing system such as a host adapter including a SCSI.I/F unit.
Such an information storage system in the related art is idle after completing a specified information transfer work until subsequent information is specified by the mother information processing system. Thus, the efficiency of the information storage system is degraded.
The inventor of the present invention has proposed the advance reading function, as mentioned above, used in an information storage system which has also been proposed by the inventor, as an information storage system controller' in Japanese Patent Application No. 4-280671. The proposed advance reading function actively uses an idle time such as that mentioned above generated after the information storage system has completed a specified information transfer work. More particularly, the advance reading function, after the information storage system has completed the specified information transfer work, reads data blocks subsequent to the data blocks which have been transferred in the above specified information transfer work, in advance of subsequent information being specified by the mother information processing system. The advance reading function then stores the thus read data blocks into a spare-data storage memory. Then, if the above mother-system'subsequent specified information includes a work of reading data blocks out from the information storage medium, which data blocks are identical to the data blocks previously stored in the spare-data storage memory as mentioned above, the previously stored data blocks may be transferred to the mother system immediately after the relevant information is specified. Thus, the information processing efficiency may be improved.
However, the information storage system previously proposed by the inventor stops such an advance reading operation immediately after the system receives subsequent information specified by the mother system which does not specify that the same advance reading operation is to be continued, and thus the information storage system performs the work thus specified by the mother system instead of performing the advance reading operation. Thus, the advance reading function may not always be used effectively.
SUMMARY OF THE INVENTION
An object of the present invention is to eliminate the above problem which prevents the advance reading function from always being used effectively.
In order to achieve the object of the present invention, the present invention enables an advance reading function to be used more efficiently by preventing an already started advance reading operation from being unnecessarily stopped as long as it is possible. If subsequent information is specified by the mother system while the advance reading operation is being carried out, the contents of the subsequent specified information are examined first, instead of immediately stopping of the advance reading operation. Then if, as a result of the examination, it is found that the specified information does not include contents whereby it is necessary to immediately stop the advance reading operation, the advance reading operation is continued. That is, if the mother system has requested to transfer data blocks (or sectors of data) already read in the advance reading operation, the read data blocks are transferred to the mother system while the advance reading operation is continued. Further, if the mother-system's subsequent specified information does not include a request to read data from the information storage medium and thus does not include a request to stop the advance reading, the advance reading operation being currently performed is continued.
Thus, the present invention may improve the advance reading function previously proposed by the inventor.
An information storage system according to the present invention comprises:
reading means for reading first data blocks among the data blocks stored in an information storage medium according to information specified by a mother system;
buffering means for temporarily storing said first data blocks read by said reading means;
transferring means for transferring said first data blocks temporarily stored by said buffering means to said mother system;
advancing means for causing, in an advance reading operation, said reading means to read in advance second data blocks subsequent to said first data blocks in said information storage medium, said means then causing said buffer means to store said second data blocks; and
controlling means for controlling said advancing means appropriately according to the information specified by said mother system.
Due to the provision of the control means, the advance reading function is controlled according to the specified information so that the advance reading function may be used in the optimum manner.
It is preferable that said controlling means causes said advancing means to continue the advance reading operation if the information specified by said mother system does not indicate that said information storage medium is to be accessed.
Thus, the advance reading function may be used effectively.
It is preferable that said controlling means causes said advancing means to stop the advance reading operation if the information specified by said mother system indicates to access said information storage medium but does not indicate to read data blocks therefrom.
Thus, it is possible for the information storage system to execute the work specified by the mother system specification as if the system did not have such an advance reading function.
It is preferable that said controlling means examines whether or not the data blocks to be read out from said information storage medium according to the information specified by said mother system include the second data blocks already stored by said buffering means.
Due to the provision of the control means, the advance reading function is controlled with the specified information so that the advance reading system may be used in the optimum manner.
It is preferable that, if said controlling means determines that all of the data blocks to be read out from said information storage medium are data blocks of the second data blocks stored by said buffering means, said controlling means causes said advancing means to continue the operation and then causes said transferring means to transfer the specified data blocks, of the second data blocks already stored by said buffering means, to said mother system.
Thus, the advance reading function is effectively used.
It is preferable that, if said controlling means determines that the data blocks to be read out from said information storage medium include data blocks not stored by said buffering means in advance and also include data blocks of the second data blocks already stored by said buffering means, said controlling means causes said advancing means to stop the operation and then causes said reading means to read out said data blocks, not stored by said buffering means in advance, from said information storage medium, the thus read out data blocks being then transferred to said mother system. Further, said controlling means causes said transferring means to transfer the specified data blocks, of the second data blocks already stored by said buffering means, to said mother system.
Thus, the advance reading function may be suitably controlled so that the advance reading function may be effectively used.
It is preferable that, if said controlling means determines that the data blocks to be read out from said information storage medium do not include data blocks of the second data blocks stored by said buffering means, said controlling means causes said advancing means to stop the operation and then causes said reading means to read out said data blocks from said information storage medium, the thus read out data blocks being then transferred to said mother system.
Thus, the advance reading operation is suitably controlled so that the advance reading function may be effectively used.
Other objects and further features of the present invention will become more apparent from the following detailed description when read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an example of a manner of information-storage-medium data formatting used in an information storage system;
FIG. 2 shows a function block diagram including essential function blocks in an information storage system controller in an embodiment of the information storage system according to the present invention;
FIG. 3 shows a structure of a memory which may be used in the controller 2 shown in FIG. 2;
FIGS. 4 and 5 show an operation flow chart including essential steps in a data transfer operation in the information storage system previously proposed by the inventor; and
FIG. 6 shows an operation flow chart including essential steps relevant to an advance reading operation in the information storage system according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
An example of a manner of information-storage-medium data formatting used in an information storage system will now be described with reference to FIG. 1.
As shown in FIG. 1, disposed blocks i, i+1, i+2, . . . are included in an information storage medium, each of the blocks including a block address (ID) area and a data area. Generally speaking, data is stored in the blocks of the information storage medium in the order the blocks are disposed. In an information transfer process, a number of blocks which can be transferred in a single transfer operation is commonly limited. Thus, if the number of blocks requested to be transferred is larger than the number of blocks which it is possible to transfer in a single transfer operation, a plurality of transfer operations are needed to satisfy the request. In such a case, the data consisting of the number of blocks requested to be transferred is separated into a plurality of portions so that each of the data portions will thus be transferred in a respective one of the plurality of transfer operations, successively. In such a case, the mother system may specify the plurality of transfer operations successively, the transfer operations corresponding to the data portions in the order of the block disposition. Thus, it is possible to predict which blocks will be requested, to be read and then transferred according to the subsequent information specified by the mother system.
This is the basis of the advance reading function previously proposed by the inventor. Since it is possible to predict the data blocks which will be requested to be read and then transferred, the advance reading function is effective, in improving the data processing efficiency, to enable the relevant data blocks to be read in advance of a time the relevant information specified by the mother system. The predictable blocks are commonly the blocks subsequent to the blocks which it has been requested be read and then transferred by the current specified information due to the plurality of the transfer operations (specified by the corresponding information) corresponding to the data portions in the order of the data block disposition as described above. Thus, the advance reading function, in advance, reads the blocks subsequent to the blocks which has been already read and transferred in accordance with the corresponding current specified information, then stores the thus in-advance read blocks in a memory.
With reference to FIG. 2, an information storage system controller in an embodiment of the information storage system according to the present invention will now be described.
The information storage system controller 2 is connected to a mother information processing system 1. The information storage system controller 2 includes a control unit 3, a data buffer memory 4 and an information storage medium 5.
In the controller 2, data is transferred from the mother system 1 to the control unit 3, then to the data buffer memory 4, then to the control unit 3, and then to the storage medium 5, when the data output by the mother system 1 is stored into the storage medium 5.
In the controller 2, data is transferred from the storage medium 5 to the control unit 3, then to the data buffer memory 4, then to the control unit 3, and then to the mother system 1, when the data read out from the storage medium 5 is supplied to the mother system 1.
The controller 2 has an advance reading function identical to that previously proposed by the inventor. Thus, the controller 2, after completion of a data transfer operation in which the first series of data blocks is read out from the storage medium 5 and are then transferred to the mother system 2 in accordance with the relevant information specified by the mother system 1, carries out such an advance reading operation. That is, the controller 2 reads a second series of data blocks subsequent to the last block of the first series of data blocks in the storage medium 5 according to the advance reading function. The controller 2 then stores the thus read second series of data blocks into the data buffer memory 4 or the like.
If the controller 2 receives subsequent information specified by the mother system 1 during the above advance reading operation, the controller 2 controls the current advance reading operation appropriately in accordance with the above subsequent specified information after examining the contents of the information.
The controller 2 continues the current advance reading operation if the above subsequent information does not indicate to access the information storage medium 5. The operation controlled according to the specified information is performed by the controller 2 in parallel with the above advance reading operation.
The controller 2 stops the current advance reading operation if the above subsequent specified information indicates to access the information storage medium 5 but does not indicate to read data blocks therefrom. In this case, the controller 2 performs the operation according to the specified information instead of performing the above advance reading operation.
The controller 2 examines whether or not the data blocks to be read out from the information storage medium 5 according to the above subsequent specified information include the second data blocks already read and then stored into the memory 4 in the current advance reading operation.
The controller 2, if all of the data blocks to be read out from the information storage medium 5 are data blocks of the second data blocks already stored in the memory 4 according to the results of the above examination, thus continues the current advance reading operation and then transfers the specified data blocks of the second data blocks already stored in the memory 4 to the mother system 1.
The controller 2, if the data blocks to be read out from the information storage medium 5 include data blocks which have not been stored in the memory 4 in the current advance reading operation and also include data blocks of the second data blocks already stored into the memory 4 in the current advance reading operation, according to the results of the above examination, stops the current advance reading operation and then reads out the data blocks, which have not been stored in the memory in the current advance reading operation, from the information storage medium 5, the thus read out data blocks being then transferred to the mother system 1. The controller 2 also transfers the specified data blocks of the second data blocks already stored in the memory 4 in the current advance reading operation to the mother system 1. Then, after the completion of the above reading operation, the controller 2 carries out another advance reading operation, that is, reading of the data blocks subsequent to the last block of the data blocks which have been read in the above reading operation.
If the data blocks to be read out from the information storage medium 5 do not include data blocks of the second data blocks already stored into the memory 4 in the current advance reading operation, the controller 2 stops the current advance reading operation and then reads out the specified data blocks from the information storage medium 5, the thus read out data blocks being then transferred to said mother system 1. Then, after the completion of the above reading operation, the controller 2 carries out another advance reading operation, that is, reading the data blocks subsequent to the last block of the data blocks which have been read in the above reading operation.
A structure of a memory which may be used as the data buffer memory 4 shown in FIG. 2 will now be described with reference to FIG. 3. The memory includes a data buffer memory area 4a and a spare-data memory area 4b.
As shown in the figure, the information storage system according to the present invention uses not only the data buffer memory area 4a but also the spare-data memory area 4b. The memory area 4a acts as a memory which is also used in the information storage system in the related art. The memory area 4a temporarily stores data which is transferred between the mother information processing system 1 and the information storage medium 5 those shown in FIG. 2. The spare-data memory area 4b stores data which is read out from the storage medium 5 particularly in the advance reading operation.
In order to use the two memory areas separately as described above, it is necessary to previously separate the memory into the two areas.
In the advance reading operation, data is read out from the storage medium 5 and transferred to the mother system 1 via the spare-data memory area 4b. Thus, the spare-data memory area 4b acts as an intermediate buffer in the data transfer operation.
With reference to FIG. 2, if the controller 2 receives reading-out instructions from the mother system 1, the control unit 3 reads out data from the storage medium 5 according to the received instructions. Then, if the instructed reading out operation has been completed, the controller 2 reports to the mother system 1 the operation completion.
The control unit 3 internally reads out information blocks from the storage medium 5 subsequent to the last information block of the information blocks which have been read out according to the above instructions given by the mother system 1. This internal reading-out operation is automatically carried out under the condition where no instructions are given to the controller 2 from the mother system 1 to perform this operation. The thus read out blocks are then stored in the spare-data memory area 4b of the memory 4.
If other reading-out instructions are given to the controller 2 from the mother system 1, the control unit 3 checks whether or not the information blocks which should be read out according to the instructions are present in the spare-data memory area 4b.
If the relevant information blocks are present in the memory area 4b, the control unit 3 transfers the blocks to the mother system 1. If there are information blocks which should be transferred to the mother system according to the above instructions but are not present in the spare-data memory area 4b, the control unit 3 reads out the blocks from the storage medium 5 and transfers them to the mother system via the data buffer memory area 4a.
The above-described advance reading function according to the previously proposed system as described above will now be described with reference to FIGS. 4 and 5. The controller 2 in the embodiment of the present invention uses the same steps S1 through S7, shown in FIG. 4, as those which the previously proposed system uses. Further, the controller 2 uses other steps which will be described with reference to FIG. 6.
With reference to FIG. 4, in a step (the term step will be omitted from hereon) S1, the control unit 3 waits for an instruction to be given by the mother system 1.
After an instruction has been given, a data amount to be read out from the storage medium 5 during a time in which the control unit 3 waits for another instruction is specified by the mother system 1 in S2.
Then, the control unit 3 waits for another instruction to be given by the mother system 1.
After another instruction has been given by the mother system 1, the control unit 3 receives a reading-out instruction in S4.
Then, in S5, the control unit 3 reads out the data from the storage medium 5 according to the above reading-out instruction and then transfers the thus read-out data to the mother system 1.
Then, in S6, the control unit 3 reads out from the storage medium 5 the above specified amount of data starting from the block subsequent to the last blocks of the information blocks which have been read out in S5. The control unit 3 stores the thus read-out data into the spare-data memory area 4b.
The control unit 3 waits for another instruction in S7.
After the control unit 3 has received another instruction from the mother system 1, the control unit 3 determines whether or not the thus received instruction is a reading-out instruction in S8 shown in FIG. 5.
If the current instruction is not a reading-out instruction in S8, the control unit 3 carries out the appropriate process according to the current instruction in S10, the control unit 3 then returning to S3.
If the current instruction is a reading-out instruction in S8, the control unit 3 checks whether or not the data to be transferred to the mother system 1 according to the reading-out instruction is one which has been stored in the spare-data memory area 4b in S9.
If the above data to be transferred is not one previously stored in the memory area 4b in S9, the control unit 3 carries out the appropriate process according to the above reading-out instruction, that is, reading out the above data from the storage medium 5 and transferring the read-out data to the mother system 1. Then, the control unit 3 returns to S3.
If the above data to be transferred includes one previously stored in the memory area 4b in S9, the control unit 3 reads out the relevant data from the memory area 4b and transfers it to the mother system, in S14.
The control unit 3 then determines in S12 whether or not the above data to be transferred also includes one which has not been stored in the spare data memory area 4b.
If the above data includes one not previously stored in the memory area 4b in S12, the control unit 3 reads out the relevant data from the storage medium 5, stores it in the data buffer memory area 4a, and then transfer it to the mother system 1, in S14.
Then, the control unit 3 returns to S3 and waits for another instruction to be given by the mother system 1.
If the above data to be transferred does not include data which has not been stored in the spare-data memory area 4b in S12, the control unit 3 returns to S3 and waits for another instruction to be given by the mother system 1.
Thus, by S1 through S14, the controller 2 in the embodiment of the present invention reads out the data according to a reading-out instruction given by the mother system 1 and transfers the data to the mother system 1. Then, the controller 2 further reads out the subsequent data from the storage medium 5 automatically and stores it in the spare-data memory area 4b. Then, the data stored in the spare-data memory area 4b is immediately transferred to the mother system 1 if the same data is requested in a reading-out instruction given by the mother system 1.
The controller 2 performs processes as will be described now with reference to FIG. 6, if an instruction given by the mother system 1 is received by the controller 2 in the course of the advance reading operation, such as in S6 shown in FIG. 4.
As described above, the procedure shown in FIG. 4 used by the above-described previously proposed system is the same as that used by the controller 2 in the embodiment of the present invention. The control unit 3 carries out the determination in S7 in the course of S6, the advance reading operation. The procedure shown in FIG. 6 is executed if S7 determines that an instruction is given in the course of S6.
Then, the control unit 3 checks the contents of the above instruction so as to determine whether or not the instruction indicates to access the storage medium 5, in S21 shown in FIG. 6.
If the above instruction does not indicate accessing of the storage medium 5 in S21, the control unit 3 carries out the appropriate process according to the instruction as if no advance reading operation were being carried out, simultaneously continuing the advance reading operation actually, in S22. Then, the control unit 3 returns to S3 and waits for another instruction to be given by the mother system 1.
If the above instruction indicates to access the storage medium 5 in S21, the control unit 3 determines in S23 whether or not the relevant instruction is a reading instruction.
If it is not a reading instruction in S23, the control unit 3 stops the advance reading operation in S24 and then carries out the process according to the instruction in S25. Then, the control unit 3 returns to S3 and waits for another instruction to be given by the mother system 1.
If the relevant instruction is a reading instruction in S23, the control unit 3 determines in S26 whether or not the reading instruction indicates to read out either data which has not been stored in the spare-data memory area 4b or data which is being stored there in the advance reading operation currently being carried out.
If the reading instruction indicates to read out data previously stored or now being stored in the memory area 4b in S26, the control unit 3 continues the advance reading operation in S27 and transfers the relevant data of the data which has been stored in the spare-data memory area 4b to the mother system 1 in S28.
If the reading instruction indicates to read out data neither previously stored nor now being stored in the memory area 4b in S26, that is, it is necessary to read out data even though the advance reading operation is currently being carried out, the control unit 3 carries out S29. In S29, the control unit 3 determines whether or not the data transfer which has been requested by the mother system 1 includes data (sectors of data) which has been stored in the spare-data memory area 4b.
If the relevant data includes the data in the memory area 4b in S29, the control unit 3 stops the advance reading operation in S30 and reads out the data from the storage medium 5 which is that part of all of the requested data not previously stored in the memory area 4b simultaneously with the transferring of the remaining part of all of the requested data present in the memory area 4b to the mother system 1. Then, in S32, the control unit 3 carries out another advance reading operation simultaneously with the transferring of the data read out in S31 to the mother system 1.
If none of the requested data includes data present in the spare-data memory area 4b in S29, the control unit 3 stops the advance reading operation in S33 and reads out the relevant requested data from the storage medium 5.
Then, in S35, the control unit 3 carries out another advance reading operation simultaneously with the transferring of the data read out in S31 to the mother system 1. Then, the control unit 3 returns to S3 and waits for another instruction to be given by the mother system 1.
Summarizing the above, by S21 through S35 together with S1-S7 shown in FIG. 4, even if an instruction given by the mother system 1 is received by the controller 2 in the course of the advance reading operation, it is not always necessary to stop the advance reading operation and the advance reading operation can be appropriately controlled depending on the contents of the above instruction.
It is also possible in the embodiment of the present invention to use S8-S14 shown in FIG. 5 in addition to S1-S7 and S21-S35. In this case, as described above, the procedures S21-S35 are carried out when an instruction is received by the controller 2 while the advance reading operation is being carried out. On the other hand, the procedures S8-S14 are carried out when an instruction is received by the controller 2 after the relevant advance reading operation has been completed.
Further, the present invention is not limited to the above described embodiments, and variations and modifications may be made without departing from the scope of the present invention.
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A reading unit reads first data blocks among the data blocks stored in an information storage medium according to the information specified by a mother system. A buffering unit temporarily stores the first data blocks read by the reading unit. A transferring unit transfers the first data blocks temporarily stored by the buffering unit to the mother system. A advancing unit causes the reading unit to read in advance second data blocks subsequent to the first data blocks in the information storage medium, the unit then causing the buffer unit to store the second data blocks. A controlling unit controls the advancing unit appropriately according to the information specified by the mother system.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to the application of deuterium oxide, D 2 O, in producing O—H free materials or chemicals for optical communication. The processes involved include, hydrolysis and polycondensation of silanes and metal compounds, such as the sol-gel process, and the optical deposition of silica and metal oxides. The resulting materials could be used as optical waveguides, adhesion promoters, coatings, adhesives and other materials where low optical loss is essential in the wavelength range of 1.55 μm or 1.3 μm.
[0003] 2. Prior Art of the Invention
[0004] Low optical loss at working optical wavelengths, i.e. 1.3 and particularly 1.55 μn, is a key parameter for applying a material as light transmission medium in fiber optical communication. In silicon based materials, such as sol-gel based silica, O—H plays an undesirable role in building up high optical loss at the wavelengths of 1.3 and 1.55 μm which are the regular wavelengths used for optical communication, because O—H has a strong absorption peak in this wavelength region. Reducing O—H content in the materials is, therefore, extremely important in decreasing optical loss. However, it is very difficult to eliminate O—H in silica and metal oxidized materials. High temperature baking is the typical present way used to reduce O—H in processing the materials. For instance, high temperature baking at around 1200° C. is usually used to eliminate O—H when producing silica. This process does not experience technical problems in producing bulk components such as optical fibers, but it does cause some problems in coating deposition when the substrate is a different material. For example, the thermal expansion mismatch between a silicon substrate and the silica coating might introduce a significant stress in the silica coatings in a Flame Hydrolysis Deposition (FHD) process, and the capillary force-driven shrinkage can easily crack sol-gel deposited coatings at 600° C. or above. As for sol-gel based organic-inorganic hybrid materials, high temperature processes are completely unacceptable, because the organic part can only withstand a temperature below 300° C.
[0005] Recently, sol-gel based organic-inorganic hybrid materials were developed for fabricating optical waveguiding components. The materials contain two parts: an organic one with double bonds and an inorganic one with Si—O—Si network. They can be UV-patterned by using traditional photolithography technology and have good thermal stability. Various optical waveguide components, such as hybrid splitters, optical switches and waveguide gratings, were produced by using the hybrid materials. The materials are synthesized by hydrolyzing multi-functional methoxyl or ethoxyl silanes, followed by proper polycondensation.
[0006] U.S. Pat. No. 6,054,253 issued Apr. 25, 2000 to Fardad et al provided a method in producing waveguides by using methacryloxypropyl trimethoxysilane based on sol-gel process. High performance sol-gel waveguides were achieved with the technology. U.S. Pat. No. 5,973,176 issued Oct. 26, 1999 to Rocscher et al teaches us to use synthesize fluorinated silanes for sol-gel process in fabricating low optical loss waveguides.
[0007] However, polycondensation is never completed in the system, leaving a significant amount of residual O—H in the materials. Many approaches were used to reduce the O—H content, including, choosing proper silanes, proper sol-gel conditions (catalyst, concentration, solvent, temperature), and using a special monomer to react the O—H groups. It was reported that by eliminating O—H, the materials' optical loss can be reduced from several dB/cm to 0.5 dB/cm. Fundamentally, however, choosing proper silanes and reaction conditions cannot complete the condensation and thus eliminate the O—H in such a reactive system with multi-functional groups, because the condensation of multi-functional monomers can never be completed. This has been well recognized in polymer theory and experiment. By reacting residual O—H with a special monomer it is possible to eliminate all O—H, but the reaction may affect the network built up and thus deteriorate the material's thermal and mechanical properties.
[0008] An innovative prior art method to produce low O—H materials is to avoid the use of H 2 O for hydrolysis. For instance, diphenysilandiols were used to react with methoxysilanes directly. However, residual methoxy groups are inevitable in the materials due to the problem mentioned above, i.e. multi-functional groups polycondensation can never be completed. Since C-H also has a strong absorption peak in the region of 1.3 to 1.55 μm, the residual methoxy itself, which contains three C—H bonds, could negate the benefit achieved by reducing the O—H content. As a result, real gain in reducing optical loss in the wavelength region by such approach is limited.
[0009] Indeed, it is a challenge to significantly reduce the O—H content without deteriorating material properties, or to eliminate O—H without introducing other chemical groups which have similar effects to O—H on building optical loss.
SUMMARY OF THE INVENTION
[0010] The present invention provides an optical compound material for use in optical devices in the wavelength range between 1.0 and 1.8 micrometers, wherein substantially most O—H bonds are substituted by O-D bonds; H being protium and D being deuterium.
[0011] In a widely used compound material processes, is the sol-gel material a D 2 O-hydrolyzed silane, or a D 2 O-hydrolyzed metal compound.
[0012] The present invention also provides a method of producing optical compound materials substantially free from O—H bonds, comprises the steps of hydrolyzing and condensing of at least one of silanes and metal compounds using deuterium oxide (D 2 O).
[0013] A sol-gel process for producing optical compound materials substantially free from O—H bonds, comprises the step of using deuterium oxide (D 2 O) to provide compound materials containing Si—O—Si bonds M—O—M bonds, wherein M is a metal atom suitable for use in the sol-gel process, M is often one of the group of Aluminum (Al,), Zirconium (Zr), Titanium (Ti), Erbium (Er) and Germanium (Ge).
[0014] An optical compound material made by the process, will have low optical loss in the optical wavelength range between 1.0 and 1.8 micrometers.
[0015] A preferred application is a sol-gel process for maling optical gratings and optical index matching coatings providing low optical loss in the wavelength range between 1.0 and 1.8 micrometers.
[0016] Further, a process for producing optical compound materials substantially free from O—H bonds, comprises the step of using deuterium oxide (D 2 O) in hydrolysis and condensation of silanes and metal compounds, for use as adhesives and surface treatments agents for promoting adhesion between silicon, silica, glass, metal oxide, or metal substrates with materials containing organic groups.
[0017] The process is applicable for producing optical compound materials wherein the material is one of the group of sol-gel materials, organic/inorganic hybrids, and polymer resins such as polysiloxane.
[0018] The method enhances hydrolysis and condensation of silanes and metal compounds in sol-gel processes and is characterized by the step of substituting deuterium oxide (D 2 O) for protium oxide (H 2 O).
[0019] The method of depositing silica and metal oxides on a substrate is characterized by use of deuterium oxide (D 2 O) as hydrolysis agent.
[0020] The method of depositing silica and metal oxides on a substrate by flame hydrolysis deposition (FHD) is characterized by use of deuterium oxide (D 2 O) as hydrolysis agent.
[0021] The method for reducing optical loss in the range between 1.0 and 1.8 micrometers in optical materials, wherein O—H bonds are replaced by O—D bonds, O being oxygen, H being protium and D being deuterium.
BRIEF DESCRIPTION OF THE DRAWING
[0022] The preferred exemplary embodiments of the present invention will now be described in detail in connection with the annexed drawing figures, in which:
[0023] [0023]FIG. 1 shows the absorption of H 2 O and D 2 O in the near infrared region, measured by using Nicloet 470 FTIR/NIR spectrometer with transmission model and a 1 mm thick quart sealed liquid fell was used for the measurement; and
[0024] [0024]FIG. 2 shows the absorption of D 2 O and H 2 O based sol-gel materials in the near infrared region, measured by using Nicloet 470 FT spectrometer with transmission model and a sample thickness of 2 mm.
DETAILED DESCRIPTION OF THE INVENTION
[0025] It is well known that any protium H in materials will increase optical loss in the range of 1.3 to 1.55 μm, a typical wavelength range for optical communication. The strategy to eliminate H is to replace H with fluorine F and deuterium D. This approach has received great success in replacing C—H bonds with C—F or C—D bonds. The reason is that the C—H bond's vibrational overtones occur near 1.3 and 1.55 μm, and the related energy is inversely related to the reduced mass. Due to the highly reduced mass of F and D, the fundamental bond vibrational overtones of C—F and C—D can be lowered, shifting the related absorption peak to longer wavelength range. Fluorinated and deuterated acrylate resins and fluorinated sol-gel materials are examples of successful systems. It should be noted, however, that while the replacement of C—H with C—F can reduce the optical loss at both 1.3 and 1.55 μm, the replacement of C—H with C—D can only reduce the loss at 1.3 μm because C-D has an absorption at 1.55 μm. C—D technology is definitely not suitable for the application at 1.55 μm. This excludes the application possibility of C—D technology because 1.55 μm is the wavelength used most in fiber optical communication.
[0026] The method of the present invention is to replace H 2 O with D 2 O for hydrolysis of silanes, followed by proper polycondensation. D and H are both isotopes of hydrogen. H is the most common isotope of hydrogen. It has a mass number of 1 and an atomic mass of 1.007822. Its nucleus is a proton. D, also called heavy hydrogen, has a mass number of 2 and an atomic mass of 2.0140. Its nucleus consists of a proton plus a neutron. D 2 O, so-called heavy water, has a melting point of 3.79° C., boiling point of 101.4° C., and density of 1.107 g/cm 3 at 25° C., in comparison to H 2 O with 0°, 100° C., and 1.000 g/cm 3 , respectively. D 2 O is not radioactive and is widely used as a moderator in nuclear reactors. The chemical properties of D 2 O are generally considered same as H 2 O because both D and H have one proton. The absorption behavior of O—D in comparison with O—H, is the reason for the present D 2 O-based hydrolysis of silanes and other metal compounds, especially in sol-gel processes.
[0027] [0027]FIG. 1 shows the absorption spectrum of D 2 O with H 2 O in the near infrared region. The measurement was conducted by using Nicloet 470 FTIR/NIR spectrometer with transmission model. A 1 mm thick quart sealed liquid cell was used for the measurement. The first and second overtones of O—H are shown at 1.94 μm and 1.45 μm respectively with strong intensity. The absorption of H 2 O at 1.55 μm is greatly enhanced especially by the second overtone, peak of O—H. On the other hand, the second overtone peak of O—D occurs at 1.98 μm with intensity lower than that of the second overtone peak of O—H at 1.45 μn, and the first overtone of O-D occurs at above 2 . 61 pm (not shown in the figure).
[0028] There is no absorption peak for O—D within the range of 1.0 to 1.8 μm. As a result, the absorption of D 2 O at 1.55 μm is {fraction (1/10)} of the absorption of H 2 O at the same wavelength. The above result fits well in our theoretical calculation based on infrared theory.
[0029] Although the absorption peaks of O—D, in a material, such as polysiloxane resin, will not be the same with those in D 2 O due to the changed chemical environment, the difference is generally quite small. It implies that for the same concentration of O—H and O—D in certain materials, the O—D containing system should have much lower chemical related absorption at 1.55 μm than O—H containing system. The D 2 O based hydrolysis and condensation of silanes based on the present invention have been tested in the laboratory and can be expressed as:
Si—O—R+D 2 O→Si—O—D (1)
Si—O—D+D—O—Si→Si—O—Si (2)
Si—O—D+RO—Si→Si—O—Si+RO—D (3)
[0030] Where R is an organic group, such as CH 3 , C 2 H 5 , C 3 H 7 , . . . , etc.
[0031] The D 2 O-based hydrolysis and condensation of metal compounds can be expressed as:
M—OR+D 2 O→M—O—D (4)
M—O—D+D—O—M→M—O—M (5)
M—O—D+RO—M→M—O—M+RO—D (6)
[0032] Where R is the same as above, and M is a metal atom, such as Al, Ti, Zr, Er, Pb, . . . , etc.
[0033] As seen in the reaction equations, O—D is the only chemical residual in the materials. The obtained materials or chemicals are 100% O—H free.
[0034] The hydrolysis and condensation of silanes and metal compounds under D 2 O, can be conducted under the same condition as those under H 2 O. These reactions occur in acid or basic catalyzed environment. The difference between acid-catalyzed and basic catalyzed reaction is that acid is in favor of hydrolysis while basic is in favor of condensation. Chemicals, such as methanol, ethanol, isopropyanol, and acetone can be all used as the solvent for the reactions based on D 2 O. Bulk reaction without any solvent can be also conducted in a controlled way. Reaction temperature can be kept at a wide range from room temperature to 80° C. The advantage of applying D 2 O is that the technology based on H 2 O, which was started a hundred year ago, can be copied and transferred to D 2 O system with minor modification.
[0035] Very importantly, D 2 O involved hydrolysis and condensation were found very easily in comparison with H 2 O involved one. For instance, when H 2 O and D 2 O were respectively applied in the hydrolysis and condensation of methacryloxypropyl triethoxysilane in acid-catalyzed bulk system, the D 2 O-based reaction is faster than H 2 O-based one. The viscosity of the resulted resin from D 2 O is 100% higher than that of the H 2 O-resulted resin. Also, for a typical sol-gel process based on tetraethoxysilane in isopropyanol at acid condition, D 2 O was found to be impossible to generate a transparent sol-gel solution because the condensation was too fast to produce and precipitate gel particles. On the other hand, transparent sol-gel solution was easily prepared under the identical condition with H 2 O.
[0036] The easy hydrolysis and condensation is a real advantage for D 2 O-based reactions. It means that less O—R will be left and more Si—O—Si will be formed in D 2 O based system than H 2 O's system, and the residual O—D in D 2 O based system will be lower than the residual O—H in H 2 O's system. In other words, even if O—D bond had the same absorption behavior as O—H in the region of 1 to 1.8 μn, D 2 O based system will still have lower absorption, thus optical loss, than H 2 O based system in the region. It can be expected that, in comparison with H 2 O based system, D 2 O based system should have even lower O—D bond-caused optical loss at 1.55 μm than that obtained from FIG. 1.
[0037] [0037]FIG. 2 shows the absorption of D 2 O and H 2 O based sol-gel materials in the near infrared region. The measurement was conducted by using Nicloet 470 FTIR/NIR spectrometer with transmission model and sample thickness was 2 m for both materials. The materials were synthesized from methacryloxypropyl trimethoxysilane and diphenyldiethoxysilane by sol-gel process, one with D 2 O and another one with H 2 O as hydrolysis agent. The peak at around 1.4 μm is due to C—H bond for D 2 O based material, and C-H bond and O—H bond for H 2 O based material. Consequently, the materials based on D 2 O does not have an absorption shoulder at 1.55 μm, while the materials based on H 2 O has a stronger O—H bond related shoulder at 1.55 μm. The waveguide propagation loss of D 2 O based materials is 30% to 50% lower than that of H 2 O based materials.
[0038] Since the hydrolysis and condensation can develop easily in D 2 O-based reactions during the materials synthesis stage, less post reaction will be required for the materials processing stage for the system. The benefit is that lower baking temperature would be required for processing the materials reacted from D 2 O and the achieved materials have less shrinkage during the processing, and have better thermal and mechanical properties than H 2 O based materials. Also, it should be noted that the acid-catalyzed hydrolysis and condensation under D 2 O is a problem for the hydrolysis and condensation of fluorinated silanes which are unstable under basic environment.
[0039] The D 2 O technology has resulted in various O—H free materials in our lab. Sol-gel based silicon containing materials and metal containing materials, which can be used as waveguiding photonic device, surface treatment agent, coating, index matcher, and adhesives, are the representative examples. Such technology can be easily extended to other application for producing silica and metal oxides for optical communication. Manufacturing of waveguiding photonic devices by such as flame hydrolysis deposition (FHD), for instance, is the area where D 2 O technology can be applied because H 2 O is used in these processes and the elimination of residual O—H is big problem.
EXAMPLE 1
[0040] 25 g methacryloxypropyl trimethoxysilane was reacted with 4.4 g D 2 O with acid HCL as catalyst at 20 room temperature. The mixture was opaque at beginning, and turned backed to transparent within 3 minutes. Reaction heat resulted temperature increase was detected to start at 2 minutes. The mixture was stirred for 16 hrs with aluminum foil covering the baker's top. Viscous resin was obtained from the reaction and the viscosity of the solution which contains D 2 O and ethanol resulted from the reaction was measured at room temperature as 63.4 cp by using Brookfield viscometer. The solution was coated on silicon and glasses and baked at 110 to 130° C. for 24 hr. to produce flat, hard and transparent coatings. No O—H absorption was detected in the materials in the range of 1 to 1.8 μm by using Nicloet 470 FTIR/NIR spectrometer.
[0041] A parallel reaction with the replacement of 4.4 g D 2 O with 4.2 g H 2 O was also conducted. The reaction phenomenon was basically the same as the reaction with D 2 O. The resulted resin after the same reaction time as above was measured as 31.6 cp of viscosity at room temperature.
EXAMPLE 2
[0042] 20 tetraethoxysilanes (TEOS) was reacted with 4.10 g D 2 O with 4.8 g isopropanol in presence and HCL acid as catalyst. The mixture was opaque at the beginning, but turned backed to transparent within 3 minutes, and then turned into opaque. Reaction resulted temperature increase was detected to start within 2 minutes. After stirred for 1.5 hrs, opaque solution with fine suspended particles was obtained. These particles are visible when the solution was cast on glasses and the solvent was evaporated. Flat and hard coatings were obtained after the solution was filtered with 0.45 μm sized filter, and then coated by spinning coating, followed by baking at 110° C.
[0043] A parallel reaction with the replacement of 4.1 g D 2 O with 3.9 g H 2 O was also conducted. The reaction time was basically the same as the reaction with D 2 O, however the solution only experienced transparent-to-opaque and opaque-to-transparent process and the final solution was transparent one with no suspended particles. Flat and hard coatings were obtained without filtering the solution
[0044] The particles generated from D 2 O-based system during the reaction were silica gels. They were produced due to the fast condensation process. The solubility of silica gels in the solution is limited and the gel precipitate from the solution instantly when the gel particles reach certain size. Similar particles were reported in basic-catalyzed H 2 O-based system because condensation under basic is very fast.
EXAMPLE 3
[0045] 25 g methacryloxypropyl triethoxysilane and 3.0 g D 2 O was reacted under acid condition for 2 hr. and then mixed with the mixture of methacrylic acid and zirconium n-propoxide (18 g), and then 1.5 g D 2 O for 2 hr. The resulted solution was viscous with a viscosity at room temperature as 142 cp when the measurement was done 48 hr after the reaction was completed. In the case that H 2 O was used in the reaction, the resulted solution viscosity was measured as 52.6 cp under the same conditions. 2% mol photosensitive initiator (Irgacure) was added into the system to yield a free-flowing solution, which was passed through 0.2 μm filter.
[0046] Films were deposited on polished silicon by dip coating with the filtered solution and then prebaked at 100 for 30 min to stabilize the coating. They were then exposed to UV light through mask with desired opening to polymerize the macrylates component. After rinsing with a proper chemical and dried, desired waveguides were formed on the substrates. Channel waveguides with proper buffer and upper cladding, which were also based D 2 O resulted materials, were prepared and tested. Their propagation loss at 1.5 μm is 30% less than that of the waveguides based on H 2 O.
EXAMPLE 4
[0047] 15 g methacryloxypropyl triethoxysilane and 12 g diphenyldiethoxysilane were reacted with 5 g D 2 O. A very viscous resin was obtained after the reaction. 2% mol photosensitive initiator (Irgacure) and a proper solvent was added into the system to yield a free-flowing solution. The solution was filtered through a 0.45 μm sized filter and deposited on silicon for preparing channel waveguides and casting cylinder/rectangular blocks with proper UV exposure and thermal treatment. Similar reaction based on H 2 O was also conducted and the obtained material was used for comparison.
[0048] [0048]FIG. 2 shows the absorption of the materials in the near infrared range. The peak at around 1.4 μm is due to C—H bond for D 2 O based materials, and C—H bond and O—H bond for H 2 O based materials. Consequently, the materials based on D 2 O does not have an absorption shoulder at 1.55 μm, while the materials based on H 2 O has a stronger O—H bond related shoulder at 1.55 μm. The waveguide propagation loss of D 2 O based materials is 30% to 50% lower than that of H 2 O based materials.
EXAMPLE 5
[0049] 15 g phenyltriethoxysilane and 2.5 g diphenyldiethoxysilane were reacted with 5.8 g D2O under basic condition at 60° C. A very viscous resing was ontaied after the reaction was proceed for 7 hrs. After being cured at 130° C., the resin was measured to have a refractive index of 1.501 at 1.5 μm wavelength. The material was applied between two optical fibers and fiber to waveguide as low optical loss index matching materials.
EXAMPLE 6
[0050] 15 g methacryloxypropyl trimethoxysilane and 6.3 g diphenyldiethoxysilane were reacted with 6.3 g D2O under acid condition. After reacting for 7 hrs at 70° C., 70 ml acetone was added into the solution at room temperature, followed by adding 2 g tetraethoxysilane. 4 hrs later, 1 g of D2O was gradually added into the solution and the solution was kept stirring at room temperature for 24 hrs.
[0051] The obtained solution was used as surface promoter of silicon wager and silica for producing waveguides when using the materials as defined in EXAMPLE 4 as waveguide materials.
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Deuterium oxide, D 2 O, also called heavy water, is used for the hydrolysis of silanes and metal compounds. The D 2 O-hydrolyzed silanes polycondense much easier than H 2 O-hydrolyzed silanes, resulting in a fast Si—O—Si network build up. The most important feature of using D 2 O is that the final materials are 100% free of O—H and the residual O—D bond does not have an absorption peak in the wavelength range of 1.0 to 1.8 μm, which is crucial in reducing optical loss at the wavelengths of 1.3 and especially 1.55 μm. O—H free sol-gel materials with low optical loss have been developed based on this process. D 2 O may be applied in all kinds of hydrolysis-processes, such as the sol-gel process of silanes and metal compounds, the synthesis of polysiloxane, and may be extended to other silica and metal-oxides deposition processes for example, flame hydrolysis deposition (FHD) whenever water is used or O—H bond involved. The concept of replacing O—H bond with O—D bond is applicable to any O—H bond containing materials used in optical based telecommunication.
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BACKGROUND OF THE INVENTION
The invention relates to a device and process for the laser treatment of a workpiece.
Diode lasers are known and have been used for the laser machining of workpieces. As a result of the resonator geometry of diode lasers or their laser chips, the laser beam of these lasers has a relatively large angle of divergence (greater than 1000 mrad) in the plane perpendicular to the active layer of the semiconductor (also the fast axis), while in the plane parallel to the active layer (also the slow axis) the angle of divergence is much smaller, for example, 100 to 200 mrad. These angles of divergence are too large for direct use of laser radiation for machining of workpieces or materials, so that optical preparation of the radiation by microoptics is necessary and conventional.
If one were to use a transversely lying microcylinder lens for each semiconductor chip or for all emitters formed thereon, the beam divergence in the plane perpendicular to the active layer can be reduced to roughly 10 mrad. The beam pencil present with 10×180 mrad divergence in the two axial directions can be further worked by optics with the f/# ranging from f/1.5 to f/4. When one such beam is focussed the picture of a line appears, i.e. of a line focus, that is, as an image of the emitter of the respective laser chip which are distributed in a line next to one another over the width (conventionally roughly 10 mm) of the chip.
Since this line focus is perceived as disruptive, an attempt is made using optical means to attain resolution of this line focus, i.e. shaping of the laser beam for formation into a uniform focus as circular as possible, by concentrating numerous optical fibers in a circular cross section (U.S. Pat. No. 5,127,068; U.S. Pat. No. 4,763,975; U.S. Pat. No. 4,818,062; U.S. Pat. No. 5,268,978; and U.S. Pat. No. 5,258,989) by socalled beam turning, in which rearrangement of the individual laser beams to achieve a focus as circular as possible takes place (U.S. Pat. No. 5,168,401, FP 0 484 276; WO 95/15510; DE 44 38 368) or by parallel shifting of individual laser beams (U.S. Pat. No. 3,396,344; DE 195 00 513; DE 195 44 448).
These known processes allow almost uniform beam quality, i.e. especially uniform beam divergence and uniform beam cross section in two axial directions. Known methods however can only be accomplished with a relatively high cost in laser optics. Diode lasers with high output power become more expensive and are not competitive with conventional lasers. Furthermore, known methods of improving beam quality due to the complexity of optical components are associated with large losses in power density. In practice, with these known arrangements only power densities of 10 4 to 10 5 W/cm 2 are achieved. However power densities between 10 6 and 10 7 W/cm 2 would be possible without the lens defects and losses which occur in these optics.
The object of the invention is to avoid these defects and to devise a device and process for laser machining of workpieces using a laser head having at least one diode laser, in which the aforementioned defects are avoided. To achieve this object a device and process according to the present invention are formed.
SUMMARY OF THE INVENTION
In the device or in the process for laser machining of workpieces, shaping of the laser beam into an almost circularly focussable beam is intentionally abandoned. Rather the line focus is used. With a curved working or machining contour, the focus line is aligned such that this focus line with its longitudinal extension, forms at each point of this contour its tangent. This has the advantage that in spite of the line focus and in spite of avoiding expensive optical shaping a narrow working or machining contour is achieved. Furthermore, a higher power density than in the prior art is achieved in the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is detailed below using figures on embodiments.
FIG. 1 shows in a simplified perspective view a device as claimed in the invention for machining workpieces by means of a laser beam;
FIG. 2 shows a machining contour in an individual representation;
FIG. 3 shows in an enlarged representation the focus of a laser beam on the workpiece in the area of the machining contour;
FIG. 4 shows in a simplified representation a section through a laser diode arrangement consisting of a plurality of laser chips stacked on top of one another, which each form a plurality of emitters which are distributed over the chip width and which are located next to one another, together with laser optics in a section perpendicular to the active layer of the lasers chip or its emitters;
FIG. 5 shows a section through the diode laser arrangement and the laser optics of FIG. 4 in a sectional plane parallel to the active layers of the diode elements;
FIGS. 6 and 7 show in representations similar to FIGS. 4 and 5 the diode laser arrangement together with the laser optics in a section perpendicular to the active layer of the diode elements (FIG. 6) or parallel to the active layer (FIG. 7) in another possible embodiment;
FIGS. 8 and 9 show sectional representations similar to FIGS. 4 and 5 in a plane perpendicular to the active layer (FIG. 8) and in a plane parallel to the active layer (FIG. 9) in another embodiment in which a total of three laser diode arrangements are used;
FIG. 10 shows in positions a-f for purposes of explanation different possibilities for use of diode laser arrangements, especially also for frequency multiplexing;
FIGS. 11 and 12 show in representations similar to FIGS. 8 and 9 a diode laser in a modular design and in a section perpendicular to the active layer of the diode elements (FIG. 11) and parallel to the active layer (FIG. 12 );
FIGS. 13 and 14 show in representations similar to FIGS. 11 and 12 a diode laser in a modular design and in a section perpendicular to the active layer of the diode elements (FIG. 13) and parallel to the active layer (FIG. 14 );
FIGS. 15 and 16 show in representations similar to FIGS. 13 and 14 a diode laser or laser optics with optical means for rotating the laser beam or focus line;
FIG. 17 shows in an enlarged perspective representation a rotating or Dove prism for use in the diode laser from FIGS. 15 and 16; and
FIG. 18 shows in positions a-b overhead views on the front and back surface of the rotary prism, together with the virtual image of a strip-shaped incident or emerging laser beam in different rotary positions of the rotary prism.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a workpiece which for the sake of simpler representation is shown as a plate and which is to be worked, for example welded or cut, along curved contour 2 with focussed laser beam 3 .
To produce laser beam 3 , diode laser 4 which is shown in FIGS. 4 and 5 is used; it consists of diode laser arrangement 5 and laser optics 6 . To simplify the description, FIGS. 4 and 5, but also FIGS. 6-9 label by X, Y and Z respectively the three coordinate directions perpendicular to one another which are hereinafter called the X-axis, Y-axis, and Z-axis.
Laser diode arrangement 5 consists of several laser chips 7 which with their surface sides and active layers lie in planes perpendicular to the plane of the drawing in FIG. 4 which is defined by the Y-axis and Z-axis, i.e. in the planes which are defined by the X-axis and Z-axis. The laser chips are stacked on top of one another in the direction of the Y-axis, together with substrates which are not shown and which each form a heat sink for the laser chips. Each laser chip 7 forms several diode elements or emitters which emit the laser light and which are offset to one another in the direction of the X-axis. The Z-axis forms the optical axis of laser optics 6 .
As a result of the resonance geometry of the laser chips and their emitters, the laser beam produced by the emitters has a very large angle of divergence of more than 1000 mrad in the plane or axis perpendicular to the active layer, i.e. in the representation chosen for FIGS. 4 and 5 in the Y-axis (also the fast axis) or Y-Z plane and a smaller angle of divergence of roughly 100 to 200 mrad in the plane or axis parallel to the active layer (also the slow axis) or in the X-Z plane. It is essential to undertake collimation of the laser radiation both in the slow axis and fast axis, in the fast axis by fast axis collimator 8 which consists of an arrangement of a plurality of microcylindrical lenses, and one each microcylinder lens which extends in the direction of the X-axis for each laser diode chip 7 . With this fast axis collimator 8 , the beam divergence in the fast axis can be reduced to roughly 10 mrad at present, i.e. with conventional lenses. Smaller beam divergence is also possible. For collimation in the slow axis (X-axis), there is slow axis collimator 9 , likewise formed as a cylindrical lens.
Collimators 8 and 9 are a component of laser optics 6 . It also contains beam expanding optics which is formed by cylinder lenses 10 and 11 , and located between fast axis collimator 8 and slow axis collimator 9 in the beam path of the laser radiation and with which the laser radiation which is essentially parallel in the plane perpendicular to the active layer of laser chip 7 is expanded, roughly at a factor 1.5 to 4, the beam divergence in the direction of the fast axis (Y-axis) then being roughly 2.5 to 7 mrad. Using focussing optics 12 which is shown in FIGS. 4 and 5, as a spherical lens, and which has a focal width f=100 mm, the laser beam is focussed such that it forms on workpiece 1 a linear focus or line focus 13 which has a small focal width of 0.25 to 0.7 mm. The greater length of the line focus is determined by the dimensions of laser chips 7 in the direction of the X-axis.
Since the expanding optics is formed by cylindrical lenses 10 and 11 , with cylinder axes in the X-axis, expansion takes place solely in the plane perpendicular to the active layer such that following cylinder lens 11 in this plane, divergence which is reduced compared to the beam divergence after collimator 8 is achieved and following slow axis collimator 9 a laser beam pencil parallel in the plane parallel to the active layer is also obtained which is focussed using focussing optics 12 . Widening the beam in the plane perpendicular to the active layer with subsequent focussing results in a high power density, due to the small focal width of the line focus.
Laser optics 6 allows a relatively large distance between diode laser arrangement 5 and line focus 13 on workpiece 1 or the working point formed by this line focus 13 , such that diode laser arrangement 5 is reliably protected against fouling, etc.
Since line focus 13 has a length dictated by the distribution of emitters of laser chips 7 in the direction of the X-axis, which is much greater than the width of the line focus, the movement of line focus 13 , along curved machining contour 2 , takes place such that this line focus 13 with its longitudinal axis at each point of the curved machining contour forms tangent 14 to this working contour.
For this machining, workpiece 1 is clamped on table 15 , which can be moved, by control means 16 , in two axes which run perpendicular to one another, in the embodiment shown around the Y-axis and X-axis, which also define the top side of workpiece 1 . Above table 15 is the laser head or diode laser 4 which is oriented with the Z-axis perpendicular to the plane of the table or workpiece 1 and which is held on rotary means 17 with which diode laser 4 can be turned around axis of rotation D, i.e. around the Z-axis or around the optical axis of its laser optics 6 . Rotary means 17 is likewise controlled by control means 16 , according to a given program corresponding to machining contour 2 such that in the aforementioned manner line focus 13 with its longitudinal extension forms tangent 14 to machining contour 2 . To produce machining contour 2 the table with workpiece 1 is moved accordingly in the Y-axis and X-axis. The axis of rotation around which diode laser 4 is turned by rotary means 17 is also in the center of line focus 13 produced by this diode laser. The described device allows laser machining of workpieces 1 along very narrow machining contour 2 with high power and power density.
FIGS. 6 and 7 show diode laser 4 a which differs from the diode laser of FIGS. 4 and 5 essentially in that for laser optics 6 a there expansion optics formed by cylindrical lenses 10 a and 11 a is provided for the beam path of the laser beam following slow axis collimator 9 , and in turn in the beam path of focussing optics 12 .
FIGS. 8 and 9 show diode laser 4 b which corresponds to diode laser 4 a of FIGS. 6 and 7 with regard to its laser optics 6 b , but which in addition to diode laser arrangement 5 has two more diode laser arrangements 5 a and 5 b , each with its own fast axis collimator 8 , and with laser light coupled via optical coupling elements 18 into the beam path of diode laser arrangement 5 , between fast axis collimator 8 of diode laser arrangement 5 and slow axis collimator 9 which is provided jointly for all diode laser arrangements 5 - 5 b of diode laser 4 b . Diode laser arrangements 5 a and 5 b are oriented such that the planes are parallel to the active layers of laser chips 7 of these arrangements perpendicular to the Z-axis. The emitters of laser chips 7 of diode laser arrangements 5 a and 5 b are offset against one another on each chip 7 in turn in the direction of the X-axis. Furthermore, for diode laser arrangements 5 a and 5 b the Z-axis is perpendicular to the planes of the active layers.
Two coupling elements 18 are cascaded, i.e. arranged behind one another in the beam path between fast axis collimator 8 of diode laser arrangement 5 and slow axis collimator 9 . In the embodiments shown, coupling elements 18 are edge filters and diode laser arrangements 5 , 5 a , and 5 b are chosen such that the laser light produced by these arrangements has a different wavelength and is matched to the filter characteristics. The wavelength of laser diode arrangement 5 is for example smaller than the wavelength of laser diode arrangement 5 a and this in turn is smaller than the wavelength of laser diode arrangement 5 b . Other versions are also conceivable. In particular, it is also conceivable that laser light from only two diode laser arrangements or from more than three diode laser arrangements could be combined or added. Combining several diode laser arrangements allows maximum power density in the machining area at the cost of the broad optical spectrum of the entire laser.
In diode laser 4 b , it is important that the optical path length of the light paths between the active areas, i.e. the emitters of diode laser arrangement 5 , 5 a , 5 b and any reference plane BE perpendicular to the Z-axis in the beam path following optical coupling elements 18 , is the same.
Like diode laser 4 , diode lasers 4 a and 4 b on rotation unit 17 are also used such that when machining workpiece 1 along machining contour 2 , in turn by controlled rotation around axis of rotation D line focus 13 in the above described manner is oriented with respect to the progression of machining contour 2 .
It was assumed above that respective diode laser 4 , 4 a or 4 b is oriented with the optical axis of its laser optics 6 perpendicular to the plane of workpiece 1 and thus the Y-axis and X-axis of the respective diode laser at the same time also define the plane of workpiece 1 . Different versions are also conceivable here in which the laser beam of the diode laser is deflected and after this deflection forms line focus 13 . In this case as well, rotation takes place by rotation unit 17 around axis of rotation D which is the center axis of line focus 13 , the plane of workpiece 1 being determined in any case by the Y-axis and X-axis of diode laser 4 .
Electric power supply of respective diode laser 4 , 4 a , or 4 b provided on rotation unit 17 takes place via sliding contacts or via electrical cables which enable repeated turning. In the latter case then, at the end of each machining process, rotation unit 17 with diode laser 4 , 4 a or 4 b is turned back to its initial position. Cooling medium is supplied to and removed from diode laser 4 , 4 a or 4 b preferably via rotary couplings.
The described device is suitable for example for welding jobs (also seam welding) or cutting tasks. By guiding or controlling the orientation of the respective diode laser, weld seams or cuts with a very narrow width can be made, by which also the welding or cutting speed can be increased and the heat losses minimized. By coupling several diode laser arrangements via coupling elements 18 and also by expanding the beam, the power density is greatly increased so that welding by means of the deep welding effect becomes possible. Uniform machining behavior is achieved in all directions of the progression of this machining contour by the described alignment of line focus 13 with reference to the machining contour.
The described device is also suitable for soldering processes. In particular, depending on the location of the soldering points, it is a good idea to align line focus 13 . The invention was described above using embodiments. It goes without saying that numerous changes and modifications are possible without departing from the inventive idea underlying the invention. Thus it is also fundamentally possible to place diode laser 4 , 4 a or 4 b or the laser head having this diode laser stationary and to align line focus 13 tangentially to the machining contour by moving the optics or part of the optics of the diode laser or laser head in a controlled manner.
Thus, it is possible to use a different telescopic arrangement of lenses or mirrors for beam expansion instead of cylinder lenses 10 , 10 a , and 11 or 11 a . Furthermore, other optical arrangements or components 18 are possible, such as filter arrangements, especially short and longpass filters, optical arrangements for coupling of radiation polarized in different planes, etc.
FIGS. 10 to 14 show other possible embodiments of the diode laser. FIG. 10 again schematically shows different possibilities for use of diode laser arrangements in positions. Position a shows use of single diode laser arrangement 5 , as is described also in FIGS. 4 and 5 or 6 and 7 for diode lasers 4 and 4 a there.
Position b shows two diode laser arrangements 5 and 5 a with radiation added via optical coupling element 18 to form overall radiation.
Position c shows three diode laser arrangements 5 , 5 a , and 5 b coupled via coupling elements 18 , corresponding to diode laser 4 b.
Positions d-f show other possibilities of coupling of a total of four diode laser arrangements 5 - 5 c using three coupling elements (position d), coupling of five diode laser arrangements 5 - 5 d using four coupling elements 18 (position e), and coupling of a total of six diode laser arrangements ( 5 - 5 e ) using a total of five coupling elements 18 .
Coupling elements 18 are preferably in turn made as edge filters or other optical arrangements or elements such as filter arrangements, especially shortpass and longpass filters, an optical arrangement for coupling in different planes of polarized radiation, etc. In each case, coupling elements 18 are formed such that they enable combination or addition of the beams of individual diode laser arrangements 5 - 5 e with as little loss as possible.
FIGS. 11 and 12 show as another possible embodiment diode laser 4 c in which via five coupling elements 18 radiation from a total of six diode laser arrangements 5 - 5 e is coupled or added to form overall radiation. The fast axis collimators in this embodiment or in laser optics 6 c there which corresponds in its basic structure to laser optics 6 a are in turn each on pertinent diode laser arrangement 5 - 5 e . Diode laser arrangements 5 - 5 e , their fast axis collimators, and optical coupling elements 18 are located in module 19 .
In addition to this module 19 , there are other modules 20 , 21 and 22 , of which module 20 contains slow axis collimator 9 , module 21 contains beam expansion, i.e. cylinder lenses 10 a and 11 a, and module 22 contains the focussing optics. Modules 20 , 21 and 22 are thus attached to one another and to module 19 so that for diode laser 4 c there is laser optics 6 c which corresponds to the optics of diode laser 4 a and in which beam expansion takes place in the beam path following slow axis collimator 9 and in front of focussing optics 12 .
FIGS. 13 and 14 show diode laser 4 d which is in turn modular, i.e. consists of several modules, specifically of module 19 with diode laser arrangements 5 - 5 e and coupling elements 18 , of module 20 with slow axis collimator 9 , of module 21 a with cylindrical beam expansion, i.e. with cylinder lenses 10 and 11 , and of module 22 with focussing optics 12 .
The individual modules in diode laser 4 d are provided on one another such that laser optics 6 d corresponding to diode laser 4 or laser optics 6 is achieved in which there is cylindrical beam widening (cylinder lenses 10 and 11 ) in the beam path in front of slow axis collimator 9 .
The modularity of diode lasers 4 c and 4 d among others has the advantage that with a stipulated number of components the most varied diode lasers and/or laser optics for the most varied applications can be accomplished especially with respect to power, etc. Thus, instead of module 19 with a total of six diode laser arrangements ( 5 - 5 e ) a module can also be used which has a different number of diode laser arrangements corresponding to positions a-e of FIG. 10 .
FIGS. 15 and 16 show diode laser 4 h with laser optics 6 h which corresponds for the most part to laser optics 6 e of FIGS. 13 and 14, i.e. has modules 20 , 21 a and 22 . In the beam path of laser optics 6 h , between modules 20 and 22 there is also rotary module 32 with which rotation of laser beam 3 and thus line focus 13 is possible, this rotary module 32 can being located elsewhere. As a functional element, rotary module 32 contains optical prism 33 which is made as a Dove prism in the embodiment shown and which has a trapezoidal cross section in the cross sectional plane which includes optical axis 34 of rotary module 32 , the lateral surfaces which intersect optical axis 34 at an angle forming beam entry surface 35 or beam exit surface 36 . As FIG. 16 shows, laser beam 3 is diffracted on beam entry surface 35 when it enters prism 33 , then reflected on lower surface 37 which forms the base of the trapezoidal cross section with total reflection, and is re-diffracted upon emerging on beam exit surface 36 , so that the center axis of laser beam 3 coincides with optical axis 34 both in front of prism 33 and also following this prism. Prism 33 is driven peripherally around its beam axis for rotation of beam 3 by a drive which is not shown, such as an electric motor.
FIGS. 17 and 18 explain the optical action of rotary prism 33 . In these Figures, it is assumed that the laser beam emerging from beam exit surface 36 and incident on beam entry surface 35 is a flat, strip-shaped beam. The entering laser beam in positions a-c of FIG. 18 is labeled with the segment AB. The laser beam emerging on beam exit surface 36 is labeled with segment A′B′.
Positions a-c give three different rotary positions of rotary prism 33 . The figures show that with uniform orientation of laser beam 3 incident on beam entry surface 35 , the laser beam emerging on beam exit surface 36 or segment A′B′ which defines the orientation rotates around this optical axis 34 . This follows from the above described diffraction of the beam on surface 35 and 36 and from reflection on surface 37 as is shown again in FIG. 17 .
By using rotation module 32 , it is possible to provide a diode laser 4 h without the capacity to turn on a part of the device, i.e. to abandon rotation unit 7 . But it is also possible to use both rotation unit 17 and also rotary module 32 if this is necessary or feasible for special machining and/or controls.
It was assumed above that rotary prism 33 is rotated around its optical axis 34 . of course swivelling of the prism around this axis is conceivable when this is necessary for special applications. Instead of rotary prism 33 , other optical arrangements can also be used which have properties corresponding to a Dove prism, i.e. especially means in which the laser beam entering in one optical axis is deflected or diffracted first obliquely to this axis, then reflected in the direction to the optical axis and then deflected or diffracted again so that the beam runs again in the optical axis.
In laser optics 6 h there is rotary module 32 or rotary prism 33 in the beam path following mirror arrangement 25 and correction prism 26 . Basically rotary prism 33 could also be provided elsewhere in the beam path, but preferably wherever the beam divergences are as small as possible.
Reference Number List
1 workpiece
2 machining contour
3 laser beam
4 , 4 a , 4 b , 4 c diode laser
4 d , 4 h diode laser
5 diode laser arrangement
6 , 6 a , 6 b , 6 c laser optics
6 d , 6 h laser optics
7 laser chip
8 fast axis collimator (in the y-z plane)
9 slow axis collimator (in the x-z plane)
10 , 10 a , 10 b cylinder lens
11 , 11 a , 11 b cylinder lens
12 focussing optics
13 line focus
14 tangent
15 table
16 control means
17 rotation unit
18 optical coupling element
19 , 20 module
21 , 21 a module
22 module
32 rotary module
33 rotary prism
34 optical axis
35 beam entry surface
36 beam exit surface
37 bottom surface
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The invention relates to a novel design of a diode laser, especially for laser treatment of workpieces. As the beam source there is at least one laser chip which has at least one laser light emitter which lies with its active layer perpendicular to a first axial direction (Y-axis; Z-axis) and which extends in a second axial direction (X-axis), or several emitters provided next to one another in the second axial direction, the second axial direction (X-axis) being perpendicular to the first axial direction (Y-axis, Z-axis).
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to a method for forming a Si film, the same Si film, and a solar battery which is made of the same Si film by means of the same forming method.
[0003] 2. Description of the Telated Art
[0004] In order to diffuse safest and environmental Si solar batteries on a large scale and on a global scale, it is required to develop in low cost and in high productivity safest manufacturing technology of solar battery utilizing global rich sources. As of now, in both domestically and abroad, such as manufacturing technology as to complete a solar battery as a device from a Si melt has been mainly developed by means of casting.
[0005] Since the casting method, however, utilizes a solidifying method of melt where the temperature gradient of the solid-liquid interface is increased, it is inherently difficult to develop the crystal quality of the obtained Si polycrystal. Moreover, since pure Si raw materials are expensive, the quality of Si raw materials to be employed is restricted. In this point of view, such a thin film growing method as to form a Si film on an inorganic substrate by means of vapor phase epitaxy has been also developed, in addition to the above-mentioned manufacturing technology.
[0006] With the thin film growing method, however, since epitaxial growing technique utilizing a crystal substrate is not employed, but driving force of growth obtained on the large shift from the equilibrium condition is employed, it is difficult to develop the crystal quality of the obtained thin film. With the thin film growing method, in addition, since a substrate made of glass is employed, the growing temperature can not be enhanced, so that only micro grains are formed in the thin film, and large grains can not be formed. Therefore, the efficiency of a solar battery made of the thin film can not be enhanced.
[0007] In this point of view, as of now, it is eagerly desired to develop a forming technique of Si crystal thin film of low defect density and thus, high quality wherein expensive Si raw materials are not employed and whereby the high efficiency of a solar battery can be realized.
SUMMERY OF THE INVENTION
[0008] It is an object of the present invention to provide a forming technique of Si crystal thin film of low defect density and thus, high quality wherein expensive Si raw materials are not employed and whereby the high efficiency of a solar battery can be realized.
[0009] For achieving the above object, this invention relates to a method for forming a Si thin film, comprising the steps of:
[0010] preparing a Si melt kept at a temperature near Si melting point,
preparing a Si substrate made of Si single crystal or Si polycrystal, and contacting the Si melt to a main surface of the Si substrate to conduct liquid phase epitaxy within a temperature range around the Si melting point and to form a Si crystal thin film on the main surface of the Si substrate.
[0013] The inventors had been intensely studied to achieve the above object, and then, paid an attention to liquid phase epitaxial (LPE) technique because a crystal thin film of high quality can be easily formed by the LPE technique under near equilibrium growth condition. At first, the inventors dissolve Si raw materials in a solvent made of a melt of low melting point metal to form a metallic solution with Si therein ,and conduct the LPE technique utilizing the metallic solution. In this case, however, since the LPE technique is conducted under lower temperature condition than the melting point of Si, the intended high crystal quality and flattened Si crystal thin film can not be formed because of the large contamination of metallic elements from the metallic solution and the low growing temperature.
[0014] In this point of view, the inventors made an attempt to conduct the LPE technique under the condition almost close to the solid-liquid equilibrium by utilizing the Si melt directly, to form a low defect density-high quality and flattened Si crystal thin film. With the LPE technique utilizing the Si melt, even though a relatively low crystal quality Si substrate is employed, the crystal quality of the obtained Si thin film is not almost degraded. Therefore, the Si substrate can be made of a low cost metallurgical Si raw material, and thus, the manufacturing cost of the Si crystal thin film can be reduced largely.
[0015] As a result, according to the forming method of the present invention as mentioned above, the low defect density and thus, high quality Si crystal thin film can be formed in low cost. In the fabrication of a solar battery, therefore, if the forming method of Si crystal thin film according to the present invention is employed, the conversion efficiency of the solar battery can be enhanced sufficiently and the manufacturing cost of the solar battery can be reduced.
[0016] Herein, the wording “metallurgical Si raw material” means not expensive Si raw material which is not refined sufficiently and exist in abundance on the globe.
[0017] In a preferred embodiment of the present invention, the LPE is conducted within a temperature range of ±5° C. of Si melting point. The inherent melting point of Si is 1414° C., but fluctuated due to thermal fluctuation, so that the real melting point is shifted from the inherent melting point. In this case, since the above-mentioned temperature range is a supercooling temperature region of Si melt, the Si melt can be maintained in liquid phase not through solidification. Therefore, the LPE can be conducted in good condition.
[0018] In another preferred embodiment of the present invention, the LPE is conducted under the condition that the Si melt is maintained within a temperature range between the Si melting point and +5° C. of the Si melting point, and a portion of the Si substrate is contacted to the Si melt to be melted, and the temperature of the region of the Si melt in the vicinity of the Si substrate is maintained lower than the Si melting point. In this case, the LPE can be conducted under the condition closer to solid-liquid equilibrium, and thus, the low defect density-high quality and flattened Si crystal thin film can be obtained.
[0019] In still another preferred embodiment, at least small amount of one element selected from the group consisting of In, Ga, Sn, Al, Au—Bi and Cu is added into the Si melt. In this case, the melting point (solidifying point) of the Si melt can be slightly reduced, and the melting point zone can be enlarged. Therefore, in the LPE, the temperature control of the Si melt can be simplified, and the LPE can be conducted surely.
[0020] In the latter preferred embodiment, the amount of element to be added can be set within 0.01-10 at %.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] For better understanding of the present invention, reference is made to the attached drawings, wherein
[0022] FIG. 1 is an explanatory view illustrating one embodiment of the Si crystal thin film forming method of the present invention,
[0023] FIG. 2 is also an explanatory view illustrating the embodiment of the Si crystal thin film forming method of the present invention,
[0024] FIG. 3 is also an explanatory view illustrating the embodiment of the Si crystal thin film forming method of the present invention,
[0025] FIG. 4 is an explanatory view illustrating another embodiment of the Si crystal thin film forming method of the present invention,
[0026] FIG. 5 is also an explanatory view illustrating the another embodiment of the Si crystal thin film forming method of the present invention,
[0027] FIG. 6 is also an explanatory view illustrating the another embodiment of the Si crystal thin film forming method of the present invention, and
[0028] FIG. 7 is an explanatory view illustrating still another embodiment of the Si crystal thin film forming method of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] This invention will be described in detail hereinafter.
[0030] FIGS. 1-3 relate to one embodiment of the Si crystal thin film forming method of the present invention wherein a parallel sliding board is employed. As illustrated in FIG. 1 , a first member 11 with a depressed Si melt holder 13 and a second member 12 with a depressed Si substrate holder 14 are prepared so that the Si melt holder 13 is opposed to the Si substrate holder 14 . The Si melt holder 13 is capped with a carbon or quartz cap 19 . The first member 11 and the second member 12 are disposed, for example, in a lateral type furnace (not shown). A rotatable sliding board may be employed, instead of the parallel sliding board.
[0031] The first member 11 and the second member 12 are connected to driving shafts 15 and 16 , respectively. The driving shafts 15 and 16 are connected to a motor (not shown) so that the first member 11 and the second member 12 are moved laterally (in horizontal direction). The driving shafts 15 and 16 may be driven by man power, instead of the motor. A Si melt X is charged and supported in the Si melt holder 13 , and a Si substrate S is supported in the Si substrate holder 14 .
[0032] The Si substrate S can be made of any kind of Si raw material, and in the present invention, can be made of meta radical Si raw material which exist in abundance on the globe. Since the metallurgical Si raw material is not expensive, the intended Si crystal thin film can be formed in low cost.
[0033] Under the state illustrated in FIG. 1 , the Si melt X is heated to a given temperature within a temperature range of 1° C.˜100° C. above the Si melting point. The LPE can be conducted in good condition at a first temperature wherein the Si melt is not solidified. Concretely, the first temperature is set within a temperature range of −5° C.˜+5° C. (±˜5° C.) of Si melting point.
[0034] Then, the motor (not shown) is driven, and the first member 11 is slid in the left direction with the driving shaft 15 so that as illustrated in FIG. 2 , the Si melt holder 13 is opposed to the Si substrate holder 14 . Then, the Si substrate S is contacted to the Si melt X so that an intended Si crystal thin film is epitaxially grown on the Si substrate S.
[0035] Then, after the Si melt X approaches to a second temperature, the first member 11 is slid in the left direction as illustrated in FIG. 3 so that the Si melt X is left away from the Si substrate S to terminate the LPE. The second temperature is not restricted, but in view of the continuous epitaxial growth, preferably set to the same temperature as the first temperature or lower temperature than the first temperature so that the Si melt S is not solidified. Concretely, the second temperature is preferably set within a temperature range between −10° C.˜+5° C. of the Si melting point.
[0036] Through the above-mentioned steps, the intended Si crystal thin film can be formed on the Si substrate by means of LPE. The thickness of the Si crystal thin film can be varied by controlling the contacting period of time between the Si melt X and the Si substrate S and the temperature of the Si melt X.
[0037] At least one element selected from the group consisting of In, Ga, Sn, Al, Au—Bi and Cu can be added into the Si melt. The amount of element to be added can be set within 0.01-10 at %. In this case, the melting point (solidifying point) of the Si melt can be reduced, and the melting point zone can be enlarged. Therefore, in the LPE, the temperature control of the Si melt can be simplified, and the LPE can be conducted surely.
[0038] When such an additive element as mentioned above is added into the Si melt X, the additive element is contained in the Si crystal thin film. If the amount of the additive element to be added is set within the above-mentioned range, in Ga additive element with small distribution coefficient, the additive element content in the Si crystal thin film is set within 1×10 −9 -1×10 −2 at %.
[0039] FIGS. 4-6 relate to another embodiment of the Si crystal thin film forming method of the present invention. In this embodiment, too, an intended Si crystal thin film is formed by utilizing the sliding board. In this embodiment, like or corresponding members to the ones in the embodiment relating to FIGS. 4-6 are employed, but the second member 12 includes an additive element melt holder 17 in addition to the substrate holder 14 . Into the additive element holder 17 is charged and supported a melt of at least one element selected from the group consisting of In, Ga, Sn, Al, Au—Bi and Cu or Si crystal with a proper amount of at least one element selected from the group consisting of In, Ga, Sn, Al, Au—Bi and Cu.
[0040] First of all, as illustrated in FIG. 4 , the first member 11 and the second member 12 are prepared so that the Si melt holder 13 is opposed to the additive element melt holder 17 . In this case, the Si melt X is contacted to the additive element melt or the Si crystal with the additive element Y so that additive elements in the additive element melt or the Si crystal Y are contained in the Si melt X through convection and diffusion. The Si melt holder 13 is capped with the carbon or quartz cap 19 .
[0041] Then, the Si melt X is heated to a given temperature above the Si melting point. Since the Si melt X contains the additive elements, in order to conduct the LPE in good condition, the first temperature at which the crystal growth starts is set within a temperature range between the Si melting point and −50° C. of the Si melting point.
[0042] Then, the motor (not shown) is driven, and the first member 11 is slid in the left direction with the driving shaft 15 so that as illustrated in FIG. 5 , the Si melt holder 13 is opposed to the Si substrate holder 14 . Then, the Si substrate S is contacted to the Si melt X so that the intended Si crystal thin film is epitaxially grown on the Si substrate S.
[0043] Then, after the Si melt X approaches to a second temperature, the first member 11 is slid in the left direction as illustrated in FIG. 6 so that the Si melt X is left away from the Si substrate S to terminate the LPE. The second temperature is preferably set within a temperature range between the Si melting point and −60° C. of the Si melting point.
[0044] Through the above-mentioned steps, the intended Si crystal thin film can be formed on the Si substrate by means of LPE. The thickness of the Si crystal thin film can be also varied by controlling the contacting period of time between the Si melt X and the Si substrate S and the temperature of the Si melt X. In this embodiment, if Ga additive element is employed, the Si crystal thin film contains the Ga additive element by 1×10 −9 -1×10 −2 at %.
[0045] FIG. 7 relates to still another embodiment of the Si crystal thin film of the present invention. In FIG. 7 , the Si melt X is charged into a given container 31 , and the Si substrate is immersed into the Si melt X. In this case, the intended Si crystal thin film can be formed on the Si substrate through epitaxial growth.
[0046] The thickness of the Si crystal thin film can be varied by controlling the temperature and the immersing period of time of the Si melt X. Moreover, at least one element selected from the group consisting of In, Ga, Sn, Al; Au—Bi and Cu can be added into the Si melt. In this case, too, the melting point (solidifying point) of the Si melt can be reduced, and the melting point zone can be enlarged. Therefore, in the LPE, the temperature control of the Si melt can be simplified, and the LPE can be conducted surely.
EXAMPLE
[0047] In this Example, an intended Si crystal thin film was formed according to the steps illustrated in FIGS. 1-3 . First of all, pure Si raw material was prepared and heated to 1450° C. to form the Si melt X. Then, the Si substrate S was made of metallurgical Si raw material. The Si melt X was kept at 1415° C., and as illustrated in FIG. 2 , the Si substrate S was contacted to the Si melt X for about 0.5˜1 minutes during cooling the Si melt at 1° C./min. to form the intended Si crystal thin film on the Si substrate S through LPE. Then, as illustrated in FIG. 3 , the Si substrate S was left away from the Si melt X to terminate the LPE.
[0048] The thickness of the Si crystal thin film was 50 μm, and the lifetime was 5 μs. Then, a solar battery was made of the Si crystal thin film, and it was turned out that the conversion efficiency of the solar battery was about 8% on the process of Bell Communications Research.
[0049] Although the present invention was described in detail with reference to the above examples, this invention is not limited to the above disclosure and every kind of variation and modification may be made without departing from the scope of the present invention. For example, if a Ge melt is mixed to the Si melt, the SiGe crystal thin film can be formed, instead of the Si crystal thin film.
[0050] As mentioned above, according to the present invention can be provided a forming technique of Si crystal thin film of low defect density and thus, high quality wherein expensive Si raw materials are not employed and whereby the high efficiency of a solar battery can be realized.
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A Si melt is contacted to a main surface of a Si substrate made of metallurgical Si raw material to conduct liquid phase epitaxy within a temperature range around Si melting point and to form a Si crystal thin film on the main surface of the Si substrate.
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BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for producing a thermotropic liquid crystalline polymer of high quality at high production yield.
[0003] 2. Background Art
[0004] Thermotropic liquid crystalline polymers are expensive, since the polymers are produced from expensive aromatic monomers. Thus, reduction of the high production costs thereof is a big issue. In order to reduce costs, elevating the production yield of the polymers is considered to be one solution.
[0005] In order to increase the yield of such polymers, a technique is proposed in which the temperature of a reactor is elevated during discharging of the produced polymer after polymerization is completed, thereby lowering the melt viscosity of the polymer. However, in the technique, the polymer is discolored due to heat deterioration, forming a black-brown polymer. In addition, more severe heat deterioration produces gases of low boiling components such as phenol (PhOH), benzoic acid (BA), hydroxybenzoic acid (HBA), and a phenol ester thereof (HBA-Ph) and black specks (carbonized matter, abbreviated as BS), thereby affecting the quality of the produced polymer. Furthermore, when the reactor is filled with the low-boiling gases, discharge of the product from the reactor is unstable, resulting in decrease in the recovery ratio.
[0006] U.S. Pat. No. 4,720,424 discloses a process for preparing thermotropic LCP comprising units a)-f) in the presence of an acylating agent and catalyst in columns 7-13 and 25. However, as seen from the descriptions at column 11, lines 56-64 and all examples of U.S. Pat. No. 4,720,424, 2.0 to 4.2 percent molar excess of dicarboxylic acid monomer is essential and the range is much larger than the range of equation (1) of the present invention. If the molar excess ratio of the carboxyl group is too excessive to the value of the equation (1), the reaction time is remarkably long, and as a result, productivity lowers.
[0007] U.S. Pat. No. 5,155,204 discloses a process for preparing thermotropic LC aromatic copolymers in the presence of acylating agent such as acetic anhydride and catalysts in columns 7-9, 11-13, 15 and 19. However, as seen from the descriptions at column 9, lines 45-47 of U.S. Pat. No. 5,155,204, the molar ratio of the repeating dicarboxy units to the dioxy units is always very close to 1 and in all examples the molar ratio is 1.0 and this 1.0 corresponds to 0 in equation (1) of the present invention, and as a result, evolution of low-boiling gases increases.
[0008] In view of the foregoing, an object of the present invention is to provide a method for producing a high-quality thermotropic liquid crystalline polymer at high yield including the recovery ratio of the polymer from a reactor, and further in short production time, which method prevents evolution of low-boiling gases and discoloration due to heat deterioration.
SUMMARY OF THE INVENTION
[0009] In order to solve the aforementioned problems, the present inventor has conducted extensive studies, and have found that when the proportions among the amounts of starting monomers, the amount of an acylating agent, and the amount of a catalyst are maintained to specific conditions, then the evolution of low-boiling gases is suppressed, and discharge of a high-quality polymer without discoloration due to heat deterioration from a reactor at a high recovery ratio can be achieved, and further, without production time being prolonged. The present invention has been accomplished on the basis of this finding.
[0010] Accordingly, the present invention provides a method for producing a thermotropic liquid crystalline polymer, which method comprises polymerizing starting monomers in the presence of an acylating agent, said starting monomers comprising a carboxyl group-containing compound, a hydroxyl group-containing compound, an amino group-containing compound, an ester derivative thereof, and/or an amide derivative thereof, which are selected from the group consisting of compounds represented by the following components I, II, III, and IV:
[0011] (I) an aromatic hydroxycarboxylic acid and an ester derivative thereof;
[0012] (II) an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid;
[0013] (III) an aromatic diol, an alicyclic diol, an aliphatic diol, and an ester derivative thereof; and
[0014] (IV) an aromatic hydroxyamine, an aromatic diamine, an ester derivative thereof, and an amide derivative thereof,
[0015] wherein the starting monomers, the acylating agent, and a catalyst are charged so as to satisfy the following equations (1) to (4):
0.0015≦(( A )−( B ))/(( A )+( B ))≦0.006 (1);
1.01≦( D )/( C )≦1.08 (2);
0≦( E )≦40 (3);
[0016] and
( D )/( C )≧−0.002×( E )+1.04 (4),
[0017] wherein
[0018] (A) denotes the total amount by equivalent (with respect to a carboxyl group) of starting monomers I and/or II;
[0019] (B) denotes the total amount by equivalent (with respect to a hydroxyl group, an amino group, an ester derivative group thereof, and an amide derivative group thereof) of starting monomers I, III, and/or IV;
[0020] (C) denotes the total amount by equivalent (with respect to a hydroxyl group and an amino group) of starting monomers I, III, and/or IV;
[0021] (D) denotes the amount by equivalent of an acylating agent; and
[0022] (E) denotes the amount of a catalyst (as reduced to amount by weight of metal, unit: ppm).
[0023] In the method for producing a thermotropic liquid crystalline polymer of the present invention, (I) an aromatic hydroxycarboxylic acid and an ester derivative thereof comprises the following composition:
[0024] (Ia) hydroxybenzoic acid and an ester derivative thereof, and
[0025] (Ib) hydroxynaphthoic acid and an ester derivative thereof,
[0026] wherein molar ratio of (Ia)/((Ia)+(Ib))≧0.9, and the catalyst is charged so as to satisfy the following equation (3′):
0≦( E )≦20 (3′).
[0027] Preferably, in the method for producing a thermotropic liquid crystalline polymer, all of the starting monomers I, II, III, and IV are aromatic compounds.
[0028] Preferably, in the method for producing a thermotropic liquid crystalline polymer, all of the starting monomers, the acylating agent, and the catalyst are charged into the same reactor, and the resultant mixture is caused to react.
[0029] Preferably, in the method for producing a thermotropic liquid crystalline polymer, hydroxyl groups and/or amino groups of the starting monomers I, III, and/or IV are acylated by the acylating agent, and subsequently, the acylated product is caused to react with the starting monomer II.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0030] The thermotropic liquid crystalline polymer of the present invention is produced from starting monomers comprising a carboxyl group-containing compound, a hydroxyl group-containing compound, an amino group-containing compound, an ester derivative thereof, and/or an amide derivative thereof, which are selected from the group consisting of compounds represented by the following components I, II, III, and IV:
[0031] (I) an aromatic hydroxycarboxylic acid and an ester derivative thereof;
[0032] (II) an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid;
[0033] (III) an aromatic diol, an alicyclic diol, an aliphatic diol, and an ester derivative thereof; and
[0034] (IV) an aromatic hydroxyamine, an aromatic diamine, an ester derivative thereof, and an amide derivative thereof.
[0035] In the method for producing a thermotropic liquid crystalline polymer of the present invention, as the component (I), a specific composition of an aromatic hydroxycarboxylic acid and an ester derivative thereof, which comprises
[0036] (Ia) hydroxybenzoic acid and an ester derivative thereof, and
[0037] (Ib) hydroxynaphthoic acid and an ester derivative thereof,
[0038] (wherein molar ratio of (Ia)/((Ia)+(Ib))≧0.9), is used.
[0039] Examples of aromatic hydroxycarboxylic acids serving as the aforementioned component (I) include aromatic hydroxycarboxylic acids such as 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and 6-hydroxy-1-naphthoic acid; alkyl-substituted aromatic hydroxycarboxylic acids such as 3-methyl-4-hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, and 6-hydroxy-5-methyl-2-naphthoic acid; alkoxy-substituted aromatic hydroxycarboxylic acids such as 3-methoxy-4-hydroxybenzoic acid, 3,5-dimethoxy-4-hydroxybenzoic acid, and 6-hydroxy-5-methoxy-2-naphthoic acid; and halo-substituted aromatic hydroxycarboxylic acids such as 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid, 2,3-dichloro-4-hydroxybenzoic acid, 3,5-dichloro-4-hydroxybenzoic acid, 2,5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7-chloro-2-naphthoic acid, 6-hydroxy-5,7-dichloro-2-naphthoic acid.
[0040] Examples of ester derivatives of these aromatic hydroxycarboxylic acids include acyl derivatives such as acetyl derivatives and propionyl derivatives.
[0041] In the above hydroxycarboxylic acids and ester derivatives thereof, as (Ia) hydroxybenzoic acid and an ester derivative thereof, the above various hydroxybenzoic acids and ester derivatives thereof are illustrated, and as (Ib) hydroxynaphthoic acid and an ester derivative thereof, the above various hydroxynaphthoic acids and ester derivatives thereof are illustrated. Above all, 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferable in the specific properties of the polymers.
[0042] Examples of aromatic dicarboxylic acids serving as the aforementioned component (II) include aromatic dicarboxylic acids such as terephthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenoxyethane-4,4′-dicarboxylic acid, diphenoxybutane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3′-dicarboxylic acid, diphenoxyethane-3,3′-dicarboxylic acid, diphenoxybutane-3,3′-dicarboxylic acid, diphenylethane-3,3-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid; halo-substituted compounds of the above aromatic dicarboxylic acids such as chloroterephthalic acid, dichloroterephthalic acid, and bromoterephthalic acid; alkyl-substituted compounds of the above aromatic dicarboxylic acids such as methylterephthalic acid, dimethylterephthalic acid, and ethylterephthalic acid; and alkoxy-substituted compounds of the above aromatic dicarboxylic acids such as methoxyterephthalic acid and ethoxyterephthalic acid.
[0043] Examples of alicyclic dicarboxylic acids serving as the aforementioned component (II) include alicyclic dicarboxylic acids such as trans-1,4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid; and alkyl-, alkoxy-, or halo-substituted compounds of the above alicyclic dicarboxylic acids such as trans-1,4-(1-methyl)cyclohexanedicarboxylic acid and trans-1,4-(1-chloro)cyclohexanedicarboxylic acid.
[0044] Examples of aromatic diols serving as the aforementioned component (III) include aromatic diols such as hydroquinone, resorin, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxytriphenyl, 2,6-naphthalenediol, 4,4′-dihydroxydiphenyl ether, bis(4-hydroxyphenoxy)ethane, 3,3′-dihydroxydiphenyl, 3,3′-dihydroxydiphenyl ether, 1,4-, 1,5-, or 2,6-naphthalenediol, 2,2-bis(4-hydroxyphenyl)propane, and 2,2-bis(4-hydroxyphenyl)methane; and alkyl-, alkoxy-, or halo-substituted compounds of the above aromatic diols such as chlorohydroquinone, methylhydroquinone, butylhydroquione, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone, 4-chlororesorcin, and 4-methylresorcin.
[0045] Examples of alicyclic diols serving as the aforementioned component (III) include alicyclic diols such as trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexanedimethanol, cis-1,4-cyclohexanedimethanol, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, and trans-1,3-cyclohexanedimethanol; and alkyl-, alkoxy-, or halo-substituted compounds of the above alicyclic diols.
[0046] Examples of aliphatic diols serving as the aforementioned component (III) include linear-chain or branched aliphatic diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, and neopentyl glycol.
[0047] Examples of ester derivatives of these aromatic, alicyclic, or aliphatic diols include ester derivatives such as acetyl derivatives and propionyl derivatives.
[0048] Examples of aromatic hydroxyamines and aromatic diamines serving as the aforementioned component (IV) include 4-aminophenol, 4-acetamidophenol, 1,4-phenylenediamine, N-methyl-1,4-phenylenediamine, N,N′-dimethyl-1,4-phenylenediamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 4-amino-1-naphthol, 4-amino-4′-hydroxydiphenyl, 4-amino-4′-hydroxydiphenyl ether, 4-amino-4′-hydroxydiphenylmethane, 4-amino-4′-hydroxydiphenyl sulfide, 4,4′-diaminophenyl sulfide (also called thiodianiline), 4,4′-diaminodiphenyl sulfone, 2,5-diaminotoluene, 4,4′-ethylenedianiline, 4,4′-diaminodiphenoxyethane, 4,4′-diaminodiphenylmethane (also called methylenedianiline), and 4,4′-diaminodiphenyl ether (also called oxydianiline).
[0049] Examples of ester derivatives and/or amide derivatives of these aromatic hydroxyamines and aromatic diamines include acetyl derivatives and propionyl derivatives.
[0050] In the present invention, an acylating agent is employed. Examples of acylating agents include acid anhydrides such as acetic anhydride and acid chlorides.
[0051] Acylation may be carried out in the presence of the below-described catalysts.
[0052] In the present invention, polymerization is carried out in the presence or absence of a polymerization catalyst.
[0053] Examples of polymerization catalysts include dialkyltin oxides, diaryltin oxides, titanium dioxide, alkoxytitaniums, silicate salts, titanium alcoholates, alkali metal carboxylate salts or alkaline earth metal carboxylate salts, and Lewis acids such as boron trifluoride (BF 3 ).
[0054] When the liquid crystalline polymer of the invention is produced from the aforementioned starting monomers, acylating agent, and catalyst, it is important that these components are charged so as to satisfy the following equations (1) to (4):
0.0015≦(( A )−( B ))/(( A )+( B ))≦0.006 (1);
1.01≦( D )/( C )≦1.08 (2);
0≦( E )≦40 (3);
[0055] and
( D )/( C )≧−0.002×( E )+1.04 (4),
[0056] wherein
[0057] (A) denotes the total amount by equivalent (with respect to a carboxyl group) of starting monomers I and/or II;
[0058] (B) denotes the total amount by equivalent (with respect to a hydroxyl group, an amino group, an ester derivative group thereof, and an amide derivative group thereof) of starting monomers I, III, and/or IV;
[0059] (C) denotes the total amount by equivalent (with respect to a hydroxyl group and an amino group) of starting monomers I, III, and/or IV;
[0060] (D) denotes the amount by equivalent of an acylating agent; and
[0061] (E) denotes the amount of a catalyst (as reduced to amount by weight of metal, unit: ppm).
[0062] When ((A)−(B))/((A)+(B)) is less than 0.0015, production yield of the polymer decreases, whereas when the ratio is in excess of 0.006, a long period of polymerization time is required, thereby causing discoloration of the produced polymer due to heat deterioration.
[0063] When (D)/(C) is less than 1.01, starting monomers are not sufficiently acylated, thereby extending the polymerization time. Thus, the produced polymer is readily discolored due to heat deterioration and the amount of evolved gases increases.
[0064] In contrast, when (D)/(C) is in excess of 1.08, discoloration of the polymer due to heat deterioration is promoted by the acylating agent.
[0065] The amount (E) of the catalyst is defined by the total amount of metal components contained in an employed catalyst and is based on ppm by weight to total amounts of the starting monomers.
[0066] When (E) is in excess of 40 ppm, gas evolution predominates.
[0067] In the method for producing a thermotropic liquid crystalline polymer of the present invention, in the case where (I) an aromatic hydroxycarboxylic acid and an ester derivative thereof comprises
[0068] (Ia) hydroxybenzoic acid and an ester derivative thereof, and
[0069] (Ib) hydroxynaphthoic acid and an ester derivative thereof,
[0070] wherein molar ratio of (Ia)/((Ia)+(Ib))≧0.9, it is important that the catalyst is charged so as to further satisfy the following equation (3′):
0≦( E )≦20 (3′).
[0071] When (E) is in excess of 20 ppm in the case, thereby causes a problem that the gas evolution increases.
[0072] Even though (D)/(C) falls within the aforementioned range represented by equation (2), (D)/(C) must satisfy the aforementioned equation (4), since (D)/(C) is also closely related to the amount (E) of catalyst.
[0073] When (D)/(C) is less than the value calculated from equation (4), starting monomers are not sufficiently acylated, thereby extending the polymerization time. Thus, the produced polymer is readily discolored due to heat deterioration, thereby failing to attain the aforementioned object of the present invention.
[0074] Some polymers produced from the aforementioned components do not form an anisotropic melt phase depending on the compositional proportions of the components in the polymer or on distribution of a monomer sequence. However, the liquid crystalline polymers according to the present invention are limited to thermotropic liquid crystalline polymers which form an anisotropic melt phase.
[0075] The liquid crystalline polymer of the present invention is produced through polymerization such as direct polymerization or transesterification. Examples of polymerization methods include melt polymerization, solution polymerization, and slurry polymerization.
[0076] The polymer which is produced through any one of these polymerization methods may further be subjected to solid state polymerization by heating under reduced pressure or in an inert gas, so as to elevate the molecular weight.
[0077] In order to carry out solution polymerization or slurry polymerization, a solvent such as liquid paraffin, high-heat-resistant synthetic oil, or inert mineral oil is employed.
[0078] Polymerization is carried out under conditions, i.e., reaction temperature of 200-370° C. and a terminal pressure of 1-760 Torr (133-101,300 Pa).
[0079] Particularly, melt polymerization is carried out at a reaction temperature of 260-370° C. and a terminal pressure of 1-100 Torr (133-13,300 Pa), preferably at 300-360° C. and 1-50 Torr (133-6,670 Pa).
[0080] Solid state polymerization, which is carried out in order to elevate the molecular weight after completion of melt polymerization, is carried out at a reaction temperature of 230-350° C., preferably 260-330° C., and a terminal pressure of 10-760 Torr (1,330-101, 300 Pa), preferably under inert gas flow at atmospheric pressure.
[0081] Polymerization may be carried out in a one-step manner, i.e., all starting monomers, an acylating agent and a catalyst are placed into the same reactor, and the reaction is initiated. Alternatively, polymerization may be carried out in a two-step manner, i.e., hydroxyl groups and amino groups of starting monomers I, III, and/or IV are acylated in advance with an acylating agent, then the acylated product is caused to react with carboxyl groups in monomer II.
[0082] After the temperature of the reaction system reaches a predetermined temperature, the system is evacuated to control the inside pressure to a predetermined reduced pressure. Under such conditions, melt polymerization is carried out. When the torque of an agitator disposed in a reactor reaches a predetermined value, an inert gas is introduced into the reactor so as to convert reduced pressure conditions to pressurized conditions via atmospheric pressure, thereby discharging the resultant polymer from a bottom portion of the reactor.
[0083] In the present invention, melt viscosity of the thermotropic liquid crystalline polymer is in the range of 10-100 Pa·s, and preferably 20-50 Pa·s. The melt viscosity was measured as follows:
[0084] Apparatus: CAPIROGRAPH made by TOYO SEIKI Co.,
[0085] Orifice: 1 mm inner φ and 20 mm length,
[0086] Temperature: Tm (melting point of the liquid crystalline
[0087] polymer)+15° C., and
[0088] Shear rate: 1,000/sec.
EXAMPLES
[0089] The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention thereto.
Example 1
[0090] To a polymerization reactor equipped with agitation paddles, a reflux column, a monomer-introducing inlet, a nitrogen conduit, and an evacuation/purge line, the following starting monomers, polymerization catalyst, and acylating agent were placed, and the atmosphere in the reactor was substituted by nitrogen:
4-hydroxybenzoic acid: 1444 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 550 g 4,4′-dihydroxydiphenyl: 426 g 4-acetamidophenol: 141 g potassium acetate (catalyst) 188 mg
[0091] (30 ppm by weight as reduced to metallic K, to the total amount of the monomers)
[0092] (equivalent ratio of 1.04 to the sum of hydroxyl groups and amino groups).
[0093] In the above formulation, terephthalic acid was added in excess by 0.5 mol % (that is, the value of equation (1) is 0.005. And so forth.) to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0094] After starting materials had been charged to the reactor, the reaction system was heated to 140° C., and the mixture was allowed to react at 140° C. for 3 hours. Subsequently, the temperature was elevated to 340° C. over approximately four hours, and then the pressure was lowered to 5 Torr (667 Pa) over 30 minutes, thereby carrying out melt polymerization while acetic acid, excessive acetic anhydride, and other low-boiling components were removed through distillation. After the torque of the agitator reached a predetermined value, nitrogen was introduced into the reactor so as to convert reduced pressure conditions to pressurized conditions via atmospheric pressure, thereby discharging the resultant polymer from a bottom portion of the reactor.
[0095] The yield of the discharged polymer was as high as 94.2 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C.
[0096] The thus-obtained thermotropic liquid crystalline polymer (70 wt. %) and glass fiber (30 wt. %) were blended, and the mixture was kneaded by means of a biaxial extruder, to thereby prepare pellets of a thermotropic liquid crystalline polymer composition.
[0097] By means of a Curie-point-head-space/gas chromatograph, the pellets were heated at 320° C. for 10 minutes, and the gas evolved from the pellets was subjected to quantitative determination. The analysis revealed that the gas comprised HBA (24 ppm), HBA-Ph (5 ppm), and PhOH (10 ppm). The amount of evolved gas was smaller than that of gas evolved from a conventional thermotropic liquid crystalline polymer composition. Thus, a high-quality thermotropic liquid crystalline polymer composition was obtained.
Comparative Example 1-1
[0098] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1442 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 542 g 4,4′-dihydroxydiphenyl: 434 g 4-acetamidophenol: 141 g potassium acetate (catalyst) 188 mg
[0099] (30 ppm by weight as reduced to metallic K, to the total amount of the monomers)
acetic anhydride 1881 g
[0100] (equivalent ratio of 1.04 to the sum of hydroxyl groups and amino groups).
[0101] In the above formulation, terephthalic acid was added in an equimol amount to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0102] The yield of the discharged polymer was as low as 93.4 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C. By employing a compositional ratio similar to that employed in Example 1, pellets of a thermotropic liquid crystalline polymer composition were prepared from the thus-obtained thermotropic liquid crystalline polymer. The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1. The analysis revealed that the gas comprised HBA (35 ppm), HBA-Ph (6 ppm), and PhOH (19 ppm). The amount of evolved gas was relatively large and the obtained thermotropic liquid crystalline polymer composition was of low quality.
Comparative Example 1-2
[0103] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1446 g 2-hydroxy-6-naphthoic acid: 317 g terephthalic acid: 562 g 4,4′-dihydroxydiphenyl: 414 g 4-acetamidophenol: 141 g potassium acetate (catalyst) 188 mg
[0104] (30 ppm by weight as reduced to metallic K, to the total amount of the monomers)
acetic anhydride 1861 g
[0105] (equivalent ratio of 1.04 to the sum of hydroxyl groups and amino groups).
[0106] In the above formulation, terephthalic acid was added in excess by 1.2 mol % to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0107] In Comparative Example 1-2, polymerization rate was considerably low, and a long period of time was required to attain a predetermined value of the torque of the agitator as compared with Example 1. The thus-produced and discharged polymer assumed black-blown.
Example 2
[0108] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1444 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 550 g 4,4′-dihydroxydiphenyl: 426 g 4-acetamidophenol: 141 g potassium acetate (catalyst) none acetic anhydride 1927 g
[0109] (equivalent ratio of 1.07 to the sum of hydroxyl groups and amino groups).
[0110] In the above formulation, terephthalic acid was added in excess by 0.5 mol % to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0111] The yield of the discharged polymer was as high as 94.4 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C.
[0112] By employing a compositional ratio similar to that employed in Example 1, pellets of a thermotropic liquid crystalline polymer composition were prepared from the thus-obtained thermotropic liquid crystalline polymer. The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1. The analysis revealed that the gas comprised HBA (22 ppm), HBA-Ph (4 ppm), and PhOH (9 ppm). The amount of evolved gas was relatively small. Thus, a high-quality thermotropic liquid crystalline polymer composition was obtained.
Comparative Example 2-1
[0113] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1444 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 550 g 4,4′-dihydroxydiphenyl: 426 g 4-acetamidophenol: 141 g potassium acetate (catalyst) 375 mg
[0114] (60 ppm by weight as reduced to metallic K, to the total amount of the monomers)
acetic anhydride 1819 g
[0115] (equivalent ratio of 1.01 to the sum of hydroxyl groups and amino groups).
[0116] In the above formulation, terephthalic acid was added in excess by 0.5 mol % to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0117] Since the catalyst was added in an excessive amount, the yield of the discharged polymer was as low as 92.6 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C.
[0118] By employing a compositional ratio similar to that employed in Example 1, pellets of a thermotropic liquid crystalline polymer composition were prepared from the thus-obtained thermotropic liquid crystalline polymer. The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1. The analysis revealed that the gas comprised HBA (69 ppm), HBA-Ph (16 ppm), and PhOH (23 ppm). The amount of evolved gas was relatively large and the obtained thermotropic liquid crystalline polymer composition was of low quality.
Comparative Example 2-2
[0119] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1444 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 550 g 4,4′-dihydroxydiphenyl: 426 g 4-acetamidophenol: 141 g potassium acetate (catalyst) none acetic anhydride 1819 g
[0120] (equivalent ratio of 1.01 to the sum of hydroxyl groups and amino groups).
[0121] In the above formulation, terephthalic acid was added in excess by 0.5 mol % to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0122] In Comparative Example 2-2, polymerization rate was considerably low due to insufficient acylation of starting monomers, and the torque of the agitator did not finally reach a predetermined value. The thus-produced and discharged polymer had a very low viscosity and assumed black-blown.
Example 3
[0123] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1443 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 546 g 4,4′-dihydroxydiphenyl: 430 g 4-acetamidophenol: 141 g catalyst none acetic anhydride 1931 g
[0124] (equivalent ratio of 1.07 to the sum of hydroxyl groups and amino groups).
[0125] In the above formulation, terephthalic acid was added in excess by 0.25 mol % to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0126] The yield of the discharged polymer was as high as 94.8 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C.
[0127] By employing a compositional ratio similar to that employed in Example 1, pellets of a thermotropic liquid crystalline polymer composition were prepared from the thus-obtained thermotropic liquid crystalline polymer. The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1. The analysis revealed that the gas comprised HBA (25 ppm), HBA-Ph (4 ppm), and PhOH (15 ppm). The amount of evolved gas was relatively small. Thus, a high-quality thermotropic liquid crystalline polymer composition was obtained.
Comparative Example 3
[0128] The procedure of Example 1 was repeated, except that the following starting materials were placed, to thereby produce and discharge a polymer:
4-hydroxybenzoic acid: 1443 g 2-hydroxy-6-naphthoic acid: 316 g terephthalic acid: 546 g 4,4′-dihydroxydiphenyl: 430 g 4-acetamidophenol: 141 g potassium acetate (catalyst) 375 mg
[0129] (60 ppm by weight as reduced to metallic K, to the total amount of the monomers)
acetic anhydride 1823 g
[0130] (equivalent ratio of 1.01 to the sum of hydroxyl groups and amino groups).
[0131] In the above formulation, terephthalic acid was added in excess by 0.25 mol % to the sum of 4,4′-dihydroxydiphenyl and 4-acetamidophenol.
[0132] The yield of the discharged polymer was as low as 91.6 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C.
[0133] By employing a compositional ratio similar to that employed in Example 1, pellets of a thermotropic liquid crystalline polymer composition were prepared from the thus-obtained thermotropic liquid crystalline polymer. The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1. The analysis revealed that the gas comprised HBA (78 ppm), HBA-Ph (40 ppm), and PhOH (37 ppm). The amount of evolved gas was relatively large and the obtained thermotropic liquid crystalline polymer composition was of low quality.
Example 4
[0134] To a polymerization reactor equipped with agitation paddles, a reflux column, a monomer-introducing inlet, a nitrogen conduit, and an evacuation/purge line, the following starting monomers, polymerization catalyst, and acylating agent were placed, and the atmosphere of the reactor was substituted by nitrogen:
4-hydroxybenzoic acid: 1444 g 2-hydroxy-6-naphthoic acid: 316 g 4,4′-dihydroxydiphenyl: 426 g 4-acetamidophenol: 141 g catalyst none acetic anhydride 1927 g
[0135] (equivalent ratio of 1.07 to the sum of hydroxyl groups and amino groups).
[0136] After starting materials had been charged to the reactor, the reaction system was heated to 140° C., and the mixture was allowed to react at 140° C. for 3 hours. Subsequently, terephthalic acid (550 g) was added to the reaction mixture, and the resultant mixture was heated to 340° C. over approximately four hours, and then the pressure was lowered to 5 Torr (667 Pa) over 30 minutes, thereby carrying out melt polymerization while acetic acid, excessive acetic anhydride, and other low-boiling components were removed through distillation. After the torque of the agitator reached a predetermined value, nitrogen was introduced into the reactor so as to convert reduced pressure conditions to pressurized conditions via atmospheric pressure, thereby discharging the resultant polymer from a bottom portion of the reactor.
[0137] The yield of the discharged polymer was as high as 94.5 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point was 300° C.
[0138] The thus-obtained thermotropic liquid crystalline polymer (70 wt. %) and glass fiber (30 wt. %) were blended, and the mixture was kneaded by means of a biaxial extruder, to thereby prepare pellets of a thermotropic liquid crystalline polymer composition.
[0139] By means of a Curie-point-head-space/gas chromatograph, the pellets were heated at 320° C. for 10 minutes, and the gas evolved from the pellets was subjected to quantitative determination. The analysis revealed that the gas comprised HBA (23 ppm), HBA-Ph (5 ppm), and PhOH (11 ppm). The amount of evolved gas was smaller than that of gas evolved from a conventional thermotropic liquid crystalline polymer composition. Thus, a high-quality thermotropic liquid crystalline polymer composition was obtained.
Example 5
[0140] To a polymerization reactor equipped with agitation paddles, a reflux column, a monomer-introducing inlet, a nitrogen conduit, and an evacuation/purge line, the following starting monomers, polymerization catalyst, and acylating agent were placed, and the atmosphere of the reactor was substituted by nitrogen:
4-hydroxybenzoic acid: 2109 g 2-hydroxy-6-naphthoic acid: 723 g terephthalic acid: 16 g catalyst none acetic anhydride 2087 g
[0141] (equivalent ratio of 1.07 to the sum of hydroxyl groups).
[0142] In the above formulation, terephthalic acid was added in excess by 0.5 mol %.
[0143] After starting materials had been charged to the reactor, the reaction system was heated to 140° C., and the mixture was allowed to react at 140° C. for 3 hours. Subsequently, the temperature was elevated to 350° C. over approximately four hours, and then the pressure was lowered to 5 Torr (667 Pa) over 15 minutes, thereby carrying out melt polymerization while acetic acid, excessive acetic anhydride, and other low-boiling components were removed through distillation. After the torque of the agitator reached a predetermined value, nitrogen was introduced into the reactor so as to convert reduced pressure conditions to pressurized conditions via atmospheric pressure, thereby discharging the resultant polymer from a bottom portion of the reactor.
[0144] The polymerization time from the moment when the temperature reached the final polymerization temperature (350° C.) to the moment when the torque of the agitator reached a predetermined value (i.e. polymerization time in Table 1) was short as 18 minutes.
[0145] The yield of the discharged polymer was as high as 94.5 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point of the polymer was 325° C.
[0146] The thus-obtained thermotropic liquid crystalline polymer (70 wt. %) and glass fiber (30 wt. %) were blended, and the mixture was kneaded by means of a biaxial extruder, to thereby prepare pellets of a thermotropic liquid crystalline polymer composition.
[0147] The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1. The analysis revealed that the gas comprised HBA (62 ppm), HBA-ph (2 ppm), and PhOH (7 ppm) and the amount of evolved gas was small.
Comparative Example 4
[0148] To a polymerization reactor equipped with agitation paddles, a reflux column, a monomer-introducing inlet, a nitrogen conduit, and an evacuation/purge line, the following starting monomers, polymerization catalyst, and acylating agent were placed, and the atmosphere of the reactor was substituted by nitrogen:
4-hydroxybenzoic acid: 2066 g 2-hydroxy-6-naphthoic acid: 722 g terephthalic acid: 64 g potassium acetate (catalyst) 188 mg
[0149] (30 ppm by weight as reduced to metallic K, to the total amount of the monomers)
acetic anhydride 1957 g
[0150] (equivalent ratio of 1.02 to the sum of hydroxyl groups).
[0151] In the above formulation, terephthalic acid was added in excess by 2.0 mol %.
[0152] After starting materials had been charged to the reactor, the melt-polymerization reaction was conducted in the same manner as shown in Example 5, and the polymer was discharged from a bottom portion of the reactor.
[0153] The yield of the discharged polymer was as high as 94.7 wt. % based on the theoretical yield calculated from the amounts of starting monomers and the melting point of the polymer was 325° C.
[0154] The polymerization time from the moment when the temperature reached the final polymerization temperature (350° C.) to the moment when the torque of the agitator reached a predetermined value was fairly long as 167 minutes.
[0155] The thus-obtained thermotropic liquid crystalline polymer (70 wt. %) and glass fiber (30 wt. %) were blended, and the mixture was kneaded by means of a biaxial extruder, to thereby prepare pellets of a thermotropic liquid crystalline polymer composition.
[0156] The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 5. The analysis revealed that the gas comprised HBA (20 ppm), HBA-Ph (7 ppm), and PhOH (8 ppm) and the amount of evolved gas was small.
[0157] Although the polymer having a small amount of evolved gases was obtained, the polymerization method is a method requiring remarkably a long period of polymerization time.
[0158] As shown in the present invention, when ((A)−(B))/((A)+(B)) is in excess of 0.006, a long period of polymerization time is required, and the fact is confirmed by Comparative Example 4.
Comparative Example 5
[0159] The procedure of Comparative Example 4 was repeated, except that the following starting materials were placed, to thereby conduct a melt-polymerization.
4-hydroxybenzoic acid: 2009 g 2-hydroxy-6-naphthoic acid: 720 g terephthalic acid: 127 g potassium acetate (catalyst) 88 mg
[0160] (14 ppm by weight as reduced to metallic K, to the total amount of the monomers)
acetic anhydride 1989 g
[0161] (equivalent ratio of 1.06 to the sum of hydroxyl groups)
[0162] In the above formulation, terephthalic acid was added in excess by 4.0 mol %.
[0163] In Comparative Example 5, the degree of polymerization did not increase, and the torque of the agitator did not reached a predetermined value.
[0164] In EXAMPLE 3 in U.S. Pat. No. 4,720,424 as shown in background art, ((A)-(B))/((A)+(B)) is 4% molar excess, i.e. the value is 0.04.
[0165] The results of Examples and Comparative Examples are shown in Table 1.
TABLE 1 Polymeriz- ation time HBA (g) HNA (g) TA (g) BP (g) APAP (g) KOAc (mg) Ac 2 o (g) (min) Ex. 1 1444 316 550 426 141 188 1873 55 Ex. 2 1444 316 550 426 141 0 1927 60 Ex. 3 1443 316 546 430 141 0 1931 63 Ex. 4 1444 316 +550 426 141 0 1927 60 Ex. 5 2109 723 16 0 0 0 2087 18 Comp.Ex. 1442 316 542 434 141 188 1881 38 1-1 Comp.Ex. 1446 317 562 414 141 188 1861 106 1-2 Comp.Ex. 1444 316 550 426 141 375 1819 63 2-1 Comp.Ex. 1444 316 550 426 141 0 1819 Torque not 2-2 reached Comp.Ex. 1443 316 546 430 141 375 1823 51 3 Comp.Ex. 2066 722 64 0 0 188 1957 167 4 Comp.Ex. 2009 720 127 0 0 88 1989 Torque not 5 reached (A) − (B) Melt (A) + (B) (E) Yield visc. Gas components (ppm) Discolor- (x10 2 ) (D)/(C) (ppm) (%) (Pa · s) HBA HBA-Ph PhOH ation Ex. 1 0.5 1.04 30 94.2 34 24 5 10 No Ex. 2 0.5 1.07 0 94.4 37 22 4 9 No Ex. 3 0.25 1.07 0 94.8 36 25 4 15 No Ex. 4 0.5 1.07 0 94.5 37 23 5 11 No Ex. 5 0.5 1.07 0 94.5 37 62 2 7 No Comp. Ex. 0 1.04 30 93.4 32 35 6 19 No 1-1 Comp. Ex. 1.2 1.04 30 — — — — — black- 1-2 brown Comp. Ex. 0.5 1.01 60 92.6 35 69 16 23 No 2-1 Comp. Ex. 0.5 1.01 0 — — — — — black- 2-2 brown Comp. Ex. 0.25 1.01 60 91.6 33 78 40 37 No 3 Comp. Ex. 2.0 1.02 30 94.7 22 20 7 8 No 4 Comp. Ex. 4.0 1.06 14 — — — — — No 5
Examples 1′-3′
[0166] To a polymerization reactor equipped with agitation paddles, a reflux column, a monomer-introducing inlet, a nitrogen conduit, and an evacuation/purge line, the starting monomers, polymerization catalyst, and acylating agent as shown in Table 2 were placed, and the atmosphere in the reactor was substituted by nitrogen.
[0167] After starting materials had been charged to the reactor, the reaction system was heated to 140° C., and the mixture was allowed to react at 140° C. for 3 hours. Subsequently, the temperature was elevated to 340° C. over approximately four hours, and then the pressure was lowered to 5 Torr (667 Pa) over 30 minutes, thereby carrying out melt polymerization while acetic acid, excessive acetic anhydride, and other low-boiling components were removed through distillation. After the torque of the agitator reached a predetermined value, nitrogen was introduced into the reactor so as to convert reduced pressure conditions to pressurized conditions via atmospheric pressure, thereby discharging the resultant polymer from a bottom portion of the reactor.
[0168] The yield of the discharged polymer was shown on the bases of the theoretical yield calculated from the amounts of starting monomers and the melting points of the polymers were 340° C.
[0169] The thus-obtained thermotropic liquid crystalline polymer (70 wt. %) and glass fiber (30 wt. %) were blended, and the mixture was kneaded by means of a biaxial extruder, to thereby prepare pellets of a thermotropic liquid crystalline polymer composition.
[0170] By means of a Curie-point-head-space/gas chromatograph, the pellets were heated at 320° C. for 10 minutes, and the gas evolved from the pellets was subjected to quantitative determination. The results are shown in Table 2.
[0171] In Examples 1-3′, high quality thermotropic liquid crystal polymers, which evolve low-boiling gases less than conventional one, were obtained.
Comparative Examples 1′-1, 1′-2, 2′-1 and 2′-2
[0172] The procedure of Example 1′ was repeated, except that starting materials as shown in Table 2 were placed, to thereby produce and discharge a polymer.
[0173] As the results, in Comparative Examples 1′-1 and 2′-1, the theoretical yields based on the starting monomers of the polymers after discharge were lower than those of Examples and the melting points of the polymers were 340° C.
[0174] By employing a compositional ratio similar to that employed in Example 1′, pellets of the thermotropic liquid crystalline polymer composition were prepared from the thus-obtained thermotropic liquid crystalline polymer. The gas evolved from the pellets was subjected to quantitative determination under the conditions similar to those employed in Example 1′.
[0175] Every amount of evolved gases of HBA, HBA-Ph and PhOH was much, thus, low-quality thermotropic liquid crystalline polymer was obtained.
[0176] In Comparative Examples 1′-2 and 2′-2, polymerization rates were very slow, polymerization time to a predetermined torque of the agitator is fairly longer than that of Example 1′, and the discharged polymers discolored to black-brown, and evaluation of quality of the polymers were not conducted.
[0177] As described hereinabove, the present invention can provide a method for producing a high-quality thermotropic liquid crystalline polymer at high yield including the recovery ratio of the polymer from a reactor and in short polymerization time, which method prevents evolution of low-boiling gases and discoloration due to heat deterioration.
TABLE 2 Polymeriz - ation time HBA (g) HNA (g) TA (g) BP (g) APAP (g) KOAc (mg) Ac 2 o (g) (min) Ex. 1′ 1570 178 556 435 143 125 1885 74 Ex. 2′ 1570 178 559 432 143 0 1956 66 Ex. 3′ 1570 178 556 435 143 125 1885 74 Comp.Ex. 1569 178 550 441 143 125 1891 46 1′-1 Comp.Ex. 1572 178 571 420 143 125 1871 118 1′-2 Comp.Ex. 1570 178 559 432 143 375 1846 69 2′-1 Comp.Ex. 1570 178 559 432 143 0 1846 91 2′-2 (A) − (B) Melt (A) + (B) (E) Yield visc. Gas components (ppm) Discolor- (x10 2 ) (D)/(C) (ppm) (%) (Pa · s) HBA HBA-Ph PhOH ation Ex. 1′ 0.35 1.03 20 92.5 24 97 13 19 No Ex. 2′ 0.5 1.07 0 93.3 27 75 5 10 No Ex. 3′ 0.35 1.03 20 92.6 23 95 15 18 No Comp. Ex. 0 1.03 20 90.3 23 123 23 28 No 1′-1 Comp. Ex. 1.2 1.03 20 — — — — — black- 1′-2 brown Comp. Ex. 0.5 1.01 60 90.1 24 209 60 43 No 2′-1 Comp. Ex. 0.5 1.01 0 — — — — — black 2′-2 brown
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The invention provides a method for producing a thermotropic liquid crystalline polymer of high quality at high yield and in short polymerization time, which method includes polymerizing staring monomers I, II, III, and IV, i.e., (I) an aromatic hydroxycarboxylic acid, etc.; (II) an aromatic dicarboxylic acid and an alicyclic dicarboxylic acid; (III) an aromatic diol, an alicyclic diol, an aliphatic diol, etc.; and (IV) an aromatic hydroxylamine, an aromatic diamine, etc. in the presence of an acylating agent, wherein the starting materials are charged so as to satisfy the following equations (1) to (4):
0.0015≦(( A )−( B ))/(( A )+( B ))≦0.006 (1);
1.01≦( D )/( C )≦1.08 (2);
0≦( E )≦40 (3);
and
( D )/( C )≧−0.002×( E )+1.04 (4),
wherein (A) denotes the total amount by equivalent (with respect to a carboxyl group) of starting monomers I and/or II; (B) denotes the total amount by equivalent (with respect to a hydroxyl group, an amino group, an ester derivative group thereof, and an amide derivative group thereof) of starting monomers I, III, and/or IV; (C) denotes the total amount by equivalent (with respect to a hydroxyl group and an amino group) of starting monomers I, III, and/or IV; (D) denotes the amount by equivalent of an acylating agent; and (E) denotes the amount of a catalyst (as reduced to amount by weight of metal, unit: ppm).
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a division of U.S. application Ser. No. 12/429,655 filed Apr. 24, 2009, which in turn is a continuation of U.S. application Ser. No. 11/552,640, filed Oct. 25, 2006, now U.S. Pat. No. 7,529,915 issued May 5, 2009, which is a divisional of U.S. application Ser. No. 09/591,510, filed June 12, 2000, now U.S. Pat. No. 7,162,615 issued Jan. 9, 2007, each of which is fully incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates generally to the field of network communication processors, and more specifically to the field of system device instructions and context switching.
[0003] Network communication systems demand real-time performance. The performance of conventional processors in network communication systems is degraded by long latency accesses, especially to shared resources. For example, in order to look up data in a table lookup unit, a processor must send an operation with data to the table lookup unit (TLU) commanding the TLU to look up data in a table. After performing the lookup operation, the TLU stores the resulting data internally. The processor sends a load command requesting that the TLU load the result on the bus and return the data to the processor. This procedure requires two bus transactions initiated by the processor. Therefore, it would be desirable to have a single transaction both command the device to perform an operation and provide the result to the processor.
[0004] Another latency problem is that some conventional processors will await receipt of the result of the look up before processing other instructions. One way of dealing with this problem is to perform instructions in a different thread while a first thread awaits data. This is called a context switch. Context switches performed in software, store all data in the processor registers in memory and then use the processor registers for a new context. This requirement to store and restore data using a single set of registers wastes processor cycles. Therefore, it would be desirable to have a context switch performed that does not waste processor cycles.
SUMMARY OF THE INVENTION
[0005] Systems and methods consistent with the present invention allow for performing a single transaction that supplies data to a device and commands the device to perform an action and return the result to a processor.
[0006] In addition, systems and methods consistent with the present invention further allow for performing a context switch with no stall cycles by using an independent set of registers for each context.
[0007] A processing system consistent with the present invention includes a processor configured to formulate an instruction and data for sending to a device. The formulated instruction requests that the device perform a command and return data to the processor. A bus controller is configured to generate a system bus operation to send the formulated instruction and data along with a thread identifier to the device.
[0008] A processor consistent with the present invention executes instructions in threads. The processor includes a context register file having a separate set of general registers for a plurality of contexts, where the threads are each assigned a separate context, and context control registers having a separate set of control registers for the plurality of contexts.
[0009] Another processing system consistent with the present invention includes a processor configured to formulate an instruction and data, from a thread associated with a first context, for sending to a device, the instruction requesting the device to perform a command and return data to the processor, and perform a context switch to switch from processing the first context to a second context. A bus controller is configured to generate a system bus operation to send the formulated instruction and data along with a thread identifier to the device.
[0010] A method consistent with the present invention processes a single instruction that both requests a system device operation and requests the system device return data, the method comprising the steps of fetching an instruction from memory, forming a descriptor, constructing a system bus address, initiating a system bus operation to request a device to perform an operation and return data to a processor identified in a thread identifier, and retrieving return data from a system bus based on the thread identifier provided with the returned data.
[0011] Another method consistent with the present invention switches between contexts using a processor having a context register file having a separate set of general registers for a plurality of contexts, each set of registers being associated with a thread, and context control registers having a separate set of control registers for the plurality of contexts, the method comprising the steps of receiving a context switch instruction, receiving an identifier of a next context to activate from the scheduler, performing a next instruction in a current context, and pointing a processor program counter to the context program counter in the context control register associated with the next context.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate one embodiment of the invention and, together with the description, serve to explain the objects, advantages, and principles of the invention. In the drawings:
[0013] FIG. 1 is a block diagram of a processing system consistent with methods and systems of the present invention;
[0014] FIG. 2 a shows a context register file consistent with methods and systems of the present invention;
[0015] FIG. 2 b shows a context control file consistent with methods and systems of the present invention;
[0016] FIG. 3 shows an instruction format consistent with methods and systems of the present invention;
[0017] FIG. 4 is a flowchart showing the steps for processing a write descriptor load word instruction consistent with methods and systems of the present invention;
[0018] FIG. 5 is a flowchart showing the steps of a method for processing a write descriptor load word with a context switch consistent with methods and systems of the present invention; and
[0019] FIG. 6 is a flowchart showing the steps of a method for completing the load word for the instruction in FIG. 5 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] Reference will now be made in detail to embodiments consistent with this invention that are illustrated in the accompanying drawings. The same reference numbers in different drawings generally refer to the same or like parts.
[0021] Processing systems for network communications require several bus and processor cycles to perform a write to a system device and a read from the system device. Systems and methods consistent with the present invention provide a single instruction that directs a device to read and load data when the device is ready. In accordance with a preferred embodiment, the single instruction includes a thread identifier so that the device can send the data back to the requesting thread at the processor.
[0022] In addition, systems and methods consistent with the present invention provide for a context switch that prevents the introduction of stall cycles by using a different set of registers for a plurality of threads. In this manner, processing can switch quickly from one set of registers used by one thread to a different set of registers used by another thread. As used herein, the term thread describes a set of program instructions or a software program that relies on a context register set to perform a particular task.
[0023] FIG. 1 shows an exemplary processing system that may be used in systems and methods consistent with the present invention. Processor 100 is preferably a RISC type processor that may include, among other elements, those in Lexra's LX4180 processor. In this example, processor 100 connects to instruction memory 120 , which may be, for example, a cache, RAM or DRAM.
[0024] Processor 100 includes a context register file 200 and context control registers 210 . As used herein, a context is an independent set of general registers in context register file 200 and control registers in context control register 210 that are used in executing a thread. As stated, a thread may be software that relies on the contents of the context registers to perform a particular task. The term context may also generally be used to refer to a thread currently using the context's registers. Processor 100 further includes a processor program counter (PPC) 110 that points to the program counter of an active context stored in a context program counter within the context control registers 210 .
[0025] Processor 100 couples to scheduler 130 . Scheduler 130 determines the context that should execute in the event of a context switch. This context switch optimizes the processor and bus cycles. If, for example, a current active context is awaiting data, a context switch may be performed so that another context is processed while the current context awaits the data, thereby reducing the waste of valuable processing time. In accordance with the disclosed embodiment, the current context will not be reactivated until the scheduler selects it after another context switch occurs.
[0026] Processor 100 sends commands over system bus 150 to system device 160 via bus controller 140 . Bus controller 140 and system bus 150 may be similar to those used with conventional RISC processors. In systems and methods consistent with the present invention, however, bus controller 140 adds a global thread identifier (GTID) to every outgoing transaction. The GTID indicates the processor number and context number of the originating thread. System device 160 may be, for example, a table look-up unit. And, although FIG. 1 shows only one system device, one of ordinary skill in the art will recognize that multiple devices may be in communication with system bus 150 .
[0027] Bus controller 140 generates command data (CMD) for each instruction, indicating whether the instruction is, for example, a read, a write, a split read, a write-twin-word split read. In this embodiment, a word consists of 32 bits and a twin word has 64 bits. Among its other tasks, bus controller 140 outputs a device address to system bus 150 along with the CMD, the GTID, and any data to be sent to the device. The device address identifies the device that will receive the command and the GTID is used by the device in returning data to a requesting processor. Again one of ordinary skill will recognize that processor 100 may include additional parts, many of which are common and whose description is unnecessary to understand the systems and methods consistent with the present invention.
[0028] FIG. 2 a shows an exemplary context register file 200 having 8 contexts, context 7 through context 0. In this figure, each context has 32 physical general registers, but the number of contexts and the number of registers may vary depending on the complexity of the particular system, the amount of data communication on the system bus, the number of system devices present, etc.
[0029] FIG. 2 b shows an exemplary context control file 210 having 3 control registers for each of the 8 contexts shown in FIG. 2 a . Context control file 210 includes a context program counter (CXPC) 212 for keeping track of the next instruction to be executed in the context and a context status register (CXSTATUS) 214 having a wait load bit, which, when set, indicates that the context is awaiting data from an external device. CXSTATUS 214 may include additional status information such as an indication that the context requires external events or data to complete its task. A write address register 216 , also within context control file 210 , is configured to store the address of a general purpose register in an inactive context that may be awaiting data from an external device.
[0030] FIG. 3 is an exemplary representation of an instruction 300 stored in instruction memory 120 . Instruction 300 includes an opcode field 310 and sub-opcode field 360 that indicate the particular operation requested. The requested operations may be commands such as read, write, and write-split read. In this example, a write-split read is an instruction that writes to a system device and directs the device to return read data when available. Instruction 300 also includes rS 320 , rT 330 , and rD 340 ; fields referring to the general purpose registers in FIG. 2 a . The identified registers hold data used by the instruction or the registers that will ultimately be receiving the instruction results. In a write-split read instruction, for example, rS 320 and rT 330 identify the registers holding data that will be written to system device 160 at system device address 350 . rD 340 is the identifier of the destination register, indicating the location in which the result of the load instruction should be stored. The identity of register rD may be stored in the write address register 216 so that when load data is returned, processor 100 reads the context control file 210 to determine the particular register in which to write the result.
[0031] FIG. 4 shows the steps of a method 400 for processing a write-split read instruction consistent with the methods and systems of the present invention. First, processor 100 fetches instruction 300 from instruction memory 120 based on a value in PPC 110 (step 410 ). Processor 100 then forms a 64 bit descriptor by concatenating bits [63:32] of register S 320 and bits [31:0] of register T 330 (step 420 ). Processor 100 constructs a system bus address using device address 350 provided in the instruction (step 430 ). The actual device address is less than 32 bits, so the remaining system bus address bits are set to zero or some constant predefined value.
[0032] Following the construction of the system bus address, processor 100 initiates a system bus operation to write the descriptor to the device, having the device perform some function, and requests that the device provide a read word response back to the processor identified with a GTID (step 440 ). Bus controller 140 sends out instruction 300 to the device address including data, the command, and a GTID. System device 160 saves the descriptor in a memory, performs an operation using information in the descriptor, and returns the result of the operation as read data directed to the processor identified in the GTID (step 450 ). Bus controller 140 then receives a read word or twin word response from the system device (step 460 ). Finally, processor 100 writes the received data to rD register 340 (step 470 ) thus, completing the operation.
[0033] FIG. 5 show the steps of a method 500 for processing a write descriptor load word (WDLW) instruction in accordance with systems and methods of the present invention. Referring to FIG. 5 , processor 100 initially fetches instruction 300 from instruction memory 120 based on the value in PPC 110 (step 510 ). Using this value, processor 100 forms a 64-bit descriptor by concatenating bits [63:32] of register S 320 and bits [31:0] of register T 330 (step 520 ). Processor 100 next sets the wait load bit in context status register 210 of the active context (step 530 ). Processor 100 then constructs a system bus address using device address 350 provided in the instruction (step 540 ). The device address is less than 32 bits, so the remaining system bus address bits are set to zero or some constant predefined value.
[0034] Once the system bus address is constructed, processor 100 initiates a system bus operation to write the descriptor to the device and requests that the device provide a read word response (step 550 ). Processor 100 stores the register identified in rD 340 in write address register 216 in the active context's control file 210 indicating the register that will receive any returned data from system device 160 (step 560 ).
[0035] Steps 565 - 590 describe the steps used to perform a context switch in systems and methods consistent with the present invention. Processor 100 first receives an identifier of the next context to be activated from scheduler 130 (step 565 ). Processor 100 then performs the following instruction in the active context (step 570 ). By performing the next step in this instruction before moving on to the next context, the processor is able to execute an instruction, and is performing useful work instead of stalling for a cycle while the context switch is performed. Processor 100 then stores program counter (PC) of the next instruction in this active context in the CXPC 212 of the active context (step 580 ). Processor next points PPC to CXPC 212 of the new context designated by scheduler 130 (step 590 ).
[0036] FIG. 6 shows the remaining steps 600 for completing the load word portion of the WDLW instruction described in the method of FIG. 5 . After system device 160 receives the command, data, and the GTID from system bus 150 , it writes the descriptor to a memory. System device 160 then performs any requested function and loads the resulting data onto system bus 150 along with the GTID (step 610 ). Upon receiving the read word response from system bus 150 (step 620 ), bus controller 140 forwards it to processor 100 . Processor 100 writes this read word to the register indicated in the write address register 216 by obtaining the identity of the originating context from the GTID (step 630 ). Processor 100 next clears the originating context's wait load flag in CXSTATUS register 214 , indicating that the context is available for execution (step 640 ). Finally, scheduler 130 monitors the wait load flags of all of the contexts and will select this context when appropriate (step 650 ).
[0037] There are many variations that may be made consistent with the present invention. For example, in another embodiment, system device 160 returns a twin word in response to a write twin word read twin word instruction (WDLT). Further, while the implementations above specifically mention word or twin word data reads and writes, systems and methods consistent with the present invention may be used with other sized data reads and writes. In addition, there may be multiple processors sharing the system bus and accessing the system bus devices.
[0038] The foregoing description is presented for purposes of illustration and description. It is not exhaustive and does not limit the invention to the precise form disclosed. Modifications and variations are possible in light of the above teachings or may be acquired from practicing the invention. The scope of the invention is defined by the claims and their equivalents.
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Systems and methods for managing context switches among threads in a processing system. A processor may perform a context switch between threads using separate context registers. A context switch allows a processor to switch from processing a thread that is waiting for data to one that is ready for additional processing. The processor includes control registers with entries which may indicate that an associated context is waiting for data from an external source.
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CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of Provision Patent Application Ser. No. 60/619,337 filed by the present inventors.
TECHNICAL FIELD OF THE INVENTION
[0002] The invention relates generally to the exploitation of hydrocarbon-containing formations. More specifically, the invention relates to fluids that are used to optimize and/or enhance the production of hydrocarbon from a formation (“well completion fluids”). Specifically this invent relates to Viscoelastic Surfactant Mixtures (VESM) useful in increasing the viscosity of certain fluids injected into subterranean oil reservoirs.
BACKGROUND OF THE INVENTION
[0003] Hydrocarbons (oil, natural gas, etc.) are typically obtained from a subterranean geologic formation (i.e., a “reservoir”) by drilling a well that penetrates the hydrocarbon-bearing formation. In order for hydrocarbons to be “produced,” that is, travel from the formation to the wellbore (and ultimately to the surface), there must be a sufficiently unimpeded flowpath from the formation to the wellbore. This flowpath is through the formation rock, e.g., solid carbonates or sandstones having pores of sufficient size, connectivity, and number to provide a conduit for the hydrocarbon to move through the formation.
[0004] Recovery of hydrocarbons from a subterranean formation is known as “production.” One key parameter that influences the rate of production is the permeability of the formation along the flowpath that the hydrocarbon must travel to reach the wellbore. Sometimes, the formation rock has a naturally low permeability; other times, the permeability around the wellbore is reduced due to the damage caused by drilling the well. When a well is drilled, a drilling fluid is often circulated into the hole to contact the region of a drill bit, for a number of reasons such as: to cool the drill bit, to carry the rock cuttings away from the point of drilling, and to maintain a hydrostatic pressure on the formation wall to prevent production during drilling. During well operations, drilling fluid can be lost by leaking into the formation. To prevent this, the drilling fluid is often intentionally modified so that a small amount leaks off and forms a coating on the wellbore surface (often referred to as a “filtercake”). Once drilling is complete, and production is desired, this coating or filtercake must be removed.
[0005] Techniques used to increase the net permeability of the reservoir are referred to as “stimulation” techniques. Typically, stimulation techniques include methods such as: (1) injecting chemicals into the wellbore to react with and dissolve the damage (e.g., scales, filtercakes); (2) injecting chemicals through the wellbore and into the formation to react with and dissolve small portions of the formation to create alternative flowpaths for the hydrocarbon; and (3) injecting chemicals through the wellbore and into the formation at pressures sufficient to actually fracture the formation, thereby creating a large flow channel through which hydrocarbon can more readily move from the formation into the wellbore.
[0006] In particular, methods to enhance the productivity of hydrocarbon wells (e.g., oil wells) by removing (by dissolution) near-wellbore formation damage or by creating alternate flowpaths by fracturing and dissolving small portions of the formation at the fracture face are respectively known as “matrix acidizing,” and “acid fracturing.” Generally speaking, acids, or acid-based fluids, are useful in this regard due to their ability to dissolve both formation minerals (e.g., calcium carbonate) and contaminants (e.g., drilling fluid coating the wellbore or penetrated into the formation) introduced into the wellbore/formation during drilling or remedial operations.
[0007] Both the inhibition or removal of filtercakes and scales, and fluid placement are key concerns in well completion operations. Typical prior art techniques involve a multiple stage process. For example, in a typical prior art application, during completion operations, an acid treatment is performed, followed by a spacer. After this treatment, the well is cleaned, and a scale inhibitor is injected. A spacer is then injected, followed by a diverter. The process of additive (which may be an acid or a diverter, for example), spacer, additive, spacer, is repeated until all of the required treatments have been finished. This is a costly and time-consuming procedure.
[0008] Typically, matrix acidizing treatments have three major limitations: (1) limited radial penetration; (2) non-optimal axial distribution; and (3) corrosion of the pumping and well bore tubing. The first problem, limited radial penetration, occurs because once the acid is introduced into the formation (or wellbore), the acid reacts very quickly with the wellbore coating or formation matrix (e.g., sandstone or carbonate). In the case of treatments within the portion of the formation (rather than wellbore treatments), the formation near the wellbore that first contacts the acid is adequately treated. However, because most or all of the acid reacts upon contact, portions of the formation more distal to the wellbore (as one moves radially outward from the wellbore) remain untouched by the acid.
[0009] For instance, sandstone formations are often treated with a mixture of hydrofluoric and hydrochloric acids at very low injections rates (to avoid fracturing the formation). This acid mixture is often selected because it will dissolve clays (found in drilling mud) as well as the primary constituents of naturally occurring sandstones (e.g., silica, feldspar, and calcareous material). In fact, the dissolution is so rapid that the injected acid is essentially spent by the time it reaches a few inches beyond the wellbore. As a result, over 100 gallons of acid per foot is required to fill a region five feet from the wellbore (assuming 20% porosity and 6-inch wellbore diameter).
[0010] Similarly, in carbonate systems, the preferred acid is hydrochloric acid, which again, reacts so quickly with the limestone and dolomite rock that acid penetration is limited to between a few inches and a few feet. In fact, due to such limited penetration, it is believed matrix treatments are limited to bypassing near-wellbore flow restrictions—that is, they do not provide significant stimulation beyond what is achieved through (near-wellbore) damage removal. Yet damage at any point along the hydrocarbon flowpath can impede flow (hence production). Therefore, because of the prodigious fluid volumes required, these treatments are severely limited by their cost.
[0011] A second major problem that severely limits the effectiveness of matrix acidizing technology is non-optimal axial distribution. This problem relates to the proper placement of the acid-containing fluid—i.e., ensuring that it is delivered to the desired zone (that is, the zone that needs stimulation) rather than another zone.
[0012] More particularly, when a hydrocarbon-containing carbonate formation is injected with acid (e.g., hydrochloric acid), the acid begins to dissolve the carbonate. As acid is pumped into the formation, a dominant channel through the matrix is inevitably created. As additional acid is pumped into the formation, the acid naturally flows along that newly created channel—i.e., the path of least resistance—and, therefore, leaves the rest of the formation untreated. This, of course, is undesirable. It is exacerbated by intrinsic heterogeneity with respect to permeability (common in many formations)—this occurs to the greatest extent in natural fractures in the formation and due to high permeability streaks.
[0013] Again, these regions of heterogeneity in essence attract large amounts of the injected acid, hence keeping the acid from reaching other parts of the formation along the wellbore—where it is actually needed most. Thus, in many cases, a substantial fraction of the productive, oil-bearing intervals within the zone to be treated are not contacted by acid sufficient to penetrate deep enough (laterally in the case of a vertical wellbore) into the formation matrix to effectively increase its permeability and therefore its capacity for delivering oil to the wellbore.
[0014] The problem of proper placement is significant in these systems because the injected fluid preferentially migrates to higher permeability zones (the path of least resistance) rather than to the lower permeability zones—yet it is those latter zones, which require the acid treatment (i.e., because they are low permeability zones, the flow of hydrocarbon through them is restricted). In response to this problem, numerous, disparate techniques have evolved to achieve more controlled placement of the fluid—i.e., to divert the acid away from naturally high permeability zones and zones already treated and towards the regions of interest. A variety of prior art techniques (including emulsified acid systems, foamed systems, mechanical systems, and gelling agents) have been developed to control acid placement.
[0015] It has been difficult to find systems compatible over a wide range of temperatures with the wide variety of additives that are commonly used in well completion fluids that are suitable for inhibiting scale formation and can be properly, placed (i.e., self diverting).
[0016] Accordingly, what is desired are fluids that can inhibit the formation of scales and can be easily “spotted” or placed in the wellbore over the entire length of the desired zone. In addition, what is desired are fluids that are compatible with a wide range of additives over a broad range of temperatures and concentrations.
[0017] Viscous fluids play many important roles in oilfield service applications. The viscosity of the fluids allows them to carry particles from one region of the formation, the wellbore, or the surface equipment to another. For instance, one of the functions of a drilling fluid is to carry drilling cuttings from around the drilling bit out of the wellbore to the surface. Fluid viscosity also plays an essential role for instance in gravel packing placement. Gravel packing essentially consists of placing a gravel pack around the perimeter of a wellbore across the production zone to minimize sand production from highly permeable formations.
[0018] Viscoelastic fluids can also be used in hydraulic fracturing. Solid suspension properties are an important requirement for fracturing fluids. For a well to produce hydrocarbons from a subterranean geologic formation, the hydrocarbons have to follow a sufficiently unimpeded flow path from the reservoir to the wellbore. If the formation has relatively low permeability, either naturally or through formation damages resulting for example from addition of treatment fluids or the formation of scales as described above, it can be fractured to increase the permeability. Fracturing involves literally breaking a portion of the surrounding strata, by injecting a fluid directed at the face of the geologic formation, at pressures sufficient to initiate and/or extend a fracture in the formation. A fracturing fluid typically comprises a proppant, such as ceramic beads or sand to hold the fracture open after the pressure is released. It is therefore important for the fluid to be viscous enough to carry the proppant into the fracture.
[0019] The fluid viscosity is most commonly obtained by adding water-soluble polymers, such as polysaccharide derivatives. Recently, viscoelastic surfactants have been used as thickeners for example as described in U.S. Pat. Nos. 6,258,859, 6,435,277, 6,637,517, 6,667,280, 6,762,154, 6903,054 as well as published U.S. Patent Applications 2004/0214725, 2005/0003965, 2005/0124500, 2005/0209108, 2005/00379238, 2005/0067165, 2005/0124525. Also several recent patents have been involved in methods of breaking viscoelastic fluids such as described in U.S. Pat. No. 6,908,888. Unlike the polymers, viscoelastic surfactants based fluids do not lead to reduction of permeability due to solid deposits, and exhibit lower friction pressure. In addition, the viscosity of the fluid is reduced or lost upon exposure to formation fluids such as for instance crude oil thereby ensuring better fracture clean-up.
[0020] VESM are normally made by mixing in appropriate amounts suitable surfactants such as anionic, cationic, nonionic and zwitterionic surfactants. U.S. Pat. No. 4,375,421 discloses the use of Lonzaine C a coconut oil derived alkylamido betaine combined with anionic surfactants and in the presence of inorganic salts such as sodium chloride to form viscous liquids to ringing gels. U.S. Pat. No. 5,902,784 discloses the use of amphoteric surfactants in combination anionic surfactants to be used as drag-reducing agents. The viscosity of viscoelastic surfactant fluids, that is fluids containing VESM, is attributed to the three dimensional structure formed by the components in the fluids. When the concentration of surfactants in a viscoelastic fluid significantly exceeds a critical concentration, and in most cases in the presence of an electrolyte, surfactant molecules aggregate into species such as micelles, which can interact to form a network exhibiting elastic behavior.
[0021] Cationic viscoelastic surfactants—typically consisting of long-chain quaternary ammonium salts such as cetyltrimethylammonium bromide (CTAB)—have been so far of primarily commercial interest in wellbore fluid. Common reagents that generate viscoelasticity in the surfactant solutions are salts such as ammonium chloride, potassium chloride, sodium salicylate and sodium isocyanate and non-ionic organic molecules such as chloroform. The electrolyte content of surfactant solutions is also an important control on their viscoelastic behavior. Reference is made for example to U.S. Pat. Nos. 4,725,372, 5,964,295, and 5,979,557. However, fluids comprising this type of cationic viscoelastic surfactants usually tend to lose viscosity at high brine concentration (10 pounds per gallon or more). Therefore, these fluids have seen limited use as gravel-packing fluids or drilling fluids, or in other applications requiring heavy fluids to balance well pressure.
[0022] It is also known from International Patent Publication WO 98/56497, to impart viscoelastic properties using amphoteric/zwitterionic surfactants and an organic acid, salt and/or inorganic salt. The surfactants are for instance dihydroxyl alkyl glycinate, alkyl ampho acetate or propionate, alkyl betaine, alkyl amidopropyl betaine and alkylamino mono- or di-propionates derived from certain waxes, fats and oils. The surfactants are used in conjunction with an inorganic, water-soluble salt or organic additives such as phthalic acid, salicylic acid or their salts. Amphoteric/zwitterionic surfactants, in particular those comprising a betaine moiety are useful at temperature up to about 150° C. and are therefore of particular interest for medium to high temperature wells. However, like the cationic viscoelastic surfactants mentioned above, they are not compatible with high brine concentration.
SUMMARY OF INVENTION
[0023] The present invention relates to VESM for use in treating a hydrocarbon-containing formation. The VESM is injected with injection fluid into a well, wherein the VESM includes about 1% to 99% by weight of one or more amphoteric viscoelastic surfactant(s) (VES) selected from a family of compounds defined by structure I below:
Where,
[0024] R 2 and R 3 are the same or different and preferably represent a low molecular weight alkyl residue, especially straight-chain alkyl residue with 1 to 4 carbon atoms, or hydroxy alkane; and R 1 is C12 to C30 linear or branch alkylene, preferably C16 to C24 or R 1 is structure II below:
where R 4 is C12 to C30, preferably C16 to C24 linear or branched alkylene, and x is 2 to 6.
[0025] The VESM also includes from about 0.1% by weight to about 20% by weight of one or more cosurfactant(s) that is a member of the class arylalkyl sulfonates and is required for optimum performance. This cosurfactant is defined by structure III below:
where:
[0026] R is none, branched or linear C1 to C30 alkyl, or an alkoxylate,
[0027] R′ is none, branched or linear C1 to C30 alky,
[0028] R″ is none, branched or linear C1 to C30 alkyl,
[0029] R′″ is a terminally sulfonated alkyl chain of 14 to 30 carbons in length having the structure:
CH 3 (CH 2 )nCH(CH 2 )mSO 3 M
where:
[0030] M is H, mono valent anion, divalent anion or amine.
[0031] Finally the VESM of the present invention contains one or more polar solvent(s). Suitable solvents include but are not restricted to water, C1-C6 linear or branched alcohol, ethylene glycol mono-butyl ether, glycerine, propylene glycol, ethylene glycol. The solvent is added to reduce the viscosity of the VESM but not interferer with the final viscosity enhancing properties of the VESM. In summary, the VESM of the present invention contains the following:
a) one or more amphoteric surfactant(s), b) one or more co-surfactants of the class arylalkyl sulfonates, and c) one or more polar solvent(s).
The ratio of the amphoteric surfactant(s) to the cosurfactants is from about 50 to 1 to about 5 to 1 by weight and the solvent makes up the remainder of the VESM.
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] FIG. 1 shows the viscosities at various temperatures for two different viscoelastic surfactant mixtures in 300% CaCl 2 solutions.
DETAILED DESCRIPTION
[0036] The composition of the present invention is designed to treat the hydrocarbon-containing formations. The composition of present invention is added to various injection fluids and imparts viscoelastic properties to these injection fluids with the advantage of providing superior viscosities and better economics than the prior art. The VESM of the present invention are relatively easy to place, are compatible with a broad range of additives, and function within a wide range of temperatures and salinities. Additives such as scale inhibitors, corrosion inhibitors, biocides that are known to the art can be employed along with the VESM when deemed necessary for their specific use.
[0037] One particular useful application of the present invention is in producing a fluid containing the VESM along with an acid. The combination of the VESM and the acid forms a viscoelastic diverting acid (VDA).
[0038] VDA is a term given to a class of compounds that exhibit reversible gelling behavior—that is, the fluid can be made to gel, then deliberately be un-gelled as needed. The ability to controllably gel and un-gel is important in fluid placement. Being able to gel, the VDA minimizes the axial distribution and radial penetration problems described above. Because the VDA forms a gel upon acid reaction with the formation, the VDA prevents additional, unneeded acid from entering the treated zones in the formation. U.S. Pat. No. 6,399,546 discusses VDA in detail.
[0039] Many mineral or organic acids (e.g., hydrochloric acid, hydrofluoric acid, sulfuric, phosphoric, formic, acetic, citric, maleic acids, and mixtures thereof) can be used with the VESM of the present invention to form VDA. Hydrofluoric acid is preferred for silicate formations and hydrochloric acid is preferred for carbonate formations. The VESM also contains one or more polar solvent(s), such as water, lower molecular weight alcohol(s), ether(s) and the like to enhance the handling and its viscosity building properties during its application in the formation.
[0040] The VESM of the present invention includes one or more amphoteric viscoelastic surfactant(s) from a family of compounds defined by structure I below:
Where,
[0041] R 2 and R 3 are the same or different and preferably represent a low molecular weight alkyl residue, especially straight-chain alkyl residue with 1 to 4 carbon atoms, or hydroxy alkane; and
[0042] R 1 is C12 to C30 linear or branch alkyl or alkylene, preferably C16 to C24 or R 1 is structure II below:
where R 4 is C12 to C30, preferably C16 to C24 linear or branched alkyl or alkylene, and x is 2 to 6.
[0043] The VESM also includes from about 0.1% by weight to about 20% by weight of one or more cosurfactant(s) that is a member of the class arylalkyl sulfonates and is required for optimum performance. This cosurfactant is defined by structure III below:
where:
[0044] R is none, branched or linear C1 to C30 alkyl or an alkoxylate
[0045] R′ is none, branched or linear C1 to C30 alkyl.
[0046] R″ is none, branched or linear C1 to C30 alkyl.
[0047] R′″ is a terminally sulfonated alkyl chain of 7 to 30 carbons in length having the structure: CH 3 (CH 2 )nCH(CH 2 )mSO 3 M where M is H, mono valent anion, divalent anion or amine.
[0048] Finally the VESM of the present invention contains one or more polar solvent(s). Suitable solvents include but are not restricted to water, C1-C6 linear or branched alcohol, ethylene glycol mono-butyl ether, glycerine, propylene glycol, ethylene glycol. The solvent is added to reduce the viscosity of the VESM but not interfere with the final viscosity enhancing properties of the VESM. Other ingredients such as biocides, scale inhibitors, corrosion inhibitors as known in the art can be added as needed.
[0049] The preferred examples of the VES are betaines called Mirataine BET-O-30™ and Mirataine BET-E-40™ from Rhodia, Inc. (Cranbury, N.J., U.S.A.). BET O-30™ contains an oleyl acid amide group (i.e., R 4 is a C 17 H 33 alkene tail group in the above formula II) and is supplied as a solution having about 30% active surfactant; the remainder is substantially water, sodium chloride, and propylene glycol.
[0050] An analogous material, BET-E-40™, is also available from Rhodia and contains an erucic acid amide group (R 4 is a C 21 H 41 alkene tail group in the above formula II), and is supplied as a solution having about 40% active ingredient, with the remainder substantially water, sodium chloride, and isopropanol. The structures of these two BET surfactants, and others, are described in U.S. Pat. No. 6,676,280. Chemical equivalents of these surfactants are available from several other suppliers and they can also be easily synthesized by methods known to those familiar with the art. Thus this invention is not limited to the use of BET surfactants exclusively and betaines sourced from other suppliers are equally as effective.
[0051] One or more arylalkyl sulfonate cosurfactant(s) is used in the present invention of the VESM as the cosurfactant to optimize the performance of the applications.
[0052] Both the VES and the co-surfactant may be used neat or premixed in the proper ratio prior to preparing the VDA. The ratio based on active ingredient is usually from about 5 to about 50 parts by weight of VES to about 1 part by weight of cosurfactant on a 100% active basis. Commercial samples of both the VES and the arylalkyl sulfonates cosurfactant are usually supplied as 30 or 50% by weight solutions in water or mixtures of water and glycols, glycol ethers, low carbon number alcohol solvent and the like. Particularly useful solvents are water, ethylene glycol monobutyl ether, propylene glycol, and glycerine either used alone or in combination. When solvents are employed, the appropriate concentration of active ingredient in the VDA is obtained by adjusting for the dilution effect of the solvent. Commercial samples of the VES also usually contain small amounts, up to about 8% sodium chloride that is a result of the process used to manufacture the VES. In most cases the salt does not interfere with the performance of the VES or the resulting VESM and therefore it does not have to be removed.
[0053] The VES is capable of forming structures such are micelles that are sheet-like, spherical, vesicular, or worm-like, this latter form being preferred. A most preferred zwitterionic surfactant comprises a betaine moiety and an oleic acid moiety, such as the previously mentioned surfactant BET-O-30. It should be noted that the oleic acid stock from which the oleic acid moiety is derived is generally about 75% pure to about 85% pure, and the balance of the stock comprises other fatty acids, such as linolenic acid, linoleic acid, etc. Some of these other fatty acids may be present in about 15% to about 25% of the total fatty acid moieties in the surfactant.
[0054] The VESM can be used for many other applications in addition to the matrix acidizing application described above. Other components can be included in the treating fluid along with the VESM, such as scale and corrosion inhibitors or biocides, depending on its intended use, formation conditions and other parameters readily apparent to one of ordinary skill in the art. For example, as a drilling fluid, the VESM is used along with other surface active agents, other viscosifiers such as polymers, filtration control agents such as Gilsonite and modified starches, density increasing agents such as powdered barites or hematite or calcium carbonate, or other wellbore fluid additives known to those skilled in the art.
[0055] As a gravel packing fluid, the VESM is preferably used along with gravel and other optional additives such as filter cake clean up reagents such as chelating agents, acids (e.g. hydrochloric, hydrofluoric, formic, acetic, citric acid), corrosion inhibitors, scale inhibitors, biocides, leak-off control agents, among others. For this application, suitable gravel or sand typically has a mesh size between 8 and 70 U.S. Standard Sieve Series mesh.
[0056] When used as part of a fracturing fluid, the VESM of this invention is used preferably with a proppant. Suitable proppants include, but are not limited to, sand, bauxite, glass beads, and ceramic beads. If sand is used, it will typically be from about 20 to about 100 U.S. Standard Mesh in size. Mixtures of suitable proppants can be used. The fracturing fluid can also comprise a proppant flowback inhibitor, for instance the proppant can be coated with a resin to allow consolidation of the proppant particles into a mass. The concentration of proppant in the fracturing fluid can be any concentration known in the art, and will typically be in the range of about 0.5 to about 20 pounds of proppant added per gallon of clean fluid.
EXAMPLE 1
[0057] The following example is for illustrative purposes and compares the performance of a viscoelastic surfactant mixture in a 30% by weight Calcium Chloride (CaCl 2 ) solution. The 30% Calcium Chloride solution was chosen for the test because this is approximately the amount of Calcium Chloride that would be formed if a 15% by weight Hydrochloric Acid (HCl) was reacted with Calcium Carbonate (CaCO 3 ). In a typical acidizing project, a 15% HCl solution would be injected into the carbonate formation to be acidized along with the VESM. The acid would become spent by reaction with the Calcium Carbonate in the reservoir rock forming Calcium Chloride, water and carbon dioxide by the reaction shown below.
2HCl+CaCO 3→ CaCl 2 +CO 2 +H 2 O
[0058] Thus, this example simulates the reactions that take place down-hole during acidizing. This example compares the viscosity building characteristics of a VESM containing BET-0-30™ and two different cosurfactants. The first is sodium linear dodecylbenzene sulfonate (Na LABS), and is the preferred cosurfactant disclosed in U.S. Pat. No. 6,399,546. The second cosurfactant is the sodium salt of C14-16 arylalkyl xylene sulfonate (Na XSA-1416). The structure difference of the Na LABS and Na XSA-1416 are shown below.
[0059] Without being bound any theory the inventors believe the difference in structure between the two surfactants accounts for the superior properties of VESM of the present invention containing the Na XSA-1416 cosurfactant. Note that the Na XSA-1416 has the sulfonate group attached to the end of the alkyl chain while the Na LABS has the sulfonate directly attached to the aromatic ring.
[0060] Two samples were prepared and compared to illustrate the superior temperature stability using the VESM of the present invention over the prior art.
[0061] Testing Procedure:
1. Add 27 grams of BET-O-30 and 3.0 grams of a 30% aqueous solution of Na LABS to 270 gram sample of 30% by weight of CaCl 2 solution. This sample is designated as 1099A in the following discussion. 2. Add 27 grams of BET-O-30 and 3.0 grams of a 30% aqueous solution of Na XSA-1416 to 270 gram sample of 30% by weight of CaCl 2 solution. This sample is designated as 1099B in the following discussion. 3. The viscosities of the samples were measured at various temperatures using a Brookfield LVT viscometer, No. 3 Spindle at 60 rpm. The data is shown in FIG. 1 .
[0065] As is shown in FIG. 1 , the viscosity of the 1099A system provides higher viscosities only at temperatures less than 35° C. and between about 60° C. to 75° C.; whereas the viscosity of the 1099B yields high viscosities over a wide temperature range, which is very important for oil field applications. For example, the service companies can use one product to cover the wide temperature ranges experienced in filed applications and therefore reduce their inventory and cost. Furthermore, for fracturing applications, if the viscosity drops prior to reaching the bottom hole temperature this may cause the proppant to drop out of the gelled fluid and cause a “sand-out”. For temperatures higher than 60° C., the 1099A drops its viscosity rapidly while the 1099B maintains its viscosity.
[0066] The behavior of the VESM of the present invention containing the arylalkyl sulfonate cosurfactant is quite unexpected. It is unexpected that the viscosity should increase continuously over the temperature range as the temperature in increased. The superior viscosity building characteristics of VESM of the present invention containing arylalkyl sulfonate cosurfactants has been found to hold true for other applications such as fracturing fluids, gravel packing fluids, and drilling fluids This demonstrates the superior high temperature performance of the viscoelastic systems containing the VESM of this invention over the prior art.
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A viscoelastic surfactant mixture (VESM) has been developed that is useful as a viscosity modifying additive for stimulating subterranean hydrocarbon containing formations. The VESM contains an amphoteric surfactant, an arylalkyl sulfonate cosurfactant and a polar solvent. The VESM may be employed as part of systems used in fracturing, acidizing, gravel packing and similar operations where a viscous fluid is required. The VESM can be applied over a wide range of temperatures and is especially useful if performance at elevated temperatures is required.
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CROSS-REFERENCE TO RELATED APPLICATIONS
Related subject matter may be found in the following commonly assigned, co-pending U.S. patent applications, both of which are hereby incorporated by reference herein:
(1) Ser. No. 08/781,770, entitled "A Document Feed Roller Opener and Method Therefor" by Richard H. Harris, et al. (Attorney Docket No. RA9-96-064), which is filed concurrently herewith; and
(2) Ser. No. 08/781,633, entitled "Curvilinear Pressure Pad for Improved MICR Reading and Method Therefor" by Robert A. Myers (Attorney Docket No. RA9-96-084), which is also filed concurrently herewith.
TECHNICAL FIELD
The invention is drawn to the field of point of sale check printers in general and in particular to point of sale check printers having document handling systems.
BACKGROUND INFORMATION
In ongoing attempts to provide more efficient and convenient service to customers, many retailers have begun to use "point of sale check printers" to reduce the time required for a customer to manually fill out and sign a check. Most people have encountered delays at checkout lines when another customer waits until all of his or her items are checked or scanned to begin to fill out a check for the total purchase. Faster service is provided if the retailer uses a point of sale check printer. A point of sale check printer automatically enters the date, amount of purchase and the name of the retail establishment in the proper spaces on a check, leaving only the signature line blank for the customer to sign. The process of paying by check is therefore made similar to a purchase by credit card, in which all information regarding the date, the amount of the sale and the name of the retail establishment is provided for the customer, who then needs only to sign a receipt to complete the transaction.
A major difference between a credit card purchase and a check purchase, however, is the need for the back of a check to be endorsed, or "franked" by the retail establishment. This step is not required at the point of sale, but, for security reasons, many retail establishments which use a point of sale check printer have a practice of franking each check (with "for deposit only" or other similar notation) as it is received. This lessens the possibility of unrecoverable losses from stolen checks which are later stamped or printed with forged endorsements.
Because the standard location for endorsing or franking a check is on the back, and the standard location for providing all other information is on the front, any check processed by a point of sale check printer must be printed on both sides before such a check may be accepted as payment. Thus, the check must be removed and reinserted to the point of sale printer for information to be printed on both sides.
It is known in the art to encode data on a check with Magnetic Ink Character Recognition ("MICR") technology. In MICR technology, magnetic ink is used to print the customer's account number, a number identifying the bank, and the actual check number on each check. MICR reading machines read this information during the check clearing process to insure the proper account is charged with the amount for which the check is drawn.
Current point of sale check printers are able to read MICR encoding on the check and transmit the encoded data to credit verification agencies. After the information regarding the customer's bank and account number is transmitted to the credit verification agency, a decision may then be made by the retailer whether to accept the presented check. The verification step is not necessary, as some point of sale check printers merely read and record the MICR-encoded data. To use a current point of sale check printer, a cashier inserts the check for reading and verification. After the MICR is read and any verification or approval completed, the back of the check is endorsed or franked.
As previously referred to, all point of sale check printers require that the check be manually removed from the printer and then re-inserted to print the date, the name of the retail establishment and the amount in numeral and word form on the face of the check. This step requires the attention of the cashier, who is thereby temporarily prevented from accomplishing another task such as "bagging" the purchased items. The check must be correctly oriented during the re-insertion, or the information printed on the face will be printed in the wrong places, rendering the check unusable. If the check is rendered unusable, the customer would be asked for a replacement check, which would lessen the customer's confidence in the retail establishment and the check printing process. Also, the interval in which a check is endorsed but not filled out on the face presents a security risk to the customer, who may not want a "blank" check to be out of his or her control. If the check is held in the point of sale printer for a length of time for verification, the cashier may become distracted or may get involved with other tasks. The cashier's attention would have to be regained when the franking step is completed and the check is ready for reinsertion. Until the cashier's attention is redirected to the point of sale printer, the check could be removed by an unauthorized party.
What is needed is a point of sale check printer that completes the steps of MICR-reading, verification (if any), franking, and printing more efficiently. Such a printer would ideally ensure the endorsement and all data on the front are correctly printed, minimize the risk associated with having an incomplete check in the control of store personnel instead of the customer, and would not need constant attention by the cashier during the payment process.
SUMMARY OF THE INVENTION
This invention enhances the usability for check handling in point of sale printers. It frees the operator from the task of retrieving the check after it is endorsed and then having to reinsert it into the printer so that the front face can be printed. A document handling system apparatus is disclosed, comprising a first path for transporting a document having first and second faces, the first path receiving the document with the first face in a first selected orientation and the second face in a second selected orientation, and a circular path for receiving the document from the first path with the first face in the first orientation and the second face in the second orientation and returning the document with the first face in the second orientation and the second face in the first orientation.
The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood. Additional features and advantages of the invention will be described hereinafter which form the subject of the claims of the invention.
BRIEF DESCRIPTION OF THE DRAWING
For a more complete understanding of the present invention, and the advantages thereof, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
FIG. 1 illustrates an exploded view of a point of sale check printer having a print head and check flipper subassembly in accordance with the present invention;
FIG. 2 illustrates an isometric view of a print head and check flipper subassembly for a point of sale check printer in accordance with the present invention;
FIG. 3 illustrates a left side view of the print head and check flipper subassembly of FIG. 2 in the normal print mode, with the outer frame removed for clarity;
FIG. 4 illustrates the right side of the print head and check flipper subassembly of FIG. 2 in the normal print mode, with the outer frame removed for clarity;
FIG. 5 illustrates the right side of the print head and check flipper subassembly of FIG. 2 in the flipping mode, with the outer frame removed for clarity;
FIG. 6 illustrates the left side of the print head and check flipper subassembly of FIG. 2 in the flipping mode, with the outer frame removed for clarity;
FIG. 7 illustrates the left side of the print head and check flipper subassembly of FIG. 2 in the flipping mode, with the upper gate moved towards its first position, and with the outer frame removed for clarity;
FIG. 8 illustrates a point of sale check printer having a print head and check flipper subassembly in accordance with the present invention, and shows the access door in an opened position;
FIG. 9 illustrates the point of sale check printer of FIG. 9 with the access door removed;
FIG. 10 illustrates the point of sale check printer of FIG. 9 with the flipper cartridge lifted; and
FIG. 11 illustrates the point of sale check printer of FIG. 9 with the flipper cartridge removed.
DETAILED DESCRIPTION
In the following description, well-known elements are presented without detailed description in order not to obscure the present invention in unnecessary detail. For the most part, details unnecessary to obtain a complete understanding of the present invention have been omitted inasmuch as such details are within the skills of persons of ordinary skill in the relevant art.
There is illustrated in FIG. 1 a view of a point of sale check printer assembly 100. Upper housing 100a covers inner assembly 100b. Lower housing 100c provides additional support.
There is illustrated in FIG. 2 a isometric view of a print head and check flipper subassembly 200 for a point of sale check printer in accordance with the present invention. Print head and check flipper subassembly 200, when used with a point of sale check printer 100, allows a check to be printed on both sides in one multi-step operation. Print head 202 is attached to print head carrier 204. Print head carrier 204 is substantially perpendicular to and slidably disposed on print head carrier bar 206. Print head carrier bar 206 is carried by outer frame 208. Frame 208 has an end plate 208a, a first side plate 208b and a second side plate 208c. Print head carrier 204 is driven from side to side, back and forth between first side plate 208b and second side plate 208c, along print head carrier bar 206 by well known means. Such means may include a direct current reversing stepper motor connected to print head carrier 204 by a drive belt and pulley mechanism.
Platen 210 is attached to outer frame 208 and opposite end plate 208a. Printing surface 212 is attached to platen 210 such that printing surface 212 faces end plate 208a.
Depending downwardly from print head carrier 204 is post 214. Outer frame 208 defines slot 216, with actuator 218 extending therethrough. Actuator 218 has angled surface 220 extending diagonally towards end plate 208a and second side plate 208c at an angle to both print head carrier 204 and print head carrier bar 206. As print head carrier 204 is driven towards actuator 218, post 214 engages angled surface 220, driving actuator 218 forward along slot 216 towards platen 210.
Inner frame 209 is connected to outer frame 208. Front feed roller axle 222 is carried by inner frame 209. Rear feed roller axle 224 is carried at one end by outer frame 208 near side plate 208b and at the other end by inner frame 209, near side plate 208c. Front feed roller axle 222 and rear feed roller axle 224 are substantially perpendicular to print head carrier 204 and substantially parallel to print head carrier bar 206. Front feed roller axle 222 is positioned near platen 210 and rear feed roller axle 224 positioned near end plate 208a.
There is illustrated in FIG. 3 a left side view of print head and check flipper subassembly 200 along line 3--3 of FIG. 2. Print head and check flipper subassembly 200 is illustrated in normal print mode. Normal print mode is one of two modes of operation of print head and check flipper subassembly 200, wherein the other mode of operation is a flipping mode. In FIG. 3, outer frame 208 has been removed and is not illustrated for clarity. It should be understood that the view illustrated in FIG. 3 is of the side of print head and check flipper subassembly 200 which would display first side plate 208b, had outer frame 208 not been removed and had print head and check flipper subassembly 200 not been sectioned along line 3--3.
Print head 202 and printing surface 212 of platen 210 define document entrance 302. Upper paper path 304 is defined by document entrance 302, front feed roller 306 and lower feed roller 308, along with upper gate 310, lower gate 312 and upper surface 314. Checks to be printed are inserted through document entrance 302 into upper paper path 304. Document entrance 302 is a first point along upper paper path 304. Various operations and mechanisms are located at points along upper paper path 304, as will be subsequently described herein.
MICR reader 316 is attached to platen 210 below printing surface 212. MICR reader 316 is a second point of upper paper path 304 After a check is inserted through document entrance 302 and into upper paper path 304, the check is moved past MICR reader 316 to allow MICR reader 316 to read the information printed in ferromagnetic indicia, or "magnetic ink" on the check and translate the information into a format usable by computers or other devices. The operation of MICR reader 316 is well known in the data processing art and will not be described in greater detail herein. Upper sensor 318 is provided adjacent MICR reader 306 to detect the presence of a check in upper paper path 304. Upper sensor 318 may be attached to inner frame 209, platen 210 or to print head and check flipper subassembly 200 by other means. Upper sensor 318 may be electrical, photo-electrical, mechanical, or may operate by other methods, so long as it is capable of detecting the presence or absence of a check in upper paper path 304 and providing a signal in response thereto.
A third point along upper paper path 304 is defined by front feed roller 306 and rear feed roller 308. Front feed roller 306 is mounted on front feed roller axle 222 and rear feed roller 308 is mounted on rear feed roller axle 224. Both front and rear feed rollers 306 and 308 preferably have circumferential surfaces of rubber, soft plastic or the like. Rear feed roller 308 is biased toward front feed roller 306, so that front and rear feed rollers 306 and 308 are in contact with each other. Front and rear feed rollers 306 and 308 are separable, however, by separating one end of front and rear feed rollers 306 and 308 by providing a lever to be actuated by post 214 or other element connected to print head carrier 204. Such a lever would be operativley connected one of front or rear feed rollers 306 or 308 or front or rear feed roller axles 222 and 224 such that displacement of the lever by post 214 would move one of front or rear feed rollers 306 or 308 away from the other. Alternatively, front and rear feed rollers 306 and 308 may be separated by well known means in which the circumferential surfaces of front and rear feed rollers 306 and 308 are parallel to each other once front and rear feed rollers 306 and 308 are separated.
A fourth point along upper paper path 304 is defined by upper gate 310, lower gate 312, and upper surface 314. Upper gate 310 and lower gate 312 are hingedly coupled to pin 320 so that upper gate 310 and lower gate 312 may swing between first and second positions. Pin 320 is attached to inner frame 209. Upper gate 310, in its first position, is positioned toward platen 210. When in a second position, upper gate 310 is extended toward end plate 208a. Lower gate 312, in its first position, is positioned toward end plate 208a of outer frame 208. When in a second position, lower gate 312 is extended toward platen 210. In normal print mode, upper gate 310 is in its first position, extended toward platen 210 and lower gate 312 is in its first position, extended towards end plate 208a, such that upper gate 310 and lower gate 312 are substantially parallel to upper surface 314. Upper paper path 304 continues past upper gate 310, lower gate 312, and upper surface 314 into lower document throat 322.
A fifth point along upper paper path 304 is lower sensor 323. Lower sensor 323 is attached to inner frame 209 behind rear feed roller 308. Lower sensor 323 may be electrical, photo-electrical, mechanical, or may operate by other methods, so long as it is capable of detecting the presence or absence of a check in upper paper path 304 and providing a signal in response thereto.
In operation of a point of sale check printer in accordance with the present invention, the lower edge of a check having a front side and a back side is inserted in upper paper path 304 until the lower edge is detected by upper sensor 318 as the lower edge is pushed against front and rear feed rollers 306 and 308 respectively. The check is inserted with its back side toward print head 202. The presence of the lower edge of the check, as detected by upper sensor 318, provides a signal to enable front feed roller 306 and rear feed roller 308 to start rotating in the forward direction. Because front and rear feed rollers 306 and 308 are in contact with each other, the check is drawn between front and rear feed rollers 306 and 308 and moved forward along upper paper path 304. Power to rotate front and rear feed rollers 306 and 308 is provided by well known means, such as an electric motor connected to front feed roller axle 222 (motor is not shown). The operation of an electric motor in both the forward and the reverse direction, along with the control mechanism and circuitry to reverse such a motor is well known in the printer art and will not be described in greater detail herein.
As illustrated in FIG. 3, during the forward direction rotation of front and rear feed rollers 306 and 308, front feed roller 306 rotates clockwise and rear feed roller rotates counterclockwise to advance the check along upper paper path 304. As the check is advanced along upper paper path 304, the information printed on the check in magnetic ink is read by the MICR reader 316, translated, and transmitted for any desired recordkeeping or verification.
After the check has advanced sufficiently along upper paper path 304, the upper edge of the check will advance beyond upper sensor 318. Upper sensor 318 senses that the upper edge of the check has advanced beyond upper sensor 318 and provides a signal to stop the rotation of front and rear feed roller 306 and 308. The check is held therebetween, with the lower edge of the check in lower document throat 322.
If the MICR-encoded information is used to verify that the account upon which the check is written contains enough funds to cover the amount purchased, for a review of the credit history of the customer, or for any other purpose, the information detected by MICR reader 316 is transmitted to an appropriate location by well known means. During this time, the check is held between front and rear feed rollers 306 and 308 in print head and check flipper subassembly 200.
Once any desired approval for the check is received, front and rear feed rollers 306 and 308 begin to rotate in reverse. As illustrated in FIG. 2 during reverse rotation, front feed roller 306 rotates counterclockwise and rear feed roller 308 rotates clockwise, causing the check to reverse its direction of travel back along upper paper path 304 towards document entrance 302. As the check is being pushed backwards along upper paper path 304, information such as "for deposit only," is printed by print head 202 on the back side of the check. The printing is done in "portrait mode," by moving print head 202 laterally along print head carrier bar 206 back and forth between first side plate 208b and second side plate 208c of frame 208, while print head 202 prints characters and information by well known means.
After the check has been endorsed by print head 202, the check continues to be driven backwards along paper path 204 until the lower edge of the check is retracted past lower sensor 323. Lower sensor 323 senses that the lower edge of the check has retracted past lower sensor 323 and provides a signal to stop the rotation of front and rear feed rollers 306 and 308, which holds the check therebetween.
There is illustrated in FIG. 4 a right side view of print head and check flipper subassembly 200 along line 4--4 of FIG. 2. Print head and check flipper subassembly 200 is illustrated in the normal print mode. Outer frame 208 has been removed for clarity. It shall be understood that the view in FIG. 4 is of the side of print head and check flipper subassembly 200 which would display second side plate 208c, had outer frame 208 not been removed and had print head and check flipper subassembly 200 not been sectioned along line 4--4 of FIG. 2.
Front feed roller gear 402 is coupled to front feed roller axle 222. Rear feed roller gear 404 is coupled to rear feed roller axle 224. Gears 402 and 404 are in engagement with each other, such that the rotation of one gear is in the opposite direction to the rotation of the other. Accordingly, when rear feed roller gear 404 is rotating in the clockwise direction, front feed roller gear 402 rotates in the counterclockwise direction, and when rear feed roller gear 404 is rotating in the counterclockwise direction, front feed roller gear 402 rotates in the clockwise direction. Power to rotate gears 402 and 404 is provided by well known means, such as an electric motor connected to front feed roller axle 222 (motor is not shown). Idler gear 406 is driven by front feed roller gear 402. Idler gear bracket 408 is loosely mounted to front feed roller axle 222 such that rotation of front feed roller axle 222 will cause idler gear bracket 408 to also rotate. Idler gear bracket 408 is not securely fastened to front feed roller axle 222; therefore should the rotation of idler gear bracket 408 be stopped from further rotation, then front feed roller axle 222 will be allowed to continue rotating. The teeth of idler gear 406 are maintained in engagement with the teeth of front feed roller gear 402 by idler gear bracket 408. Idler gear 406 is rotatably mounted to idler gear bracket 408 by idler gear axle 409.
Front frame 410 is attached to inner frame 209 below platen 210. Check flipper drive gear 412 is rotatably connected to front frame 410. Check flipper drive gear 410 drives drive belt 414 in corresponding rotation such that clockwise rotation of check flipper drive gear 410 results in clockwise travel of drive belt 414.
Inner frame 209 comprises plate 416, to which lever 418 is rotatably mounted along axis 419. Lever 418 is spring biased in its counterclockwise, or rearward, position towards end plate 208a. Lever 418 comprises rear arm 420, front arm 422, and middle slot 424. Rear arm 420 extends through slot 216 and is attached to actuator 218. Front arm 422 extends in front of axle 409 and holds axle 409 and idler gear 406 towards end plate 208a.
Tab 426 is disposed in middle slot 424. Tab 426 extends from middle slot 424 and tab 426 to lower gate 312, and is attached to lower gate 312, such that rotating lever 418 towards platen 210 will also move lower gate 312 towards platen 210.
Turning now to FIG. 5, print head and check flipper subassembly 200 is illustrated from a same view as that illustrated in FIG. 4. In FIG. 5, however, print head and check flipper subassembly 200 is in the flipping mode. Flipping mode is initiated as print head carrier 204 is moved towards second side plate 208c and plate 416, causing post 214 to engage angled surface 220 of actuator 218 and causing actuator 218 to be driven forward toward platen 210. It should be noted that this will happen when print head carrier 204 is positioned outside a normal zone. As lever 418 is driven toward platen 210, front arm 422 is lifted off of idler gear axle 409. Rotational force is then applied to front feed roller axle 222, causing front feed roller 306 and rear feed roller 308 to rotate in the forward direction. As illustrated in FIG. 5, the forward rotation of front and rear feed rollers 306 and 308 corresponds to a counterclockwise rotation of front feed roller gear 402 and a corresponding clockwise rotation of rear feed roller gear 404 and idler gear 406. Idler gear bracket 408 is mounted on front feed roller axle 222 with a slight amount of drag, so that the rotation of front feed roller axle 222 will tend to cause idler bracket 408 to rotate also. The rotation of idler gear bracket 408, however, may be stopped without stopping the rotation of front feed roller axle 222.
The counterclockwise rotation of front feed roller gear 402 and front feed roller axle 222 will also cause idler bracket 408 to turn in a counterclockwise direction. Opposing further counterclockwise rotation of idler gear bracket 408 and idler gear 406 is check flipper drive gear 412. As the teeth of idler gear 406 are brought into contact with the teeth of check flipper drive gear 412, check flipper drive gear 412 begins to rotate in a counterclockwise direction. The counterclockwise rotation of check flipper drive gear 412 causes a subsequent counterclockwise rotational travel of drive belt 414.
Should print head carrier 204 be moved away from plate 416, post 214 will become disengaged from actuator 218. Lever 418 is spring biased to its counterclockwise, or rearward position, causing front arm 422 to pull idler gear axle 409 and idler gear 406 away from check flipper drive gear 412 and allow check flipper drive gear 412 to come to a stop.
In initial flipping mode, lever 418 is shifted towards platen 210. During this shifting, middle slot 424 also pushes tab 426 towards platen 210. Tab 426 extends through print head and check flipper subassembly 200 and is connected to lower gate 312, such that pushing tab 426 towards platen 210 will also cause lower gate 312 to be pushed towards platen 210.
Turning now to FIG. 6, print head and check flipper subassembly 200 is illustrated from the same view as that illustrated in FIG. 3. In FIG. 6, however, print head and check flipper 200 is in the flipping mode. In flipping mode upper gate 310 and lower gate 310 are rotated in a clockwise fashion. Lower gate 312 is driven from its rear position towards platen 210 by the action of middle slot 424 of lever 418, as lever 418 is driven to towards platen 210. Upper gate 310 is spring biased to maintain its alignment with lower gate 312, therefore upper gate 310 concurrently travels from its frontward position away from platen 210.
The shift of upper gate 310 away from platen 210 and the shift of lower gate 212 towards platen 210, opens lower paper path 600. Lower paper path is defined by upper gate 310, lower gate 312, and lower surface 601.
Drive belt 414 is driven by check flipper drive gear 412 of (check flipper drive gear 412 is not viewable in FIG. 6). Drive belt 414 is wrapped around check flipper drive wheel 602. Therefore the rotation of check flipper drive gear 412 causes rotation of check flipper drive wheel 602 in the same direction. Check flipper drive wheel 602 is preferably provided with gear teeth. Check flipper drive wheel 602 is mounted to flipper frame 604.
Flipper cartridge 606 is removably inserted into flipper frame 604. Flipper cartridge 606 contains a front wheel 608 and rear wheel 610. Around front wheel 608 and rear wheel 610 is disposed belt 612. Belt 612 is preferably made of natural or synthetic rubber, or a soft plastic material to enable frictional contact between belt 612 and a check or other document. Front wheel 608 has gear teeth which engage the gear teeth of check flipper drive wheel 602 when flipper cartridge 606 is installed in flipper frame 604.
Flipper frame 604 and print head and check flipper subassembly 200 have access door 614. Access door 614 is preferably removable from print head and check flipper subassembly 200, but may be hinged at the edge of access door nearest platen 210. As access door 614 is hinged up or removed, flipper cartridge 606 may be inserted or removed from flipper frame 604.
Flipper frame 604 is provided with a plurality of idler wheels 620. Idler wheels 620 are in contact with belt 612. In a preferred embodiment, two idler wheels are attached to the lower surface of access door 614 and a third idler wheel is attached to flipper frame 604. As access door 614 is raised, the upper two idler wheels 620 are also raised away from flipper cartridge 606. This allows flipper cartridge 606 to be removed from flipper frame through the opening created by the lifting of access door 614 in the event a check has become jammed in lower paper path 600 or circular paper path 624. Flipper frame 604 has bottom support 618 and rear guide 622.
Circular paper path 624 is defined by check flipper drive wheel 602 and belt 612, belt 612 and bottom support 618, and front wheel 608, belt 612 and rear wheel 610. As circular paper path 624 passes check flipper drive wheel 602, it is further defined as bottom support 618, rear guide 622, the underside of access door 614, and idler wheels 620.
Bottom support 618 has upturned portion 626 to direct the check between belt 612 supported by rear wheel 610 and idler 620. Rear guide 622 has a similar upturned portion 628 to guide the check between belt 612 and idler 620.
Print head and check flipper subassembly 200 is put into flipping mode by post 214 of print head carrier 204 contacting angled surface 220 of actuator 218, and moving lever 418 towards platen 210. After print head and check flipper subassembly 200 has been put into flipping mode, front and rear feed rollers 306 and 308 begin to rotate in the forward direction. Due to the shift of upper and lower gates 310 and 312, lower paper path 600 is opened to direct the check along lower surface 601 towards check flipper drive wheel 602 and front wheel 608. Because the surface of check flipper drive wheel 602 is in contact with belt 612, the check is drawn between check flipper drive wheel 602 and belt 612. As the lower end of the check passes between check flipper drive wheel 602 and belt 612, the check enters circular paper path 624.
As the check enters and is advanced along circular paper path 624, the upper edge of the check advances beyond lower sensor 323, providing a signal for front and rear feed rollers 306 and 308 to separate. Check flipper drive wheel and belt 612 continues to advance the check along circular paper path 624. Upturned portions 626 and 628 direct the check in between idlers 620 and belt 612.
There is illustrated in FIG. 7, a view of print head and check flipper subassembly 200 as illustrated in FIG. 3. In FIG. 7, however, print head and check flipper subassembly 200 is shown with upper gate 310 moved toward its first position toward platen 210. As the check advances between the last idler 620, it is in a reversed, or "flipped" orientation such that the front face of the check, upon which the amount of purchase and the date will be printed is toward print head 202, and the lower edge of the check is closest to document entrance 302. As the lower edge of the check contacts upper gate 310, upper gate 310 moves in response toward its first position towards platen 210 to allow the check to pass. Lower gate 312 remains in the flipped position.
As the check is advanced past lower sensor 323, print head and check flipper subassembly 200 reverts to the normal print mode and front and rear feed rollers 306 and 308 close and begin to rotate in the reverse direction, pulling the check out of circular paper path 624. This advances the check past print head 202 where information such as the amount of the purchase, the date and the name of the selling establishment is printed in "landscape mode" along the width of the front face of the check. After printing is completed, front and rear feed rollers 306 and 308 advance the check out of document entrance 302, for retrieval by the cashier or operator. At the end of the process, a check is verified, endorsed and printed, ready to be presented to the customer for signing.
It should be understood that the process and mechanism described above would serve equally well for other documentation besides a check. Any document which would fit within the physical dimensions of the print head and check flipper subassembly 200 could be printed, whether such document is required to be printed on both sides, and whether such document contained MICR information. It shall also be understood that additional information could be printed on the face of a check or other document, such as a drivers license or phone number of the consumer, if such information is provided to the print head at the time of printing. Furthermore, it should be understood that print head and check flipper subassembly 200 could be modified to perform this flipping operation on larger and smaller documents.
Turning now to FIGS. 8 and 9, point of sale check printer 100 is used with a print head and check flipper subassembly (not shown). Point of sale check printer 100 has access door 614, which is lifted in FIG. 8 and is removed in FIG. 9.
Turning now to FIGS. 10 and 11, point of sale check printer 100, used with print head and check flipper subassembly (not shown) is illustrated with flipper cartridge 606 lifted in FIG. 10 and removed in FIG. 11. Flipper cartridge 606 is removable to allow retrieval of a jammed or stuck check or other document in print head and check flipper subassembly, or to allow repair or replacement of flipper cartridge 606.
While preferred embodiments of the invention have been shown and described, it will be apparent to those skilled in the art that the conception and the specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for carrying out the same purpose as the present invention. It should also be realized by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
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A print head and check flipper subassembly having a removable flipper cartridge allows printing of both sides of a check or other document in one continuous operation, in which the orientation of the check or other document is reversed in relation to a print head, eliminating the need for an operator to remove and reinsert the check during the printing or handling process.
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CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. patent application Ser. No. 12/091,868 filed Oct. 16, 2008 now U.S. Pat. No. 8,109,140, which is a U.S. National Stage Entry of Patent Cooperation Treaty patent application Serial No. PCT/GB06/03092 filed Aug. 18, 2006, which claims priority to British patent application Serial No. 0521774.0 filed Oct. 26, 2005, and all of which are hereby incorporated herein by reference in their entirety.
This invention relates generally to the evaluation of a formation penetrated by a wellbore. More particularly, this invention relates to downhole sampling tools capable of collecting samples of fluid from a subterranean formation.
BACKGROUND
The desirability of taking downhole formation fluid samples for chemical and physical analysis has long been recognized by oil companies, and such sampling has been performed by the assignee of the present invention, Schlumberger, for many years. Samples of formation fluid, also known as reservoir fluid, are typically collected as early as possible in the life of a reservoir for analysis at the surface and, more particularly, in specialized laboratories. The information that such analysis provides is vital in the planning and development of hydrocarbon reservoirs, as well as in the assessment of a reservoir's capacity and performance.
The process of wellbore sampling involves the lowering of a downhole sampling tool, such as the MDT® wireline formation testing tool, owned and provided by Schlumberger, into the wellbore to collect a sample (or multiple samples) of formation fluid by engagement between a probe member of the sampling tool and the wall of the wellbore. The sampling tool creates a pressure differential across such engagement to induce formation fluid flow into one or more sample chambers within the sampling tool. This and similar processes are described in U.S. Pat. Nos. 4,860,581; 4,936,139 (both assigned to Schlumberger); U.S. Pat. Nos. 5,303,775; 5,377,755 (both assigned to Western Atlas); and U.S. Pat. No. 5, 934,374 (assigned to Halliburton).
Various challenges may arise in the process of obtaining samples of fluid from subsurface formations. Again with reference to the petroleum-related industries, for example, the earth around the borehole from which fluid samples are sought typically contains contaminates, such as filtrate from the mud utilized in drilling the borehole. This material often contaminates the clean or “virgin” fluid contained in the subterranean formation as it is removed from the earth, resulting in fluid that is generally unacceptable for hydrocarbon fluid sampling and/or evaluation. As fluid is drawn into the downhole tool, contaminants from the drilling process and/or surrounding wellbore sometimes enter the tool with fluid from the surrounding formation.
To conduct valid fluid analysis of the formation, the fluid sampled preferably possesses sufficient purity to adequately represent the fluid contained in the formation (i.e. “virgin” fluid). In other words, the fluid preferably has a minimal amount of contamination to be sufficiently or acceptably representative of a given formation for valid hydrocarbon sampling and/or evaluation. Because fluid is sampled through the borehole, mudcake, cement and/or other layers, it is difficult to avoid contamination of the fluid sample as it flows from the formation and into a downhole tool during sampling.
Various methods and devices have been proposed for obtaining subsurface fluids for sampling and evaluation. For example, U.S. Pat. No. 6,230,557 to Ciglenec et al., U.S. Pat. No. 6,223,822 to Jones, U.S. Pat. No. 4,416,152 to Wilson, U.S. Pat. No. 3,611,799 to Davis and International Pat. App. Pub. No. WO 96/30628 have developed certain probes and related techniques to improve sampling. Other techniques have been developed to separate virgin fluids during sampling. For example, U.S. Pat. Nos. 6,301,959 to Hrametz et al. and discloses a sampling probe with two hydraulic lines to recover formation fluids from two zones in the borehole. Borehole fluids are drawn into a guard zone separate from fluids drawn into a guard zone. In the published international application WO 03/100219 A1 there are disclosed sampling devices using inner and outer probes with a varying ratio of flow area.
Despite such advances in sampling, there remains a need to develop techniques for fluid sampling optimized for heavy oils and bitumens. The high viscosity of such hydrocarbon fluids often presents significant challenges for sampling representative fluids. Effective in-situ reduction of the viscosity of heavy oils without inducing phase and/or compositional changes is thus necessary to obtain a representative sample.
The reduction in the viscosity of heavy oil and bitumen for the purposes of increasing the recovery factor of a reservoir has been a topic of interest in the oil industry for many years. Several methods for the viscosity reduction are known and employed in the field today. It has long been established that heating of heavy oils and bitumens significantly reduce the fluid viscosity and subsequently, increases the fluid mobility. Small thermal changes can result in a relatively large drop in the viscosity of the oil. For example, it is known from AOSTRA Technical Report #2, The Thermodynamic and Transport Properties of Bitumens and Heavy Oils, Alberta Oil Sands Technology and Research Authority, July 1984, that the viscosity of typical Athabasca bitumen from Canada can be reduced by two orders of magnitude by increasing the temperature from 50° C. to 100° C. The plot of FIG. 1 is based on the AOSTRA report. Such a lowering in viscosity will allow for increased mobility of the viscous oil or bitumen required for sampling.
There are many literature examples, both tried and tested along with conceptual, of ways to heat in situ viscous oil in a reservoir to aid recovery. As described below in greater details with reference to examples of known recovery-enhancing techniques, these techniques are generally not immediately suitable for sampling.
Currently, the primary thermal method for heavy oil recovery is steam assisted gravity drainage (SAG-D). This process uses the injection of super-heated steam to improve the mobility of the oil. The process mainly relies on the conduction of heat from the steam to the oil. Efficient transfer of the heat requires intimate mixing of the oil and steam. During the exchange of heat, portions of the steam will be converted to liquid water, often in the form of millimeter or micron sized water droplets suspended in the oil. While it depends on the source of the oil, this process normally results in the formation of stable water-in-oil emulsion. Samples of emulsion containing oils cannot be characterized in a laboratory environment without removal of the emulsion and most demulsification protocols result in irreversible and undesirable changes to the chemical composition of the oil.
An alternative method of reducing the viscosity of the oil has been to use solvents or gases to dilute the oil and thus, form a mixture that has a lower viscosity. Depending on concentration, the dilution of the oil can cause the precipitation of the higher order species from the mixture that can also aid viscosity reduction. However, this method of viscosity reduction for sampling results in an undesirable change in the composition of the oil that prevents proper characterization of the oils chemical and physical properties.
Methods for in situ heating of oils that will not alter their composition are limited. They can be divided into two categories, Joule (or Ohmic) heating and electromagnetic heating. Ohmic heating relies on the principle of applying an electric current through a resistive element to generate heat. A recent U.S. published patent application, US 2005/0006097 A1, discloses a potential method using a downhole heater whereby variable frequencies could be applied across the resistor in order to modulate and control the heating. This method requires good placement of the heating element within the formation as conduction has to be optimized.
Electromagnetic heating uses high frequency radiation to penetrate the reservoir and heat the formation. Many examples of this type of technology for the recovery of heavy oils have been reported. Abernethy, in: Abernethy, E. R., ‘Production increase of heavy oils by electromagnetic heating,’ Journal of Canadian Petroleum Technology, 1976, 91, has developed a steady state model that indicates the depth of penetration of the radiation and its heating potential for the oil. This parameter is then used to determine the viscosity reduction in the oil and the subsequent improvement in the mobility. Although the model may be quite crude, it does appear to indicate that many forms of electromagnetic heating may be used to locally heat oil for the purposes of sampling. Fanchi in: Fanchi, J. R., ‘Feasibility of reservoir heating by electromagnetic radiation,’ SPE 20438, 1990, 189, devised an algorithm for determining temperature increase of an oil as a result of electromagnetic heating and also describes attempted field implementation of some of these devices.
The use of microwaves and radio frequencies for the heating of in place oil has been extensively studied. Most of the microwave work has been carried out using standard microwave frequencies of 2.45 GHz with variable power input. An evaluation of microwave heating for the heavy oil recovery published as Brealy, N., ‘Evaluation of microwave methods for UKCS heavy oil recovery,’ SHARP IOR newsletter, 2004, 7, indicates that field wide application of this technology may not be economic.
In U.S. Pat. No. 5,082,054 to Kiamanesh there is disclosed a system for reservoir heating that uses tunable microwaves for oil recovery. The data indicates that this process can lead to cracking of the oil and several of the claims made support this observation. This type of heating technology has been used in a field environment for differing viscosities of oil as reported in: Ovalles, C., Fonseca, A., Lara, A., Alvarado, V., Urrechega, K., Ranson, A., and Mendoza, H., ‘Opportunities of downhole dielectric heating in Venezuela: Three case studies involving medium, heavy and extra heavy crude oil reservoirs’, SPE 78980, 2002. The oil types were medium, heavy and extra heavy and all types responded with increased mobility after irradiation. No mention was made to the composition of these oils and changes induced by the heating process.
Radio frequency heating has been applied to reservoirs containing heavy oils as described in: Kasevich, R. S., Price, S. L., Faust, D. L. and Fontaine, M. F., ‘Pilot testing of a radio frequency heating system for enhanced oil recovery from diatomaceous earth’, SPE 28619, 1994, and also to aid bitumen recovery from the tar sands. These reports indicate that a positive response, regarding the mobility of the oil, was observed due to irradiation at around 13 MHz. In the first case, 250 Kwatts of power was delivered efficiently in this manner.
In all the above cases, no mention was made regarding the changes in composition of the oil except when upgrading had occurred. High temperatures and irradiation can cause fragmentation and isomerisation of components of the oil. Studies on plant oils have shown unsaturation and heteroatoms are affected by prolonged exposure to microwave sources. This is possibly due to local heating or hot spots within the oil.
The use of heat as a way to improve the characterization of the formation has been proposed in the published US patent application no. 2004/0188140 to S. Chen and D. T. Georgi. The described method proposes the heating the oil to increase the T 2 relaxation time of the system. This results in more accurate NMR measurements. No information on the monitoring and control of this process are given.
In the light of the described prior art, which to the extend as it refers to heating methods for and properties of heavy oil is incorporated herein, it remains the need to develop apparatus and methods for the reservoir sampling of reservoir with heavy oil or bitumen content.
SUMMARY
One embodiment of the invention achieves its objects by providing a reservoir sampling apparatus having at least one probe adapted to provide a fluid flow path between a formation and the inner of the apparatus with the flow path being sealed from direct flow of fluids from the borehole annulus, wherein the apparatus includes a heating projector adapted to project heat into the formation surrounding the probe and a controller to limit the temperature rise in the formation below a threshold value.
The apparatus may be conveyed into the borehole on either a wireline cable, coiled tubing or production tubing. The probe may include at least one inner and one outer probe. The heating projector includes a heat source based Joule (or Ohmic) heating and/or electromagnetic heating.
In another embodiment, at least one probe is heated. In a further embodiment, at least one probe is used to conduct heat from the heat source into the formation. In yet another embodiment, the apparatus includes a temperature sensor such as thermo couple to monitor the temperature of the sampled fluid and/or an in situ viscometer. In one aspect of the invention, signals representative of the temperature of the sampled fluid are fed back into the controller. In another variant of this embodiment, the thermometer is located along the flow path outside the inner or body of the sampling apparatus.
In one embodiment of the invention, the controller maintains an upper limit for the temperature increase in the formation with the limit being determined using prior knowledge of the properties and or composition of the fluid in the formation. In an aspect of this embodiment of the invention, the temperature limit is set to avoid a phase separation or “flashing out” of the formation fluid.
These and other features of the invention, preferred embodiments and variants thereof, possible applications and advantages will become appreciated and understood by those skilled in the art from the following detailed description and drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows the viscosity (logarithmic scale)of typical Athabasca bitumen from Canada with temperature (linear scale);
FIGS. 2A-B show outline and further details of a formation sampling tool as used in an example of the present invention;
FIGS. 3A-B illustrate the effect of heavy oil on conventional sampling devices;
FIG. 4 shows details of a fluid sampling device in accordance with an example of the present invention;
FIG. 5 illustrates the limits of effective temperature control;
FIG. 6 shows a schematic pressure-temperature diagram showing the typical saturation curves for different types of hydrocarbon fluids with C denotes critical point of the respective fluid;
FIG. 7 shows steps in accordance with an example of the invention; and
FIGS. 8A & B illustrate a phase change effect that may be exploited in one embodiment of the present invention.
DETAILED DESCRIPTION
Referring to FIG. 2A , an example environment within which the present invention may be used is shown. In the illustrated example, the present invention is carried by a downhole tool 10 . An example commercially available tool 10 is the Modular Formation Dynamics Tester (MDT®) by Schlumberger Corporation, the assignee of the present application and further depicted, for example, in U.S. Pat. Nos. 4,936, 139 and 4,860,581 hereby incorporated by reference herein in their entireties.
The downhole tool 10 is deployable into bore hole 14 and suspended therein with a conventional wire line 18 , or conductor or conventional tubing or coiled tubing, below a suitable rig 5 or cable feeder as will be appreciated by one of skill in the art. The illustrated tool 10 is provided with various modules and/or components 12 , including, but not limited to, a fluid sampling system 20 . The fluid sampling system 20 is depicted as having a probe used to establish fluid communication between the downhole tool and the subsurface formation 16 . The probe 26 is extendable through the mudcake 15 and to sidewall 17 of the borehole 14 for collecting samples. The samples are drawn into the downhole tool 10 through the probe 26 .
While FIG. 2A depicts a modular wireline sampling tool for collecting samples according to the present invention, it will be appreciated by one of skill in the art that such system may be used in any downhole tool. For example, the downhole tool may be a drilling tool including a drill string and a drill bit. The downhole tool may be of a variety of tools, such as a Measurement-While-Drilling (MWD), Logging—While Drilling (LWD), coiled tubing or other downhole system. Additionally, the downhole tool may have alternate configurations, such as modular, unitary, wireline, coiled tubing, autonomous, drilling and other variations of downhole tools.
Referring now to FIG. 2B , the fluid sampling system 20 of FIG. 2A is shown in greater detail. The sampling system 20 includes the probe 26 , flowline 27 , sample chambers 28 A and 28 B, pump 30 and fluid analyzer 32 . The probe 26 as shown include an outer probe 261 and an inner probe 262 connected to an intake 25 in fluid communication with a first portion 27 A of flowline 27 for selectively drawing fluid into the downhole tool. The combination of inner and outer guard probes may be based on the adaptable configuration of probes described in WO 03/100219A1 previously incorporated herein. Alternatively, a single probe or a pair of packers (not shown) may be used in place of the dual probe 26 . Examples of a fluid sampling system using probes and packers are depicted in U.S. Pat. Nos. 4, 936,139 and 4, 860,581, as previously incorporated herein.
The probe further includes a heat projector 251 and a temperature sensor 252 . Within the body of the tool there is a temperature controller 253 which is connected to the heat projector 251 and the temperature sensor 252 . Under operating conditions, the controller 253 provide a controlled amount of power to the heater 251 . The controller 253 and the temperature sensor 252 are connected such that temperature measurements can be used for the accurate control of the heater 251 .
Within the tool 10 , the flowline 27 connects the intake 25 to the sample chambers, pump and fluid analyzer. Fluid is selectively drawn into the tool through the intake 25 by activating pump 30 to create a pressure differential and draw fluid into the downhole tool. As fluid flows into the tool, fluid is preferably passed from flowline 27 , past fluid analyzer 32 and into sample chamber 28 B. The flowline 27 has a first portion 27 A and a second portions 27 B. The first portion extends from the probe through the downhole tool. The second portions 27 B connect the first portion to the sample chambers 27 B, 28 B. Valves, such as valves 29 A and 29 B are provided to selectively permit fluid to flow into the sample chambers 27 B, 28 B. Additional valves, restrictors or other flow control devices may be used as desired.
As the fluid passes by fluid analyzer 32 , the fluid analyzer is capable of detecting fluid content, contamination, optical density, gas oil ratio and other parameters. The fluid analyzer may be, for example, a fluid monitor such as the one described in U.S. Pat. No. 6,178,815 to Felling et al. and/or U.S. Pat. No. 4,994,671 to Safinya et al., both of which are hereby incorporated by reference.
The fluid is collected in one or more sample chambers 28 B for separation therein. Once separation is achieved, portions of the separated fluid may either be pumped out of the sample chamber via a dump flowline 34 , or transferred into a sample chamber 28 A for retrieval at the surface as will be described more fully herein. Collected fluid may also remain in sample chamber 28 B if desired.
The process of the known MDT is optimized for obtaining samples of light and conventional oils. Oils with a viscosity higher than 30 cP present problems as these oils have low mobility. The most mobile fluids in the reservoir will be water and the drilling fluid. In case of a probe 26 having an inner or sample probe 261 and an outer or guard probe 262 , the outer probe is designed to aid sampling in the MDT with reduced oil based mud (OBM) contamination. The mobility contrast between the oil and the drilling fluid has to be low for the outer probe 261 to divert the flow of drilling fluids from the intake 25 . When the drilling fluid is highly mobile it narrows the volume from which clean formation fluid can be sampled. This narrowing of the sampled volume at increase viscosity contrast is schematically shown in FIG. 3 .
In FIG. 3A , the mobility contrast between the drilling mud 35 and the formation fluid 36 is assumed low resulting in broad flow of formation fluid 36 entering the inner probe 262 . At a high mobility contrast ( FIG. 3B ) with the drilling mud assumed to be more mobile that the formation fluid (heavy oil) the flow of uncontaminated fluid narrows and drilling fluid is drawn into both the annulus of the guard probe 261 and sample probe 262 . As a consequence, the sampling time for obtaining uncontaminated sample increases with an increased risk that the tool gets stuck or no satisfactory sample is obtained.
According to an embodiment of the invention the sampling of the low mobility formation fluid is enabled or enhanced through the heating system 251 - 253 that is designed to least partially heat the formation surrounding the probe 26 of the downhole tool 10 . The heating is monitored to ensure the mobility of the oil is increased sufficiently so that it can be sampled, but not such that the chemical composition or physical state of the oil altered.
A variant of the tool shown in FIG. 2 is schematically shown in FIG. 4 . In FIG. 4 , the heat source or projector 451 is installed as part of the wall of the sample or inner probe 462 such that a high amount of heat is transferred into the formation. Also integrated into the wall is a thermocouple 452 to monitor the temperature of the formation fluid. More relevant parameters such as viscosity may be used to characterize the heated formation fluid. If it is desired to determine the viscosity of the fluid the thermocouple may be replaced by combined with a viscometer (not shown) providing data to the control unit 453 which controls the operation of the heater 451 .
Whilst the optimum location of the heat source in the probe is a matter of design depending on the nature of the source, i.e., whether it is electric or radiation based, the length of the probe and other considerations. It may also be located within the body of the tool if it is desired to heat a larger portion of the surrounding formation. The reservoir fluids can be heated using either electromagnetic radiation (Gamma-rays, X-rays, UV, IR, microwaves and radio frequencies) or joule heating or a combination of both. In the example the heat source 441 is a microwave source incorporated into the outer probe.
It is advantageous to also monitor the pressure profile during the operation for example through an solid state or MEMS type pressure sensor (not shown) co-located with the temperature sensor 452 to record a complete profile of the sampling procedure. After being heated and guided into the sampling tool, the sampled fluid is analyzed and either rejected or pumped into a sampling chamber following the procedures described referring to FIG. 2 . above.
During the sampling process, the controlled heating is continued until the sample has mobility such that it can be collected. The rise in temperature of the fluids in the formation is monitored using the temperature sensor 452 . When the sensor indicates that the desired temperature has been reach the sample is removed using the guarded probe 461 , 462 . The inner probe 462 is heated to ensure continual flow of fluids during the extraction procedure. This aspect of flow assurance is important to ensure the sample is taken in good time and is representative of the fluids in the reservoir.
The desired temperature may be set using formation evaluation performed prior to the sampling. Typically the formation evaluation used is the result of a wireline logging operation. The viscosity of the in situ oil can be for example determined via correlation to the T 2 relaxation time gained through NMR logging. With such prior knowledge the required temperature or its maximum can be determined using for example a database of experimental data such as illustrated in FIGS. 1 , 5 and 6 .
As mentioned earlier, an objective of any sampling operation is to obtain a “representative” sample of the hydrocarbon fluid from reservoir. A “representative” sample is an sample whose chemical composition and physical state has not been altered by changes in composition, temperature, and pressure. Ideally, the reservoir fluid to be sampled exists as a single phase fluid within the reservoir, when the pressure of the reservoir is above the saturation pressure of the fluid (i.e. bubble point or dew point). FIG. 5 is a schematic pressure-temperature plot showing the saturation curves for various types of hydrocarbon fluids, including dry gas, wet gas, condensate, volatile oil, black oil, and heavy oil.
During the sampling process, the fluid must be withdrawn from the reservoir, through the sampling probe (guard probe or otherwise), and into the sample storage chamber within the sampling tool (e.g., MDT). As such, a decreasing pressure gradient must be created from the reservoir to the storage chamber that will induce the oil to flow into the chamber. Key to this process is preventing the pressure from dropping below the saturation curve and thus, causing the fluid to flash into a mixture of gas and liquid. The presence of the two phases however makes it difficult to obtain a representative sample.
Preventing a flash requires the isothermal pressure drop due to sampling to be less than the difference between the reservoir pressure and saturation pressure. With the exception of heavy oil, the viscosity of the hydrocarbons fluids is relatively low and thus, the magnitude of the pressure drop can be easily controlled through the flow rate. However, the high viscosity of the heavy oil and bitumen leads to large pressure drops during sampling using existing technology and, in turn, greatly increases the risk of flashing the oil. The slow sampling flow rates required to reduce this risk increases the chance of having the tool stuck in the well. Also, the slow sampling flow rates do not prevent significant contamination of the sample due to the low mobility of the heavy oil relative to the drilling mud and formation water.
The heated sampling probe (guarded or otherwise) can provide a means of reducing viscosity, reducing the drawdown pressure, and reducing contamination by improving the mobility of the heavy oil relative to the drilling mud and formation water. As illustrated in FIG. 6 , heating the formation in a controlled manner, the fluid can be heated from an initial reservoir temperature T 0 to a temperature T 1 at which the viscosity at pressure (solid curve) is greatly reduced and yet the difference between the reservoir pressure and saturation pressure is sufficient to allow enough drawdown pressure to sample the heavy oil at a relatively fast flow rate. Temperature control is used to maintain the temperature at around T 1 thus avoiding temperatures T 2 too close to the bubble point curve (dashed line).
The monitoring and control of the heating process is therefore an important aspect of the present invention. Over heating of the fluid can have two main detrimental effects: It may cause thermal degradation or cracking to occur, which will alter the composition of the oil and thus produce a non-representative sample or it may push the fluid to a pressure and temperature condition that is too close to the saturation curve of the fluid. Thus, the drawdown pressure required to sample the fluid will cause an undesirable flash of the fluid resulting in uncontrolled two phase flow into the sampling chamber.
Thus, the heated sampling probed being described will heat the formation in a controlled fashion that is monitored to ensure overheating of the fluid does not occur. Heating of the fluid will reduce the viscosity of the oil, allowing for lower drawdown pressures during sampling and faster sampling flow rates. The benefit is the ability to obtain a representative sample of heavy oil bitumen that has not been altered in its chemical composition due to significant contamination, reaction, or otherwise nor has its physical state been altered from single phase fluid to two phase fluid or otherwise.
In general the present invention proposed a method having three principal stages as illustrated in FIG. 7 .
Stage 1 ( 71 ): In this step, the formation is first evaluated to determine the viscosity of the in place oil and determine its mobility. This is done using NMR or other suitable techniques such as acoustic monitoring. When the formation has been evaluated the required viscosity reduction and/or raise in temperature needed to generate good samples will be determined. This is done by comparison to prior data and use of tables and logs. The effective amount of heating needed will be determined by the use of data such as that in figure three. Heating the oil in the case shown to 120° C. will give a highly mobile fluid. If the fluid were to be heated to higher temperatures, no further significant drop in viscosity would be seen but the fluid would approach the phase change boundary. This shows that further heating of the oil is of little value and potentially detrimental to the sampling process; thereby validating the importance of the initial logging and evaluation process in this procedure.
Stage 2 ( 72 ): A thermally heated guard probe will be used to increase the formation temperature in the vicinity of the probe, hence reducing the viscosity of the oil while diverting the mud flow to the outside of the sampling chamber, where required. This can be used in conjunction with other forms of heating, such as combinations of electromagnetic radiation, which will heat the oil deeper in the formation. The probe will act as a wave guide to direct the electromagnetic waves to the desired part of the formation, hence maximizing the efficiency of the process. This changes in temperature and/or viscosity of the oil will be monitored by techniques such as acoustic or IR monitoring, NMR logging (changes in t 2 relaxation times) or a thermocouple placed in the formation and/or a combination thereof.
Stage 3 ( 73 ): When the required temperature is reached, (or desired viscosity drop obtained), the fluid is subsequently removed from the formation by use of a pump. The fluid will flow along the heated guard probe, the heat in the probe is now essential to maintain the flow of the oil and ensure the entire sample is delivered into the sampling chamber or vessel.
Within the guard probe, thermocouples, thermal switches and/or similar mechanisms, are to be used to monitor the temperature of the oil to ensure good flow assurance. The viscosity of the fluid entering the guard probe and that leaving it can also be monitored to check the performance of the procedure.
When the entire fluid sample required has been deposited in the sampling vessel, the vessel is sealed and can be allowed to cool as the sample has been obtained.
This technique can use many different ways of heating the formation, and combinations thereof, which give a uniform heating deep into the reservoir. The preferred combination of thermal heating and tunable microwaves allows near, medium and deep heating into the reservoir and the energy used will control the heat up rate and final temperature of the reservoir fluid.
In effect, the heated probe has dual functionality. It participates in the heating of the reservoir fluids in the first part of the procedure, it simultaneously ensures sampling of the reservoir fluid will be collected in a timely manner (whilst the fluid is still warm) and with minimal (if not zero) contamination. It is also instrumented such that key parameters such as viscosity and temperature are monitored during the operation.
In a variant, the probe itself may contain thermosetting ‘phase change’ materials, such as waxes or thermoplastics, which will maintain the temperature of the probe, particularly when the heating facility is not operational. This will allow the probe to be moved from location to location without large losses of heat and hence, reduce sampling time and minimize the potential for the tool to become stuck in the highly viscous formation. FIG. 8A shows the cooling curve of a typical material with no phase change. The exponential heat loss is significantly different from the behavior shown by phase change materials depicted in FIG. 8B .
Various embodiments and applications of the invention have been described. The descriptions are intended to be illustrative of the present invention. It will be apparent to those skilled in the art that modifications may be made to the invention as described without departing from the scope of the claims set out below.
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A reservoir sampling apparatus comprising at least one probe adapted to provide a fluid flow path between a formation and the inner of the apparatus with a heating projector adapted to project heat into the formation surrounding the probe and a controller to maintain the temperature in the formation below a threshold value.
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This is a division of application Ser. No. 611,109, filed Sept. 8, 1975.
BACKGROUND OF THE INVENTION
The 1-aryl-1-hydroxy-2-methylaminopropanes are optically active compounds which are pharmaceutically useful. Unfortunately, one stereo isomer is generally the active component while the other isomer is either inert, less effective or deactivating.
One of the most important 1-aryl-1-hydroxy-2-methylaminopropane is d-pseudoephedrine. It has been heretofore prepared by several methods from 1-ephedrine. For example, treatment of 1-ephedrine with aqueous HCl gave a diasteriomeric mixture of approximately 40 percent 1-ephedrine and 60 percent d-pseudoephedrine after rather long reaction times (e.g. 40 hours) and elevated temperatures. Separation of such optical isomers is tedious, time consuming, and has heretofore proceeded in rather low yields. Emde, Helv. Chem. Acta., 12, 377 (1929).
In yet another process, 1-ephedrine was converted to its monoacetate (amide) and hydrolyzed to give again a diasteriomeric mixture of approximately 35 percent 1-ephedrine and approximately 65 percent d-pseudoephedrine. Welsh, J. Am. Chem. Soc., 69, 128 (1947).
It has also been reported that the reaction of 1-ephedrine hydrochloride with 10 moles excess acetic anhydride gave d-pseudoephedrine hydrochloride. No yields were reported. Schmidt and Calliess, Arch. Pharm., 250, 154 (1912).
It was also reported that the reaction of 1-ephedrine with o-methylbenzoyl chloride and subsequent hydrolysis of the resulting amide gave d-pseudoephedrine. Welsh, J. Am. Chem. Soc., 71, 3500 (1949).
SUMMARY OF THE INVENTION
We have discovered a novel process for converting erythro isomers of 1-aryl-1-hydroxy-2-methylaminopropanes selectively to the corresponding threo isomer.
Our process comprises the steps of:
(1) reacting by contacting the erythro isomer or a diasteriomeric mixture (racemic or optically pure) of a 1-aryl-1-hydroxy-2-methylaminopropane with at least two equivalents of an organic acylating reagent; thereby forming the O,N-diacylated derivative;
(2) reacting by contacting said O,N-diacylated derivative with an anhydrous or substantially anhydrous protic acid; thereby forming an oxazolinium salt; and
(3) reacting said oxazolinium salt with an aqueous protic acid to form the corresponding threo isomer as an acid/amine salt.
The product of step (3) can be further purified, if desired, by reacting it with a base (such as sodium hydroxide) to form the free amine, thereafter recovering the free amine by crystallization from an organic solvent or water where the threo isomer selectively precipitates from solution as an essentially pure free amine, dissolving said free amine in isopropanol, and reacting the amine/isopropanol solution with a protic acid--thus precipitating the threo isomer as the essentially pure acid/amine salt.
The above process produces the desired threo isomers of 1-aryl-1-hydroxy-2-methylaminopropanes in extremely high yields and purity. The process is particularly useful in forming d-pseudoephedrine from 1-ephedrine.
DETAILED DESCRIPTION OF THE INVENTION
Step I
In Step I, the O,N-diacyl derivative of 1-aryl-1-hydroxy-2-methylaminopropane is formed. This step is conducted by reacting by contacting the erythro isomer of said arylpropanolamine with at least about 2 equivalents of an acylating reagent per mole of said arylpropanolamine. The reactants used in this step are well known classes of reactants having many members, any member of which can be used herein.
The arylpropanolamine reactant, for example, may be the optically pure erythro isomer or it may be a racemic mixture of the erythro isomer. Also, the erythro isomer may be used singly or in combination as a diasteriomeric mixture with the threo isomer in the instant process. This is commercially significant for in many instances the arylpropanolamines may be formed as diasteriomeric mixtures which can be used without separation of the isomers. From this, we conclude that the instant process is essentially nonreversible and stereo specific. Illustrative examples of this class of compounds include 1-phenyl-1-hydroxy-2-methylaminopropane and 1-(inertly-substituted) phenyl-1-hydroxy-2-methylaminopropanes, such as 1-chlorophenyl-1-methoxyphenyl-, 1-methylphenyl-, 1-butylphenyl-1-hydroxy-2-methylaminopropane, and the like.
The acylating reagent used in the process may be varied to convenience so long as the O,N-diacyl derivative of the arylpropanolamine is formed. Conventional acylating reagents include: ketenes; carboxylic acids (e.g. acetic acid, propionic acid, butenoic acid, octanoic acid, etc.); acyl chlorides (e.g. acetyl chloride, propanoyl chloride, benzoyl chloride, etc.); acid anhydrides (e.g. acetic anhydride, propionic anhydride, benzoic anhydride, phthalic anhydride, etc.); carboxylic acid esters (e.g. methyl and ethyl esters of acetic acid, propionic acid, butyric acid, hexanoic acid, etc.); and the like. The preferred acylating reagents are acid anhydrides of organic monocarboxylic acids having from 2 to about 8 carbon atoms. Of these, acetic anhydride and propionic anhydride are preferred with acetic anhydride representing the most preferred acylating reagent.
The stoichiometry of this reaction requires two equivalents of the acylating reagent per mole of arylpropanolamine reactant. Normally, we prefer to use a slight excess of acylating reagent to insure maximum conversion of the arylpropanolamine to the corresponding O,N-diacylated derivative thereof. Thus, we normally use from about 2 to about 5 equivalents of acylating reagent per mole of arylpropanolamine.
The reaction may be conducted neat but it is preferably conducted in the presence of an inert liquid, water immiscible organic solvent or diluent. By "inert" is meant that the reaction solvent or diluent is inert in the process. Suitable such solvents and diluents include hydrocarbons (e.g. benzene, toluene, octane, petroleum ether, etc.), inertly-substituted hydrocarbons (e.g. chlorobenzene, dichlorobenzene, perchloroethylene, methoxytoluene, etc.), and the like. Toluene is the solvent of choice. When a solvent or reaction diluent is used, the product yield is substantially improved by conducting the reaction under essentially anhydrous conditions.
The reaction rate will, of course, vary with temperature, degree of reactivity of the particular combination of reactants, etc. However, we have observed that normally an acceptable rate of reaction is obtained at temperatures of from about 100° to about 120° C. and that the refluxing temperature of the reaction mixture in toluene is normally quite satisfactory. Under these conditions, the reaction is generally complete in from about 4 to about 10 hours.
Step II
In this step, the O,N-diacyl derivative of the arylpropanolamine from Step I is contacted with an anhydrous or essentially anhydrous protic acid. Essentially any protic acid can be used which is of sufficient acid strength to protonate the amine but we normally prefer to use a strong inorganic protic acid (e.g. HCl, HBr, H 2 SO 4 , HClO 4 , etc). HCl is presently the current acid of choice. This step likewise can be conducted neat but is preferably conducted in the presence of an inert reaction solvent or diluent with toluene again being the solvent of choice. The stoichiometry of the reaction occurring here requires one equivalent of acid per mol of O,N-diacyl derivative of the arylpropanolamine. This reaction is likewise best conducted under anhydrous or substantially anhydrous conditions.
The product of this step is a novel oxazolinium salt. This oxazolinium salt can be represented by the formula ##STR1## wherein R is the organic residue of the acylating reagent, Ar is a monovalent aromatic radical and A.sup.⊖ is an inert neutralizing anion. For example, R is methyl when acetic anhydride is used, R is ethyl when propionic anhydride is used, etc. These oxazolinium salts are new compounds which are useful as reaction intermediates in the formation of the threo isomers of 1-aryl-1-hydroxy-2-methylaminopropanes. Such oxazolinium salts can be isolated by crystallization from the reaction medium but are normally prepared and used in solution. The anion, A.sup.⊖ , can be varied by the choice of acid used in Step II to protonate the amine, or, the anion can be varied by conventional ion-exchange techniques. A.sup.⊖ is preferably Cl.sup.⊖ since HCl is the acid of choice in Step II.
Step III
In this step, the oxazolinium salt from Step II is hydrolyzed with an aqueous protic acid to give the desired threo 1-aryl-1-hydroxy-2-methylaminopropane as an acid/amine salt. This step is conducted by merely adding an aqueous protic acid (e.g. aqueous HCl) to the oxazolinium salt or to the reaction medium containing the oxazolinium salt. The reaction rate of the hydrolysis will vary depending upon the particular oxazolinium salt and acid concentration. For example, the reaction is normally complete in from about 4 to about 6 hours at temperatures in the range of from about 80° to about 100° C. using 0.25 equivalents of acid per mole of oxazolinium salt. The product as the acid/amine salt can be precipitated by concentrating the reaction mixture under reduced pressure and subsequently cooling the reaction mixture until the solid amine/acid salt precipitates. The acid/amine salt thus obtained is relatively pure.
Alternatively, however, the reaction mixture from Step III, containing the aqueous solution of the acid/amine salt and the inert solvent (e.g. toluene) as a heterogenous mixture, is blended with sufficient strong base (e.g. sodium hydroxide, potassium hydroxide, etc.) to form the 1-aryl-1-hydroxy-2-methylaminopropane as a free amine. This mixture is normally heated, allowing the free amine to completely pass into solution in the inert solvent. The mixture is then phase separated and the organic phase containing the amine cooled. The pure threo isomer of the free amine crystallizes from the cooled solution. Preferably, the organic phase containing the amine is dried before or during cooling (e.g. by azeotropic distillation).
The following experimental information will further illustrate the invention. All "parts" are parts by weight unless otherwise specified in the examples.
EXPERIMENT 1
Preparation of d-pseudoephedrine from 1-ephedrine
Preparation of starting material: 1-ephedrine hydrochloride (110 parts) was added to toluene (236 parts) and 50 percent aqueous sodium hydroxide (45 parts). The solution was heated to approximately 40° C. and the aqueous and organic phases thus formed were separated. The lower aqueous brine layer was discarded and the upper toluene layer containing 1-ephedrine was dried by azeotropic distillation. Step I: The dried toluene solution was then blended with acetic anhydride (117 parts) and the resulting reaction mixture heated at 113°-118° C. for 6 to 7 hours. Step II: Then, anhydrous hydrochloric acid (20 parts) was added to the stirred solution over a 1.5 hour period and the reaction mixture heated at 90° C. for an additional hour. Step III: Next, 165 parts of aqueous HCl (160 parts of water and 5 parts of HCl) was added to the reaction mixture and the stirred mixture again heated at 90° C. for 4 hours. Recovery: Aqueous 50 percent sodium hydroxide (246 parts) was added to the stirred mixture over a 2 hour period. An aqueous and organic layer resulted which were separated. The upper toluene layer was dried by azeotropic distillation. Analysis of this toluene layer revealed the presence of d-pseudoephedrine in 98.7 percent of theoretical yield, based on starting materials, and 1.3 percent of unreacted 1-ephedrine. This toluene solution was cooled to approximately -5° C. which caused the d-pseudoephedrine to precipitate. The d-pseudoephedrine was collected by filtration, dried under vacuum and analyzed. The dried product represented a 91 percent overall yield of d-pseudoephedrine and had an analysis of 99+ percent purity.
EXPERIMENT 2
This reaction was carried out in essentially the same manner except that the acylating reagent used in Step I was propionic anhydride instead of acetic anhydride. Here, the reaction was conducted by blending 1-ephedrine (41 parts) with propionic anhydride (75 parts) and 300 parts of toluene. The resulting toluene solution was heated at 110°-115° C. for 12 hours. Then, anhydrous HCl (9.3 parts) were added and the mixture heated for an additional hour at 90° C. Aqueous HCl (131.5 parts water and 18.5 parts HCl) was added and the reaction mixture heated for 4 hours at 85°-90° C. Finally, aqueous 50 percent sodium hydroxide (200 parts) was added, the organic and aqueous phases separated, the organic toluene layer dried by azeotropic distillation and analyzed. The toluene layer contained 98.5 percent of d-pseudoephedrine and 1.5 percent of unreacted 1-ephedrine. The toluene solution was cooled to 0° C. and 37 parts (92 percent of theory) of d-pseudoephedrine recovered as a crystalline solid.
EXPERIMENT 3
In this experiment 2,2-dimethylpropionic anhydride was used as the acylating reagent in Step I. The reaction was otherwise conducted in a manner analogous to Experiment 2. The final toluene solution contained 98.4 percent of the d-pseudoephedrine and 1.6 percent of unreacted 1-ephedrine. Upon cooling, 18.1 parts (87 percent of theory) of d-pseudoephedrine was recovered as a crystalline solid.
EXPERIMENT 4
In this experiment benzoic anhydride was used as the acylating reagent under conditions analogous to Experiment 2. In this experiment, however, the reaction of the oxazolinium salt with aqueous HCl (Step III) was run for 16 hours at 85°-90° C. The workup was the same and the toluene layer contained approximately 97.2 percent d-pseudoephedrine and 2.8 percent unreacted 1-ephedrine. Upon cooling, the recovered yield of d-pseudoephedrine was approximately 84 percent.
EXPERIMENT 5
Under similar conditions, ethyl acetate was used as the acylating reagent. The final toluene solution contained 72 percent of theory of d-pseudoephedrine and 28 percent of unreacted 1-ephedrine.
EXPERIMENT 6
Under similar conditions, formic acid was used as the acylating reagent and the conversion of 1-ephedrine to d-pseudoephedrine was approximately 62 percent.
EXPERIMENT 7
Under similar conditions, benzoic acid was used as the acylating reagent and the conversion to d-pseudoephedrine was approximately 40 percent.
EXPERIMENT 8
Essentially identical results to Experiment 1 were obtained when concentrated sulfuric acid was used in place of anhydrous HCl in Step II of the reaction. All other conditions were essentially the same as in Experiment 1.
EXPERIMENT 9
Likewise, essentially identical results to Experiment 1 were obtained using trifluoroacetic acid in place of anhydrous HCl in Step II of the process.
EXPERIMENT 10
1-Ephedrine diacetate was prepared by reacting 1-ephedrine with acetic anhydride in benzene solution. This benzene solution was dried by passing it through a column of "K-type" DOWEX® ion-exchange resin. Anhydrous HCl (0.07 mol) was added as a gas to an aliquot of the predried 1-ephedrine diacetate solution (0.05 mole of 1-ephedrine and 80 ml of benzene) and the solution heated at 50° C. for 0.5 hours. During this time an oil precipitated. Benzene and other volatiles were removed from the reaction mixture under vacuum leaving a heavy viscous oil as the residue. This oil was soluble in water and acetone at room temperature and contained 2,3-dimethyloxazolinium chloride as the predominant ingredient.
The above oxazolinium chloride (as the oil) was dissolved in approximately 50 ml of water and 70 percent perchloric acid added. A crystalline solid immediately precipitated which was quickly filtered and dried at 60° C. under reduced pressure. This solid product was 2,4-dimethyloxazolinium perchlorate. The product structure was confirmed by nuclear magnetic resonance and infrared spectroscopy and by elemental analysis. This oxazolinium perchlorate hydrolyzed on treatment with water over a period of 2 to 3 hours giving a product whose nuclear magnetic resonance spectrum was consistent with the following structure: ##STR2##
Both oxazolinium salts described above reacted with aqueous HCl to give d-pseudoephedrine hydrochloride.
Other oxazolinium salts can be similarly prepared and used in the preparation of threo isomers of the 1-aryl-1-hydroxy-2 -methylaminopropanes.
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1-Aryl-1-hydroxy-2-methylaminopropanes are rearranged from the erythro isomer to the threo isomer by the process of (1) forming the O,N-diacyl derivative of the arylpropanolamine; (2) reacting the product of step (1) with an anhydrous or substantially anhydrous protic acid (thereby forming a novel oxazolinium salt); and (3) reacting the oxazolinium salt from step (2) with an aqueous protic acid. The threo isomer of the arylpropanolamine is thus produced as an amine/acid salt. This salt can be further purified, if desired, by neutralizing the acid/amine salt with caustic isolating the free amine and reprotonating the free base in isopropanol with, for example, anhydrous HCl. This process is particularly applicable to manufacture of d-pseudoephedrine from 1-ephedrine.
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