description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
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FIELD OF THE INVENTION
[0001] The present invention relates generally to the field of wireless communications where it is desirable to communicate between wireless devices, at the highest possible communication rate, while reducing the complexity, cost of deployment and power consumption of each device, and reducing the complexity, cost of deployment and power consumption of the network infrastructure (base station, backhaul etc.), without significantly increasing the communication latency between devices.
[0002] The present invention relates to wireless devices which communicate over a varied number of physical communications channel such as satellite, radio, and microwave.
[0003] The present invention relates to a varied number of applications such as point to point communications, point to multipoint communications, multipoint to point communications, and multipoint to multipoint communications.
BACKGROUND OF THE INVENTION
[0004] In many applications, it is desirable to communicate between wireless devices in an efficient way where power consumption and cost of each device are reduced while the transmission rate between devices is increased. In most applications, cost reduction is obtained by reducing the complexity of the device. Moreover, reducing the power consumption of each device while increasing the transmission rate between devices can be usually considered as a trade-off between power efficiency and bandwidth efficiency. This trade-off takes place on one of the most hostile communication channels, the wireless channel, where one must contend with shadowing, radio interference, multipath fading as well as thermal noise. Shadowing is caused by obstacles along the direct path between a transmitting antenna, A T , and a receiving antenna, A R , which force the received signal to be weak and the thermal noise to dominate, hence creating a noise-limited environment. On the other hand, interference from other intentional radiators creates an environment where the received signal is limited by the so-called background noise and the environment is said to be interference-limited. Multipath fading is caused by objects surrounding the direct path between A T and A R , which act as radio reflectors reflecting the transmitted signal from A T back to the receiving antenna, A R , using multiple paths, each path having a corresponding carrier amplitude, phase and time delay. When the receiving antenna, A R , receives signals from the various paths in a multipath environment, the signals can be received either out-of-phase (also known as destructive multipath interference) or in-phase (also known as constructive multipath interference) depending on the frequency of operation.
[0005] A common way to overcome shadowing in a wireless channel is by using a number of active (regenerative) repeaters between A T and A R . Active repeaters have several shortcomings. They require by definition a power source. They are relatively complex, as they must contain a full transceiver capable of regenerating the received information, and unless some type of Frequency Division Duplex (FDD) protocol is adopted and the RF receiver in each active repeater is well isolated from its RF transmitter, every active repeater between A T and A R can either transmit or receive at a time, but not transmit and receive simultaneously. In other words, unless some type of FDD protocol is adopted, the bit rate between transmitting antenna, A T , and receiving antenna, A R , is linearly reduced by the number of active repeaters between them and the latency between them is directly increased by the same factor. Lastly, an active repeater can only exacerbate the Hidden Terminal Problem (HTP), a problem which occurs when active nodes cannot hear each other (or equivalently cannot sense each other), thereby potentially colliding with each other when transmitting simultaneously in the Carrier Sense Multiple Access with Collision Avoidance (CSMA/CA) environment.
[0006] There are two types of passive repeaters: (1) reflector repeaters and (2) back-to-back antenna repeaters. Reflector repeaters reflect the wireless signals in the same way a mirror reflects light. The same laws apply. Back-to-back antenna repeaters work just like an ordinary active repeater, but without radio frequency transposition or amplification of the signal. In other words, back-to-back antenna repeaters are neither active nor regenerative. Reflector repeaters are more attractive than back-to-back antenna repeaters due to the fact that their efficiency is close to 100% as opposed to efficiency between 50% and 60% for back-to-back antenna repeaters. Reflector repeaters are also more flexible in terms of size, shape and cost than back-to-back antenna repeaters, which are usually limited by the type of directional high gain antenna selected, e.g., parabolic or yagi.
SUMMARY OF THE INVENTION
[0007] In an embodiment, there is disclosed an easy to deploy RF reflector repeater, which is referred to as a wave bender. It can be used as a way to mitigate shadowing and to reduce multipath fading and the Hidden Terminal Problem over the wireless channel. The wave bender can accomplish this by supplementing the direct path between a transmitting antenna, A T , and a receiving antenna, A R , with an indirect path, which follows free space path loss attenuation.
[0008] There are several applications of the wave bender:
[0009] The RF wave bender can be used as a reflector repeater between one stationary transmitting antenna, A T , and one stationary receiving antenna, A R . In this case, it is considered to create one deterministic indirect path between the two antennas. We will refer to such a communication application as point-to-point communication. Examples include fixed wireless communications.
[0010] The RF wave bender can be used as a reflector repeater between one (or more) fixed (stationary) transmitting antenna(s) and a number of mobile receiving antennas, or vice versa, between a number of mobile transmitting antennas and one (or more) fixed (stationary) receiving antenna(s). Once again, the RF wave bender can be considered to create one deterministic indirect path between each fixed antenna and a corresponding coverage area where the mobile antennas could be located attempting to communicate with the fixed antenna(s). We will refer to such a communication application as point-to-multipoint communication. Examples include Global Positioning Systems (GPS), cellular (such as LTE), Metropolitan Area Networks (also known as Fixed Wireless Access networks such as WiMAX) and WiFi (IEEE802.11) communications, which are centralized via a satellite (GPS), a Base Station (cellular) or an Access Point (WiFi) respectively. The examples are not limited to the listed systems but can be extended to any point-to-multipoint communication system by one familiar with the art.
[0011] The RF wave bender can be used as a reflector repeater between a number of fixed transmitting antennas and a number of fixed receiving antennas. In this case, the RF wave bender can be considered to create deterministic indirect paths between several fixed transmitting antennas, and several fixed receiving antennas, or equivalently to create two coverage areas: one where the fixed transmitting antennas could be located and one where the fixed receiving antennas could be located. We will refer to such a communication application as fixed multipoint-to-multipoint communication. Examples include mesh and ad-hoc communications, which are both peer-to-peer (non-centralized), and do not require either a Base Station or an Access Point.
[0012] The RF wave bender can be used as a reflector repeater between a number of mobile transmitting antennas and a number of mobile receiving antennas. In this case, the RF wave bender can be considered to create random (probabilistic) indirect paths between several mobile transmitting antennas, and several mobile receiving antennas, or equivalently to create two coverage areas: one where the mobile transmitting antennas could be located and one where the mobile receiving antennas could be located. We will refer to such a communication application as mobile multipoint-to-multipoint communication. Examples include mesh and ad-hoc communications, which are both peer-to-peer (non-centralized), and do not require either a Base Station or an Access Point.
[0013] The RF wave bender can also be used in a combined fixed and mobile multipoint to multipoint communication network by applying the two principles listed above of random and deterministic coverage areas simultaneously.
[0014] In order for the wave bender to be easily deployed, its elements are preferably lightweight, small in size and easy to configure. On the other hand, in order for the wave bender to require low maintenance, its elements are preferably passive (i.e. no power source), withstand heavy wind loading and be unaffected by severe weather conditions.
DESCRIPTION OF THE DRAWINGS
[0015] The present invention, both as to its organization and manner of operation, may best be understood by reference to the following description, and the accompanying drawings of various embodiments wherein like reference numerals are used throughout the several views, and in which:
[0016] FIG. 1 a is a 2-dimensional schematic view of a generic embodiment of a wave bender ( 103 ) used as a reflector repeater between a transmitting antenna ( 106 ), A T , and a receiving antenna ( 107 ), A R , where the direct path ( 108 ) between A T ( 106 ) and A R ( 107 ) is shadowed (i.e. impaired) by an obstacle ( 109 ). The wave bender ( 103 ) bends the incoming wave ( 101 ) by a desired angle α 2 ( 104 ), relative to the incoming wave ( 101 ), to an outgoing wave ( 105 ) thereby creating an indirect non-shadowed path ( 101 , 105 ) between A T ( 106 ) and A R ( 107 ) to replace the impaired direct path ( 108 ).
[0017] FIG. 1 b is a 3-dimensional schematic view of a generic embodiment of a wave bender ( 103 ) used as a reflector repeater between a transmitting antenna ( 106 ), A T , and a receiving antenna ( 107 ), A R , where the direct path ( 108 ) between A T ( 106 ) and A R ( 107 ) is shadowed (i.e. impaired) by an obstacle ( 109 ). The wave bender ( 103 ) bends the incoming wave ( 101 ) by a desired angle α 2 ( 104 ), relative to the incoming wave ( 101 ), to an outgoing wave ( 105 ) thereby creating an indirect non-shadowed path ( 101 , 105 ) between A T ( 106 ) and A R ( 107 ) to replace the impaired direct path ( 108 ). In this invention, we refer to the plane that is made up of the incident wave ( 101 ) and of the reflected wave ( 105 ) as the “wave plane.” It is easily shown that the wave plane contains both the desired angle α 2 ( 104 ) and the axis ( 112 ) of the reflector. In this invention, the axis of the reflector is perpendicular to the structure of the reflector, regardless whether the reflector is a 2D structure or a 3D structure. Equivalently, in this invention we will say that the wave plane is perpendicular to the reflector, regardless of the structure of the reflector. In FIG. 1 b , bending the incoming wave ( 101 ) by the desired angle α 2 ( 104 ) corresponds to shifting the incoming wave ( 101 ) in the horizontal plane by an angle π-φ 2 ( 111 ), and in the vertical plane by an angle γ 2 ( 110 ).
[0018] FIG. 2 is a 2-dimensional schematic view of a generic embodiment of two reflectors ( 203 , 207 ) used as a wave bender between transmitting antenna ( 210 ), A T , and receiving antenna ( 211 ), A R , where the direct path ( 213 ) between A T ( 210 ) and A R ( 211 ) is shadowed by several obstacles ( 212 , 214 ). The two reflectors ( 203 , 207 ) bend the incoming wave ( 201 ) by a desired angle α 3 ( 209 ), relative to the incoming wave ( 201 ), to an outgoing wave ( 208 ) thereby creating an indirect non-shadowed path ( 201 , 205 , 208 ) between A T ( 210 ) and A R ( 211 ) to replace the impaired direct path ( 213 ). In FIG. 2 , the wave plane for the first reflector ( 203 ) is parallel to the wave plane of the second reflector ( 207 ). Generally, this is not always true, and FIG. 2 can be easily generalized to depict a 3-dimensional wave bender, where the wave plane for the first reflector ( 203 ) is not necessarily parallel to the wave plane of the second reflector ( 207 ).
[0019] FIG. 3 is a 2-dimensional schematic view of a generic embodiment of three reflectors ( 303 , 307 , 311 ) used as a wave bender between transmitting antenna ( 314 ), A T , and receiving antenna ( 315 ), A R , where the direct path ( 319 ) between A T ( 314 ) and A R ( 315 ) is shadowed by several obstacles ( 317 , 318 ). The three reflectors ( 303 , 307 , 311 ) bend the incoming wave ( 301 ) by a desired angle α 4 ( 313 ), relative to the incoming wave ( 301 ), to an outgoing wave ( 312 ) thereby creating an indirect non-shadowed path ( 301 , 305 , 308 , 312 ) between A T ( 314 ) and A R ( 315 ) to replace the impaired direct path ( 319 ). Once again, FIG. 3 can be easily generalized to depict a 3-dimensional wave bender, where the wave plane for the first reflector ( 303 ) is not necessarily parallel to the wave plane of either the second reflector ( 307 ) or the third reflector ( 311 ). All 2-dimensional wave benders can be easily generalized to depict 3-dimensional wave benders where the wave planes of the individual reflectors are not necessarily parallel to one another.
[0020] FIG. 4 is a 2-dimensional schematic view of a generic embodiment of a reflector ( 403 ) used as a wave bender between transmitting antenna ( 406 ), A T , and receiving antenna ( 407 ), A R , where the direct path between A T ( 406 ) and A R ( 407 ) is shadowed by an obstacle ( 408 ). The wave bender ( 403 ) bends the incoming wave ( 401 ) to an outgoing wave ( 405 ) thereby creating the illusion of a direct path, ( 410 , 405 ), between the image ( 409 ) of the transmitting antenna, A T , ( 406 ) and the receiving antenna ( 407 ), A R . In FIG. 4 , the incident wave ( 401 ), the outgoing wave ( 405 ) and the imaged wave ( 110 ) are all contained in the wave plane that is perpendicular to the reflector ( 403 ).
[0021] FIG. 5 is a 2-dimensional schematic view of a generic embodiment of two reflectors ( 503 , 507 ) used as a wave bender between transmitting antenna ( 510 ), A T , and receiving antenna ( 511 ), A R , where the direct path between A T ( 510 ) and A R ( 511 ) is shadowed by several obstacles ( 512 , 513 ). The first reflector ( 503 ) reflects the incoming wave ( 501 ) to an outgoing wave ( 505 ) thereby creating the illusion of a direct path, ( 506 , 505 ), between the image ( 504 ) of the transmitting antenna, A T , ( 510 ) and the second reflector ( 507 ). The second reflector ( 507 ) reflects the first image ( 504 ) to an outgoing wave ( 508 ) thereby creating the illusion of a direct path, ( 510 , 509 , 508 ), between the image ( 514 ) of the first image ( 504 ) and the receiving antenna, A R , ( 511 ). In FIG. 5 , the waves ( 501 ), ( 504 ) and ( 505 ), are all contained in the wave plane that is perpendicular to the first reflector ( 503 ). Similarly, the waves ( 505 ), ( 508 ) and ( 514 ) are all contained in the wave plane that is perpendicular to the second reflector ( 507 ).
[0022] FIG. 6 is a 2-dimensional schematic view of a generic embodiment of three reflectors ( 602 , 607 , 611 ) used as a wave bender between transmitting antenna ( 614 ), A T , and receiving antenna ( 620 ), A R , where the direct path between A T ( 614 ) and A R ( 620 ) is shadowed by several obstacles ( 615 , 617 ). The first reflector ( 602 ) reflects the incoming wave ( 601 ) to an outgoing wave ( 605 ) thereby creating the illusion of a direct path, ( 604 , 605 ), between the image ( 603 ) of the transmitting antenna, A T , ( 614 ) and the second reflector ( 607 ). The second reflector ( 607 ) reflects the incoming wave ( 605 ) to an outgoing wave ( 608 ) thereby creating the illusion of a direct path, ( 610 , 613 , 608 ), between the image ( 609 ) of the first image ( 603 ) of the transmitting antenna ( 614 ) and the third reflector ( 611 ). The third reflector ( 611 ) reflects the second image ( 609 ) of the transmitting antenna ( 614 ) to an outgoing wave ( 612 ) thereby creating the illusion of a direct path, ( 618 , 619 , 621 , 612 ), between the third image ( 622 ) of the second image ( 609 ) of the transmitting antenna ( 614 ) and the receiving antenna, A R , ( 620 ). In FIG. 6 , the waves ( 601 ), ( 604 ) and ( 605 ), are all contained in the wave plane that is perpendicular to the first reflector ( 602 ). Similarly, the waves ( 605 ), ( 608 ) and ( 609 ) are all contained in the wave plane that is perpendicular to the second reflector ( 607 ). Similarly, the waves ( 608 ), ( 612 ) and ( 621 ) are all contained in the wave plane that is perpendicular to the second reflector ( 611 ).
[0023] FIG. 7 a is a 3-dimensional depiction of a preferred embodiment of a reflector, the rectangular reflector, which consists generally of three components: a rectangular framed conducting grid ( 701 ), which is attached to a tripod ( 703 ) via an articulated arm ( 702 ).
[0024] FIG. 7 b is a 3-dimensional depiction of another preferred embodiment of a reflector, the elliptical reflector, which consists generally of three components: an elliptical framed conducting grid ( 704 ), which is attached to a tripod ( 706 ) via an articulated arm ( 705 ).
[0025] FIG. 8 a is a zoomed-in 3-dimensional depiction of the preferred embodiment of the rectangular reflector from FIG. 7 a . FIG. 8 a shows once again the three general components of a rectangular reflector: a rectangular framed conducting grid ( 801 ), which is attached to a tripod ( 803 ) via an articulated arm ( 802 ). The framed conducting grid ( 801 ) is made of a conducting material where all crossings form an electrical contact, i.e. the electrical resistance between any two points on the grid is negligible.
[0026] FIG. 8 b is a zoomed-in 3-dimensional depiction of the preferred embodiment of the elliptical reflector from FIG. 7 b . FIG. 8 b shows once again the general components of an elliptical reflector: an elliptical frame ( 805 ) and a conducting grid ( 804 ), both attached to a tripod ( 809 ) via an articulated arm. The articulated arm comprises 3 sub-components: the first rubber ball ( 808 ) that is attached to a second rubber ball ( 807 ) using a lateral holder ( 806 ), which is capable to tighten its grip on both balls ( 808 ) and ( 807 ). The framed conducting grid ( 804 ) is made of a conducting material where all crossings form an electrical contact, i.e. the electrical resistance between any two points on the grid is negligible.
[0027] FIG. 9 is a break-down of the 3-dimensional depiction of a preferred embodiment of the rectangular reflector including the framed conducting grid ( 701 , 801 ), which comprises two sub-components: a conducting grid ( 901 ) and a frame ( 902 ); and the articulated arm ( 702 , 802 ), which comprises 3 sub-components: the first rubber ball ( 903 ) that is attached to the second rubber ball ( 905 ) using a lateral holder ( 904 ), which is capable to tighten its grip on both balls ( 903 ) and ( 905 ). The tripod ( 703 , 803 ) is not shown in FIG. 9 .
[0028] FIG. 10 is a 2-dimensional schematic view of a preferred embodiment of the conducting grid ( 801 ), which is a rectangular conducting grid with a width W 1 ( 1001 ) and a height H 1 ( 1004 ). The grid ( 801 ) is made up of rectangular openings with width w 1 ( 1003 ) and height h 1 ( 1002 ).
[0029] FIG. 11 is a 2-dimensional schematic view of a generic embodiment of a system intended to locate a transmitting antenna ( 106 ) using one reflector ( 103 ) of known location and one active node ( 113 ) of known location. In FIG. 11 , it is assumed that the active node ( 113 ) comprises an antenna array ( 112 ) and a receiver, which together are able to estimate angles β 1 ( 114 ) and β 2 ( 115 ), corresponding to direct path ( 108 ) and indirect path ( 105 ) respectively.
[0030] FIG. 12 is a 2-dimensional schematic view of a generic embodiment of a system intended to locate a transmitting antenna ( 106 ) using one reflector ( 103 ) of known location and one active node ( 117 ) also of known location. In FIG. 12 , it is assumed that the active node ( 117 ) comprises one antenna ( 118 ) and a receiver, which together are able to estimate the Time of Arrival of any wireless signal transmitted by the transmitting antenna. Given that the transmitted wireless signal in FIG. 12 is able to travel via either the direct path ( 108 ) or the indirect path ( 101 , 105 ), it assumed in this invention that the active node ( 117 ) is able to estimate the two received signals with respect to their respective Times of Arrival: τ 1 and τ 2 which correspond to the direct path ( 108 ) and the indirect path ( 101 , 105 ) respectively.
[0031] FIG. 13 is a 2-dimensional schematic view of a generic embodiment of a system intended to locate a receiving antenna ( 121 ) using one reflector ( 103 ) of known location and one active node ( 119 ) also of known location. In FIG. 13 , it is assumed that the active node ( 119 ) comprises one antenna ( 120 ) and a transmitter. In FIG. 13 , it is also assumed that the receiving antenna is able to, estimate the Time of Arrival of any wireless signal transmitted by the active node. Given that the transmitted wireless signal in FIG. 13 is able to travel via either the direct path ( 122 ) or the indirect path ( 123 , 124 ), it assumed in this invention that the receiving antenna ( 121 ) is able to estimate the two received signals with respect to their respective Times of Arrival: τ 1 and τ 2 which correspond to the direct path ( 122 ) and the indirect path ( 123 , 124 ) respectively.
DETAILED DESCRIPTION OF THE INVENTION
[0032] The most convenient way to describe the problem that the current invention attempts to solve is through the figures. In FIG. 1 , obstacle ( 109 ) is said to form a shadowing effect between transmitting antenna ( 106 ), A T , and receiving antenna ( 107 ), A R , when the signal traveling along the direct path ( 108 ) between A T ( 106 ) and A R ( 107 ) is attenuated to the point that the Signal Power-to-Noise Power Ratio (SNR) falls below a certain threshold. In this case, the thermal noise is said to dominate the received signal, and the channel is said to be noise-limited. Such a channel can be adequately modeled using the following equation:
[0000]
P
r
=
P
t
(
λ
4
π
d
)
n
G
t
G
r
(
1
)
[0000] where
P t is the transmitted power from A T ;
P r is the received power at A R ;
G t is the antenna gain for A T ;
G r is the antenna gain for A R :
d is the length of the direct path ( 108 ) between A T and A R ;
Δ is the wavelength of the transmitted wave ( 101 ) and of the reflected wave ( 105 ); and
n is the path loss exponent which is modeled as 2. i.e. as free space, when the direct path between A T and A R contains no obstructions nor multipath components. However, when the direct path ( 108 ) between A T and A R is shadowed by obstacles ( 109 ), such as the case in FIG. 1 , the path loss exponent, n, generally grows larger than 2 depending on the absorption properties of the obstacles ( 109 ) at the operating wavelength λ.
[0033] The RF Wave Bender provides a way to circumvent the obstacles ( 109 ) through the use of a number of passive reflector repeaters, such as one ( 103 ) in FIG. 1 , two ( 203 , 207 ) in FIG. 2 , and three ( 303 , 307 , 311 ) in FIG. 3 . The collection of passive reflector repeaters (or reflectors for short) is a wave bender.
[0034] Traditionally, reflectors have been modeled using the following radar equation:
[0000]
P
r
=
P
t
(
λ
4
π
d
t
)
2
(
1
4
π
d
r
)
2
G
t
(
4
π
A
r
λ
2
)
=
P
t
(
1
4
π
d
t
2
)
(
1
4
π
d
r
2
)
G
t
A
r
σ
(
2
)
[0000] where
P t is the transmitted power from A T ( 106 );
P r is the received power at A R ( 107 );
G t is the antenna gain for A T ( 106 );
A T is the effective antenna aperture for A R ( 107 );
d t is the length of the direct path ( 101 ) between A T ( 106 ) and the reflector ( 103 );
d r is the length of the direct path ( 105 ) between the reflector ( 103 ) and A R ( 107 ):
λ is the wavelength of the transmitted wave ( 101 ) and reflected wave ( 105 ); and
σ is the radar cross section of the reflector ( 103 ).
[0035] However, in radar, the targeted reflector is generally designed to be undetected. In fact, the targeted reflector is usually designed to reflect back as little power as possible to the radar's receiving antenna. For this reason, the above radar model, assumes a worst-case scenario where the reflector ( 103 ) is assumed to turn the incident wave ( 101 ) into an isotropic point source ( 105 ). That is why the distances d t and d r are multiplied by one another.
[0036] On the other hand, the targeted reflector ( 103 ) is designed to reflect back as much power as possible. Therefore, a more adequate model for the reflector is as follows:
[0000]
P
r
=
P
t
(
λ
4
π
(
d
t
+
d
r
)
)
2
G
t
G
r
η
(
3
)
[0000] where
P t is the transmitted power from A T ( 106 );
P r is the received power at A R ( 107 );
G r is the antenna gain for A T ( 106 );
G r is the antenna gain for A R ( 107 );
d t is the length of the direct path ( 101 ) between A T ( 106 ) and the reflector ( 103 );
d r is the length of the direct path ( 105 ) between the reflector ( 103 ) and A R ( 107 ):
λ is the wavelength of the transmitted wave ( 101 ) and reflected wave 9105 ); and
η is the reflection power efficiency of the wave reflector ( 103 ) defined as the ratio between reflected power to incident power.
[0037] The model in Equation (3) assumes that the wave reflector reflects back the incident wave ( 101 ) with a power efficiency, η, similar to a mirror, and not similar to an isotropic point source. In other words, when the incident signal on the reflector is made up of locally substantially planar waves, the reflected signal from the reflector is also made up of locally substantially planar waves as long as the reflector is “designed properly.” In this document. “planar” will hereafter be used to denote “locally substantially planar.” For example, when the wave bender is composed of one properly designed reflector, the reflected image ( 409 ) in FIG. 4 of the transmitting antenna gives the illusion of a direct path ( 410 , 405 ) between A T and A R that is made up of planar waves. When the wave bender is composed of two properly designed reflectors, the reflected image ( 514 ) in FIG. 5 of the transmitting antenna gives the illusion of a direct path ( 512 , 509 , 508 ) between A T and A R that is made up of planar waves. When the wave bender is composed of three properly designed reflectors, the reflected image ( 609 ) in FIG. 6 of the transmitting antenna gives the illusion of a direct path ( 618 , 619 , 621 , 612 ) between A T and A R that is made up of planar waves.
[0038] In summary to this section, a reflector is said to be “designed properly” if Equation (3) applies instead of Equation (2). The model in Equation (3) is in contrast with the model in Equation (2) where the reflected signal from the reflector behaves as a point source even if the incident signal on the reflector is made up of planar waves. The combined effect of having a point source at the transmitting antenna A T ( 106 ) and another point source at the reflector ( 103 ) is to multiply the distance, d t , between the direct path ( 101 ) between A T ( 106 ) and the reflector ( 103 ) with the distance, d r , of the direct path ( 105 ) between the reflector ( 103 ) and the receiving antenna, A R ( 107 ). This multiplication forces the received power. P r , to be excessively low, especially when d t and d r are large. To counteract the effect of having an excessively low received power, P r , σ in Equation (2) must be selected to be excessively high, or equivalently, the physical area of the reflector must be selected to be excessively large. In other words, a lightweight, easy to deploy passive reflector repeater is impossible to achieve if the reflector is “not designed properly.”
[0039] There is disclosed how to properly design the reflector such that Equation (3) applies, instead of Equation (2), and that a lightweight, easy to deploy reflector is feasible. A proper design of the reflector is explained after we discuss the factors affecting the efficiency q of the reflector.
[0040] Several factors affect the efficiency, q, of the reflector such as:
[0041] the footprint of the incident wave ( 101 ) on the reflector ( 103 );
[0042] the effective incident area, A i1 , of the reflector ( 103 ) as seen by the incident wave ( 101 );
[0043] the reflectivity of the reflector ( 103 );
[0044] the effective reflected area, A r1 , of the reflector ( 103 ) as seen by the outgoing wave ( 105 ); and
[0045] the footprint of the incident wave ( 105 ) on A R ( 107 ).
[0046] The reflection efficiency, η, can be made high as long as the following constraints are satisfied:
[0047] Constraint a1: The reflector ( 103 ) is contained within the 3 dB-beamwidth of A T ( 106 ). One way to fulfill such a constraint is to point the +3 dB beam of the transmitting antenna A T ( 106 ) towards the center of the reflector ( 103 ), and to place the reflector ( 103 ) in the far field of the transmitting antenna ( 106 );
[0048] Constraint b1: The reflector ( 103 ) is contained within the 3 dB-beamwidth of A R ( 107 ). One way to fulfill such a constraint is to point the ±3 dB beam of the receiving antenna A R ( 107 ) towards the center of the reflector ( 103 ), and to place the reflector ( 103 ) in the far field of the receiving antenna ( 107 );
[0049] Constraint c1: The effective incident area, A i1 , of the reflector ( 103 ) relative to the incident wave ( 101 ) is >>λ 2 . One way to fulfill such a constraint is to select the reflector to have an “incident minor radius” b i1 >λ/√{square root over (π)} and an incident major radius” a i1 >λ/√{square root over (π)}, assuming that the reflector is “seen” by the transmitting antenna A T ( 106 ) to be elliptical in shape with a minor radius b i1 and a major radius a i1 . This constraint should not be understood to limit the shape of the reflector as seen by the transmitting antenna to an elliptical shape. For example, when the reflector is “seen” by the transmitting antenna A T ( 106 ) to be rectangular in shape, its “incident width” W i1 and “incident height” H i1 must both comply with the constraint that b i1 >λ/√{square root over (π)} and a i1 >λ/√{square root over (π)}, or equivalently that W i1 /√{square root over (π)}>b i1 and H i1 /√{square root over (π)}>b i1 . In conclusion to this constraint, regardless of the shape of the reflector, it must be seen by the transmitting antenna A T ( 106 ) to contain an ellipse of minor radius b i1 and of major radius a i1 ;
[0050] Constraint d1: The effective reflected area, A r1 , of the reflector relative to the reflected wave ( 105 ) is >>λ 2 . One way to fulfill such a constraint is to select the reflector to have a “reflected minor radius” b r1 >λ/√{square root over (π)} and a reflected major radius” a r1 >λ/√{square root over (π)}, assuming that the reflector is “seen” by the receiving antenna A R ( 107 ) to be elliptical in shape with a minor radius b r1 and a major radius a r1 . This constraint should not be understood to limit the shape of the reflector as seen by the receiving antenna to an elliptical shape. For example, when the reflector is “seen” by the receiving antenna A R ( 107 ) to be rectangular in shape, its “reflected width” W r1 and “reflected height” H r1 must both comply with the constraint that b r1 >λ/√{square root over (π)} and a r1 >λ/√{square root over (π)}, or equivalently that W r1 /√{square root over (π)} and H r1 /√{square root over (π)}>b r1 . In conclusion to this constraint, regardless of the shape of the reflector, it must be seen by the receiving antenna A R ( 107 ) to contain an ellipse of minor radius b r1 and of major radius a r1 ; and
[0051] Constraint e1: The reflectivity of the reflector is ≈1 where reflectivity is defined as the ratio between the reflected power to absorbed power.
[0052] Wave Bender with One 2D-Reflector: In FIG. 1 a , the effective incident area, A i1 , of the reflector ( 103 ) relative to A T is equal to A i1 =A 1 sin(θ 1 ) where A 1 is the physical area of the reflector ( 103 ) and θ 1 ( 102 ) is the incident angle from A T to the reflector ( 103 ), while the effective reflected area, A r1 , of the reflector ( 103 ) relative to A R is equal to A r1 =A 1 sin(α 2 −θ 1 ) where α 2 ( 104 ) is the desired angle for bending the incident wave ( 101 ) to a reflected wave ( 105 ).
[0053] It can be easily shown that the relationship between θ 1 ( 102 ) and α 2 ( 104 ) is such that θ 1 =(α 2 )/2. Therefore, A i1 =A r1 =A 1 sin(θ 1 ). This relationship together with constraints c1 and d1 above imply that the reflector ( 103 ) must be designed such that A i1 =A r1 =A 1 sin(θ 1 )>>λ 2 .
[0054] Wave Bender with One 3D-Reflector: In FIG. 1 b , the effective incident area, A i1 , of the reflector ( 103 ) relative to A T is equal to A i1 =A 1 sin(θ 1 ) where A 1 is the physical area of the reflector ( 103 ) and θ 1 ( 102 ) is the incident angle from A T to the reflector ( 103 ), while the effective reflected area, A r1 , of the reflector ( 103 ) relative to A R is equal to A r1 =A 1 sin(α 2 −θ 1 ) where α 2 ( 104 ) is the desired angle for bending the incident wave ( 101 ) to a reflected wave ( 105 ).
[0055] It can be easily shown once again that the relationship between θ 1 ( 102 ) and α 2 ( 104 ) in FIG. 1 b is such that θ 1 =(α 2 )/2. Therefore. A i1 =A r1 =A 1 sin(θ 1 ). This relationship together with constraints c1 and d1 above imply that the reflector ( 103 ) must be designed such that A i1 =A r1 =A 1 sin(θ 1 )>>λ 2 .
[0056] Even though FIG. 1 b is a 3-dimensional (3D) wave bender, θ 1 =(α 2 )/2 is still valid in the wave plane that is made-up of the incident wave ( 101 ) and of the reflected wave ( 105 ) regardless of the shape of the reflector ( 103 ). In other words. A i1 =A r1 =A 1 sin(θ 1 ) is still valid where θ 1 is obtained from the following relationship: cos(π−2θ 1 )=−cos(2θ 1 )=cos(φ 2 )cos(γ 2 ) where φ 2 is the horizontal angle shift corresponding to α 2 while γ 2 is the vertical angle shift corresponding to α 2 regardless of the shape of the reflector ( 103 ) and whether the wave plane that is perpendicular to the reflector ( 103 ) is horizontal or not.
[0057] Wave Bender with Two 2D-Reflectors: In FIG. 2 , the effective incident area, A i1 , of the first reflector ( 203 ) relative to A T is equal to A i1 =A 1 sin(θ 1 ) where A 1 is the physical area of the first reflector ( 203 ) and θ 1 ( 202 ) is the incident angle from A T to the first reflector ( 203 ), while the effective reflected area, A r1 , of the first reflector ( 203 ) relative to the second reflector ( 207 ) is equal to A r1 =A 1 sin(α 2 −θ 1 ) where α 2 ( 104 ) is the desired angle for bending the incident wave ( 201 ) to a reflected wave ( 205 ). It can be easily shown that the relationship between θ 1 ( 202 ) and α 2 ( 204 ) is such that θ 1 =(α 2 )/2. Therefore. A i1 =A r1 =A 1 sin(θ 1 ). This relationship together with constraints c1 and d1 above imply that the first reflector ( 203 ) must be designed such that A i1 =A r1 =A 1 sin(θ 1 )>>λ 2 .
[0058] In FIG. 2 , the effective incident area, A i2 , of the second reflector ( 207 ) relative to wave ( 205 ) is equal to A i2 =A 2 sin(θ 2 ) where A 2 is the physical area of the second reflector ( 207 ) and θ 2 ( 206 ) is the incident angle from the first reflector ( 203 ) to the second reflector ( 207 ), while the effective reflected area, A r2 , of the second reflector ( 207 ) relative to A R is equal to A r2 =A 2 sin(−(a 3 −α 2 )−θ 2 ) where α 3 ( 209 ) is the desired angle for bending the incident wave ( 201 ) to a reflected wave ( 208 ). It can be easily shown that the relationship between θ 2 ( 206 ), α 2 ( 204 ) and α 3 ( 209 ) is such that θ 2 =−(a 3 −α 2 )/2, then A i2 =A r2 =A 2 sin(θ 2 ). This relationship together with constraints c1 and d1 above imply that the second reflector ( 207 ) must be designed such that A i2 =A r2 =A 2 sin(θ 2 )>>λ 2 .
[0059] Wave Bender with Two 3D-Reflectors: In FIG. 2 , the effective incident area, A i1 , of the first reflector ( 203 ) relative to A T is equal to A i1 =A 1 sin(θ 1 ) where A 1 is the physical area of the first reflector ( 203 ) and θ 1 ( 202 ) is the incident angle from A T to the first reflector ( 203 ), while the effective reflected area, A r1 , of the first reflector ( 203 ) relative to the second reflector ( 207 ) is equal to A r1 =A 1 sin(α 2 −θ 1 ) where α 2 ( 104 ) is the desired angle for bending the incident wave ( 201 ) to a reflected wave ( 205 ). It can be easily shown that the relationship between θ 1 ( 202 ) and α 2 ( 204 ) is such that θ 1 =(α 2 )/2, then A i1 =A r1 =A 1 sin(θ 1 ). This relationship together with constraints c1 and d1 above imply that the first reflector ( 203 ) must be designed such that A i1 =A r1 =A 1 sin(θ 1 )>>λ 2 .
[0060] Even though the wave bender is 3-dimensional (3D), θ 1 =(α 2 )/2 is still valid in the wave plane made-up of the incident wave ( 201 ) and the reflected wave ( 205 ). In other words, A i1 =A r1 =A 1 sin(θ 1 ) is still valid where θ 1 is obtained from the following relationship: cos(π−2θ 1 )=−cos(2θ 1 )=cos(φ 2 )cos(γ 2 ) where φ 2 is the horizontal angle shift corresponding to α 2 while γ 2 is the vertical angle shift corresponding to α 2 .
[0061] In FIG. 2 , the effective incident area, A i2 , of the second reflector ( 207 ) relative to wave ( 205 ) is equal to A i2 =A 2 sin(θ 2 ) where A 2 is the physical area of the second reflector ( 207 ) and θ 2 ( 206 ) is the incident angle from the first reflector ( 203 ) to the second reflector ( 207 ), while the effective reflected area, A r2 , of the second reflector ( 207 ) relative to A R is equal to A r2 =A 2 sin(−(α 3 −α 2 )−θ 2 ) where α 3 ( 209 ) is the desired angle for bending the incident wave ( 201 ) to a reflected wave ( 208 ). It can be easily shown that the relationship between θ 2 ( 206 ), α 2 ( 204 ) and α 3 ( 209 ) is such that θ 2 =−(a 3 −α 2 )/2, then A i2 =A r2 =A 2 sin(θ 2 ). This relationship together with constraints c1 and d1 above imply that the second reflector ( 207 ) must be designed such that A i2 =A r2 =A 2 sin(θ 2 )>>λ 2 .
[0062] Even though the wave bender is 3-dimensional (3D), θ 2 =(α 3 )/2 is still valid in the wave plane made-up of the incident wave ( 205 ) and the reflected wave ( 208 ). In other words. A i2 =A r2 =A 2 sin(θ 2 ) is still valid where θ 2 is obtained from the following relationship: cos(π−2θ 2 )=−cos(2θ 2 )=cos(φ 3 )cos(γ 3 ) where β 3 is the horizontal angle shift corresponding to α 3 while γ 3 is the vertical angle shift corresponding to α 3 .
[0063] Wave Bender with Three 2D-Reflectors: In FIG. 3 , the effective incident area, A i1 , of the first reflector ( 303 ) relative to A T is equal to A i1 =A 1 sin(θ 1 ) where A 1 is the physical area of the first reflector ( 303 ) and θ 1 ( 302 ) is the incident angle from A T to the first reflector ( 303 ), while the effective reflected area, A r1 , of the first reflector ( 303 ) relative to the second reflector ( 307 ) is equal to A r1 =A 1 sin(α 2 −θ 1 ) where α 2 ( 104 ) is the desired angle for bending the incident wave ( 301 ) to a reflected wave ( 305 ). It can be easily shown that the relationship between θ 1 ( 302 ) and α 2 ( 304 ) is such that θ 1 =(α 2 )/2, then A i1 =A r1 =A 1 sin(θ 1 ). This relationship together with constraints c1 and d1 above imply that the first reflector ( 303 ) must be designed such that A i1 =A r1 =A 1 sin(θ 1 )>>λ 2 .
[0064] In FIG. 3 , the effective incident area, A i2 , of the second reflector ( 307 ) relative to wave ( 305 ) is equal to A i2 =A 2 sin(θ 2 ) where A 2 is the physical area of the second reflector ( 307 ) and 02 ( 306 ) is the incident angle from the first reflector ( 303 ) to the second reflector ( 307 ), while the effective reflected area, A r2 , of the second reflector ( 307 ) relative to the third reflector ( 311 ) is equal to A r2 =A 1 sin(−(α 3 −α 2 )−θ 2 ) where α 3 ( 309 ) is the desired angle for bending the incident wave ( 305 ) to a reflected wave ( 308 ). If the relationship between θ 2 ( 306 ), α 2 ( 34 ) and α 3 ( 309 ) is such that θ 2 =−(α 3 −α 2 )/2, then A i2 =A r2 =A 2 sin(θ 2 ). This relationship together with constraints c1 and d1 above imply that the second reflector ( 307 ) must be designed such that A 2 sin(θ 2 )>>λ 2 .
[0065] In FIG. 3 , the effective incident area, A i3 , of the third reflector ( 311 ) relative to wave ( 308 ) is equal to A i3 =A 3 sin(θ 3 ) where A 3 is the physical area of the third reflector ( 311 ) and θ 3 ( 310 ) is the incident angle from the second reflector ( 307 ) to the third reflector ( 311 ), while the effective reflected area, A r3 , of the third reflector ( 103 ) relative to A R ( 315 ) is equal to A r3 =A 3 sin((α 4 −α 3 )−θ 3 ) where α 4 ( 313 ) is the desired angle for bending the incident wave ( 308 ) to a reflected wave ( 312 ). If the relationship between θ 3 ( 310 ), α 3 ( 309 ) and α 4 ( 313 ) is such that θ 3 =(α 4 −α 3 )/2, then A i3 =A r3 =A 3 sin(θ 3 ). This relationship together with constraints c1 and d1 above imply that the third reflector ( 311 ) must be designed such that A i3 =A r3 =A 3 sin(θ 3 )>>λ 2 .
[0066] Wave Bender with Three 3D-Reflectors: In FIG. 3 , the effective incident area, A i1 , of the first reflector ( 303 ) relative to A T is equal to A i1 =A 1 sin(θ 1 ) where A 1 is the physical area of the first reflector ( 303 ) and θ 1 ( 302 ) is the incident angle from A T to the first reflector ( 303 ), while the effective reflected area, A r1 , of the first reflector ( 303 ) relative to the second reflector ( 307 ) is equal to A r1 =A 1 sin(α 2 −θ 1 ) where α 2 ( 104 ) is the desired angle for bending the incident wave ( 301 ) to a reflected wave ( 305 ). It can be easily shown that the relationship between θ 1 ( 302 ) and α 2 ( 304 ) is such that θ 1 =(α 2 )/2, then A i1 =A r1 =A 1 sin(θ 1 ). This relationship together with constraints c1 and d1 above imply that the first reflector ( 303 ) must be designed such that A i1 =A r1 =A 1 sin(θ 1 )>>λ 2 .
[0067] Even though the wave bender is 3-dimensional (3D), θ 1 =(α 2 )/2 is still valid in the wave plane made-up of the incident wave ( 301 ) and the reflected wave ( 305 ). In other words, A i1 =A r1 =A 1 sin(θ 1 ) is still valid where θ 1 is obtained from the relationship cos(π−2θ 1 )=−cos(2θ 1 )=cos(φ 2 )cos(γ 2 ) where θ 2 is the horizontal angle shift corresponding to α 2 while γ 2 is the vertical angle shift corresponding to α 2 .
[0068] In FIG. 3 , the effective incident area, A i2 , of the second reflector ( 307 ) relative to wave ( 305 ) is equal to A i2 =A 2 sin(θ 2 ) where A 2 is the physical area of the second reflector ( 307 ) and θ 2 ( 306 ) is the incident angle from the first reflector ( 303 ) to the second reflector ( 307 ), while the effective reflected area, A r2 , of the second reflector ( 307 ) relative to the third reflector ( 311 ) is equal to A r2 =A 1 sin(−(α 3 −α 2 )−θ 2 ) where α 3 ( 309 ) is the desired angle for bending the incident wave ( 305 ) to a reflected wave ( 308 ). It can be easily shown that the relationship between θ 2 ( 306 ), α 2 ( 304 ) and α 3 ( 309 ) is such that θ 2 =−(α 3 −α 2 )/2, then A i2 =A r2 =A 2 sin(θ 2 ). This relationship together with constraints c1 and d1 above imply that the second reflector ( 307 ) must be designed such that A 2 sin(θ 2 )>>λ 2 .
[0069] Even though the wave bender is 3-dimensional (3D), θ 2 =(α 3 )/2 is still valid in the plane made-up of the incident wave ( 305 ) and the reflected wave ( 308 ). In other words. A i2 =A r2 =A 2 sin(θ 2 ) is still valid where θ 2 is obtained from the following relationship: cos(π−2θ 2 )=−cos(2θ 2 )=cos(φ 3 )cos(γ 3 ) where φ 3 is the horizontal angle shift corresponding to α 3 while γ 3 is the vertical angle shift corresponding to α 3 .
[0070] In FIG. 3 , the effective incident area, A i3 , of the third reflector ( 311 ) relative to wave ( 308 ) is equal to A i3 =A 3 sin(θ 3 ) where A 3 is the physical area of the third reflector ( 311 ) and θ 3 ( 310 ) is the incident angle from the second reflector ( 307 ) to the third reflector ( 311 ), while the effective reflected area, A r3 , of the third reflector ( 103 ) relative to A R ( 315 ) is equal to A r3 =A 3 sin((α 4 −α 3 )−θ 3 ) where α 4 ( 313 ) is the desired angle for bending the incident wave ( 308 ) to a reflected wave ( 312 ). It can be easily shown that the relationship between θ 3 ( 310 ), α 3 ( 309 ) and α 4 ( 313 ) is such that θ 3 =(α 4 −α 3 )/2, then A i3 =A r3 =A 3 sin(θ 3 ). This relationship together with constraints c1 and d1 above imply that the third reflector ( 311 ) must be designed such that A i3 =A r3 =A 3 sin(θ 3 )>>λ 2 .
[0071] Even though the wave bender is 3-dimensional (3D), θ 3 =(α 4 )/2 is still valid in the plane made-up of the incident wave ( 308 ) and the reflected wave ( 312 ). In other words, A i3 =A r3 =A 3 sin(θ 3 ) is still valid where θ 3 is obtained from the relationship cos(π−2θ 3 )=−cos(2θ 3 )=cos(φ 4 )cos(γ 4 ) where φ 4 is the horizontal angle shift corresponding to α 4 while γ 4 is the vertical angle shift corresponding to α 4 .
[0072] Wave Bender with N 2D-Reflectors: In general, it can be easily shown that for a wave bender with N reflectors, the 2-dimensional relationship between the incident angle, θ n , corresponding to the n th reflector, and the reflected angle, α n , corresponding to the n th reflector must be
[0000] θ n =(−1) n+1 (α n −α n−1 )/2 for n =1, . . . , N (4a)
[0073] Without loss of generality, the reflected angle, α 1 , in Equation (4a) for the first reflector is selected as a reference, i.e, α 1 =0, for the 2-dimensional deployment of a wave bender with N reflectors.
[0074] Wave Bender with N 3D-Reflectors: In general, it can be easily shown that for a wave bender with N reflectors, the relationship between the incident angle, θ n , corresponding to the n th reflector, and the reflected angle, α n , corresponding to the n th reflector is
[0000] θ n =(−1) n+1 (α n −α n−1 )/2 for n= 1, . . . , N (4b)
[0075] Even though the wave bender is 3-dimensional (3D), Equation (4b) is still valid in the wave plane made-up of the n th incident wave ( 308 ) and the n th reflected wave ( 312 ). In other words, A in =A rn =A n sin(θ n ) is still valid where θ n is obtained from the relationship cos(π−2θ n )=−cos(2θ n )=cos(φ n+1 )cos(γ n+1 ) where φ n+1 is the horizontal angle shift corresponding to α n+1 while γ n+1 is the vertical angle shift corresponding to a n+1 .
[0076] Without loss of generality, the reflected angle, α 1 , in Equation (4b) for the first reflector is selected as a reference, i.e, α 1 =0, for the 2-dimensional deployment of a wave bender with N reflectors.
[0077] Practical Design Considerations for Properly Designed Reflectors: Important practical design considerations for meeting the 5 constraints a1, b1, c1, d1 and e1 are discussed here. In order for the wave bender to be easily deployed, its elements, the reflectors, must be lightweight, small in size and easy to configure. On the other hand, in order for the wave bender to require low maintenance, its elements must be passive (i.e. no power source), withstand heavy wind loading and are unaffected by severe weather conditions.
[0078] The “small in size” requirement for the reflectors directly affects the two constraints c1 and d1. As previously mentioned, Equation (2) implies a received signal at A R with very low power, P r . That is why all previous designs of passive reflector repeaters selected the physical area of the reflectors, A, to be quite large in order to compensate for the weak received signal. From Equation (3), one can meet constraints c1 and d1 without selecting an excessively large reflector, as long as
[0000] A in =A rn =A n sin(θ n )>>λ 2 , for n= 1, . . . , N.
[0079] The “easy to configure” requirement for the reflectors directly affects the two constraints a1 and b1. However, the two constraints are easily met using a single flat mirror at every reflector to be configured using Method I as follows:
[0080] Method I:
[0000] a) Select the number N of the required reflectors and their location using Method II below.
b) Point the ±3 dB beam of the transmitting antenna A T towards the center of the first reflector, where the first reflector is placed in the far field of the transmitting antenna.
c) Place the flat mirror at the center of the first reflector.
d) Position a viewer to have his/her back perpendicular to the corresponding incident wave.
e) Ask the viewer to look at the image formed by the mirror.
f) Adjust the reflector either in a 2-dimensional fashion or in a 3-dimensional fashion until the formed image that is viewed by the viewer is that of the next reflector.
g) Repeat steps b) to e) for every reflector, until you reach the last reflector. In this case, the following steps must be followed:
h) Place the flat mirror at the center of the last reflector.
i) Position a viewer to have his/her back perpendicular to the corresponding incident wave.
j) Ask the viewer to look at the image formed by the mirror.
k) Adjust the reflector either in a 2-dimensional fashion or in a 3-dimensional fashion until the formed image that is viewed by the viewer is that of the receiving antenna A R .
l) Point the ±3 dB beam of the receiving antenna A R towards the center of the last reflector.
[0081] Although a “viewer” is referred to as if it were a person, the “viewer” can also be an automatic device or a viewing device used by a person. The notion of viewing can be extended to the notion of “sighting” where sighting an object along a line can be either viewing the object in a direction along the line or sending a beam of light in the direction of the object along the line (see method IV below). Similarly, sighting an object in a mirror can be seeing an image of the object in the mirror or reflecting light from the mirror to the object.
[0082] The “lightweight” requirement for the reflectors together with the “able to withstand heavy wind loading” requirement also for the reflectors, directly affect constraint e1. In order to meet constraint e1, while keeping the weight light and the wind loading low, a grid metallic structure for the reflectors may be selected as shown in FIGS. ( 7 ), ( 8 ), ( 9 ) and ( 10 ). In FIG. 10 , a rectangular grid structure is shown as a preferred embodiment of the reflector. In FIG. 10 , the rectangular grid structure has a physical width W n ( 1001 ) and a physical height H n ( 1004 ). Also, in FIG. 10 , the eyes of the grid are rectangular with a width w n ( 1003 ) and a height h n ( 1002 ). In order to satisfy constraint e1, we must have
[0000] A in =A rn =A n sin(θ n )= W n ×H n sin(θ n )>>λ 2 , or equivalently
[0000] W n √{square root over (sin(θ 1 ))}>λ and H n √{square root over (sin(θ 1 ))}>λ; and
[0000] w n ×h n <<λ 2 , or equivalently
[0000] w n <λ and h n <λ.
[0083] As previously mentioned, the rectangular grid structure in FIG. 10 can be generalized to take any structure. For example, an elliptical structure with a minor radius b 1 and a major radius α 1 corresponds to an area A 1 =πb 1 a 1 , or equivalently A 1 sin(θ 1 )=πb 1 α 1 sin(θ 1 )>>λ 2 , i.e. b 1 √{square root over (sin(θ 1 ))}>λ/√{square root over (π)} and a 1 √{square root over (sin(θ 1 ))}>λ/√{square root over (π)}.
[0084] In general, the 2D rectangular grid structure shown as a preferred embodiment of the reflector in FIG. 10 can be generalized to take any 3D shape, which contains a rectangular shape of area A 1 . In this case, we need to define an equivalent width. W eq,1 , and an equivalent height, H eq,1 , of the new shape to have their product equal to A 1 , i.e.
[0000] A 1 W eq,1 ×H eq,1 (5a)
[0085] Similarly, the 2D rectangular grid structure shown as a preferred embodiment of the reflector in FIG. 10 can be generalized to take any 3D shape, which contains an elliptical structure. In this case, we need to define an equivalent minor radius, b eq,1 and an equivalent major radius, a eq,1 of the new shape as
[0000] A 1 πb eq,1 a eq,1 (5b)
[0086] Furthermore, the eyes of the grid can be generalized to take any shape. For example, the eyes of the grid can take a shape, which contains a rectangular shape. Once again, we need to define an equivalent width, w eq,1 , and an equivalent height, h eq,1 , of the new shape to have their product equal to 1 , i.e.
[0000] 1 w eq,1 ×h eq,1 (6a)
[0087] Similarly, the eyes of the grid can take a shape, which contains an elliptical shape. Once again, we need to define an equivalent minor radius, b eq,1 , and an equivalent major radius, a eq,2 , of the new shape as
[0000] 1 πb eq,1 a eq,1 (6b)
[0088] In conclusion to this design consideration, to satisfy constraint e1, we must have
[0000] A i1 =A r1 =A 1 sin(θ 1 )= W eq,1 ×H eq,1 sin(θ 1 )>>λ 2 , or equivalently
[0000] W eq,1 √{square root over (sin(θ 1 ))}>λ and H eq,1 √{square root over (sin(θ 1 ))}>λ (7a)
[0000] 1 w eq,1 ×h eq,1 <<λ 2 , or equivalently
[0000] w eq,1 <λ and h eq,1 <λ (8a)
[0089] Alternatively, to satisfy constraint e1, we must have
[0000] A i1 =A r1 =A 1 sin(θ 1 )=π b eq,1 a eq,1 sin(θ 1 )>>λ 2 , or equivalently
[0000] b eq,1 √{square root over (sin(θ 1 ))}>λ/π and a eq,1 √{square root over (sin(θ 1 ))}>λ/π (7b)
[0000] 1 =πb eq,1 a eq,1 <<λ 2 , or equivalently
[0000] b eq,1 <λ/π and a eq,1 <λ/π (8b)
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0090] Method II
[0091] There is disclosed a method, we refer to as Method II, for selecting the number, N, of properly designed reflectors in a wave bender, and their location. The method follows an iterative approach, which starts by selecting the number of reflectors to be one and to check if all above constrains a1, b1, c1, d1 and e1 are satisfied based on a number of appropriate locations for the reflector. If they are, then the method ends, otherwise, the number of reflectors is incremented by one and the steps are repeated one more time. The iterative approach carries on until all constraints are satisfied, or an upper limit on the number of reflectors is reached. In order to limit the number of options that are available, the following assumptions are made:
[0092] Assumption A1: All N reflectors are designed properly.
[0093] Assumption A2: The deployment is a 2-dimensional deployment. This assumption is easily extended to include a 3-dimensional deployment.
[0094] Assumption A3: The locations of the transmitting antenna, A T , receiving antenna, A R , and obstacles are known, i.e. the desired angle bending, α N+1 , between A T and A R is known once the location of the wave bender is known.
[0095] Assumption A4: The wave bender is composed of reflectors that are made of a material, which satisfies constraint e1.
[0096] Assumption A5: The reflectors are all flat, and either rectangular or elliptical in shape. This assumption is easily extended to include any 3-dimensional shape of the reflector.
[0097] Assumption A6: The “method to configure a reflector to comply with constraints a1 and b1” (above) is met.
[0098] Assumption A7: When the n th reflector is assumed to be flat and rectangular, and when its equivalent width, W eq,n , and its equivalent height, H eq,n , are both larger than 4 times the wavelength, i.e. when W eq,n ≧4λ and H eq,n ≧4λ, constrains c1 and d1 are assumed to be satisfied for all value of n=1, . . . , N. Alternatively, when the n th reflector is assumed to be flat and elliptical, and when its equivalent minor radius, b eq,n , and its equivalent major radius, a eq,n , are both larger than 4 times the wavelength/√{square root over (π)}, i.e. when b eq,n ≧4λ/√{square root over (π)} and a eq,n ≧4λ/√{square root over (π)}, constrains c1 and d1 are assumed to be satisfied for all value of n=1, . . . , N.
[0099] The above assumptions are further discussed (and sometimes relaxed) later in the disclosure.
[0100] The following are the iterations (and corresponding steps) of Method II, which applies to both 2D and 3D wave benders:
[0101] First Iteration:
[0102] Step 1,1: Select N=1 which corresponds to using one reflector.
[0103] Step 1,2: Find all acceptable locations for the reflector such that there is a direct Line-of-Sight (LOS) between the reflector and both the transmitting antenna, A T , and the receiving antenna, A R . If this is not possible, go to Step 2,1.
[0104] Step 1,3: For each acceptable location for the reflector, solve for θ 1 using the relationship: θ 1 =(α 2 −α 1 )/2 where α 1 =0 and α 2 , the desired angle bending between the wave transmitted by A T and the wave received by A R , is known from assumption A2, (or equivalently both φ 2 and γ 2 are known in a 3D deployment).
[0105] Step 1,4: For each acceptable location for the reflector, solve for the effective width, W e,1 , and effective height H e,1 for the first reflector using the relationship: W e,1 =W eq,1 √{square root over (sin(θ 1 ))} and H e,1 =H eq,1 √{square root over (sin(θ 1 ))} where W eq,1 and H e,1 are the equivalent width and height of the first reflector respectively (Equation 5a) assuming that the first reflector is flat and rectangular (assumption A5). Alternatively, when the first reflector is assumed to be flat and elliptical, for each acceptable location for the reflector, solve for its effective minor radius, b e,1 , and for its effective major radius, a e,1 , using the relationship: b e,1 =b eq,1 √{square root over (sin(θ 1 ))} and a e,1 =a eq,1 √{square root over (sin(θ 1 ))} where b eq,1 and a eq,1 are the equivalent minor radius and major radius of the first reflector respectively (Equation 5b).
[0106] Step 1,5: Select all acceptable locations for the reflector where W e,1 ≈4λ and H e,1 ≈4λ where λ is the wavelength of the RF wave, or equivalently select all acceptable locations for the reflector where b e,1 ≈4λ/√{square root over (π)} and a e,1 ≧4λ/√{square root over (π)}. If none exists, then go to Step 2,1. Otherwise, select the acceptable location for the reflector which corresponds to an appropriate value of W e,1 H e,1 , or alternatively to an appropriate value of b e,1 a e,1 , then stop (assumption A7).
[0107] Second Iteration:
[0108] Step 2,1: Select N=2 which corresponds to using two reflectors.
[0109] Step 2,2: Find all acceptable locations for the two reflectors such that there is a direct Line-of-Sight (LOS) between the first reflector and both the transmitting antenna, A T , and the second reflector, and there is a direct LOS between the second reflector and both the first reflector and the receiving antenna, A R . If this is not possible, go to Step 3,1.
[0110] Step 2,3: For each acceptable location for both reflectors, solve for θ 1 such that W e1 =W 1 sin(θ 1 )>4λ (assumption A7).
[0111] Step 2,4: For each acceptable location for both reflectors, solve for α 2 using the relationship: θ 1 =(α 2 −α 1 )/2 where α 1 =0.
[0112] Step 2,5: For each acceptable location for both reflectors, solve for θ 2 using the relationship: θ 2 =(α 3 −α 2 )/2 where α 3 , the desired angle bending between the wave transmitted by A T and the wave received by A R , is known from assumption A2, (or equivalently both φ 3 and γ 3 are known in a 3D deployment).
[0113] Step 2,6: For each acceptable location for both reflectors, solve for the effective widths, W e,1 and W e,2 , for both reflectors using the relationships: W e,1 =W eq,1 √{square root over (sin(θ 1 ))} and W e,2 =W eq,2 √{square root over (sin(θ 1 ))} respectively, and the effective heights H e,1 and H e,2 for both reflectors using the relationships: H e,1 =H eq,1 √{square root over (sin(θ 1 ))} and H e,2 =H eq,2 √{square root over (sin(θ 2 ))} respectively, where W eq,2 and H e,2 are the equivalent width and height of the second reflector respectively, (Equation 5a) assuming that the second reflector is flat and rectangular (assumption A5). Alternatively, when the second reflector is assumed to be flat and elliptical, for each acceptable location for the reflector, solve for both effective minor radii, b e,1 and b e,2 , and for both effective major radii, a e,1 and a e,2 , using the relationships: b e,1 =b eq,1 √{square root over (sin(θ 1 ))}, a eq,1 =a eq,1 √{square root over (sin(θ 1 ))}, b e,2 =b eq,2 √{square root over (sin(θ 2 ))} and a e,2 =a eq,2 √{square root over (sin(θ 2 ))} where b eq,2 and a eq,2 are the equivalent minor radius and major radius of the second reflector respectively (Equation 5b).
[0114] Step 2,7: Select all acceptable locations for the reflector where W e,1 ≧4λ. H e,1 ≧4λ, W e,2 ≧4λ and H e,2 ≧4λ, or equivalently, select all acceptable locations for the reflector where b e,1 ≧4λ/√{square root over (π)}, a e,1 ≧4λ/√{square root over (π)}, b e,2 ≧4λ/√{square root over (π)} and a e,2 ≧4λ/√{square root over (π)}. If none exists, then go to Step 3,1. Otherwise, select the acceptable location for the first reflector which corresponds to appropriate value of W e,1 H e,1 , or alternatively to an appropriate value of b e,1 a e,1 , Then select the acceptable location for the second reflector which corresponds to an appropriate value of W e,2 H e,2 , or alternatively to an appropriate value of b e,2 a e,2 , then stop, (assumption A7).
[0115] Third Iteration:
[0116] Step 3,1: Select N=3 which corresponds to using three reflectors.
[0117] Step 3,2: Find all acceptable locations for the three reflectors such that (1) there is a direct Line-of-Sight (LOS) between the first reflector and both the transmitting antenna, A T , and the second reflector; (2) there is a direct LOS between the second reflector and both the first reflector and the third reflector; (3) there is a direct LOS between the third reflector and both the second reflector and the receiving antenna, A R . If this is not possible, go to Step N,1.
[0118] Step 3,2: For each acceptable location for all three reflectors, solve for θ 1 such that W e,1 =W 1 sin(θ 1 )≧4λ (assumption A7).
[0119] Step 3,3: For each acceptable location for all three reflectors, solve for α 2 using the relationship: θ 1 =(α 2 −α 1 )/2 where α 1 =0.
[0120] Step 3,4: For each acceptable location for all three reflectors, solve for θ 2 such that W e,2 =W 2 sin(θ 2 )≧4λ(assumption A7).
[0121] Step 3,5: For each acceptable location for all three reflectors, solve for α 3 using the relationship: θ 2 =(α 3 −α 2 )/2.
[0122] Step 3,6: For each acceptable location for all three reflectors, solve for θ 3 using the relationship: θ 3 =(α 4 −α 3 )/2 where α 4 , the desired angle bending between the wave transmitted by A T and the wave received by A R , is known from assumption A2, (or equivalently both φ 94 and γ 4 are known in a 3D deployment).
[0123] Step 3,7: For each acceptable location for all three reflectors, solve for the effective widths, W e,1 , W e2 , and W e,3 , and the effective heights, H e,1 , H e,2 and H e,3 using the relationships: W e,1 =W eq,1 √{square root over (sin(θ 1 ))}, W e,2 =W eq,2 √{square root over (sin(θ 2 ))} and W e,3 =W eq,3 √{square root over (sin(θ 3 ))}, H e,1 =H eq,1 √{square root over (sin(θ 1 ))}, H e,2 =H eq,2 √{square root over (sin(θ 2 ))} and H e,3 =H eq,3 √{square root over (sin(θ 3 ) )} where W eq,3 and H e,3 are the equivalent width and height of the third reflector respectively (Equation 5a) assuming that the third reflector is flat and rectangular (assumption A5). Alternatively, when the third reflector is assumed to be flat and elliptical, for each acceptable location for the reflector, solve for all effective minor radii, b e,1 , b e,2 , and b e,3 , and for all effective major radii, a e,1 , a e,2 , and a e,3 using the relationships: b e,1 =b eq,1 √{square root over (sin(θ 1 ))}, a e,1 √{square root over (sin(θ 1 ))}, b e,2 =a eq,2 √{square root over (sin(θ 2 ))}, a e,2 =a eq,2 √{square root over (sin(θ 2 ))}, b e,3 =b eq,3 √{square root over (sin(θ 3 ))} and a e,3 =a eq,3 sin(θ 3 ) where b eq,3 and a eq,3 are the equivalent minor radius and major radius of the third reflector respectively (Equation 5b).
[0124] Step 3,8: Select all acceptable locations for the reflector where W e,1 ≧4λ. H e,1 ≧4λ, W e,2 ≧4λ, H e,2 >4λ, W e,3 >4λ and H e,3 ≧4λ or equivalently, select all acceptable locations for the reflector where b e,1 ≧4λ/√{square root over (π)}, a e,1 ≧4λ/√{square root over (π)}, b e,2 ≧4λ/√{square root over (π)}, a e,2 ≈4λ/√{square root over (π)}, b e,3 ≧4λ/√{square root over (π)} and a e,3 >4λ/√{square root over (π)}. If none exists, then go to Step N,1. Otherwise, select the acceptable location for the first reflector which corresponds to appropriate value of W e,1 H e,1 , or alternatively to an appropriate value of b e,1 a e,1 . Then select the acceptable location for the second reflector which corresponds to an appropriate value of W e,2 H e,2 , or alternatively to an appropriate value of b e,2 a e,2 . Finally, select the acceptable location for the third reflector which corresponds to an appropriate value of W e,3 H e,3 , or alternatively to an appropriate value of b e,3 a e,3 , then stop, (assumption A7).
[0125] N th Iteration:
[0126] Step N,1: Increment N by 1.
[0127] Step N,2: Find all acceptable locations for all N reflectors such that (1) there is a direct Line-of-Sight (LOS) between the first reflector and both the transmitting antenna, A T , and the second reflector; (2) there is a direct LOS between the second reflector and both the first reflector and the third reflector; etc. (3) there is a direct LOS between the last reflector and both the second last reflector and the receiving antenna, A R . If this is not possible, repeat all steps from Step N,1 to Step N,M.
[0128] Step N,2: For each acceptable location for all reflectors, solve for θ 1 such that W e,1 =W 1 sin(θ 1 )≧4λ (assumption A7).
[0129] Step N,3: For each acceptable location for all reflectors, solve for α 2 using the relationship: θ 1 =(α 2 −α 1 )/2 where α 1 =0.
[0130] Step N,4: For each acceptable location for all reflectors, solve for θ 2 such that W e2 =W 2 sin(θ 2 )≧4λ (assumption A7).
[0131] Step N,5: For each acceptable location for all reflectors, solve for α 3 using the relationship: θ 2 =(α 3 −α 2 )/2.
[0132] Step N,M−1: For each acceptable location for all reflectors, solve for ON using the relationship: θ N =(α N+1 −α N )/2 where α N+1 , the desired angle bending between the wave transmitted by A T and the wave received by A R , is known from assumption A2, (or equivalently both φ N+1 and γ N+1 are known in a 3D deployment).
[0133] Step N,M−1: Solve for the effective width, W e,n , and the effective height H e,n for the n th reflector using the relationship: W e,n =W eq,n √{square root over (sin(θ n ))} and H e,n =H eq,n √{square root over (sin(θ n ))} where W eq,n and H eq,n are the equivalent width and height of the n th reflector respectively (Equation 5a) assuming that the n th reflector is flat and rectangular (assumption A5) for all values of n. Equivalently, when the n th reflector is assumed to be flat and elliptical, solve for its effective minor radius, b e,n , and for its effective minor radius, a e,n, using the relationship: b e,n =h eq,n sin(θ n ) and a e,n =a eq,n √{square root over (sin(θ n ))} where b eq,n and a eq,n are the equivalent minor radius and major radius of the n th reflector respectively (Equation 5b) for all values of n.
[0134] Step N,M: Select all acceptable locations for the n th reflector where W e,n ≧4λ, and H e,n ≧4λ, or equivalently, select all acceptable locations for the n th reflector where b e,n ≧4λ/√{square root over (π)}, and a e,n ≧4λ/√{square root over (π)} for all values of n. If none exists, then repeat Step N,1 to Step N,M. Otherwise, select the acceptable location for the n th reflector which corresponds to an appropriate value of W e,n H e,n , or alternatively to an appropriate value of b e,n a e,n for all values of n, then stop, (assumption A7).
[0135] Notes:
[0136] In the above method, Method II, M is equal to M=4+2(N−1).
[0137] In the above method, Method II, when W n is selected equal to 60 cm for n=1, . . . , N, and the wavelength λ is selected equal to 12.5 cm (which corresponds to a carrier frequency of 2.4 GHz), then the maximum number of required reflectors is 3 and the breakdown for the angles is as follows.
[0138] When the desired angle bending, α N+1 , between the wave transmitted by A T and the wave received by A K is as follows:
[0000] 1. 0<α N+1 ≦60°, then the number N of reflector is two;
2. 60°≦α N+1 ≦110°, then the number N of reflector is three;
3. 110°≦α N+1 ≦180°, then the number N of reflector is one.
[0139] Selecting the location of the wave bender: Selecting an acceptable location for the n th reflector to correspond to an appropriate value of W e,n H e,n , or alternatively to an appropriate value of b e,n a e,n , sometimes corresponds to having more than one solution. When there is more than one choice of placing the elements of the wave bender, the question arises of how to choose between the various choices. Usually, an important factor is the desired angle bending, α N+1 , between the wave transmitted by A T and the wave received by A R , (or equivalently φ N+1 and γ N+1 in a 3D deployment). Angle α N+1 is important since it determines the number of reflectors in a wave bender. The number of reflectors affects the cost and ease of deployment among other things. Another important factor when choosing the placement of the wave bender is the effective distance between the transmitting antenna A T and the receiving antenna A R , which is computed as the sum of all indirect paths between the two antennas. The lower the sum, the better the received SNR at A R .
[0140] Selecting non-flat Reflectors in a Wave Bender: Assumption A5 assumes that the reflectors are flat. A flat properly designed reflector reflects incident planar waves as reflected planar waves. If the reflector is not flat, but curved, it reflects planar waves into non-planar waves. Most curved reflectors have surfaces that are shaped like part of a sphere, but other shapes are sometimes used. The most common non-spherical type is parabolic reflectors. Curved reflectors that are shaped like a sphere can be either convex (bulging outward) or concave (bulging inward). A convex reflector or diverging reflector is a curved reflector in which the reflective surface bulges toward the transmitting antenna A T . Convex reflectors reflect planar waves outwards in a spread out manner, i.e. they are not used to focus the waves but in fact, they suffer a loss in efficiency, η. A concave or converging reflector has a reflecting surface that bulges inward (away from the incident waves). Concave reflectors reflect planar waves inward to one focal point. They are used to focus waves, and therefore offer a gain in efficiency.
[0141] From the above assessment, one can argue that a concave reflector can offer a gain in efficiency over a flat reflector, which depends on the size of the reflector. This is true. However, the deployment of concave reflectors can be complicated since one needs to place the focal point of the first concave reflector at the center of the second reflector. Nonetheless, some applications might require high gain concave reflectors.
[0142] Selecting Reflectors of any shape in a Wave Bender: Assumption A5 assumes that the reflectors are either rectangular or elliptical. This is only for convenience in manufacturing and in storing (stacking) the reflectors. A rounded reflector is as effective as a rectangular one. In fact a rounded reflector can be made lighter than a rectangular one if it does not contain corners. In other words, Assumption A5 can be simply modified to include any shape for a reflector as long as an elliptical shape is contained within the reflector.
[0143] Selecting a 3-dimensional deployment: Assumption A2 assumes that the deployment is 2-dimensional. In some cases, a 3-dimensional deployment is required such as in a hilly terrain. The same method, Method I, which is used to configure a reflector to comply with constraints a1 and b1, is applicable using the articulated arm ( 702 ) in FIG. 7 and ( 802 ) in FIG. 8 . A detailed description of the articulated arm is shown in FIG. 9 , which shows that the articulated arm consists generally of 3 components: a first rubber ball ( 903 ) attached to a second rubber ball ( 905 ) through a lateral holder ( 904 ), which can be tightened on both rubber balls.
[0144] Selecting point to multi-point communication or multipoint to multipoint communications:
[0145] Even though the disclosure has relied on point to point communications (such as in FIGS. 1 to 6 ), to explain the wave bender, the same methods can be easily extended to include multipoint communications. The reason this is true is because the theory is the same in both cases. The only difference between the two cases is instead of having a known position for the fixed transmitter or for the fixed receiver, we now have a known area of coverage for mobile transceivers. For example, Method I, which is used to configure a reflector to comply with constraints a1 and b1 in point to point communications is now replaced by Method III, which is used to configure a reflector to comply with constraints a1 and b1 in point to multipoint or multipoint to multipoint communications:
[0146] Method III:
[0000] a) Select the number N and location of the reflectors using Method II.
b) In a point to multipoint system: Point the ±3 dB beam of the transmitting antenna A T towards the center of the first reflector, where the first reflector is placed in the far field of the transmitting antenna.
c) Place the flat mirror at the center of the reflector.
d) Position a viewer to have his/her back perpendicular to the corresponding incident wave.
e) Ask the viewer to look at the image formed by the mirror.
f) Adjust the reflector either in a 2-dimensional fashion or in a 3-dimensional fashion until the formed image that is viewed by the viewer is that of the next reflector.
g) Repeat all above steps for every reflector, until you reach the last reflector. In this case, the following steps must be followed:
h) Place the flat mirror at the center of the last reflector.
i) Position a viewer to have his/her back perpendicular to the corresponding incident wave.
j) Ask the viewer to look at the image formed by the mirror.
k) Adjust the reflector either in a 2-dimensional fashion or in a 3-dimensional fashion until the formed image that is viewed by the viewer is that of the center of the intended coverage area.
l) In a multipoint to point system: Point the ±3 dB beam of the receiving antenna A R towards the center of the last reflector.
[0147] A mixture of active and passive repeaters: So far, this disclosure has introduced the concept of adding one wave bender between a transmitting antenna A T and a receiving antenna A R (or between a number of transmitting antennas and a number of receiving antennas). In some situations, obstacles obstruct partial segments in the selected indirect paths. One way to resolve such a situation is by circumventing the obstructed paths using additional wave benders as long as the link budget permits it. Otherwise, an active repeater is the only way to make a connection between the two antennas. A wise decision is to always minimize the number of active repeaters because of the shortcomings associated with active repeaters as long as the link budget permits it, i.e. as long as
[0000] PL 1 +PL 2 + . . . +PL N ≦L B (9)
[0000] where PL 1 is the path loss between the transmitting antenna and the first reflector; PL N is the path loss between the N th reflector and the receiving antenna; PL 1 is the path loss between the (i−1) th reflector and the i th reflector; and L B is the link budget.
[0148] Using a laser beam to configure the reflectors
[0149] Methods I and III can use a laser beam instead of light to configure the reflectors. For example, Method I is replaced by Method IV as follows:
[0150] Method IV:
[0000] a) Select the number N and location of the reflectors using Method II.
b) Place the flat mirror at the center of a reflector.
c) Position a first person to have his/her back perpendicular to the corresponding incident wave.
d) Ask the first person to point a laser beam at the mirror.
e) Ask a second person to have his/her back perpendicular to the corresponding intended outgoing direction towards the next reflector.
f) Adjust the reflector either in a 2-dimensional fashion or in a 3-dimensional fashion until the second person can see the laser beam.
g) Repeat all above steps for every reflector, until you reach the last reflector. In this case, the following steps must be followed:
h) Place the flat mirror at the center of the last reflector.
i) Position a first person to have his/her back perpendicular to the corresponding incident wave.
j) Ask the first person to point a laser beam at the mirror.
k) Ask a second person to have his/her back perpendicular to the corresponding intended outgoing direction towards the receiving antenna A R .
l) Adjust the reflector either in a 2-dimensional fashion or in a 3-dimensional fashion until the second person can see the laser beam.
[0151] Using Radio Signal Strength to Configure the Reflectors:
[0152] Methods I and III can use a Received Signal Strength Indicator (RSSI), or alternatively the Signal to Interference+Noise Ratio (SINR), instead of either light (Method II) or a laser beam (Method IV) to configure the reflectors. For example, Methods I and IV are replaced by Method V as follows:
[0153] Method V:
[0000] a) Select the number N and location of the reflectors using Method II.
b) Point the ±3 dB beam of the transmitting antenna A T towards the center of the first reflector, where the first reflector is placed in the far field of the transmitting antenna.
c) Point the ±3 dB beam of the second reflector towards the center of the first reflector, where the second reflector is placed in the far field of the first reflector.
d) Place an antenna at the center of the second reflector along its axis. We will refer to such an antenna as the “reflector antenna.”
e) Read the RSSI, or alternatively the Signal to Interference+Noise Ratio (SINR), that is measured at the reflector antenna indicating the link strength between itself and the transmitting antenna, A T .
f) Rotate the first reflector until the RSSI, or alternatively the Signal to Interference+Noise Ratio (SINR), that is measured by the reflector antenna is maximized.
g) Repeat all above steps for every reflector, until you reach the receiving antenna, A K . In this case, the following steps must be followed:
h) Read the RSSI, or alternatively the Signal to Interference+Noise Ratio (SINR), that is measured at the receiving antenna, A R indicating the link strength between itself and the transmitting antenna, A T .
i) Rotate the last reflector until the RSSI, or alternatively the Signal to Interference+Noise Ratio (SINR), that is measured by the receiving antenna, A R , is maximized.
[0154] Using a wave bender to locate a transmitting antenna with AOA: FIG. 11 is a 2-dimensional schematic view of a generic embodiment of a system intended to locate a transmitting antenna ( 106 ) using one reflector ( 103 ) of known location and one active node ( 113 ) also of known location. In FIG. 11 , it is assumed that the active node ( 113 ) comprises an antenna array ( 112 ) and a receiver, which together are able to estimate angles β 1 ( 114 ) and β 2 ( 115 ), corresponding to direct path ( 108 ) and indirect path ( 105 ) respectively. Since reflector ( 103 ) is of known location and of known axis, then, the angle β 1 ( 116 ) that is due to the intersection between the axis of the reflector and the axis of the antenna array is known. Therefore, the angle θ 1 ( 102 ) of the incident wave ( 101 ) can also be estimated as
[0000] θ 1 =π 1 +β 2 −π/2 (10)
[0000] once β 2 is estimated by the receiving node ( 113 ). The intersection between the direct path ( 108 ) (which is estimated once β 1 ( 114 ) is estimated) and the incident wave ( 101 ) (which is estimated once θ 1 ( 102 ) is estimated) provides a 2-dimensional estimate of the location of the transmitting antenna ( 106 ).
[0155] Using a wave bender to locate a transmitting antenna with TOA or TDO: FIG. 12 is a 2-dimensional schematic view of a generic embodiment of a system intended to locate a transmitting antenna ( 106 ) using one reflector ( 103 ) of known location and one active node ( 117 ) also of known location. In FIG. 12 , it is assumed that the active node ( 117 ) comprises one antenna ( 118 ) and a receiver, which together are able to estimate the Time of Arrival of any wireless signal transmitted by the transmitting antenna. Given that the transmitted wireless signal in FIG. 12 is able to travel via either the direct path ( 108 ) or the indirect path ( 101 , 105 ), it may be assumed that the active node ( 117 ) is able to estimate the two received signals with respect to their respective Times of Arrival: τ 1 and τ 2 which correspond to the direct path ( 108 ) and the indirect path ( 101 , 105 ) respectively. Since reflector ( 103 ) is of known location, then, the distance d 1 between its axis and antenna ( 118 ) of the active node ( 117 ) is also known. Therefore, a circle of radius c(τ 1 −τ 0 ) can be drawn centered at antenna ( 118 ) which represents all possible locations of the transmitting antenna ( 106 ), where c is the velocity of the wireless signal and τ 0 is the Time of Transmission of the transmitted wireless signal. Moreover, a second circle of radius cτ 2 −d 1 can be drawn centered at reflector ( 103 ) which also represents all possible locations of the transmitting antenna ( 106 ). When the accuracy of the estimated Time of Arrivals is acceptable, the two circles intersect at two points, i.e. an ambiguity exists which must be resolved. One way to resolve such an ambiguity is to include an extra circle either from another active node or from another reflector.
[0156] In the above analysis, it was assumed that the time of transmission τ 0 is known. This is often an unrealistic assumption given the fact that clocks drift in time and cannot be synchronized to an acceptable degree. For this reason, Time Difference of Arrival is an alternative technology to Time of Arrival, which does not assume perfect knowledge of τ 0 . In this case, one can assume that two reflectors are used together with an active node, and that the active node is able to estimate three Times of Arrival: τ 1 , τ 2 and τ 3 , τ 1 corresponds to the direct path between the transmitting antenna and the active node while τ 2 and τ 3 correspond to the two indirect paths. Once again, since each reflector is of known location, then, the distance d 1 and d 2 between each reflector and the antenna of the active node is also known. Therefore, two hyperbolas that are based on the two values: c(τ 1 −τ 2 ) and c(τ 2 −τ 3 ) can be drawn centered at the antenna of the active node and centered at the first reflector respectively, each hyperbola representing all possible locations of the transmitting antenna. The intersection of the two hyperbolas correspond to the possible location of the transmitting antenna. Occasionally, the two hyperbolas intersect in two points, however, this happens when the geometry of the system is poor, i.e. when the dilution of precision is large. When the system is deployed properly, i.e. with small dilution of precision, the two hyperbolas intersect at one point.
[0157] So far, we have discussed estimating the 2-dimensional location of a transmitting antenna. When the 3-dimensional location of the transmitting antenna is required, one extra reflector or one extra active node is required.
[0158] Using a wave bender to locate a receiving antenna with TOA or TDOA: FIG. 13 is a 2-dimensional schematic view of a generic embodiment of a system intended to locate a receiving antenna ( 121 ) using one reflector ( 103 ) of known location and one active node ( 119 ) also of known location. In FIG. 13 , it is assumed that the active node ( 119 ) comprises one antenna ( 120 ) and a transmitter. In FIG. 13 , it is also assumed that the receiving antenna is able to, estimate the Time of Arrival of any wireless signal transmitted by the active node. Given that the transmitted wireless signal in FIG. 13 is able to travel via either the direct path ( 122 ) or the indirect path ( 123 , 124 ), it may be assumed that the receiving antenna ( 121 ) is able to estimate the two received signals with respect to their respective Times of Arrival: τ 1 and τ 2 which correspond to the direct path ( 122 ) and the indirect path ( 123 , 124 ) respectively. Since reflector ( 103 ) is of known location, then, the distance d 1 between its axis and antenna ( 120 ) of the active node ( 119 ) is also known. Therefore, a circle of radius c(τ 1 −τ 0 ) can be drawn centered at antenna ( 120 ) which represents all possible locations of the receiving antenna ( 121 ), where c is the velocity of the wireless signal and τ 0 is the Time of Transmission of the transmitted wireless signal. Moreover, a second circle of radius cτ 2 −d 1 can be drawn centered at reflector ( 103 ) which also represents all possible locations of the receiving antenna ( 121 ). When the accuracy of the estimated Time of Arrivals is acceptable, the two circles intersect at two points, i.e. an ambiguity exists which must be resolved. One way to resolve such an ambiguity is to include an extra circle either from another active node or from another reflector.
[0159] In the above analysis, it was assumed that the time of transmission τ 0 is known. This is often an unrealistic assumption given the fact that clocks drift in time and cannot be synchronized to an acceptable degree. For this reason, Time Difference of Arrival is an alternative technology to Time of Arrival, which does not assume perfect knowledge of τ 0 . In this case, one can assume that two reflectors are used together with an active node, and that the active node is able to estimate three Times of Arrival: τ 1 , τ 2 and τ 3 where τ 1 corresponds to the direct path between the transmitting antenna and the active node while τ 2 and τ 3 correspond to the two indirect paths. Once again, since each reflector is of known location, then, the distance d 1 and d 2 between each reflector and the antenna of the active node is also known. Therefore, two hyperbolas that are based on the two values: c(τ 1 −τ 2 ) and c(τ 2 − 3 ) can be drawn centered at the antenna of the active node and centered at the first reflector respectively, each hyperbola representing all possible locations of the receiving antenna. The intersection of the two hyperbolas correspond to the possible location of the receiving antenna. Occasionally, the two hyperbolas intersect in two points, however, this happens when the geometry of the system is poor, i.e. when the dilution of precision is large. When the system is deployed properly, i.e. with small dilution of precision, the two hyperbolas intersect at one point.
[0160] So far, we have discussed estimating the 2-dimensional location of a transmitting antenna. When the 3-dimensional location of the transmitting antenna is required, one extra reflector or one extra active node is required.
[0161] It will be apparent from the foregoing disclosure that various embodiments of what is disclosed may provide these advantages:
[0162] Reducing the effect of shadowing in a wireless channel by creating new indirect paths between the transmitting antenna, A T , and the receiving antenna, A R , without increasing either power consumption, or latency between the two antennas, and without compromising their bit rate.
[0163] Creating new indirect paths using low cost, easy to deploy devices that are able to withstand severe weather conditions.
[0164] Replacing active repeaters by passive ones, which are easy to deploy and to maintain, have low cost and do not affect either the bit rate, the collision rate nor the latency between transmitting antenna, A T , and receiving antenna, A R .
[0165] Increasing the number of multipath components in a wireless Multiple Input Multiple Output (MIMO) channel by creating new indirect paths between the transmitting antenna, A T , and the receiving antenna, A R , without increasing either power consumption, or latency between the two antennas, and without compromising their bit rate.
[0166] Using a reflector repeater when locating either a transmitting antenna, A T or a receiving antenna A R . Several technologies exist for locating an active antenna such as Angle of Arrival (AOA), Time of Arrival (TOA) and Time Difference of Arrival (TDOA), among others. The minimum number of nodes of known locations that are required to estimate the 2-dimensional location of an active antenna using either AOA or TOA is two, while it is three when using TDOA.
[0167] Replacing active nodes of known location with reflector repeaters of known location when estimating the location of an active antenna. This is especially advantageous when replacing expensive active nodes such as GPS satellites or cellular Base Stations with inexpensive reflectors. | The present invention relates generally to the field of wireless communication and, in particular, to the field of reducing shadowing and multipath fading over a wireless link. According to a broad aspect of this invention, there is provided a novel design of a passive reflector repeater and a set of methods to be used to configure a set of reflector repeaters to bend RF waves around obstacles along the direct path of a wireless link. | 6 |
FIELD OF THE INVENTION
[0001] The present invention relates to regeneration of cartilaginous tissue in load bearing regions and/or the tendency toward the resorption of subchondral bone and, more particularly, to an implant device for reducing the resorption of subchondral bone and thereby enhancing the regeneration of cartilaginous tissue in load bearing regions.
BACKGROUND OF THE INVENTION
[0002] Current techniques for repair and/or regeneration of articular lesions (autogenous chondrocyte transplantation and mosaicplasty) are generally considered to be unsatisfactory due to the fact that they require the harvesting of healthy tissue. As such, research has focused on the development of engineered devices that have the ability to stimulate conduction of hyaline-like tissue into the treated regions without using autogenous tissue sources. Such devices would be considered optimized scaffolds.
[0003] In vivo studies of articular cartilage regeneration typically utilize one of two animal models: the osteochondral defect and the full-thickness chondral defect. The osteochondral defect model is ideal for the generation of cartilage neotissue because access to the traumatized bone bed allows for recruitment of precursor cells, thereby enhancing the intrinsic wound healing response. In fact, osteochondral defects in the non-load-bearing areas heal spontaneously, albeit with fibrous tissue. The load-bearing region, however, is known to not heal spontaneously, and is characteristically accompanied by resorption of osseous walls and the formation of cavitary lesions.
[0004] In cases where load-bearing surfaces have been investigated with good outcomes, care has been taken not to compromise the subchondral plate (e.g. full-thickness chondral defect model). However, because the chondral defect model does not generate a hematopoietic wound healing response, spontaneous regeneration does not occur and thus cellular therapies are usually used in such circumstances. One notable exception is mosaicplasty. Mosaicplasty in femoral condyle (osteochondral) defects has been shown to maintain subchondral bone structure, further indicating that application of physiologic force plays a role in maintaining subchondral bone integrity.
[0005] Particularly, mosaicplasty utilizes cartilaginous plugs, but due to the need to harvest tissue from other sites, this technique is sometimes viewed as being suboptimal. Therefore, research has focused on the use of implant devices. In published U.S. patent application 2001/0039455A1, prosthetic bio-compatible polyurethane plugs that mimic the materials properties of the adjacent bone or cartilage tissue layer are described. These implants are intended to fill a cartilaginous defect with a non-resorbable cartilage-like material. However, application of load to subchondral bone is not described.
[0006] The use of load during cartilage regeneration has been described in several publications. In U.S. Pat. No. 6,530,956 a resorbable cage-like scaffold is described that consists of high porosity material seeded with transplanted chondrocytes. Loading is discussed with respect to the cage-like scaffold for withstanding and resisting compressive forces so that cell growing compartments of the cage-like scaffold are protected during tissue regeneration.
[0007] U.S. Pat. No. 6,511,511 describes a fiber-reinforced, porous, biodegradable implant in which the fibers act like struts to provide strength and stiffness to the scaffold and provide support for physiological loads. One particular embodiment is for osteochondral defects. Loading, however, is discussed only with respect to the device resisting high compressive stresses in the defect region thereby protecting the implant during tissue regeneration. In a similar manner, U.S. published U.S. patent application 2002/0119177 describes a method for reinforcing the mechanical and handling properties of a resorbable foam matrix using a mesh-like fabric. The primary purpose of the reinforcing mesh is to maintain the integrity of the foam component for surgical handling.
[0008] In published U.S. patent application 2003/0108587, an implantable device is described that can induce compression, tension, shear and other biomechanical forces to cells in order to induce cell proliferation and thus wound healing. The device is essentially a bioreactor that exerts micromechanical stimulation to cells through materials properties or application of external forces. This is taught, however, with respect to the regeneration of cartilage and not with respect to the healing of the subchondral bone as in the present invention.
[0009] Thus the need exists for a device for regeneration of articular cartilage that simultaneously applies load to subchondral bone.
[0010] It is thus an object of the present invention to provide an implant for cartilage regeneration in load-bearing regions.
[0011] It is thus another object of the present invention to provide an implant that applies a load from an articulating surface of a bone platform to an area of subchondral bone.
[0012] It is yet another object of the present invention to provide a load bearing implant for that reduces subchondral bone resorption.
SUMMARY OF THE INVENTION
[0013] In one form, the present invention is an implant device for applying a load to osteochondral defects. In another form, the present invention provides cartilage regeneration of osteochondral defects in load bearing regions. The implant may be fashioned as one integral device or may be fashioned as two or more portions that are attached to one another.
[0014] The implant includes an upper platform structure and a lower platform structure with a load transfer structure situated there between. A fixation structure may be included that aids in anchoring the implant to the defect area. The implant is comprised of a resorbable polymeric material or materials such as polyesters (polylactide, polyglycolide, polycaprolactone, polydioxanone, or combination thereof), co-polymers of resorbable polymers, or blends thereof.
[0015] The lower platform structure is preferably rigid (and alternatively the upper platform structure as well) and may be porous, or include pores or holes that allow for access to biologic elements (e.g. blood and bone marrow) from the subchondral bone. The implant also allows the receipt and retention of a resorbable scaffold or matrix material for cartilage regeneration in the defect area.
[0016] Particularly, in one form there is provided an implant device for an osteochondral defect. The implant device includes a first plate made of a resorbable biocompatible material, a second plate made of the resorbable biocompatible material, and a load transfer structure made of the resorbable biocompatible material and situated between the first plate and the second plate.
[0017] In another form, there is provided an implant device for an osteochondral defect. The implant device includes an upper plate made of a resorbable biocompatible polymer, a lower plate made of the resorbable biocompatible polymer and having a plurality of exposure bores, and a load transfer structure situated between the upper plate and the lower plate.
[0018] In yet another form, there is provided an implant for load bearing bone articulation surfaces. The implant includes an upper plate made of a bio-resorbable polymer and having an upper center bore, a lower plate made of the bio-resorbable polymer and having a lower center bore surrounded by a plurality of exposure bores, and a plurality of load transfer supports situated between a lower surface of the upper plate and an upper surface of the lower plate, the load transfer supports surrounding the upper and lower center bores.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] FIG. 1 is a diagrammatic view showing a tibial platform, representing an exemplary bone platform, being below the condyles of the femur; representing exemplary condyles; may also want to show patella.
[0020] FIG. 2 is a block diagram illustrating an exemplary general form of a load bearing cartilage regeneration device in accordance with the principles of the subject invention;
[0021] FIG. 3 is an enlarged perspective view of an exemplary embodiment of a load bearing cartilage regeneration device in accordance with the principles of the subject invention;
[0022] FIG. 4 is a side view of the load bearing cartilage regeneration device of FIG. 3 ;
[0023] FIG. 5 is a sectional view of the load bearing cartilage regeneration device of FIG. 4 taken along line 5 - 5 thereof, particularly showing the lower platform thereof;
[0024] FIG. 6 is a sectional view of the load bearing cartilage regeneration device of FIG. 4 taken along line 6 - 6 thereof, particularly showing the upper platform thereof; including the load transferring structure.
[0025] FIG. 7 is an enlarged perspective view of another exemplary embodiment of a load bearing cartilage regeneration device in accordance with the principles of the subject invention;
[0026] FIG. 8 is a side view of the load bearing cartilage regeneration device of FIG. 7 ;
[0027] FIG. 9 is a sectional view of the load bearing cartilage regeneration device of FIG. 8 taken along line 9 - 9 thereof, particularly showing the lower platform thereof; including the load transferring structure.
[0028] FIG. 10 is a side view of another exemplary embodiment of a load bearing cartilage regeneration device in accordance with the principles of the subject invention;
[0029] FIG. 11 is a sectional view of the load bearing cartilage regeneration device of FIG. 10 taken along line 11 - 11 thereof, particularly showing the lower platform thereof; including the load transferring structure.
[0030] FIG. 12 is an enlarged bottom perspective view of an alternative upper platform utilizable with the various exemplary embodiments;
[0031] FIG. 13 is a side view of the upper platform of FIG. 12 ;
[0032] FIG. 14 is an enlarged top perspective view of an alternative embodiment of a platform having integral load transfer structures for a two-piece load bearing cartilage regeneration device, the load transfer structures designed to engage mating structures on a mating platform of the two-piece load bearing cartilage regeneration device such as that depicted in FIG. 16 ;
[0033] FIG. 15 is a top view of the platform of FIG. 14 ;
[0034] FIG. 16 is an enlarged top perspective view of an exemplary mating platform for the platform structure of FIG. 14 ;
[0035] FIG. 17 is a side view of the exemplary mating platform of FIG. 16 ;
[0036] FIG. 18 is a sectional view of the exemplary mating platform of FIG. 17 taken along line 18 - 18 thereof;
[0037] FIG. 19 is a top plan view of the exemplary mating platform of FIG. 16 ;
[0038] FIG. 20 is a sectional view of the exemplary mating platform of FIG. 19 taken along line 20 - 20 thereof;
[0039] FIG. 21 is an enlarged top perspective view of another exemplary mating platform for the platform structure of FIG. 14 ;
[0040] FIG. 22 is a top plan view of the exemplary mating platform of FIG. 21 ;
[0041] FIG. 23 is a side view of the exemplary mating platform of FIG. 21 ;
[0042] FIG. 24 is a sectional view of the exemplary mating platform of FIG. 23 taken along line 24 - 24 thereof;
[0043] FIG. 25 is an enlarged top perspective view of another alternative embodiment of a platform having integral load transfer structures for a two-piece load bearing cartilage regeneration device, the load transfer structures designed to engage mating structures on a mating platform of the two-piece load bearing cartilage regeneration device;
[0044] FIG. 26 is an enlarged top perspective view of yet another alternative embodiment of a platform having integral load transfer structures for a two-piece load bearing cartilage regeneration device, the load transfer structures designed to engage mating structures on a mating platform of the two-piece load bearing cartilage regeneration device;
[0045] FIG. 27 is an enlarged top perspective view of an exemplary mating platform for the platform structures of FIGS. 25 and/or 26 ;
[0046] FIG. 28 is a side view of the exemplary mating platform of FIG. 27 ;
[0047] FIG. 29 is a sectional view of the exemplary mating platform of FIG. 28 taken along line 29 - 29 thereof;
[0048] FIG. 30 is a top plan view of the exemplary mating platform of FIG. 27 ;
[0049] FIG. 31 is a sectional view of the exemplary mating platform of FIG. 30 taken along line 31 - 31 thereof; and
[0050] FIG. 32 is an enlarged side sectional view of a bone and cartilage platform depicting an exemplary load bearing cartilage regeneration device in accordance with the principles of the present invention implanted therein.
DETAILED DESCRIPTION OF THE INVENTION
[0051] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that there is no intent to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
[0052] Referring now to FIG. 1 , there is depicted a bone platform generally designated 40 being situated below condyles 42 . The bone platform 40 of FIG. 1 is depicted as a tibial platform 40 of a tibia 41 while the condyles 42 are of a femur/knee. It should be appreciated that the tibial platform 40 and condyles 42 are representative of any similar bone platform. The tibial platform 40 supports a meniscus 44 that is over subchondral bone 45 . The tibial platform 40 is assumed to have an osteochondral defect. The subject invention provides an implantable device for the osteochondral defect. The condyles 42 typically exert a load represented by arrows L onto the tibial platform 40 . Particularly, the condyles 42 of the femur 43 exert physiological loading on the tibial platform 40 during normal joint use. The implant is actually intended for a medial femoral condylar (MFC) defect, and our initial data is in the MFC. Perhaps we should describe FIG. 1 relating to a MFC defect, and mention the other load-bearing surfaces such as the tibia and patella?
[0053] Referring now to FIG. 2 , there is depicted a block diagram of a load bearing subchondral bone resorption reduction and/or cartilage regeneration implant device generally designated 50 (and, hereinafter, “load bearing implant device”, “implant” or the like) in accordance with the principles of the subject invention. The load bearing implant device 50 is representative of a general structure of the various embodiments of the present load bearing implant device shown and/or described herein.
[0054] The load bearing implant device 50 includes a first or upper platform, plate or the like 52 and a second or lower platform, plate or the like 54 . It should be appreciated that the designations “first”, “second”, “upper” and “lower” are arbitrary. A load transfer structure 56 is interposed between the upper and lower platforms 52 , 54 . The load transfer structure 56 may take various forms but supports and transfers loading (e.g. physiological loading) exerted on the upper platform 52 to the lower platform 54 . The lower platform 54 transfers the loading exerted thereon by the load transfer structure 56 to the substance of the area in which it is implanted (e.g. subchondral bone).
[0055] The load bearing implant device 50 is also shown with a fixation device 58 . The fixation device 58 is depicted in dashed lines to indicate the optional nature thereof. Thus, the fixation device 58 is not a necessary portion of the implant 50 . It is preferable, however, that the implant has some sort of fixation device. The fixation device 58 extends generally axially from the lower platform 54 and is utilized to aid in mounting the load bearing implant device 50 into the bone platform. The fixation device 58 may take various forms which are suitable for mounting the implant into bone (e.g., tibia 41 or condyle 43 ).
[0056] The upper and lower platforms 52 , 54 are axially spaced from one another by the load transfer structure 56 . An area 60 between the upper platform 52 and the lower platform 54 may be utilized to retain a scaffold, matrix or the like of a resorbable material that supports cartilage regeneration (e.g. a bio or artificial material). As such, the area 60 may be termed a scaffold or matrix retention area. The load bearing implant device 50 is designed such that the scaffold or matrix may be inserted before or after the device 50 has been implanted into the bone platform. Whether or not the scaffold or matrix is inserted before or after implantation may depend on the particular form of the load bearing implant device 50 . Particularly, a one-piece implant design may have the scaffold before implantation thereof, while a two-piece implant may receive the scaffold after implantation thereof.
[0057] The load bearing implant device 50 is comprised of a bio-resorbable (resorbable) material. The resorbable material is preferably a poly(ester)s such as poly(lactide), poly(glycolide), poly(caprolactone), poly(dioxanone) or any combination, co-polymer or blend thereof. Other types of resorbable material(s) may also be used.
[0058] The lower platform 54 is preferably, but not necessarily, rigid yet porous. Such porosity may be effected by a porous material or the incorporation of bores, holes, pores or the like. As such the lower platform 54 allows the body access to biologic elements (bone and marrow) from the subchondral bone of the bone platform when the implant device 50 is implanted. The upper plate 52 is preferably likewise rigid, but may or may not be porous.
[0059] The load transfer structure 56 may be rigidly attached to both the upper plate 52 and the bottom plate 54 such that the load bearing implant device 50 is generally of a unitary or single piece structure. Particularly, the load transfer structure 56 adjoins the lower surface 53 of the upper plate 52 and the upper surface 55 of the lower plate 54 . Alternatively, the load transfer structure 56 may be rigidly attached to the upper plate 52 and include a mechanism, structure or configuration that attaches or connects to the lower plate 54 via a mating mechanism, structure or configuration.
[0060] It should be appreciated that the attributes of the general load bearing implant device 50 as described above is applicable to the various particular embodiments of the load bearing implant device described hereinafter. Therefore, unless noted otherwise, the load bearing implant devices described hereinbelow, have and/or exhibit the same attributes as those described for the implant device 50 .
[0061] Referring now to FIGS. 3-6 , there is depicted an exemplary embodiment of a load bearing implant generally designated 62 in accordance with the present principles. Initially, it should be appreciated that the load bearing implant 62 is shown inverted 180° with respect to the load bearing implant device 50 of FIG. 3 . This is for ease of depicting the optional fixation device portion 70 thereof.
[0062] The load bearing implant device 62 includes a first plate, platform or the like 64 having a plurality of exposure pores, holes, bores or the like 65 . The plurality of exposure holes 65 (here six of which are shown) are arranged in an annular manner about the plate 64 . The number and/or arrangement of the exposure holes 65 is generally arbitrary, but may be arranged to control the exposure of the defect area and scaffold to the normal joint environment. The greater the hole area (hole size and hole number), the greater the exposure. The plate 64 also includes a center hole or bore 76 that aids in insertion of the device 62 into the bone platform. 76 is the load-transferring mechanism, which in this case is a ring-shaped structure.
[0063] The load bearing implant device 62 also includes a second plate, platform or the like 66 having a plurality of exposure pores, holes, bores or the like 67 . Again, the plurality of exposure holes 67 (here six of which are shown) are arranged in an annular manner about the plate 66 . The number and/or arrangement of the holes 67 is generally arbitrary, but may be arranged to control the exposure of the defect area and scaffold to the normal joint environment. The greater the hole area (hole size and hole number), the greater the exposure. The plate 66 also includes a center hole or bore 75 that aids in insertion of the device 62 into the bone platform. The center hole 75 is intended to be just another bore.
[0064] The fixation device 70 comprises a tubular body 71 that axially projects from the second plate 66 . The tubular body 71 has an axial bore 72 that is aligned coaxially with the center holes 75 and 77 of plates 66 and 64 respectively. A plurality of fins (anchors) 73 radially project from the tubular body 71 . The fins 73 are fashioned as triangles. The fins may be embodied as ribs, barbs or the like and aid in the retention of the tubular body 71 in a bore in a defect area in the bone platform (see FIG. 32 and accompanying description). Of course, the fixation device 70 , may takes other forms.
[0065] The load bearing implant device 62 of FIGS. 3-6 includes a load transfer structure 68 . The load transfer structure 68 is embodied as a plurality (e.g. four as shown) of arc shaped or arcuate walls, portions, sections or the like 76 . The arcuate walls 76 are situated about the center holes 75 and 77 of the plates 66 and 64 . In this embodiment, the load transfer structure 68 is rigidly attached to both the first and second plates 64 and 66 to comprise a one-piece load bearing implant device.
[0066] The load bearing implant device 62 also defines a cartilage scaffold/matrix retention area 74 between the platforms 64 and 66 . The retention area 74 receives and retains a cartilage scaffold/matrix such as is known in the art.
[0067] Referring now to FIGS. 7-9 , there is depicted an alternative embodiment of the present load bearing implant device generally designated 80 . The load bearing implant device 80 is preferably made of the same material(s) as previously discussed. The load bearing implant device 80 has an upper or first plate or platform 82 and a lower or second plate or platform 84 . The upper plate 82 includes a plurality of bores or holes 83 for defect area exposure in like manner to the load bearing implant device 62 . The plurality of exposure bores 83 are arcuately spaced about a center bore 86 . The lower plate includes a plurality of bores or holes 85 for defect area exposure in like manner as the upper plate 82 . The plurality of bores 85 are arcuately spaced about the center bore 87 . The number, size and/or arrangement of the bores 83 and 85 of the respective plates 82 and 84 may be modified as appropriate.
[0068] The load bearing implant device 80 also defines a cartilage scaffold/matrix retention area 90 between the platforms 82 and 84 . The retention area 90 receives and retains the cartilage scaffold/matrix.
[0069] The load bearing implant device 80 of FIGS. 7-9 also includes a load transfer structure 88 . The load transfer structure 88 is embodied as a plurality (e.g. six as shown) of columns, cylinders or the like 92 . The columns walls 92 are situated about the center holes 86 and 87 of the plates 82 and 84 . In this embodiment, the load transfer structure 88 is rigidly attached to both the first and second plates 82 and 84 to comprise a one-piece load bearing implant device. Placement of the load transfer columns 92 may vary as appropriate.
[0070] Referring now to FIGS. 10 and 11 , another alternative embodiment of a load bearing implant device is shown, generally designated 96 . The load bearing implant device 80 is preferably made of the same material(s) as previously discussed. The load bearing implant device 96 includes an upper plate 98 and a lower plate 100 . The upper plate 98 may or may not have exposure holes.. The lower plate 100 includes a plurality of exposure bores 101 that are arcuately arranged in the plate about a center bore 108 . The number, size and/or arrangement of the bores 101 of the plate 100 may be modified as appropriate.
[0071] The load bearing implant device 96 also defines a cartilage scaffold/matrix retention area 104 between the platforms 98 and 100 . The retention area 104 receives and retains the cartilage scaffold/matrix.
[0072] The load bearing implant device 80 of FIGS. 10 and 11 includes a load transfer structure 102 . The load transfer structure 102 is embodied as a plurality (e.g. three as shown) of rectangular walls, blocks or the like 106 . The rectangular walls 92 extend radially from the center hole 108 of the plate 100 . In this embodiment, the load transfer structure 102 is rigidly attached to both the first and second plates 98 and 100 to comprise a one-piece or unitary load bearing implant device.
[0073] Referring now to FIGS. 12 and 13 , an alternative embodiment or modification of an upper plate or platform is shown, generally designated 110 . The upper plate 110 is preferably, but not necessarily, made of a polymeric material such as that described above. The upper plate 110 may be used in any of the implant embodiments shown herein. Particularly, the upper plate 110 may be used in place of the upper plate of any of the load bearing implant devices shown and/or described herein, or may be attached to the upper plate of any of the load bearing implant devices shown and/or described herein.
[0074] The plate 110 is defined by a body 112 having a domed portion 114 surrounded by a rim 118 . The dome portion 114 defines a convex articulating surface 115 and thus a concave underside surface 117 . The configuration of the modified top 110 provides a condylar-shaped articulating surface. Preferably, but not necessarily, the plate 110 does not include exposure holes. In lieu of such exposure holes, the plate 110 may be porous or solid.
[0075] As indicated above, one form of the present load bearing implant device is a two-piece design rather than a single piece design. It should be appreciated, however, that the load bearing implant device may be fashioned from more than two pieces if appropriate.
[0076] Referring now to FIGS. 14 and 15 , an alternative embodiment of an upper platform structure is shown, generally designated 120 , for a two-piece load bearing implant device. The upper platform structure 120 is again preferably made of a polymeric material as described above.
[0077] The upper platform structure 120 includes a plate 122 having a plurality of exposure holes or bores 124 arcuately arranged about a center bore 123 . A load transfer structure 125 is integral with the plate 122 (i.e. a unitary structure). The load transfer structure 125 consists of a plurality (e.g., three as depicted) of rectangular blocks or walls 126 each having a mating structure 128 . Of course, the load transfer structure 125 may consist of columns, rings, wedges or the like. The rectangular blocks extend radially outward from the center hole 123 toward the periphery of the plate 122 . Each mating or attachment structure 128 includes first and second prongs 130 and 131 . Each prong extends axially upward then radially outward to define a hook shape. The hook shape provides mating of the prongs with a configured lower plate as shown in FIGS. 16-20 .
[0078] Referring now to FIGS. 16-20 , there is depicted an exemplary lower platform structure generally designated 132 that may be used with the upper plate structure 120 of FIGS. 14-15 . The upper and lower platform structures 120 and 132 provide a two-piece snap or press fit implant design. The lower plate structure 132 is defined by a platform or plate 134 having a plurality of exposure bores 136 . The plurality of exposure bores 136 are arcuately provided about a center bore 137 . Again, the size, number and/or arrangement of the exposure bores 136 are appropriate for the degree of exposure desired.
[0079] The plate 134 further defines a rim 141 having a tapered, beveled, or radiused edge 138 . Extending radially outwardly from the center bore 137 is a plurality of rectangular bores 139 each of which has a ledge, shelf, protrusion, tab or the like 140 that extends therein as part of a connection, attachment or mating structure. Each bore and ledge combination is configured to receive a prong 130 / 131 of each load transfer structure 126 . This provides a snap or press fit attachment or connection of the upper platform structure 120 with the lower platform structure 132 .
[0080] It should be appreciated that the upper platform structure 120 is shown with two prongs 130 / 131 on each load transfer structure 126 , while the receiving bores 139 of the lower plate structure 132 shows only one snap receiving structure 140 for clarity. In order to actually receive the upper platform structure onto the lower platform structure, there would either be only one prong on the load transfer structure of the upper platform structure, or there would be two receiving structures in the receiving bore.
[0081] The two-piece structure of the load bearing implant device defined by the upper platform structure 120 and the lower platform structure 132 allows for easier manufacture of the implant device. Moreover, once the lower platform structure 132 is implanted into the patient, the resorbable cartilage scaffold/matrix is situated thereon. The upper platform structure 120 is then situated onto the lower platform structure 120 . This gives the user the ability to select the type of resorbable scaffold/matrix material to be used with the load bearing implant device.
[0082] With the two-piece axial snap or press fit design of FIGS. 14-20 , almost all of the force that will be exerted onto the implant device will be axial loading. As such, there the upper platform structure 120 will resist separation from the lower platform structure.
[0083] Referring now to FIGS. 21-24 , there is depicted an alternative embodiment of a lower platform structure, generally designated 150 , that may be used with the upper platform structure of FIGS. 14-15 . The lower platform structure 150 provides a twist and lock configuration for receiving, attaching and retaining an upper platform structure. The lower platform structure 150 is preferably made of a resorbable polymeric material such as that described above. Moreover, the lower platform structure 150 is preferably a unitary piece.
[0084] The lower platform structure 150 is defined by a disk-shaped body, plate or the like 152 defining a first surface 153 and an opposite second surface 155 . The plate 152 further defines an annular rim or periphery 157 having an annular taper, bevel or angled portion 158 transitioning between the rim 157 and the angled portion 158 .
[0085] The plate 152 includes a plurality of exposure bores or holes 154 that are arranged about a center bore or hole 156 . As with previous plates, the size, number and arrangement of the exposure holes 154 and/or the center hole 156 , as well as whether to incorporate exposure holes or not, are subject to discretion depending on exposure factors. Additionally, the plate 152 has a plurality (e.g. three as shown) of configured bores 160 arranged about the center hole 156 and adjacent the exposure holes 154 . Each configured bore 160 is adapted to receive and retain a mating structure (e.g., mating structure 128 of FIG. 14 ) of the load transfer structure (e.g., load transfer structure 125 of FIG. 14 ) of the upper platform (e.g., upper platform structure 120 of FIG. 14 ).
[0086] Each configured bore 160 has a projection, ledge, shelf or the like 162 projecting into the interior of the bore. The ledge 162 defines a retention mechanism for a prong of the upper platform structure. Each prong would require a separate ledge. Thus, to receive the two-pronged load transfer structure of the upper platform structure of FIGS. 14-15 , each configured bore 160 would require two ledge structures. Once a prong is inserted into the configured bore, a twist thereof sets the ledge into under each prong. This motion, twist locks the upper plate platform into the lower plate platform.
[0087] In FIG. 25 , there is depicted another exemplary embodiment of an upper platform structure generally designated 170 . The upper platform structure 170 provides another example of one portion of a two-piece load bearing implant structure. Particularly, the upper platform structure 170 provides a structure that is retained onto a lower plate (see, e.g., plate 210 of FIGS. 27-31 ) in a press or snap fit manner.
[0088] The upper platform structure 170 is made of a polymeric material such as that described above and includes a plate 172 and a plurality of load transfer structures 176 that each axially extend from an upper surface 175 of the plate 172 . The plate 172 also includes a center bore 174 .
[0089] Each load transfer structure 176 is fashioned as a wedge having a mating structure 178 thereon. Each mating structure 178 is configured to be press fit received into a complementary lower platform structure or plate. Particularly, each mating structure 178 is here embodied as a truncated cone (cone section) 180 having two, diametrically opposed flanges 181 . While only two flanges 181 are shown, the cone section 180 may support more or less flanges 181 as deemed appropriate.
[0090] Referring now to FIG. 26 , there is shown another exemplary embodiment of an upper platform structure generally designated 190 . The upper platform structure 190 provides another example of one portion of a two-piece load bearing implant structure. Particularly, the upper platform structure 190 provides a structure that is retained onto a lower plate (see, e.g., plate 210 of FIGS. 27-31 ) in a press or snap fit manner.
[0091] The upper platform structure 190 is made of a polymeric material such as that described above and includes a plate 192 having a plurality of exposure bores 194 arranged about a center hole 196 . The plate 192 supports a plurality of load transfer structures 198 that each axially extend from an upper surface 195 of the plate 192 . Each load transfer structure 198 is configured as a column, tube or the like having a first conical section or annular taper 200 and a second conical section, cone or tapered head 202 . The cone 202 defines a skirt 203 that provides a manner of preventing the pulling out or reversal of the load transfer structure 198 when inserted into the corresponding lower platform structure. Cone 202 is intended to provide a mechanism for fixation into the subchondral bone.
[0092] Referring now to FIGS. 27-31 , there is depicted an exemplary lower platform structure, generally designated 210 , that can accommodate either one of the two exemplary upper platform structures 170 of FIG. 25 and 190 of FIG. 26 . The lower platform structure 210 is defined by a body 212 in the shape of a plate, platform or the like that is fashioned from a suitable resorbable polymeric material such as that described above. The plate 212 defines an annular rim or periphery 218 between a first surface 213 and a second surface 215 . Additionally, the plate 212 has an annular taper, bevel or angled surface 219 providing a transition between the rim 219 and the second surface 215 .
[0093] The plate 212 further includes a plurality of exposure holes 216 that are arranged about a center bore 214 . The size, number and/or arrangement of the exposure bores 216 are modifiable as necessary. Situated between each exposure bore 216 is a receiving, reception or mating bore 220 for a plurality of receiving bores 220 . As best seen in FIG. 31 , each receiving bore 220 is conical in shape and includes notches 221 . The notches 221 allow for the reception of the flanges 181 of the load transfer structures 180 of the upper platform structure 170 of FIG. 25 , and the reception of the skirt 203 of the upper platform structure 190 of FIG. 26 .
[0094] Referring lastly to FIG. 32 , there is depicted an exemplary illustration depicting a load bearing implant device 240 fashioned in accordance with the principles of the subject invention implanted into a defect area 230 of a bone platform 228 . A bore 236 has been formed in the subchondral bone 232 below the defect area in order to accommodate the fixation device 248 of the load bearing implant device 240 .
[0095] The first or lower plate 244 of the load bearing implant device 240 is situated proximate and/or adjacent the subchondral bone 232 where the cartilage 234 meets the subchondral bone 232 . The second or upper plate 242 of the load bearing implant device 240 is situated at the surface of the cartilage 234 . A scaffold or matrix 252 is situated in between the two plates 242 , 244 within the scaffold/matrix reception area of the load bearing implant device.
[0096] In each embodiment, load or pressure exerted onto the load bearing implant device structure (e.g., upper plate) at the articulating surface transfers the physiologic load to the load transfer structure. The load transfer structure then transfers the load to the device structure (e.g., lower plate) adjacent the defect area of the subchondral bone. This exerted pressure on the subchondral bone reduces the resorption of subchondral bone and/or the stimulation of subchondral bone synthesis. The load bearing implant device itself is resorbable, being preferably made of a resorbable polymeric material or materials. The subject invention also aids in the regeneration of cartilage tissue in load bearing regions with the ability to receive and retain a resorbable, cartilage regeneration scaffold or matrix (mesh, foam or the like). | An implant device for cartilage regeneration in loading-bearing regions uses the osteochondral defect model. The implant is formed of resorbable polymeric materials. The implant is designed such that load is transmitted from the articulating surface of the bone platform through the implant to the entire area of subchondral bone of the bone platform. Application of load in this manner results in reduced subchondral bone resorption, leading to joint stabilization and maintenance of normal joint biomechanics. The implant allows for the incorporation therein of a resorbable scaffold or matrix material. The present implant solves the current inability to regenerate cartilage in load-bearing articulating surfaces using engineered scaffold devices. | 0 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation of copending International Application No. PCT/EP01/14116, filed Dec. 3, 2001, which designated the United States and was not published in English.
BACKGROUND OF THE INVENTION
Field of the Invention
The invention relates to an apparatus for pressing shirts having a flexible inflatable body, a bottom part having a fan for inflating the inflatable body and on which the inflatable body is fastened by way of a bottom section, and a top part, which is disposed above the bottom part and on which the inflatable body is fastened by way of a top section and is connected to the bottom part by a load-bearing structure disposed within the inflatable body, the load-bearing structure being connected in a vertically displaceable manner to the bottom part.
Such an apparatus is known, for example, from German Published, Non-Prosecuted Patent Application DE 199 13 642 A1. This document describes an apparatus for drying and/or pressing damp laundry, in the case of which a collar-retaining device is firmly disposed above the inflatable body. Furthermore, a bottom part with further necessary components is disposed beneath the inflatable body, which has to be at least as high as the shirts that are to be pressed. This results in the appliance having a considerable overall height, which makes it difficult to accommodate.
SUMMARY OF THE INVENTION
It is accordingly an object of the invention to provide an apparatus for pressing shirts that overcomes the hereinaforementioned disadvantages of the heretofore-known devices of this general type and that achieves a more compact configuration to render the apparatus easier to accommodate.
With the foregoing and other objects in view, there is provided, in accordance with the invention, an apparatus for pressing shirts, including a flexible inflatable body having a bottom section and a top section, a bottom part having a fan communicating with the inflatable body for inflating the inflatable body, the inflatable body fastened to the bottom part at the bottom section, a load-bearing structure disposed within the inflatable body and connected in a vertically displaceable manner to the bottom part, a top part being disposed above the bottom part, the inflatable body fastened to the top part at the top section, the load-bearing structure connecting the top part to the bottom part, and the load-bearing structure being movably disposed to assume an extended position in which the load-bearing structure is extended out of the bottom part when the apparatus is in operation and a retracted position in which the load-bearing structure is retracted into the bottom part when the apparatus is not in operation.
By virtue of the inflatable body contributing largely to the overall height of the shirt-pressing apparatus, the invention makes it possible to achieve considerably more compact dimensions of the shirt-pressing apparatus outside the operating state. It is precisely in this state in which the apparatus has to be stowed away that small dimensions are necessary. In the operating state, in contrast, a large height does not prove disadvantageous because, in order to be used, the shirt-pressing apparatus has to be set up in unconfined conditions in any case. Within the inflatable body, it is possible to dispose further inner inflatable bodies, which are subjected, in particular, to relatively high pressure and can, likewise, be folded up when the top part is lowered. These inner inflatable bodies can be supported on the load-bearing structure to make possible for the inflatable-body enclosure to be forced specifically outward at certain locations. It is possible, here, for the connecting elements between the inner inflatable bodies and the load-bearing structure, for the purpose of absorbing the compressive forces, to be fastened in a displaceable manner on the load-bearing structure so that they can be pushed together when the load-bearing structure is lowered. The inner inflatable bodies may, thus, be provided with loops or rings that can be displaced along the load-bearing structure. Use may also be made, as load-bearing structure, of lowerable bars between which nettings or air-permeable fabric sections are tensioned, it being possible for the inner inflatable bodies to be supported against these and for their connections to the bars to be displaced along the latter. For example, the nettings or the air-permeable fabric sections may be fastened on the bars by straightforward loops or rings.
In accordance with another feature of the invention, there is provided a connecting device for transmitting at least one of tensile forces and compressive forces, the connecting device connecting the load-bearing structure to the inflatable body between regions in which the inflatable body is fastened to the bottom part and to the top part, the connecting device being displaceably connected along the load-bearing structure.
To insure that the operation of lowering a button-strip clamp is not obstructed, a connection between the load-bearing structure and the button-strip clamp is, advantageously, only disposed at the top end. As a result, the region of the inflatable body that is located therebetween can fold up during lowering of the load-bearing structure and/or of the button-strip clamp.
In accordance with a further-feature of the invention, the inflatable body has an inside and the connecting device is pulling strips fastened on the inside and delimit inflation of the inflatable body.
In accordance with an added feature of the invention, the connecting device is inflatable air cushions disposed in the inflatable body and forcing the inflatable body outward at given locations.
It is the case with the button-strip clamp envisaged that the inflatable body, which is tensioned during operation, butts at the rear against the rear side of the button-strip clamp. This may result, on the two sides of the button-strip clamp, in producing a spacing between the inflatable body and a tensioned shirt because both the shirt and the inflatable body are pulled taut and located between the shirt and the inflatable body is a part of the button-strip clamp against which the button strip or buttonhole strip is clamped for fixing purposes. Such a spacing results in the inflatable bag not fitting closely against those regions of the shirt that are located in the vicinity of the button-strip clamp, and this may impair the pressing result in these regions.
To prevent this, the rear side of the button-strip clamp is substantially curved and, at the borders, moves at a shallow angle toward the plane in which the button strip or the buttonhole strip of a shirt that is to be pressed is clamped firmly. It is, thus, possible for the inflatable body in the inflated state, at a very small spacing from the borders of the button-strip clamp, to fit closely from the rear against the shirt that is to be pressed. The regions of the shirt in the vicinity of the button strip or of the buttonhole strip are, thus, not exposed to any abrupt transitions. As a result, it is possible to achieve pressing of the shirt without folds.
In accordance with an additional feature of the invention, there is provided a button-strip clamp for fixing one of the button strip of a shirt and a buttonhole strip of the shirt, the button-strip clamp being fastened in a vertically displaceable manner on the bottom part.
In accordance with yet another feature of the invention, the button-strip clamp and the load-bearing structure are coupled to one another with respect to vertical displacement.
In accordance with yet a further feature of the invention, the button-strip clamp and the load-bearing structure are vertical displaceably coupled to one another.
In accordance with yet an added feature of the invention, the button-strip clamp has a top connected to the top part.
In accordance with yet an additional feature of the invention, the button-strip clamp has a rear side, the inflatable body with the load-bearing structure pushes upward in an inflated state of the inflatable body and butts against the rear side of the button-strip clamp in the pushed upward state, the button-strip clamp has clamping surfaces against which one of the button strip or the buttonhole strip are to be pressed for fixing the button strip or the buttonhole strip, the clamping surfaces define a plane and have lateral borders, and the rear side of the button-strip clamp is located in a vicinity of the plane of the clamping surfaces at least at the lateral borders.
In accordance with again another feature of the invention, the clamping surfaces have outer borders, the rear side of the button-strip clamp has borders, and the borders of the rear side of the button-strip clamp are connected to the outer borders of the clamping surfaces and enclose an acute angle with the outer borders of the clamping surfaces.
In accordance with a concomitant feature of the invention, the load-bearing structure has a plurality of supporting rods connected to one another and disposed substantially parallel to one another, only one of the supporting rods is mounted axially in the bottom part and is secured against tilting, and a remainder of the supporting rods are guided axially in the bottom part and are not secured against tilting.
Other features that are considered as characteristic for the invention are set forth in the appended claims.
Although the invention is illustrated and described herein as embodied in an apparatus for pressing shirts, it is, nevertheless, not intended to be limited to the details shown because various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims.
The construction and method of operation of the invention, however, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a vertical cross-sectional view from the front of an apparatus for pressing shirts according to the invention in an extended, operating state;
FIG. 2 is a vertical cross-sectional view from the front of the shirt-pressing apparatus of FIG. 1 in the pushed-together state;
FIG. 3 is a perspective and partially cut away view of a number of interior components of the shirt-pressing apparatus of FIG. 1; and
FIG. 4 is a fragmentary, horizontal, cross-sectional view through a button-strip clamp of the shirt-pressing apparatus according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the figures of the drawings in detail and first, particularly to FIG. 1 thereof, there is shown a shirt-pressing apparatus having a bottom part 3 with a shirt-form inflatable body 1 that is fastened thereon and serves for tensioning a shirt that is pulled thereover. Disposed for such a purpose in the bottom part 3 are a fan 6 , a heating device 7 , and an air channel 8 , by means of which a hot air stream can be produced. The air stream is divided up by the air channel 8 into two partial air streams, which are directed to a left-hand and a right-hand outlet opening of the bottom part 3 .
In each case one of the two supporting bodies 2 is connected to the two outlet openings, the supporting bodies being disposed in the interior of the inflatable body 1 and serving for forcing the trunk section of the inflatable body 1 outward at the sides in order, thus, to provide it with a flat cross-section. The supporting bodies 2 , like the inflatable body 1 , are produced from an air-permeable, flexible material, for example, synthetic-fiber fabric. The supporting bodies 2 extend substantially over the entire height of the trunk section of the inflatable body 1 .
Furthermore, a load-bearing framework 5 is fastened on the bottom part 3 such that it can be displaced vertically by bushings 9 . In the extended state, the load-bearing framework 5 extends beyond the height of the supporting bodies 2 in the inflated state.
Fastened on the load-bearing framework 5 is a top part 4 , on which the inflatable body 1 is fastened at the top and which serves for fixing and clamping the collar of a shirt fitted onto the inflatable body. Disposed for such a purpose on the top part 4 are two clamping flaps 10 , by which the two ends of a turned-up collar can be fixed. The top part 4 also has a not illustrated device that is disposed at the rear and is intended for tensioning in the circumferential direction a shirt collar that is fixed at its ends.
The interior structure for retaining and supporting the inflatable body 1 is illustrated in perspective, with further details, in FIG. 3 . The load-bearing framework 5 includes four supporting tubes 11 , which are mounted in a vertically disposable manner within the bushings 9 in the bottom part. In each case, one supporting netting 12 is tensioned between the two supporting tubes 11 disposed on the left (with respect to FIG. 3) and the two supporting tubes 11 disposed on the right. The supporting nettings 12 are fastened on the supporting tubes 11 on the sides by loops, it being possible for the loops to slide along the supporting tubes 11 . The supporting nettings 12 serve for supporting the supporting bodies 2 so that the supporting bodies 2 , in the inflated state, can subject the sides of the trunk section of the inflatable body 1 to an outwardly directed pressure from the inside. The supporting bodies 2 have a bottom section fastened on the outlet openings of the bottom part 3 and a top section fastened at the top end of the load-bearing framework 5 . The supporting nettings 12 are fastened on the bottom part 3 at the bottom and at the top end of the load-bearing framework 5 at the top.
Furthermore, the bottom part 3 has a button-strip clamp 13 , which is mounted in a vertically adjustable manner substantially in the center of the front border of the bottom part 3 . The button-strip clamp 13 , which is illustrated in cross-section in FIG. 4, serves for fixing the button strip or the buttonhole strip of a shirt 19 fitted onto the inflatable body so that the shirt 19 can be tensioned by the inflatable body 1 . The button-strip clamp 13 has an oval supporting tube 18 and a supporting bar 17 , between which is disposed an air-permeable clamping body 14 , which may be produced, for example, from a perforated sheet. If the rest of the parts, in particular, the supporting bar 17 and the clamping body 14 , are sufficiently stable, it is possible to dispense with the oval supporting tube 18 . The clamping body 14 is in the form of a shallow trapezoid, of which the base surface is located on the side that is directed away from the inflatable body 1 and the side surfaces slope upward at a shallow angle.
Articulated on the borders of the supporting bar 17 in each case are flaps 15 , which are subdivided into a plurality of sections over the height of the button-strip clamp 13 . The flaps 15 each have fillings 16 made of a flexible and, if appropriate, air-permeable material. The fillings 16 may be provided with a non-slip coating on the surface on which the fabric of the shirt 19 ends up resting when the button strip or buttonhole strip is clamped firmly. This coating may have, for example, short bristles that are inclined inward, in the direction of the supporting bar 17 to make possible a retaining of the fabric of the shirt 19 counter to the outwardly directed pull when the inflatable body 1 is inflated. Each of the flaps 15 is assigned a respective spring element. The spring elements ensure that the flaps 15 are pressed against the clamping body 14 up to a certain point and, above the point, are retained in an open position, away from the clamping body. The individual spring elements may be individual links of a single spring plate. It is, thus, easily possible to use one part to create a plurality of spring elements that act independently of one another.
For pressing purposes, the shirt 19 is fitted, in particular, in a damp state, onto the inflatable body 1 , with the load-bearing framework 5 extended. In such a case, in the first instance, the flaps 15 of the button-strip clamp 13 and the correspondingly configured flaps 10 of the top part 4 are opened. The button strip or the buttonhole strip and the collar tips are positioned beneath the flaps 15 and 10 , respectively, and are fixed by virtue of the flaps 15 and 10 being closed. The shirt collar, for pressing purposes, is tensioned in the circumferential direction by actuation of the collar-tensioning and collar-clamping device in the top part 4 . The fan 6 is, then, set in operation, together with the heating device 7 , whereupon heated air is directed into the supporting body 2 . From the supporting bodies 2 , the air flows, through the air-permeable enclosures of the same, into the inflatable body 1 , inflates the latter, and, then, flows through the, likewise, air-permeable enclosure of the latter, to the shirt 19 that has been fitted thereon, and is pressed by the action of tensioning and heat. In the stationary state, the pressure prevailing in the supporting bodies 2 is higher than that in the inflatable body 1 , for example, a level of 6 mbar in the supporting bodies 2 in relation to a pressure of 3 mbar in the inflatable body 1 . The supporting bodies 2 are supported in the inward direction against the supporting nettings 12 and force the trunk section of the inflatable body 1 outward at the sides.
A shirt 19 fitted onto the inflatable body in a damp state is tensioned by the inflated inflatable body 1 , dried in the process, and, thus, pressed. In such a case, the inflatable body 1 positions itself against the button-strip clamp 13 from the rear, it being possible for the air to flow through the air-permeable clamping body 14 to the fixed button strip or buttonhole strip to dry the same. On account of the inclined side surfaces of the clamping body 14 , the inflatable body 1 , from a very small spacing from the clamping body 14 , butts against the shirt 19 from the rear. The regions of the shirt 19 in the vicinity of the button strip or of the buttonhole strip are, thus, retained without creases. As a result, no folds are produced by the fixing device during pressing.
Following operation, it is advantageous, for the purpose of accommodating the shirt-pressing apparatus, if the latter has small dimensions. For such a purpose, as is illustrated in FIG. 2, the load-bearing framework 5 is pushed downward, the supporting tubes 11 being pushed, through the bushings 9 , into the bottom part 3 . At the same time, the button-strip clamp 13 is also pushed into the bottom part 3 . Because both the inflatable body 1 and the supporting bodies 2 and supporting nettings 12 are only fastened at two points at the bottom and top, these are folded up above the bottom part 3 when the load-bearing structure 5 is lowered. In such a state, the inflatable body 1 , the supporting bodies 2 , and the supporting nettings 12 only take up a fraction of the space that they take up in the extended state.
In a development, it is possible for just one of the supporting rods 11 to be mounted axially in the bottom part 3 such that they are secured against tilting, and for the rest of the supporting rods 11 merely to be guided in the bottom part 3 . For such a purpose, for example, the one supporting rod 11 may be mounted in two pairs of rollers that are disposed one above the other and, in such a case, in each case at least one roller has a constriction or indent to make possible a securing of the supporting rod against tilting in all directions. The rest of the supporting rods 11 , in this configuration, may be guided in simple openings in the bottom part 3 . It is, thus, possible to achieve the situation where skewing of two or more supporting rods 11 does not result in the entire load-bearing structure 5 skewing during the extending and pushing-in operations. The guidance is, thus, improved to a considerable extent. In this configuration, provision may be made for the front supporting tubes, which are disposed on both sides of the button-strip clamp 13 , to be connected to one another by a cross member, beneath the axial mount or guide, within the bottom part 3 , in order to achieve additional stabilization. Above the guide or the mount, all the supporting rods 11 are connected to one another, in particular, at their top end. It is also possible for the button-strip clamp 13 to be fastened on this cross member and, thus, to be coupled to the load-bearing structure 5 in respect of vertical displacement.
It may be possible for the load-bearing structure 5 to be arrested in the extended state and/or in the pushed-in state. To make it easier for the load-bearing framework 5 to be extended, it is also possible to provide a spring element that forces the load-bearing framework 5 upward counter to its weight. For example, it is possible to provide a roller spring that, advantageously, has a largely linear force profile. To simplify handling, the arresting mechanism may be configured to lock the load-bearing framework 5 at the bottom when first lowered and to unlock it again when forced in again. In such a case, the spring is, advantageously, configured such that, without any external action, it can move the load-bearing structure 5 slowly upward.
In a development, it is also conceivable for the spring to be configured such that the load-bearing framework 5 descends slowly downward without any external force action and the operation of extending the load-bearing framework 5 is brought about by virtue of the fan 6 being switched on, the supporting bodies 2 producing the necessary upwardly directed force during the inflating operation. Once at the top, the load-bearing framework 5 can lock itself, with the result that an operator, following use of the shirt-pressing apparatus, need only unlock the load-bearing structure to allow the latter to descend slowly downward.
The load-bearing structure 5 may be connected to a damping device with speed-dependent damping. As a result, the extending and/or pushing-in operations are damped. The damping device used may be, for example, a negative-pressure braking cylinder.
Furthermore, possible measures for supporting and/or moving the load-bearing structure 5 are manual drives, for example, a crank, motor drives, damped springs, or pneumatic springs. Provision may further be made for the locking and/or unlocking to be brought about by a turning action. | A shirt-smoothing device includes a lower part and an inflatable body fixed thereon. Because the inflatable body must be at least the same size as the shirt to be smoothed, the device has considerable height, however, the rigid components in the area of the inflatable body are lowerable to handle the device more easily and, more particularly, to stow it away easily. An internally disposed supporting frame and a button strip tensioner disposed in front of the inflatable body can be lowered after use into the lower part, whereby the inflatable body, which is exclusively connected to the supporting frame at the top becomes folded. The same applies to flexible inflatable support bodied and support nets disposed between the inflatable body and the supporting frame. The storage space required for the shirt smoothing device can be substantially reduced by the invention and the handling and storage thereof simplified. | 3 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a utility application that claims the benefit of and priority to U.S. Provisional Patent Application 61/145,196, filed Jan. 16, 2009, which is incorporated by reference herein in its entirety.
BACKGROUND
1. Technical Field
The disclosure generally relates to sports equipment.
2. Description of the Related Art
Many games of skill are known that involve the tossing or throwing of an object at a target. Horseshoes is a well known example that involves a horseshoe being tossed at a driven stake. Other games, such a bocce ball, involve throwing a ball at a target (e.g., another ball). Typically, a high score in such a game is related to how close the tossed horseshoe or ball lands to the target.
SUMMARY
Cups and games of skill involving such cups are provided. In this regard, an exemplary embodiment of a cup comprises: an aperture communicating with a cavity; and a barrier extending partially about the periphery of the aperture such that a portion of the cup lacking the barrier forms a lateral entrance to the cavity, the barrier having an upwardly and outwardly sloping first portion and a downwardly and outwardly sloping second portion, the first portion being located between the second portion and the aperture.
An exemplary embodiment of a game comprises: a cup having an aperture communicating with a cavity and a barrier extending partially about the periphery of the aperture; and a projectile sized to fit within the cavity via the aperture; the cup being configured such that, as a base of the barrier is in contact with an upper surface of soil, the cavity extends below the upper surface of the soil to form a hole into which the projectile is directed.
Other systems, methods, features and/or advantages of this disclosure will be or may become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features and/or advantages be included within this description and be within the scope of the present disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
Many aspects of the disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
FIG. 1 is a schematic diagram depicting an exemplary embodiment of a game including two cups and a projectile.
FIG. 2 is a side view of an exemplary embodiment of a cup.
FIG. 3 is a plan view of the cup of FIG. 2 .
FIG. 4 is a perspective view depicting the top of another exemplary embodiment of a cup.
FIG. 5 is a perspective view depicting the bottom of the embodiment of FIG. 4 .
DETAILED DESCRIPTION
FIG. 1 is a schematic diagram depicting an exemplary embodiment of a game 10 including two cups 12 , 14 and at least one projectile (e.g., projectile 16 ). In this regard, the cups can be used to play a game similar in some respects to the game of Horseshoes. Specifically, cups 12 , 14 are spaced from each other by some distance—say, 21 feet. A member of one team stands near one cup and a member of the other team stands near the other cup. Each team member then tries to get his projectile into the others' cup. This can be done by throwing, rolling, bouncing, etc. Scoring can be based, for example, on whether or not the projectile ends up in the cavity of the corresponding cup.
FIG. 2 is a side view of an exemplary embodiment of a cup and FIG. 3 is a plan view of that cup. As shown, cup 20 includes an aperture 22 (e.g., a circular aperture) that communicates with a cavity 24 . The cavity is defined by a wall 26 , which is cylindrical in this embodiment, although various other shapes can be used. In this embodiment, the width (W 1 ) of the cavity is approximately 5 inches, and the depth (D) is approximately 5 inches (e.g., a depth that exceeds a diameter of the projectile). This embodiment also includes a bottom wall 28 although, in other embodiments, a bottom wall can be omitted.
A barrier 30 extends partially about the periphery of the aperture so that a lateral entrance 32 to the cavity is formed. In this embodiment, the barrier exhibits a height (H) of approximately 2½ inches. The barrier includes a base 33 , an upwardly and outwardly sloping first portion 34 and a downwardly and outwardly sloping second portion 36 . Note that, in this embodiment, the bottom wall 28 extends below the base 33 .
An included angle (B) between the first portion of the barrier and the base is between approximately 5 and approximately 45 degrees, and an included angle (A) between the second portion of the barrier and the base is between approximately 5 and approximately 45 degrees. Preferably, the included angles (A and B) are approximately 30 degrees.
The first and second portions 34 , 36 are frusto-conical segments, with the first portion 34 having a focal point (f 1 ) located on the same side of the aperture as the cavity (e.g., within the cavity), and the second portion 36 having a focal point (f 2 ) outside the cavity (e.g., on the opposite side of the aperture). Notably, the first portion is located between the second portion and the aperture.
A lip 38 is positioned between the first portion of the barrier and the aperture. In this embodiment, the aperture is positioned within a plane and the lip is oriented substantially perpendicular with respect to the plane. The lip in this embodiment exhibits a width (W 2 ) of approximately 1.5 inches. In some embodiments, a lip may not be included, while in others, a lip extending about only a portion of the aperture may be included. For instance, a lip may be positioned between the barrier and the aperture, but may be omitted between at locations corresponding to a lateral entrance.
A distal surface 40 is positioned between the first portion of the barrier and the second portion of the barrier. In this embodiment, the distal surface is an annular segment that oriented substantially parallel to the lip and exhibits a width (W 3 ) of approximately 1.5 inches. In other embodiments, distal surface distinct from the first and second portions of the barrier wall may be omitted.
With reference to FIG. 3 , the barrier includes ends ( 42 , 44 ) that are spaced from each other to form lateral entrance 32 . An included angle (C) between the ends is approximately 120 degrees in this embodiment although, in other embodiments, different angles can be used, such as between approximately 45 and approximately 180 degrees. Optional end walls 46 , 48 extending between the first and second portions can be used. It should also be noted that inner sides of the end walls can be positioned at various locations with respect to the aperture. In some embodiments, the walls may be set farther back than depicted in FIG. 3 (e.g., inner diameter edges of the end walls may be rear of a centerline of the aperture) to more effectively redirect the projectile toward the aperture.
It should also be noted that end walls may be oriented and/or configured in various manners. By way of example, the end walls may be inclined from bottom to top. Additionally or alternatively, the end walls may be inclined from respective outer diameter edges to respective inner diameter edges. The end walls, much like others of the surfaces, also may be curved.
Preferably, a cup is made of suitably rigid and weather resistant materials (e.g., injection molded plastic) to accommodate outdoor use. For instance, cups can be used at the beach, at which a cup can be pushed into the sand until the corresponding cavity is below the surface, with the aperture (and corresponding lip (if included)) being located at surface level ( FIG. 1 ).
FIGS. 4 and 5 are perspective views depicting the top and bottom, respectively, of another exemplary embodiment of a cup. As shown, cup 120 includes an aperture 122 that communicates with a cavity 124 . Side wall 126 and bottom wall 128 define cavity 124 .
A barrier 130 extends partially about the periphery of aperture 122 to form a lateral entrance 132 . Barrier 130 includes a first portion 134 and a second portion 136 , with the first portion being located between the second portion and the aperture. End walls 146 , 148 of the barrier form the lateral entrance 132 .
An annular lip 138 is positioned between the first portion 134 of the barrier and the aperture 122 . Additionally, a distal surface 140 is positioned between the first portion of the barrier and the second portion of the barrier.
As shown in FIG. 5 , this embodiment is a relatively thin-walled structure that incorporates structural ribs (e.g., rib 142 ). The ribs extend between the underside surfaces of the first and second portions of the barrier. Clearly, other forms of support (such as those that do not incorporate the use of ribs) can be used in other embodiments.
It should be emphasized that the above-described embodiments are merely possible examples of implementations set forth for a clear understanding of the principles of this disclosure. Many variations and modifications may be made to the above-described embodiments without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the accompanying claims. | Cups and games of skill involving such cups are provided. A representative cup includes: an aperture communicating with a cavity; and a barrier extending partially about the periphery of the aperture such that a portion of the cup lacking the barrier forms a lateral entrance to the cavity, the barrier having an upwardly and outwardly sloping first portion and a downwardly and outwardly sloping second portion, the first portion being located between the second portion and the aperture. | 0 |
BACKGROUND OF THE INVENTION
The span lengths of a traditional short span bridge is limited by the length of the bridge's beams and/or girders. For an existing bridge, when a length extension of a span is needed, the traditional solution is to replace the existing span or bridge with a new, longer span or bridge. This invention, instead, could provide longer spans by relocating traditional substructure supports from the traditional beam support locations to the desired longitudinally offset locations. Therefore, the same beams/girders provide a longer bridge span with shorter beam/girder lengths or smaller member sections. This invention increases the bridge span length, opening between substructures, or lateral underclearance of either a new or existing bridge (or span) by constructing this “longitudinally offset bridge substructure support system” while saving in construction cost as well as construction time.
When a facility underneath a grade separation overpass bridge or similar structures must be expanded or widened, it is always difficult and expensive using traditional methods to rebuild the structure with longer beams or girders. The underneath existing supporting substructures (piers or abutments) limit the expansion/widening of the facility.
SUMMARY OF THE INVENTION
This invention is to resolve the above-discussed problems. To construct a bridge using this invention, the offset support substructures (configured with any acceptable construction material) and their corresponding foundations are constructed at desired longitudinal offset locations away from conventional beam support pier/abutment locations. This invention provides the extra lateral underclearance, opening, or span length between bridge substructures to meet the needs of the facility below the span. In addition, a link-support system is necessary to support the bridge beams (with shorter lengths and/or weaker sections than traditionally designed beams) at an offset distance to the offset support. This invention can be used for new-construction, retrofitting, or rehabilitation of bridge structures. This invention can also utilize any applicable construction materials, such as: structural steel, CIP or pre-cast concrete, pre- or post-tensioned pre-stressed concrete, fiber reinforced polymer (FRP) composites, etc.
The procedure to construct “longitudinally offset bridge substructure support system” varies, depending on site conditions and/or other requirements. One approach, with various types of construction materials, such as: structural steel, pre-tensioned/post-tensioned pre-stressed concrete, FRP composites, or a combination, etc., the pier cap beam or similar configurations can be constructed either “below” (if there is sufficient vertical clearance) or “integrally” within the bridge superstructure. If the pier cap is an integral cap, the depth of the cap beam is about the same as that of the bridge beam or girder at the cap location; therefore, the cap beam does not reduce or limit the bridge's vertical underclearance. At the least, one substructure support, such as a super-column (concrete, steel or any applicable construction material), on each side of the bridge superstructure needs to be constructed as the “offset supports” at desirable locations offset longitudinally (or offset both ways: longitudinally & transversely). The support super-columns could be either vertical or slanted to reduce bending. This offset support combines a “link-support system”, of cable, tension tie-rods, framing, cantilever, or a combination, etc. of any construction material, to support the cap beam from the offset supports, which in term supports the bridge's superstructure. If the offset distance is large, it is possible to use tie-downs and/or counter-weights (an adjacent substructure could be used as counter-weights) to reduce the large cantilever force applying to the offset support of super-column and its foundation.
Another way to construct the longitudinally offset substructure support is to construct the “offset supports” at the desired locations in the forms of walls, columns, beam/column framing, or a combination, etc. At the traditional beam support location, where the traditional substructure is eliminated, construct beam-to-beam connections to provide continuity of the bridge span for the case of simple spans, or strengthen/modify the continuous span beams. At the other traditional beam-end location(s), construct tie-downs and/or counter weights to counteract the extra cantilever or negative moment forces as required.
BRIEF DESCRIPTION OF THE DRAWINGS
The following drawings with reference numbers and exemplary embodiments are referred for explanation purposes:
FIG. 1 illustrates the elevation view of a new bridge constructed using this invention;
FIG. 2A shows the elevation view of a multi-span bridge constructed by using traditional method;
FIG. 2B illustrates the existing bridge of FIG. 2A modified using this invention, that the underpass four-lane road is widened into a six-lane road;
FIG. 3A shows the elevation view of a single span bridge constructed using traditional method;
FIG. 3B illustrates the existing bridge of FIG. 3A modified using this invention, that the underpass four-lane road is widened into a six-lane road;
FIG. 4 illustrates elevation view of another embodiment of a link-support system where a steel frame instead of cable being used;
FIG. 5A illustrates the elevation view of a link-support system where a cantilever instead of cable being used;
FIG. 5B illustrates the section view of the link-support system of FIG. 5A ;
FIG. 6 illustrates the elevation view of the link-support system where multi cables being used;
FIG. 7A shows an elevation view of a bridge span constructed by using traditional method;
FIG. 7B illustrates the existing bridge span of FIG. 7A modified using this invention. It shows another way to construct the offset support system. For this example, bridge beam connections, tie-downs & counter weights are provided as required.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1 , a new bridge is implemented with this invention having one super-column ( 102 ) on each side of the bridge as the longitudinally offset substructure supports. The super-columns, which offset longitudinally from beam-end (or beam support) locations, in this case are located at the center of the bridge. The link-support system is made up of cables ( 104 , 106 ) anchored at top of super-columns and extended down to support the integral cap beams. One end of each cable is anchored to support one end of each cap beam ( 108 , 110 ), and the other end of each cable is anchored near the top of the super-columns so that the cables can support at offset distances the cap beams that support the weight of the bridge's spans. Without using this arrangement of using the super-column, cable, and integral cap beam as the longitudinal offset substructure support components, this bridge requires more supporting piers underneath, which will take up more space, reduce the span lengths or opening between substructures, and limit the lateral underclearance that can be used below the bridge.
Overall, when using this invention to construct a new bridge or modify an existing bridge, it can be described in following detail steps: First, for the pier (or other substructure), one can build the longitudinally offset supports with their foundations at desired locations of the bridge. Second, one can provide temporary supports for the bridge's superstructure and construct new integral cap beams. If post-tensioned, pre-stressed concrete is used for the cap beams, one must wait for the concrete to reach design strength before applying the post-tensioning. Third, one can install the link-support system composed of cables, tension tie-rods, steel or concrete frames, or a combination, etc. to support the superstructure at offset distance from the offset support. Lastly, one can remove the temporary supports. Referring back to FIG. 1 , compared to a traditional pier (or substructure) supporting system, this invention provides extra wide openings between the center “offset support” super-columns and the adjacent piers.
The new bridge construction example shown in FIG. 1 uses pre-cast, pre-stressed concrete beams at near-limit transportation lengths. The set of pre-stressed concrete bridge beams in the middle and centered at super-columns, are supported by the integral cap beams at both ends. This set of bridge beams provide bearing notches as seats for the adjacent sets of pre-stressed concrete bridge beams to bear on and/or tied to the integral cap beams. Besides, to achieve “wider than extra wide” openings for the two center spans, one can use two sets of pre-stressed concrete bridge beams end-to-end in the middle, one set each on each side of the super-column. In addition, it requires a structural support component, between the two mid super-columns, to support the beam ends where the two sets of pre-stressed concrete beam ends meet, in the middle at super-column location.
FIG. 2A shows a grade separation overpass bridge ( 212 ) crossing over a four-lane road. The drawing shows the elevation view of a three span continuous multi-beam bridge. This bridge has two piers ( 214 , 216 ). The road below has outside shoulders ( 218 , 220 ). When it is necessary to widen the road, it is expensive and difficult to achieve the goal using traditional methods.
However, FIG. 2B illustrates how this invention can achieve the goal of widening the underpass road below the existing bridge of FIG. 2A . First, one must construct the pier offset support super-columns ( 222 , 224 ) at the desired locations that provide sufficient space for the underpass road widening. Next, integral cap beams ( 228 , 230 ) must be constructed above the existing piers. Finally, the link-support system cables ( 232 ) must be installed by anchoring one end of each cable near the top of the super-columns ( 222 , 224 ), extending down the cables and anchoring the other ends of the cables: some to the exterior sides of super-columns to abutments ( 226 ) and the others to the interior mid-span side to cap beams ( 228 , 230 ). Once these cables are properly anchored, the existing piers, as temporary supports during construction, can be demolished. By eliminating existing piers underneath the superstructure, the existing 4-lane road has sufficient space to be widened into a six-lane road with full-width shoulders.
Here is a more detailed description of the above example. First, the longitudinally offset supports of super-columns ( 222 , 224 ) and their foundations must be constructed at the desirable locations by using the existing piers as temporary supports. Second, one must construct the integral cap beams ( 228 , 230 ). If post-tensioned, pre-stressed concrete would be used for the cap beam, one must wait for the concrete to reach design strength before applying the post-tensioning. Third, the link-support system must be installed as follows: cables ( 232 ) must be installed to support the cap beams from the offset support super-columns. Lastly, the existing pier structures can be demolished. This invention provides “extra lanes with full shoulders” for roadway below the bridge, thus avoiding replacing the bridge spans or even the entire bridge structure, and saving construction cost, construction time, and ultimately reducing traffic interruptions.
FIG. 3A shows another example of a grade separation overpass bridge crossing over a four-lane road. The drawing shows the elevation view of a single span multi-beam bridge. To widen the existing road below the bridge, it is necessary to extend the span, as well as the total length of the bridge. Using the traditional method, this procedure requires total replacement of the entire bridge (both super and sub-structures). FIG. 3B illustrates the elevation view of the rebuilt bridge implemented with this invention. First, the longitudinally offset supports of new abutments with super-columns ( 332 , 334 ) must be constructed, and their foundations placed at desirable locations behind the existing abutments, where the existing abutments ( 346 , 348 ) may act as temporary supports. (For maintaining the traffic on the overpass, provide temporary spans over the new abutment construction areas.) Second, the integral cap beams ( 350 ) must be constructed. If post-tensioned pre-stressed concrete is the choice for the cap beams, one must wait for the concrete to reach design strength before applying post-tensioning. Third, the sets of extension beams ( 336 , 338 ) are installed spanning between: the existing beam ends above existing abutments and the new abutments. This increases the total span/bridge length. Near the tops of the new abutment super-columns ( 332 , 334 ), one must install the sets of cables ( 338 , 342 ) and extend to the new abutment foundations as counter-weights; and one must install the other sets of cables ( 340 , 344 ) and extend to support the new cap beams. Lastly, the existing abutment structures ( 346 , 348 ) can be demolished, and the road can be widened below the bridge to accommodate additional traffic lanes with full shoulders.
FIG. 4 illustrates another configuration of a link-support system of this invention. Instead of using cables to support the new cap beam ( 450 ), a steel frame ( 446 , 448 , 452 ) or any similar framing system built by any material with satisfying specifications can be used.
FIG. 5A illustrates another configuration of a link-support system of this invention. Instead of using cables to support the new cap beam ( 562 ), a concrete cantilever ( 558 ) or any similar cantilever system built by any material with satisfying specifications can be used. FIG. 5B , illustrates the cross section view of FIG. 5A example. As shown in FIG. 5A , the cantilever ( 558 ) is an extended part from the offset support of super-column ( 556 ), where the new cap beams ( 562 ) are seated. FIG. 5B section view shows how the cap beam ( 562 ) can be extended and seated on top of the cantilever ( 558 ).
FIG. 6 illustrates another configuration of a link-support system of this invention. Instead of using one new cap beam, one can use one cap beam ( 676 , 678 ) on each set of the beam-ends of bridge span, where the two sets of beams of bridge span meet and where the traditional pier support is removed and replaced with offset support at a desired offset location. This link-support system uses multi-cables ( 672 , 674 ) to support individual cap beams ( 676 , 678 ). Beam-to-beam connections could be installed to provide a better continuity of the span. This multi-cable link support system could be substituted with any similar multi-cable system built by any material with satisfying specifications.
FIG. 7A illustrates an example, which shows one span of a multi-span traditional bridge with two supporting piers ( 780 , 782 ) one at each end of beam of the span. FIG. 7B shows the pier ( 782 ) is necessary to be demolished for providing additional space for the adjacent span under the bridge. A longitudinally offset support substructure ( 790 ) is constructed at a desired offset location closer to pier ( 780 ) than the original configuration. The offset support could be a concrete wall, a concrete frame, a steel frame, a combination, etc. or any form or any construction material with sufficient strength and that meets the construction specifications. The new configuration changes the action of the existing bridge beams in the span. It creates a cantilever (or large negative moment and shear forces, for the case of continuous beam/girder) for the beam ( 792 ) over the new offset support ( 790 ). Therefore it is likely these beams ( 792 ) need to be modified or strengthened. At the original pier ( 782 ) location, the support for the adjacent span is demolished. Consequently, connections ( 788 ) tying the ends of cantilever ( 792 ) with the adjacent set of bridge span beams are necessary to provide the continuity (except for the case with continuous beam/girder). Furthermore, the extra load over the new substructure ( 790 ), from the adjacent set of bridge span beams for the case of cantilever or increased span length for the case with continuous beam/girder, may create an uplift load at the other beam end of the bridge span above pier ( 780 ). Tie-downs ( 786 ) and/or counter-weights ( 784 ) are constructed to counter-act the uplift as required | This invention provides a novel construction method to longitudinally offset a traditional bridge substructure to a desired location by utilizing unconventional link-support or alternative support systems. This invention describes an approach to achieve longer span length, wider opening and/or greater lateral underclearance for the needed facility below a bridge span that no other traditional bridge construction methods could provide. | 4 |
BACKGROUND
1. Technical Field
The present disclosure is related to the field of network traffic management. More specifically, the present disclosure is related to load placement in data center networks.
2. Description of Related Art
As the value and use of information continues to increase, individuals and businesses seek additional ways to process and store information. One option available to users is information handling systems. An information handling system generally processes, compiles, stores, and/or communicates information or data for business, personal, or other purposes thereby allowing users to take advantage of the value of the information. Because technology and information handling needs and requirements vary between different users or applications, information handling systems may also vary regarding what information is handled, how the information is handled, how much information is processed, stored, or communicated, and how quickly and efficiently the information may be processed, stored, or communicated. The variations in information handling systems allow for information handling systems to be general or configured for a specific user or specific use similar to financial transaction processing, airline reservations, enterprise data storage, or global communications. In addition, information handling systems may include a variety of hardware and software components that may be configured to process, store, and communicate information and may include one or more computer systems, data storage systems, and networking systems.
Traditional data center networks include a top of rack (TOR) switch layer, an aggregation switch layer, and a backbone switch layer. In data center networks for data packet routing, data flow is established and forwarded using static hash functions when there exists more than one path to the destination from a switch. Static hash functions do not consider the current load on specific links in allocating the flow through the link. Moreover, static hash functions may be biased as they merely perform regular hash operations on fixed header fields. As a result of such biasing, traffic load through the network links may be highly polarized. Thus, while some links may bear the burden of a high traffic load, other links at the same layer level may have little or no traffic flowing through. This leads to imbalance and inefficiencies in the data center network traffic management.
In state-of-the-art data center networks a node failure or a link failure typically is resolved by re-routing traffic at a point close to, or directly on, the point of failure. Furthermore, in state-of-the-art data center networks a node failure or a link failure is resolved after a failure notification is sent to a controller or manager, at which point the controller or manager makes the re-routing decision. This failure recovery process is time consuming and results in inefficient re-routing architectures and results in time periods where the traffic is black-holed.
What is needed is a system and a method for load placement in a data center that uses current traffic information through the links in the system. Also needed is a system and a method to engineer data traffic in order to avoid congested links in a data center network. Further needed is a system and a method for resolving node failure and link failure in a data center network.
SUMMARY
According to embodiments disclosed herein, a system for operating a plurality of information handling systems forming a network may include a plurality of switches; an open flow controller coupled to each of the plurality of switches; a plurality of links, each link configured to transmit data packets between two switches from the plurality of switches; wherein: the open flow controller is configured to determine a traffic flow across each of the plurality of links; and each one of the plurality of switches is configured to re-route a data packet when the traffic flow in a link associated to the switch exceeds a threshold.
A computer program product in embodiments disclosed herein may include a non-transitory computer readable medium having computer readable and executable code for instructing a processor in a management unit for a plurality of information handling systems forming a network to perform a method, the method including performing a discovery of the network topology; receiving a load report for a link between information handling systems in the network; determining a flow rate for a link in the network; and computing a label switch path.
A network managing device according to embodiments disclosed herein is configured to be coupled to a service provider having resources, and to be coupled to a storage component and a computational component to provide a service to a plurality of users through a network may include a link to a plurality of switches; a processor circuit configured to discover a topology of the network, to determine a flow rate for a link in the network, and to compute a label switch path; and a memory circuit to store the label switch path and the topology of the network.
These and other embodiments will be described in further detail below with reference to the following drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a data center network, according to some embodiments.
FIG. 2 shows an open flow (OF) controller coupled to a switch, according to some embodiments.
FIG. 3 shows a flow chart of a method for load placement in a data center network, according to some embodiments.
FIG. 4 shows a flow chart of a method for load placement in a data center network, according to some embodiments.
FIG. 5 shows a flow chart of a method for load placement in a data center network, according to some embodiments.
FIG. 6 shows a flow chart of a method for load placement in a data center network, according to some embodiments.
FIG. 7 shows a data center network configured for a node failure recovery, according to some embodiments.
FIG. 8 shows a data center network configured for a link failure recovery, according to some embodiments.
In the figures, elements having the same reference number have the same or similar functions.
DETAILED DESCRIPTION
For purposes of this disclosure, an information handling system may include any instrumentality or aggregate of instrumentalities operable to compute, classify, process, transmit, receive, retrieve, originate, switch, store, display, manifest, detect, record, reproduce, handle, or utilize any form of information, intelligence, or data for business, scientific, control, or other purposes. For example, an information handling system may be a personal computer, a network storage device, or any other suitable device and may vary in size, shape, performance, functionality, and price. The information handling system may include random access memory (RAM), one or more processing resources similar to a central processing unit (CPU) or hardware or software control logic, ROM, and/or other types of nonvolatile memory. Additional components of the information handling system may include one or more disk drives, one or more network ports for communicating with external devices similar to various input and output (IO) devices, similar to a keyboard, a mouse, and a video display. The information handling system may also include one or more buses operable to transmit communications between the various hardware components.
FIG. 1 shows a data center network 100 , according to some embodiments. Data center network 100 includes three layers of nodes, or switches. A top-of-rack (TOR) layer 110 includes switches 111 - 1 , 111 - 2 , 111 - 3 , 111 - 4 , 111 - 5 , 111 - 6 , 111 - 7 , and 111 - 8 , collectively referred hereinafter as TOR switches 111 . TOR switches 111 normally are placed on top of server racks at server locations. An aggregation layer 120 may include switches 121 - 1 , 121 - 2 , 121 - 3 , 121 - 4 , 121 - 5 , 121 - 6 , 121 - 7 , and 121 - 8 , collectively referred hereinafter as aggregation switches 121 . A backbone layer 130 may include switches 131 - 1 , 131 - 2 , 131 - 3 , and 131 - 4 , collectively referred hereinafter as backbone switches 131 . Data center network 100 may also include Open Flow (OF) controller circuit 150 . In some embodiments, OF controller 150 configures switches 111 , 121 , and 131 in order to handle the traffic flow through data center network 100 . OF controller 150 is coupled to each of switches 111 , 121 , and 131 in data center network 100 . FIG. 1 shows eight (8) TOR switches 111 , eight (8) aggregation switches 121 , and four (4) backbone switches 131 for illustrative purposes only. One of ordinary skill would recognize that there is no limitation in the number of switches that may be included in each of a TOR layer, an aggregation layer, and a backbone layer. Data traffic in data center network 100 may be unicast (point-to-point transmission). In some embodiments the data traffic may be multicast (single-point-to-multiple point transmission).
Data center network 100 also includes links between the switches, so that data packets may be transmitted from one switch to the other. The switches shown in FIG. 1 include four ports each, coupled to links. In some embodiments, each of TOR switches 111 may include two ports in the ‘south’ direction, coupling the TOR switches to the servers in a server layer. Also, in some embodiments each of TOR switches may include two ports in the ‘north’ direction, coupling each of the TOR switches with at least two aggregation switches 121 . Likewise, each of aggregation switches 121 may include two ports in the ‘south’ direction coupling each aggregation switch 121 with at least two TOR switches. Also, in some embodiments each of aggregation switches 121 may include two ports in the ‘north’ direction coupling each aggregation switch 121 with at least two backbone switches 131 . In some embodiments, backbone layer 130 may be the top most layer in the data center network. Thus, ports in each backbone switch 131 may couple the switch to four aggregation switches 121 in the ‘south’ direction. The specific number of ports for switches 111 , 121 , and 131 is not limiting of the embodiments of the present disclosure. Furthermore, in some embodiments a switch in any one of TOR layer 110 , aggregation layer 120 , and backbone layer 130 , may include one or more ports in the East or West direction, coupling the switch to at least another switch in the same layer level. For example, link 115 couples switches 111 - 6 and 111 - 7 in an East-West direction in TOR layer 110 . Likewise, link 125 couples switches 121 - 2 and 121 - 3 in an East-West direction in aggregation layer 120 . And link 135 couples switches 131 - 3 and 131 - 4 in backbone layer 130 .
Accordingly, an ingress data packet in TOR switch 111 - 1 may be transmitted to aggregation switch 121 - 1 through link 160 - 1 . From aggregation switch 121 - 1 , the ingress data packet may be routed to backbone switch 131 - 1 through link 161 - 1 . Backbone switch 131 - 1 may transmit the data packet to aggregation switch 121 - 7 through link 161 - 2 . Aggregation switch 121 - 7 may transmit the data packet to TOR switch 111 - 8 through link 160 - 4 , so that the ingress data packet becomes an egress data packet and is forwarded to the appropriate server below TOR switch 111 - 8 .
According to some embodiments, link 161 - 1 between aggregation switch 121 - 1 and backbone switch 131 - 1 may have a heavy traffic polarization with respect to link 160 - 2 . Link 160 - 2 couples aggregation switch 121 - 1 and backbone switch 131 - 2 . For example, while link 161 - 1 may carry about nine (9) Gigabit per second (GBs) of data flow, link 161 - 2 may carry only one (1) or less GBs of data flow. Accordingly, OF controller 150 may decide to re-route the ingress data packet from link 161 - 1 to link 160 - 2 , using a re-routing strategy. The decision to re-route the ingress data packet may be triggered when a traffic flow in a link exceeds a pre-selected threshold value. The pre-selected threshold value may be 5 GBs, 6 GBs, or more, according to the number of ports and configuration of the switch supporting the link.
In embodiments where OF controller 150 uses a multiple protocol label switching (MPLS) configuration as a re-routing strategy, labels 151 - 1 , 151 - 2 151 - 3 , 151 - 4 , and 151 - 5 (collectively referred hereinafter as labels 151 ) are placed in headers of the ingress data packet. Labels 151 include flow identifiers used to establish a route for the ingress data packet through the data center network. In some embodiments, flow identifiers may be included in an N-tuple, in labels 151 . A flow is identified by an associated N-tuple. In some embodiments, an N-tuple may include information such as IP-Source-Address, Destination-IP-Address, Source-Port number, Destination Port-number, and Protocol type. Typically, a flow identifier related to a five-tuple as described above may be used by OF controller 150 for setting up flow information.
In some embodiments an N-tuple may include a Source Mac-Address and a Destination Mac-Address. Further according to some embodiments, an N-tuple may be a two-tuple including the Source MAC and the destination MAC alone. The contents of an N-tuple may identify traffic flow passing through the router in a given direction, or in both directions.
Labels 151 may be placed in headers of the ingress data packets by each of the switches receiving the packets. For example, switch 111 - 1 may ‘push’ label 151 - 1 in the ingress data packet in switch 111 - 1 . Label 151 - 1 routes the data packet through link 160 - 1 . Further, aggregation switch 121 may ‘swap’ label 151 - 1 with label 151 - 2 in the data packet header. Label 151 - 2 routes the data packet through link 160 - 2 towards backbone switch 131 - 2 , instead of using link 161 - 1 to backbone switch 131 - 1 . Thus, switch 121 - 1 reduces the traffic load through link 161 - 1 , effectively balancing the load between links 161 - 1 and 160 - 2 . Backbone switch 131 - 2 may ‘swap’ label 151 - 2 in the data packet header with label 151 - 3 , re-routing the data packet through link 160 - 3 towards aggregation switch 121 - 7 . Aggregation switch 121 - 7 may ‘swap’ label 151 - 3 with label 151 - 4 , routing the data packet through link 160 - 4 toward TOR switch 111 - 8 . Switch 111 - 8 may then ‘pop’ or remove label 151 - 5 from the data packet header, and forward the data packet to the intended recipient.
Accordingly, OF controller 150 may prepare and distribute labels 151 to each of switches 111 - 1 , 121 - 1 , 131 - 2 , 121 - 7 , and 111 - 8 when a load imbalance is detected between links 161 - 1 and 160 - 2 . Thus, a data packet may have a re-routing trace assigned at the point of ingress to the data center network. This strategy reduces the time delay introduced in the data center network for load balancing. Also, embodiments using this strategy are able to distribute traffic flow comprehensively through the data center network. For example, OF controller 150 may use knowledge of the data center network topology to implement a re-routing strategy that results in load balancing in distant nodes.
FIG. 2 shows an OF controller 250 coupled to a switch 270 , according to some embodiments. OF controller 250 and switch 270 may be as OF controller 150 and any one of TOR switches 111 , aggregate switches 121 , or backbone switches 131 , in data center network 100 (cf. FIG. 1 ). OF controller 250 may include a processor circuit 261 and a memory circuit 262 . Memory circuit 262 stores commands and data used by processor circuit 261 to execute operations on switch 270 , through an OF agent 275 . Switch 270 includes processor circuit 271 and memory circuit 272 . Memory circuit 272 stores commands and data used by processor circuit 271 to perform the tasks of switch 270 . According to some embodiments, the commands stored in memory circuit 272 may be provided by OF controller 250 through OF agent 275 . In particular, in some embodiments OF agent 275 provides an operating system to processor circuit 271 in order to execute the commands stored in memory circuit 272 .
Thus, OF controller 250 may instruct OF agent 275 to ‘push,’ swap; or ‘pop’ a label on a data packet header in a re-routing configuration using labels 151 , as described in detail above in relation to FIG. 1 . A ‘push’ instruction includes writing a label in the data packet header. A ‘swap’ instruction includes replacing a first label with a second label in the data packet header. A ‘pop’ instructions includes removing a label from the data packet header.
According to embodiments disclosed herein, switch 270 may be a hybrid switch configured by OF agent to operate in an open flow environment. A hybrid switch may also be configured to perform bidirectional forwarding detection (BFD) sessions with neighbors in a data center network. In a BFD session, switch 270 sends a test packet, or hand-shake packet to a neighbor switch, expecting a return of the packet after a certain period of time. When the hand-shake packet fails to return to switch 270 , switch 270 may determine that the destination switch, or a link to the destination switch, has failed. Likewise, during a BFD session switch 270 may return a hand-shake packet to a neighbor in the data center network. In some embodiments, a BFD session may involve only nearest neighbors, so that the hand-shake takes place across a single-hop. In some embodiments a BFD session may involve a plurality of hops in the data center network. In such embodiments, the BFD session is a multi-hop session where the neighbor with which the BFD session is being run is multiple hops away and not an immediate neighbor. When a failure is discovered during a BFD session, a flag may be raised on OF agent 275 . Thus, OF agent 275 may send a report to OF controller 250 . OF agent 275 may also provide commands to processor 271 in switch 270 without waiting for instructions from OF controller 250 .
In some embodiments, a BFD session may be run on the switches to detect single hop failures. In some instances a BFD session may detect multi-hop failures. Some embodiments may include pre-built bypass paths for specific links, using BFD sessions. Once the pre-built bypass paths are computed, they may be downloaded to the OF Agent in the switch running the BFD session. Thus, when the BFD session detects failure then bypass paths are installed in the hardware to perform a fast failover.
In embodiments where switch 270 is a hybrid switch, OF agent 275 may store in memory circuit 272 a fast re-route (FRR) set of paths for re-routing data packets through switch 270 . The FRR set of paths may include links and IP addresses of switches in data center network 100 . According to some embodiments, each path in the FRR set may be associated to switch 270 and to a failed link, a failed switch, or a combination of a failed link and a failed switch. For example, each path in the FRR set includes paths having switch 270 as a node, excluding a failed link coupled to switch 270 , or a failed switch coupled to switch 270 . Furthermore, the FRR set may exclude a combination of a link and a switch coupled to switch 270 , both of which may have a failure at some point in time.
Data plane programming is done through OF agent 275 in switch 270 . For example, data plane programming may include computing the FRR set of paths by the OF controller. OF controller 250 may in turn pass the FRR set of paths for circuit 270 to OF agent 275 . Thus, by computing the FRR sets the OF controller in a data center network 100 , has a comprehensive image of the traffic architecture across data center network 100 and their respective backup paths.
FIG. 3 shows a flow chart of a method 300 for load placement in a data center network, according to some embodiments. Some embodiments may deploy an OF controller such as OF controller 150 in data center network 100 (cf. FIG. 1 ). Thus, method 300 may be performed by processor circuit 261 executing commands stored by memory circuit 262 in OF controller 250 . The OF controller may execute operations on the switches and links of the data center network, as described in detail above (cf. FIG. 1 ). In some embodiments, an OF controller deployed in a data center network may be coupled to each of the switches in the data center network through an OF agent such as OF agent 275 (cf. FIG. 2 ). Thus, in some embodiments steps in method 300 may be partially performed by a processor circuit in some OF agents in the data center network, upon configuration by the OF controller. The processor circuit coupled to an OF agent in a switch may be similar to processor circuit 271 , performing commands stored in memory circuit 272 (cf. FIG. 2 ).
In step 310 , OF controller 150 performs topology discovery and creates a database of the data center network. In step 320 top of rack, aggregation, and backbone switches report traffic flow rates on each of their links to the OF controller. In step 330 OF controller 150 determines flow rates to specific links in the data center network. In step 340 forwarding entries are programmed in the form of one level multiple protocol label switching (MPLS) labels mapped to flow entries.
FIG. 4 shows a flow chart of a method 400 for load placement in a data center network, according to some embodiments. In some embodiments, method 400 may be performed by processor circuit 261 executing commands stored in memory circuit 262 in OF controller 250 . Furthermore, in some embodiments steps in method 400 may be partially performed by a processor circuit in some OF agents in the data center network, upon configuration by the OF controller. The data center network in method 400 may be as data center network 100 described in detail above (cf. FIG. 1 ).
In step 410 the OF controller programs a ‘push label’ operation in forwarding top of rack switches. The OF controller may perform step 410 by determining the flow rate to specific links in TOR layer 110 with ‘push label’ and flow entry programming operations. In step 420 , the OF controller programs ‘swap label’ operations in less loaded paths on switches in aggregation layer 120 . In step 430 the OF controller programs swap labels in less loaded paths on switches in backbone layer 130 . In step 440 the OF controller programs POP label operations on receiving switch in TOR layer 110 .
FIG. 5 shows a flow chart of a method 500 for load placement, according to some embodiments. In some embodiments, method 500 may be performed by processor circuit 261 executing commands stored in memory circuit 262 in OF controller 250 . Furthermore, in some embodiments some of the steps in method 500 may be partially performed by a processor circuit in some OF agents in the data center network, upon configuration by the OF controller. The data center network in method 500 may be similar to data center network 100 described in detail above (cf. FIG. 1 ).
In step 510 the OF controller receives notification of traffic flow through data center network 100 . In some embodiments, traffic flow information may be included in the appropriate N-tuple. In step 520 the OF controller allocates label space for each switch in the topology based on the switch's layer. When labels are pushed into switches in step 530 , label based forwarding is set to ‘ON’ in the switches in step 540 . Thus, the data packet may be forwarded to the address specified in the label. When step 550 determines an end flow status, the OF controller receives notification in step 560 . Also in step 560 , the OF controller releases the labels from the paths. In some embodiments, the flow information may be an aggregate entry such as a prefix rather than a complete IP address within a N-Tuple. This aggregate entry would indicate entire sub-networks or networks reachable at the far ends of the data center. Thus achieving a minimization of flow information space occupancy in the hardware tables of the switch.
FIG. 6 shows a flow chart of a method 600 for load placement in a data center network, according to some embodiments. In some embodiments, method 600 may be performed by processor circuit 261 executing commands stored in memory circuit 262 of OF controller 250 . Furthermore, in some embodiments some of the steps in method 600 may be partially performed by a processor circuit in some OF agents in the data center network, upon configuration by the OF controller. The data center network in method 600 may be as data center network 100 described in detail above (cf. FIG. 1 ).
In step 610 the OF controller maintains label space for each switch. In step 620 the OF controller constantly monitors traffic load through the data center network. Accordingly, in some embodiments step 620 includes monitoring traffic load through the data center network periodically. The periodicity in step 620 is not limiting and may vary from a few seconds up to minutes, or more. In some embodiments including a particularly large data center network, the OF controller may sequentially poll each of the nodes in step 620 . In step 630 the OF controller may select paths when traffic flow starts. In step 640 the OF controller releases paths when traffic flow ends.
FIG. 7 shows a data center network 700 configured for a node failure recovery, according to some embodiments. In some embodiments, the configuration of data center network 700 may be used under any circumstance where traffic re-routing may be desired. Data center network 700 may include a server layer 701 , according to some embodiments. Data center network 700 may include a TOR layer 710 , and aggregate layer 720 , and a backbone layer 730 . Thus, TOR layer 710 may include TOR switches 711 - 1 , 711 - 2 , 711 - 3 , and 711 - 4 . Aggregate layer 720 may include aggregate switches 721 - 1 , 721 - 2 , 721 - 3 , and 721 - 4 . And backbone layer 730 may include backbone switches 731 - 1 , 731 - 2 , 731 - 3 , and 731 - 4 . Data center network 700 may be configured for fail-re-routing (FRR) orchestration using bidirectional forwarding detection (BFD) between two nodes of the network.
Embodiments disclosed herein may include FRR providing a ‘make-before-break’ solution for protecting traffic flow in data center network 700 . Accordingly, in some embodiments when a node or link failure occurs in data center network 700 , the failure may be resolved without involving OF controller 150 . In some embodiments OF controller 150 calculates possible FRRs for each of the nodes and links in data center network 700 . The FRRs are stored by the OF agents associated with each node in the data center network, in memory circuit 272 (cf. FIG. 2 ). When a failure occurs at a particular point, traffic is rerouted according to the FRR associated with the point of failure. Thus, some embodiments reduce the round trip time for failure correction in the data center network by involving the OF agent installed locally on each of the nodes or switches in the network (cf. OF agent 275 in FIG. 2 ).
In some embodiments, the OF agent may install the FRR set for a particular TOR-Aggregation-Backbone combination of nodes in the hardware, and use the installed FRR set as backup paths for various scenarios. According to some embodiments, the OF agent may store the backup FRR set in memory. Thus, in the event of failure the FRR set is installed in the hardware (e.g., in the switches in data center network 700 ). OF controller 150 computes multiple FRR paths for each node or switch in data center network 700 . OF controller 150 is able to perform such computation by using detailed knowledge of the topology of data center network 700 .
According to some embodiments, each switch in data center network 700 is locally configured for BFD with respective adjacent layers. For example, switch 721 - 1 in aggregation layer 720 may be configured to perform BFD with a switch in backbone layer 730 (e.g., 731 - 1 or 731 - 2 ), and also with a switch in TOR layer 710 (e.g., 711 - 1 or 711 - 2 ). Likewise, in some embodiments switch 711 - 1 in TOR layer 710 may be configured to perform BFD with a switch in aggregation layer 720 . And switch 731 - 1 in backbone layer 730 may be configured to perform BFD sessions with a switch in aggregation layer 720 .
FIG. 7 shows an exemplary scenario wherein a failure is detected in backbone switch 731 - 3 . Thus, a data packet route from server 701 - 1 to server 701 - 2 through links 760 - 1 , 761 - 1 , 761 - 2 , 761 - 3 , 761 - 4 and 760 - 6 , is re-routed. The new route passes through links 760 - 1 , 760 - 2 , 760 - 3 , 760 - 4 , 760 - 5 , and 760 - 6 . In the example shown in FIG. 7 , a failure in backbone switch 731 - 3 involves a re-routing that begins in TOR switch 711 - 1 , changing from link 761 - 1 to link 760 - 2 . Thus, in the exemplary scenario a failure in the backbone layer produces a readjustment two layers ‘south,’ at the TOR level.
FIG. 8 shows data center network 700 configured for a link failure recovery, according to some embodiments. Data center 700 may be configured for FRR orchestration using bidirectional forwarding detection (BFD) between two nodes of the network, in case of a link failure.
FIG. 8 shows an exemplary scenario wherein a failure is detected in either one of link 861 - 1 or link 861 - 2 . Thus, a data packet route from server 701 - 1 to server 701 - 2 through links 860 - 1 , 860 - 2 , 861 - 1 , 861 - 2 , 860 - 5 , and 860 - 6 , is re-routed. The new route passes through links 860 - 1 , 860 - 2 , 860 - 3 , 860 - 4 , 860 - 5 , and 860 - 6 .
In some embodiments, OF controller 150 computes multiple FRR paths associated with each link in data center network 700 . For example, multiple FRR paths may be associated to link 861 - 1 such that each of the FRR paths is able to transfer a data packet from source server 701 - 1 to destination server 701 - 2 assuming a failure of link 861 - 1 . Thus, the path including links 860 - 1 , 860 - 2 , 860 - 3 , 860 - 4 , 860 - 5 , and 860 - 6 , and TOR switch 711 - 1 , aggregation switch 721 - 1 , backbone switch 731 - 3 , aggregation switch 721 - 3 , and TOR switch 711 - 3 may be included in an FRR set associated to either one of links 861 - 1 , and 861 - 2 . In some embodiments, OF controller 150 computes FRR paths for protection against a combination of a link failure and a node failure. In such embodiments, an FRR path set may be associated to both the link and the node whose failure is recovered. Further according to some embodiments, OF controller 150 may compute FRR paths in combination with user input, so that an administrator may select the type of protection path needed or desired for a data center network.
Accordingly, BFD sessions are performed between pairs of nodes, sending hand-shaking packets back and forth between the two nodes. When a BFD session between a pair of nodes reports a switch failure or a link failure, then the device which detects the failure reports the failure to the OF agent associated with the device. The OF agent in the device that detects the failure directs the flow to a backup path selected from the FRR set stored in memory.
In some embodiments, a user may select a recovery path from a group of FRR paths for a failed link and FRR paths for a failed switch, where the failed link and the failed switch may not be directly coupled to each other. In such scenario, OF controller 150 may configure the network to select the appropriate recovery path.
Some embodiments may implement a multi-hop BFD strategy, wherein the hand shaking packets are sent across multiple nodes and links in data center network 700 . For example, a multi-hop configuration may use a BFD session between two nodes in TOR layer 710 , so that the hand-shake packet transits across aggregation layer 720 and backbone layer 730 . In some embodiments, a BFD session may provide hand-shake packets between two nodes in aggregation layer 720 , across backbone layer 730 . More generally, some embodiments may implement multi-hop BFD sessions within a single layer and across multiple nodes, using an East-West links between switches (cf. FIG. 1 ).
In some embodiments, a single-hop BFD session coupling two adjacent nodes through a single link may take less than 50 milliseconds (ms) to complete. In the case of a multi-hop BFD session, latency times may be higher than 50 ms, but well below one (1) sec.
Thus, according to embodiments consistent with the present disclosure recovery through FRR paths may be implemented locally, through an OF agent associated to a switch, rather than being implemented at the OF controller level. This reduces the latency for implementation of the recovery protocol.
Embodiments of the disclosure described above are exemplary only. One skilled in the art may recognize various alternative embodiments from those specifically disclosed. Those alternative embodiments are also intended to be within the scope of this disclosure. As similar to such, the invention is limited only by the following claims. | A system for operating information handling systems forming a network including a plurality of switches is provided. The system includes an open flow controller coupled to each of the plurality of switches; a plurality of links, each link configured to transmit data packets between two switches from the plurality of switches; wherein: the open flow controller is configured to determine a traffic flow across each of the plurality of links; and each one of the plurality of switches is configured to re-route a data packet when the traffic flow in a link associated to the switch exceeds a threshold. A computer program product including a non-transitory computer readable medium having computer readable and executable code for instructing a processor in a management unit for a plurality of information handling systems as above is also provided. A network managing device coupled to a service provider having resources is also provided. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to a method for forming spherical particles of thermoplastic materials having relatively low-melting points, such as natural resins, synthetic resins, and the like, and also to apparatus for carrying out the same method.
Conventionally, a number of methods for forming spherical particles of thermoplastic materials have been available. They include dry processes in which thermoplastic particles are either suspended in a hot atmosphere for a predetermined period of time so as to form a fluidized bed or dropped into a heated tube, and wet processes in which a solute dispersed or dissolved in water or an organic solvent is sprayed in a hot atmosphere to evaporate the solvent and thereby obtaining spherical solute particles.
In the aforesaid dry processes, however, it is difficult to keep the particles in the specified heating space for a desired period of time under an individually separate condition. Especially when the particles are not greater than 100 μm in diameter, they tend to fuse together into an agglomerate and/or stick to the vessel walls during the operation for forming them into spherical particles, resulting in a non-uniform degree of sphericity and an unduly decreased yield.
On the other hand, the wet processes (for example, the spray drying process) have the advantage of producing uniformly spherical particles over a wide range of particle diameter extending from several micrometers to several hundred micrometers. However, the solvent present in the sprayed particles must be evaporated almost completely before they can be collected. This poses the problems of requiring an immense drying space and hence an oversized apparatus; causing an increase of incidental facilities (due to the need for recovering the solvent) if the evaporated solvent is other than water; and involving risks of fire, toxicity, and the like.
SUMMARY OF THE INVENTION
This invention has been made for the purpose of overcoming the disadvantages of prior art methods as described above.
Accordingly, it is an object of this invention to provide a method for forming spherical particles of thermoplastic material which method can produce a good yield of uniform thermoplastic particles exhibiting a high degree of sphericity and can effect a reduction in size of apparatus and a simplification of operation.
It is another object of this invention to provide apparatus for carrying out the foregoing method.
In accordance with this invention, there is provided a method for forming spherical particles of thermoplastic material which comprises the steps of blowing a stream of gas having thermoplastic particles dispersed therein from a peripheral region into a jet of pressurized hot gas to melt and form spherical particles of thermoplastic material, and then cooling the spherical particles. In addition, there is also provided apparatus for forming spherical particles of thermoplastic material which includes means for discharging a jet of pressurized hot gas from an outlet port and means for ejecting a stream of gas having thermoplastic particles dispersed therein from at least one opening toward the jet of pressurized hot gas, the opening being spaced from the outlet port so as to provide a gap for permitting the flow of cooling air through the periphery of the outlet port.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of the essential part of an apparatus for carrying out the method of the invention;
FIG. 2 is a schematic side view of an apparatus in accordance with another embodiment of the invention;
FIG. 3 is a sectional view taken along the line III--III of FIG. 2;
FIG. 4 is a sectional view of the essential part of an apparatus in accordance with a further embodiment of the invention;
FIG. 5 is a sectional view taken along the line V--V of FIG. 4;
FIG. 6 is a sectional view of the essential part of an apparatus in accordance with a still further embodiment of the invention;
FIG. 7 is a perspective view of the essential part of an apparatus in accordance with a still further embodiment of the invention;
FIG. 8 is a sectional view of the essential part of an apparatus in accordance with a still further embodiment of the invention;
FIG. 9 is a sectional view of the essential part of an apparatus in accordance with a still further embodiment of the invention; and
FIG. 10 is a sectional view taken along the line X--X of FIG. 9.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
This invention will hereinafter be described with reference to the embodiments thereof illustrated in the accompanying drawings.
Referring first to FIG. 1, there is shown a feed tube 1 for discharging a jet 2 of pressurized hot gas. In its periphery, for example, a pair of opposed nozzles 3 are disposed with their orifices facing obliquely downward. Each of these nozzles 3 serves to blow a stream 4 of gas having thermoplastic particles dispersed therein (hereinafter referred to as "stream of dispersed thermoplastic particles") into the jet 2 of pressurized hot gas, and has its open end located under the open end of feed tube 1 but set aside so as to prevent its exposure to the jet 2 of pressurized hot gas. When a jet 2 of pressurized hot gas is discharged from feed tube 1 and, at the same time, a stream 4 of dispersed thermoplastic particles is ejected from each nozzle 3, they creates a negative pressure which causes ambient air to be drawn through the gap between the open end of feed tube 1 and the open ends of nozzles 3. This flow of air serves to block effectively the conduction of heat from the jet 2 of pressurized hot gas to the tips of nozzles 3 and simultaneously cool the latter. The thermoplastic particles present in streams 4 are softened upon contact with the jet 2 of pressurized hot gas and formed into spherical particles. These spherical particles fall downward as they are cooled and solidified.
Most commonly, the jet of pressurized hot gas used in the practice of the invention consists of compressed and heated air. However, where the thermoplastic particles to be treated are unstable, for example, under oxidizing conditions, it is desirable to use a compressed and heated inert gas such as nitrogen. In addition, the temperature of the jet of pressurized hot gas should be sufficiently high to soften the thermoplastic particles in a very short period of time after they are brought into contact with the jet of pressurized hot gas. Usually, it is set at a value which is at least 100° C. higher than the softening point of the thermoplastic particles.
The stream of dispersed thermoplastic particles used in the practice of the invention means a stream of gas in which thermoplastic particles alone are dispersed to form a suspension. The diameter of the thermoplastic particles is usually not greater than 100 μm. The concentration of the thermoplastic particles present in the stream may vary according to the diameter thereof. However, it is generally not higher than 2 kg/cm 3 and preferably in the range of 50 to 1000 g/m 3 . The reason why such limits are imposed on the concentration of the thermoplastic particles is that, if the concentration is higher than 2 kg/m 3 , the particles softened in the jet of pressurized hot gas tend to fuse together into an agglomerate. Specific examples of the aforesaid thermoplastic particles include thermoplastic resin particles consisting essentially of natural resins such as rosin, copal, and shellac or synthetic resins such as solid paraffin, polystyrene, acrylic resin, polyethylene, polyvinyl chloride, polyamide, alkyd resin, phenolic resin, polycarbonate, epoxy resin, polyvinyl acetate, and blends or copolymers thereof; dye or pigment particles capable of being melted by heating; ceramic and metallic particles having a relatively low melting point; particles of organic materials such as sugar and pitch; sulfur particles; particles of fertilizer such as ammonium sulfate and the like.
The flow velocities of the jet of pressurized hot gas and the stream of dispersed thermoplastic particles used in the practice of the invention may be suitably determined depending on the temperature of pressurized hot gas, the softening point of the thermoplastic particles, and the size (or specific surface area) of the thermoplastic particles. More specifically, if the temperature of the jet of pressurized hot gas is substantially higher than the softening point of the thermoplastic particles to be treated, the flow velocities of the jet of pressurized hot gas and the stream of dispersed thermoplastic particles may be determined at higher levels because a short time of contact with the jet of pressurized hot gas is sufficient to form the thermoplastic particles into satisfactorily spherical granules. On the other hand, if the temperature of the jet of pressurized hot gas is not so much higher than the softening point of the thermoplastic particles to be treated, the flow velocities of the jet of pressurized hot gas and the stream of dispersed thermoplastic particles should be determined at lower levels because a relatively long time of contact with the jet of pressurized hot gas is required to form the thermoplastic particles into satisfactorily spherical granules. Similarly, if the diameter of the thermoplastic particles to be treated is small, the flow velocities of the jet of pressurized hot gas and the stream of dispersed thermoplastic particles may be determined at higher levels because a short time of contact is sufficient as described above. On the other hand, if the diameter of the thermoplastic particles to be treated is large, the flow velocities of the jet of pressurized hot gas and the stream of dispersed thermoplastic particles should be determined at lower levels because a relatively long time of contact is required as described above.
Generally, the flow velocity of the jet of pressurized hot gas is chosen in the range of 10 to 50 m/sec, and the flow velocity of the stream of dispersed thermoplastic particles is determined so that it is lower than that of the jet of pressurized hot gas.
Furthermore, the stream of dispersed thermoplastic particles is ejected in such a direction as to make an angle of not greater than 80°, and preferably 30° to 60°, with the jet of pressurized hot gas.
Now, specific examples of the means for feeding dispersed thermoplastic particles are described with reference to the accompanying drawings.
FIGS. 2 and 3 illustrate an exemplary apparatus for carrying out the method of the invention. There is shown a feed tube 1 for discharging a jet of pressurized hot gas, the open end of which is surrounded by a distributing ring 5 for dispersed thermoplastic particles. This distributing ring 5 is provided with four nozzles 6 at equal intervals, the nozzles 6 projecting in a centripetal and slightly downward direction. For the same purpose as described in connection with FIG. 1, the open ends of nozzles 6 are spaced from the open end of feed tube 1. More specifically, they are located under the open end of feed tube 1 but set aside so as to prevent their exposure to the jet of pressurized hot gas. In addition, an inlet pipe 7 is attached to one side of distributing ring 5 so that they are in flow communication with each other. Thus, the thermoplastic particles fed from a hopper 9 are dispersed in the compressed air flowing through a pipe line 8 and introduced into the distributing ring 5.
With this arrangement, compressed air is fed from a pipe line 10, heated by passing it through a heat exchanger 11, and introduced into the feed tube 1, whereby a jet of pressurized hot gas is provided. At the same time, a total of four streams of dispersed thermoplastic particles are ejected from four nozzles 6 and blown into the jet of pressurized hot gas.
FIGS. 4 and 5 present another example of the means for feeding dispersed thermoplastic particles. In this embodiment, a double-walled tube 12 is employed as the means for distributing and feeding dispersed thermoplastic particles. More specifically, an annular passageway 15 is defined by its inner wall 13 and outer wall 14, and a plurality of openings 16 facing obliquely downward are provided in the lower part of inner wall 13. Similarly to the embodiment illustrated in FIG. 2, an inlet pipe 9 for introducing dispersed thermoplastic particles is provided in flow communication with the annular passageway 15. A feed tube 1 for discharging a jet of pressurized hot gas is so arranged that its open end is located slightly above the openings 16. For the same purpose as described above, a gap 17 is provided between the open end of feed tube 1 and the openings 16 so that cooling air may be supplied from the upper open end 18 of double-walled tube 12. The behavior of the jet of pressurized hot gas and the streams of dispersed thermoplastic particles is as described above in connection with the preceding embodiment.
In the above-described embodiments, the jet of pressurized hot gas is discharged from a tubular member having an opening of circular cross section. However, it is also possible to discharge the jet of pressurized hot gas radially from a feed tube.
This arrangement is exemplified by the embodiment illustrated in FIG. 6. The feed tube 19 for discharging a jet of pressurized hot gas has a lower end of conical shape, and a plurality of radially arranged openings 20 are provided in the surface of the tapered end. On the other hand, the distributing ring 21 for feeding dispersed thermoplastic has a double-walled tubular construction similar to that illustrated in FIGS. 4 and 5, but its lower end is tapered. In the inner wall of the tapered end are provided a plurality of openings 22 corresponding to the aforesaid openings 20. With this arrangement, while the jet of pressurized hot gas is discharged radially from the openings 20 of feed tube 19, the dispersed thermoplastic particles introduced into the aforesaid distributing ring 21 by way of an inlet pipe are ejected from the openings 22 toward the jet of pressurized hot gas, whereby the thermoplastic particles are formed into globular bodies. As described in connection with FIG. 4, cooling air is supplied through the gap 23 formed between the distributing ring 21 and the feed tube 19. Thus, the lower end of distributing ring 21 is cooled so as to prevent its openings from clogging.
FIG. 7 illustrates a modified embodiment in which the jet of pressurized hot gas is discharged radially from a feed tube and, at the same time, the stream of dispersed thermoplastic particles is ejected in the form of a filmy current and blown into the jet of pressurized hot gas. More specifically, the feed tube 24 for discharging a jet of pressurized hot gas comprises a closed-end cylindrical member provided with a plurality of radially arranged openings 25 in the side wall of the lower end, which is surrounded by a cuplike distributing ring 28 having an annular slit 27 at the bottom. The dispersed thermoplastic particles introduced into the distributing ring 28 by way of an inlet pipe 7 are ejected from the slit 27 in the form of a filmy current and blown into the jet of pressurized hot gas, whereby the thermoplastic particles are formed into globular bodies. Similarly to the embodiment illustrated in FIG. 6, a gap 29 is provided between the distributing ring 28 and the feed tube 24 so as to permit the flow of cooling air.
FIG. 8 illustrates another modified embodiment in which the stream of dispersed thermoplastic particles is ejected in the form of a filmy current (as in FIG. 7) and, at the same time, the jet of pressurized hot gas is also discharged in the form of a filmy current. More specifically, the feed tube 30 for discharging a jet of pressurized hot air comprises a cylindrical member having an internally tapered open end. Upon this open end is arranged a beveled plate 31 with a desired space therebetween. Thus, an annular slit 32 is formed between the tapered open end of feed tube 30 and the bevel of plate 31, and the jet of pressurized hot gas is discharged from this slit 32 in the form of a diverging filmy current.
On the other hand, the distributing ring for feeding dispersed thermoplastic particles is similar to that of FIG. 7. More specifically, the feed tube 30 is surrounded by a distributing ring 34 of double-walled tubular construction having an annular slit 33 at the bottom. With this arrangement, the dispersed thermoplastic particles introduced into the distributing ring 34 by way of an inlet pipe are ejected from the slit 33 in the form of a converging filmy current. Meanwhile, the jet of pressurized hot gas strikes against the plate 31 which is spaced from the open end of feed tube 30 to form the slit 32. As a result, it is discharged from the slit 32 in the form of a diverging filmy current and brought into contact with the converging filmy current of dispersed thermoplastic particles, whereby the thermoplastic particles are heated and formed into spherical granules. Similarly to the embodiment illustrated in FIG. 7, a gap is provided between the distributing ring 34 and the feed tube 30 so as to permit the flow of cooling air.
FIGS. 9 and 10 illustrate still another embodiment in which the jet of pressurized hot gas and the stream of dispersed thermoplastic particles are both discharged in the form of eddies so that they dash against and mix with each other. More specifically, as illustrated in FIG. 9, the tapered open end 36 of a feed chamber 35 for discharging a jet of pressurized hot gas is surrounded by a distributing ring 35 of double-walled tubular construction. Although the aforesaid arrangement is similar to that of FIG. 8, this embodiment is further characterized in that, as illustrated in FIG. 10, an inlet pipe 38 is attached tangentially to one side of feed chamber 35 and an inlet pipe 7 is attached tangentially to one side of distributing ring 39. Thus, the pressurized hot gas introduced into feed chamber 35 by way of the inlet pipe 38 is rotated along the wall of feed chamber 35 and then discharged from an open end 36 in the form of a diverging and eddying filmy current. On the other hand, the dispersed thermoplastic particles introduced into the distributing ring 39 by way of the inlet pipe 7 are rotated within the annular passageway 40 of distributing ring 39 and then ejected from an annular opening 41 facing slightly inward in the form of a converging and eddying filmy current. As is evident from FIG. 10, the filmy currents of pressurized hot gas and of dispersed thermoplastic particles are preferably caused to eddy in opposite directions so that these filmy currents may exhibit a higher efficiency of contact with each other and the thermoplastic particles may become easier to melt and form into spherical granules. Although the filmy currents of pressurized hot gas and of dispersed thermoplastic particles are both caused to eddy in this embodiment, it is also possible to discharge only one of them in the form of an eddy. Similarly to the preceding embodiments, a gap is again provided between the feed chamber 35 and the distributing ring 39 so as to permit the flow of cooling air.
According to the method of the invention, a stream of dispersed thermoplastic particles is blown into a jet of pressurized hot gas. As a result, the thermoplastic particles are heated in the jet of pressurized hot gas, they are softened uniformly because the stream of dispersed thermoplastic particles dashes against the jet of pressurized hot gas and vice versa, and the softened surface layer of the thermoplastic particles are subjected to surface tension, whereby uniformly spherical granules are produced with ease. Furthermore, the particles which have been formed into spherical granules are kept in the dispersed state and forcedly transferred to a cooling zone by the action of the jet of pressurized hot gas.
Accordingly, the present invention can bring about a variety of effects as described below:
(1) A large volume of uniformly spherical particles exhibiting an exceptionally high degree of sphericity can be produced in a short period of time.
(2) During the operation, the particles can be prevented from fusing together into an agglomerate and sticking to the vessel walls of the apparatus, whereby an improvement in production efficiency and a simplification of operation can be effected.
(3) As compared with prior art wet processes, much higher particle concentrations may be employed during the operation. This enables one to employ a substantially smaller space for the purpose of forming spherical particles of thermoplastic materials and thereby achieve a remarkable improvement in thermal efficiency.
(4) The apparatus for forming spherical particles of thermoplastic materials in accordance with the present invention are smaller in size and simpler in operation than those employed for carrying out prior art wet and dry processes.
In order to further illustrate the practice of the invention, the following examples are given.
EXAMPLE 1
As illustrated in FIGS. 2 and 3, compressed air was fed from a pipe line 10 and heated to 400° C. by passing it through a heat exchanger 11. Thereafter, it was introduced into a feed tube 1 and discharged from its open end (15 mm in diameter) to provide a jet of pressurized hot air having a pressure of 0.3 kg/cm 2 .
On the other hand, 90 parts by weight of an expoxy resin (having a melting point of 130° C.) and 10 parts by weight of carbon black were hot milled, ground, and classified to produce black toner particles (thermoplastic particles) having an average diameter of 20 μm. These particles were fed from a hopper 9 to a pipe line 8 through which compressed air having a pressure of 0.3 kg/cm 2 was flowing, introduced into a distributing ring 5, and then ejected from four nozzles 6 (with an orifice diameter of 4 mm) provided thereon. Thus, a total of four streams of dispersed black toner particles having a particle concentration of 300 g/m 3 were blown into the aforesaid jet of pressurized hot air (having a temperature of 400° C.) to form the black toner particles into spherical particles.
Most of the black toner particles thus obtained were spherical exhibiting an exceptionally high degree of sphericity. Moreover, no agglomeration of the particles was noted.
EXAMPLE 2
As illustrated in FIGS. 4 and 5, a jet of pressurized hot air having a pressure of 0.2 kg/cm 2 and a temperature of 500° C. was discharged from a feed tube 1 (with an orifice diameter of 25 mm).
On the other hand, opoxy resin particles (thermoplastic particles) having an average diameter of 10 μm and a melting point of 130° C. were dispersed in compressed air having a pressure of 0.2 kg/cm 2 , introduced into a distributing ring 12 whose lower half had a double-walled tubular construction, and then ejected from eight openings 16 (3 mm in diameter) provided symmetrically in the lowermost part of the inner wall of distributing ring 12. Thus, a total of eight streams of dispersed epoxy resin particles having a particle concentration of 100 g/m 3 were blown into the aforesaid jet of pressurized hot air (having a temperature of 500° C.) to form the epoxy resin particles into spherical granules.
Just as in Example 1, most of the epoxy resin particles thus obtained were spherical exhibiting an exceptionally high degree of sphericity. Moreover, no agglomeration of the particles was noted.
EXAMPLE 3
Employing an apparatus as illustrated in FIGS. 9 and 10, compressed air was heated to 400° C. by passing it through a heat exchanger and then introduced tangentially through an inlet pipe 38 into a feed chamber 35 of hollow cylindrical shape. As a result, it was rotated within the feed chamber 35 and then discharged from an opening 36 at a flow velocity of 30 m/sec in the form of a diverging and eddying filmy current.
On the other hand, expoxy resin particles having an average diameter of 10 μm and a melting temperature of 140° C. was fed from a hopper to a Venturi pipe through which compressed air was flowing. The particles thus dispersed in compressed air was introduced through an inlet pipe 7 into a distributing ring 39, rotated within it, and then ejected from its annular opening 41 at a flow velocity of 15 m/sec in the form of a converging and oppositely eddying filmy current. Thus, the filmy current of dispersed epoxy resin particles having a particle concentration of 400 g/m 3 was blown into the filmy current of compressed hot air (having a temperature of 400° C.).
Approximately 100% of the epoxy resin particles thus obtained were spherical, exhibiting an exceptionally high degree of sphericity. Moreover, no agglomeration of the particles was noted.
EXAMPLE 4
Employing an apparatus similar to that of FIG. 3, compressed air (having a pressure of 0.4 kg/cm 2 ) was heated to about 500° C., introduced through an inlet pipe 38 into a feed chamber 35, and then discharged from an open end 36 in the form of a divergently extending and eddying film.
On the other hand, 80 parts by weight of a styrene resin (having a melting point of 150° C.) and 20 parts by weight of carbon black were hot milled, ground, and classified to produce black toner particles having an average diameter of 20 μm. These particles were dispersed in compressed air (having a pressure of 4 kg/cm 2 ), introduced into a distributing ring 39 by way of an inlet pipe 7 attached tangentially thereto, and then ejected from its annular opening 41 in the form of a converging and oppositely eddying filmy current. Thus, the filmy current of dispersed black toner particles having a particle concentration of 600 g/m 3 was blown into the filmy current of compressed hot air (having a temperature of 500° C.).
Microscopic examination revealed that the black toner particles thus obtained were spherical, exhibiting almost perfect sphericity. Moreover, no agglomeration of the particles was noted. | This invention is concerned with a method for forming spherical particles of thermoplastic material, characterized by the step of blowing a stream of gas having thermoplastic particles dispersed therein from a peripheral region into a jet of pressurized hot gas to form the thermoplastic particles into uniform spherical particles. It also provides apparatus for carrying out the foregoing method which includes means for discharging a jet of pressurized hot gas from an outlet port and means for ejecting a stream of gas having thermoplastic particles dispersed therein from the periphery of the outlet port toward the jet of pressurized hot gas. | 1 |
[0001] The present application is a continuation of U.S. Ser. No. 09/594,637 filed Jun. 15, 00 which is a continuation of U.S. Ser. No. 09/045,330 filed Mar. 20, 1998, now issued as U.S. Pat. No. 6,099,859, the enclosures of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to controlled release unit dose formulations containing an antihyperglycemic drug. More specifically, the present invention relates to an oral dosage form comprising a biguanide such as metformin or buformin or a pharmaceutically acceptable salt thereof such as metformin hydrochloride or the metformin salts described in U.S. Pat. Nos. 3,957,853 and 4,080,472 which are incorporated herein by reference.
[0003] In the prior art, many techniques have been used to provide controlled and extended-release pharmaceutical dosage forms in order to maintain therapeutic serum levels of medicaments and to minimize the effects of missed doses of drugs caused by a lack of patient compliance.
[0004] In the prior art are extended release tablets which have an osmotically active drug core surrounded by a semipermeable membrane. These tablets function by allowing a fluid such as gastric or intestinal fluid to permeate the coating membrane and dissolve the active ingredient so it can be released through a passageway in the coating membrane or if the active ingredient is insoluble in the permeating fluid, pushed through the passageway by an expanding agent such as a hydrogel. Some representative examples of these osmotic tablet systems can be found in U.S. Pat. Nos. 3,845,770, 3,916,899, 4,034,758, 4,077,407 and 4,783,337. U.S. Pat. No. 3,952,741 teaches an osmotic device wherein the active agent is released from a core surrounded by a semipermeable membrane only after sufficient pressure has developed within the membrane to burst or rupture the membrane at a weak portion of the membrane.
[0005] The basic osmotic device described in the above cited patents have been refined over time in an effort to provide greater control of the release of the active ingredient. For example U.S. Pat. Nos. 4,777,049 and 4,851,229 describe an osmotic dosage form comprising a semipermeable wall surrounding a core. The core contains an active ingredient and a modulating agent wherein the modulating agent causes the active ingredient to be released through a passageway in the semipermeable membrane in a pulsed manner. Further refinements have included modifications to the semipermeable membrane surrounding the active core such as varying the proportions of the components that form the membrane, i.e U.S. Pat. Nos. 5,178,867, 4,587,117 and 4,522,625 or increasing the number of coatings surrounding the active core, i.e U.S. Pat. No. 5,650,170 and 4,892,739.
[0006] Although vast amounts of research has been performed on controlled or sustained release compositions and in particular on osmotic dosage forms, very little research has been performed in the area of controlled or sustained release compositions that employ antihyperglycemic drugs.
[0007] The limited work on controlled or sustained release formulations that employ antihyperglycemic drugs such as metformin hydrochloride has been limited to the combination of the antihyperglycemic drug and an expanding or gelling agent to control the release of the drug from the dosage form. This limited research is exemplified by the teachings of WO 96/08243 and by the GLUCOPHAGE® product which is a commercially available product from Bristol-Myers Squibb Co. containing metformin HCl.
[0008] It is reported in the 50th Edition of the Physicians' Desk Reference, copyright 1996, p. 753, that food decreases the extent and slightly delays the absorption of metformin delivered by the GLUCOPHAGE® dosage form. This decrease is shown by approximately a 40% lower peak concentration and a 25% lower AUC in plasma and a 35 minute prolongation of time to peak plasma concentration following administration of a single GLUCOPHAGE® tablet containing 850 mg of metformin HCl with food compared to the similar tablet administered under fasting conditions.
[0009] It is an object of the present invention to provide a controlled or sustained release formulation for an antihyperglycemic drug wherein the bioavailability of the drug is not decreased by the presence of food.
[0010] It is a further object of the present invention to provide a controlled or sustained release formulation for an antihyperglycemic drug that does not employ an expanding polymer.
[0011] It is also a further object of the present invention to provide a controlled or sustained release formulation for an antihyperglycemic drug that can provide continuous and non-pulsating therapeutic levels of an antihyperglycemic drug to an animal or human in need of such treatment over a twelve hour to twenty-four hour period.
[0012] It is an additional object of the present invention to provide a controlled or sustained release formulation for an antihyperglycemic drug that obtains peak plasma levels approximately 8-12 hours after administration.
[0013] It is also an object of this invention to provide a controlled or sustained release pharmaceutical tablet having only a homogeneous osmotic core wherein the osmotic core component may be made using ordinary tablet compression techniques.
SUMMARY OF THE INVENTION
[0014] The foregoing objectives are met by a controlled release dosage form comprising:
[0015] (a) a core comprising:
[0016] (i) an antihyperglycemic drug;
[0017] (ii) optionally a binding agent; and
[0018] (iii) optionally an absorption enhancer;
[0019] (b) a semipermeable membrane coating surrounding the core; and
[0020] (c) at least one passageway in the semipermeable membrane.
[0021] The dosage form of the present invention can provide therapeutic levels of the antihyperglycemic drug for twelve to twenty-four hour periods and does not exhibit a decrease in bioavailability if taken with food. In fact, a slight increase in the bioavailability of the antihypoglycemic drug is observed when the controlled release dosage form of the present invention is administered with food. In a preferred embodiment, the dosage form will be administered once a day, ideally with or after a meal and most preferably with or after the evening meal, and provide therapeutic levels of the drug throughout the day with peak plasma levels being obtained between 8-12 hours after administration.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] [0022]FIG. 1 is a graph which depicts the dissolution profile in simulated intestinal fluid (pH 7.5 phosphate buffer) and simulated gastric fluid (SGF) of the formulation described in Example 1 as tested according to the procedure described in United States Pharmacopeia XXIII, Apparatus 2@75 rpm.
[0023] [0023]FIG. 2 is a graph which depicts the dissolution profile in simulated intestinal fluid (pH 7.5 phosphate buffer) and simulated gastric fluid (SGF) of the formulation described in Example 2 as tested according to the procedure described in United States Pharmacopeia XXIII, Apparatus 2@75 rpm.
[0024] [0024]FIG. 3 is a graph which depicts the dissolution profile in simulated intestinal fluid (pH 7.5 phosphate buffer) and simulated gastric fluid (SGF) of the formulation described in Example 3 as tested according to the procedure described in United States Pharmacopeia XXIII, Apparatus 2@75 rpm.
[0025] [0025]FIG. 4 is a graph depicting the in vivo metformin plasma profile of the formulation described in Example 1 and the in vivo metformin plasma profile of the commercially available metformin HCl product GLUCOPHAGE® under fasting conditions.
[0026] [0026]FIG. 5 is a graph depicting the in vivo metformin plasma profile of the formulation described in Example 2 and the in vivo metformin plasma profile of the commercially available metformin HCl product GLUCOPHAGE® under fasting conditions.
[0027] [0027]FIG. 6 is a graph depicting the in vivo metformin plasma profile of the formulation described in Example 2 and the in vivo metformin plasma profile of the commercially available metformin HCl product GLUCOPHAGE® under fed conditions.
[0028] [0028]FIG. 7 is a graph depicting the in vivo metformin plasma profile of the formulation described in Example 3 and the in vivo metformin plasma profile of the commercially available metformin HCl product GLUCOPHAGE® under fed conditions (after breakfast).
[0029] [0029]FIG. 8 is a graph depicting the in vivo metformin plasma profile of the formulation described in Example 3 and the in vivo metformin plasma profile of the commercially available metformin HCl product GLUCOPHAGE® under fed conditions (after dinner).
DETAILED DESCRIPTION OF THE INVENTION
[0030] The term antihyperglycemic drugs as used in this specification refers to drugs that are useful in controlling or managing noninsulin-dependent diabetes mellitus (NIDDM). Preferably, the antihyperglycemic drug is a biguanide such as metformin or buformin or a pharmaceutically acceptable salt thereof such as metformin hydrochloride.
[0031] The binding agent may be any conventionally known pharmaceutically acceptable binder such as polyvinyl pyrrolidone, hydroxypropyl cellulose, hydroxyethyl cellulose, ethylcellulose, polymethacrylate, waxes and the like. Mixtures of the aforementioned binding agents may also be used. The preferred binding agents are water soluble such as polyvinyl pyrrolidone having a weight average molecular weight of 25,000 to 3,000,000. The binding agent comprises approximately about 0 to about 40% of the total weight of the core and preferably about 3% to about 15% of the total weight of the core.
[0032] The core may optionally comprise an absorption enhancer. The absorption enhancer can be any type of absorption enhancer commonly known in the art such as a fatty acid, a surfactant, a chelating agent, a bile salt or mixtures thereof. Examples of some preferred absorption enhancers are fatty acids such as capric acid, oleic acid and their monoglycerides, surfactants such as sodium lauryl sulfate, sodium taurocholate and polysorbate 80, chelating agents such as citric acid, phytic acid, ethylenediamine tetraacetic acid (EDTA) and ethylene glycol-bis(β-aminoethyl ether)-N,N,N,N-tetraacetic acid (EGTA). The core comprises approximately 0 to about 20% of the absorption enhancer based on the total weight of the core and most preferably about 2% to about 10% of the total weight of the core.
[0033] The core of the present invention which comprises the antihyperglycemic drug, the binder which preferably is a pharmaceutically acceptable water soluble polymer and the absorption enhancer is preferably formed by wet granulating the core ingredients and compressing the granules with the addition of a lubricant into a tablet on a rotary press. The core may also be formed by dry granulating the core ingredients and compressing the granules with the addition of a lubricant into tablets or by direct compression.
[0034] Other commonly known excipients may also be included into the core such as lubricants, pigments or dyes.
[0035] The homogeneous core is coated with a semipermeable membrane; preferably a modified polymeric membrane to form the controlled release tablet of the invention. The semipermeable membrane is permeable to the passage of an external fluid such as water and biological fluids and is impermeable to the passage of the antihyperglycemic drug in the core. Materials that are useful in forming the semipermeable membrane are cellulose esters, cellulose diesters, cellulose triesters, cellulose ethers, cellulose ester-ether, cellulose acylate, cellulose diacylate, cellulose triacylate, cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate. Other suitable polymers are described in U.S. Pat. Nos. 3,845,770, 3;916,899, 4,008,719, 4,036,228 and 4,11210 which are incorporated herein by reference. The most preferred semipermeable membrane material is cellulose acetate comprising an acetyl content of 39.3 to 40.3%, commercially available from Eastman Fine Chemicals.
[0036] In an alternative embodiment, the semipermeable membrane can be formed from the above-described polymers and a flux enhancing agent. The flux enhancing agent increases the volume of fluid imbibed into the core to enable the dosage form to dispense substantially all of the antihyperglycemic drug through the passageway and/or the porous membrane. The flux enhancing agent can be a water soluble material or an enteric material. Some examples of the preferred materials that are useful as flux enhancers are sodium chloride, potassium chloride, sucrose, sorbitol, mannitol, polyethylene glycol (PEG), propylene glycol, hydroxypropyl cellulose, hydroxypropyl methycellulose, hydroxypropyl methycellulose phthalate, cellulose acetate phthalate, polyvinyl alcohols, methacrylic acid copolymers and mixtures thereof. The preferred flux enhancer is PEG 400.
[0037] The flux enhancer may also be a drug that is water soluble such as metformin br its pharmaceutically acceptable salts or a drug that is soluble under intestinal conditions. If the flux enhancer is a drug, the present dosage form has the added advantage of providing an immediate release of the drug which is selected as the flux enhancer.
[0038] The flux enhancing agent comprises approximately 0 to about 40% of the total weight of the coating, most preferably about 2% to about 20% of the total weight of the coating. The flux enhancing agent dissolves or leaches from the semipermeable membrane to form paths in the semipermeable membrane for the fluid to enter the core and dissolve the active ingredient.
[0039] The semipermeable membrane may also be formed with commonly known excipients such a plasticizer. Some commonly known plasticizers include adipate, azelate, enzoate, citrate, stearate, isoebucate, sebacate, triethyl citrate, tri-n-butyl citrate, acetyl tri-n-butyl citrate, citric acid esters, and those described in the Encyclopedia of Polymer Science and Technology, Vol. 10 (1969), published by John Wiley & Sons. The preferred plasticizers are triacetin, acetylated monoglyceride, grape seed oil, olive oil, sesame oil, acetyltributylcitrate, acetyltriethylcitrate, glycerin sorbitol, diethyloxalate, diethylmalate, diethylfumarate, dibutylsuccinate, diethylmalonate, dioctylphthalate, dibutylsebacate, triethylcitrate, tributylcitrate, glyceroltributyrate, and the like. Depending on the particular plasticizer, amounts of from 0 to about 25%, and preferably about 2% to about 15% of the plasticizer can be used based upon the total weight of the coating.
[0040] As used herein the term passageway includes an aperture, orifice, bore, hole, weaken area or an erodible element such as a gelatin plug that erodes to form an osmotic passageway for the release of the antihyperglycemic drug from the dosage form. A detailed description of the passageway can be found in United States Patents such as U.S. Pat. Nos. 3,845,770, 3,916,899, 4,034,758, 4,077,407, 4,783,337 and 5,071,607.
[0041] Generally, the membrane coating around the core will comprise from about 1% to about 5% and preferably about 2% to about 3% based on the total weight of the core and coating.
[0042] In an alternative embodiment, the dosage form of the present invention may also comprise an effective amount of the antihyperglycemic drug that is available for immediate release. The effective amount of antihyperglycemic drug for immediate release may be coated onto the semipermeable membrane of the dosage form or it may be incorporated into the semipermeable membrane.
[0043] In a preferred embodiment the dosage form will have the following composition:
Preferred Most Preferred CORE: drug 50-98% 75-95% binder 0-40% 3-15% absorption enhancer 0-20% 2-10% COATING: semipermeable polymer 50-99% 75-95% flux enhancer 0-40% 2-20% plasticizer 0-25% 2-15%
[0044] The dosage forms prepared according to the present invention should exhibit the following dissolution profile when tested in a USP type 2 apparatus at 75 rpms in 900 ml of simulated intestinal fluid (pH 7.5 phosphate buffer) and at 37° C.:
Time (hours) Preferred Most Preferred 2 0-25% 0-15% 4 10-45% 20-40% 8 30-90% 45-90% 12 NTL 50% NTL 60% 16 NTL 60% NTL 70% 20 NTL 70% NTL 80%
[0045] NTL=NOT LESS THAN
[0046] In the preparation of the tablets of the invention, various conventional well known solvents may be used to prepare the granules and apply the external coating to the tablets of the invention. In addition, various diluents, excipients, lubricants, dyes, pigments, dispersants etc. which are disclosed in Remington's Pharmaceutical Sciences, 1995 Edition may be used to optimize the formulations of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
EXAMPLE 1
[0047] A controlled release tablet containing 850 mg of metformin HCl and having the following formula is prepared as follows:
I Core metformin HCl 90.54% povidone 1 , USP 4.38% sodium tribasic phosphate 4.58% magnesium stearate 0.5%
[0048] (a) Granulation
[0049] The metformin HCl is delumped by passing it through a 40 mesh screen and collecting it in a clean, polyethylene-lined container. The povidone, K-30, and sodium tribasic phosphate are dissolved in purified water. The delumped metformin HCl is then added to a top-spray fluidized bed granulator and granulated by spraying the binding solution of povidone and sodium tribasic phosphate under the following conditions: inlet air temperature of 50-70° C.; atomization air pressure of 1-3 bars; and spray rate of 10-100 ml/min.
[0050] Once the binding solution is depleted, the granules are dried in the granulator until the loss on drying is less than 2%. The dried granules are passed through a Comil equipped with the equivalent of an 18 mesh screen.
[0051] (b) Tableting
[0052] The magnesium stearate is passed through a 40 mesh stainless steel screen and blended with the metformin HCl granules for approximately five (5) minutes. After blending, the granules are compressed on a rotary press fitted with {fraction (15/32)}″ round standard concave punches (plain lower punch, upper punch with an approximately 1 mm indentation pin).
[0053] (c) Seal Coating (Optional)
[0054] The core tablet is seal coated with an Opadry material or other suitable water-soluble material by first dissolving the Opadry material, preferably Opadry Clear, in purified water. The Opadry solution is then sprayed onto the core tablet using a pan coater under the following conditions: exhaust air temperature of 38-42° C.; atomization pressure of 28-40 psi; and spay rate of 10-15 ml/min. The core tablet is coated with the sealing solution until a theoretical coating level of approximately 2% is obtained.
II Sustained Release Coating cellulose acetate (398-10) 2 85% triacetin 5% PEG 400 10%
[0055] (d) Sustained Release Coating
[0056] The cellulose acetate is dissolved in acetone while stirring with a homogenizer. The polyethylene glycol 400 and triacetin are added to the cellulose acetate solution and stirred until a clear solution is obtained. The clear coating solution is then sprayed onto the seal coated tablets in a fluidized bed coater employing the following conditions: product temperature of 16-22° C.; atomization pressure of approximately 3 bars; and spray rate of 120-150 ml/min. The sealed core tablet is coated until a theoretical coating level of approximately 3% is obtained.
[0057] The resulting tablet is tested in simulated intestinal fluid (pH 7.5) and simulated gastric fluid (SGF) according to the procedure described in United States Pharmacopeia XXIII, Apparatus 2@75 rpm and found to have the following release profile:
TIME (hours) % Released (SGF) % Released (pH 7.5) 2 9 12 4 27 32 8 62 82 12 82 100 16 88 105 20 92 108
[0058] The release profile in pH 7.5 and SGF of the sustained release product prepared in this Example is shown in FIG. 1.
[0059] [0059]FIG. 4 depicts the in vivo metformin plasma profile of the sustained release product prepared in this Example. Also shown in FIG. 4 is the in vivo metformin plasma profile of GLUCOPHAGE®, a commercially available pharmaceutical product containing the drug metformin HCl.
EXAMPLE 2
[0060] A controlled release tablet containing 850 mg of metformin HCl and having the following formula is prepared as follows:
I Core metformin HCl 88.555% povidone 3 , USP 6.368% sodium lauryl sulfate 4.577% magnesium stearate 0.5%
[0061] (a) Granulation
[0062] The metformin HCl and sodium lauryl sulfate are delumped by passing them through a 40 mesh screen and collecting them in a clean, polyethylene-lined container. The povidone, K-90F, is dissolved in purified water. The delumped metformin HCl and sodium lauryl sulfate are then added to a top-spray fluidized bed granulator and granulated by spraying with the binding solution of povidone under the following conditions: inlet air temperature of 50-70° C.; atomization air pressure of 1-3 bars; and spray rate of 10-100 ml/min.
[0063] Once the binding solution is depleted, the granules are dried in the granulator until the loss on drying is less than 2%. The dried granules are passed through a Comil equipped with the equivalent of an 18 mesh screen.
[0064] (b) Tableting
[0065] The magnesium stearate is passed through a 40 mesh stainless steel screen and blended with the metformin HCl granules for approximately five (5) minutes. After blending, the coated granules are compressed on a rotary press fitted with {fraction (15/32)}″ round standard concave punches (plain lower punch, upper punch with an approximately 1 mm indentation pin).
[0066] (c) Seal Coating (Optional)
[0067] The core tablet is seal coated with an Opadry material or other suitable water-soluble material by first dissolving the Opadry material, preferably Opadry Clear in purified water. The Opadry solution is then sprayed onto the core tablet using a pan coater under the following conditions: exhaust air temperature of 38-42° C.; atomization pressure of 28-40 psi; and spay rate of 10-15 ml/min. The core tablet is coated with the sealing solution until a theoretical coating level of approximately 2% is obtained.
II Sustained Release Coating cellulose acetate (398-10) 4 85% triacetin 5% PEG 400 10%
[0068] (d) Sustained Release Coating
[0069] The cellulose acetate is dissolved in acetone while stirring with a homogenizer. The polyethylene glycol 400 and triacetin are added to the cellulose acetate solution and stirred until a clear solution is obtained. The clear coating solution is then sprayed onto the seal coated tablets in a fluidized bed coater employing the following conditions: product temperature of 16-22° C.; atomization pressure of approximately 3 bars; and spray rate of 120-150 ml/min. The sealed core tablet is coated until a theoretical coating level of approximately 3% is obtained.
[0070] The resulting tablet is tested in simulated intestinal fluid (pH 7.5) and simulated gastric fluid (SGF) according to the procedure described in United States Pharmacopeia XXIII, Apparatus 2@75 rpm and found to have the following release profile:
TIME (hours) % Released (SGF) % Released (pH 7.5) 2 13 12 4 29 27 8 55 52 12 72 71 16 81 83 20 87 91
[0071] The release profile in pH 7.5 and SGF of the sustained release product prepared in this Example is shown in FIG. 2.
[0072] [0072]FIG. 5 depicts the in vivo metformin plasma profile of the sustained release product prepared in this Example under fasting conditions. FIG. 5 also shows the in vivo metformin plasma profile of the GLUCOPHAGE® product under fasting conditions.
[0073] [0073]FIG. 6 depicts the in vivo metformin plasma profile of the sustained release product prepared in this Example under fed conditions. FIG. 6 also shows the in vivo metformin plasma profile of the GLUCOPHAGE® product under fed conditions.
[0074] [0074]FIGS. 5 and 6 clearly show that the dosage forms prepared in accordance with the present invention exhibit consistent bioavailability under both fed and fasting conditions while the GLUOPHAGE® product's bioavailability decreases in the presence of food.
EXAMPLE 3
[0075] A controlled release tablet containing 850 mg of metformin HCl and having the same formula as in Example 2 is prepared as described in Example 2 except that an additional hole was drilled on the plain side of the coated tablet. The additional hole had a diameter of approximately 1 mm.
[0076] The resulting tablet is tested in simulated intestinal fluid (pH 7.5) and simulated gastric fluid (SGF) according to the procedure described in United States Pharmacopeia XXIII, Apparatus 2@75 rpm and found to have the following release profile:
TIME (hours) % Released (SGF) % Released (pH 7.5) 2 13 14 4 27 28 8 50 63 12 67 84 16 84 95 20 97 102
[0077] The release profile in pH 7.5 and SGF of the sustained release product prepared in this Example is shown in FIG. 3.
[0078] [0078]FIG. 7 depicts the in vivo metformin plasma profile of the sustained release product prepared in this Example when administered shortly after breakfast. FIG. 7 also shows the in vivo metformin plasma profile of the GLUCOPHAGE® product administered shortly after breakfast.
[0079] [0079]FIG. 8 depicts the in vivo metformin plasma profile of the sustained release product prepared in this Example when administered shortly after dinner. FIG. 8 also shows the in vivo metformin plasma profile of the GLUCOPHAGE® product administered shortly after dinner.
[0080] Table 1 is a summary of the bioavailability comparision data, test/reference ratio, shown in FIGS. 4 - 8 wherein the GLUCOPHAGE® product is the reference product in a two way crossover biostudy with n=6.
TABLE 1 Formula FIG. Study AUC Cmax Tmax Ex. 1 4 Fasting 0.202 0.12 2.15 Ex. 2 5 Fasting 0.369 0.214 1.73 Ex. 2 6 Fed (bkft) 0.628 0.305 1.94 Ex. 3 7 Fed (bkft) 0.797 0.528 1.82 Ex. 3 8 Fed (dinner) 0.850 0.751 2.00
[0081] The results reported in Table 1 and FIGS. 4 - 8 show that dosage forms prepared in accordance with the present invention exhibit an increase in the bioavailability of the antihyperglycemic drug in the presence of food, especially when taken with or shortly after the evening meal.
[0082] While certain preferred and alternative embodiments of the invention have been set forth for purposes of disclosing the invention, modifications to the disclosed embodiments may occur to those who are skilled in the art. Accordingly, the appended claims are intended to cover all embodiments of the invention and modifications thereof which do not depart from the spirit and scope of the invention. | Sustained release pharmaceutical formulations comprising an antihyperglycemic drug or a pharmaceutically acceptable salt thereof are disclosed. The formulations provide therapeutic plasma levels of the antihyperglycemic drug to a human patient over a 24 hour period after administration. | 0 |
BACKGROUND
This invention uses, for illustration purposes only, as a matrix, the closed-toe shoe illustrated, (FIGS. 11, 12, 13, 14) in U.S. Pat. No. 6,212,798 as a model for the invention. The specific design of the closed-toe shoe should not be considered part of this patent application.
1. Field of Invention
This invention relates to shoes and devices used to give relief to tired, achy feet, specifically following prolonged activity.
2. Prior Art
Persons that stand for long periods or walk excessive distance during a normal day are subject to tired, achy feet which may be compounded by swelling. Traditionally, these persons will desire the removal of their shoes at the earliest opportunity. Often they have soaked their feet and massaged them to reduce discomfort.
Thereafter, inventors created various whirlpool bath machines that allowed water to be swirled causing a massaging effect on the foot. Other portable machines warmed water or allowed warm water to be kept warm while having a vibrating action employed to bring comfort. Still other machines had a vibrating platform with which to apply the feet, for the same desired effect. The difficulty with each modality is the lack of portability, the machines being cumbersome and heavy, especially those that are filled with water. Vibrating machines are heavy to move, difficult to store and require that the user be stationary during therapy sessions.
My current invention is an improved way to bring comfort to therefore mentioned condition, with the advantage of portability while allowing ambulation.
OBJECTS AND ADVANTAGES
Accordingly, among the objects and advantages of the present invention include:
(a) Lightweight construction of the therapeutic vibrating shoe; (b) Portability of having a soothing modality included in a shoe; (c) The person using the Therapeutic Vibrating Shoe does not have to maintain a single position, but can move about while soothing vibration is being applied; (d) Therapy can be appreciated while a person is in transit, as in riding in a car or flying on an airplane; (e) The person using the Therapeutic Vibrating Shoe may choose to remain seated with feet elevated or dependent, reclining, supine, prone or ambulatory while soothing vibration is experienced but feet are enclosed and thus body warmth is preserved; (f) This type of shoe/therapy construction is inexpensive, therefore making this type of soothing vibratory therapy affordable.
DRAWING FIGURES
FIG. 1 is outside lateral view of shoe revealing vibrator motor (a) installed in central arch of the sole of the shoe, battery source pack (b) installed in the heel of the sole of the shoe, and wiring harness (c) from battery source pack (b) to vibrator motor (a).
FIG. 2 is inside medial view of shoe revealing vibrator motor (a) installed in central arch of the sole of the shoe, battery source pack (b) installed in the heel of the sole of the shoe, wiring harness (c) from battery source pack (b) to power on/off switch (d) and then to vibrator motor (a).
FIG. 3 is top view reveal of the sole of the shoe with vibrator motor (a), connected to wiring harness (c), connecting to power on/off switch (d) and making connection with battery source pack (b).
FIG. 4 is medial inside view of sole of shoe containing vibrator motor (a), battery source pack (b), and power on/off switch (d).
FIG. 5 is top view of shoe revealing inside of shoe to expose hatch for accessibility to battery source pack (b).
DESCRIPTION
A typical embodiment of the vibrator of the present invention is illustrated in FIG. 1 (outside lateral view) and FIG. 2 (inside medial view). The vibrator motor is mounted in the sole of the shoe in the central region of the arch. One section of the center framework of the sole has been removed to accommodate the vibrator motor. The motor is cemented in place. In the preferred embodiment of the shoe, the sole is injection-molded polyurethane. The battery pack frame is installed in the heel of the sole and cemented in place, with an access door in the lining and insole of the shoe to allow battery change. An on/off switch is mounted through the medial wall of the sole at the heel. Wiring is through small channels in the sole framework, so that wiring is flush inside the sole. The circuitry consists of a direct wire from the negative pole of the battery pack to the vibrator motor. The wire from the positive pole of the battery pack is interrupted by the on/off switch and continues on to the positive pole entering the motor.
Additional illustrations of the embodiment of the vibrator mechanism in the sole are shown in FIG. 3 (top view) and FIG. 4 (side view). FIG. 5 (top view of completed shoe) shows the access to battery pack.
OPERATION
The vibrator is an electric motor and short armature to which is mounted an eccentric lobe, and housed in a plastic box. As the motor spins, off-balance of the eccentric lobe causes vibration. Vibration frequency is estimated at 5000 revolutions per minute. The vibration is translated into the motor housing and then into the sole of the shoe. The vibrations are transmitted from the motor housing, radiating to the toes of the foot through the axis of the framework of sole of the shoe and at the same time, radiate to the heel of the foot. With the strategic placement of the vibrator motor, soothing vibration is perceived throughout the foot, dissipating at the level of the ankle joint. The power source is 2 AAA batteries in series creating 3 volts of current.
The theory of the vibrating shoe' therapeutic action is related to the concept of temporarily increased circulation to a vibrating muscle. This increase in circulation causes the removal of built-up lactic acid in the muscles, creating soreness. Lactic acid accumulation is the result of muscle activity during fatigue. In addition, vibration has long been recognized as a soothing sensation to the body. There may be some transient heat increase as a result of increased muscular circulation. Gentle increases in heat have also, long been recognized as soothing to the body.
SUMMARY, RAMIFICATIONS, AND SCOPE
Accordingly, the reader will see that the invention, the vibrating shoe can be used to comfort the feet following activity. This form of foot comfort is portable, allowing movement around the abode while receiving this treatment. In addition, the vibrating shoes can be used while riding in a car, airliner and other forms of travel. Vibrating shoes are lightweight and are powered by 2 AAA batteries, allowing for shoes to be carried in personal luggage and therefore may be used on business and pleasure trips in hotels or other guest facilities, without the need for power converters. The vibration treatment of the feet with the vibrating shoe has many advantages over previous modalities because;
it is personal and will not disturb others in a public place therefore can be used during long waiting in terminals; it is self-contained and does not require hook-ups, so the user is free to move about; it does not require water in a basin as a vehicle to translate vibration into the foot and is therefore not messy or dangerous; it does not require AC or DC current to power the vibrator source and is therefore portable and useable in any environment; it is contained within the confines of a soft shoe with a semi-firm sole and therefore maintains body warmth and uses the body warmth to augment soothing treatment; it employs inexpensive parts and technology therefore making this form of treatment, inexpensive and affordable.
Although the description above contains many specificities, these should not be construed as limiting the scope of the vibrating shoe but as merely providing illustrations of some of the presently preferred embodiments of this invention. For example, the shoe can have other shapes such as a broader, less contoured sole and closure configurations such as elastic strap closure instead of hook and loop strap closure. The on/off switch could be a push button instead of a sliding switch.
Thus the scope of the invention should be determined by the appended claims and their legal equivalents, rather than by the examples give. | A soft body shoe with a semi-rigid molded unit-bottom sole having a self-contained battery powered vibrator mechanism built in to the sole at the arch. The sole of the shoe so constructed as to transmit vibrations through the entire bottom of the shoe, and into the wearer's foot. In addition, battery power is rechargeable via an adapter port in the rear part of the heel of each shoe | 0 |
FIELD OF THE INVENTION
This invention relates to a method of regulating silver halide emulsion formation. It particularly relates to the determination of the tabular silver halide grain population during nucleation and ripening.
BACKGROUND OF THE INVENTION
The formation of tabular silver halide photographic emulsions generally comprises of three main steps. These steps are, as described in U.S. Pat. No. 4,797,354 (Saitou, Urabe and Ozeki, 1989) (a) the nucleation step whereby the conditions are selected to generate mostly doubly twinned nuclei with parallel twin planes, which are suitable for producing tabular grains; (b) the ripening step whereby the conditions are changed to promote the dissolution of any nuclei that are not suitable for forming tabular grains (e.g., multiply twinned nuclei with nonparallel twin planes, singly twinned nuclei, octahedral and cuboctahedral nuclei), so that a high population of tabular crystals is achieved; and (c) the growth step whereby the surviving tabular grain nuclei are grown in size without changing their total number, by adding silver and halide reactants at rates which do not exceed the maximum growth rate as described by Wey and Strong in "Growth Mechanism of AgBr Crystals in Gelatin Solution", Photographic Science and Engineering, Vol. 21, 1977, pp. 14-18.
The nucleation and ripening steps are very important because they determine the final stable number of tabular crystals, and hence the average grain volume per mass of silver reactant added, as well as the tabular grain population of the final emulsion. Of these two steps, the nucleation step is the most critical because the effect of the ripening step is limited to reducing nontabular grain nuclei.
The final tabular grain population of AgBr emulsions containing small amounts of iodide and/or chloride is consequently, largely dependent on the nucleation step, which can be carried out by the single-jet method, where silver reactant is added to a well-mixed solution of gelatin, or other appropriate peptizer, and halide, or by the double-jet method, where silver and halide reactants are simultaneously added to a well-mixed solution of gelatin, or other appropriate peptizer, at a controlled pBr, as described by Duffin in "Photographic Emulsion Chemistry", Ch. IV, 1966, by Berry in "The Theory of the Photographic Process", Ch. 3, T. H. James (Ed.), 4th Ed. 1977, and by Wey in "Preparation and Properties of Solid State Materials", Vol. 6, Ch. 2, W. R. Wilcox (Ed.), 1981. The nucleation step can also be carried out by a dual-zone process, using a two-reactor system, where the silver reactant, the halide reactant, and gelatin or other appropriate peptizer are first mixed in a continuous reactor and then added to a second semi-batch reactor, which is used in the nucleation step as a holding vessel, and subsequently as a growth vessel, as described in U.S. Pat. No. 5,035,991 (Ichikawa, Ohnishi, Urabe, Kojima and Katoh, 1991) and U.S. Pat. No. 5,104,785 (Ichikawa, Ohnishi, Urabe and Katoh, 1992).
It is well known that there are several factors during the nucleation step that facilitate the formation of a large population of twinned AgBr nuclei which are suitable for growth to tabular crystals. Several of these factors which are important in the double-jet nucleation method are given in U.S. Pat. No. 4,945,037 (Saitou, 1990) col. 12, line 46, to col. 13, line 40, and of these the most important are the gelatin concentration, the rate of agitation in the nucleation vessel, the silver reactant addition rate, the temperature, the pBr, the presence of halides other than bromide, the pH, and the gelatin type.
PROBLEM TO BE SOLVED BY THE INVENTION
In order to determine the effect of all these nucleation factors on the propensity for tabular grain nuclei formation, in the interest of maximizing the morphological purity of the final tabular grain emulsions, the general method is to amplify the resulting stable nuclei through growth and without generating new nuclei (i.e., below the critical growth rate) and to examine the population of tabular grains in the final emulsion. This procedure poses several problems. Firstly, the effect of the nucleation step cannot be distinguished from the effect of the ripening step. Secondly, there is always the possibility of inadvertently producing new nuclei during the growth process, and thus compromising the effectiveness of this procedure. Thirdly, the growth time is generally much longer than the nucleation time, and consequently a relatively long process is used to study a much shorter one. In addition, the manual determination of the tabular grain population is very tedious.
SUMMARY OF THE INVENTION
The object of this invention is to provide a method, whereby the population of grains with tabular morphology in a photographic AgBr emulsion, which is dispersed in gelatin or other appropriate peptizer and which may contain small amounts of iodide and/or chloride can be maximized without growing the crystals but by simply examining the nucleation step.
Another object of this invention is to provide a method that can be used to monitor the formation of the tabular grains during the nucleation step.
These and other objects of the invention are generally accomplished by a method of measuring in order to control silver halide grain formation during nucleation and ripening comprising
combining a source of silver ions and a source of halide ions to form a suspension of nucleated particles,
removing a portion of said suspension,
measuring turbidity of said portion,
determining floc size from the turbidity measurement,
determining the difference between floc size and individual silver halide nuclei size. The difference between floc size and nuclei size allows prediction of the percentage of tabular grain population.
ADVANTAGEOUS EFFECT OF THE INVENTION
Since the turbidity measurements are made during the nucleation step they reveal specific information regarding only the nucleation process. In addition, no lengthy growth process is required to determine the tabular grain population. Instead, the information is made available directly and appropriate action may be taken immediately. If the population of tabular grains is too low, the nucleated emulsion may be dumped prior to wasting time and materials by growing the grains. Further, less material needs to be recycled for silver recovery.
DETAILED DESCRIPTION OF THE INVENTION
The invention method can be used as a research tool, as well as a production monitoring tool, and as a tool in scale-up operations. These objects and the determination of fundamental information on nuclei size and nuclei number can be accomplished by measuring the turbidity of appropriately treated samples which are taken from the reaction vessel at appropriate times during nucleation.
As is described below, these turbidity measurements can provide a metric for the extent of nuclei flocculation, which was discovered to be an indicator of the twinning propensity of nuclei and the formation of tabular grains in the presence of gelatin or other peptizers. The term "flocculation" herein refers to the reversible agglomeration of fine silver halide crystals resulting from bridging between the crystals by the gelatin or other peptizing polymers, as described by Kragh in the "Science and Technology of Gelatin", Ch. 4, A. G. Ward and A. Courts (Ed.), 1977. Similarly the term "floc" will refer to the aggregates formed by flocculation.
It is believed that the correlation between flocculation and the formation of tabular grains is because twinning results from the coalescence of fine crystals, which is, in this case, facilitated and attenuated by the flocculation produced by the gelatin or other peptizing polymer.
During the nucleation of silver halide crystals by the reaction of an aqueous silver salt with an aqueous halide salt, a large number of fine silver halide crystals is rapidly generated due to the low solubility of silver halides. The resulting phase change is governed by the supersaturation ratio (the ratio of the dissolved reagents and their solubility at the prevailing conditions) and the surface energy of the crystals, as described by Nielsen in "Kinetics of Precipitation", Ch. 1, 1964. These fine crystals are thermodynamically unstable because of the resulting decrease in surface energy when the particles are aggregated.
The stability of colloids has been extensively studied (see, for example, Adamson "Physical Chemistry of Surfaces", Ch. VI, 2nd Ed., 1967). In silver halide photographic emulsions, gelatin or other polymeric peptizers are added to overcome the inherent instability of the precipitated crystals. However, at low concentrations of gelatin where the same peptizer molecule may interact with two or more silver halide nuclei, flocculation occurs as disclosed by Antoniades and Wey in "Precipitation of Fine AgBr Crystals in a Continuous Reactor: Effect of Gelatin on Agglomeration", Journal of Imaging Science and Technology, Vol. 36, pp. 517-524, 1992 (hereinafter designated as Antoniades and Wey I), and in "Effect of Gelatin on the Agglomeration of Fine AgBr Crystals in Double-Jet Precipitation", Journal of Imaging Science and Technology, Vol. 37, pp. 272-280, 1993 (hereinafter designated as Antoniades and Wey II).
The extent of flocculation caused by the peptizer, as described above, can be quantified by measuring the effective average floc size, D f , and the average individual crystal size, D i , and calculating their difference ΔD f =D f -D i . If there is no significant difference between D i and D f , then, the nuclei cannot be flocculated. However, if ΔD f is large, then, there is significant flocculation.
The above measurements can be made using turbidity at wavelengths in the range of 400 to 900 nm. As shown by Berry in "Effects of Crystal Surface on the Optical Absorption Edge of AgBr", Physical Review, Vol. 153, pp. 989-992, 1967, the light absorbed by the crystals may be neglected as compared to the light scattered by the crystals in this wavelength range and for particle sizes from 20 to 100 nm. In addition, the suspension density of the crystals is relatively low during nucleation, and the wavelength used can be selected so that the particle size is much smaller than the wavelength so that Rayleigh scattering may be assumed and the Rayleigh equation can be used as given by Kerker, in "The Scattering of Light", p. 325, 1969, whereby the effective particle diameter, Dτ, is calculated from ##EQU1## In Eq. 1, τλ is the turbidity at wavelength, λ, given by ##EQU2## where l is the path length and T is the transmittance. Also, Φ v is the volume fraction of the solid particles, λ m is the wavelength in the medium (λ/n m ), and μ is given by ##EQU3## where n m is the refractive index of the medium and n p is the refractive index of the particles.
In Equation 1, the turbidity, τλ, can be measured by a spectrophotometer, and all other parameters are known, or can be calculated. Therefore, D f , D i , and ΔD f can be calculated. These measurements, their significance and their applications are described below in more detail, for the double-jet nucleation process and a continuous nucleation process, but can be analogously applied to any other nucleation process.
Double-Yet Nucleation:
During double-jet nucleation whereby a silver salt and a halide salt are added to a vigorously mixed solution of gelatin or other peptizer, there is initially a generation of a large number of nuclei when the supersaturation ratio exceeds that of a critical level. The nuclei number first increases, then decreases as the supersaturation ratio is relieved by the growth of the nuclei and then remains relatively constant, thus producing a stable number of nuclei. At this point the nucleation step is over and the resulting nuclei may be grown to a larger size without altering their total number, as discussed previously. This mechanism is consistent with the findings of Leubner, Jagannathan, and Wey in "Formation of Silver Bromide Crystals in Double-Jet Precipitation", Photographic Science and Engineering, Vol. 24, pp. 268-272, 1980, of Jagannathan and Wey in "Nucleation Behavior in the Precipitation of a Sparingly Soluble Salt - AgBr", Journal of Crystal Growth, Vol. 73, pp. 73-82, 1985, and of Sugimoto in "The Theory of the Nucleation of Monodisperse Particles in Open Systems and its Application to AgBr Systems", Journal of Colloid and Interface Science, Vol. 150, pp. 208-225, 1992.
In this invention a time is selected in the time-domain where the number of nuclei becomes relatively constant and D f is obtained by withdrawing a sample from the reaction vessel, measuring the turbidity and calculating the effective floc size from Equation 1. Alternatively, the turbidity can be measured in line, by circulating a small portion of the contents of the reaction vessel through a flow cell. The "time domain, where the number of nuclei becomes relatively constant" referred to above, is the period during nucleation when no additional stable nuclei are generated and all reactants added are consumed by the growth of the existing nuclei. The time domain where the number of nuclei relatively constant is generally from about 10 seconds to about 10 minutes after the beginning of nucleation. In addition, D i can be obtained by withdrawing a sample from the reaction vessel, appropriately quenching it to eliminate flocculation, measuring turbidity, and calculating the mean particle size from Equation 1. Alternatively, the deflocculation may be done in line by in-line dilution, quenching, and pumping through a flow cell, as discussed above, except that in this case the withdrawn samples cannot be returned to the vessel. Then, the difference ΔD f =D f -D i is used to provide a measure of the propensity for flocculation, which was found to be an indicator of the propensity for twinning and the formation of tabular grains from the nuclei generated at the conditions used to obtain ΔD f .
If there is no significant difference between D f and D i , it is concluded that no reversible aggregation occurred and no flocculation is inferred. However, if ΔD f is significant, it is concluded that reversible aggregation occurred, and significant flocculation is inferred. It is found that for the desirable high populations of tabular grains, substantial flocculation must be obtained; that is, ΔD f must be higher than 20 nm and preferably higher than 50 nm and most preferably higher than 100 nm. The correlation between the extent of flocculation (i.e., ΔD f ) and twinning propensity (i.e., the tabular grain population obtained) is demonstrated in the examples given below. Once this correlation is established, then, only ΔD f needs to be used to optimize tabular grain populations.
In such optimizations as discussed above, uncontrolled coalescence should be avoided, as it may lead to multiply twinned grains which are not suitable for tabular grain formation. As shown in Antoniades and Wey I and II, this occurs when the gelatin-to-silver ratio at the silver reactant introduction point is lower that about 50 g/mole.
Continuous Nucleation:
In this case, nucleation is occurring continuously, and a sample for determining D f from Equation 1 can be withdrawn and the turbidity measured, at any time after the reactor reaches a steady state. Also, D i can be determined from Equation 1 by withdrawing a sample from the continuous reactor, quenching it appropriately, and measuring the turbidity. Alternatively, these measurements may be made in line by directing part of the reactor effluent through a flow cell (with in-line dilution and quenching in the case of D i ). As above ΔD f is then used to indicate the propensity for twinning and the probability of tabular grain formation from the nuclei generated in the reactor at the conditions used to determine ΔD f . For high populations of tabular grain, ΔD f must be higher than 20 nm and preferably higher than 50 nm and most preferably higher than 100 nm.
While the description as set forth that the difference between individual silver halide nuclei size and the floc size is measured by determining both the individual particle size and the floc size, this as a practical matter may not be necessary in production. In the repetitious formation of production runs of silver halide, it will be known what the individual particle size is at a certain point by initial testing. Therefore, after a production process is set, it is merely necessary to determine the flocculated particle size, as the individual particle size will already be known. Therefore, in each instance, the individual particle size need not be determined, as the size may be known from previous nucleation. It usually is true that the individual particle size is so small (about 1-10 nm) that it is a relatively insignificant number in the calculation and may be neglected.
The term "floc" as utilized in this specification is meant to refer to an agglomeration of silver halide nuclei that are reversibly joined together and may be easily separated by a process such as dilution or addition of a deflocculant which adsorbs to the crystal surface and provides steric stabilization. This is in contrast to "coalescence" in which the particles would be joined into an agglomeration so firmly that they are not easily separated. In the formation of tabular silver halide emulsions it has been found that during nucleation, flocculation is desirable, and that emulsions in which flocculation has taken place to form flocs of silver halide nuclei will result in satisfactory tabular grain formation after growth. This is because flocculation produces a controlled amount of coalescence which results in twinning dislocations and the formation of tabular grains. In contrast, uncontrollably coalesced particles (e.g., in the absence of gelatin) will not result in grains useful for commercial photography after growth.
EXAMPLES
The following examples demonstrate the correlation between ΔD f as defined and discussed above, and the tabular grain population, and show how ΔD f can be used to optimize tabular grain populations. These examples also show the utility of using turbidity to predict and monitor the formation of AgBr tabular grains.
EXAMPLE 1
This example shows the correlation between ΔD f and the tabular grain population when the gelatin concentration and silver reactant flow rate during nucleation are varied, at 40° C. and several pBr conditions.
To an agitated 4.8 L solution containing lime processed ossein type gelatin (with a concentration of 2 g/L or 10 g/L) at 40° C., pH 4.5, and a specified pBr (1.5, 2.3, or 4.6), 100 mL of 3 M silver nitrate solution and 100 mL of sodium bromide at a concentration needed to maintain the initial pBr, were added at a constant flow rate (20 mL/min. or 150 mL/min.). The turbidity of the suspension during the precipitation was measured in line, by circulating a small amount of the suspension through a flow cell placed in a spectrophotometer. This measurement provided a means to measure D f at the end of the precipitation, using Equation 1 as described above. Similar D f results were obtained by using a wavelength of 430 nm with a flow cell of 1 mm path length and a wavelength of 830 nm with a flow cell of 2 mm path length. The values for n m at 430 and 830 nm were 1.343 and 1.327, respectively, and incorporate the effect of gelatin in the solution; and the values estimated for n p at 430 and 830 nm were 2.385 and 2.205, respectively. At the end of the reactant addition, a small sample was withdrawn from the reaction vessel and quenched with 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene (TAI) at high pH (>8) and by diluting to a suspension density of 0.03 mol AgBr/L. This procedure readily deflocculated the crystals (if they were flocculated) and greatly restrained Ostwald ripening. The level of TAI used was 350 g/mol AgBr which is much higher than the saturation coverage as given by Padday and Herz in "The Theory of the Photographic Process", Ch. 1-III, T. H. James, Ed., 4th Ed. 1977. This measurement provided D i at the end of the precipitation using Equation 1. Similar D i results were obtained by using a wavelength of 430 and 830 nm with a path length of 1 cm, and the same values of n m and n p as those given above. Finally, ΔD f was calculated from D f -D i as discussed above.
The twinning propensity for each nucleation carried out in the above experiments was also examined as follows. To an agitated 4.8 L solution containing gelatin (with a concentration of 2 g/l or 10 g/L) at 40° C., pH 4.5, and a specified pBr (1.5, 2.3 or 4.6), 25 mL of 3 M silver nitrate solution and 25 mL of a sodium bromide solution at a concentration needed to maintain the initial pBr were added at a constant flow rate (20 mL/min or 150 mL/min.). The gelatin type used was the same as in the first part of this example, and the agitation rate was also kept the same by monitoring the speed of the mixing device. After nucleation, the gelatin concentration and pBr in each experiment were changed to the same conditions (pBr of 1.5 and 10 g/L gelatin) by dumping a 1 L solution containing the appropriate amount of sodium bromide and gelatin. The temperature was then raised from 40° to 70° C. over 18 min., silver nitrate solution (at constant 20 mL/min. flow rate) was first used until the pBr was raised to 2.0 (10 min.), and then double-jet addition of 1M silver nitrate and sodium bromide solutions (at a linearly increased flow rate of 20 to 100 mL/min. for 30 min) was used at this pBr until 2 moles of AgBr was precipitated. The morphology of the resulting crystals was then determined using a scanning electron microscope, and the tabular grain population of the resulting emulsions was determined. The tabular grain population was then rated as low if the projected area and number of tabular grains were both less than 50%, medium if the projected area of the tabular grains was higher than 50%, but the number of tabular grains was lower than 50%, and high if the projected area and number of tabular grains were both higher than 50%.
The results of ΔD f and the tabular grain population for each variation of gelatin concentration and reactant flow rate at the different pBr values used are given in Table I.
TABLE I______________________________________Correlation of ΔD.sub.f and Tabular Grain Population whenthe Concentration of Regular Gelatin and theReactant Flow Rate were Varied at 40° C. and SeveralpBr Conditions.Gelatin Conc Reactant Flow ΔD.sub.f Tabular Grain(g/L) Rate (mL/min) (nm) Population______________________________________pBr 4.610 150 --.sup.a Low2 150 65.9 High2 20 --.sup.a LowpBr 2.310 150 --.sup.a Low2 150 >100 High2 20 5.4 LowpBr 1.510 150 --.sup.a Low2 150 >100 High2 20 >100 High______________________________________ .sup.a No statistically significant difference between D.sub.i and D.sub.
EXAMPLE 2
This example shows the correlation between ΔD f and the tabular grain population when the nucleation gelatin was replaced with peroxide treated gelatin.
In this example, everything was the same as in Example 1, except the gelatin added to the reactor initially was gelatin that was treated with peroxide as disclosed by Maskasky in U.S. Pat. No. 4,713,320 (1987). The gelatin added at the end of the nucleation step by the dumped solution was the same as that used in Example 1. The results of these experiments are given in Table II.
TABLE II______________________________________Correlation of ΔD.sub.f and Tabular Grain Population whenthe Concentration of Peroxide Treated Gelatin andthe Reactant Flow Rate were Varied at 40° C. andSeveral pBr Conditions.Gelatin Conc Reactant Flow ΔD.sub.f Tabular Grain(g/L) Rate (mL/min) (nm) Population______________________________________pBr 4.610 150 --.sup.a Low2 150 26.7 High2 20 --.sup.a LowpBr 2.310 150 --.sup.a Low2 150 >100 High2 20 14.1 LowpBr 1.510 150 --.sup.a Low2 150 >100 High2 20 >100 High______________________________________ .sup.a No statistically significant difference between D.sub.i and D.sub.
EXAMPLE 3
This example shows the correlation between ΔD f and the tabular grain population when the rate of agitation during nucleation was varied.
In this example, everything was the same as in Example 1, except the initial gelatin concentration was 5 g/L, the reactant flow rates during nucleation were 150 mL/min., and the initial pBr was 2.3. For one condition of this experiment the rate of agitation was the same as in Example 1 (herein designated as high), and for the second condition the rate of agitation was decreased by a factor of two (herein designated as low). The results from these experiments are shown in Table III.
TABLE III______________________________________Correlation of ΔD.sub.f and Tabular Grain Population when theRate of Agitation was VariedRate of Reactant Flow ΔD.sub.f Tabular GrainAgitation Rate (mL/min) (nm) Population______________________________________pBr 2.3High 150 10 LowLow 150 >50 High______________________________________
EXAMPLE 4
This example shows the correlation between ΔD f and the tabular grain population at a higher temperature of 70° C.
In this example everything was identical to Example 1, except the temperature was raised to 70° C. In the second part of the experiment where the nuclei were grown in order to examine the tabular grain population, instead of the temperature ramp from 40° to 70° C., the nuclei were held at 70° C. for 10 min. The results from these experiments are shown in Table IV.
TABLE IV______________________________________Correlation of ΔD.sub.f and Tabular Grain Population whenthe Concentration of Regular Gelatin and theReactant Flow Rate were Varied at 70° C. and SeveralpBr Conditions.Gelatin Conc Reactant Flow ΔD.sub.f Tabular Grain(g/L) Rate (mL/min) (nm) Population______________________________________pBr 4.610 150 --.sup.a Low2 150 4.8 Medium2 20 --.sup.a LowpBr 2.310 150 --.sup.a Low2 150 7.8 Medium2 20 --.sup.a LowpBr 1.510 150 --.sup.a Low2 150 49.4 High2 20 13.7 Medium______________________________________ .sup.a No statistically significant difference between D.sub.i and D.sub.
The above examples show that there is a correlation between flocculation and the generation of nuclei that form tabular crystals. This correlation is explained as follows. At conditions of low availability of gelatin or other peptizer, the fine nuclei which are rapidly formed at the silver reactant introduction point are forced to initially share the limited available gelatin through bridging, thus causing flocculation. The flocculation then facilitates further interaction between the crystals which results in controlled coalescence. During coalescence, twinning occurs if there is misalignment of the coalescing [111] faces, and multiple twinning results in the formation of tabular grains as discussed by Mumaw and Haugh in "Silver Halide Precipitation Coalescence Processes", Journal Imaging Science, Vol. 30, pp. 198-209, 1986. Therefore, flocculation (i.e., ΔD f ) is a good predictor of desirable twinning that produces crystals which are suitable for tabular grain formation.
In the absence of gelatin uncontrolled coalescence occurs, thus, producing crystals which are not suitable for the formation of tabular grain emulsions with high aspect ratios and high populations of tabular grains, due to the formation of uncontrolled multiple twinning which results in thicker grains and grains with nonparallel multiple twins. As a result, such a condition, as well as very low gelatin-to-silver ratios below 50 g/mole at the silver reactant introduction point (see Antoniades and Wey I and II), should be avoided. On the other hand, when sufficient gelatin or other peptizer is available at the silver reactant introduction point, the fine crystals produced during nucleation are stabilized by the gelatin or other peptizer, so that no flocculation or coalescence occurs (ΔD f below 20 nm), and no significant amount of twinning is obtained.
This mechanism also explains the observed effects of the factors, listed in U.S. Pat. No. 4,945,037 (Saitou, 1990) on the twinning propensity, since the same factors were found to affect flocculation and coalescence, as discussed in Antoniades and Wey I and II. For example, in double-jet nucleation, (1) when the gelatin concentration is increased, flocculation and coalescence are decreased and the probability of twinned crystal plane formation is decreased; (2) when the rate of agitation is increased, flocculation and coalescence are decreased and the probability of twinned crystal formation is decreased; (3) when the rate of silver reactant addition is reduced, flocculation and coalescence are decreased and the probability of twin crystal formation is decreased; and (4) when the temperature during nucleation is increased, flocculation and coalescence are decreased and the probability of twin crystal formation is decreased.
Advantages
In this invention we describe a method for predicting twinning and the formation of tabular crystals, by appropriate turbidity measurements of the AgX suspension during the nucleation step, so that no lengthy growth steps are required to determine the population of tabular crystals. This provides a means of rapidly and efficiently optimizing tabular grain nucleations.
Similar turbidity measurements can be used to monitor twin crystal formation during the precipitation of tabular crystals so that appropriate action may be taken immediately. For example, the turbidity measurements described here for obtaining D i and D f can be made in-line (i.e., in-line τλ measurement for D f , and in-line dilution, quenching, and τλ measurement for D i ). Alternatively, in most cases D f >>D i and ΔD f ≅D f . Therefore, an in-line measurement of the turbidity during nucleation would yield D f and, hence, ΔD f . In such cases, the magnitude of the in-line turbidity would reveal the propensity of twinning. Consequently, corrective action may be taken based on this real time measurement. For instance, if the turbidity is lower than a specific value required for a particular nucleation, then the silver reactant addition rate could be increased, or the mixing intensity could be decreased. Finally, the precipitation may be terminated if a specific turbidity value is not attained, thus significantly reducing waste.
Furthermore, these measurements may be used in scale-up operations. In this case, the turbidity measurements would indicate if all the key nucleation parameters are scaled up properly, thus, accelerating the scale-up process.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications, can be effected within the spirit and scope of the invention. | The invention provides a method of measuring to control silver halide grain formation during nucleation and ripening comprising
combining a source of silver ions and a source of halide ions to form a suspension of nucleated particles,
removing a portion of said suspension,
measuring turbidity of said portion,
determining floc size from the turbidity measurement,
determining the difference between floc size and individual silver halide nuclei size. | 6 |
DESCRIPTION OF THE DRAWINGS
[0001] FIG. 1 is a perspective view of an embodiment of the invention;
[0002] FIG. 2 is a front view of the cylindrical downhole camera comprising the embodiment of FIG. 1 ;
[0003] FIGS. 3 a and 3 b are front and side views, respectively, illustrating the tilting characteristics of the downhole camera assembly of FIG. 2 ;
[0004] FIG. 4 is a perspective view illustrating the downhole viewing coverage obtained by tilting the camera of FIG. 2 ;
[0005] FIG. 5 is a perspective view illustrating the semi-spherical field of view of the downhole imaging tool of the invention obtained by both tilting and rotating the camera's antenna;
[0006] FIG. 6 is a block diagram illustrating the functional operation of the camera of FIG. 2 ;
[0007] FIG. 7 is a block diagram illustrating the functional operation of the overall downhole tool comprising the embodiment of FIG. 1 ;
[0008] FIG. 8 is a perspective view illustrating the downhole imaging tool of FIG. 1 used to detect and inspect damaged or stuck tools in a downhole well casing;
[0009] FIG. 9 is a perspective view illustrating the downhole imaging tool of FIG. 1 used to detect and inspect slots, slits, frac holes, cracks, pipe collars, protrusions and other obstructions in a downhole well casing;
[0010] FIG. 10 is a perspective view illustrating the downhole imaging tool of FIG. 1 used to detect and inspect stuck pipes, tools, and other structures in a downhole open well bore; and
[0011] FIG. 11 is a block diagram of the above ground equipment for the downhole inspection system of FIG. 1 .
DETAILED DESCRIPTION
[0012] Referring to the drawings, and particularly to FIGS. 1-11 , an embodiment of a downhole imaging tool and its method of use incorporating the invention is shown and generally designated by the reference numeral 10 .
[0013] In FIG. 1 , a new and improved downhole inspection tool 10 comprising an embodiment of the invention. The downhole inspection tool 10 is self contained and is comprised of a downhole camera assembly 18 , an antenna 20 , a data and control electronics assembly and memory 16 , a downhole tool power supply 14 , a backup battery module 15 , and a downhole centralizing unit 12 . The downhole camera assembly 18 may utilize millimeter wave imaging technology, typically operating in the frequency range from about 20 to about 300 GHz, however the tool is likewise capable of utilizing other imaging technologies including but not limited to of RF devices, microwave devices, infra-red devices, ultrasonic devices, acoustical devices, and optical devices. An appropriate antenna 20 is incorporated on the bottom end of the camera assembly 18 for directing the imaging source downward in a well bore onto a subject and for receiving images reflected therefrom. A data and control electronics assembly 16 is comprised of a microcontroller and a memory for storing programs, image data, and tool status data. The electronics assembly 16 further comprises means for two-way communication to above ground equipment via either wire or fiber optics or both. A downhole power supply 14 , which receives electric current at between about 200 volts and about 600 volts from an above ground AC or DC source, is used to develop required tool operating voltages ranging from between about plus and about minus 5 to 40 volts for use in powering the downhole tool. Optionally, the tool further comprises a backup battery module 15 as a secondary means of powering the camera and additional tool functions. The downhole inspection tool 10 is further comprised of a means for stabilizing itself inside a well tubing or casing through the utilization of devices comprised of one or more centralizing unit(s) 12 , and/or stabilizer locking feet. Finally, the downhole imaging tool further comprises a temperature sensor, a pressure sensor, a pressure safety relief valve, and other sensors as required.
[0014] The downhole inspection tool 10 is used for various inspection functions in a well bore. Such inspections include, but are not limited to locating other downhole tools that may be stuck or otherwise impaired, observing how best to loosen and retrieve, stuck or impaired tools, and assisting in attaching other retrieval devices to stuck or impaired tools for removal from the well bore. The downhole inspection tool is further useful in locating other areas of interest in a well bore, such as, locating frac holes in well casings, slots in well casings, cracks or fractures in casings or tubing, obstructions in casings or tubing, and protruding structures inside casings or tubing.
[0015] FIG. 2 is a more detailed description of the downhole camera assembly 18 of FIG. 1 . The camera assembly 18 houses the imaging module 26 , which includes the high frequency millimeter wave or other imaging components and associated electronics. A rotation motor 22 , located near the top of the camera assembly 18 , has a rotating shaft 24 extending from the bottom end and attaching to the top portion of the imaging module 26 . The rotating shaft 24 is limited to rotating the imaging module 26 in azimuth through 360 degrees in steps as small as 0.8 degrees or multiples thereof. Furthermore, an antenna tilting device 28 is attached between the bottom end of the imaging module 26 and the antenna 20 and is used to tilt the antenna through 180 degrees in elevation.
[0016] FIGS. 3 a and 3 b illustrate one configuration of the tilting device 28 for the camera assembly's antenna 20 . The tilting device 28 rotates a pin 32 , which is attached to a rotating antenna mounting plate 30 , so that when the pin 32 rotates the antenna 20 rotates through a 180 degree arc. In another embodiment a servo controlled swivel rotates the antenna 20 through a 180 degree arc.
[0017] FIG. 4 illustrates tilting the camera antenna 20 over a 180 degree arc to illuminate a circular field of interest 36 . The camera antenna 20 is shown positioned at 0 degrees 35 looking directly into the wall of a well casing 34 , at 90 degrees 36 straight down the well bore casing, and at 135 degrees 37 , respectively.
[0018] FIG. 5 illustrates the semi-hemispherical field of view 38 capability of the inspection tool 10 which is achieved by coupling the 360 degree rotation of the imaging module 26 with the 180 degree tilting characteristics of the tilting device 28 . The combination of rotating the imaging module 26 , which has the tilting device 28 and the antenna 20 attached at the bottom end thereof, through up to 360 degrees and tilting the antenna using the tilting device 28 through an angle up to 180 degrees allows the antenna to be focused 40 at any desired location within a hemispherical field of view 38 . In another embodiment the antenna is positioned by a servo controlled swivel.
[0019] FIG. 6 is block diagram for the milli-meter wave camera assembly 18 utilized in the downhole inspection tool 10 which, in one embodiment of the invention operates in the frequency range of between about 20 and about 300 GHz. The basic components of the camera assembly 18 comprise a voltage controlled oscillator 42 coupled to a pre-amplifier 43 , which drives the input of feedback control circuitry 44 . The output of the feedback control circuitry 44 connects both to the antenna 20 and a low noise amplifier 45 , which couples to a signal output takeoff 46 and back into the feedback circuit 44 . A low noise intermediate frequency (IF) output signal is then taken from the output takeoff 46 .
[0020] FIG. 7 is a block diagram illustrating the functional operation of a downhole inspection tool comprising an embodiment of the invention. A microcontroller unit (MCU) 50 , which communicates with an above ground control console by means of a transceiver 49 and tool interface 48 , provides master control of a downhole inspection tool comprising an embodiment of the invention. The MCU 50 controls the camera controller 54 , the data acquisition unit 58 , the imaging and control data memory bank 60 , the motor controller 52 , and antenna position controller 56 of the downhole inspection tool. The MCU 50 also tracks and communicates tool status to an above ground control console by means of the transceiver 49 .
[0021] FIG. 8 is a perspective view illustrating an embodiment of the downhole inspection tool 10 used to detect and inspect damaged or stuck tools in a downhole well casing. The camera of the downhole inspection tool 10 focuses the circular field-of-view 36 from the antenna 20 on a broken drill bit 62 that is lodged sideways in a well casing 34 . The picture from the camera assembles of the downhole inspection tool is displayed on an above ground computer monitor for viewing by personnel of the tool retrieval crew to aid in more efficiently removing the broken drill bit.
[0022] FIG. 9 is a perspective view illustrating an embodiment of the downhole inspection tool 10 used to inspect the conditions in a well bore casing 34 . This illustrates the use of the tool for locating and inspecting such features as casing slots 64 and smaller slits 66 , casing frac holes 68 , casing cracks 70 , casing pipe joint collars 72 , casing wall protrusions 74 , and other unwanted obstructions within a downhole well bore. In FIG. 9 the camera's antenna 20 is shown focused at 0 degrees 35 on a slot 64 in a well casing 34 .
[0023] FIG. 10 is a perspective view illustrating an embodiment of the downhole inspection tool 10 used to inspect the conditions in an open well bore 76 . This illustrates the use of the tool in which the tool's antenna 20 is focused 36 on a broken pipe 78 being lodge crosswise in an open well bore, thereby blocking access to the well bore for other tools and/or equipment to be placed therein.
[0024] FIG. 11 is a block diagram of the above ground equipment control console for operating embodiments of the downhole inspection tool 10 . The above ground equipment control console is comprised of a controller 80 and computer/display 82 for controlling the overall operation of the system and displaying operational, status, and image data, a memory bank 84 for storing system and image information, an image processor 86 for processing image data, a transmitter/receiver (transceiver) 88 for communicating through a slip-ring interface 92 and downhole cable 94 , and a power supply 90 for supplying power to both the downhole tool power supply 14 and above ground equipment.
[0025] Embodiments of the downhole inspection tool 10 can be operated in either wireline or slickline modes of operation. In the slickline mode there is no electrical connection with above ground equipment. In this mode the system operates from onboard battery power and stores image and status data in an onboard data storage memory bank. In this mode of operation, the tool is automatically turned on by onboard means, such as a timer, pressure sensor, or temperature sensor and takes downhole pictures based on a stored onboard operational program. The image data is then stored in the onboard data storage memory bank for above ground viewing later.
[0026] Various embodiments of a downhole inspection tool and method have been described in detail herein. It will be appreciated, however, that the invention provides applicable inventive concepts that can be embodied in a wide variety of contexts. For example, while the description has included embodiments of the tool used in downhole oil and gas well applications, it can provide inspective functions in many other applications and especially so where high pressure and/or high temperature environments are involved.
[0027] Although the invention has been described with reference to an illustrative embodiment, the foregoing description is not intended to limit the scope of the invention. Various modifications and combinations of the illustrative embodiments as well as other embodiments of the invention will be apparent to persons skilled in the art upon reference to the description. It is therefore intended that the appended claims incorporate any such modifications or embodiments. | A downhole inspection tool for observing conditions in the harsh environment of a well bore. An embodiment of the tool comprises a high frequency camera, which operates in the millimeter wave frequency range with the capability of seeing through opaque environments. In use, the tool system provides pictures of conditions downhole for use by operators attempting to repair and/or remove broken downhole equipment by being able to observe the actual downhole conditions that exist. Furthermore, the system can be used to inspect the inside of a well casing or tubing for the presence of cracks, frac holes, slots, slits, protruding structures, stuck hardware, environmental conditions, etc. | 4 |
BACKGROUND OF THE INVENTION
[0001] Typically topical, otic, or ophthalmic products containing water insoluble steroid(s) alone or in combination with antimicrobial agent(s) are very greasy because of mineral oil or petrolatum present in the suspension. Such products are very hard to instill and spread into the ear canal or skin folds, especially on haired areas. In the case of otic application, the “oily residue” stays in the ear canal after application for prolonged periods of time, which is not desirable.
[0002] There are some aqueous suspensions (for example, Lotemax Suspension, for ophthalmic use) or oil-in-water lotion products for topical use. However, many of these products still leave non-drug residues because of high concentrations of suspending agents (0.2% w/w for example), surfactants (2-5% w/w) and/or oily components (2-10% w/w) which may cause harmful effects. The ideal topical, otic, or ophthalmic formulation should be low in residues, isotonic, aqueous based, and physically and chemically stable.
[0003] In U.S. Pat. No. 5,540,930, the non-ionic polymer concentration in its steroid composition is about 0.2-2% w/w and the claimed molar concentration range for the steroid:non-ionic-polymer:surfactant is between about 1:20:1 and about 1:0.01:0.5. U.S. Pat. No. 5,540,930 indicates that the polymer used in the formulation has to be non-ionic.
[0004] A reduction in amount of polymer and surfactant used in a steroid composition should be beneficial to the biological membrane. Thus, there exists a need for aqueous suspensions of water insoluble corticosteroids, which are free of problems of prior art formulations which can be easily applied.
SUMMARY OF THE INVENTION
[0005] The present invention provides formulations having very low concentrations of non-ionic polymers and very low concentrations of surfactants. The present invention also provides formulations having ionic polymers and very low concentrations of surfactants. It is surprisingly found that at the low concentrations of non-ionic polymers (e.g., 0.005% to 0.2% w/w), the re-suspension of the drug substance is better than the formulation comprising conventional concentrations (i.e., 0.2˜2% w/w) of non-ionic polymers. The following table shows molar ratios of steroid, polymers, and surfactant that can be used in this invention. These molar ratios of non-ionic polymer and surfactant range from about 1.7 to more than 1300 fold below the limits of U.S. Pat. No. 5,540,930,
U.S. Pat. No. 5,540,930 MW % w/w mM Molar ratio Molar Ratio Lower limit Etiprednol 485.41 0.2 4.120228 1 1 Dicloacetate Methocel ® 86,000 0.005-0.2 0.005814-0.0232558 0.000141-0.0056443 0.01 F4M Merquat ® 1,600,000 0.005-2 0.000313-0.0125 0.0000076-0.003034 Doesn't have non- 550 (9% ionic polymers. solid) Tyloxapol 5,000 0.005-0.3 0.01-0.2 0.0024271-0.0485410 0.5 Loteprednol 466.96 0.2 4.2830221 1 1 etabonate Methocel ® 86,000 0.005-0.2 0.005814-0.0232558 0.000141-0.0056443 0.01 F4M Merquat ® 1,600,000 0.005-2 0.000313-0.0125 0.0000076-0.003034 Doesn't have non- 550 (9% ionic polymers. solid) Tyloxapol 5,000 0.005-0.3 0.01-0.2 0.0024271-0.0485410 0.5
[0006] In addition to the unexpected improvements in physical properties, the use of low concentrations of surfactant and non-ionic polymer also surprisingly improves the pharmacological profile when compared to the formulation of drug suspended in mineral oil or without polymer. This second unexpected result is the reduction in systemic absorption of steroid, which is highly desirable given the side effects of steroidal drugs. Furthermore, contrary to U.S. Pat. No. 5,540,930, which is limited to non-ionic polymer only, however, we have also discovered that ionic polymers (e.g., Merquat® 550 and/or Xanthan gum) also work well in the present steroidal formulations.
[0007] Thus, surprisingly, we have found that by reducing the concentration of surfactant (e.g., Tyloxapol) from the prior art teaching of 0.3-2% w/w to 0.005-0.3% w/w and by either adding an ionic polymer or a low concentration, 0.005-0.2% w/w, of non-ionic polymer, the systemic absorption and as a consequence, the systemic (side) effect of anti-inflammatory corticosteroids, could be reduced by approximately 60%.
DETAILED DESCRIPTION OF THE INVENTION
[0008] A soft steroid antimicrobial combination topical and/or otic formulation has broad application for inflammatory conditions complicated by secondary bacterial and/or fungal infections. In fact, most ear and skin infections in companion animals are precipitated by an inflammatory process.
[0009] Examples of cutaneous and otic inflammatory diseases include but are not limited to:
Parasites such as Otodectes cynotis, Demodex spp., Sarcoptes scabiei, Notoedres cati, Cheyletiella spp., Ctenocephalides felis Foreign bodies such as plant awns Hypersensitivity and allergic diseases such as atopic dermatitis and otitis, food related dermatitis and otitis, contact allergic and irritant cutaneous and otic reactions, feline eosinophilic dermatitis Autoimmune diseases such as pemphigus foliaceus, pemphigus erythematosus, pemphigus vulgaris, pemphigus vegitans, discoid lupus erythematosus, cutaneous vasculitis, bullous pemphigoid, and mucous membrane pemphigoid
[0014] Bacterial and fungal infections may present secondary to the above inflammatory diseases or as primary infections. Common canine and feline cutaneous and/or otic pathogens include but are not limited to:
Staphylococcus intermedius Staphylococcus aureus Staphylococcus schleiferi Pseudomonas aeruginosa Streptococcus spp. Proteus mirabilis Escherichia coli Corynebacterium spp. Enterococcus spp. Malassezia pachydermatis Candida spp.
[0026] Systemic side effects are a limiting factor in the long-term use of anti-inflammatory corticosteroids. These side effects are well documented and include
suppression of the adreno-pituitary axis resulting in Cushing-syndrome, immunosuppression by a reduction in cell-mediated immunity and decreased antibody production, thus, increasing the risk of infections, retention of sodium and water and hence edema, urinary potassium increase, which leads to hypokalemia and metabolic alkalosis, hyperglycemia, delay in wound healing, altered calcium metabolism with prolonged treatment, resulting in osteoporosis and bone fractures, reduction in GI motility, thinning of the gastric mucosa, and reduced mucus production, thus resulting in gastrointestinal ulceration.
[0035] Therefore, a significant reduction in systemic absorption of steroid from formulation, which results in a safer long-term use of corticosteroids is highly desirable.
[0036] Some of the materials and their sources that can be used in the current inventions are listed below. The first table lists examples of water insoluble corticosteroids and anti-microbial agents that can be combined with the steroids. More than one steroid or more than one anti-microbial can be used in the present invention.
Drug substance Manufacturer Address Hydrocortisone Acetate micronized Shandong China Xinhua Hydrocortisone Acetate micronized Roussel Uclaf Paris, France Betamethasone dipropionate Sicor Via micronized Terrazzano, Italy Betamethasone dipropionate Pfizer Kalamazoo, MI Micronized Betamethasone Valerate, Micronized Pfizer Kalamazoo, MI Triamcinolone acetonide, Micronized Pfizer Kalamazoo, MI Clotrimazole micronized Erregierre, Sovere, Italy S.p.A. Polymyxin B sulfate Alphrama APS Copenhagen, Denmark
[0037]
Generic name
Trade Name
Manufacturer
Address
Hydroxypropylcellulose
Klucel GF Pharm
Hercules
Wilmington DE
HydroxyETHYLcellulose
Natrosol 250HHX
Hercules
Wilmington DE
HydroxyETHYLcellulose
Natrosol 250H
Hercules
Wilmington DE
Hydroxypropylmethylcellulose
Methocel ® F4M Prem
Dow Chem
Midland Michigan
Hydroxypropylmethylcellulose
Methocel ® K4M Prem
Dow Chem
Midland Michigan
Polyvinyl alcohol
Celvol V540
Celanese
Dallas, Tx
Polyethylene glycol
Polyox WSR N60K NF
Dow Chem
Midland Michigan
Xanthan gum
Kaltrol CGF
Kelco Biopolymers
Chicago, IL
Polyquaternium 7 series
Merquat ® 550 (9% solid)
Nalco
Naperville, IL
Tyloxapol
Tyloxapol, USP
Ruger Chemical Co.
Irvington, NJ
[0038] Additional surfactants include, but are not limited to, polysorbate 80, TWEEN 80 (ICI America Inc., Wilmington, Del.), PLURONIC F-68 (from BASF, Ludwigshafen, Germany) and poloxamer surfactants. Additional non-ionic polymers include, but are not limited to dextrans and other hydroxypropylmethylcelluloses, hydroxyethylcelluloses, hydroxypropylcelluloses, polyvinyl alcohols, and polyethylene glycols not listed above. Additional ionic polymers include, but are not limited to other xanthan gums and other highly charged cationic homo- or co-polymers (e.g., other copolymer of diallyl dimethyl ammonium chloride and acrylamide) not listed above.
[0039] The amount of surfactant present can range from 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, to 0.3% w/w, with other ranges and examples including (a) 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, to <0.3% w/w, (b) 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, to 0.05% w/w, and (c) 0.01% w/w. When no ionic polymer is present in the formulation, then the amount of surfactant present is preferably <0.3% w/w. The amount of non-ionic polymer present can range from 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, to 0.20% w/w with other ranges and examples including (a) 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, to <0.20% w/w, (b) 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, to 0.05% w/w, and (c) 0.01% w/w. When no ionic polymer is present in the formulation, then the amount of non-ionic polymer present is preferably <0.2% w/w. The amount of ionic polymer is not specifically limited, but can range from 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, to 2.0% w/w with other ranges and examples including (a) 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.90, to 1.0% w/w, (b) 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.20, 0.30, 0.40, to 0.50, % w/w, (c) 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, to 0.12% w/w, (d) 0.12% w/w and (e) 0.01% w/w. Both a non-ionic and ionic polymer can be present in the present invention.
[0040] The molar ratio of water insoluble corticosteroid, polymer (e.g., non-ionic polymer), and surfactant can be between about 1:0.000001:0.001 to about 1:0.01:0.49. Another example of this molar ratio is between about 1:0.0014:0.002 to about 1:0.006:0.15. These ratios are typically used when a non-ionic polymer is present, but can also apply when an ionic polymer is present.
[0041] Pharmaceutically acceptable excipients, as used herein, include anything that one of ordinary skill in the art would add to a composition in order to aid in its manufacture, stability, marketing, etc. Examples of excipients include, but are not limited to, preservatives (e.g., EDTA salts), glycerin, mineral oil, additional surfactants (e.g., Brij® 72 and Brij® 721), base (e.g., sodium hydroxide), acid (e.g., hydrochloric acid), methyl paraben, and water.
[0042] As an example, the present invention includes oil/lotion based suspensions. This type of suspension includes an oil (e.g., mineral oil) and a second surfactant capable of emulsifying the oil. The second surfactant can be two (or more) surfactants. Surfactants capable of emulsifying oil in pharmaceutical compositions are well known. Examples of surfactant pairs include, but are not limited to Brij® 72/Brij® 721, Brij® 78/Arlacel SM 60, Brij® 72/Brij® 78, and Brij® 52/Brij® 58 (Brij® surfactants are etherified polyethylene glycols, which are available from Uniqema) (Arlacel™ 60 is a sorbitan stearate surfactant available from Uniqema). The amount of second surfactant present can be from about 0.1 to 2% w/w. This amount includes the total amount of second surfactant, if the second surfactant is a pair (or more). The molar ratio of second surfactant to corticosteroid can be about 1:1.2 to 1:10 and 1:7 to 1:9. This ratio includes the total amount of second surfactant, if the second surfactant is a pair (or more).
EXAMPLES
[0043] Formulations in this invention include the following.
ED-Poly-B-Clo Otic suspension 1578- 1578- 1578- 1578- 1578- 1578- 1578- 57A 64 89T 90B 90D 90E 90F Ingredients % w/w % w/w % w/w % w/w % w/w % w/w % w/w Etiprednol 0.2 0.2 0.2 0.2 0.2 0.2 0.2 dicloacetate Polymyxin B 0.125 0.125 0.125 0.125 0.125 0.125 0.125 sulfate 10,000 U/g Clotrimazole 1 1 1 1 1 1 1 Micronized Tyloxapol 0.300 0.300 0.01 0.01 0.01 0.01 0.01 Methocel ® K4M 0.2 — — 0.01 — — 0.01 Methocel ® F4M — — — — 0.01 — — Merquat ® 550 — 2 0.556 — — 0.278 0.01 Methylparaben — 0.18 0.18 0.18 0.18 0.18 0.18 EDTA disodium 0.100 0.1 0.1 0.1 0.1 0.1 0.1 salts Glycerin 2.50 2.50 2.50 2.50 2.50 2.50 2.50 NaOH pH 5.0-5.5 QS QS QS QS QS QS QS Purified water 95.775 93.595 95.33 95.775 95.775 95.61 95.775 Total 100 100 100 100 100 100 100
[0044] The following procedures can be used to manufacture the formulations of the present invention. The non-ionic polymer, Methocel® F4M, is used as a non-limiting example.
1. Heat the purified water to 57-85° C., dissolve disodium edentate and tyloxapol first, then dissolve methylparaben. Disperse the Methocel® F4M and then cool to about 30° C. (Methocel® does not dissolve in hot water, so first disperse it in hot water and upon cooling, the Methocel® solution will become clear.) 2. Add glycerin to the vehicle in Step 1 and mix to dissolve. 3. For active drug substances, dissolve the water soluble drug substance (Polymyxin B sulfate in this example) in the vehicle first. 4. Add and disperse the water insoluble clotrimazole and etiprednol dicloacetate. High shear mixer would facilitate the dispersion for better uniformity. 5. Adjust the pH and QS to the final proper weight.
[0050] Formulation 1578-90D (Methocel® F4M 0.01%, tyloxapol 0.01%) can be re-suspended easily when compared to formulation 1578-57A, which comprises higher concentration of non-ionic polymer (0.2%) and surfactant (0.3%). It takes about 25˜30 vigorous shakes to suspend the drug substances in formulation 1578-57A. It takes only about 4 shakes for formulation 1578-90D. As non-ionic polymer concentration increases, it becomes harder to re-suspend the water insoluble corticosteroid.
[0051] The following additional formulations demonstrated the applicability of this type of formulation to other steroids (hydrocortisone acetate, betamethasone dipropionate, betamethasone valerate, triamcinolone acetonide) as well as polymer (Klucel, Natrosol, Methocel®, polyethylene glycol, polyvinyl alcohol, xanthan gum) combinations,
Steroid-antimicrobial suspensions 2170-96- 2170-96- 2170-90 2170-93-3 TRM10 TRM17 Ingredients % w/w % w/w % w/w % w/w Hydrocortisone Acetate, Microniced 1.12 — — — Etiprednol dicloacetate Micronized — 0.1 — — Triamcinolone acetonide Micronized — — 0.1 0.1 Clotrimazole Micronized 1.00 1.00 1.00 1.00 Tyloxapol 0.010 0.01 0.01 0.01 Hydroxypropyl methylcellulose 0.010 — 0.01 — (Methocel ® F4M) Hydroxypropyl cellulose, Klucel GF — 0.01 — — Polyethylene glycol, Polyox WSR N60K — — — 0.01 Methylparaben 0.18 0.18 0.18 0.18 EDTA disodium Salts 0.100 0.1 0.1 0.1 Glycerin 2.50 2.50 2.50 2.50 NaOH pH 5.0-5.5 QS QS QS QS Purified Water 95.775 95.775 95.775 95.775 Total 100 100 100 100 Steroid-antimicrobial suspensions 2170-96- 2170-96- 2170-96- 2170-96- 2170-96- BD5 BD-15 BV4 BV15 BV20 Ingredients % w/w % w/w % w/w % w/w % w/w Betamethasone dipropionate, 0.10 0.10 — — — Micronized Btamethasone valerate, Micronize — 0.10 0.10 0.10 Clotrimazole Micronized 1.00 1.00 1.00 1.00 1.00 Tyloxapol 0.01 0.01 0.01 0.01 0.01 Hydroxyethylcellulose, Natrosol 0.01 — — — — 250H Hydroxyethylcellulose, — — 0.01 — — Natrosol 250HHX Polyvinal alcohol — 0.01 — 0.01— — (Celvol V540) Xanthan gum (Kaltrol) — — — — 0.01 Methylparaben 0.18 0.18 0.18 0.18 0.18 EDTA disodium Salts 0.10 0.1 0.1 0.1 0.1 Glycerin 2.50 2.50 2.50 2.50 2.50 Purified Water 95.775 95.775 95.775 95.775 95.775 Total 100 100 100 100 100
[0052] The formulation with low concentration of surfactant (for example Tyloxapol at 0.01%) and non-ionic polymer (for example Methocel® F4M at 0.01% w/w) also reduced the systemic absorption of anti-inflammatory corticosteroids when applied topically. This was demonstrated in a validated mouse model as follows.
[0053] In the following experiment, the irritant, croton oil, was applied to one earlobe of the mice in the untreated control group and to both earlobes of the mice in the treatment groups to induce inflammation. The control group was left untreated after induction of inflammation. In the treatment group, the anti-inflammatory treatment was applied to one ear, one hour after croton oil application; the opposite ear was left untreated. Assessment of the reduction in ear-weight and ear-thickness on the non-treated earlobe was performed 3 hours after treatment application. Since the measurement is performed on the untreated ear, the reduction of ear weight or thickness is due to the drug that reached the untreated ear from systemic circulation after absorption of drug at the area of treatment. Results showed statistical significance (p<0.05) when the aqueous formulation with low concentration of surfactant and non-ionic polymer (Formulation 2170-79 & 2170-64) was compared to pure mineral oil formulation or aqueous formulation with no polymer (Formulation 2170-20).
[0054] Systemic effect of aqueous suspension and oil suspension on the opposite non-treated ear,
Ear weight (mg) mean +/− sd N = 20 N = 20 N = 20 Untreated control Betamethasone 0.1% in Betamethasone 0.1% in group aqueous formulation pure mineral oil* group 2170-64* group 47.53 +/− 5.66 40.18 +/− 4.29 a 34.93 +/− 3.09 a,b Reduction in (40.18-47.53)/(34.93-47.53) × 100 = 58% systemic effect= Ear thickness (×10 −2 mm)) mean +/− sd N = 20 N = 20 N = 20 Untreated control Betamethasone 0.1% in Betamethasone 0.1% in group aqueous formulation pure mineral oil* group 2170-64* group 36.4 +/− 4.85 28.95 +/− 3.97 a 24.92 +/− 2.20 a,b Reduction in (28.95-36.4)/(24.92-36.4) × 100 = 65% systemic effect=
[0055] Systemic effect of two aqueous suspensions on the opposite non-treated ear,
Ear weight (mg) mean +/− sd N = 40 N = 20 N = 20 Untreated control Etiprednol dicloacetate Etiprednol dicloacetate group 0.2% in aqueous 0.2% in aqueous suspension 2170-79* suspension 2170-20* with 0.01% polymer with. no polymer 46.51 +/− 4.77 39.34 +/− 6.27 a 35.75 +/− 3.27 a,b Reduction in (39.34-46.51)/(35.75-46.51) × 100 = 67% systemic effect Ear thickness (×10 −2 mm)) mean +/− sd N = 40 N = 20 N = 20 Untreated control Etiprednol dicloacetate Etiprednol dicloacetate group 0.2% in aqueous 0.2% in aqueous suspension 2170-79* suspension 2170-20* with 0.01% polymer with. no polymer 34.58 +/− 4.58 28.60 +/− 3.95 a 25.40 +/− 3.23 a,b Reduction in (28.60-34.58)/(25.40-34.58)_× 100 = 65% systemic effect *See below for formulation. ANOVA (p < 0.05; Two-sides) a Statistically significant when compared to the untreated control group b Statistically significant when compared to the formulation 2170-64 or 2170-79
[0056]
ED-Otic suspension
2170-20
2170-79
2170-64 with
Betamethasone
series
series
betamethasone
in mineral oil
Ingredients
% w/w
% w/w
% w/w
% w/w
Etiprednol
0.2-0.8
0.05-0.2
—
—
dicloacetate
Betamethasone
—
—
0.1
0.1
Tyloxapol
0.300
0.01
0.01
—
Methocel ® F4M
—
0.01
0.01
—
Methylparaben
0.18
0.18
0.18
—
EDTA disodium
0.050
0.1
0.1
—
Salts
Glycerin
2.500
2.50
2.50
—
Mineral oil
—
—
—
QS
NaOH pH 5.0-5.5
QS
QS
QS
—
Purified Water
95.775
95.775
95.775
—
Total
100
100
100
100
[0057] When comparing re-suspensions of (1) an aqueous based suspension and (2) an oil/lotion based suspension, it was found that the better choice was the oil/lotion based suspension. Surprisingly, the suspension in oil/lotion improved upon aging as it stayed suspended for a longer period than the non-lotion suspension (i.e., no mineral oil or Brij® surfactants). Oil/lotion based suspension have an oil (e.g., mineral) that is suspended by the presence of a surfactant (e.g., Brij® 72 and 721). The surfactant of the oil/lotion based suspension is in addition to the first surfactant discussed previously. An example of an oil/lotion formulation is shown below.
Oil/lotion based suspension Ingredient % w/w Etidprednol dicloacetate, micronized 0.2 Clotrimazole, micronized 1 Polymyxin B sulfate USP 0.1375 Tyloxapol USP 0.01 disodium Edetate, USP 0.1 Glycerine USP 2.5 Hypromellose USP 2906 (Methocel ® F4M) 0.01 Merquat ® 550 9% 0.12 Light mineral oil 2 Brij ® 72 (Polyethylene Glycol 2 Sterayl ether)* 0.45 Brij ® 721 (Polyethylene Glycol 21 Sterayl ether)* 0.55 Sodium hydroxide NF 0.001 Sodium hydroxide NF adjust pH to 5.0˜5.5 QS Hydrochloric acid, adjust pH to 5.0˜5.5 QS Purified water USP, QS QS *Brij ® 72 and Brij ® 721 are surfactants the act in combination as the second surfactants of the present invention. | The invention provides novel compositions of water-insoluble corticosteroid drug in combination with antimicrobial agents and very low concentrations of polymers and surfactants for topical, otic and ophthalmic treatment. The invention provides stable aqueous suspension where the ingredients remain in such a state so as to allow for immediate re-suspension, when desired, even after extended periods of settling. The invention provides also a method for treating inflammation with low systemic absorption and side-effects of the corticosteroid. | 0 |
FIELD OF THE INVENTION
The present invention is a restraint system for automobiles and other passenger vehicles, in which the airbag inflates from the passenger seatbelt instead of from vehicle cabin surfaces or structures.
BACKGROUND OF THE INVENTION
If any two improvements have dramatically improved vehicular safety for vehicle occupants, those two improvements are the seatbelt and the airbag. As provision and use of these two important safety devices has increased, automotive and vehicular safety has improved dramatically. At the same time, both of these safety devices have disadvantages--with the airbag's faults being the most serious of the two.
Traditional airbags are detonated by crash sensors, and sudden airbag inflation is caused by gas generation--typically sodium azide, sodium hydroxide or carbon dioxide gas delivered from strategically positioned canisters. Thus the traditional airbag propels toward the driver or the passenger, on the wave of an exploding gas, and immobilizes the driver or passenger for a brief period. Although the potential contusion and noise/ear damage risks are appreciated in a general way by the public, usually only health care providers see the serious injury airbag deployment can cause. And while relatively lesser injury is certainly preferable to life-threatening injury or death, any injuries caused by so-called "safety" devices should be avoided if at all possible.
For example, clinicians have documented instances in which a driver or passenger smoking a pipe has been impaled through the back of the throat with the pipe stem upon airbag inflation. Similar injuries are sustained by passengers who may be eating or working while riding--any pens, pencils or dining implements (even plastic ones) in the vicinity of the head pose injury risks, especially considering the widespread unconscious habit of chewing on the end of a writing implement. An even greater injury risk is the wearing of ordinary eyeglasses: the surgical removal of eyeglasses embedded around a driver's or passenger's eyes after airbag inflation is already documented in the medical literature, and clearly head injuries of this kind should be avoided if there is any way to do so.
A further disadvantage with traditional airbags has to do with their directionality. A typical, steering-column driver's side airbag can protect a driver from a head-on vehicular impact, but offers little or no protection in a side collision, particularly to the driver's left. Likewise, a passenger-side airbag offers little or no protection to the passenger's right side. Automobile manufacturers are at this writing beginning to introduce side airbags in an effort to address this problem, but the costs involved in this approach are prohibitive. For one thing, side airbags do not replace front airbags and the provision of both therefore at least doubles the cost of providing a single airbag. Also, door designs have not to date lent themselves to airbag incorporation, so that side air bags have required door redesigns which increase costs even further.
Even seatbelts are known to have been plagued with unique problems. A traditional seatbelt can cause its own contusion depending on the force of impact, and while most of these contusions lead only to bruises, more serious damage has also occurred. It is known from the literature to provide for localized inflation to a seat belt, upon vehicle impact, to provide a cushion between the belt and the individual wearing it, but this design has not been widely adopted. A goal of improved vehicular restraint technology thus includes the elimination of seatbelt contusions resulting from vehicle impact.
In view of all of the above, a need remains for a vehicular restraint system in which the benefits of seatbelts and airbags are preserved but the injury caused by the impact of the seatbelt and/or the airbag is minimized or avoided.
SUMMARY OF THE INVENTION
The present invention is a vehicular restraint in which the airbag and the seatbelt structures are combined. In the preferred embodiment of the invention, the airbag is packed into a pouch and either the lap or shoulder belt of the seatbelt assembly is threaded through the pouch together with gas flow means. The gas flow means connect the airbag within the pouch to the source of gas for inflation, which in one preferred embodiment is remotely positioned within the adjacent seat assembly. Upon sensor indication of crash or impact, the remote source of gas releases the gas through the gas flow means and into the airbag, which inflates in place, bursting out of its pouch in so doing. If the airbag pouch is positioned on the vehicle occupant's lap, the airbag inflates up from the lap position. If the airbag pouch is positioned on the shoulder belt, the airbag inflates in both the upward and downward directions. Particular design of the pouch according to the preferred embodiments ensures that the direction of inflation and deployment will protect both the front and one side of the vehicle occupant, and the airbag design itself also contributes to this front-and-side protection. Mirror image designs as compared with the designs disclosed herein may be used in cars designed for left-of-road driving outside the United States.
Vehicle airbags and gas generating means therefor are generally already documented in the general and patented literature. For example, U.S. Pat. No. 5,275,433 to Klober et al., entitled "Gas Generator for an Airbag," which is hereby incorporated herein by reference, discloses a gas generator for an airbag and as well as various aspects of prior art airbag designs. U.S. Pat. No. 5,324,075 to Sampson, also incorporated herein by reference, is entitled "Gas Generator for Vehicle Occupant Restraint," with the restraint being the airbag itself and the gas generator being a housing containing gas generating material positioned apart from the airbag. For example, the Sampson patent is exemplary of the above-summarized creating of inflatable seat belts (see column 2, line 38 of the patent) intended to reduce seatbelt inflicted contusions. These and other issued patents establish that airbag manufacture and deployment, as well as the gas generation means used in conjunction therewith, are already known and their fabrication and use is within the skill of the art. Crash sensors (in the periphery of the vehicle) and igniters for the gas generating means are also well-known in the art, as well as the necessary communications systems therebetween.
The present invention is an improvement over the state of the art in that the present airbag is placed within a pouch (or the airbag is the pouch) which literally rides on a lap or shoulder seatbelt adjacent the vehicle occupant. The airbag pouch is provided with gas flow means to carry generated gas from the gas generating means to the airbag. One example of such a design is a gas generation canister located in the adjacent vehicle seat assembly, with soft polymer conduit connecting the canister and the airbag. The conduit can run alongside--preferably underneath and associated with--the seatbelt, and this design is described further below.
In the preferred embodiments of the invention, the pouch on the seatbelt is designed so as to deploy the airbag both to the front and to one side of the vehicle occupant. In United States cars, the driver's airbag should deploy to the front and to the left of the driver; the front right passenger's airbag should deploy to the front and to the right of that passenger, and so on. Cars designed for left-of-road driving will observe the opposite conventions. Airbags of this type can be provided for each seatbelt assembly, with at least six airbags per average car being typical.
Also preferably, the present seatbelt airbags are preferentially included in "passive restraint" type seat belt designs in which the seatbelt automatically positions over the vehicle occupant as the vehicle door closes. As will become more apparent from the following description, the present seatbelt airbag inflates upon vehicle impact directly in front of the driver or passenger wearing the seatbelt. It is easy to see that if a vehicle occupant were to sit on a seatbelt bearing the present airbag, instead of wearing the seatbelt properly, an inflating airbag during a crash situation would offer no impact protection and might exacerbate the occupant's forward acceleration.
In summary, the present invention is a vehicular restraint system in which the airbag and the seatbelt structures are combined. In the preferred embodiment of the invention, the airbag is packed into a pouch and either the lap or shoulder belt of the seatbelt assembly is threaded through the pouch together with gas flow means. The gas flow means connect the airbag within the pouch to a remote source of gas for inflation, which in the preferred embodiment is positioned within the adjacent seat assembly. Upon sensor indication of crash or impact, the remote source of gas releases the gas through the gas flow means and into the airbag, which inflates in place. If the airbag pouch is positioned on the vehicle occupant's lap, the airbag inflates up from the lap position. If the airbag pouch is positioned on the shoulder belt, the airbag inflates in both a downward and an upward direction. Particular design of the pouch ensures that the direction of inflation and deployment will protect both the front and one side of the vehicle occupant, and special designs for the driver seatbelt airbag ensure that the airbag does not become entangled with the steering column and/or steering wheel.
A complete understanding of the invention will be obtained from the following description when taken in connection with the accompanying drawing figures wherein like reference numerals identify like parts throughout.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of a seatbelt airbag according to the present invention;
FIG. 2 is a reverse view of the seatbelt airbag shown in FIG. 1;
FIG. 3 is a plan view of another embodiment of the seatbelt airbag according to the present invention;
FIG. 4 is a reverse view of the seatbelt airbag shown in FIG. 3;
FIG. 5 is a plan view of another embodiment of the invention intended for use with a shoulder seatbelt;
FIG. 6 is a plan view of yet another embodiment of the invention intended for use with a shoulder seatbelt;
FIG. 7 is a perspective view of an embodiment of a seatbelt buckle according to the present invention;
FIG. 8 is a perspective view of a deployed airbag according to the invention; and
FIG. 9 is a perspective view of a deployed airbag according to the invention as it shields a vehicle occupant seated in a vehicle seat.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1 of the drawings, the seatbelt airbag 10 is shown in plan view, i.e., facing the wearer, with the seatbelt 14 threaded through the airbag pouch 12. The airbag pouch 12 is a protective covering for an actual airbag contained therein in a deflated, folded configuration (not shown). The airbag pouch may be made of virtually any material suitable for fabricating pouches as long as the material has enough softness or pliability to be tolerated when strapped adjacent to a vehicle occupant. Most often, the pouch is fabricated of the same vinyl material as is used in the vehicle interior. Preferably, the pouch has a weak area or break line 16 in the position as illustrated, so as to encourage airbag deployment in the correct direction. In other words, the airbag inside the airbag pouch 12 will inflate upwardly and toward the wearer, due to the position of the weak area 16.
In FIG. 2 of the drawings, the seatbelt airbag 10 is shown from the side of the wearer. The weak area 16 faces the wearer near the top of the airbag pouch 12. FIG. 2 also illustrates gas flow means 18 which are colinear with the seatbelt 14. Preferably, the gas flow means 18 are gas channels made of soft, flat polymer tubing or conduit. Such soft polymer tubing is adequately strong to convey generated gas under pressure, to deploy the airbag, but is soft and pliable enough to coincide with the seatbelt without causing a vehicle occupant discomfort or inconvenience.
FIG. 3 of the drawings is a plan view of an embodiment of the invention in which the seatbelt airbag 20 includes an airbag pouch 22 having an inclined surface 23 thereon. The airbag pouch 22 rides on the seatbelt 24 in the same manner as illustrated in FIGS. 1 and 2. The inclined surface 23 of the airbag pouch 22 enhances the ability of the airbag to deploy upwardly and to the right of the wearer. The seatbelt airbag 20 of FIG. 3 is viewed from in front of the wearer and is intended for use by the front right passenger of a made-for-United States-use vehicle. FIG. 4 shows the reverse view of the seatbelt airbag 20 of FIG. 3, and illustrates the weak area or break line 26 and gas flow means 28.
In the above description, "weak area" or "break line" literally means an area as illustrated of the respective airbag pouch which does not have the same tensile or elongation strength as the rest of the airbag pouch. The weak area is thus the area through which the contained airbag is certain to deploy upon inflation, as the weak area offers the path of least resistance. The weak area may be a score or perforation in the airbag pouch, or may simply be an area where the gauge of the pouch material is relatively thinner. Those skilled in the art will easily be able to derive variations on the theme of weakening an area of the airbag pouch to direct airbag deployment.
FIGS. 1-4 illustrate airbag pouches for use with lap seatbelts. Accordingly, the weak areas are positioned near the top and on the occupant side of the airbag pouch. FIGS. 5 and 6 illustrate top and bottom weak areas on the pouch intended for positioning on a shoulder seatbelt, so that the airbag will deploy both upwardly toward the occupant's head, as well as downwardly toward the lap. FIG. 5 is a plan view of a seatbelt airbag 30 in which the seatbelt 34 passes through an airbag pouch 32 having weak areas 36 thereon. FIG. 6 is a plan view of a seatbelt airbag 40 in which an airbag pouch 42 has a seatbelt 44 threaded therethrough, with dual weak areas 46. Airbag pouch 42 has an inclined surface 43 thereon, to encourage airbag deployment preferentially toward one side of the wearer.
FIG. 7 is a perspective view of a seatbelt buckle according to the present invention. Since gas flow means are to direct a gas from a remote gas generating means to the airbag site adjacent to the lap or the shoulder belt, the gas must travel to the airbag without interruption by a seatbelt buckle. One design for accomplishing this gas transport is the seatbelt buckle 50 of FIG. 7, which includes a seatbelt 52 having a metal flap 54 and a flap latch 62 with a release button 64. The gas flow means is a channel 56 which is coupled when the seatbelt is fastened by inserting the channel tip 58 into the channel receptacle 60 when metal flap 54 is inserted into latch 62. Channel tip 58 and channel receptacle 60 fit together in a press fit, and the seal is enhanced when the tip and the receptacle are constructed of a pliable polymeric material. It should be noted, that if the present seatbelt airbag is positioned on a passive restraint type seatbelt, which uses no buckles, a structure such as is shown in FIG. 7 is unnecessary.
It should be borne in mind that the present seatbelt airbag invention also encompasses the use of gas generating means in situ. In other words, gas generation may be effected at the point of inflation of the airbag, by suitable gas generating cartridges or chemical charges, without departing from the scope of the invention. An advantage of remote gas generation, however, is that the possibility of the vehicle occupant's sustaining burns from the gas generating means is reduced or eliminated. See for example FIG. 9, wherein the gas generator 96 is housed within the seat assembly and the seat thus protects the adjacent occupant from excessive gas ejection force and/or leaked chemicals.
Referring further to FIG. 9 of the drawings, a vehicle driver 100 is shown seated in a vehicle seat 98, while wearing a seatbelt airbag according to the invention which has just deployed under vehicle crash conditions. The deployed airbag 90 is shown in front of and to the left of the driver, and the gas generator 96 is embedded in the vehicle seat 98. Gas channels 94 connect gas generator 96 to deployed airbag 90; much of their length is colinear with and contiguous to seatbelts 92.
FIG. 8 is a perspective view of a seatbelt airbag 79 which has already undergone airbag deployment, in which a lap belt 80 holds the torn airbag pouch 82 from which the deployed airbag 84 has erupted. The lap belt 80 is colinear with the gas channel 88 which carried the gas which deployed the airbag. The deployed airbag 84 has a left-curving portion 86. The airbag is originally fabricated to take the shape as illustrated, so as to protect the front and left side of the wearer. The seatbelt airbag 79 of FIG. 8 is shown from the wearer's side and is intended for the driver's side in a United States vehicle--or for the rear left passenger. It cannot be overemphasized that mirror image designs are intended for the opposite side of a vehicle or for use in non-U.S. countries which observe opposite-side-of-road driving conventions.
Any materials suitable for use in known airbags and gas generators may be incorporated or adapted for use in the present invention. In fact, it is expected that as the state of the art of airbag materials and gas generation improves, such improvements will automatically be incorporated in the present designs without departing from the scope thereof.
As mentioned above, vehicles fitted with the present seatbelt airbags will bear the same crash or impact sensors as are known in the art, together with the necessary interconnections (communications systems) between the sensors and the gas generator(s) as are also known in the art. However, because the preferred embodiments of the present seatbelt airbags provide protection in front of and usually to one side of any vehicle occupant, it is likewise preferred that crash or impact sensors be provided at multiple locations at the front and the sides of the vehicle. Apart from this multiplied installation of sensors, however, it is intended that known impact sensor technology and transmitting systems therefor be used in the context of the present invention.
In operation, the present seatbelt airbag is much less likely to cause injury to the vehicle occupant than prior art airbags or seatbelts. With airbag deployment being immediately adjacent the seatbelt assembly, the airbag itself prevents the relative motion of the occupant versus the seatbelt and thus prevents contusions. Also, when the airbag inflates upwardly from the lap or the torso instead of directly toward the vehicle occupant, it tends to push eyeglasses and other hard objects up and away instead of toward the occupant. Finally, gas generation burns are less likely with the present design either because gas generation takes place from a remote location as illustrated in FIG. 9 or because the gas generated in the area of the lap or torso is less likely to cause burns than gas generated and propelled directly toward the head of a vehicle occupant.
The above description is not intended to be limiting, because innumerable variations on the present seatbelt airbag are possible without departing from the scope of the invention. For example, a single gas generating cartridge or charge can be incorporated in a vehicle seat and configured to inflate 2 or more airbags, possible by a single gas channel each. Also, the gas channel material may be selected from a wide variety of materials, as long as the material is strong enough to withstand the force of the gas. Therefore, the invention is intended to be limited only insofar as is set forth in the accompanying claims. | A vehicular restraint system in which the airbag and the seatbelt structures are combined. The airbag is located in a pouch and either the lap or shoulder belt of the restraint assembly is threaded through the pouch together with a gas flow channel which is connected to the airbag within the pouch from a source of gas for inflating the airbag. Upon sensor indication of vehicle impact, the source of gas releases the gas through the gas flow channel into the airbag which is inflated in place. When the airbag is positioned on the vehicle occupant's lap, the airbag inflates upwardly from the lap position and when the airbag is positioned on the shoulder belt, the airbag inflates in both a downward and an upward direction. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method for preparing and controlling aircraft navigation.
It is more particularly aimed at enhancing the security of the aircraft while reducing the burden on the pilot, by reducing the operations to be performed for in-flight modification of the navigational parameters, and by eliminating risks of error to a large extent.
2. Description of the Prior Art
In a general manner, it is known that the basic equipment of a pilot undertaking a journey on board an aircraft, more particularly of the type of the aircraft used in light aviation, is the flight instrument panel. Such a panel consists of a small tablet to which it is possible to attach a sheet of paper called navigation sheet or navigation "log". This log comes in the form of a table in which, prior to take-off, the pilot enters the elements required for the various stages of navigation.
The first elements to be entered are: the way points marking out the route planned (aerodromes, towns, radio navigation beacons, etc.), and the frequencies relating to the radio communication and radio navigation means available along the route. The pilot must then, by means of an aeronautical map and length and angle measuring instruments, take the distance and true heading readings between each of the points along his path. Finally, the pilot will calculate the magnetic headings and estimated times between each point and will enter them on his navigation sheet.
Immediately prior to departure, the pilot computes the effects of the wind on the headings and the times entered on his sheet and makes a note of the result for each segment of the flight.
Throughout the flight, the pilot, who must know his position at all times, follows his route sheet point by point, timing the duration of each segment, making a note of variances observed and recalculating his estimated time of passage at the next point.
OBJECT OF THE INVENTION
The main object of this invention is to remedy the preceding disadvantages, particularly to provide a method enabling the pilot to prepare his navigation without reading measurements and without performing the long and fastidious calculations enumerated above, and following navigational developments throughout the flight.
SUMMARY OF THE INVENTION
Accordingly, there is provided a method using a device comprising a processor equipped with a memory and a man/machine dialogue means that can comprise a viewing screen and a keyboard fitted with keys.
It comprises the following operational phases:
the preparing of the route to be followed by the aerodyne by loading in the above-mentioned memory a route already prepared and previously memorized on a medium, or by keying in the way points along the route by means of said keyboard;
the defining of the parameters characterizing the environment in which the navigation will take place (these parameters may consist of features of the aircraft, its load, wind speed and direction, and fuel taken on board);
the displaying of at least a first couple of way points as well as information required to control navigation between these points (this information may consist of the magnetic heading, distance, estimated time of passage at the next point with and without wind).
According to the invention, this method is characterized in that it comprises the updating of the displayed information by action on a function key as the aircraft passes over each way point, this action causing the erasing from the screen of the way point preceding the point entered and the displaying of a new way point following the previous displayed point, and the computing and displaying of new information taking into account the updating that has just been performed, and in that the route information loaded into the memory during the preparatory phase includes parameters relating to the way points marking out the planned route as well as to radio navigation aids marking each of these points, the search for the points and markers being carried out in an "Aerodromes and markers" database contained in the above-mentioned memory.
Advantageously, the device for implementing the method previously described could be in the form of a flight instrument panel comprising a flat case housing the electronic circuits of the processor and on one side of which are disposed said screen and said keyboard. This device can be supplied with electrical power by means of a battery of cells or accumulators housed inside the case or by means of an external converter that can be plugged into an external socket provided on the case.
By way of its shape, dimensions and appropriate ergonomics, such a flight instrument panel is particularly suited to use on board an aircraft.
BRIEF DESCRIPTION OF THE DRAWINGS
Further features and advantages of the invention will be apparent from a sample embodiment of the interactive flight instrument panel according to the invention described, by way of a non-limiting example, in reference to the corresponding accompanying drawings in which:
FIGS. 1 and 2 represent a perspective view of the interactive flight instrument panel;
FIG. 3 represents a top view of the interactive flight instrument panel;
FIG. 4 represents a specimen synopsis of the electronics managing the interactive flight instrument panel;
FIGS. 5 and 6 represent a specimen display used by the method according to the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As represented in FIGS. 1 to 3, the interactive flight instrument panel is comprised of a flat case 1 housing a processor and of which the upper wall comprises three successive zones, i.e.
a viewing zone equipped with a screen 2, e.g. of the liquid crystal display type,
a first dialogue zone comprising a set of function keys 3, in this instance the "Start", "Stop", "Time", "Position", "Map" and "MENU" keys, as well as four directional keys 4 disposed in conventional manner,
a second dialogue zone equipped with a means enabling information to be entered, this means consisting of an alphanumeric keyboard 6 in this instance.
A rigid flap 5 is mounted pivotally about a hinge oriented parallel to a lateral edge of the case 1 so as to be susceptible of folding over the second dialogue zone to mask the keyboard 6. Furthermore, this flap is fitted with a means such as an elastic clip P enabling a sheet F or block of sheets of paper to be secured, so that, in the folded back position of the flap, the panel can serve as a conventional instrument panel while enabling dialogue with the processor due to the fact that the viewing zone and first dialogue zone remain uncovered.
The flight instrument panel is managed by the microprocessor 35, the latter being associated with ROM 36 and RAM 37 memories, a screen controller 38, a controller 39 for the keys of the keyboard 2 and keys of the first dialogue zone, a serial line controller 40 and a clock 41 (FIG. 4).
The electric power supply to the electronic circuit of the panel (block 42) is an autonomous system using cells or batteries. An external power supply is also possible via an optional voltage converter that can be connected to a connector 7 fitted on the right-hand lateral edge of the case 1.
A connection for a printer or microcomputer is possible by means of the RS 232 type serial link (interface 20) accessible by a connector 8.
A housing 12 also formed in the right-hand lateral edge enables an optional memory board 11 to be inserted.
The lower wall of the interactive flight instrument panel is equipped with an elastic strap 9 ended by VELCRO type securing means. This strap enables the flight instrument panel to be secured to the pilot's thigh, a position particularly suited to the configuration of the cockpit of an aircraft.
Good positional retention is ensured by the shape of the lower wall of the case which comprises two longitudinal protuberances 10.
The dimensions of the case may be e.g. the following: 250 mm long, 160 mm wide and 15 mm deep.
The viewing screen 2 can consist of a monochrome or colour graphic display of approximately 480×160 points. As an example, this screen uses LCD technology in the reflective mode.
The alphanumeric keyboard 6, used especially during the pre-flight preparatory phase, can be masked by the flap 5 thus forming a tablet enabling a sheet of paper to be lodged for note taking during the flight.
The four function keys 3, as well as the four directional keys 4 are used in flight to monitor and control navigation. They are therefore accessible at all times.
In principle, the electronics of the flight instrument panel are permanently powered up. It is then possible to switch to a minimum consumption mode by simultaneously pressing the "Start" and "Stop" keys, thereby causing the screen to turn off without loss of information. Return to the normal mode of utilisation is obtained by pressing the "Start" key.
The method used according to the invention offers a set of functions accessible via a menu presented on the viewing screen when the "MENU" function key has been pressed. These functions are as follows:
NAVIGATION/Parameters: this function enables the parameters required for the flight to be initialized: true airspeed of the aircraft, magnetic deviation at departure and arrival, wind speed and direction, quantity of fuel taken on board, load, etc.
NAVIGATION/Preparation: this function enables the entering of the points marking out the planned route, as well as the radio navigation aids marking each of these points. The points and markers are automatically searched for in an "Aerodromes and beacons" database contained in the memory of the interactive flight instrument panel.
NAVIGATION/Display: this function enables the entire active navigation log to be displayed. The different points are displayed, as is the following information: altitude, ICOA aerodrome identification code, radio frequencies, orientation of runways, etc., all this information having been automatically searched for in the "Aerodromes and beacons" database.
The distance and times with and without wind, as well as the headings are calculated as a function of the geographical coordinates presented in the "Aerodromes and beacons" database and are then displayed.
NAVIGATION/Modify: this function enables the memorized flight plan to be modified.
NAVIGATION/Plan: this function enables a graphical representation of the entire planned route to be displayed.
NAVIGATION/En route: this function enables interactive in-flight utilisation of the active navigation log.
As illustrated in FIGS. 5 and 6, this function, once it has been selected, enables the displaying of the current time 13, the information on the next two flight segments S1, S2; the names 14, 29 of the first and second way points PT1, PT2; any corresponding frequencies 15, the magnetic heading 16, the distance 17, the time without wind 18 and the time with wind 19. A graphic 20 representing the next two flight segments S1, S2 and any radials PTV, CHW marking the next way point PT2, on a fix having the axis of the aircraft as vertical axis, is also displayed. The scale used for the graphical representation is calculated automatically to take up all the available space on the screen, irrespective of the length of the flight segments S1, S2.
The entire flight plan can be scrolled through by using the vertical directional keys.
For each flight segment S1, S2, the ground speed of the aircraft 21 is computed as a function of the wind and is then displayed.
When the engine(s) of the aircraft are started up, a pressing of the "Start" key triggers the timer indicating the total "engine" duration 22. The remaining range 23 and the quantity of fuel left, calculated as a function of the fuel taken on board, the type of aircraft and the amount of time lapsed 22, are then displayed.
Upon passing over the first point PT1, an action on the "Map" key activates the automatic flight plan monitoring. The time of passage 25 over the point PT1 is displayed in the corresponding box. The estimated time of arrival 26 at the next way point PT2, the estimated time of arrival at the final destination 27 and the duration of the flight 28 are displayed. The real ground speed 29 calculated on the last segment SO is displayed.
To control navigation, the pilot need only operate the "Map" key at the passing over each point and follow the information presented by the electronic log.
It is possible at all times to return to the parameters menu, to perform modifications there and then return to follow the navigation log.
The next point PT2 on the route 20 is marked by one or two radials 31, PTV, CHW represented by the name of the radio beacon, its frequency, and the magnetic bearing of this beacon in relation to said point PT2.
NAVIGATION/Position: this function enables the aircraft to be located by establishing a fix by means of radio navigation marker readings (e.g. VOR or ADF). This function can be called up automatically by pressing the "Position" key.
When this function is called up via the NAVIGATION/En route function, the position of the aircraft is stated, by default, in relation to the next point on the planned route. In other words, the heading to reach this point (block 31) and the distance separating it from the aircraft (block 32) and the time with and without wind (block 33) are displayed. A graphical representation of the aircraft in relation to the planned route is also displayed.
FILE/Load: this function enables a flight plan to be selected from among all the flight plans in the memory.
FILE/Save: this function enables the active flight plan to be saved in the memory.
DATA/Add coord: this function enables points identified by the geographical coordinates (latitude and longitude) to be added to the "Aerodromes and beacons" database.
DATA/Add radial: this function enables points identified by a radial (bearing and distance) of any point in the database to be added to the "Aerodromes and beacons" database.
DATA/Add aircraft: this function enables a "new aircraft" (parameters of a new aircraft) to be added to the "Aerodromes and beacons" database.
DATA/Modify: this function enables the data in the "Aerodromes and beacons" and "Aircraft" databases to be modified.
INFORMATION/Field: this function enables the information relating to a field to be displayed. The next field along the route is proposed by default.
INFORMATION/Aircraft: this function enables the technical information on the aircraft contained in the "Aircraft" database to be displayed. The aircraft selected in the parameters menu is proposed by default.
WEIGHT/: this function enables the displaying of the results of the weight and balance calculations as a function of the parameters automatically collected in the "Aircraft" database and of the load data entered by the pilot.
A graphical representation of weight and balance in relation to the aircraft's limits is displayed. | A method for preparing and controlling navigation of an aircraft uses a processor equipped with memories, a screen and keys. It comprises the steps of preparing the route to be followed by an aircraft by loading into the memory data pertaining to a route, defining parameters characterizing the environment in which the navigation will take place, and displaying during navigation a couple of way points including the last point through which the aircraft has passed and the next way point, the segment joining these two points together, and information required to control navigation between these two points. The invention enables the pilot to prepare his navigation without taking measurement readings and performing calculations. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of application Ser. No. 12/412,918, filed Mar. 27, 2009 now U.S. Pat. No. 8,222,774, entitled “System And Method For Enclosing Information Handling System Component Devices” naming James Utz, Kyle Spiess, Kevin Mundt, Karlene Berger as inventors, and which is hereby incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates in general to the field of information handling system components, and more particularly to a system and method for enclosing information handling system component devices.
2. Description of the Related Art
As the value and use of information continues to increase, individuals and businesses seek additional ways to process and store information. One option available to users is information handling systems. An information handling system generally processes, compiles, stores, and/or communicates information or data for business, personal, or other purposes thereby allowing users to take advantage of the value of the information. Because technology and information handling needs and requirements vary between different users or applications, information handling systems may also vary regarding what information is handled, how the information is handled, how much information is processed, stored, or communicated, and how quickly and efficiently the information may be processed, stored, or communicated. The variations in information handling systems allow for information handling systems to be general or configured for a specific user or specific use such as financial transaction processing, airline reservations, enterprise data storage, or global communications. In addition, information handling systems may include a variety of hardware and software components that may be configured to process, store, and communicate information and may include one or more computer systems, data storage systems, and networking systems.
Information handling systems are typically built in portable or stationary configurations. Portable information handling systems have smaller-sized housings that allow use of the system on the go. Integrated power, I/O and display devices support system operation free from permanent connections to external power and peripherals. Stationary information handling systems have housings of a wide variety of shapes and sizes that support use of the system in a fixed location. Desktop, tower and server information handling systems typically interface with external power and I/O devices. Manufacturers generally try to build information handling systems in as small a chassis as possible for the functionality supported by the information handling systems. Smaller sized stationary information handling systems are more convenient because a smaller footprint fits better in space-constrained locations, such as a user desk or a data center. Smaller sized portable information handling systems are more convenient for users since a smaller size and decreased weight make a portable information handling system less awkward to handle and less burdensome to carry. Generally, as an information handling system housing decreases in size, functionality also decreases because less room is available to fit in component devices and smaller space makes thermal transfer more difficult to accomplish.
Component devices used to build an information handling system include hard disk drives and optical drives, such as CD, DVD and BD drives, which store information for use in processing by a CPU or other processor. Some component devices are built in their own housing so that the component device housing fits within the information handling system housing. For example, optical drives that include one or more lasers to read and write information typically are built into a class 1 laser enclosed device housing. ANSI standards require that class 1 laser device housings have safety interlocks wherever the housing can be opened so that the laser within the device will not emit laser light that could injure an end user. The safety interlocks prevent emission of a beam of radiant energy above a minimum standard from leaving the laser or laser system. Service adjustments or maintenance work performed on the optical drive must not render the interlocks inoperative or cause exposure levels outside the housing to exceed the minimum standard unless the work is performed in an approved area with limited access and appropriate safeguards, supervision and control. The protective housing and optical drive must have a fail-safe design so that, if a failure occurs, the system will continue to meet the safety requirements for enclosed laser operations. The use of an optical drive housing within an information handling system housing tends to add to the size and weight of the information handling system.
SUMMARY OF THE INVENTION
Therefore a need has arisen for a system and method which encloses information handling system component devices and information handling systems in a common housing.
In accordance with the present invention, a system and method are provided which substantially reduce the disadvantages and problems associated with previous methods and systems for enclosing information handling system component devices. At least a portion of a safety enclosure for an information handling system component is formed with a portion of the housing of the information handling system. A lock out device detects removal of the shared housing portion to disable one or more functions of the component.
More specifically, an information handling system is built from a plurality of electronic components, such as a CPU, RAM, a hard disk drive and chipset, which cooperate to process information. A component disposed in a housing of the information handling system performs one or more functions that call for a safety enclosure, such as an optical disc drive, which uses a laser to read and write information. A safety enclosure for the component is formed at least in part by a portion of the housing that encloses the information handling system, such as a side wall, a keyboard or a palm rest. A lock out device detects a breach of the safety enclosure, such as removal of the information handling system housing relative to a chassis of the optical disc drive. For example, a Hall effect switch disposed in the optical disc drive chassis detects proximity to a magnet integrated in the information handling system housing portion that forms a portion of the optical disc drive safety enclosure. For example, if a keyboard, palm rest or side wall of the information handling system housing proximate the optical disc drive is removed, movement of the magnet in the housing portion distal from the Hall effect sensor in the optical disc drive chassis causes the Hall effect sensor to command disablement of a laser in the optical disc drive.
The present invention provides a number of important technical advantages. One example of an important technical advantage is that the housing of an information handling system also serves as a safety housing of an internal component so that the weight and size of the internal component is reduced. A lock out device detects removal of the information handling system housing to lock out operation of one or more component functions in response to removal of the information handling system housing. In the case of an optical disc drive, a laser device internal to the optical drive is prevented from operation upon removal of a portion of the information handling system housing that also forms the optical disc drive housing. The information handling system housing forms an ANSI Class 1 Enclosure of the laser device. Combining the optical disc drive housing and information handling system housing reduces the size and weight of the information handling system for improved usability.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be better understood, and its numerous objects, features and advantages made apparent to those skilled in the art by referencing the accompanying drawings. The use of the same reference number throughout the several figures designates a like or similar element.
FIG. 1 depicts a block diagram of an information handling system having an internal component with a safety enclosure formed at least in part by portions of the information handling system housing; and
FIG. 2 depicts a block diagram of an optical disc drive having a safety enclosure formed at least in part by information handling system housing portions.
DETAILED DESCRIPTION
Forming a safety enclosure around an information handling system component with at least a portion of the housing of the information handling system limits the need for redundant enclosures of the component. For purposes of this disclosure, an information handling system may include any instrumentality or aggregate of instrumentalities operable to compute, classify, process, transmit, receive, retrieve, originate, switch, store, display, manifest, detect, record, reproduce, handle, or utilize any form of information, intelligence, or data for business, scientific, control, or other purposes. For example, an information handling system may be a personal computer, a network storage device, or any other suitable device and may vary in size, shape, performance, functionality, and price. The information handling system may include random access memory (RAM), one or more processing resources such as a central processing unit (CPU) or hardware or software control logic, ROM, and/or other types of nonvolatile memory. Additional components of the information handling system may include one or more disk drives, one or more network ports for communicating with external devices as well as various input and output (I/O) devices, such as a keyboard, a mouse, and a video display. The information handling system may also include one or more buses operable to transmit communications between the various hardware components.
Referring now to FIG. 1 , a block diagram depicts an information handling system 10 having an internal component 12 with a safety enclosure formed at least in part by portions of the information handling system housing 14 . In the example embodiment depicted by FIG. 1 , internal component 12 is an optical disc drive. Information handling system 10 is built from a plurality of electronic components disposed in information handling system housing 14 , such as a CPU 16 that processes information, RAM 18 that stores information for access by CPU 16 , a hard disk drive 18 that provides permanent storage of information and a chipset 20 that coordinates interaction of the electronic components to process information. Information handling system 10 includes an integrated display 24 that presents information as visible images. A keyboard 26 fits over the top of the electronic components and accepts end user inputs. A palm rest 28 near keyboard 26 provides a resting surface for an end user during typing at keyboard 26 .
Optical disc drive 12 has a microcontroller 30 that controls a laser 32 for illumination of an optical disc 34 during information reads and writes. Laser 32 is, for example, an infrared laser that reads and writes to CD optical media, a red laser that reads and writes to DVD optical media or a blue laser that reads and writes to BD optical media. Optical disc drive 12 is an ANSI Class 1 Enclosure that must restrict illumination of laser 32 if an end user is at risk of exposure to the illumination. In order to limit end user exposure to illumination by laser 32 , keyboard 26 and palm rest 28 rest across the upper surface of optical disc drive 12 so that information handling system housing 14 includes keyboard 26 and palm rest 28 and forms at least a portion of the safety enclosure around optical disc drive 12 to protect end users from exposure to illumination by laser 32 during operation of optical disc drive 12 . A lock out device 36 detects the presence of keyboard 26 and palm rest 28 to restrict operation of laser 32 in the event of removal of keyboard 26 and palm rest 28 . If keyboard 26 or palm rest 28 are removed, thus breaching the safety enclosure around optical disc drive 12 , disabling of laser 32 maintains optical disc drive 12 within the requirements for ANSI Class 1 enclosures. In alternative embodiments, information handling system housing 14 forms all or other portions of optical disc drive 12 's safety enclosure. In other alternative embodiments, other types of components having a variety of functions have a safety enclosure defined by information handling system housing 14 , such as hard disk drives. Lock out device 36 disables one or more of the functions as desired to maintain a desired safety standard. Forming a safety enclosure of an internal component with the information handling system housing 14 reduces weight and footprint by limiting or eliminating the need for a separate housing around the component to form the safety enclosure.
Referring now to FIG. 2 , a block diagram depicts an optical disc drive 12 having a safety enclosure formed at least in part by information handling system housing portions 14 , 26 and 28 . In the example embodiment depicted by FIG. 2 , lock out device 36 is built from a Hall effect sensor 38 disposed in optical disc drive 12 and a magnet 40 disposed in portions of information handling system housing 14 that form a safety enclosure about optical disc drive 12 . Hall effect sensor 38 detects the presence of a magnet 40 and provides an enable signal to microcontroller 30 when in proximity to a magnet 40 . When microcontroller 30 has an enable signal, microcontroller 30 allows application of power to laser 32 ; when microcontroller 30 loses the enable signal, microcontroller 30 disables one or more functions of optical disc drive 12 . For example, in the absence of an enable signal, microcontroller 30 disables laser 32 but allows operation of other functions, such as spin at spindle 44 . Disabling laser 32 in the absence of an enable signal from Hall effect sensor 38 ensures that laser 32 will not operate if a safety enclosure formed by information handling system housing 14 is breached. Requiring an enable signal by Hall effect sensor 38 fails optical disc drive 12 to a safe condition in the event of a failure of Hall effect sensor 38 .
As depicted in the example embodiment of FIG. 2 , multiple magnets 40 and Hall effect sensors 38 may be used to monitor the enclosure about optical disc drive 12 . Optical disc drive chassis 42 contains the operational components of optical disc drive 12 within a bottom surface 46 and two side surfaces 48 . A portion of information handling system housing 14 forms another side surface of optical disc drive 12 with a magnet 40 aligned with a Hall effect sensor 38 . Removal of the side portion of information handling system housing 14 to remove magnet 40 from proximity to Hall effect sensor 38 will result in disablement of laser 32 . The upper surface of optical disc drive 12 is formed by keyboard 26 and palm rest 28 , each of which have a magnet 40 proximate a Hall effect sensor 38 . If keyboard 26 or palm rest 28 are removed from their assigned positions over optical disc drive 12 , the loss of the enablement signal from Hall effect sensor 38 causes microcontroller 30 to disable laser 32 . In alternative embodiments, the loss of the enablement signal can cause microcontroller 30 to remove power from other functions of optical disc drive 12 . In one alternative embodiment, magnet 40 is placed in optical disc drive chassis 42 and Hall effect sensors are placed in housing portions 14 , 26 or 28 to command removal of power to optical disc drive 12 by components within information handling system 10 . Optical disc drive chassis 42 can form a portion of the safety enclosure about optical disc drive 12 or, alternatively, the entire safety enclosure can be formed my information handling system housing 14 . In another alternative embodiment, specific portions of information handling system components form the safety enclosure, such as a keyboard deflection plate that rests underneath the keyboard to provide physical support during use of the keyboard. Alternatively, the safety enclosure is formed by components, such as a PCIMCIA card, an Express card, a hard disk drive, a battery or other components that are proximate the laser drive. In other alternative embodiments, other types of lock out devices 36 may be used, such as a physical switch that is engaged by proximity of housing 14 to optical disc drive 12 or other types of proximity sensors.
Although the present invention has been described in detail, it should be understood that various changes, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims. | An information handling system component contained within an information handling system housing uses the information handling system housing as at least a portion of a safety enclosure for hazardous functions of the component. A lock out device disables the hazardous function if the information handling system housing is moved relative to the component. For example, an optical disc drive laser is disabled if a Hall effect sensor in the chassis of the optical disc drive no longer senses a magnet placed in a portion of the information handling system housing used to enclose the optical disc drive. | 6 |
FIELD OF THE INVENTION
This invention relates to a novel class of heterocyclic amidinoureas and heterocyclic amidinothioureas that exhibit pharmacological activity and may be incorporated into a pharmacological preparation useful for producing cardiovascular, gastrointestinal and antiparasitic action.
REPORTED DEVELOPMENTS
The phenylamidinoureas have been reported as possessing antisecretory, antispasmodic, anti-ulcerogenic, anesthetic, antidiarrheal and antihypertensive activity in a series of recent patents and publications. See, Arzneimittel Forschung, (Drug Research) 28 (II), 1443-1480 (1978), and U.S. Pat. Nos. 4,025,652, 4,058,557, 4,060,635, 4,088,785, 4,115,564, 4,115,647, 4,117,165, 4,147,804, 4,150,154, 4,169,115, 4,178,387, 4,204,000, and 4,220,658.
This invention relates to a novel class of amidinoureas substituted by a heterocyclic group, possessing pharmaceutical activity including, for example, blood pressure lowering activity.
SUMMARY OF THE INVENTION
This invention relates to a novel class of compounds according to Formula I ##STR1## where:
X is O or S;
R 1 is a 5 to 7 atom ring or a 7 to 13 atom fused or bridged ring which may include 1 to 4 hetero atoms of N, O or S; and containing a total of about 3 to about 20 carbon atoms; and the N-- or S-- oxides thereof;
R 2 , R 3 and R 4 are hydrogen or lower alkyl;
R 5 and R 6 are hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, aryl, alkoxy or a heterocyclic group, or R 5 and R 6 together with the nitrogen to which they are attached form a 3 to 7 atom ring which may include 0 to 2 additional hetero atoms of N, O or S;
and the nontoxic acid addition salts thereof.
Compounds according to Formula I exhibit pharmaceutical activity including, for example, blood pressure lowering activity. This invention also relates to a method for the treatment of human and veterinary gastrointestinal disorders, cardiovascular disorders, spasmolytic disorders and parasitic infestations by the administration of a compound according to Formula I.
Preferred compounds of this invention include amidinoureas substituted in the R 1 position by pyridyl, pyridyl N-oxide, thiophenyl, pyrrole, dihydroquinolinyl, quinolinyl, and dihydroindolinyl, among others.
DETAILED DESCRIPTION OF THE INVENTION
R 1 in Formula I above may be any one of the following heterocyclic groups: 1-pyrrole, 2-pyrrole, 3-pyrrole, 2-furan, 3-furan, 2-thiophene, 3-thiophene, 2-tetrahydrothiophene, 3-tetrahydrothiophene, 1-imidizole, 2-imidizole, 4-imidizole, 5-imidizole, 2-oxazole, 4-oxazole, 5-oxazole, 2-thiazole, 4-thiazole, 5-thiazole, 1-pyrazole, 3-pyrazole, 4-pyrazole, 5-pyrazole, 1-pyrrolidine, 2-pyrrolidine, 3-pyrrolidine, 1-(3-pyrroline), 2-(3-pyrroline), 3-(3-pyrroline), 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidine, 4-pyrimidine, 5-pyrimidine, 6-pyrimidine, 2-purine, 6-purine, 8-purine, 9-purine, 2-quinoline, 3-quinoline, 4-quinoline, 5-quinoline, 6-quinoline, 7-quinoline, 8-quinoline, 1-isoquinoline, 3-isoquinoline, 4-isoquinoline, 5-isoquinoline, 6-isoquinoline, 7-isoquinoline, 8-isoquinoline, or carbazole.
The heterocyclic groups may be mono-, di-, tri- or tetra-substituted by ring substituents such as lower alkyl, lower alkenyl, aryl, lower alkynyl, aralkyl, halo, nitro, cyano, sulfonyl, hydroxyl, carboxyl, lower alkanoyl, lower alkoxy, aryl lower alkoxy, halo lower alkoxy, amido, amino, lower alkyl amino, acyloxy, carbamoyl, lower alkoxyamino, and aralkoxyamino.
Preferred compounds of this invention are those where:
R 1 is a substituted or unsubstituted 5 or 6 membered hetero ring containing 1 to 3 hetero atoms of sulfur, oxygen or nitrogen, and S- and N-oxides thereof:
R 2 is hydrogen or lower alkyl;
R 3 and R 4 are hydrogen; and
R 5 and R 6 are hydrogen, lower alkyl, cyclo lower alkyl, lower alkoxy, alkenyl, aryl, aralkyl, or a heterocyclic group, or R 5 and R 6 together with the nitrogen to which they are attached form a 3 to 7 atom ring which may include 0 to 2 additional hetero atoms of N, O or S;
and non-toxic acid addition salts thereof.
One preferred embodiment of this invention is a compound described by any of Formulae II-IV ##STR2## where: n is 0 to 4;
X is O or S;
(R) represents a ring substituent selected from the group including lower alkyl, lower alkoxy, lower alkenyl, lower alkynyl, aralkyl, aryl, alkaryl, nitro, halo, cyano, lower alkanoyl, carboxyl, sulfonyl, amino, lower alkylamino, lower alkyl acyloxy, lower alkylamido, amino lower alkyl, carbamoyl, halo lower alkyl, hydroxy and the N-oxide of the pyridyl nitrogen atom;
R 2 is hydrogen or lower alkyl;
R 5 and R 6 are hydrogen, lower alkyl, cycloalkyl, aryl, lower alkenyl, aralkyl, lower alkoxy, or heterocycle;
R 5 and R 6 together form a 3 to 7 atom ring which may include 1 to 3 hetero atoms of N, O or S;
and the non-toxic acid addition salts thereof.
Another preferred embodiment of this invention is a compound according to Formula V or VI ##STR3## where: X is O or S;
n is 0 to 3;
(R) represents a ring substituent selected from the group including lower alkyl, lower alkoxy, lower alkenyl, lower alkynyl, aralkyl, aryl, alkaryl, nitro, halo, cyano, carbamoyl, lower alkyl acyloxy, carboxyl, sulfonyl, amino, lower alkanoyl, lower alkylamino, amino lower alkyl, lower alkyl amido, halo lower alkyl, hydroxy and the S-oxides of the thiophene sulfur atom, such as, a thiophenyl sulfoxide or thiophenyl sulfone;
R 2 is hydrogen or lower alkyl;
R 5 and R 6 are hydrogen, lower alkyl, cycloalkyl, aryl, lower alkoxy, lower alkenyl, aralkyl, or heterocycle or R 5 and R 6 together with the nitrogen to which they are attached form a 3 to 7 membered ring which may include 0 to 2 additional hetero atoms of N, O or S;
and the non-toxic acid addition salts thereof.
In any discussion of the true structure of an amidinourea, tautomerism must be considered. It should be clear to anyone skilled in the art that the amidinourea side chain can be legitimately represented in any one of several tautomeric forms. In solution, one form may predominate over another, depending upon the degree and location of substitution and on the nature of the solvent. The rates of conversion of one tautomer to another will depend upon the nature of the solvent, the degree of hydrogen bonding permitted, the temperature, and possibly other factors (such as pH, trace impurities and the like).
To illustrate what is meant by this, a number of tautomeric structures are here shown for just one of the compounds of this invention: ##STR4##
Of course, other structures are possible, such as those with hydrogen bonding. ##STR5##
Furthermore, the heterocyclic atom may contribute to structures reflecting hydrogen bonding. ##STR6##
As employed above and throughout the disclosure, the following terms, unless otherwise indicated, shall be understood to have the following meanings.
"Alkyl" means a saturated aliphatic hydrocarbon which may be either straight- or branched-chain. Preferred alkyl groups have no more than about 12 carbon atoms and may be methyl, ethyl and structural isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. Also included are the cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, etc., and the cycloalkylalkyl groups such as cyclopropylmethyl and the like.
"Lower alkyl" means an alkyl group as above, having about 1 to 6 carbon atoms. Suitable lower alkyl groups are methyl, ethyl, n-propyl, isopropyl, butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl and neopentyl.
"Cycloalkyl" means an aliphatic monocyclic saturated carbocyclic group. Preferred groups have 3 to 6 carbon atoms, for example, cyclopropyl, cyclopentyl and cyclohexyl.
"Alkenyl" means an unsaturated aliphatic hydrocarbon. Preferred alkenyl groups have no more than about 12 carbon atoms and 1 to 3 carbon-carbon double bonds and may include straight or branched chains, and may be any structural and geometric isomers of ethenyl, propyenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, and dodecenyl or butadienyl, pentadienyl etc. Also included are the cycloalkylene groups such as cyclopropenyl, cyclopentenyl, cyclohexenyl, etc. and the cycloalkylalkylene groups such as cyclopropylenylmethyl, cyclohexenylmethyl and the like.
"Lower alkenyl" means alkenyl of 2 to 6 carbon atoms such as ethylene, propylene, butylene, isobutylene, etc., including all structural and geometrical isomers thereof.
"Alkynyl" means an unsaturated aliphatic hydrocarbon. Preferred groups have no more than about 12 carbon atoms and contain one or more triple bonds, including any structural or geometric isomers of acetylenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, etc.
"Lower alkynyl" means alkynyl of 2 to 6 carbon atoms such as structural and geometric isomers of propargyl, butynyl, pentynyl, etc.
"Aryl" means phenyl and substituted phenyl.
"Substituted phenyl" means a phenyl group in which one or more of the hydrogens has been replaced by the same or different substituents including halo, lower alkyl, halo-lower alkyl, nitro, amino, acylamino, hydroxy, lower alkoxy, aryl lower alkoxy, acyloxy, cyano, halo-lower alkoxy or lower alkyl sulfonyl.
"Aralkyl" means an alkyl (preferably a lower alkyl) in which one or more hydrogens is substituted by an aryl moiety (preferably phenyl or substituted phenyl), e.g., benzyl, phenethyl, etc.
"Heterocyclic group" or "heterocycle" means a 3,5, 6 or 7 membered ring having 1 to 3 hetero atoms which may be nitrogen, oxygen or sulfur, including pyridyl, pyrimidyl, pyrazolyl, imidazolyl, furyl, thienyl, oxazolyl, thiazolyl, piperidyl, morpholinyl, oxazolidinyl, thiazolidinyl, pyrazolidinyl, imidazolidinyl, piperazinyl, thiamorpholinyl, trimethylenetriaminyl and ethyleneiminyl.
"Substituted heterocycle" means a heterocycle in which one or more of the hydrogens on the ring carbons have been replaced by substituents as given above with respect to substituted phenyl.
The terms "halo" and "halogen" include all four halogens; namely, fluorine, chlorine, bromine and iodine. The halo alkyls, halophenyl and halo-substituted pyridyl include groups having more than one halo substituent which may be the same or different such as trifluoromethyl, 1-chloro-2-bromo-ethyl, chlorophenyl, 4-chloropyridyl, etc.
"Acyloxy" means an organic acid radical of a lower alkanoic acid such as acetoxy, propionoxy, and the like.
"Lower alkanoyl" means the acyl radical of a lower alkanoic acid such as acetyl, propionyl, butyryl, valeryl, stearoyl, and the like.
"Alkoxy" is intended to include hydroxy alkyl groups. Preferred lower alkyl groups include methoxy, ethoxy, n-propoxy, i-propoxy, and the like.
"R 5 and R 6 together with the nitrogen to which they are attached form a 3 to 7 atom ring" means a heterocycle selected from the group including oxazolidinyl, thiazolidinyl, pyrazolidinyl, imidazolidinyl, piperidyl, piperazinyl, thiamorpholinyl, trimethylenetriaminyl, ethyleneiminyl and morpholinyl; where the heterocycle may be mono-, di-, tri- or tetra-substituted by hydrogen, lower alkyl, lower alkenyl, lower alkynyl, aryl, aralkyl, halo, nitro, cyano, sulfonyl, hydroxyl, carboxyl, lower alkanoyl, lower alkoxy, aryl lower alkoxy, halo lower alkoxy, amido, amino, lower alkylamino, aralkylamino, lower alkoxyamino, and aralkylamino.
The preferred "aryl" group is phenyl.
The preferred "aralkyl" groups are benzyl and phenethyl.
The preferred "halo lower alkyl" group is trifluoromethyl.
The preferred "halo lower alkoxy" group is trifluoromethoxy.
It is well known in the pharmacological arts that nontoxic acid addition salts of pharmacologically active amine compounds do not differ in activities from their free base. The salts merely provide a convenient solubility factor.
The amidinoureas of this invention may be readily converted to their nontoxic acid addition salts by customary methods in the art. The nontoxic salts of this invention are formed from the amidinourea base and on acid which is pharmacologically acceptable in the intended dosages. Such salts would include those prepared from inorganic acids, organic acids, higher fatty acids, high molecular weight acids, etc. Exemplary acids are hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, methane sulfonic acid, benzene sulfonic acid, acetic acid, propionic acid, malic acid, succinic acid, glycolic acid, lactic acid, salicylic acid, benzoic acid, nicotinic acid, phthalic acid, stearic acid, oleic acid, abietic acid, etc.
Representative examples of the compounds of this invention are listed in Tables I and I-A.
TABLE I
1-(2-pyridyl)-3-methylamidinourea
1-(2-pyridyl)-3-ethylamidinourea
1-(2-pyridyl)-3-propylamidinourea
1-(2-pyridyl)-3-i-propylamidinourea
1-(2-pyridyl)-3-butylamidinourea
1-(2-pyridyl)-3-i-butylamidinourea
1-(2-pyridyl)-3-pentylamidinourea
1-(2-pyridyl)-3-propargylamidinourea
1-(2-pyridyl)-3-allylamidinourea
1-(2-pyridyl)-3-methoxyethylamidinourea
1-(2-pyridyl)-3-benzyloxyethylamidinourea
1-(2-pyridyl)-3-phenethoxyethylamidinourea
1-(2-pyridyl)-3-(N,N-dimethylamidino)urea
1-(2-pyridyl)-3-(N,N-diethylamidino)urea
1-(2-pyridyl)-3-(N,N-tetramethyleneamidino)urea
1-(2-pyridyl)-3-(N,N-pentamethyleneamidino)urea
1-(2-pyridyl)-3-(N,N-hexamethyleneamidino)urea
1-(2-[3-methylpyridyl])-3-methylamidinourea
1-(2-[3-methylpyridyl])-3-ethylamidinourea
1-(2-[3-methylpyridyl])-3-propylamidinourea
1-(2-[3-methylpryidyl])-3-i-propylamidinourea
1-(2-[3-methylpyridyl])-3-i-butylamidinourea
1-(2-[3-methylpyridyl])-3-pentylamidinourea
1-(2-[3-methylpyridyl])-3-allylamidinourea
1-(2-[3-methylpyridyl])-3-propargylamidinourea
1-(2-[3-methylpyridyl])-3-cyclopropylamidinourea
1-(2-[3-methylpryidyl])-3-methoxyethylamidinourea
1-(2-[3-methylpyridyl])-3-benzyloxyethylamidinourea
1-(2-[3-methylpyridyl])-3-phenethoxyethylamidinourea
1-(2-[3-methylpyridyl])-3-benzylamidinourea
1-(2-[3-methylpyridyl])-3-(N,N-dimethylamidino)urea
1-(2-[3-methylpyridyl])-3-(N,N-diethylamidino)urea
1-(2-[3-methylpyridyl])-3-(N,N-tetramethyleneamidino)urea
1-(2-[3-methylpyridyl])-3-(N,N-pentamethyleneamidino)urea
1-(2-[3-chloropyridyl])-3-methylamidinourea
1-(2-[3-chloropyridyl])-3-ethylamidinourea
1-(2-[3-chloropyridyl])-3-propylamidinourea
1-(2-[3-chloropyridyl])-3-i-propylamidinourea
1-(2-[3-chloropyridyl])-3-butylamidinourea
1-(2-[3-chloropyridyl])-3-i-butylamidinourea
1-(2-[3-chloropyridyl])-3-t-butylamidinourea
1-(2-[3-chloropyridyl])-3-pentylamidinourea
1-(2-[3-chloropyridyl])-3-allylamidinourea
1-(2-[3-chloropyridyl])-3-propargylamidinourea
1-(2-[3-chloropyridyl])-3-cyclopropylamidinourea
1-(2-[3-chloropyridyl])-3-cyclobutylamidinourea
1-(2-[3-chloropyridyl])-3-([3-cyclopentenyl]amidino)urea
1-(2-[3-chloropyridyl])-3-cyclopropylmethylamidinourea
1-(2-[3-chloropyridyl])-3-methoxyethylamidinourea
1-(2-[3-chloropyridyl])-3-benzyloxyethylamidinourea
1-(2-[3-chloropyridyl])-3-phenethoxyethylamidinourea
1-(2-[3-chloropyridyl])-3-benzylamidinourea
1-(2-[3-chloropyridyl])-3-(N,N-dimethylamidino)urea
1-(2-[3-chloropyridyl])-3-(N,N-diethylamidino)urea
1-(2-[3-chloropyridyl])-3-(N,N-tetramethyleneamidino)urea
1-(2-pyridyl)-3-(N,N[3-methyl-3-azapentamethylene]amidino)urea
1-(2-pryidyl)-3-(N,N[3-oxapentamethylene]amidino)urea
1-(3-pyridyl)-3-methylamidinourea
1-(3-pyridyl)-3-ethylamidinourea
1-(3-pyridyl)-3-propylamidinourea
1-(3-pyridyl)-3-i-propylamidinourea
1-(3-pyridyl)-3-butylamidinourea
1-(3-pyridyl)-3-i-butylamidinourea
1-(3-pyridyl)-3-t-butylamidinourea
1-(3-pyridyl)-3-pentylamidinourea
1-(3-pyridyl)-3-allylamidinourea
1-(3-pyridyl)-3-propargylamidinourea
1-(3-pyridyl)-3-cyclobutylamidinourea
1-(3-pyridyl)-3-cyclohexylamidinourea
1-(3-pyridyl)-3-benzylamidinourea
1-(3-pyridyl)-3-methoxyethylamidinourea
1-(3-pyridyl)-3-benzyloxyethylamidinourea
1-(3-pyridyl)-3-methoxyethylamidinourea
1-(3-pyridyl)-3-benzyloxyethylamidinourea
1-(3-pyridyl)-3-phenethoxyethylamidinourea
1-(3-pyridyl)-3-(N,N-diethylamidino)urea
1-(3-pyridyl)-3-(N,N-dimethylamidino)urea
1-(3-pyridyl)-3-(N,N-pentamethyleneamidino)urea
1-(4-pyridyl)-3-methylamidinourea
1-(4-pyridyl)-3-ethylamidinourea
1-(4-pyridyl)-3-propylamidinourea
1-(4-pyridyl)-3-i-propylamidinourea
1-(4-pyridyl)-3-butylamidinourea
1-(4-pyridyl)-3-t-butylamidinourea
1-(4-pyridyl)-3-pentylamidinourea
1-(4-pyridyl)-3-hexylamidinourea
1-(4-pyridyl)-3-propargylamidinourea
1-(4-pyridyl)-3-allylamidinourea
1-(4-pyridyl)-3-methoxyethylamidinourea
1-(4-pyridyl)-3-benzyloxyethylamidinourea
1-(4-pyridyl)-3-phenethoxyethylamidinourea
1-(4-pyridyl)-3-(N,N-dimethylamidino)urea
1-(4-pyridyl)-3-(N,N-diethylamidino)urea
1-(4-pyridyl)-3-(N-methyl-N-ethylamidino)urea
1-(4-pyridyl)-3-(N,N-tetramethyleneamidino)urea
1-(4-pyridyl)-3-(N,N-pentamethyleneamidino)urea
1-(4-pyridyl)-3-(N,N-hexamethyleneamidino)urea
1-(4-[2-ethylpyridyl])-3-methylamidinourea
1-(4-[2-ethylpyridyl])-3-ethylamidinourea
1-(4-[2-ethylpyridyl])-3-propylamidinourea
1-(4-[2-ethylpyridyl])-3-butylamidinourea
1-(4-[2-ethylpyridyl])-3-i-butylamidinourea
1-(4-[2-ethylpyridyl])-3-pentylamidinourea
1-(4-[2-ethylpyridyl])-3-allylamidinourea
1-(4-[2-ethylpyridyl])-3-propargylamidinourea
1-(4-[2-ethylpyridyl])-3-methoxyethylamidinourea
1-(4-[2-ethylpyridyl])-3-benzyloxyethylamidinourea
1-(4-[2-ethylpyridyl])-3-(N,N-dimethylamidino)urea
1-(4-[2-ethylpyridyl])-3-(N,N-diethylamidino)urea
1-(4-[2-ethylpyridyl])-3-(N,N-tetramethyleneamidino)urea
1-(3-[2,4-dimethylthiophenyl])-3-amidinourea
1-(3[2-chloro-4-methylthiophenyl])-3-methylamidinourea
1-(4-[2,6-dichloropyridyl])-3-methylamidinourea
1-(4-[2,6-dimethylpyridyl])-3-methylamidinourea
1-(4-[2-methyl-6-chloropyridyl])-3-methylamidinourea
1-(2-thiophenyl)-3-methylamidinourea
1-(3-thiophenyl)-3-methylamidinourea
1-(2-[3-methylthiophenyl])-3-methylamidinourea
1-(2-[3-chlorothiophenyl])-3-methylamidinourea
1-(2-pyridyl-N-oxide)-3-(N,N-dimethylamidino)urea
1-(2-[3-cyanopyridyl])-3-methylamidino urea
1-(2-[3-carbomethoxypyridyl])-3-methylamidino urea
1-(2-[3-carboethoxypyridyl])-3-methylamidino urea
1-(2-[6-chloropyridyl])-3-methylamidino urea
1-(2-[6-methylpyridyl])-3-methylamidino urea
1-(2-[3-ethylpyridyl])-3-methylamidino urea
1-(3-[2-methylpyridyl)-3-methylamidino urea
1-(3-[2-ethylpyridyl])-3-methylamidino urea
1-(3-[2,-dimethylpyridyl])-3-methylamidino urea
1-(2-[3-cyanothiophenyl])-3-methylamidino urea
1-(2-[3-carbomethoxythiophenyl])-3-methylamidino urea
1-(2-[3-carboethoxythiophenyl])-3-methylamidino urea
1-(3-[2-methoxypyridyl])-3-methylamidino urea
1-(3-[2-ethoxypyridyl])-3-methylamidino urea
1-(3-[2-chloropyridyl])-3-methylamidino urea
1-(2-furyl)-3-amidinourea
1-(3-furyl)-3-amidinourea
1-(2-[3-methylfuryl])-3-amidinourea
1-(2-furyl)-3-ethylamidino urea
1-(2-furyl)-3-propylamidino urea
1-(2-furyl)-3-i-propylamidino urea
1-(2-furyl)-3-butylamidino urea
1-(2-furyl)-3-i-butylamidino urea
1-(2-furyl)-3-sec-butylamidino urea
1-(2-furyl)-3-t-butylamidino urea
1-(2-furyl)-3-pentylamidino urea
1-(2-furyl)-3-hexylamidino urea
1-(2-furyl)-3-heptylamidino urea
1-(2-furyl)-3-cyclopropylamidino urea
1-(2-furyl)-3-cyclobutylamidino urea
1-(2-pyridyl-N-oxide)-3-methylamidinourea
1-(3-pyridyl-N-oxide)-3-methylamidinourea
1-(4-pyridyl-N-oxide)-3-methylamidinourea
1-(2-furyl)-3-methylamidinourea
1-(3-furyl)-3-methylamidinourea
1-(2-tetrahydrofuryl)-3-methylamidinourea
1-(3-tetrahydrofuryl)-3-methylamidinourea
1-(1-imidazolyl)-3-methylamidinourea
1-(2-imidazolyl)-3-methylamidinourea
1-(4-imidazolyl)-3-methylamidinourea
1-(2-oxazolyl)-3-methylamidinourea
1-(4-oxazolyl)-3-methylamidinourea
1-(5-oxazolyl)-3-methylamidinourea
1-(1-pyrazolyl)-3-methylamidinourea
1-(1-[3-pyrrolidyl])-3-methylamidinourea
1-(2-pyrrolyl)-3-methylamidinourea
1-(1-morpholinyl)-3-methylamidinourea
1-(2-morpholinyl)-3-methylamidinourea
1-(2-pyrimidinyl)-3-methylamidinourea
1-(4-pyrimidinyl)-3-methylamidinourea
1-(2-quinolinyl)-3-methylamidinourea
1-(4-quinolinyl)-3-methylamidinourea
1-(1-isoquinolinyl)-3-methylamidinourea
1-(2-furyl)-3-cyclopentylamidino urea
1-(2-furyl)-3-cyclohexylamidino urea
1-(2-furyl)-3-phenylamidino urea
1-(2-furyl)-3-benzylamidino urea
1-(2-furyl)-3-phenethylamidino urea
1-(2-furyl)-3-(N-methyl-N-benzylamidino)urea
1-(2-furyl)-3-(N,N-dibenzylamidino)urea
1-(2-tetrahydrofuryl)-3-amidinourea
1-(2-[3-methyltetrahydrofuryl])-3-amidinourea
1-(3-tetrahydrofuryl)-3-amidinourea
1-(3-[2-methyltetrahydrofuryl])-3-amidinourea
1-(1-imidazolyl)-3-amidinourea
1-(1-[2-methylimidazolyl])-3-amidinourea
1-(3-[2,4-dichlorothiophenyl])-1-methyl-3-amidinourea
TABLE I-A______________________________________ ##STR7##R.sub.1 R.sub.5 R.sub.6______________________________________ ##STR8## H H ##STR9## H CH.sub.3 ##STR10## H C.sub.2 H.sub.5 ##STR11## CH.sub.3 CH.sub.3 ##STR12## H OCH.sub.3 ##STR13## H CH.sub.3 ##STR14## CH.sub.3 CH.sub.3 ##STR15## C.sub.2 H.sub.5 C.sub.2 H.sub.5 ##STR16## H H ##STR17## H CH.sub.3 ##STR18## H C.sub.2 H.sub.5 ##STR19## H OCH.sub.3 ##STR20## CH.sub.3 CH.sub.3 ##STR21## CH.sub.3 C.sub.2 H.sub.5 ##STR22## H H ##STR23## H CH.sub.3 ##STR24## H C.sub.2 H.sub. 5 ##STR25## H H ##STR26## H CH.sub.3 ##STR27## CH.sub.3 CH.sub.3 ##STR28## H CH.sub.3 ##STR29## H C.sub.2 H.sub.5 ##STR30## CH.sub.3 CH.sub.3 ##STR31## H H ##STR32## H CH.sub.3 ##STR33## CH.sub.3 CH.sub.3 ##STR34## H C.sub.2 H.sub.5 ##STR35## H H ##STR36## H CH.sub.3 ##STR37## H H ##STR38## H CH.sub.3 ##STR39## H C.sub.2 H.sub.5 ##STR40## H H ##STR41## H CH.sub.3 ##STR42## H CH.sub.3 ##STR43## H H ##STR44## H CH.sub.3 ##STR45## H C.sub.2 H.sub.5 ##STR46## H CH.sub.3 ##STR47## CH.sub.3 CH.sub.3 ##STR48## H CH.sub.3 ##STR49## H C.sub.2 H.sub.5 ##STR50## H CH.sub.3 ##STR51## H CH.sub.3 ##STR52## H C.sub.2 H.sub.5 ##STR53## H CH.sub.3 ##STR54## H C.sub.2 H.sub.5 ##STR55## H CH.sub.3 ##STR56## H C.sub.2 H.sub.5 ##STR57## H CH.sub.3 ##STR58## H C.sub.2 H.sub.5 ##STR59## H CH.sub.3 ##STR60## H CH.sub.3 ##STR61## H C.sub.2 H.sub.5 ##STR62## H CH.sub.3 ##STR63## H C.sub.2 H.sub.5 ##STR64## H CH.sub.3 ##STR65## H C.sub.2 H.sub.5 ##STR66## H CH.sub.3 ##STR67## H C.sub.2 H.sub.5 ##STR68## H CH.sub.3 ##STR69## H C.sub.2 H.sub.5______________________________________
The compounds of this invention may be prepared by the following general synthesis.
Condensation of a N-heterocyclic carbamate, for example a phenyl-N-heterocyclic carbamate, with an appropriately substituted guanidine results in a 1-heterocyclic-3-substituted amidinourea. The reaction is carried out in a polar media using solvents such as alcohol, tetrahydrofuran, etc. It is convenient to carry out the reaction by preparing the guanidine in situ by hydrolyzing a guanidine carbonate with base. Condensation of the carbamate takes place when the guanidine forms and the amidinourea compounds result.
When R 2 substitution is desired, the starting material can be a N-heterocyclic N-substituted carbamate, obtained from the corresponding N-alkyl heterocyclic amine, which is then reacted with the appropriate substituted guanidine to prepare the amidinourea. (Scheme I) ##STR70##
One method to obtain an amidinothiourea is where the starting material is a triethylamine salt of a heterocyclic dithiocarbamic acid which can be obtained from the heterocyclic amine. Reaction with FeCl 3 eliminates H 2 S to form the isothiocyanate. Subsequent reaction with an appropriate substituted guanidine forms the heterocyclic amidinothiourea. (Scheme II) ##STR71##
The starting heterocyclic amines are known or may be prepared by known techniques.
Reactions may also be carried out at other stages of synthesis depending on the substituents present and the substituents desired. Various combinations of the foregoing reactions can be determined by one skilled in the art in order that the desired product results. Thus, a pyridylamidinourea may be halogenated or nitrated, etc.
The following are detailed examples which show the preparation of the compounds of this invention.
EXAMPLE I
The preparation of 1-methyl-3-[(2-pyridyl-1-oxide)carbamoyl]guanidine
Step 1
2-Oxo-2H-[1,2,4[oxadiazolo]2,3-a]pyridine
2-Ethoxy carbonyl amino pyridine-1-oxide (41.90 g) is heated to 140°-150° C. for one hour and then 150°-160° C. for an additional hour with removal of ethyl alcohol. The resulting solid is cooled, recrystallized from absolute ethanol, and dried to afford 9.87 grams of tan crystals, M.P. 203°-205° C.
Step 2
1-methyl-3-[(2-pyridyl-1-oxide)carbamoyl]guanidine
Finely powdered methyl quanidine sulfate (7.33 g) is added to a stirred solution of NaOCH 3 (3.24 g) in 20 ml absolute ethanol. The mixture is stirred at room temperature for three hours and filtered through a celite pad. The filtrate is evaporated in vacuo and the residual oil is triturated with dry toluene to yield a white solid. The toluene is evaporated in vacuo. 2-Oxo-2H-(1,2,4[oxadiazolo]2,3-a)pyridine (8.17 g) in 150 ml of dry toluene is added to the white solid and the reaction mixture heated to reflux for 30 minutes. A brown solid forms. The reaction mixture is stirred under reflux for an additional 30 minutes. A brown crystalline solid is collected, washed with toluene and dried. The solid is recrystallized from absolute ethanol to give a 24% yield of the desired amidinourea as a white solid, M.P. 177°-179° (dec).
EXAMPLE II
Preparation of 1-(2-chloro-4-bromo-6-methylphenyl)-3-[(2-pyridyl-1-oxide)carbamoyl]-guanidine
A mixture of 1-(2-chloro-4-bromo-6-methylphenyl)guanidine (13.13 g), and 2-Oxo-2H-[1,2,4]oxadiazolo[2,3-a]pyridine (6.81 g) in 150 ml of dry toluene is heated slowly to boiling for one hour and stirred under gentle reflux overnight. The reaction mixture is cooled to room temperature and the solid collected, washed with toluene and dried to afford 16.34 grams of a gray powder. The gray powder is extracted with 1.5 l of boiling acetonitrile, filtered through celite, and concentrated to approximately 500 ml and cooled. A crystalline solid is formed which is washed with acetonitrile, and dried to afford 8.58 grams of the desired N-oxide as gray crystals, M.P. 175°-176° C. (dec).
EXAMPLE III
1-(2-pyridyl)-3-methylamidinourea
A 50% aqueous sodium hydroxide solution (6.54 g) is added to a stirred suspension of methyl guanidine sulfate (9.77 g) and 500 ml of THF. The suspension is stirred for 1/2 hour and anhydrous Na 2 SO 4 (20 g) is added. The reaction mixture is stirred 1/2 hour and phenyl-N-(2-pyridyl)carbamate (17.12 g) is added. The reaction mixture is stirred for four hours and the reaction mixture filtered. The residue is taken up with 500 ml of boiling methanol and filtered. The filtrate is concentrated in vacuo, taken up in chloroform and washed with water and brine. The aqueous washes were back extracted and the organic extracts combined, dried, filtered and concentrated in vacuo to yield a yellow oil. [A white solid is insoluble in both water and organic layers. This solid is filtered, washed and dried to give a white solid, M.P. 183.5°-185° C. The residue filtrate from above is concentrated to 300 ml and a precipitate is formed. Precipitate has a melting point of 186°-188° C.] The yellow oil is taken up in 100 ml of chloroform, washed, dried, filtered and concentrated in vacuo to yield a white solid, M.P. 182°-183° C. The white solids are combined to give 10.7 grams of crude amidinourea. The hydrochloric acid salt is formed by partially dissolving the white solids in boiling methanol and acidifying with methanolic HCl. The methanolic solution is concentrated in vacuo to yield a white solid which is dissolved in methanol and filtered through charcoal and celite. The filtrate is concentrated and the resultant solid recrystallized from methanol/acetonitrile to yield the desired hydrochloric acid salt, M.P. 164.5°-165° C.
EXAMPLE IV
The preparation of 1-(2,5-dimethylpyrrole)-3-methylamidinourea
3.2 grams of a 50% aqueous sodium hydroxide solution are added to a suspension of N-methylguanidine sulfate (4.89 g) in 75 ml THF. The suspension is stirred for 45 minutes and anhydrous sodium sulfate added. The suspension is stirred for an additional hour at room temperature and a solution of N-2,5-dimethylpyrrolyl-O-phenylcarbamate (4.61 g) in 50% ml THF is added dropwise. The reaction mixture is stirred at RT for one week, evaporated in vacuo and the residue partitioned between water and chloroform. The aqueous layer is washed with chloroform. The organic layer is combined, back extracted and dried. The chloroform is evaporated in vacuo and the product residue titriated in ether to give 0.68 gram of a yellow solid, M.P. 180°-182° C.
EXAMPLE V
1-(2-pyridyl)-3-methoxyamidinourea hydrochloride
2.6 grams of a 50% aqueous sodium hydroxide solution are added to a suspension of methoxy guanidine hydrochloride (4.1 g) in 50 ml of THF. The reaction mixture is stirred for one hour, anhydrous sodium sulfate (5.0 g) added and the mixture stirred for an additional hour. The mixture is filtered and the solid material washed well with THF. The THF is removed to give 3.0 grams of a semi-crystalline solid. This material is dissolved in 100 ml of THF to which is added phenyl N-(2-pyridyl)carbamate (6.4 g) and the mixture stirred at RT over the weekend. The THF is removed in vacuo and the residue dissolved in chloroform and passed through a column of 18 grams of silica gel. The column is washed with ethyl acetate and the ethyl acetate fraction dissolved in methanol and acidified with methanolic HCl. The methanol is removed in vacuo to give a foam which is crystallized from acetonitrile to give 0.4 gram of the desired hydrochloride salt as a pink solid, M.P. 152°-153° C.
EXAMPLE VI
The preparation of 1-[2-(5-chloropyridyl)]-3-methylamidinothiourea hydrochloride
Step 1
5-chloro-2-isothiocyanate pyridine
A solution of FeCl 3 .6H 2 O (59.5 g) in 240 ml of H 2 O is rapidly added to a stirred suspension of 5-chloro-2-pyridyl dithiocarbamic acid triethylamine salt (61.4 g) in 250 ml of methylene chloride containing 20.2 grams of triethylamine. The reaction mixture is stirred for 5 minutes and then poured through a celite pad. The celite pad is washed with methylene chloride. The layers of the filtrate are separated and the aqueous layer extracted with methylene chloride. The combined organic extracts are dried, concentrated in vacuo to give an orange solid. The residue is extracted with dry refluxing ether and the combined extracts concentrated in vacuo to give a yellow orange solid. This material is taken up in hexane and filtered. The filtrate is concentrated in vacuo to give 7.8 grams of an orange solid which is sublimed (70° C./vacuum pump) to give 4.3 grams of the thioisocyanate, M.P. 44°-44.5° C.
Step 2
1-[2-(5-chloropyridyl)]-3-methylamidinothiourea hydrochloride
2.1 grams of a 50% aqueous sodium hydroxide solution are added to a stirred suspension of methyl guanidine sulfate (3.2 g) in 100 ml of THF and the mixture stirred for one hour. 6.0 grams of anhydrous sodium sulfate are added and the mixture stirred an additional hour. A solution of 5-chloro-2-isothiocyanatopyridine (4.2 g) in 80 ml THF is added to the reaction mixture over a period of one and one-half hours and the mixture stirred for an additional hour. The reaction mixture is filtered and concentrated in vacuo to give an orange red foam which is partitioned between methylene chloride and water. Saturated sodium chloride is added to break up the emulsion and the layers are separated. The aqueous layers are extracted with methylene chloride and the combined extracts are dried and concentrated under reduced pressure. The residual oil solidifies on standing. The solid is crystallized from ethyl acetate to give 3.6 grams of a light yellow solid. The solid is taken up in methanol and acidified with methanolic HCl. The solution was filtered through a celite pad and the filtrate concentrated in vacuo to give a yellow solid which is crystallized from methanol/acetonitrile to give 3.9 grams of a light yellow powder. This material is recrystallized from 95% ethanol to give 2.9 grams of the desired hydrochloride salt, M.P. 193°-194° C. (dec.)
EXAMPLE VII
The preparation of 1-amidino-3-(2-chloro-4-methyl-3-thienyl)urea hydrochloride
Step 1
2-Chloro-3-isocyanato-4-methylthiophene
A solution of 2-chloro-4-methyl-3-thiophene carboxylic acid (44.16 g) and thionyl chloride (36 ml, 59.5 g) in toluene (1 liter) is stirred under reflux for 20 hours. The reaction mixture is evaporated under reduced pressure and the resultant yellow-brown oil dissolved in 280 ml of acetone and cooled in a methanol-ice bath. A solution of sodium azide (69.07 g) in H 2 O (265 ml) is added dropwise to the vigorously stirred reaction mixture while maintaining the reaction temperature below 0° C. After the addition is complete, the mixture is stirred for 1 hour, and concentrated under reduced pressure at RT. The concentrate is extracted with carbon tetrachloride, and the extracts washed (sat'd aq. NaCl), dried (MgSO 4 ), filtered and concentrated under reduced pressure to a volume of about 500 ml. The concentrated extract is heated slowly to boiling while controlling temperature by cooling. Heating is accompanied by rapid gas evolution. The concentrated extract is refluxed overnight. The concentrated extract is evaporated under reduced pressure and the residue distilled, affording 33.57 g of the thiophenyl isocyanate as a water-white liquid, b.p. 42° C. (0.20 mm).
Step 2
1-Amidino-3-(2-chloro-4-methyl-3-thienyl)urea hydrochloride
A mixture of guanidine hydrochloride (14.33 g), and 50% aqueous NaOH (10.00 g) in THF (250 ml) is stirred at room temperature overnight. THF (250 ml), and anhydrous Na 2 SO 4 (7.5 g) are added to the mixture and stirring continued for 1 hour. A solution of 2-chloro-3-isocyanato-4-methylthiophene (8.68 g) in THF (500 ml) is added dropwise to the stirred mixture. After the addition is complete, stirring is continued for 30 minutes. The solvent is decanted, leaving a THF insoluble material. The solvent is evaporated under reduced pressure. The evaporated residue is suspended in 500 ml of 2% aqueous HCl and added to the THF insoluble material. This mixture is stirred vigorously with 250 ml of Et 2 O for 30 minutes. Insoluble material is separated by decantation. The aqueous layer is separated, washed with Et 2 O and alkalinized with NaHCO 3 , forming a precipitate. The precipitate is washed with H 2 O and air dried to afford 8.85 g of a tan crystalline solid. The tan solid is dissolved in 5% aqueous HCl (175 ml), filtered through Celite, and the filtrate cooled rapidly to room temperature. After standing overnight in the cold, the precipitate is collected, washed with a portion of the mother liquor, dried in vacuo, and stirred in 100 ml of CH 2 Cl 2 , and air dried in vacuo (50° C.) overnight to yield 7.20 g of the amidinourea hydrochloride as a tan powder, m.p. 173°-174.5° C. w/dec.
This invention also relates to a method for lowering blood pressure in mammalian species by administering to a patient an effective blood pressure lowering amount of a compound according to Formula I, and preferably, a compound according to Formula VII: ##STR72## where: X is O or S;
n is zero to four;
(R) is a ring substituent as defined above including pyridyl N-oxide
R 2 is hydrogen or alkyl;
R 5 and R 6 are hydrogen, alkoxy, alkenyl, alkyl, or aryl;
and the pharmaceutically acceptable salts thereof.
Various tests can be carried out in animal models to show the ability of the compounds of this invention to exhibit reactions that can be correlated with pharmacological activity in humans. The following test protocol can be used to determine the blood pressure effect of compounds according to this invention.
Determination of Antihypertensive Activity
A description of the test protocol used in the determination of the antihypertensive activity of the compounds of this invention follows:
(a) Male TAC spontaneously hypertensive rats (SHR's), eleven weeks old, weighing 200-220 grams, are chosen for testing. The average systolic blood pressure (as measured below) should be 165 mmHg or above. Any rat not initially meeting this criterion is not utilized.
(b) A Beckman dynograph is balanced and calibrated using a Beckman indirect blood pressure coupler. A mercury monometer is placed on one arm of the glass "T" tube. The known pressure head in the tail cuff is synchronized with the recorder output so that 1 mm pen deflection=5 mmHg. Any correction is made using the chart calibration screw on the pressure coupler. The pulse amplitude is controlled by the pre-amplifier using a 20 v/cm setting.
The rats are prewarmed in groups of five for twenty minutes to dilate the tail artery from which the arterial pulse is recorded. After prewarming, each rat is placed in an individual restraining cage with continued warming. When the enclosure temperature has been maintained at 35° C. for 5 minutes, recordings are started. The tail cuff is placed on the rat's tail and the rubber bulb of the pneumatic tail cuff transducer is taped securely to the dorsal surface of the tail. When the rat's pulse reaches maximum amplitude and is unwavering, the cuff is inflated and the air slowly released. A reading of systolic blood pressure is read at the point of the chart when the first deflection appears on the chart recording while the air in the cuff is being released. The exact point of the systolic blood pressure reading is where the first deflection forms a 90° angle to the falling cuff pressure base line. After obtaining nine or ten consistent readings, the average of the middle five readings is calculated.
(c) Three groups of twenty rats receive the test compound at doses of 0.125 mg/kg, 0.5 mg/kg, and 2 mg/kg b.i.d. A fourth group of twenty control rats receives distilled water. Statistical comparisons of systolic pressure (four hours after the first dose and sixteen hours after the second dose) are made on a daily basis using the Student t test for dependent variables (see, E. Lord, Biometrika, 34, 56 (1947)), with the predose observations serving as baseline values for each rat.
The test results on compounds according to Formulae I and VII show that these compounds possess significant blood pressure lowering activity and are useful in lowering blood pressure in humans and animals. In particular, compounds of Formula VII are useful for relieving hypertensive disorders by administering to a patient suffering from hypertension a therapeutically effective amount between about 0.5 mg to about 500 mg per dosage unit of at least one of said compounds.
This invention also relates to a method of treating gastrointestinal disorders by administering to a patient compounds according to Formula I, and preferably compounds according to Formula VIII: ##STR73## where: X is oxygen or sulfur;
R 1 is pyridyl, 1-pyrrole, substituted 2-pyridyl, substituted 2-pyrrole or substituted 3-thienyl;
R 2 is hydrogen or alkyl;
R 5 and R 6 are each independently hydrogen, alkyl, alkenyl, alkoxy or aryl;
and the pharmaceutically acceptable salts thereof.
Various tests can be carried out in animal models to show the ability of these compounds to exhibit gastrointestinal activity. These tests are well known in the art and are disclosed in U.S. patents discussed above and are hereby incorporated by reference.
One such test is the gastric secretion inhibition test, the test protocol of which is as follows.
The method used has been reported by Shay. Male Sprague-Dawley rats (140-160 g) are fasted 24 hours prior to the test. The rats are allowed water ad libitum only during the fasting period. One hour before pyloric ligation the rats (5/group) are given either atropine sulfate or the vehicle. The compounds are prepared in methylcellulose. Pyloric ligation is performed in the rats under sodium methohexital anesthesia. Four hours after pyloric ligation, the rats are sacrificed by cervical dislocation, the stomachs are removed, and the gastric contents are assayed for volume, titratable acidity, and titratable acid output (TAO). A 1 ml aliquot of the gastric contents are titrated with 0.1 N NaOH to pH 7.0 for titratable acidity. The percent of inhibition is calculated according to the formula ##EQU1##
It has been found that the compounds of this invention, particularly the compounds of Formula VIII possess the ability to markedly decrease gastric volume and gastric acidity and are useful as antisecretory, antidiarrheal and anti-ulcerogenic agents.
The compounds of Formula I are useful for relieving gastrointestinal hyperacidity or ulceration by administering to a patient suffering from said gastrointestinal hyperacidity or ulceration a therapeutically effective amount between about 0.5 mg and about 500 mg per dosage unit of at least one of said compounds.
The compounds of Formula I are also useful for relieving diarrheal conditions by administering to a patient suffering from said diarrheal condition a therapeutically effective amount between about 0.5 mg and about 500 mg per dosage unit of at least one of said compound. | This invention relates to a novel class of heterocyclic amidinourea and heterocylic amidinothiourea compounds wherein the heterocyclic substitution is at the 1-N urea nitrogen atom. These compounds exhibit pharmaceutical activity and may be incorporated into pharmaceutical preparations for producing anti-ulcerogenic, antisecretory, antispasmodic, antimotility, cardiovascular, antidiarrheal or antiparasitic action. | 2 |
FIELD OF THE INVENTION
[0001] This invention relates, inter alia, to low-contamination energy generation methods and devices for effecting the same. The methods and devices are useful for removal and/or destruction of diesel engine exhaust pollutants such as particulate matter, nitrogen oxides and sulfur oxides.
BACKGROUND OF THE INVENTION
[0002] Diesel engines emit flue gas, which is released to the atmosphere. The flue gas contains pollutants, which include particulate matter (PM) comprising, among others, soot, ash, organic compounds and in many cases sulphur compounds. Sulphur compounds concentration in the flue gas is correlated with the concentration of sulphur compounds in the fuel, typically measured as the sulphur (S) content in the fuel. Fuels differ in their S content from low sulphur ones containing less than 100 ppm S to high sulphur ones containing more than 4% S. The flue gas from burning high S fuels is also high in gaseous sulphur oxides with various S to O ratios, mainly SO 2 , collectively referred to as SO x . Other undesired gaseous components of the emitted flue gas are nitrogen oxides with various N to O ratios, collectively referred to as NO x .
[0003] Large diesel engines operate in both stationary and mobile power generation units. Among the mobile ones, of particular importance are diesel engines operating on board ships and marine oil exploration vessels, also referred to as marine diesel engines. Typically, a ship has in its engine room one or more engines for propulsion purposes (ranging from 4,000 kW to 60,000 kW) and two to four sets of auxiliary engines for electrical power generation or other specific utility purposes. The auxiliary engines typically have a rated power of 500 kW to 1,500 kW). Under normal sea passage, the utilization of the propulsion engines will be between 80% and 85% of MCR (Maximal Continuous Rating) and the required electric power generation will be between 400 kW and 600 kW. Typical marine oil exploration units have several large diesel engines all producing electrical power for propulsion and auxiliary purposes.
[0004] Marine diesel engines possess the capability for utilization of high quality fuels (e.g. distillates such as DMA, DMB and DMC according to ISO 8217). Such fuels are quite expensive. Therefore, typically much coarser (lower quality) fuels are utilized. An example of such coarser oil is the heavy fuel oil (HFO), e.g. of ISO 8217 grade characterized by high viscosity, density, carbon, ash and sulphur. The amount of contaminants generated in operating an engine is dependent upon various parameters; such as the type and origin of the fuel, the ambient conditions, the size and speed of the engine, the lubrication system and lubricant consumption, the operating load and the state of maintenance. The term content or amount, when in reference to a contaminating material, may mean its concentration in the effluents, e.g. expressed as weight per weight (w/w), weight per volume (w/v) or volume per volume (v/v). This term may also refer to the amount produced per time of operation (e.g. gram per hour, g/h) or per energy provided (e.g. gram per kilowatt hour, g/kWh). Typically, the flue gas formed when HFO is used in marine diesel engines contains between 1.0 g/kWh and 2.0 g/kWh PM, between 500 ppm and 1,000 ppm SO x and between 8 g/kWh and 17 g/kWh NO x . Higher or lower contents are also found, depending upon the above-listed parameters.
[0005] Various methods have been described for minimizing PM, SO x and NO x emissions. Recent patent applications describe SO x removal using a cyclone unit (Israel specification 177901) and PM removal using a cyclone unit (Israel specification 194614).
[0006] It is known that recycling of effluent gas, via mixing with the air prior to engine intake, reduces NO formation. Systems using such recycling are implemented in trucks and are referred to as exhaust gas recycle (EGR) systems. Engine modification to incorporate an EGR results in heat absorption by exhaust gas components (CO 2 ) and less O 2 density, which contributes to a lower cylinder temperature and reduces NO x formation.
[0007] Operating EGR systems for marine diesel engines presents complications related to the impurities in the flue gas formed when burning marine fuels (ISO 8217 grades). PM and SO x present a risk for fouling and corrosion of the turbo charger, of the air cooler and of the scavenging systems employed in marine diesel engines.
[0008] Thus, the presence of high levels of PM and SO x negatively impact various engine components, for example, in the turbocharger, where high temperature and corrosion might damage the rotor, rotor shaft and housing.
[0009] Similarly, the air cooler is negatively impacted by the presence of high levels of PM and SO x resulting in corrosion.
[0010] Reduction of PM and SO x content in the exhaust gas to be recycled is therefore essential and its accomplishment at an acceptable cost presents a major challenge. In addition, while methods for reduction of PM and SO x content are known, they typically fail to totally eliminate those components. The yield of actual elimination is reported in terms of overall percentage. Yet, PM in the exhaust gas differs in size, as well as in chemical composition, chemical properties and physical properties. The yields associated with their removal depend upon such properties and on the method employed for removal. As a result, exhaust gas is enriched in some PM compared with other. PM remaining in the treated gas recycled to EGR systems may be more problematic for the EGR system than the PM removed by existing methods and the same situation may arise with regards to the various types of SO x in the gas. Therefore the prior art does not provide a teaching as to the effect of removal of PM by the prior art methods on the ability of the remaining gas to be used for recycling.
[0011] There is therefore a need for improved methods of treating flue gases to enable better removal of impurities, such as PM, SO x and NO x and for the reduction of related costs.
SUMMARY OF THE INVENTION
[0012] According to a first aspect, the present invention provides a method for low-contamination generation of energy comprising:
[0013] (a) forming a gas mixture by mixing a treated gaseous effluent stream and air;
[0014] (b) introducing said gas mixture and fuel at a given gas to fuel ratio into at least one diesel engine;
[0015] (c) burning said fuel in said diesel engine to generate energy and a flue gas stream comprising particulate matter (PM), and nitrogen oxides (NOx);
[0016] (d) treating at least a portion of said flue gas stream with an aqueous stream in a cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec, whereby a treated gaseous effluent stream and an aqueous effluent stream are formed;
[0017] (e) emitting a portion of said treated gaseous effluent stream to form an emitted portion;
[0018] (f) using a portion of said treated gaseous effluent stream to form said gas mixture, and
[0019] (g) repeating steps (a) through (f) multiple times;
[0000] whereby said emitted portion has reduced PM, and reduced NOx content when compared with a reference gaseous effluent stream formed by standard burning of the same fuel in an identical engine to which air and fuel are provided in the same given gas to fuel ratio as above. In some embodiments, the method is a method of low-contamination generation of energy from heavy fuel oil (HFO).
[0020] The invention provides, in some embodiments, a device for low contamination generation of energy from fuel comprising:
[0021] (a) at least one diesel engine, which burns fuel and concurrently generates a flue gas;
[0022] (b) a cyclone unit for treating said flue gas, operationally connected thereto, said cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec and whereby treating said flue gas generates a treated gaseous effluent stream and a aqueous effluent stream;
[0023] (c) a mixer which mixes said treated gaseous effluent stream and air to form a gas mixture; and
[0024] (d) a shunt for directing said gas mixture to said diesel engine.
[0025] The invention further provides in some embodiments, a method for low-contamination generation of energy from fuel comprising
[0026] (a) providing a device comprising:
at least one diesel engine which burns fuel and concurrently generates a flue gas; a cyclone unit for treating said flue gas, operationally connected thereto, said cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec and whereby treating said flue gas generates a treated gaseous effluent stream and an aqueous stream; a mixer for mixing said treated gaseous effluent stream with air to form a gas mixture; and a shunt for directing said gas mixture to said diesel engine.
[0031] (b) forming a gas mixture by mixing a treated gaseous effluent stream and air in said mixer;
[0032] (c) introducing said gas mixture and fuel in a given gas to fuel ratio to said at least one diesel engine;
[0033] (d) burning said fuel in said engine to generate energy and a flue gas stream comprising particulate matter (PM), and nitrogen oxides (NOx);
[0034] (e) treating at least a portion of said flue gas stream in said cyclone unit whereby a treated gaseous effluent stream is formed;
[0035] (f) emitting a first portion of said treated gaseous effluent stream to form an emitted portion;
[0036] (g) using a portion of said treated gaseous effluent stream to form said gas mixture wherein said treated gaseous effluent stream forms between 10% and 40% by volume of said mixture; and
[0037] (h) repeating steps (a) through (g) multiple times;
[0038] whereby said emitted portion has reduced PM, and reduced NOx content when compared with a reference gaseous effluent stream formed by standard burning of the same fuel in an identical engine to which air and fuel are provided in the same given gas to fuel ratio as above.
[0039] The invention provides, in some embodiments, methods and devices for the low-contamination generation of energy from fuel.
[0040] In some embodiments, the invention is directed to methods and/or devices for energy generation from diesel fuel. In some embodiments, the methods and/or device are directed in particular to low-contamination generation of energy via such methods and devices. By reference to the term “low-contamination”, it is to be understood that the methods of this invention significantly reduce concentration of sulphur oxides to be less than 500 ppm and nitrogen oxides to be significantly less than 9 grams per kilowatt hour. In some embodiments, the term “significantly” is to be understood to refer to statistically significant reduction.
[0041] In some embodiments, the invention surprisingly allows for low contamination energy generation methods and/or devices, which produce between 0.2 g/kWh and 0.5 g/kWh PM, between 50 ppm and 100 ppm SO x , and between 3 g/kWh and 8 g/kWh NO x , respectively.
[0042] In some embodiments, the methods of this invention comprise burning the fuel in a diesel engine to generate energy and a flue gas stream comprising particulate matter (PM), nitrogen oxides (NO x ) and sulphur oxides (SO x ).
[0043] In some embodiments, the diesel engine is a turbo-charged, marine diesel engine. It is to be understood that any appropriate diesel engine may be utilized, for example as described in U.S. Pat. Nos. 4,760,702; 4,719,756; 4,167,857; and others, as will be appreciated by the skilled artisan.
[0044] In some embodiments, the invention provides a method for low-contamination generation of energy from heavy fuel oil (HFO) comprising (a) forming a gas mixture by mixing treated effluent stream and air; (b) providing said gas mixture and HFO in w/w ratio in the range between 20:1 and 75:1 to at least one diesel engine; (c) burning said HFO in said engine to generate energy and a flue gas stream comprising particulate matter (PM) and nitrogen oxides (NO x ); (d) treating at least a portion of said flue gas stream in a cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said gaseous stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec, whereby a treated gaseous effluent stream is formed; (e) using a portion of said treated gaseous effluent stream to form said gas mixture and (f) emitting another portion of said treated gaseous effluent stream to form a gaseous effluent, wherein said gaseous effluent has reduced PM and reduced NO x content compared with a reference flue gas stream formed by standard burning of the same HFO in an identical engine to which air and HFO are provided in the same ratio.
[0045] In some embodiments, the engine is of two or four stroke type and the recycled treated gaseous effluent stream forms between 10% and 40% (v/v) of said gas mixture. In another embodiment, the treated stream is not filtered prior to mixing with air to form the gas mixture.
[0046] In another embodiment, NO x , and PM content in the emitted portion is reduced by at least 60% and 70%, respectively, as compared to that of a reference stream. According to still another embodiment, the HFO, e.g. of ISO 8217 grade, comprises sulphur compounds. The sulphur oxides (SO x ) and SO x content in the emitted portion is reduced by at least 95% as compared to that of the reference stream.
[0047] In another embodiment, the diesel engine is one of a group of engines, preferably operating on board of a ship or a marine oil exploration unit, each engine of which is generating energy and a flue gas and the method further comprises combining flue gases of multiple engines or all the engines for said treating in step (d). According to a related embodiment, the unit of step (d) comprises an exhaust collecting hat element on top of the funnel and combining such flue gasses is conducted in this element.
[0048] In other embodiments, the flue gas stream generated is at a temperature in a range of between 180° C. and 300° C. and the treated gaseous effluent stream of step (d) is at a temperature in a range of between 40° C. and 60° C.
[0049] In another embodiment, during flue gas stream generation, at least a portion of the flue gas stream is treated in a cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec, whereby a treated gaseous effluent stream is formed (step d). In one embodiment, the treated gaseous effluent stream and/or the mixture is further treated, before using to form said gas mixture. Such treatment comprises, in some embodiments, a step of compressing, e.g. to a pressure in a range between 1 and 3 bar. In some embodiments, the compressing is conducted at least partially by the turbo charger compressor.
[0050] In some embodiments, this invention provides a device for low-contamination generation of energy from fuel comprising:
a. At least one diesel engine which burns fuel and concurrently generates a flue gas; b. a cyclone unit for treating said flue gas, operationally connected thereto, said cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec and whereby treating said flue gas generates a treated gaseous effluent stream and an aqueous stream; c. a mixer which mixes said treated gaseous effluent stream with air to form a gas mixture; and d. a shunt for directing said gas mixture to said diesel engine.
[0055] In some embodiments, the device further comprises at least one of:
a. a turbo charger; b. a raw flue gas collector hat operationally connected to two or more diesel engines such that flue gas steams generated by each engine is shunted to said collector hat; c. an exhaust fan; d. a clean flue gas uptake device e. a collecting tank for said treated gaseous stream; f. a unit for treating said aqueous stream; or g. a pumping unit supplying a water solution or sodium hydroxide to said cyclone unit.
[0063] n some embodiments, the device further comprises at least one of:
a. a regulation device for maintaining level pressure in the collecting tank and in an engine room; b. a regulation device for the mixer; or c. a self adjusting recirculation device for said treated gaseous stream; and d. a regulation device for the pumping unit.
[0068] In one embodiment, the device for low-contamination generation of energy from fuel comprises: (a) a diesel engine burning a fuel in a provided gas mixture and generating energy and a flue gas; (b) a cyclone unit for treating the flue gas, comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein the cyclone unit is characterized in that the velocity of the flue gas stream inside the cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec, whereby a treated gaseous effluent stream and an aqueous stream are formed; (c) a mixer which mixes treated gaseous stream with air to form the gas mixture and (d) a shunt for directing said gas mixture to said diesel engine.
[0069] In some embodiments, the invention provides a method for low-contamination generation of energy from fuel comprising:
[0070] (a) providing a device comprising:
at least one diesel engine which burns fuel and concurrently generates a flue gas; a cyclone unit for treating said flue gas, operationally connected thereto, said cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec and whereby treating said flue gas generates a treated gaseous effluent stream and an aqueous stream; a mixer for mixing said treated gaseous effluent stream with air to form a gas mixture; and a shunt for directing said gas mixture to said diesel engine.
[0075] (b) forming a gas mixture by mixing a treated gaseous effluent stream and air in said mixer;
(c) introducing said gas mixture and fuel in a given gas to fuel ratio to said at least one diesel engine; (d) burning said fuel in said engine to generate energy and a flue gas stream comprising particulate matter (PM), and nitrogen oxides (NO x ); (e) treating at least a portion of said flue gas stream in said cyclone unit whereby a treated gaseous effluent stream is formed; (f) emitting a second portion of said treated stream as a gaseous effluent; (g) using a first portion of said treated gaseous effluent stream to form said gas mixture wherein said treated gaseous effluent stream forms between 10% and 40% by volume of said mixture;, and (h) repeating steps (a) through (g) multiple times;
whereby said emitted portion has reduced PM, and reduced NO x content when compared with a reference gaseous effluent stream formed by standard burning of the same fuel in an identical engine to which air and fuel are provided in the same given ratio as above.
[0082] Methods for the treatment of flue gases are clearly necessary for the ability to better remove impurities, such as PM, SO x and NO x and for the reduction of costs associated with low-contamination energy generation methods. Of particular interest are large diesel engines, such as marine engines, particularly engines burning HFO at least in part.
[0083] In some embodiments, the phrase “particulate matter” refers to solid particles and/or particles of other condensed matter, such as liquid droplets, that generally range in size from fine particles (less than about 2.5 micrometers in diameter) to coarse particles (larger than about 2.5 micrometers in diameter), and that are environmental pollutants and/or hazardous materials. Particulate matter, such as PM-10 (fine particulates) and PM-2.5 (ultrafine particulates), is generally emitted from conventional coal- and other fuel-burning electrical power plants, and often carries heavy metals and/or cancer-causing organic compounds into the lungs of human beings and animals, thereby increasing the incidence and severity of respiratory diseases. Particulate matter includes dust, smoke, soot, ash (coal ash, fly ash and other types of ash), the non-combustible material such as that in coal and other tiny bits of solid materials that are released into, and/or move around in, the air. Ultrafine particulates are primarily nitrates and sulfates formed from NO x and SO x emissions.
[0084] The term “engine” is meant in the broad sense to include all combustors which combust fuel to provide heat, e.g., for direct or indirect conversion to mechanical or electrical energy. The term “Diesel engine” is meant to include all compression-ignition engines, for both mobile (including marine) and stationary power plants and of the two-stroke per cycle, four-stroke per cycle and rotary type engines.
[0085] The term “diesel fuel” means fuel suitable for diesel engines, including diesel fuels meeting the ASTM definition for diesel fuels or others even though they are not wholly comprised of distillates and may comprise alcohols, ethers, organo-nitro compounds and the like (e.g., methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane). Also within the scope of this invention, are emulsions and liquid fuels derived from vegetable or mineral sources such as corn, alfalfa, shale, and coal. These fuels may also contain other additives known to those skilled in the art, including dyes, cetane improvers, anti-oxidants such as 2,6-di-tertiary-butyl-4-methylphenol, corrosion inhibitors, rust inhibitors such as alkylated succinic acids and anhydrides, bacteriostatic agents, gum inhibitors, metal deactivators, upper cylinder lubricants, antiicing agents and the like.
[0086] Surprisingly, the methods of this invention allow for removal of PM and SO x from treated gaseous effluent steams to an extent and in a manner that enables recycling a portion of that treated gaseous effluent stream to the engine in an EGR mode of operation. As a result, the emitted portion of the treated gaseous effluent stream has a much reduced content of PM, SO x and NO x .
[0087] In some embodiments, regulation of injection timing, load, ratio of air to treated gaseous effluent stream or a combination thereof provides a clear advantage to the devices and methods of this invention. In some embodiments, the higher the load of the engine, the greater the benefit of the methods of this invention.
[0088] In some embodiments, the exhaust temperature may be lowered using various approaches, such as by throttling, adjusting valve timing, adjusting air-fuel ratio to be less lean, externally loading the engine (e.g., by engaging clutches/etc.), by increasing an exhaust gas recirculation rate, changing combustion and/or injection timing, operating with additional late injections or exhaust gas injections, and/or various others. In one example, an oxidation catalyst may be employed upstream of the introduction of the gas mixture to the diesel engine.
[0089] According to an embodiment of the present invention, the engine is a diesel engine of two or four stroke type with a capacity in the range between 200 kW and 30,000 kW. In one embodiment, the engine is a marine diesel engine operating on board of a ship in an engine room. In some embodiments, the engine room has multiple engines. In some embodiments, the engine or multiple engines are turbocharged engines.
[0090] In one embodiment the engine burns, at least part of the time, fuel of ISO fuel standard 8217.
[0091] In one embodiment the engine burns, at least part of the time, distillate oil.
[0092] In one embodiment the engine burns, at least part of the time, MGO (Marine Gas Oil.) In some embodiments, in the devices and methods of this invention, a gas mixture formed by mixing treated gaseous effluent stream and air is introduced into the engine. In some embodiments, the air is treated prior to the mixing, e.g. by filteration (mechanically or by other systems), adding moisture, controlling the air temperature and more in some embodiments, at least a second stream is mixed with the air and the treated gaseous effluent stream to form the gas mixture introduced into the diesel engine. According to an embodiment of the invention, the treated gaseous effluent stream forms between 10% and 40% (v/v) of the gas mixture.
[0093] In one embodiment, the given ratio at which the gas mixture and fuel are introduced into a diesel fuel engine is between 20:1 and 75:1, preferably 30:1 and 50:1 w/w.
[0094] The operation of the engine according to the present invention produces flue gas comprising PM, NOx and in most cases also SOx. Typical operation of a marine diesel engine according to the present invention generates flue gas at a rate of 3,000-100,000 Normal meter (Nm) 3 /hour. Typically the PM, SOx and NOx content of the emitted portion and of the treated gaseous effluent stream formed according to the present invention are less than 0.5 g/kWh, less than 100 ppm, and less than 8 g/kWh, respectively.
[0095] According to other preferred embodiments, flue gas stream generated in step (c) is at a temperature in a range of between 180 and 300° C.
[0096] The flue gas formed following burning a fuel in the diesel engine [step (c)] is treated at least partially in a cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said gaseous stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec whereby a treated gaseous stream is formed. In some embodiments, the cyclone unit is as described in WO 08/035,326, hereby incorporated by reference in its entirety.
[0097] In some embodiments, said swirling means comprises a plurality of vanes, the vanes being arranged regularly along a circular path, tangentially with respect thereto and passages are formed by open spaces between adjacent vanes.
[0098] According to another embodiment at least two aqueous streams are contacted with the flue gas stream whereas the location of this contact is selected from the group consisting of before, in and after the cyclone unit and combinations thereof to form the treated gaseous effluent stream and aqueous effluent stream.
[0099] In one embodiment, the aqueous stream is selected from the group consisting of water, steam, aqueous solutions, sea water, NaOH-comprising aqueous solution, waste water, bisulfite aqueous solution and basic aqueous solutions and combinations thereof.
[0100] In another embodiment, the amount of aqueous medium contacted with the flue gas stream prior to introduction into the cyclone unit is in a range between 3 and 100 grams per Nm 3 of the flue gas stream.
[0101] In another embodiment, the ratio between the flow of the aqueous medium contacted with the flue gas stream in the cyclone unit and flue gas stream is between 1 Kg per 1 Nm 3 and 2.5 Kg per 1 Nm 3 .
[0102] In another embodiment treating is conducted in multiple cyclone units.
[0103] In another embodiment, the method further comprises the step of adjusting the used aqueous product for discharge into the sea.
[0104] In another embodiment, the adjusting comprises controlling pH, controlling temperature, controlling the turbidity, reducing the content of sulfites, sulfates, oil, odor molecules, toxic metals, particles, soot, PAH, sulfur oxides other than SO 2 , nitrogen oxides, CO or any combination thereof.
[0105] Treatment of the flue gas forms a treated gaseous effluent stream. In one embodiment the temperature of the treated gaseous effluent stream is in a range of between 40° C. and 60° C. In another embodiment, the PM, SO x and NO x contents of the treated gaseous effluent stream and of the emitted portion formed according to the present invention are less than 0.5 g/kWh, less than 100 ppm, and less than 8 g/kWh, respectively.
[0106] In another embodiment, the engine is operating in an engine room of a ship or a marine oil exploration unit which may contain multiple engines, at least part of which are burning HFO and using for that purpose an identical or a similar gas mixture. In some embodiments, each engine produces flue gases. In one embodiment, the method of the present invention further comprises combining flue gases of multiple engines or all the engines for treatment in a cyclone as herein described [step (d)]. In one embodiment, the cyclone unit [of step (d)] comprises an exhaust collecting hat element, which facilitates combining of the gases, which may be placed, e.g. as shown in FIG. 1 . In some embodiments, each engine has an exhaust pipe which extends to the funnel top. In some embodiments, the collecting hat provides a closed compartment at the funnel top in which all flue gas streams may be combined prior to be directed into the cyclone unit, for example by the operation of the fan unit within the cyclone unit. In one embodiment of the invention, the collecting hat element may comprise a hatch which allows for the by-pass of the cyclone unit, if desired.
[0107] In some embodiments, the treated gaseous effluent stream [formed in step (d)] and/or the gas mixture is further treated subsequent to or prior to introduction into the cyclone unit.
[0108] In some embodiments, such further treatment may comprise compressing the gas to a desired pressure range, which in some embodiments, is between about 1 to 3 bar.
[0109] In some embodiments, compression is accomplished, at least partially, with the aid of a turbo charger compressor, for example, as described in U.S. Pat. No. 7,437,874, US Patent Publication No. 20080022966, US Patent Publication No. 20080026651, and any suitable system as will be appreciated by the skilled artisan.
[0110] As explained above, recycling untreated flue gas is contraindicated, in particular, when recycling of flue gas from HFO combustion. Reduction of PM content is required. Systems were suggested where filtration is introduced for PM removal from flue gas to be recycled. Filtration, however, suffers many limitations including increased expense associated with such systems, poor efficiency as a consequence of filtrate accumulation on the filters, and others as understood in the art. Treatment of the flue gas according to the present invention drastically reduces its PM content. In one embodiment, the treated stream is not filtered prior to mixing with air to form the gas mixture. In some embodiments, the treated stream is filtered to further reduce the PM content, yet some of the limitations noted are ameliorated, for example filter replacement is required less frequently when employed in conjunction with the devices and/or methods of this invention.
[0111] In one embodiment of the methods of the present invention, a portion of the treated stream is used to form the gas mixture by mixing the stream with air and optionally another gas stream. According to an embodiment of the invention, multiple treated streams are formed, and such streams may comprise, for example a stream which has undergone filtration in combination with a stream which has not undergone filtration. Formation of the gas mixture may use, according to various related embodiments, one of the multiple treated streams or any combination of the same. Such combinations include using multiple treated streams at various ratios.
[0112] In one embodiment, a portion of the treated stream is emitted and is not re-circulated [as in step g]. In another embodiment, an entire treated stream following a single recycling round, is emitted, or in another embodiment, only part of such stream is emitted. Optionally, the portion to be emitted is further treated prior to emission.
[0113] The emitted portion forms the gaseous effluent in an operating engine (or multiple engines) or part of it. The term gaseous effluent, as used herein, refers to the total amount of gas stream emitted following energy generation via the methods of the present invention. The treated gaseous effluent stream according to the method of the present invention has reduced PM content, reduced NO content and reduced SO x content, as compared to a flue gas stream, which does not comprise multiple (which refers to at least two) repetitions of forming a gas mixture by mixing a gaseous effluent stream and air where at least a portion of the gaseous effluent stream has been treated in a cyclone at least once prior to introduction into the diesel engine in accordance with the methods of this invention.
[0114] In some embodiments, this invention provides for reduced PM, NO x and SO x which can be determined by simultaneous application of gas mixtures in two devices of this invention, wherein a first gas mixture comprises a gaseous effluent which has been previously treated in a cyclone unit prior to introduction into the diesel engine of the device at lease once, in comparison to a gaseous effluent which had not previously been thus treated (the latter effluent referred to herein as a reference gas effluent). In some embodiments, other than the absence of the step of pre-treatment of the reference effluent in the cyclone unit, the conditions in terms of engine composition, ratios utilized and other conditions are identical, in terms of air temperature and moisture, pressure, engine yield, etc. The methods and devices of this invention provide for marked reduction of PM, NOx, SOx or a combination thereof, when compared with a reference gaseous effluent stream formed by standard burning of the same fuel in an identical engine to which air and fuel are provided in the same given ratio as above.
[0115] In one embodiment, NO x content in the treated gaseous effluent stream of the present invention is reduced by at least 50%, more preferably at least 60%, most preferably at least 70% compared with said reference gaseous effluent stream. According to another embodiment, PM content in the treated gaseous effluent stream of the present invention is reduced by at least 60%, more preferably at least 70%, most preferably at least 80% when compared with said reference gaseous effluent stream. According to still another embodiment, SO x content in the treated gaseous effluent stream of the present invention is reduced by at least 90%, more preferably at least 95%, most preferably at least 98% when compared with said reference gaseous effluent stream.
[0116] In another embodiment, the present invention provides a device for low-contamination generation of energy from fuel comprising: (a) a diesel engine burning a fuel in a provided gas mixture and generating energy and a flue gas; (b) a cyclone unit for treating said flue gas, comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec, whereby a treated gaseous effluent stream and an aqueous stream are formed; and (c) a mixer for mixing said treated gaseous stream with air to form said gas mixture.
[0117] According to preferred embodiments of the second aspect, said device further comprises at least one of:
i. a turbo charger ii. a raw flue gas collector hat serving more than one diesel engine iii. an exhaust fan iv. a collecting tank for said treated gaseous stream with cooling v. a unit for treating said aqueous stream. vi. a pumping unit supplying sea water and, NaOH solution to said cyclone unit
[0124] According to preferred embodiments of the second aspect, said device further comprises at least one of:
a. regulation device for maintaining level pressure in said collecting tank and engine room b. regulation device for said mixing means c. a self adjusting recirculation device for said treated gaseous stream
d. regulation device for said pumping unit
[0129] The invention further provides in some embodiments, a method for low-contamination generation of energy from fuel comprising:
a. providing a device comprising:
at least one diesel engine which burns fuel and concurrently generates a flue gas; a cyclone unit for treating said flue gas, operationally connected thereto, said cyclone unit comprising a housing defined by a cylindrical peripheral wall and provided with at least one inlet opening for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, and wherein said cyclone unit is characterized in that the velocity of said flue gas stream inside said cyclone unit is between 20 m/sec and 120 m/sec preferably between 60-100 m/sec and whereby treating said flue gas generates a treated gaseous effluent stream and an aqueous stream; a mixer for mixing said treated gaseous effluent stream with air to form a gas mixture; and a shunt for directing said gas mixture to said diesel engine.
b. forming a gas mixture by mixing a treated gaseous effluent stream and air in said mixer; c. providing said gas mixture and fuel in a given w/w ratio to said at least one diesel engine; d. burning said fuel in said engine to generate energy and a flue gas stream comprising particulate matter (PM), and nitrogen oxides (NO x ); e. treating at least a portion of said flue gas stream in said cyclone unit whereby a treated effluent stream is formed; f. emitting a first portion of said treated stream as a gaseous effluent; g. using a second portion of said treated effluent stream to form said gas mixture wherein said treated recycled effluent stream forms between 10% and 40% by volume of said mixture; and h. repeating steps (a) through (f) multiple times;
whereby said emitted portion has reduced PM, and reduced NO x content when compared with a reference gaseous effluent stream formed by standard burning of the same fuel in an identical engine to which air and fuel are provided in the same given ratio as above.
[0142] In some embodiments, the shunt for directing the gas mixture to the diesel engine is to be understood as any operational connectivity, which allows for the direction of the gas mixture to the diesel engine, and can comprise any physical means to accomplish such direction.
[0143] The invention will now be described in connection with certain preferred embodiments with reference to the following illustrative figures so that it may be more fully understood.
[0144] With specific reference now to the figures in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.
BRIEF DESCRIPTION OF THE DRAWINGS
[0145] FIG. 1 schematically depicts one embodiment of the devices of this invention, indicating different modular elements of which the device is comprised.
[0146] FIG. 2 depicts an embodiment of a mixer for mixing air and a treated gaseous effluent stream.
[0147] FIG. 3 depicts an embodiment of a cyclone unit.
[0148] FIG. 4 depicts another embodiment of a cyclone unit.
DETAILED DESCRIPTION OF THE INVENTION
[0149] In the following detailed description, numerous specific details are set forth in order to provide a thorough understanding of the invention. However, it will be understood by those skilled in the art that the present invention may be practiced without these specific details. In other instances, well-known methods, procedures, and components have not been described in detail so as not to obscure the present invention.
EXAMPLES
[0150] Referring to FIG. 1 , an engine room onboard a ship or oil exploration unit, is fed air through one or more fans ( 1 ) to meet the scavenging air requirements for the diesel engines ( 3 ) ( 5 ) ( 7 ) and boilers (not shown) on board such vessels. One or more fans ( 1 ) may be turned off during a period of time when the engines are not in use. Filters ( 9 ) may or may not be attached to the fan.
[0151] Air in the engine room is drawn in through coarse filter pads ( 9 ) into the turbocharger ( 11 ) where it is compressed for up to about 1-3 bars (pending engine loads). The heated compressed air is cooled by the air cooler ( 13 ) down to about 40-45° C. before accessing the cylinders of diesel engines ( 3 ) ( 5 ) and ( 7 ). The air cooler ( 13 ) relies on application of water for cooling, with the amount of water applied being sufficient to keep the scavenging air constant while ambient temperature changes. Conditions will be adjusted to accommodate engine use in different climactic conditions, for example, in ISO ambient conditions (25° C. air, 25° C. sea water, 1000 mbar) or in tropical conditions (45° C. air, 36° C. sea water, 1000 mbar), where the exhaust amount (kg/hr) and temperature differ.
[0152] Two stroke engines have a common air receiver ( 15 ) placed after the air cooler ( 13 ) from where air is drawn into each cylinder.
[0153] A Clean Flue Gas Collector ( 17 ), having a certain buffer capacity and a pressure equal to the engine room air creates a reservoir containing cleaned flue gas. As used here, “clean flue gas” may mean the treated gaseous effluent stream of the present invention. This reservoir provides a repository from which the turbocharger ( 11 ) draws a given portion in the same manner that engine room air is drawn.
[0154] A Clean Flue Gas Uptake Device ( 19 ) has a diameter such that it enables the greatest amount of flue gas supply to the engines ( 3 ) ( 5 ) and ( 7 ) and comprises a flap to regulate the pressure of such gas and actual capacity needed. (Note that when the engine load is reduced the amount of cleaned flue gas will also be reduced). The Clean Flue Gas Uptake Device ( 19 ) therefore controls the pressure inside the flue gas collector ( 17 ). The Clean Flue Gas Uptake Device is located as far as possible from the cyclone unit in order to reduce as much as possible the temperature of the treated gaseous effluent stream and the content of heavy PM contained therein.
[0155] A flue gas fan ( 23 ) keeps a constant amount of gas circulation via the cyclone unit ( 27 ) by drawing in treated gaseous effluent. The Self regulating recirculation ( 47 ) connection allows treated flue gas to re-enter the cyclone unit.
[0156] Nozzles ( 25 ) prior to and in the cyclone unit inject aqueous media as indicated in FIGS. 3 and 4 . In one embodiment the aqueous media is selected from the group consisting of water, steam, aqueous solutions, sea water, NaOH-comprising aqueous solution, waste water, bisulfite aqueous solution and basic aqueous solutions and combinations thereof. In one embodiment, sea water enters from the sea water inlet ( 33 ) and is mixed with NaOH from the NaOH tank ( 31 ) by the NaOH dosage pump ( 29 ), which constitutes the aqueous solution drawn to the nozzles ( 25 ) by the aqueous solution pressure pump ( 35 ).
[0157] In one embodiment flocculants are used for treating the used aqueous stream. Flocculants from the flocculants tank ( 37 ) are pumped by the flocculants dosage pump ( 39 ) and mixed with the used aqueous stream from the cyclone unit ( 27 ) to remove suspended matter contained in it at the flocculants skimmer Tank ( 43 ) and then collected at the PM filter Bag ( 41 ) before discharging.
[0158] In same embodiments high press pre injection pump ( 45 ) route part of the aqueous media to the Pre injection nozzle ( 49 ) that inject it to the flue gas prior to the entrance to the cyclone unit.
[0159] A raw flue gas collecting hat ( 51 ) gathers the flue gas that forms in any individual diesel engine ( 3 ) ( 5 ) and ( 7 ) for further treatment. The raw flue gas hat ( 51 ) has a by-pass hatch ( 53 ).
[0160] In some embodiments, contrary to the several advanced valves necessary for regulating exhaust in an EGR application for trucks and smaller engines, by having neutralized any pressure difference via the Flue Gas Uptake device ( 19 ), simpler regulating devices are sufficient.
[0161] In preferred embodiments, a Clean Flue Gas Uptake device ( 19 ) is used for taking a portion of said treated gaseous effluent stream after the treatment in said cyclone unit ( 27 ). Said Uptake device is located as far as possible from the cyclone unit (closer to the atmosphere) in order to let the treated gaseous effluent stream become colder as much as possible. In addition to the cooling taking said portion from the pipe line as far as possible from the cyclone unit reduces the content of the large PM in said treated gaseous effluent stream.
[0162] In some embodiments, the device comprises an Air and Clean Gas mixer ( 21 ) (see FIG. 2 ) suitable for use with a large turbocharger appropriate for use with two stroke main engines. The turbocharger draws air from the side toward the center and into the compressor wheel.
[0163] In some embodiments, the device further comprises a cover extending over a certain segment of the air inlet house, allowing for an easy retrofit and adaptive solution for existing turbochargers to be adapted for incorporation into the devices of this invention.
[0164] Referring to FIG. 2 , depicting an embodiment of a mixer ( 41 ) for mixing entering air via the inlet ( 43 ) and a treated gaseous effluent stream entering via the inlet ( 45 ), the mixer comprises a retractable cone ( 47 ), which provides for free passage of air (retracted) or no passage (extended) with fine tuning (in-between) and with minimum turbulence. In some embodiments, the mixer may comprise other comparable elements, such as a flap or sliding device ( 49 ) to comparably regulate air passage. The air volume may be measured by a calibrated venturi in the pipeline from the collector, which in turn may also comprise a mechanism, such as a closing butterfly valve, for regulating air flow, when the engine is off. In some embodiments, movement of the cone may be accomplished via matching input from the engines governor (engine load) and the venturi (flow device). A predefined combination may govern the regulation.
[0165] In some embodiments, the scavenging air temperature after the cooler and the engine fuel oil injection timing may be adjusted.
[0166] Referring to FIGS. 3 and 4 , an embodiment of a cyclone unit for use according to the present invention is provided. The unit may comprise a housing (H) defined by a cylindrical peripheral wall ( 2 ) thereof and by upper ( 4 ) and lower ( 6 ) extremities, said housing having a longitudinal axis (X-X) and being provided with at least one inlet opening ( 8 ) for receiving said gaseous stream and at least one inlet opening ( 10 ) for receiving said aqueous stream thereinto. Said cyclone unit further comprises an outlet means from said housing (H) preferably formed as a hollow truncated cone ( 12 ), having a large base ( 14 ) and a spaced apart small base ( 16 ), the large base thereof being in communication with the lower extremity ( 6 ) of said housing (H). A pipe means ( 18 ) is placed within said housing (H), preferably coaxially with the longitudinal axis (X-X) wherein an uppermost extremity ( 20 ) of the pipe means ( 18 ) is located outside of the housing, and a lowermost extremity ( 22 ) of said pipe means is located within the housing.
[0167] Said cyclone unit further comprises at least one swirling means ( 24 ) being formed as a cylindrical ring and being mounted within said housing, coaxially with the longitudinal axis (X-X) so as to provide an annular space ( 26 ) between the housing central wall ( 28 ) and the peripheral wall ( 30 ) of said swirling means and to provide an inner annular space ( 32 ) between the central wall ( 34 ) of the swirling means ( 24 ) and the lowermost extremity ( 22 ) of said pipe means ( 18 ).
[0168] Said swirling means ( 24 ) are defined by a plurality of openings ( 36 ) so as to enable passage from said annular space ( 26 ) towards said inner annular space ( 32 ). Said swirling means is formed with plurality of vanes ( 39 ) said vanes being arranged regularly along a circular path, preferably tangentially with respect thereto and said plurality of openings ( 36 ) are formed by open spaces between the adjacent vanes ( 39 ).
[0169] Using the cyclone unit described above, said gaseous stream enters through at least one of said inlet openings ( 8 ) to said annular space ( 26 ) and then passes through at least one of said plurality of openings ( 36 ) and then at least one passages ( 37 ) towards said inner annular space ( 32 ), while said aqueous stream enters through at least one of said inlet openings ( 10 ) into said housing and is contacted with said gaseous stream. These two mixed streams are then caused to flow through said hollow truncated cone ( 12 ) whereas said gaseous product is exiting though said pipe means ( 18 ), while said wash solution is collected through said small base ( 16 ) of said hollow truncated cone ( 12 ) into said appropriate collecting receptacle.
[0170] The passage of said gaseous stream through said plurality of openings ( 36 ), and then passages ( 37 ) results in an unexpectedly high velocity of said gaseous stream, said velocity being between 20 m/sec-120 m/sec, and in preferred embodiments being between 60-70 m/sec. As a result a very efficient contact between said gaseous and aqueous streams is achieved. This is compared to a typical cyclone scrubber that is characterized by the ability to produce a velocity of about 15-50 m/sec.
[0171] While certain features of the invention have been illustrated and described herein, many modifications, substitutions, changes, and equivalents will now occur to those of ordinary skill in the art. It is, therefore, to be understood that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
[0172] The following claims particularly point out certain combinations and sub-combinations. These claims may refer to “an” element or “a first” element or the equivalent thereof. Such claims should be understood to include incorporation of one or more such elements, neither requiring nor excluding two or more such elements. Other combinations and sub-combinations of the disclosed features, functions, elements, and/or properties may be claimed through amendment of the present claims or through presentation of new claims in this or a related application. Such claims, whether broader, narrower, equal, or different in scope to the original claims, also are regarded as included within the subject matter of the present disclosure. | A method for low-contamination generation of energy comprising: (a) forming a gas mixture by mixing a treated gaseous effluent stream and air; (b) introducing the gas mixture and fuel at a given gas to fuel ratio into at least one diesel engine ( 3 ); (c) burning the fuel in the diesel engine to generate energy and a flue gas stream comprising particulate matter (PM), and nitrogen oxides (NOx); (d) treating at least a portion of the flue gas stream with an aqueous stream in a cyclone unit ( 27 ) comprising a housing defined by a cylindrical peripheral wall ( 2 ) and provided with at least one inlet opening ( 10 ) for receiving flue gas and at least one inlet opening for receiving fluids thereinto and with at least one swirling means, whereby a treated gaseous effluent stream and an aqueous effluent stream are formed; (e) emitting a portion of the treated gaseous effluent stream to form an emitted portion; (f) using a portion of the treated gaseous effluent stream to form the gas mixture, and (g) repeating steps (a) through (f) multiple times; | 5 |
BACKGROUND OF THE INVENTION
[0001] The invention relates to a device comprising two hollow profiles arranged in a butt-jointed manner approximately at right angles to one another, each of which has a profile channel parallel to its profile longitudinal axis and also, in at least one profile side surface, an undercut longitudinal groove parallel to the profile channel, according to the preamble of the independent claim. The invention furthermore relates to a tool for operating the connecting bolt.
[0002] Document DE 201 06 561 discloses a device for connecting a first profile bar to a second profile bar which bears with a front face against a longitudinal side of the first profile bar. These profile bars are provided with undercut longitudinal grooves along their longitudinal sides and contain a clamping screw with a screw head and a threaded shaft which can be fixed in the region of the screw head in the undercut longitudinal groove of the first profile bar and can be screwed with its threaded shaft into a longitudinal bore formed in the second profile bar. Said screw head has, on a disc-shaped collar, a toothing which can be brought into active connection with a turning tool. The turning tool is a bar with a toothing integrally formed in an axis-parallel manner at one of its ends, which toothing can be brought into contact with the toothing on the collar.
[0003] Another device is described in EP 0 136 431 A2. Two hollow profiles of square cross section with a central profile channel and a longitudinal groove running centrally in each profile side surface are connected by means of a commercially available screw. The latter passes through an elongate insertion plate which is arranged in the undercut groove space of the longitudinal groove, said plate having legs which protrude in a U-shaped manner and which pass through the longitudinal groove for holding purposes and to prevent twisting. In order to be able to operate the screw, there must be in the bottom of the groove a number of openings which penetrate the hollow profile; the screwdriver which is to be inserted into a slot in the screw head is introduced through one of these openings.
[0004] The hollow profiles, which are usually extruded from an aluminium alloy, must therefore be reworked in a special way after they have been manufactured; the making of the radial openings is very complicated and considerably reduces the stability of the profile.
[0005] Knowing this prior art, the inventor set himself the aim of improving the system outlined above and avoiding additional processing of the holding profiles that are used. The longitudinal grooves are to remain open so that it is possible where necessary to introduce flat elements.
SUMMARY OF THE INVENTION
[0006] This aim is achieved by a device comprising two hollow profiles arranged approximately at right angles to one another, each of which has a profile channel parallel to its profile longitudinal axis (A) and also, in at least one profile side surface, an undercut longitudinal groove parallel to the profile channel, wherein the two hollow profiles are held together by a connecting screw, the shaft of which engages in the profile channel of one hollow profile and the screw head of which is mounted in an undercut longitudinal groove of the other hollow profile, wherein the screw head is provided on its periphery with grooves or notches which run in planes extending from the shaft longitudinal axis (M) and form ribs between them.
[0007] According to the invention, the screw head of the connecting screw tapers provided on its periphery—which is circular in cross section—with grooves or notches which run in planes extending from the shaft longitudinal axis—and defined by the latter in terms of their course—and form ribs between them. It has proven to be advantageous that the screw head tapers conically towards a head surface remote from the shaft, and this wall surface which is inclined at an angle with respect to the shaft longitudinal axis contains said grooves or notches. This angle should preferably be approximately 45°.
[0008] According to a further feature of the invention, the screw head should have, between a shaft-facing connection surface and the inclined wall surface, an annular section of constant diameter in which the shaft-facing ends of the grooves or notches form a crenellated edge pattern. The inclined wall surface should end at the head surface of the screw head or—in another embodiment—at a radial step surface, which latter surrounds in an annular manner an integrally formed top body. This tooth-free or notch-free end section is supported on the groove bottom when screwed on, and ensures a mating hold.
[0009] The shaft of the connecting screw (also referred to as a connecting bolt) which adjoins this screw head is advantageously provided with a cutting thread which cuts a counter-thread in the inner surface of the profile channel during assembly.
[0010] According to the invention, assigned to the shaft of the connecting screw is a slip-on collar which is provided with a central opening and can be placed against the connection surface of the screw head, the width of said slip-on collar being shorter than the width of the longitudinal groove of the hollow profile; the slip-on collar can thus be lowered into the latter. Preferably, a collar piece should be integrally formed on a base strip of the slip-on collar, wherein the length of said base strip is greater than the width of the longitudinal groove of the hollow profile; as a result, when the slip-on collar is rotated, the latter strikes the inside of the longitudinal groove on both sides in a retaining manner.
[0011] This embodiment is supplemented in that a threaded sleeve with outer thread is axially assigned to the collar piece of the slip-on collar, said threaded sleeve receiving the free end of the shaft. In this case, the length of the shaft should correspond approximately to the height of the slip-on collar plus the length of the threaded sleeve. However, an axially oriented widening of the opening should be integrally formed in the lower surface of the base strip in order to temporarily—and securely—receive a region of the annular section of the screw head. Said threaded sleeve is advantageously designed such that its outer diameter corresponds approximately to the width of the slip-on collar, so that the threaded sleeve can thus be inserted in the longitudinal groove.
[0012] The scope of the invention also includes a tool for operating the connecting screw in a screw head arranged in a groove space of a hollow profile. This tool comprises a round profile with an insertion head provided at one end, said insertion head having longitudinal notches which are made in its (preferably conically tapering) peripheral surface and receive the radially protruding ribs of the screw head so as to operate or rotate the connecting bolt; the pattern of the longitudinal notches on the tool thus corresponds to the arrangement of the ribs on the screw head.
[0013] It has proven advantageous to make the diameter of the round profile shorter than the depth of the groove space of the hollow profile, in order to make it possible to insert the tool into the groove space.
[0014] Moreover, the angle between the axis of the round profile and the peripheral or outer surface of the insertion head should be approximately 20° to 40°, in particular approximately 25°. This likewise facilitates insertion of the tool, the grooves of which are to receive the ribs of the screw head on the connecting screw.
[0015] In order to prevent damage to the hollow profile, according to the invention a protective section of a protective surface bears against the described peripheral or outer surface of the insertion head, said protective surface being releasably fixed to the round profile, namely on the selected groove bottom. This protective surface should be designed as a protective plate and have a holding section which is radial with respect to the axis of the round profile and surrounds the latter and also a lateral section which is bent out from the surface of said holding section, on which lateral section said protective section is integrally formed in an inclined manner.
[0016] By virtue of the embodiment according to the invention, there is no longer any need for special configuration or reworking of the hollow profile. The connecting screw is simply rotated into the core hole—coarse-pitch thread or self-cutting thread—of one hollow profile and then pushed into the end of the other hollow profile. It is also conceivable firstly to screw the aforementioned threaded sleeve into the core hole, so as to provide for example a steel coarse-pitch thread for screwing in the connecting screw or toothed screw. To reduce friction, the latter can be provided with a coating of lubricant to make it easier to screw in.
[0017] Moreover, to prevent it from being screwed out, the screw head can be provided on the underside with raised areas in the form of dotted lines or teeth.
[0018] The screw head with the toothed edge should be as large as possible so as to achieve the greatest tightening torque. At the same time, however, it should not protrude in a disruptive manner beyond the core region of the profile. The greater the difference between the number of teeth of the screw and the number of teeth of the screwdriver, the greater the translation and thus the peripheral force which act on the toothed screw or connecting screw during tightening.
[0019] In addition, a drive may be provided in the screw head, which drive corresponds either to that of the toothed edge screwdriver in order to be able to operate with just one key or another profile (e.g. hexagon socket, six-lobe drives) by means of which the screw is firstly to be screwed into the core hole and then screwed back out somewhat, before it is introduced together with the hollow profile into the slot of the mating profile and tightened.
[0020] The dimensions for the screw and the screwdriver of course depend on the profiles to be connected. However, all compatible profiles can be connected by means of the same screw. The stability of the connection is sufficient for simple frames, protective fences, housings, etc. Securing against twisting of the profiles to be connected is provided if at least one groove is occupied by a flat element. The connection is extremely simple, fast and thus of course very cost-effective.
[0021] The tool is inserted close to said connecting bolt into the longitudinal groove which receives it, and its inclined insertion head is pushed in between the groove bottom and the screw head. When the ribs of said screw head mesh with the grooves of the tool, operation of the connecting bolt can readily be carried out. The inventor's aim is thus achieved in a particularly simple manner.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Further advantages, features and details of the invention will emerge from the following description of preferred examples of embodiments and with reference to the drawing, in which:
[0023] FIG. 1 shows the front view of an extruded hollow profile comprising longitudinal grooves;
[0024] FIG. 2 shows an enlarged longitudinal section through parts of two hollow profiles arranged at right angles with respect to one another, with a connecting member;
[0025] FIG. 3 shows a detail from FIG. 2 ;
[0026] FIG. 4 shows a partially cut-away side view of a connecting member configured differently from FIGS. 2, 3 , in an axially offset position of its individual parts;
[0027] FIG. 5 shows a side view of the connecting member rotated through 90° compared to FIG. 4 .
DETAILED DESCRIPTION
[0028] A hollow profile 10 of square cross section extruded from a light metal alloy, having cross-sectional axes B, B 1 as axes of symmetry placed through the centre Z of its front face 18 —said centre Z being defined by a profile channel 14 of circular cross section of diameter d which runs in its central profile body 12 in the profile longitudinal axis A and is provided with radial edge grooves 16 —has in each case in the centre of its profile side surfaces 20 a longitudinal groove 22 having a width b of for example 8 mm, said longitudinal groove being delimited at both ends by shaped ribs 24 with a thickness a of in this case 4 mm and merging into an undercut groove space 26 towards the profile longitudinal axis A. Said groove space is a channel-like recess of approximately triangular cross section which is overlapped by said shaped ribs 24 and has a depth e determined from the groove bottom 27 of 10 mm and a maximum width f of 22 mm and provides an axial insertion track 28 of height h on the inner side of the shaped ribs 24 .
[0029] As shown in FIGS. 2, 3 , assigned to the front face 18 of the hollow profile 10 is a hollow profile 10 a of the same shape which crosses over its profile longitudinal axis A. In order to be able to fix the two hollow profiles 10 , 10 a to one another, use is made of a specially designed connecting screw 30 . This is made of a hard metal—compared to the hollow profile 10 , 10 a —and comprises a screw shaft 32 having a length i of for example 25 mm and a disc-shaped screw head 36 having a diameter g of in this case 15 mm and a height n of 5 mm. Said screw shaft 32 is provided with a cutting thread 34 (shown only schematically in FIGS. 2, 3 for the sake of clarity), the outer diameter d 1 of which is greater than the diameter d of said profile channel 14 . The cutting thread 34 has cut into the inner surface of said profile channel in the illustrated connecting position, and the shaft longitudinal axis M runs in the profile longitudinal axis A.
[0030] The shaft-facing stop surface 38 of the screw head 36 , which crosses over the shaft longitudinal axis M, merges into a cylindrical annular section 40 having a height n 1 and said diameter g of the peripheral wall of the screw head 36 . Adjoining the annular section 40 is a wall surface 42 of axial height n 2 which in cross section is inclined at an angle w of in this case 45° with respect to the shaft longitudinal axis M; integrally formed in this wall surface 42 in the radial direction are grooves or notches 43 which between them form ribs 44 and a crenellated edge pattern 45 in said annular section 40 . At a distance from said stop surface 38 , the conically tapering wall section 42 and thus also each of the notches 43 merge into an annular, radially oriented step surface 46 which surrounds an integrally formed top body 48 having a height n 3 . The smooth peripheral surface thereof is inclined towards the axis in cross section in a manner corresponding to the associated wall section 42 within the screw head 36 . The top body 48 ends at a head surface 50 which adjoins the screw head 36 , wherein a hexagonal socket 49 can be seen in said head surface.
[0031] In order to produce the desired connection of the two hollow profiles 10 , 10 a , the screw head 36 of the connecting bolt or connecting screw 30 is pushed into one of the groove spaces 26 of the lower hollow profile 10 a in FIGS. 2, 3 ; in the process, the screw shaft 32 slides in the longitudinal groove 22 of the hollow profile 10 a in an axis-parallel direction. At a predefined point, the front face 18 of the other hollow profile 10 is brought towards the profile longitudinal axis A of the first hollow profile 10 a at right angles, and the profile channel 14 of said second hollow profile 10 is axially assigned to the screw shaft 32 .
[0032] Rotation of the screw shaft 32 into the profile channel 14 or the profile body 12 of the other hollow profile 10 which surrounds the latter is carried out by means of a tool 52 which is partially shown schematically in FIG. 2 . This tool consists of a round profile 54 having a diameter q of in this case 8 mm, preferably a steel rod, said round profile optionally being bent at an angle in the longitudinal direction. Said diameter q should be shorter than the height or depth e of the groove space 26 of the hollow profile 10 , 10 a . This round profile 54 is designed to a length t of approximately 10 mm at one end as an insertion head 56 with a peripheral surface 57 which tapers conically at an angle γ of approximately 25°, said peripheral surface being provided with parallel longitudinal notches 58 for receiving ribs 44 of the screw head 36 . A correspondingly inclined protective section 66 of a protective plate which is essentially designed as an angled piece bears against the peripheral or outer surface of said insertion head 56 ; said protective plate is placed onto the round profile 54 by means of a radial section 62 , with a lateral section 64 of the protective plate 60 running parallel to the longitudinal axis Q of said round profile at a distance therefrom. This lateral section is angled towards the insertion head 56 close to the latter at a bend point 65 , forming said protective section 66 .
[0033] As shown in FIG. 3 , the insertion head 56 of this tool 52 is pushed in between the screw head 36 of the installed connecting screw 30 and the groove bottom 27 (covered by the protective plate 60 ) of the corresponding longitudinal groove 22 , with which the insertion head axis Q delimits an angle w 1 . By rotating the insertion head 56 about its longitudinal axis Q, with the insertion head rolling on the protective section 66 of the protective plate 60 , the toothed screw head 36 of the connecting screw 30 is operated and thus the screw shaft 32 is screwed in.
[0034] A different embodiment of the connecting bolt 30 a is shown in FIGS. 4, 5 . The screw head 36 a thereof has a relatively high annular section 40 which is adjoined by a conical wall section 42 of approximately the same height n 2 . The latter ends at a free head surface 50 a ; the above-described top body is omitted here.
[0035] Assigned to the connecting bolt 30 a is a slip-on collar 70 of rectangular outline having a height i 1 and a width g 1 on a base strip 71 —having a height i 2 , a length c and a width b 1 —and an integrally formed collar piece 72 having a height i 3 . The rectangular slip-on collar 70 is provided with a central opening 74 of diameter d 2 for receiving the shaft 32 of diameter d 1 , which opening opens at the lower surface 73 into a circular widening 76 for receiving the annular section 40 of the screw head 36 a . Said widening has a small axial depth i 4 and a diameter g 1 which slightly exceeds the diameter g of the screw head 36 a .
[0036] Shown above the slip-on collar 70 in FIGS. 4, 5 is an axially assigned M8 threaded sleeve 80 having a length k and an outer diameter g 2 which corresponds approximately to the diameter g of the screw head 36 a . The wall 82 of this threaded sleeve 80 is provided with an outer thread 89 . Once the slip-on collar 70 has been fitted, the shaft 32 is introduced into the interior 78 of the threaded sleeve 80 , in which it is then securely seated. This unit consisting of connecting bolt 30 a , slip-on collar 70 and threaded sleeve 80 is then supplied to a hollow profile 10 a . Since the width b of the longitudinal grooves 22 of the latter is somewhat greater than the width b 1 of the slip-on collar 70 , the latter can be passed radially through one of the longitudinal grooves 22 in an axis-parallel manner and be rotated in the associated groove space 26 ; the width f of said groove space is somewhat greater than the length c of the base strip 71 . In a hollow profile according to FIG. 1 , the height i 2 of said base strip corresponds to the height h of the insertion track 28 of said groove space, or to the radial height of said groove space in the case of groove spaces of rectangular cross section.
[0037] The described embodiment according to FIGS. 4, 5 has the advantage that it does not have to be pushed in from the front face 18 of the profile; following the described rotation of the slip-on collar 70 , the fixing operation for the other hollow profile 10 as shown in FIGS. 1 to 3 can begin immediately.
[0038] Overall, therefore, the connecting screw or toothed screw 30 , 30 a can be screwed into the core hole or profile channel 14 of the hollow profile 10 to be butt-jointed in such a way that, thereafter, the screw shaft or toothed bolt 32 together with the screw head 36 , 36 a can be inserted into the longitudinal groove 22 at the point to be connected. The movable screw head 36 , 36 a is rotated in the fixing position transversely to the longitudinal groove 22 and then the toothed bolt 32 is tightened by means of the tool 52 . | A device comprising two hollow profiles which are arranged approximately at a right angle from each other and each of which is provided with a profiling channel that extends parallel to the longitudinal axis (A) of the profile and an undercut longitudinal groove in at least one lateral face of the profile, the longitudinal groove extending parallel to the profiling channel. The two hollow profiles are held together by a connecting screw whose shaft engages into the profiling channel of one hollow profile and whose screw head is mounted within an undercut longitudinal groove of the other hollow profile. The periphery of the screw head is provided with grooves or notches that run on planes extending from the longitudinal axis (M) of the shaft while forming ribs therebetween. | 5 |
TECHNICAL FIELD
The present disclosure relates to a digital photo frame (DPF) with a picture-in-picture (PIP) output function and method thereof.
DESCRIPTION OF RELATED ART
Along with rapid developments in electronic technology, DPFs have become familiar to consumers. Some types of DPFs have been designed not only to play image files, but also to broadcast television (TV) programs.
A great number of commercials are inserted into the TV programs. Many people dislike commercials and prefer spending the time during commercials to do other things. For example, if a commercial break begins on a DPF, a viewer might prefer to switch views on the screen to browse or edit image files rather than to endure the commercials. However, the viewer is left to guess when the commercial break is over and he or she should switch back to the TV channel, which is inconvenient and not-in-time, and may cause viewers to miss a part of their favorite TV program.
BRIEF DESCRIPTION OF THE DRAWINGS
The components of the drawings are not necessarily drawn to scale, the emphasis instead being placed upon clearly illustrating the principles of a DPF with a PIP output function and method thereof. Moreover, in the drawings, like reference numerals designate corresponding parts throughout several views.
FIG. 1 is a front view of a DPF with a PIP output function in accordance with an exemplary embodiment of the present disclosure.
FIG. 2 is a block diagram of the DPF of FIG. 1 in accordance with an exemplary embodiment of the present disclosure.
FIG. 3 is a flowchart of the DPF of FIG. 1 outputting multimedia files and broadcast contents in a PIP output mode in accordance with an exemplary embodiment of the present disclosure.
FIG. 4 is an schematic view of the DPF of FIG. 1 , illustrating the multimedia files and broadcast contents outputted in the PIP output mode in accordance with an exemplary embodiment of the present disclosure.
DETAILED DESCRIPTION OF THE EMBODIMENTS
FIG. 1 is a front view of a DPF 10 with a PIP output function in accordance with an exemplary embodiment of the present disclosure.
The DPF 10 includes a control panel 11 . The control panel 11 mainly includes a power button 12 , a previous button 13 , a next button 14 and a PIP button 15 . The power button 12 is configured for powering on and powering off the DPF 10 . The previous button 13 and the next button 14 are configured for selecting multimedia files for the DPF 10 to reproduce under a DPF mode of the DPF 10 . The previous button 13 and the next button 14 are further configured for changing television (TV) channels under a TV mode of the DPF 10 . The PIP button 15 is configured for activating a PIP output mode of the DPF 10 .
FIG. 2 is a block diagram of the DPF 10 in accordance with an exemplary embodiment of the present disclosure.
The DPF 10 includes a processor 20 connected to a TV receiving module 21 , a multimedia player module 22 , a storage 24 , and a display module 26 , which are controlled by the processor 20 .
The storage 24 is configured for storing multimedia files. The multimedia files may include image files, audio files, video files, and so on. When the DPF 10 is in the DPF mode, the processor 20 fetches the multimedia files from the storage 24 and transfers the multimedia files to the multimedia player module 22 . The multimedia player module 22 then reproduces image/video data of the multimedia files on the display module 26 . When the DPF 10 is in the TV mode, the TV receiving module 21 is controlled by the processor 20 to receive broadcast and transfer the contents of the broadcasts to the multimedia player module 22 . The multimedia player module 22 then reproduces image/video data of the contents of the broadcasts on the display module 26 . The multimedia player module 22 is connected to an audio output module 23 (e.g., a speaker) and the display module 26 . The audio output module 23 is configured for outputting audio data of the multimedia files and the contents of the broadcasts.
The DPF 10 also includes an infrared control module 25 . The infrared control module 25 is configured for receiving infrared control signals from a remote control (not shown) and converts the infrared control signals to digital serial signals. The digital serial signals are sent to the processor 20 and the processor 20 adjusts various parameters of the controllable modules according to the digital serial signals. The buttons on the control panel 11 can also be integrated with the remote control to control the operation of the DPF 10 .
The processor 20 includes a multimedia file reading module 201 , a TV tuning module 202 , and a PIP output module 203 .
The multimedia file reading module 201 is configured for fetching the multimedia files from the storage 24 . The TV tuning module 202 is configured for tuning the TV receiving module 21 to receive broadcasts over different TV channels according to user input. The PIP output module 203 is configured for outputting the multimedia files and contents of the TV broadcasts on the display module 26 in a PIP output mode via the multimedia player module 22 upon receiving a PIP signal transferred from the PIP button 15 .
Generally, according to an exemplary embodiment, under the DPF mode, the PIP output module 203 defines a PIP region on the display module 26 upon receiving the PIP signal. The TV tuning module 202 tunes the TV receiving module 21 to a selected TV channel. The PIP output module 203 outputs the multimedia files and the broadcast contents of the selected channel on the display module 26 in the PIP output mode via the multimedia player module 22 .
FIG. 3 is a flowchart of the DPF 10 outputting the multimedia files and broadcast contents in the PIP output mode in accordance with an exemplary embodiment of the present disclosure.
In step S 301 , the DPF 10 is in the DPF mode and plays the multimedia files.
In step S 302 , the PIP button 15 is pressed and generates a PIP signal. The PIP signal is transferred to the processor 20 .
In step S 303 , upon receiving the PIP signal, the PIP output module 203 defines the PIP region at a predetermined area of the display module 26 . The TV tuning module 202 tunes the TV receiving module 21 to a selected TV channel. The PIP output module 203 outputs the broadcast contents of the selected TV channel outside the PIP region and the multimedia files in the PIP region of the display module 26 via the multimedia player module 22 . The PIP output module 203 signals the multimedia player module 22 to output the audio data of the broadcast contents, and not output the audio data of the multimedia files. At this time, the previous button 13 and the next button 14 are enabled for tuning to various TV channels.
In step S 304 , the PIP button 15 is pressed for a second time.
In step S 305 , the PIP output module 203 exchanges output regions of the multimedia files and the broadcast contents of a selected TV channel. That is, the multimedia files are outputted outside the PIP region and the broadcast contents are outputted in the PIP region of the display module 26 via the multimedia player module 22 . At this time, the PIP output module 203 signals the multimedia player module 22 to output the audio data of the multimedia files, and not output the audio data of the broadcast contents. At this time, the previous button 12 and the next button 13 are enabled for controlling the playing of the multimedia files.
In step S 306 , the PIP button 15 is pressed for a third time.
In step S 307 , the PIP output module 203 signals the multimedia file reading module 201 to stop fetching the multimedia files from the storage 24 . The settings and progress of playing the multimedia files are automatically stored in the storage 24 .
In step S 308 , the PIP output module 203 outputs the broadcast contents on the display module 26 via the multimedia player module 22 . The broadcast contents take up the full screen of the display module 26 . The DPF 10 enters the TV mode.
In step S 309 , the PIP button 15 is pressed for a fourth time.
In step S 310 , the PIP output module 203 signals the TV tuning module 202 , and the TV tuning module 202 controls the TV receiving module 21 to stop receiving the broadcasts.
In step S 311 , the processor 10 fetches the stored settings and progress of playing the multimedia files from the storage 24 and resumes the play of the multimedia files. The DPF 10 enters the DPF mode.
FIG. 4 is a schematic view of the DPF 10 , illustrating the multimedia files and broadcast contents outputted in the PIP output mode in accordance with an exemplary embodiment of the present disclosure.
Firstly, at stage “A”, the PIP mode is not activated and the DPF 10 is in the DPF mode. The multimedia files are outputted using the full screen of the display module 26 . Users may view and edit the multimedia files through operating buttons on the control panel 11 . At stage “B”, the PIP button 15 is pressed for a first time and the PIP mode is activated. A rectangular PIP region 260 appears and takes up a predetermined area of the display module 26 . The broadcast contents are outputted outside the PIP region 260 and the multimedia files are outputted in the PIP region 260 . The users may operate the previous button 13 and the next button 14 to tune into a TV channel of their choice. At stage “C”, the PIP button 15 is pressed for a second time, as a result, output regions for the multimedia files and the broadcast contents of the users' tuned TV channel are exchanged, and the users again may view and edit the multimedia files through operating buttons on the control panel 11 . In addition, the users can keep an eye on the broadcast contents of the users' tuned TV channel, and easily know when their show begins. At stage “D”, the PIP button 15 is pressed for a third time, and the PIP mode is deactivated. The rectangular PIP region 260 disappears and the DPF 10 enters the TV mode. The broadcast contents of the users' tuned TV channel are outputted through the full screen of the display module 26 .
By employing the PIP output function, the DPF 10 provides a PIP region for users to monitor broadcasts while using other function of the DPF 10 , and the users will not miss their shows.
Although the present disclosure has been specifically described preferred embodiments and method thereof, the invention is not to be construed as being limited thereto. Various changes or modifications may be made to the embodiments without departing from the scope and spirit of the invention. | A method for outputting multimedia files and broadcast contents of a selected television (TV) channels on the DPF in a picture-in-picture (PIP) output mode is provided. The method includes: starting the PIP output mode when the DPF plays multimedia files under a DPF mode; defining a PIP region on the DPF; receiving broadcasts of a selected TV channel; and outputting the multimedia files and the broadcast contents of the selected TV channel in the PIP output mode. A related DPF is also provided. | 7 |
FIELD OF THE INVENTION
The invention pertains generally to the field of cooling towers which cool a warm liquid by interaction with cooler ambient air.
BACKGROUND OF THE INVENTION
Cooling towers are in wide use in industry. These towers are typically used to receive a warm or relatively warm fluid, such as, for example, warm water from an industrial operation. The warm water is passed through the tower and, by a heat exchange interaction with ambient air that is cooler than the water, the water is cooled and then can be discharged or returned to the industrial operation. Cooling towers include various configurations such as cross-flow cooling towers in which the air enters from a side of the tower and passes generally laterally horizontally across the fill media, and also counterflow cooling towers where the air generally enters beneath the fill material and is drawn upward through the fill material.
There are at least two general types of such cooling towers. The first general category includes evaporative type systems in which the water enters the top of the tower and falls through the tower while interacting with splash bars and/or sheet fill packs, also referred to herein as wet media. The water itself thus has contact with the ambient air and is cooled by its contact with the air, and then is collected in a lower collection basin. Evaporative cooling towers can take many configurations, and typically utilize a fan to move air through the tower and past the liquid being cooled, although natural draft cooling towers without fans are also known.
In evaporative cooling towers, depending on the operating and ambient conditions, some of the water will tend to evaporate and exit the tower with the exiting air. In some cases, the water vapor may exit the tower in the form of a visible water vapor or plume which is sometimes considered undesirable depending on location and other circumstances.
Another general category of cooling towers is closed circuit or dry cooling towers. A dry cooling tower contains the liquid to be cooled inside a conduit and air interacts with the conduit material and thus cools the liquid. The dry approach has the advantage that there is no evaporation into the cooling air and thus no plume. However, depending on the operating and ambient temperatures, in some cases dry cooling can be less efficient than wet cooling in terms of the energy consumption and/or construction expense of the tower. Moreover, dry cooling tends in some circumstances to be more dependent on the ambient temperature, and thus less suitable for climates where the weather and ambient temperature change through a wide range. Dry cooling towers can also use one or more fans or can be natural draft.
There are also known so-called hybrid towers which pass the fluid through a combination of evaporative and dry heat exchangers. In the prior art these combination or hybrid cooling towers have operated in a single mode where the water passes serially through one type of heat exchanger media (wet or dry) and then is recollected and passes through a second different type of heat exchanger media (wet or dry). The water travels serially through the two heat exchangers. Turning to air flow, it has been known to arrange the media so that each heat exchanger is contacted by its own air path. That is, the air paths through the two types of heat exchangers are separated from each other, at least to some extent, and thus the air itself passes through one or the other media section in a parallel fashion. In the parallel fashion of air flow, one air stream passes through one media and a second different air stream passes through the other media. It has been known to subsequently mix these two air streams for discharge from the tower. A potential difficulty in operating and designing such hybrid systems is that the optimum configuration for reducing plume is dependent on the operating and ambient temperatures, and when these temperatures vary, for example due to seasonal changes, there can be too much plume, or less than optimal efficiency.
Accordingly, it would be desirable to have a cooling tower that can provide desirable efficiencies while also reducing plume.
SUMMARY OF THE INVENTION
Some embodiments according to the present invention provide a cooling tower and method that can provide desirable efficiencies while also reducing plume.
An atmospheric cooling tower apparatus includes a housing structure having an air inlet and an air outlet, a first evaporative heat transfer media disposed in the housing, a closed coil heat transfer media disposed in the housing, a first water distribution assembly disposed above the first evaporative heat transfer media configured to distribute water onto the first evaporative fill heat transfer fill media, a first collection basin disposed beneath the first evaporative heat transfer media configured to collect water that has passed through the first evaporative heat transfer media, a first control valve that controls an inflow of water to supply water to one or both of the first evaporative heat transfer media and the closed coil heat transfer media, wherein the first control valve has one position where all of the water is supplied to the first evaporative heat transfer media, and another position where all of the water is supplied to the closed coil heat transfer media, wherein the closed coil heat transfer media and the first evaporative heat transfer media are disposed laterally next to each other and wherein a first air path is defined between the first water distribution assembly and the first collection basin, through the first evaporative heat transfer media, and through the closed coil heat transfer media.
Another embodiment includes an atmospheric cooling tower apparatus with a housing means having an air inlet and an air outlet, a first evaporative heat transfer means disposed in the housing, a closed coil heat transfer means disposed in the housing, a first water distribution means disposed above the first evaporative heat transfer means configured to distribute water onto the first evaporative fill heat transfer fill means, a first collection means disposed beneath the first evaporative heat transfer means configured to collect water that has passed through the first evaporative heat transfer means, a first control valve means that controls an inflow of water to supply water to one or both of the first evaporative heat transfer means and the closed coil heat transfer means, wherein the first control valve means has one position where all of the water is supplied to the first evaporative heat transfer means, and another position where all of the water is supplied to the closed coil heat transfer means, wherein the closed coil heat transfer means and the first evaporative heat transfer means are disposed laterally next to each other and wherein a first air path is defined between the first water distribution means and the first collection means, through the first evaporative heat transfer means, and through the closed coil heat transfer means.
Yet another embodiment of the atmospheric cooling method for a tower apparatus having a housing structure having an air inlet and an air outlet, includes distributing water to a first evaporative heat transfer media disposed in the housing using a first water distribution assembly disposed above the first evaporative heat transfer media configured to distribute water onto the first evaporative fill heat transfer fill media, distributing water to a closed coil heat transfer media disposed in the housing, collecting water using a first collection basin disposed beneath the first evaporative heat transfer media configured to collect water that has passed through the first evaporative heat transfer media, controlling an inflow of water to supply water to one or both of the first evaporative heat transfer media and the closed coil heat transfer media using a first control valve, wherein the first control valve has one position where all of the water is supplied to the first evaporative heat transfer media, and another position where all of the water is supplied to the closed coil heat transfer media, wherein the closed coil heat transfer media and the first evaporative heat transfer media are disposed laterally next to each other and wherein a first air path is defined between the first water distribution assembly and the first collection basin, through the first evaporative heat transfer media, and through the closed coil heat transfer media.
There has thus been outlined, rather broadly, certain embodiments of the invention in order that the detailed description thereof herein may be better understood, and in order that the present contribution to the art may be better appreciated. There are, of course, additional embodiments of the invention that will be described below and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of embodiments in addition to those described and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein, as well as the abstract, are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception upon which this disclosure is based may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic and cross-sectional view providing a diagram of a cooling tower according to a first preferred embodiment of the invention.
FIG. 2 is a diagrammatic air flow view corresponding to the view and embodiment of FIG. 1 .
FIG. 3 is another diagrammatic air flow view corresponding to the view and embodiment of FIG. 1 .
FIG. 4 is a schematic and cross-sectional view providing a diagram of a cooling tower according to a second preferred embodiment of the invention.
FIG. 5 is a diagrammatic air flow view corresponding to the view and embodiment of FIG. 4 , and showing further variations.
FIG. 6 is a diagrammatic air flow view corresponding to the view and embodiment of FIG. 4 , and showing further variations.
FIG. 7 is a schematic and cross-sectional view providing a diagram of a cooling tower according to another preferred embodiment of the invention.
DETAILED DESCRIPTION
Some embodiments according to the invention provide a cooling tower and method that can provide desirable efficiencies while also reducing plume. Examples of preferred embodiments will now be described with reference to the drawing figures, in which like reference numbers refer to like parts throughout.
FIG. 1 is a schematic diagram of a first preferred embodiment of the invention. In this embodiment, a generally or completely symmetrical structure is provided, where air enters the side of the tower 10 , passes through various media, as shown, and exits out the top of the tower 10 . The cooling tower 10 includes a fan 12 which draws air out of an air outlet structure 14 . The tower 10 also has an internal framework (not illustrated) which supports the various components that will be discussed. The tower 10 may have a basin cover 16 forming a roof of the tower, or may simply have an open roof. Turning next to the water flow, relatively warm water or other liquid to be cooled is supplied to the tower via water inlet conduit 18 , as shown. The tower 10 has two sides which are essentially mirror images of each other. For convenience, one side is discussed below, and both sides have reference numbers.
The water supplied to inlet 18 , which is referred to herein as inlet water, may in some exemplary industrial applications may range from 80° F. to 120° F. Although water is described in the following examples, various embodiments can be used with other fluids, including treated water or other liquids, any or all of which are referred to as water herein. The inlet hot water is passed to a three-way diverter valve, or control valve 20 . The operation of this control valve 20 will be discussed in more detail below. In one configuration, the control valve 20 directs all or some of the water through a conduit 22 so that it enters an upper water distribution basin 24 . The water distribution basin 24 , for example, can take the form of a tray having nozzles therethrough so that water is collected in the water distribution basin 24 and drips downward from the nozzles of the tray in a distributed fashion.
As it drops, the water will contact and pass through an upper heat exchange media 26 . The upper heat exchange media 26 in this example is an evaporative fill media such as a series of splash bars or a sheet fill pack.
After falling through the evaporative media 26 , the water is collected in an intermediate distribution tray, or re-distribution tray, 28 . The re-distribution tray 28 is similar in structure to distribution tray 24 . The water in the re-distribution tray 28 falls downward onto a lower heat transfer media 30 , which in this example is also an evaporative media such as a splash bar or sheet fill pack media. Some embodiments thus have both upper and lower evaporative media. Moreover, in some embodiments having both of these be a film fill type media is also preferred. However, as will be illustrated for example with respect to a version of the second embodiment, shown in FIGS. 5 and 6 , there may be instances where one or the other of the upper media 26 or the lower media 30 may be a closed dry media, such as a coil type. Also either of the upper media 26 and lower media 30 can be a compound media, wherein liquid is to be cooled passing through a coil and also another liquid is being sprayed over the coil.
Returning to FIG. 1 , a lower water collection basin 31 is located at the bottom of the tower 10 to collect water for discharge from the tower. After being cooled, the water is collected in the lower water collection basin 31 . The water in the water collection basin 31 can be extracted by a pump or gravity flow and returned to the process location or exhausted into the environment.
The control valve 20 may also direct the water into a conduit 34 where it enters a closed circuit heat transfer coil 32 . This water travels through the coil 32 and is cooled by the coil operating as a closed circuit heat exchanger with the ambient air. The water exits the coil 32 via conduit 35 at which point it can be collected by the re-distribution tray 28 . In an example of an optional embodiment, the discharge conduit of the coil 32 may be connected to a second control valve 36 which can divert the water leaving the coil 32 so that instead of entering the re-distribution basin 28 , it instead is directed to a bypass conduit 38 which directs the water directly to the lower water collection basin 31 , and thus the water bypasses the intermediate collection basin 28 in this mode. This feature is optional as are many other features described herein, such as for example a purely closed loop mode that is discussed farther below.
Continuing with FIG. 1 , it will be appreciated that when the control valve 20 is a gradual diverter valve, it can gradually shift the operation of the upper section of the tower such that the water flow can transition between (1) a fully evaporative condition (with all the water entering the conduit 22 , the top distribution basin 24 , and passing through the media 26 to be collected in the intermediate tray 28 ), and (2) when the valve is operated in completely the other direction, the top section of the tower operates as a purely closed circuit tower (with all of the water being directed through the coil 32 and exiting the coil 32 and upon exit of the coil 32 , depending on the condition of the secondary valve 36 , the water being directed either into the intermediate distribution tray 28 or sent directly to the lower water basin 31 ).
The top section of the tower 10 can also be operated with the inlet water supply being split fractionally as a percentage by the control valve 20 so that some of the water is operating in an evaporative condition through the media 26 and another proportion of the water is operating in a closed dry configuration through the coil 32 . Again, water may be sent after it has passed through the coil 32 either through the lower media 30 or can bypass the lower media 30 directly into the lower basin 31 . The coil 32 is illustrated as being outward of the media 26 ; however, if desired the coil 32 can be inbound of the media 26 , which may have benefits such as protection of the coil 32 from the elements and/or external debris.
FIGS. 2 and 3 further illustrate the air flow through the system of FIG. 1 and also depict an arrangement wherein the lower air inlets of the tower feature dampers 40 that can be opened or closed. In FIGS. 2 and 3 , dashed lines indicate a heat exchange media that is not in use, and the arrows represent active air flow paths. FIG. 2 shows a mode of operation where the water is being sprayed over the upper fill 26 , is recollected and also passes through the lower fill 30 . In FIG. 3 the left side shows a mode of operation which may for example be a purely closed dry configuration in which fluid is flowing only through the coil 32 . Thus, the dampers 40 can be closed off and air is drawn only through the coil 32 . This completely dry operation would be most desirable in the case of very cool conditions. In this mode shown on the left side of FIG. 3 , the bypass valve 36 (see FIG. 1 ) is activated in the configuration of FIG. 3 so that the liquid also does not fall over the lower fill 30 , although in some embodiments the water may fall over the tower fill. The right side of FIG. 3 shows a configuration in which the dampers 40 are open and air is flowing both over the coil 32 and the lower media 30 . This shows an operation wherein the upper section the coil 32 is being used, and in the lower half the fill media 30 is being used.
FIGS. 2 and 3 show the extreme end point modes, in which in the upper section of the tower all the water is passing through only one or the other of the evaporative media 26 ( FIG. 2 ) or the coil 32 ( FIG. 3 ). However, although not specifically depicted in its own figure, it will be appreciated that the control valve 20 is a continuously adjustable valve in some embodiments, so that any proportion of the water in the upper section of the tower may be passing through one or the other of the two upper fill media 26 and 32 . Also, the bypass valve 36 can be a continuous adjustable valve to control a traditional flow through the lower media 30 .
FIG. 4 is a view similar to FIG. 1 , but shows a tower 50 that is essentially one-sided. The systems being depicted in FIG. 4 are thus similar to one side of FIG. 1 except that a solid end wall 54 is provided. FIG. 4 also schematically depicts the concepts of exit air mixing baffles 52 . The air baffles 52 may be provided to enhance mixing of the upper air flow with the lower air flow before the air is exhausted from the tower. In some situations, the lower air flow may tend to have more water vapor suspended in it compared to the upper air flow, and if these paths remain unmixed, there can tend to be plume from the higher water vapor air flow. Mixing the air flows in some circumstances can thus reduce the plume overall. The baffles 52 are illustrated solely in a schematic nature, and any of the wide variety of air mixing baffles that are known could be utilized, as well as other air mixing baffles.
FIGS. 5 and 6 illustrate a variant embodiment generally corresponding to FIG. 4 . Also in FIGS. 5 and 6 dashed lines indicate a heat exchange media that is not in use, and the arrows represent active air flow paths. In this embodiment the lower fill media ( 30 in FIG. 4 ) is a coil circuit 56 which could incorporate an evaporative enhancing component 58 , as disclosed in U.S. Pat. No. 6,702,004. In this embodiment, the process fluid at its warmest entering temperature can first enter the coil 56 in the lower section of the tower, then exit the coil 56 at a cooler temperature to be discharged or returned to the process equipment. The fluid passing through the coil 56 has its cooling enhanced by a second circuit of falling evaporative heat exchange water, which is being pumped from the lower water collection basin up into a top water distribution system 24 . Thus, this system provides heat exchange to a primary fluid by virtue of the circulation of a secondary fluid through the tower. The secondary fluid flow is similar to that described for FIGS. 1-4 .
Thus, FIGS. 5 and 6 illustrate an embodiment schematically as in FIG. 4 , but with the addition of the lower coil circuit 56 . Of course, an embodiment according to FIG. 1 can also be implemented with a lower coil similar to that illustrated in FIGS. 5 and 6 disposed with the lower fill media 30 of the embodiment of FIG. 1 . In this way the above description for FIGS. 1-6 includes four sub-groups of embodiments, the embodiment of FIGS. 1-3 without the additional lower coil, the embodiment of FIG. 4 without the additional lower coil, the embodiment of FIG. 1 but also having an additional lower coil (not shown), and the embodiment of FIGS. 5-6 having an additional lower coil.
FIG. 5 shows the top section in evaporative mode, and FIG. 6 shows closed circuit mode for the top section. In both FIGS. 5 and 6 the lower section is active to pass water over the coils being cooled.
FIG. 7 is a view similar to FIG. 1 but showing yet another alternative embodiment. In this embodiment, each side has a lower closed coil 60 opposed next to the lower heat transfer media 30 . In the case where the lower heat transfer media 30 is an evaporative media, it will be appreciated that this entire lower cooling section in this embodiment operates similarly to the upper cooling section. That is, the valve 36 in this embodiment can be used to selectively direct fluid either into the intermediate collection basin 28 so that it (1) falls over the evaporative fill media 30 or (2) flows to the coil 60 . In this way, the valve 36 would operate similarly in function to the valve 20 . Valve 36 can be a continuous valve to direct a portion of the flow through one media and the rest through the other media. It will be appreciated that this embodiment can have a mode where it is run entirely as a “dry” cooling tower wherein valve 20 directs all of the fluid through the coil 32 , and valve 36 directs all of the fluid through the coil 60 . Fluid leaving the coil 60 is directed to the lower collection basin 31 . Various embodiments according to FIG. 7 can be two-sided or one-sided, and use sheet media or coil media or the lower media 30 .
It is believed that the above description fully describes components and operation of the system in detail with reference to the drawings. However, the discussion below even further describes the modes of operations of some embodiments of the system.
Taking the embodiment of FIG. 1 as an example, for near design heat load conditions, water passes from the control valve 20 to the top distribution basin 24 (bypassing the dry heat exchanger 32 ). The water then passes over the top evaporative fill 26 and into the re-distribution spray system 28 where it finally passes over the bottom evaporative heat exchanger 30 .
In this example, for less than design heat load conditions, the valve 20 is opened to maintain a pre-determined cold water set point. The more the valve 20 is opened, the more water passes through the dry heat exchanger 32 , and the warmer the water gets, less water is consumed by evaporation and less plume is generated as well. The more the valve 20 is closed, the more water passes over the evaporative heat exchanger 26 , the cooler the water gets and more water is consumed and more plume is generated as well. A control system for actuating the valve 20 can be used to maintain at or near an optimum balance condition, or this can also be done manually. The air in the upper section thus moves through both evaporative and closed heat exchanges in a series path, but the upper and lower sections are therefore arranged as in a parallel path system. The ability to switch between evaporative and dry heat transfer, and do it gradually provides advantageous operation in the “shoulder” seasons.
The water from the dry coil 32 combines with the water from the upper evaporative heat exchanger 26 at the re-distribution basin 28 before passing over the bottom evaporative heat exchanger 30 .
At far less than design heat load conditions, or at sufficiently cool conditions, the top evaporative heat exchanger 26 is completely bypassed so that no evaporation takes place. At this point all heat transfer in the top section is done through the dry heat exchanger 32 . The bottom evaporative heat exchanger 30 can continue to operate, enabling the system to operate as a true parallel path wet dry cross flow cooling tower, or can be bypassed (with or without the addition of dampers).
For extreme cold conditions or for additional water conservation, air inlet dampers 40 can be placed at the bottom heat exchanger 30 as shown in FIG. 3 . If water is completely bypassing the top evaporative heat exchanger 26 , water temperature can be maintained at full fan speed by fully or partially closing the bottom heat exchanger dampers 40 . This reduces the air flow, which reduces the heat transfer and conserves water, and reduces plume as well, maintaining full fan speed allows for maximum heat transfer through the dry heat exchanger 34 . Once the dampers 40 are completely closed, the tower now operates in a completely dry mode. In this mode, very little water is consumed, and no plume is emitted.
Turning now to yet another variation which can be applied to any of the embodiments of the invention, although not specifically illustrated in any figure a variation is described in this paragraph. Each of the drawing figures illustrates the closed coil such as, for example, closed coil 32 , being disposed outwardly or outbound of the evaporative film media 26 . That is, in the embodiments that are illustrated in the configuration of the figures, the coil is closer to the air inlet, and closer to the outside of the tower, and the evaporative film media is inboard or closer to the center of the tower. However, the position of these elements can be reversed. That is, embodiments are possible where the coil is inbound of the evaporative film media. This can be advantageous in protecting the coils from environmental effects such as snow, ice, or wind-driven or falling debris such as tree branches or leaves. In some instances, the fill may be less expensive to replace than the coils. Further, if the fill is contacted by debris its effectiveness is generally affected only slightly, whereas if a coil is punctured, a leak can be very undesirable. Therefore, placing the fill towards the outboard as described in this paragraph may in some instances provide for a more weather and debris resistant configuration. The desirability of placing the coil inboard and the fill media outboard as described in this paragraph may also depend on whether external louvers are present on the outer side of the tower.
The many features and advantages of the invention are apparent from the detailed specification, and thus, it is intended by the appended claims to cover all such features and advantages of the invention which fall within the true spirit and scope of the invention. Further, since numerous modifications and variations will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation illustrated and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | An atmospheric cooling tower apparatus includes a housing structure having an air inlet and an air outlet, a first evaporative heat transfer media disposed in the housing, and a closed coil heat transfer media disposed in the housing. A water distribution assembly is disposed above the evaporative heat transfer media and configured to distribute water onto the evaporative fill heat transfer fill media. A collection basin is disposed beneath the evaporative heat transfer media configured to collect water that has passed through the evaporative heat transfer media. A first control valve controls an inflow of water to supply water to one or both of the evaporative heat transfer media and the closed coil heat transfer media. The closed coil heat transfer media and the evaporative heat transfer media are disposed laterally next to each other. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority benefit under 35 U.S.C. Section 119(e) to U.S. Provisional Patent Ser. No. 61/245,321 filed on Sep. 24, 2009 the entire disclosure of which is incorporated herein by reference.
FIELD OF THE INVENTION
Embodiments of the invention relate to a method for recovering hydrocarbons with in situ combustion.
BACKGROUND OF THE INVENTION
In situ combustion (ISC) processes are applied for the purpose of recovering oil from light oil, medium oil, heavy oil and bitumen reservoirs. In the process, oil is heated and displaced to an open production well for recovery. Historically, in situ combustion involves providing spaced apart vertical injection and production wells within a reservoir. Typically, an injection well will be located within a pattern of surrounding production wells. An oxidant, such as air, oxygen enriched air or oxygen, is injected through an injection well into a hydrocarbon formation, allowing combustion of a portion of the hydrocarbons in the formation in place, i.e., in-situ. The heat of combustion and the hot combustion products warm the portion of reservoir adjacent the combustion front and drive (displace) hydrocarbons toward offset production wells.
One difficulty associated with applying in situ combustion as a stand alone recovery method in heavy oil and bitumen reservoirs is the lack of mobility of the oil. For example, in situ combustion involves the injection of an oxidant into a formation. The oil in place serves as a fuel for the combustion front once ignition has occurred. As with any burning process, heat, oxygen, and fuel must be readily available to sustain combustion. In heavy oil and bitumen reservoirs this process is interrupted by the fact that the oil in the reservoir is not mobile. Therefore, combustion gas products (CO, CO 2 , H 2 S, etc.) and mobilized oil can become trapped in the reservoir which leads to the suffocation of the combustion front. Therefore, a need exists for a method of initiating enhanced communication between the injection and production wells along with a method for extracting both oil and gas from the reservoir for in situ combustion processes.
SUMMARY OF THE INVENTION
In one embodiment, a method of conducting in situ combustion in an underground reservoir, includes: forming at least one injection well disposed in the underground reservoir, wherein the injection well includes a vertically deviated well, a first horizontal injector well and a second horizontal injector well, wherein the first and second horizontal injector wells can vary from 30° to 120° from the vertically deviated well, wherein the injection well including the first and second horizontal injector wells are at least 5 meters above a hydrocarbon producing zone, wherein the distal ends of the first and second horizontal injector wells include a toe portion, wherein the opposite ends of the first and second horizontal injector wells include a heel portion, wherein the heel portions connect the first and second horizontal portions to the vertically deviated well; forming a first production well having a first substantially horizontal producer portion and a first substantially vertical producer portion disposed in the underground reservoir, wherein the distal end of the horizontal producer portion includes a toe portion, wherein the opposite end of the horizontal portion includes a heel portion, wherein the heel portion connects the first horizontal producer portion to the first vertical portion of the first production well; forming a second production well having a second substantially horizontal producer portion and a second substantially vertical producer portion disposed in the underground reservoir, wherein the distal end of the horizontal producer portion includes a toe portion, wherein the opposite end of the horizontal portion includes a heel portion, wherein the heel portion connects the second horizontal producer portion to the second vertical portion of the second production well, wherein the second production well is located lower in the reservoir than the first production well; injecting an oxidant into the injection well to establish a combustion front of ignited hydrocarbons to propagate a combustion front through the reservoir; recovering hydrocarbons from the reservoir via the second production well due to gravity drainage; and recovering combustion gas from the reservoir via the first production well.
In another embodiment, a method of conducting in situ combustion in an underground reservoir, includes: forming at least one injection well disposed in the underground reservoir, wherein the injection well includes a vertically deviated well, a first horizontal injector well and a second horizontal injector well; forming a first production well having a first substantially horizontal producer portion and a first substantially vertical producer portion disposed in the underground reservoir; forming a second production well having a second substantially horizontal producer portion and a second substantially vertical producer portion disposed in the underground reservoir; injecting an oxidant into the injection well to establish a combustion front of ignited hydrocarbons which propagate a combustion front through the reservoir; and recovering hydrocarbons through the production well.
In another embodiment, a method of conducting in situ combustion in an underground reservoir, includes: forming at least one injection well disposed in the underground reservoir, wherein the injection well includes a vertically deviated well, a first horizontal injector well and a second horizontal injector well; forming a first production well having a first substantially horizontal producer portion and a first substantially vertical producer portion disposed in the underground reservoir; forming a second production well having a second substantially horizontal producer portion and a second substantially vertical producer portion disposed in the underground reservoir; heating the reservoir surrounding the injection well, wherein the heating occurs without igniting oil in the reservoir and with operations conducted through the injection well; initiating in situ combustion after heating the reservoir, within the initiating includes injecting an oxidant into the injection well to establish a combustion front of ignited hydrocarbons which propagate a combustion front through the reservoir; and recovering hydrocarbons through the production well.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention, together with further advantages thereof, may best be understood by reference to the following description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic section of an injection well and a series of production wells according to an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Reference will now be made in detail to embodiments of the present invention, one or more examples of which are illustrated in the accompanying drawing. Each example is provided by way of explanation of the invention, not as a limitation of the invention. 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 or spirit of the invention. For instance, features illustrated or described as part of one embodiment can be used on another embodiment to yield a still further embodiment. Thus, it is intended that the present invention cover such modifications and variations that come within the scope of the appended claims and their equivalents.
Referring to FIG. 1 , an underground reservoir 108 contains an injection well 106 and a series of production wells 100 , 102 , 104 disposed therein. The “x-axis” is parallel to the earth surface 109 . The “y-axis” is orthogonal to the x-axis and vertical to the earth surface 109 . The “z-axis” is orthogonal to both the x-axis and the y-axis.
The injection well 106 is a single well with a vertically deviated well from the surface, i.e., along the y-axis, with multiple wells at angles varying from 30° to 120° from the vertically drilled well into the reservoir along the x-axis and/or the y-axis and/or the z-axis. The configuration of the injection well is similar to a fishbone configuration. Depicted in FIG. 1 , the injection well defines a first horizontal injector well 124 and a second horizontal injector well 126 . The first and second horizontal injector wells 124 and 126 , respectively, may progress through the reservoir at angles which differ from the original angle facilitating the best placement of the well within the reservoir. In an embodiment, the injection well may contain multiple horizontal injector wells. Furthermore, the horizontal injector portions 124 and 126 increase potential area for communication between the injection well 106 and the production wells relative to only utilizing vertical injection wells where lateral area for establishing communication is limited. The injection well 106 along with the first horizontal injector well 124 and second horizontal injector well 126 are at least 5 meters above the bottom pay zone.
The reservoir 108 contains at least two production wells each having a vertical producer portion and a substantially horizontal producer portion completed via horizontal drilling techniques known in the art. The horizontal producer portions of the production wells can be placed at the base of the reservoir pay zone, where at least one or more of the horizontal producer portions are arranged parallel or perpendicular to one or more of the horizontal producer portions situated vertically beneath the other wells. In an embodiment, as depicted in FIG. 1 , the reservoir contains two horizontal producer wells 103 and 105 situated along the z-axis above a single perpendicular horizontal producer well 101 situated along the x-axis.
The production wells 100 , 102 , 104 have the general shape of a foot, and are defined by a “toe” portion 110 , 114 , 118 and a “heel” portion 112 , 116 , 120 . The toe portion is located at the distal end of the horizontal producer portion, while the heel portion is located at the intersection of the horizontal producer portion and vertical producer portion. The production wells contain slots at various desired locations along the horizontal producer portion to facilitate production of fluids from the reservoir. The slots are narrowly cut either axially or transversely in the wall of the horizontal producer portion. The slots are made sufficiently narrow to exclude particles greater than a selected size, while allowing flow into or out of the wellbore. The number of slotted wall sections, the size of the slots, and the location of the slots are solely dependent on operational requirements and desires.
In situ combustion cannot be applied directly to an immobile reservoir without prior stimulation due to inadequate initial communication between the injection well and the production well. The cold heavy oil and/or bitumen in the formation cause this lack of communication resulting in an inability to produce combustion gas products or mobile oil from the reservoir. The inability to vacate the products from the reservoir ultimately results in the suffocation of the combustion front and termination of the process. Cyclic steam stimulation (CSS), also known as the huff-and-puff method, is typically applied to heavy-oil reservoirs to boost recovery and can ultimately initiate the required communication between the injection and production wells. During the primary production phase, the cyclic steam stimulation method assists natural reservoir energy by melting the oil so it will more easily move through the formation.
Preheating the formation 108 around the fishbone injection well configuration 106 with steam, for example, may facilitate in establishing initial communication between the fishbone injection well configuration 106 and the production wells 100 , 102 , 104 . In an embodiment of the huff-and-puff method, a predetermined amount of steam is injected into the fishbone injection well configuration, which has been drilled or converted for injection purposes. In another embodiment, a predetermined amount of steam is injected into the fishbone injection well configuration and one or more of the injection wells. In another embodiment, a predetermined amount of steam is injected into one or more of the injection wells. Once the pay zone between the wells has been heated (>90° F.), the well is then shut in to allow the steam to heat or “soak” the producing formation around the well. After a sufficient time has elapsed to allow adequate heating, the injection well is back in production until the heat is dissipated with the production fluids. The huff phase (steam injection), the soak phase, and the puff phase (production phase) are repeated as necessary to heat the formation around the fishbone injection well configuration and to establish fluid communication between the injection well and the production wells for in situ combustion.
Once communication is established, the in situ combustion process may begin. In operation, the in situ combustion process begins with the injection of an oxidant 122 through the injection well 106 to initiate combustion. Air is usually used; however it may be substituted directly with oxygen or with recycled gases enriched with oxygen. Water may also be injected continuously or as slugs along with an oxidant to improve the combustion process. Continuous gas injection and cold water circulation in the injection well can be used to minimize combustion damage to the well.
The major driver for recovery of oil through the combustion process will be gravity drainage. For example, as the combustion front propagates from the injection well at the top of the formation, oil and gas drain to the base of the reservoir. Specifically, combustion is initiated and maintained by the injection of an oxygen containing gas at the top of the reservoir into the injection well 106 , with mobilized oil draining to lower horizontal producer wells, i.e., 101 , 103 , 105 .
The preferred embodiment of the present invention has been disclosed and illustrated. However, the invention is intended to be as broad as defined in the claims below. Those skilled in the art may be able to study the preferred embodiments and identify other ways to practice the invention that are not exactly as described in the present invention. It is the intent of the inventors that variations and equivalents of the invention are within the scope of the claims below and the description, abstract and drawings not to be used to limit the scope of the invention. | An underground reservoir is provided comprising an injection well and a production well. The production well has a horizontal section oriented generally perpendicularly to a generally linear and laterally extending, upright combustion front propagated from the injection well. | 4 |
BACKGROUND
[0001] This invention relates generally to drilling devices and, more particularly, to an expandable diameter drill bit having a torsion spring for biasing one or more blades outwardly such that a hole being drilled is enlarged.
[0002] Rotary drilling devices are used to bore a generally cylindrical hole into the ground to a depth at which a fluid may be extracted, such as water, oil, natural gas, or the like. Sometimes an existing well needs to be re-drilled, cleaned out, or the diameter expanded. A rotary drill may include one or more blades that scrape or dig into the ground surface as the drill rotates. The blades often wear out, break, or otherwise fail and must be replaced, especially when operated at high speed. Another problem with drilling devices is that a drill bit having one diameter may be used and then replaced with a drill bit having a larger diameter in order to increase the diameter of the well.
[0003] Although existing rotary drilling devices are presumably effective to drill subsurface wells, they are less effective in operating to increase the diameter of the hole. For instance, some expanding diameter drill bits urge their blades outwardly by centrifugal force and, as a result, require high speed rotation which may not be possible in some subsurface conditions or if debris is building up too quickly within a hole.
[0004] Therefore, it would be desirable to have an expandable diameter drill bit having one or more blades that are automatically biased outwardly by respective torsion springs. Further, it would be desirable to have an expandable diameter drill bit having a construction that is less susceptible to blade breakage and more effective in cutting through rock.
SUMMARY
[0005] An expandable diameter drill bit according to the present invention includes a cutting blade having a receiving end and a contacting end, the receiving end having a pivot shaft and the contacting end having a tip. A drill bit includes a drill head body having an upper attachment portion and a lower body portion, the lower body portion defining a blade opening for receiving the receiving end of the cutting blade and a bolt receiving hole on each of two opposing sides transverse the blade opening. The drill bit includes a torsion spring having a helical coil, a first blade leg, and a second body leg. The blade bolt passes through the bolt receiving holes and the pivot shaft and is secured into position with a blade bolt set screw. The first blade leg is coupled to the cutting blade with a spring retainer bolt, the second body leg is coupled to the drill head body, and the torsion spring biases the blade outwardly from the drill head body.
[0006] The drill bit 10 may be inserted into a hole with the purpose of expanding the hole diameter as it is lowered therein. The drill bit is spun around such that the blades cut away at the edges of the hole. As the diameter of the hole becomes larger, the oppositely biased torsion springs force the blades outward, thus causing the hole to become even larger.
[0007] Therefore, a general object of this invention is to provide an expandable diameter drill bit for efficiently drilling a well beneath the surface of the Earth.
[0008] Another object of this invention is to provide an expandable diameter drill bit, as aforesaid, in which a pair of blades is pivotally movable between a retracted configuration not extending outwardly from a drill body and an extended configuration extending outwardly from the drill body.
[0009] Still another object of this invention is to provide an expandable diameter drill bit, as aforesaid, in which each cutting blade is naturally biased toward the extended configuration by a respective torsion spring.
[0010] Yet another object of this invention is to provide an expandable diameter drill bit, as aforesaid, in which each cutting blade may be coated with or include materials that cut more effectively through subsurface compositions and debris.
[0011] A further object of this invention is to provide an expandable diameter drill bit, as aforesaid, that cuts more effectively through subsurface compositions and debris.
[0012] A still further object of this invention is to provide an expandable diameter drill bit, as aforesaid, in which each cutting blade includes serrated teeth.
[0013] Other objects and advantages of the present invention will become apparent from the following description taken in connection with the accompanying drawings, wherein is set forth by way of illustration and example, embodiments of this invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] FIG. 1 is a perspective view of an expandable diameter drill bit according to a present embodiment of the present invention illustrated in an expanded configuration;
[0015] FIG. 2 a is a front view of the expandable diameter drill bit as in FIG. 1 ;
[0016] FIG. 2 b is a side view of the expandable diameter drill bit as in FIG. 2 a;
[0017] FIG. 2 c is a section view taken along line 2 c - 2 c of FIG. 2 b;
[0018] FIG. 2 d is an isolated view on an enlarged scale taken from FIG. 2 c;
[0019] FIG. 2 e is an isolated view on an enlarged scale taken from FIG. 2 c;
[0020] FIG. 2 f is an isolated view on an enlarged scale taken from FIG. 2 c;
[0021] FIG. 3 a is an exploded view of the expandable diameter drill bit as in FIG. 1 ;
[0022] FIG. 3 b is an isolated view on an enlarged scale taken from FIG. 3 a;
[0023] FIG. 3 c is an isolated view on an enlarged scale taken from FIG. 3 a;
[0024] FIG. 3 d is an isolated view on an enlarged scale taken from FIG. 3 a;
[0025] FIG. 3 e is an isolated view on an enlarged scale taken from FIG. 3 a;
[0026] FIG. 4 a is a front view of the expandable diameter drill bit according to the present invention illustrated in a retracted configuration; and
[0027] FIG. 4 b is a side view of the expandable diameter drill bit as in FIG. 4 a.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0028] An expandable diameter drill bit and method of use will now be described with reference to FIGS. 1 to 4 b of the accompanying drawings. The drill bit 10 may generally include a drill head body 100 and a plurality of blades 200 secured to the drill head body 100 with a bolt and set screw combination and held in tension with the drill head body 100 via tension springs 300 .
[0029] With reference to FIGS. 3 a and 3 b , the drill head body 100 serves as the structural support for the expandable blades 200 . The drill head body 100 may have an upper threaded portion 105 for attaching the drill bit to various devices useful for guiding the drill bit underground and a lower body portion 110 for attaching the blades 200 to the drill bit 10 . Although not required, the upper threaded portion 105 may be generally conically shaped as shown in the figures.
[0030] An outside edge 107 of the upper threaded portion 105 may be inserted into, for example, a drill string (not shown). The threaded portion 105 may be configured such that when the drill bit 10 is connected to the drill string and in use the drill bit 10 does not become loosened. Other means for ensuring semi-permanent connection to the drill string (or other guiding device) is contemplated within the scope of the present invention. It shall also be understood that drill bits generally have a shortened lifespan due to the conditions under which they are used, and therefore, as will be appreciated by those skilled in the art, it may be preferable that the drill bit 10 is removable from the drill string (or other guiding device) at the end of its life.
[0031] The upper threaded portion 105 terminates at an inside edge 109 of a top face of the lower body portion 110 . The lower body portion 110 may define blade openings 112 for accepting receiving ends 205 of the blades 200 . The blade openings 205 may be separated by a divider 115 for ensuring proper positioning of the blades 200 and to prevent the blades 200 from rubbing against each other during use.
[0032] Bolt receiving holes 120 in opposing sides of the drill head lower body portion 110 and though the center of the divider 115 may generally correspond to holes 210 (pivot shafts) in receiving ends 205 of the blades 200 . Referring now to FIG. 3 c , a threaded end 131 of a blade bolt 130 may be inserted through a first bolt receiving hole 120 a ( FIG. 4 a ) in the drill head lower body portion 110 , through the hole 210 (pivot shaft) in the receiving end 205 of a first blade 200 , through the hole in the divider 115 , through the hole 210 (pivot shaft) in the receiving end 205 of a second blade 200 , and through a second bolt receiving hole 120 b in the drill head lower body portion 110 . A head 132 on the end opposite the threaded end 131 of the blade bolt 130 may subsequently come to rest along an outer perimeter 119 of the first receiving hole 120 a to keep the blade bolt 130 in its preferred position.
[0033] A channel 133 ( FIG. 3 c ) may be cut around a perimeter of the blade bolt 130 at a length L of the bolt 130 such that when the bolt 130 is inserted through the drill bit lower body portion 110 as described above, the channel 133 is at a position corresponding generally to the hole in the divider 115 . A blade bolt set screw hole 125 ( FIG. 3 e ) in one or both outside ends of the divider 115 may receive a blade bolt set screw 135 , which may fit within the channel 133 in the blade bolt 130 . In some embodiments, it may be preferable for the blade bolt set screw 135 to fit within the channel 133 to prevent the blade bolt 130 from shifting laterally but still allow the blade bolt 130 to rotate within the bolt receiving holes 120 a , 120 b . In other embodiments, it may be desirable for the blade bolt set screw 135 to be tightened such that the blade bolt 135 is prevented from both shifting laterally and rotating.
[0034] The lower body portion 110 may further be equipped with a fluid discharge hole 128 . Fluids are often used to reduce friction, provide buoyancy to the drill string, and remove cuttings from the well bore. As the well bore in which the drill is operating is flooded with fluids, the fluid discharge hole 128 may allow for fluids to be discharged away from the drill head body 100 .
[0035] The blades 200 provide the means by which surface material is displaced to form a hole, and in some particular embodiments, a well bore hole. Each blade 200 may be generally rectangular at the receiving end 205 and culminate at a tip at the surface contacting end 215 . The tip may have a rounded configuration as shown in the drawings although a pointed tip may also be used in other embodiments not shown). An upper corner 212 of the blade at the receiving end 205 may be rounded to facilitate rotation of the blade 200 about the blade bolt 130 while situated inside of the blade openings 112 .
[0036] Outer edges 214 of the blades may be serrated to increase the performance of the blades. Serrated edges may be superior to plain edges because serrated edges tend to grab and cut the material as the blades come into contact with the surface. The blades may be made of any material strong enough to withstand the high forces exerted on the blades as they rotate and cut away at the surface. Exemplary materials include steel, steel alloys, tungsten carbide, cubic boron nitride, et cetera.
[0037] In addition to the blades themselves, the edges may be coated in a material exhibiting superior hardness properties thereby increasing the effectiveness of the blades and the life of the drill. In some embodiments, the edges 214 may additionally or alternately be equipped to receive an insert 220 , such as that shown in FIG. 3 a . The insert 220 may also be constructed of a material exhibiting superior hardness properties. Exemplary materials include tungsten carbide, cubic boron nitride, diamond, et cetera.
[0038] It should be noted that the blades may be any desired length based on the requirements of a particular project (e.g., 20″, 25″, 30″, 35″, 40″, 45″, etc.). Additionally, while the embodiments described herein focus on the use of two opposing blades, additional or fewer blades could be used depending on the particular project.
[0039] With reference to FIG. 2 c , tension springs 300 may act to keep the blades 200 in tension with respect to the drill head body 100 . The springs 300 may be, for example, helical torsion springs having a central coil 305 with a first blade leg 310 extending along a length of the blade 200 and a second body leg 315 extending toward and attaching to the base 100 . The central coil 305 may fit into a recess 240 in the pivot shaft 210 and the first blade leg 310 may fit into a recess 242 in the blade 200 ( FIGS. 2 e and 3 d ). The first blade leg 310 may be secured into place via one or more spring retainer bolts 320 ( FIG. 2 f ). The second body leg may be inserted into a cavity 140 in the drill head body 100 ( FIG. 2 d ).
[0040] When the springs 300 are in full tension, the blades 200 are in a retracted position as illustrated in FIGS. 1 and 2 a . When retracted, such as to about a 4″ diameter, the drill bit 10 may be inserted into a ground hole that is intended to be drilled or enlarged. In a retracted position, the blades 200 may not exhibit any substantial hole-widening capabilities. However, the mechanical energy stored in the springs 300 as a result of the central coil 305 constantly acts to push the blades outward or away from the retracted position. FIG. 2 a illustrates the springs 300 pushing the blades 200 outward toward an expanded configuration ( FIG. 1 ). The mechanical energy can thus be altered by modifying the central coil 305 (e.g., increasing the tension or decreasing the tension in the spring). Therefore, as the blades 200 cut away at the interior surface of a hole, the blades may be pushed further outward as a result of the tension springs 300 , thereby increasing the diameter of the hole in the surface. It may be preferable for the blades 200 to extend in opposite directions from each other to obtain the highest possible degree of surface displacement. In an embodiment, a diameter of the blades in the extended configuration may be about 24″ although other diameters would be effective depending on individual blade lengths.
[0041] In use, the drill bit 10 is inserted into a hole with the purpose of expanding the hole diameter. The blades 200 may first be in the retracted configuration so as to fit into the hole as described above. The drill bit 10 is spun around such that the blades 200 cut away at the edges of the hole. As the hole becomes larger (i.e. has a larger diameter), the springs 300 force the blades 200 outwardly, thus causing the hole to become even larger.
[0042] While many methods of manufacturing the drill head body 100 and blades 200 are contemplated within the scope of the present invention, some exemplary methods include die casting, molding, forging, extruding, machining, et cetera.
[0043] Many different arrangements are possible without departing from the spirit and scope of the present invention. Embodiments of the present invention are described herein with the intent to be illustrative rather than restrictive. Alternative embodiments will become apparent to those skilled in the art that do not depart from its scope. A skilled artisan may develop alternative means of implementing the disclosed improvements without departing from the scope of the present invention. Further, 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. The description should not be restricted to the specific described embodiments. | An expandable diameter drill bit includes a cutting blade having receiving and contacting ends, the receiving end having a pivot shaft and the contacting end having a tip. A drill bit includes a drill head body having an upper attachment portion and a lower body portion, the lower body portion defining a blade opening for receiving the receiving end of the cutting blade and a bolt receiving hole on opposing sides transverse the blade opening. The drill bit includes a torsion spring, a first blade leg, and a second body leg. The blade bolt passes through the bolt receiving holes and the pivot shaft and secured with a set screw. The first blade leg is coupled to the cutting blade with a spring retainer bolt, the second body leg is coupled to the drill head body, and the torsion spring biases the blade outwardly from the drill head body. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to novel 1-hydroxyvitamin D derivatives.
More particularly, it is concerned with esters of 1-hydroxyvitamin D with vitamin A acid.
The 1-hydroxyvitamin D derivatives are useful as an agent for preventing or treating osteoporosis, cutaneous ulcers and tumors.
2. Description of the Prior Art
There have been widely used active vitamin D having a hydroxyl group at the 1-position of the vitamin D as an agent for treating osteoporosis. Recently, the vitamin D derivatives have been found to have inducing activities on the differentiation of cells and tried to apply to the treatment of psoriasis and tumors.
On the other hand, vitamin A acid is biochemically synthesized from vitamin A and guessed to be an active intermediate at the expression of vitamin A effects. It is clarified that the functions of vitamin A such as growth stimulation, protein metabolism and stabilization of cuticula cell tissues are achieved via vitamin A acid. Considering those activities of vitamin A acid, there has been an idea to get useful compounds by esterification of such vitamin A acid with alcohols having physiological activities. For example, Japanese patent unexamined publication Nos. 469/1973 and 92967/1979 disclose esters of vitamin A acid with α-tocopherol (vitamin E). However, none of esters of vitamin A acid with vitamin D is known.
SUMMARY OF THE INVENTION
It is an object of the invention to provide 1-hydroxyvitamin D derivatives which are useful as an agent for preventing or treating osteoporosis, cutaneous ulcers and tumors.
DETAILED DESCRIPTION OF THE INVENTION
In accordance with the invention there are provided novel 1-hydroxyvitamin D derivatives having the formula (I) ##STR1## wherein A represents an acyl residue derived from vitamin A acid, X means a hydroxyl group and R represents a group of the formula (II) ##STR2## wherein R 1 and R 2 each represent hydrogen atoms or together form a carbon-carbon double bond, R 3 represents a hydrogen atom, a C 1 -C 4 alkyl group or a hydroxyl group and R 4 represents a hydrogen atom or a hydroxyl group.
In the above formula (I), A represents an acyl group derived from vitamin A acid. The acyl group may be one derived from all trans-vitamin A acid having the formula (III) ##STR3## or one derived from 13-cis-vitamin A acid having the formula (IV) ##STR4##
X represents a hydroxyl group. R 1 and R 2 each represent hydrogen atoms or together form a carbon-carbon double bond.
R 3 represents a hydrogen atom, C 1 -C 4 alkyl group or a hydroxyl group. The alkyl group may be straight or branched and include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl
R 4 represents a hydrogen atom or a hydroxyl group.
In the above formula (I), X can be bonded to the asymmetric carbon atom to form α- or β-configuration.
In case where R 3 is a C 1 -C 4 alkyl group or a hydroxyl group, it can be bonded to the asymmetric carbon atom to form R- or S-configuration.
In case where R 1 and R 2 together form the carbon-carbon double bond, it can be trans or cis form.
The 1-hydroxyvitamin D derivatives (I) can be prepared by protecting hydroxyl groups existing in 3β-acetoxy-1-hydroxyvitamin D (V) to give the compound (VI), deacetylating the latter compound to afford the compound (VII), subjecting the latter compound to esterification with vitamin A acid to obtain the compound (VIII) and then eliminating the hydroxyl-protecting group in the compound (VIII). The above process can be illustrated by the following reaction sequence: ##STR5##
In the above formulae, A, X and R have the same meanings as defined above, X' represents a protected hydroxyl group and R' represents a group of the formula (IX) ##STR6##
In the above formula (IX), R 1 and R 2 have the same meanings as defined above, R' 3 represents a hydrogen atom, a C 1 -C 4 alkyl group or a protected hydroxyl group and R' 4 represents a hydrogen atom or a protected hydroxyl group.
The hydroxyl-protecting groups in R' 3 and R' 4 are desirably such groups that can chemically be distinguished from the acetyl group of the 3-position and can easily be eliminated without decomposing the forms of vitamin A and vitamin D. Preferable examples of such groups include a t-butyldimethylsilyl group or a triethylsilyl group. The above compound (V) is a known compound disclosed in Deluca, J. Org. Chem. 45, 3253 (1980).
The compound (VI) can be prepared by protecting the free hydroxyl groups existing in the compound (V) by a conventional means. For example, the compound (VI) can be obtained by reacting the compound (V) with t-butyldimethylsilyl chloride or triethylsilyl chloride in the presence of a weak base such as imidazole in an inert organic solvent such as dimethylformamide.
The compound (VII) can be prepared by selectively eliminating the 3-acetyl group of the compound (VI) by a conventional means. For instance, the compound (VII) can be obtained by treating the compound (VI) with an alkali such as sodium or potassium hydroxide in a lower alcohol such as methanol and ethanol.
The compound (VIII) can be prepared by reacting the compound (VII) with vitamin A acid or its reactive derivatives by a conventional means. For instance, the compound (VIII) can be obtained by reacting the compound (VII) with vitamin A acid in the presence of a dehydrating agent such as dicyclohexylcarbodiimide or trifluoroacetic anhydride in an inert organic solvent such as isopropyl ether and tetrahydrofuran. Alternatively, it can be obtained by reacting the compound (VII) with a reactive derivative of vitamin A, for example, the acid halide or the acid anhydride. It is desirable to carry out the reaction in mild reaction conditions in order to retain the geometrical isomerism of the double bond of vitamin A acid and to prevent isomerization and ring closure. In view of the point, there can preferably be used trifluoroacetic anhydride.
The compound (I) can be obtained by eliminating the hydroxy-protecting groups in the compound (VIII) by a conventional means. For example, it can be prepared by treating the compound (VIII) with a weak base such as tetrabutylammonium fluoride in an inert organic solvent, e.g., tetrahydrofuran.
The product obtained in each of the above reactions can be purified by a conventional means. For instance, a solvent used in the reaction is distilled off from the reaction mixture and the resulting residue is purified by recrystallization or chromatography. Alternatively, the reaction mixture is extracted with a proper organic solvent and the solvent is distilled off from the extract and the resulting residue is purified by recrystallization or chromatography.
The compound (VIII) obtained by the acylation of the compound (VII) with vitamin A acid is desirably used in the next eliminating step without purification.
Examples of the compounds (I) and its intermediates (V)-(VIII) are listed in the following Tables 1-5. The compound numbers in the tables are referred to in Examples below.
"Double bond" appearing in Tables 1-5 represents that R 1 and R 2 together form trans-double bond.
In Tables 3-5, Z represents a t-butyldimethylsilyl group and Z' represents a triethylsilyl group.
TABLE 1______________________________________The compounds (I) ##STR7## (I) ##STR8## (II)Com-pound No. A X R.sub.1 R.sub.2 R.sub.3 R.sub.4______________________________________I-1 Acyl group α-OH H H H H (III) (all-trans)I-2 Acyl group β-OH " " " " (III) (all-trans)I-3 Acyl group α-OH double bond CH.sub.3 (R) H (III) (all-trans)I-4 Acyl group β-OH " " " (III) (all-trans)I-5 Acyl group α-OH H H H OH (III) (all-trans)I-6 Acyl group β-OH " " " " (III) (all-trans)I-7 Acyl group α-OH double bond CH.sub.3 (S) OH (III) (all-trans)I-8 Acyl group β-OH " " " (III) (all-trans)I-9 Acyl group α-OH H H OH(R) H (III) (all-trans)I-10 Acyl group α-OH H H OH(S) OH (III) (all-trans)I-11 Acyl group α-OH H H H H (IV) (13-cis)I-12 Acyl group β-OH " " " " (IV) (13-cis)I-13 Acyl group α-OH double bond CH.sub.3 (R) H (IV) (13-cis)I-14 Acyl group β-OH " " " (IV) (13-cis)I-15 Acyl group α-OH H H H OH (IV) (13-cis)I-16 Acyl group β-OH " " " " (IV) (13-cis)I-17 Acyl group α-OH double bond CH.sub.3 (S) OH (IV) (13-cis)I-18 Acyl group β-OH " " " (IV) (13-cis)______________________________________
TABLE 2______________________________________The compounds (V) ##STR9## (V) ##STR10## (II)Compound No. X R.sub.1 R.sub.2 R.sub.3 R.sub.4______________________________________V-1 α-OH H H H HV-2 β-OH " " " "V-3 α-OH double bond CH.sub.3 (R) HV-4 β-OH " " "V-5 α-OH H H H OHV-6 β-OH " " " "V-7 α-OH double bond CH.sub.3 (S) OHV-8 β-OH " " "V-9 α-OH H H OH(R) HV-10 α-OH H H OH(S) OH______________________________________
TABLE 3______________________________________The compounds (VI) ##STR11## (VI) ##STR12## (IX)Compound No. X' R.sub.1 R.sub.2 R.sub.3 ' R.sub.4 '______________________________________VI-1 α-OZ H H H HVI-2 β-OZ " " " "VI-3 α-OZ double bond CH.sub.3 (R) HVI-4 β-OZ " " "VI-5 α-OZ' H H H OZ'VI-6 β-OZ' " " " "VI-7 α-OZ' double bond CH.sub.3 (S) OZ'VI-8 β-OZ' " " "VI-9 α-OZ' H H OZ'(R) HVI-10 α-OZ' H H OZ'(S) OZ'______________________________________
TABLE 4______________________________________The compounds (VII) ##STR13## (VII) ##STR14## (IX)Compound No. X' R.sub.1 R.sub.2 R.sub.3 ' R.sub.4 '______________________________________VII-1 α-OZ H H H HVII-2 β-OZ " " " "VII-3 α-OZ double bond CH.sub.3 (R) HVII-4 β-OZ " " "VII-5 α-OZ' H H H OZ'VII-6 β-OZ' " " " "VII-7 α-OZ' double bond CH.sub.3 (S) OZ'VII-8 β-OZ' " " "VII-9 α-OZ' H H OZ'(R) HVII-10 α-OZ' H H OZ'(S) OZ'______________________________________
TABLE 5______________________________________The compounds (VIII) ##STR15## (VIII) ##STR16## (IX)Com-pound No. A X' R.sub.1 R.sub.2 R.sub.3 ' R.sub.4 '______________________________________VIII-1 Acyl group α-OZ H H H H (III) (all-trans)VIII-2 Acyl group β-OZ " " " " (III) (all-trans)VIII-3 Acyl group α-OZ double bond CH.sub.3 (R) H (III) (all-trans)VIII-4 Acyl group β-OZ " " " (III) (all-trans)VIII-5 Acyl group α-OZ' H H H OZ' (III) (all-trans)VIII-6 Acyl group β-OZ' " " " " (III) (all-trans)VIII-7 Acyl group α-OZ' double bond CH.sub.3 (S) OZ' (III) (all-trans)VIII-8 Acyl group β-OZ' " " " (III) (all-trans)VIII-9 Acyl group α-OZ' H H OZ'(R) H (III) (all-trans)VIII-10 Acyl group α-OZ' H H OZ'(S) OZ' (III) (all-trans)VIII-11 Acyl group α-OZ H H H H (IV) (13-cis)VIII-12 Acyl group β-OZ " " " " (IV) (13-cis)VIII-13 Acyl group α-OZ double bond CH.sub.3 (R) H (IV) (13-cis)VIII-14 Acyl group β-OZ " " " (IV) (13-cis)VIII-15 Acyl group α-OZ' H H H OZ' (IV) (13-cis)VIII-16 Acyl group β -OZ' " " " " (IV) (13-cis)VIII-17 Acyl group α-OZ' double bond CH.sub.3 (S) OZ' (IV) (13-cis)VIII-18 Acyl group β-OZ' " " " (IV) (13-cis)______________________________________
The compounds (I) show superior activities on preventing or treating osteoporosis, cutaneous ulcers and tumors.
The 1-hydroxyvitamin D derivatives (I) may be administered orally or parenterally in dosages of from 0.1 μg to 100 μg daily to the human adult in divided doses. The compounds (I) may be compounded and formulated into pharmaceutical preparations in unit dosage form for oral or parenteral administration with organic or inorganic solid materials or liquids which are pharmaceutically acceptable carriers, for example, calcium carbonate, starch, sucrose, lactose, talc, magnesium stearate and the like.
The compounds (I) can be formulated in admixture with pharmaceutcal carriers or excipients by a conventional method into tablets, powders, capsules or granules. In addition to the above-mentioned solid preparations, the compounds (I) may also be formulated into liquid preparations such as injectable oily suspensions or syrups or ointment preparations.
The following examples are intended to illustrate the invention more specifically, but are not to be construed as limiting the scope thereof.
EXAMPLE 1
Preparation of 1α-hydroxycholecalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-1)
(1) Preparation of 3β-acetoxy-1α-t-butyldimethylsilyloxy-vitamin D 3 (Compound VI-1)
To a solution of Compound V-1 (600 mg) dissolved in dimethylformamide (5 ml) were added t-butyldimethylsilylchloride (300 mg) and imidazole (300 mg). The mixture was maintained at 40° C. for one hour followed by extraction with ether and washing with brine. The ether was removed by distillation, and the residue was purified by chromatography on silica gel (hexane/ethyl acetate=95/5) to give 620 mg of the title Compound VI-1 (oil).
1 H-NMR (CDCl 3 ): δ2.03 (3H, s, COCH 3 ), 4.36 (1H, m, H-1), 4.93 (1H, s, 19-Z), 5.21 (1H, m, H-3), 5.27 (1H, s, 19-E), 6.05, 6.32 (2H, ABq, J=12.0 Hz, H-6H-7)
(2) Preparation of 1α-t-butyldimethylsilyloxyvitamin D 3 (Compound VII-1)
To a solution of Compound VI-1 (500 mg) dissolved in ethanol (5 ml) was added a 10% ethanolic solution of potassium hydroxide (0.5 ml). The mixture was stirred at room temperature for 30 min. followed by extraction with ethyl acetate and washing with brine. The solvent was removed by distillation, and the residue was purified by chromatography on silica gel (hexane/ethyl acetate=9/1) to give 410 mg of the title Compound VII-1 (oil).
1 H-NMR (CDCl 3 ): δ4.24 (1H, m, H-3), 4.40 (1H, m, H-1), 4.93 (1H, s, 19-Z), 5.30 (1H, s, 19-E), 6.04, 6.35 (2H, ABq, J=12.1 Hz, H-6, H-7)
(3) Preparation of 1α-hydroxycholecalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-1)
To a mixture of all-trans vitamin A acid (300 mg) and isopropyl ether (3 ml) was dropwise added trifluoroacetic anhydride (0.18 ml). The mixture was stirred for 30 min. To the reaction mixture was dropwise added a tetrahydrofuran solution (5 ml) of Compound VII-1 (400 mg) followed by stirring at room temperature for 2 hours. Addition of aqueous ammonia (0.5 ml), extraction with ether, washing with brine followed by removal of the ether and purification of the residue by chromatography on silica gel (hexane/ethyl acetate=95/5) yielded 490 mg of Compound VIII-1. To a solution of the compound in tetrahydrofuran (5 ml) was added a 1M solution of tetrabutylammonium fluoride (called Bu 4 NF herein below)(3 ml). Stirring at room temperature for 3 hours followed by extraction with ethyl acetate, washing with brine, removal of the ethyl acetate by distillation and purification of the residue by chromatography on silica gel (hexane/ethyl acetate =9/1) afforded 340 mg of the title Compound I- 1.
1 -NMR (CDCl 3 ): δ0.55 (3H, s), 0.87 (3H, s), 0.89 (3H, s), 0.93 (3H, d), 1.03 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.43 (1H, m), 5.00 (1H, s), 5.28 (1H, m), 5.34 (1H, s), 5.74 (1H, s), 6.00-6.36 (6H, m), 7.01 (1H, m)
EXAMPLE 2
Preparation of 1β-hydroxycholecalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-2)
Compound VII-2 was obtained from Compound V-2 via Compound VI-2 in the same procedures as in Example 1(1) and (2).
Compound VII-2 (300 mg) was treated in the same way as in Example 1 to give 220 mg of Compound I-2.
1 H-NMR (CDCl 3 ): δ0.55 (3H, s), 0.87 (3H, s), 0.89 (3H, s), 0.93 (3H, d), 1.03 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.20 (1H, m), 5.00 (1H, m) s), 5.04 (1H, m), 5.36 (1H, s), 5.74 (1H, s), 6.00-6.36 (6H, m), 7.01 (1H, m)
EXAMPLE 3
Preparation of 1-hydroxyergocalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-3)
(1) Preparation of 3β-acetoxy-1α-t-butyldimethylsilyloxy-vitamin D 2 (Compound VI-3)
Compound V-3 (400 mg) was treated in the same way as in Example 1(1) to give 410 mg of the title Compound VI-3 (oil).
1 H-NMR (CDCl 3 ): δ2.03 (3H, s, COCH 3 ), 4.37 (1H, m, H-1), 4.93 (1H, s, 19-Z), 5.21 (3H, m, H-3, H-22, H-23), 5.29 (1H, s, 19-E), 6.06, 6.31 (2H, ABq, J=12.1 Hz, H-6, H-7)
(2) Preparation of 1α-t-butyldimethylsilyloxyvitamin D 2 (Compound VII-3)
Compound VI-3 (300 mg) was treated in the same way as in Example 1(2) to afford 250 mg of the title compound VII-3 (oil).
1 H-NMR (CDCl 3 ): δ4.26 (1H, m, H-3), 4.40 (1H, m, H-1), 4.94 (1H, s, 19-Z), 5.23 (2H, m, H-22, H-23), 5.29 (1H, s, 19-E), 6.06, 6.37 (2H, ABq, J=12.1 Hz, H-6, H-7)
(3) Preparation of 1α-hydroxyergocalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-3)
To a mixture of all-trans vitamin A cid (200 mg) and isopropyl ether (2 ml) was added trifluoroacetic anhydride (0.13 ml). The mixture was stirred at room temperature for 15 min. Then a tetrahydrofuran solution (5 ml) of Compound VII-3 (280 mg) was dropwise added, and the mixture was allowed to stand overnight at 5° C. Aqueous ammonia (0.4 ml) was added, and the mixture was stirred for 30 min. and extracted with ether. Washing with brine, subsequent removal of the ether and chromatographing of the residue on silica gel (hexane/ethyl acetate=9/1) afforded 310 mg of Compound VIII-3. To a solution of the compound in tetrahydrofuran (4 ml) was then added a 1M solution of Bu 4 NF (2 ml), and the mixture was stirred at room temperature for 4 hours. Extraction with ethyl acetate, washing with brine, removal of the ethyl acetate by distillation and purification of the residue by chromatography on silica gel (hexane/ethyl acetate=9/1) yielded 220 mg of the title Compound I-3.
1 H-NMR (CDCl 3 ): δ0.55 (3H, s), 0.82 (3H, d), 0.84 (3H, d), 0.92 (3H, d), 1.01 (3H, d), 1.03 (6H, s), 1.71 (3H, s), 2.00 (3H, s), 2.35 (3H, s), 4.44 (1H, m), 5.01 (1H, s), 5.22 (2H, m), 5.28 (1H, m), 5.34 (1H, s), 5.76 (1H, s), 6.01-6.35 (6H, m), 7.00 (1H, m)
EXAMPLE 4
Preparation of 1β-hydroxyergocalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-4)
Compound VII-4 was prepared from Compound V-4 via Compound VI-4 in the same procedures as in Example 3(1) and (2).
Compound VII-4 (200 mg) was treated in the same way as in Example 3(3) to obtain 150 mg of the title Compound I-4.
1 H-NMR (CDCl 3 ): δ0.55 (3H, s), 0.82 (3H, d), 0.84 (3H, d), 0.92 (3H, d), 1.01 (3H, d), 1.03 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.20 (1H, m), 5.01 (1H, s), 5.04 (1H, m), 5.22 (2H, m), 5.37 (1H, s), 5.74 (1H, s), 6.00-6.36 (6H, m), 7.01 (1H, m)
EXAMPLE 5
Preparation of 1α,25-dihydroxycholecalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-5)
Compound VII-5 was prepared from Compound V via Compound VI-5 in the same procedures as in Example 3(1) and (2), except that triethylsilyl chloride was used instead of t-butyldimethylsilyl chloride in Example 3(1).
To a mixture of all-trans vitamin A acid (200 mg) and isopropyl ether (3 ml) was dropwise added trifluoroacetic anhydride (0.1 ml). and the mixture was stirred for 30 min. Then, a tetrahydrofuran solution (5 ml) of Compound VII-5 (270 mg) was added followed by stirring at room temperature for 2 hours. Addition of aqueous ammonia (0.5 ml), extraction with ether, washing with brine, subsequent removal of the ether by distillation and purification of the residue by chromatography on silica gel (hexane/ethyl acetate=95/5) afforded 330 mg of Compound VIII-5. To a solution of Compound VIII-5 (330 mg) in tetrahydrofuran (5 ml) was added a 1M solution of Bu 4 NF (3 ml), and the mixture was stirred at 50° C. for 1 hour. Extraction with ethyl acetate, washing with brine, subsequent removal of the solvent and purification of the residue by chromatography on silica gel (hexane/ethyl acetate=4/1) yielded 190 mg of the title Compound I-5.
1 H-NMR (CDCl 3 ): δ0.54 (3H, s), 0.94 (3H, d), 1.03 (6H, s), 1.21 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.42 (1H, m), 5.00 (1H, s), 5.27 (1H, m), 5.35 (1H, s), 5.74 (1H, s), 6.00-6.37 (6H, m), 7.01 (1H, m)
EXAMPLE 6
Preparation of 1β,25-dihydroxycholecalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-6)
Compound VII-6 was prepared from Compound V-6 via Compound VI-6 in the same procedures as in Example 5(1) and (2).
Compound VII-6 (200 mg) was treated in the same way as in Example 3(3) to give 90 mg of the title Compound I-6.
1 H-NMR (CDCl 3 ): δ0.53 (3H, s), 0.94 (3H, d), 1.03 (6H, s), 1.20 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.20 (1H, m), 5.00 (1H, s), 5.04 (1H, m), 5.36 (1H, s), 5.74 (1H, s), 6.00-6.36 (6H, m), 7.01 (1H, m)
EXAMPLE 7
Preparation of 1α25-dihydroxyergocalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-7)
Compound VII-7 was prepared from Compound V-7 via Compound VI-7 in the same procedures as in Example 5(1) and (2).
Compound VII-7 (400 mg) was treated in the same way as in Example 3(3) to afford 290 mg of the title Compound I-7.
1 H-NMR (CDCl 3 ): δ0.54 (3H, s), 0.93 (3H, d), 1.00 (3H, d), 1.03 (6H, s), 1.16 (3H, s), 1.17 (3H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.42 (1H, m), 5.00 (1H, s), 5.22 (2H, m), 5.27 (1H, m), 5.35 (1H, s), 5.74 (1H, s), 6.00-6.36 (6H, m), 7.02 (1H, m)
EXAMPLE 8
Preparation of 1β, 25-dihydroxyergocalciferol Vitamin A Acid (All-trans Form) Ester (Compound I-8)
Compound VII-8 was prepared from Compound V-8 via Compound VI-8 in the same procedures in Example 5(1) and (2).
Compound VII-8 (250 mg) was treated in the same way as in Example 3(3) to obtain 120 mg of the title Compound I-8.
1 H-NMR (CDCl 3 ): δ0.53 (3H, s), 0.94 (3H, d), 1.01 (3H, d), 1.02 (6H, s), 1.15 (3H, s), 1.17 (3H, s), 1.70 (3H, s), 2.01 (3H, s), 2.34 (3H, s), 4.19 (1H, m), 5.01 (1H, s), 5.04 (1H, m), 5.23 (2H, m), 5.36 (1H, s), 5.75 (1H, s), 6.00-6.36 (6H, m), 7.00 (1H, m)
EXAMPLE 9
Preparation of 1α,24R-dihydroxycholecalciferol Vitamin A (All-trans Form) Ester (Compound I-9)
Compound VII-9 was prepared from Compound V-9 via Compound VI-9 in the same procedures as in Example 5(1) and (2).
Compound VII-9 (140 mg) was treated in the same way as in Example 3(3) to give 100 mg of the title Compound I-9.
1 H-NMR (CDCl 3 ): δ0.56 (3H, s), 0.96 (3H, d), 1.03 (6H, s), 1.17 (6H, d), 1.70 (3H, s), 2.01 (3H, s), 2.36 (3H, s), 3.22 (1H, m), 4.40 (1H, m), 4.97 (1H, s), 5.27 (1H, m), 5.33 (1H, s), 5.74 (1H, s), 6.00-6.38 (6H, m), 7.01 (1H, m)
EXAMPLE 10
Preparation of 1α,24S,25-trihydroxycholecalciferol Vitamin A (All-trans Form) Ester (Compound I-10)
Compound VII-10 was prepared from Compound V-10 via Compound VI-10 in the same procedures as in Example 5(1) and (2).
Compound VII-10 (80 mg) was treated in the same way as in Example 3(3) to afford the title Compound I-10 (35 mg).
1 H NMR (CD 3 OD--CDCl 3 ): δ0.57 (3H, s), 0.97 (3H, d), 1.03 (6H, s), 1.21 (6H, d), 1.70 (3H, s), 2.01 (3H, s), 2.37 (3H, s), 3.25 (1H, m), 4.41 (1H, m), 4.97 (1H, s), 5.26 (1H, m), 5.33 (1H, s), 5.74 (1H, s), 6.01-6.39 (6H, m), 7.01 (1H, m)
EXAMPLE 11
Preparation of 1α-hydroxycholecalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-11)
Compound VII-11 was prepared from Compound V-11 via Compound VI-11 in the same procedures as in Example 3(1) and (2).
Compound VII-11 (100 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (100 mg) to give 95 mg of the title Compound I-11.
1 H-NMR (CDCl 3 ): δ0.54 (3H, s), 0.86 (3H, s), 0.87 (3H, s), 0.92 (3H, d), 1.03 (6H, s), 1.71 (3H, s), 2.03 (3H, s), 2.17 (3H, s), 4.43 (1H, m), 5.00 (1H, m), 5.30 (1H, m), 5.35 (1H, m), 5.95 (1H, s), 6.01-6.32 (5H, m), 7.04 (1H, d), 7.85 (1H, d)
EXAMPLE 12
Preparation of 1β-hydroxycholecalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-12)
Compound VII-12 was prepared from Compound V-12 via Compound VI-12 in the same procedures as in Example 3(1) and (2).
Compound VII-12 (50 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (60 mg) to obtain 30 mg of the title Compound I-12.
1 H-NMR (CDCl 3 ): δ0.54 (3H, s), 0.86 (3H, s), 0.87 (3H, s), 0.92 (3H, d), 1.03 (6H, s), 1.71 (3H, s), 2.03 (3H, s), 2.17 (3H, s), 4.20 (1H, m), 5.01 (1H, m), 5.05 (1H, m), 5.35 (1H, m), 5.95 (1H, s), 6.01-6.33 (5H, m), 7.04 (1H, d), 7.86 (1H, d)
EXAMPLE 13
Preparation of 1α-hydroxyergocalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-13)
Compound VII-13 was prepared from Compound V-13 via Compound VI-13 in the same procedures as in Example 3(1) and (2).
Compound VII-13 (60 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (50 mg) to give 30 mg of the title Compound I-13.
1 H-NMR (CDCl 3 ): δ0.55 (3H, s), 0.82 (3H, d), 0.84 (3H, d), 0.92 (3H, d), 1.01 (3H, d), 1.03 (3H, s), 1.71 (3H, s), 2.03 (3H, s), 2.17 (3H, s), 4.44 (1H, m), 5.01 (1H, m), 5.28 (1H, m), 5.34 (1H, m), 5.20 (2H, m), 5.95 (1H, s), 6.00-6.35 (5H, m), 7.04 (1H, d), 7.84 (1H, d)
EXAMPLE 14
Preparation of 1β-hydroxyergocalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-14)
Compound VII-14 was prepared from Compound V-14 via Compound VI-14 in the same procedures as in Example 3(1) and (2).
Compound VII-14 (60 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (50 mg) to give 25 mg of the title Compound I-14.
1 H-NMR (CDCl 3 ): δ0.55 (3H, s), 0.82 (3H, d), 0.84 (3H, d), 0.92 (3H, d), 1.01 (3H, d), 1.03 (6H, s), 2.03 (3H, s), 2.17 (3H, s), 4.21 (1H, m), 5.00 (1H, m), 5.04 (1H, m), 5.22 (2H, m), 5.36 (1H, m), 5.95 (1H, s), 6.01-6.35 (5H, m), 7.05 (1H, d), 7.87 (1H, d)
EXAMPLE 15
Preparation of 1α,25-dihydroxycholecalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-15)
Compound VII-15 was prepared from Compound V-15 via Compound VI-15 in the same procedures as in Example 5(1) and (2).
Compound VII-15 (60 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (50 mg) to give 40 mg of the title Compound I-15.
1 H-NMR (CDCl 3 ): δ0.54 (3H, s), 0.94 (3H, d), 1.03 (6H, s), 1.21 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.42 (1H, m), 5.00 (1H, s), 5.27 (1H, m), 5.35 (1H, s), 5.94 (1H, s), 6.01-6.35 (5H, m), 7.05 (1H, d), 7.86 (1H, d)
EXAMPLE 16
Preparation of 1β,25-dihydroxycholecalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-16)
Compound VII-16 was prepared from Compound V-16 via Compound VI-16 in the same procedures as in Example 5(1) and (2).
Compound VII-16 (60 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (50 mg) to give 25 mg of the title Compound I-16.
1 H-NMR (CDCl 3 ): δ0.53 (3H, s), 0.94 (3H, d), 1.03 (6H, s), 1.20 (6H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.21 (1H, m), 5.00 (1H, s), 5.04 (1H, m), 5.36 (1H, s), 5.95 (1H, s), 6.01-6.34 (5H, m), 7.04 (1H, d), 7.87 (1H, d)
EXAMPLE 17
Preparation of 1α,25-dihydroxyergocalciferol Vitamin A Acid (13-cis Form) Ester (Compound I-17)
Compound VII-17 was prepared from Compound V-17 via Compound VI-17 in the same procedures as in Example 5(1) and (2).
Compound VII-17 (60 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (50 mg) to afford 45 mg of the title Compound I-17.
1 H-NMR (CDCl 3 ): δ0.54 (3H, s), 0.93 (3H, d), 1.00 (3H, d), 1.03 (6H, s), 1.16 (3H, s), 1.17 (3H, s), 1.71 (3H, s), 2.01 (3H, s), 2.35 (3H, s), 4.42 (1H, m), 5.00 (1H, s), 5.23 (2H, m), 5.27 (1H, m), 5.35 (1H, s), 5.95 (1H, s), 6.01-6.34 (5H, m), 7.05 (1H, d), 7.86 (1H, d)
EXAMPLE 18
Preparation of 1β,25-dihydroxyergocalciferol Vitamin A (13-cis Form) Ester (Compound I-18)
Compound VII-18 was prepared from Compound V-18 via Compound VI-18 in the same procedures as in Example 5(1) and (2).
Compound VII-18 (60 mg) was treated in the same way as in Example 3(3) except that the all-trans vitamin A acid used therein was replaced by 13-cis-vitamin A acid (50 mg) to afford 30 mg of the title Compound I-18.
1 H-NMR (CDCl 3 ): δ0.53 (3H, s), 0.94 (3H, d), 1.00 (3H, d), 1.02 (6H, s), 1.16 (3H, s), 1.17 (3H, s), 1.70 (3H, s), 2.01 (3H, s), 2.34 (3H, s), 4.19 (1H, m), 5.01 (1H, s), 5.04 (1H, m), 5.23 (2H, m), 5.36 (1H, s), 5.95 (1H, s), 6.00-6.34 (5H, m), 7.04 (1H, d), 7.87 (1H, d) | 1-Hydroxyvitamin D derivatives which are esters of 1-hydroxyvitamin D with vitamin A acid. They are useful for an agent for preventing and treating osteoporosis, cutaneous ulcer and tumor. | 2 |
BACKGROUND OF THE INVENTION
The invention relates to methods and apparatus for metal casting, and more particularly to methods and apparatus for casting an air cooled cylinder head in a lost foam casting process. Even more particularly, the invention relates to foam patterns and methods for making foam patterns for casting an air cooled cylinder head in a lost foam casting process.
A foam mold pattern for use in a lost foam casting process is commonly formed by injecting polystyrene beads into a mold having a cavity with the shape of the desired foam pattern. While the polystyrene beads can theoretically have any size, the most readily available and by far most economical size is that used in forming styrofoam cups. Smaller beads are much more expensive, or even unobtainable. When using conventional methods, it is difficult if not impossible to obtain satisfactory "fill out" of a foam pattern, or of the passages of a mold cavity used in forming a foam pattern, if any portion of the foam pattern having a significant length (one inch, for example) has a thickness of less than three to four times the diameter of the beads being used to form the pattern. When using conventionally sized beads, it is difficult to fill out pattern portions having a thickness of less than 0.180 inches
A thickness of 0.180 inches is too thick for effective cooling fins on an air cooled cylinder head. Thus, a foam pattern for an air cooled cylinder head with satisfactorily thin cooling fins cannot be formed by molding the pattern in one piece, because the "fins" of the pattern will not satisfactorily fill out.
It is known in the lost foam casting art to form a foam pattern by gluing various pieces of a pattern together.
Attention is directed to the following United States patents which relate to casting with evaporative patterns and to casting of engine parts:
______________________________________Ernest 4,197,899 April 15, 1980Erdle 2,461,416 February 8, 1949Wittmoser 3,302,256 February 7, 1967Boyle 3,898,654 November 19, 1974Witchell 4,015,654 April 5, 1977Bretzger 4,231,413 November 4, 1980Trumbauer Re.31,488 January 10, 1984Trumbauer 4,462,453 July 31, 1984______________________________________
SUMMARY OF THE INVENTION
The invention provides a method of fabricating a foam mold pattern for forming an air cooled cylinder head in a lost foam casting process, the cylinder head including a cooling fin, the method comprising the steps of: fabricating a foam mold pattern fin portion including a cooling fin, fabricating a foam mold pattern main portion, and attaching the fin portion to the main portion.
In one embodiment, the first fabricating step includes the steps of providing a mold including a cavity having the shape of the fin portion, the mold cavity including a fin cavity portion having a base, and injecting foam particles into the mold cavity at a point adjacent the base of the fin cavity portion.
In one embodiment, the first fabricating step includes the steps of providing foam particles having a diameter, providing a mold comprising a cavity having the shape of the fin portion and including a fin cavity portion having a base, a thickness of approximately two particle diameters, and a length of approximately one inch, and injecting the foam particles into the mold cavity at a point adjacent the base of the fin cavity portion.
In one embodiment, the attaching step includes the step of gluing the fin portion to the main portion.
In one embodiment, the first fabricating step includes the step of fabricating a fin portion including a plurality of cooling fins.
The invention also provides a method of fabricating a foam mold pattern for forming an air cooled cylinder head in a lost foam casting process, the cylinder head including an exhaust port, an exhaust passage, an inlet port, an inlet passage, and a cooling fin, the method comprising the steps of: fabricating a foam mold pattern fin portion including a cooling fin by providing foam particles having a diameter, providing a mold comprising a cavity having the shape of the fin portion and including a fin cavity portion having a base, a thickness of approximately two particle diameters, and a length of approximately one inch, and by injecting the foam particles into the mold cavity at a point adjacent the base of the fin cavity portion, fabricating a foam mold pattern main portion including an exhaust port, an exhaust passage, an inlet port, and an inlet passage, and gluing the fin portion to the main portion.
The invention also provides a foam mold pattern for casting an air cooled cylinder head in a lost foam casting process, the foam mold pattern comprising a foam mold pattern main portion forming a cylinder head, and a foam mold pattern fin portion attached to the main portion and including a cooling fin.
In one embodiment, the pattern is made of foam particles having a diameter, and the cooling fin has a thickness of approximately two particular diameters and a length of approximately one inch.
In one embodiment, the main portion includes a first subportion, and a second subportion attached to the first subportion, and the fin portion is attached to the first subportion.
In one embodiment, the pattern further comprises a second fin portion attached to the first subportion, and the second subportion is attached to the first subportion and to the second fin portion.
In one embodiment, the first subportion includes an intake port, a portion of an intake passage, a portion of an exhaust port, and a portion of an exhaust passage, the second fin portion includes a portion of the exhaust port and a portion of the exhaust passage, and the second subportion includes a portion of the exhaust passage and a portion of the intake passage.
A principal feature of the invention is the provision of a method comprising the steps of fabricating a foam mold pattern fin portion including a cooling fin by providing a mold comprising a cavity having the shape of the fin portion and including a fin cavity portion having a base, and by injecting foam particles into the mold cavity at a point adjacent the base of the fin cavity portion, fabricating a foam mold pattern main portion, and attaching the fin portion to the main portion. This method produces a foam pattern for an air cooled cylinder head with satisfactorily thin cooling fins, since it allows the forming of pattern portions having a thickness of approximately two bead diameters rather than three to four bead diameters. When using conventionally sized beads, this method can produce cooling fins having a length of approximately one inch and a thickness of approximately 0.090 inches.
Another principal feature of the invention is the provision of a foam mold pattern for casting an air cooled cylinder head in a lost foam process, the foam mold pattern comprising a foam mold pattern main portion forming a cylinder head, and a foam mold pattern fin portion attached to the main portion and including one or more a cooling fins.
Other features and advantages of the invention will become apparent to those skilled in the art upon review of the following detailed description, claims, and drawings.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a foam mold pattern embodying the invention.
FIG. 2 is an exploded view of the foam mold pattern.
FIG. 3 is a cross-sectional view of a mold used in forming a fin portion of the foam mold pattern.
FIG. 4 is a side view, taken along line 4--4 in FIG. 2, of one of the fin portions of the foam mold pattern.
FIG. 5 is a bottom view of the upper subportion of the main portion of the pattern.
FIG. 6 is a bottom view of the pattern.
Before one embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangements of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or being carried out in various ways. Also, it is to be understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A foam mold pattern 10 embodying the invention is illustrated in the drawings. While it is to be understood that the foam pattern 10 is not a cylinder head, but rather a foam pattern having structure identical to a cylinder head to be made therewith, the foam pattern 10 will be described using the terminology that would be used in describing a cylinder head. For example, the passage in the foam pattern 10 that corresponds to the exhaust passage of the cylinder head will be referred to as the exhaust passage of the foam pattern 10.
As best shown in FIG. 6, a bottom view, the foam pattern 10 includes a downwardly opening inlet port 12 and a downwardly opening exhaust port 14. The foam pattern 10 also includes an inlet passage 16 communicating between the inlet port 12 and an inlet opening 18, and an exhaust passage 20 communicating between the exhaust port 14 and an exhaust opening 21 (FIG. 1). The foam pattern 10 further includes first and second sets of cooling fins 26 and 28 (FIG. 1) having a thickness of approximately 0.090 inches and a length of approximately one inch.
The foam pattern 10 comprises a main portion including a first or lower subportion 30 including the intake port 12 and a portion of the exhaust port 14, as best shown in FIGS. 2 and 6. The first subportion 30 also includes a lower portion of the inlet passage 16, and a portion of the exhaust passage 20, as best shown in FIG. 2. The first subportion 30 has a generally flat upper surface 32, a side surface 34 located adjacent the exhaust port 14 and exhaust passage 20, and a surface 35 located adjacent the inlet port 12 and inlet passage 16.
The main portion also includes a second or upper subportion 36 including an upper portion of the inlet passage 16, and an upper portion of the exhaust passage 20, as best shown in FIG. 5. The second subportion 36 has a lower surface 42 which is generally flat and is adapted to mate with the upper surface 32 of the first subportion 30.
The foam pattern 10 further comprises a first fin portion 44 (FIG. 2) including the first set of cooling fins 26. The first fin portion 44 has a bottom surface 46 which is generally flat and is closely spaced from and parallel to the base of the cooling fins 26. The bottom surface 46 is adapted to mate with the surface 35 on the first subportion 30.
The foam pattern 10 further comprises a second fin portion 48 (FIGS. 2 and 4) including the second set of cooling fins 28, a portion of the exhaust port 14 (FIG. 2), and a lower portion of the exhaust passage 20. The second fin portion 48 has a bottom surface 50 which is generally flat and is closely spaced from and parallel to the base of the cooling fins 28. The bottom surface 50 is adapted to mate with the side surface 34 of the first subportion 30. The second fin portion 48 also has an upper surface 52 adapted to mate with a portion of the lower surface 42 of the second subportion 36.
The exhaust port 14, exhaust passage 20, inlet port 12, and inlet passage 16 are divided among the first and second subportions 30 and 36 and the second fin portion 48 as described above and as shown in the drawings in order to simplify fabrication of the pieces of the foam pattern 10 by simplifying the molds required for fabrication of those pieces.
In accordance with the method of the invention, each of the fin portions 44 and 48 is fabricated by providing a mold 54 (the mold of the first fin portion 44 is shown in FIG. 3) including a cavity 56 which has the shape of the desired fin portion, and which includes fin cavity portions corresponding to the cooling fins and having a base corresponding to the base of the cooling fins. The fin cavity portions have a thickness of approximately 0.100 inches, and a length of approximately 1 inch, these dimensions corresponding to the dimensions of the cooling fins. Fabrication of the fin portion is preferably completed by injecting foam particles having a diameter into the mold cavity 56 with a foam spray nozzle 58 at a point adjacent the base of the fin cavity portions. By this it is meant that the nozzle is placed such that the beads follow a relatively straight and short path into the fin cavity portions. If the beads must turn corners or travel too far to enter the fin cavity portions, they will lose kinetic energy and will not satisfactorily fill out the fin cavity portions. It has been found during testing that a relatively straight path is more important than a relatively short path. Thus, conventionally sized beads can travel more than two inches over a relatively straight path to fill out cooling fins having a thickness of 0.090 inches (approximately two particle diameters) and a length of one inch. It has also been found that fins having a length of greater than one inch can be filled out if the thickness is greater than 0.090 inches.
This method allows the fabrication of cooling fins having a thickness of approximately two particle diameters rather than three to four particle diameters.
The fabrication of the first fin portion 44 is illustrated in FIG. 3. The location of the nozzle used in fabricating the second fin portion 48 is illustrated by an X in FIG. 2.
The first and second subportions 30 and 36 of the main portion can be fabricated by using conventional processes used for forming foam patterns. When all four pieces of the foam pattern 10 have been fabricated, the foam pattern 10 is assembled by attaching the base 46 of the first fin portion 44 to the corresponding surface 35 on the first subportion 30, by attaching the base 50 of the second fin portion 48 to the corresponding side surface 34 of the first subportion 30, and by attaching the lower surface 42 of the second subportion 36 to the corresponding upper surfaces 32 and 52 of the first subportion 30 and second fin portion 48. Preferably, these pieces are attached by gluing the corresponding surfaces together, as is known in the art.
Various other features and advantages of the invention are set forth in the following claims. | A method of fabricating a foam mold pattern for forming an air cooled cylinder head in a lost foam casting process, the cylinder head including a cooling fin, the method comprising the steps of: fabricating a foam mold pattern fin portion including a cooling fin, fabricating a foam mold pattern main portion, and attaching the fin portion to the main portion. | 1 |
CROSS-REFERENCES TO RELATED APPLICATIONS
This is a Divisional of co-pending application Ser. No. 13/960,696, filed on Aug. 6, 2013, which is incorporated herewith by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a compound and extract isolated from Antrodia camphorata , particularly relates to a method of inhibiting cancer cell growth by using the compound.
2. The Prior Arts
Antrodia camphorata is also called Chang-Zhi, Niu Chang-Zhi, red camphor mushroom and the like, which is a perennial mushroom belonging to the order Aphyllophorales, the family Polyporaceae. It is an endemic species in Taiwan growing on the inner rotten heart wood wall of Cinnamomum kanehirai Hay. Cinnamomum kanehirai Hay is rarely distributed and being overcut unlawfully, which makes Antrodia camphorata growing inside the tree in the wild became even rare. The price of Antrodia camphorata is very expensive due to the extremely slow growth rate of natural Antrodia camphorata that only grows between Junes to October.
The fruiting bodies of Antrodia camphorata are perennial, sessile, hard and woody, which exhales strong smell of sassafras (camphor aroma). The appearances are various with plate-like, bell-like, hoof-like, or tower-like shapes. They are reddish in color and flat when young, attached to the surface of wood. Then the brims of the front end become little curled tilted and extend to the surroundings. The color turns to be faded red-brown or cream yellow brown, with ostioles all over. This region is of very high medical value.
In traditional Taiwanese medicine, Antrodia camphorata is commonly used as an antidotal, liver protective, anti-cancer drug. Antrodia camphorata , like general edible and medicinal mushrooms, is rich in numerous nutrients including polysaccharides (such as β-glucosan), triterpenoids, superoxide dismutase (SOD), adenosine, proteins (immunoglobulins), vitamins (such as vitamin B, nicotinic acid), trace elements (such as calcium, phosphorus and germanium and so on), nucleic acid, agglutinin, amino acids, steroids, lignins and stabilizers for blood pressure (such as antodia acid) and the like. These physiologically active ingredients are believed to exhibit effects such as: anti-tumor activities, increasing immuno-modulating activities, anti-allergy, anti-bacteria, anti-high blood pressure, decreasing blood sugar, decreasing cholesterol and the like.
Triterpenoids are the most studied component among the numerous compositions of Antrodia camphorata . Triterpenoids are the summary terms for natural compounds, which contain 30 carbon atoms with the pent acyclic or hex acyclic structures. The bitter taste of Antrodia camphorata is from the component of triterpenoids. Three novel ergostane-type triterpenoids (antcin A, antcin B, antcin C) were isolated by Cherng et al. from the fruiting bodies of Antrodia camphorata (Cherng, I. H., and Chiang, H. C. 1995. Three new triterpenoids from Antrodia cinnamomea . J. Nat. Prod. 58:365-371). Three new compounds zhankuic acid A, zhankuic acid B and zhankuic acid were extracted from the fruiting bodies of Antrodia camphorata with ethanol by Chen et al. (Chen, C. H., and Yang, S. W. 1995. New steroid acids from Antrodia cinnamomea , —a fungus parasitic on Cinnamomum micranthum . J. Nat. Prod. 58:1655-1661). In addition, Cherng et al. also found three other new triterpenoids from the fruiting bodies of Antrodia camphorata , which are sesquiterpene lactone and 2 biphenyl derived compounds, 4,7-dimethoxy-5-methy-1,3-benzodioxole and 2,2′,5,5′-teramethoxy-3,4,3′,4′-bi-methylenedioxy-6,6′-dimethylbiphenyl (Chiang, H. C., Wu, D. P., Chemg, I. W., and Ueng, C. H. 1995. A sesquiterpene lactone, phenyl and biphenyl compounds from Antrodia cinnamomea . Phytochemistry. 39:613-616). In 1996, four novel ergostane-type triterpenoids (antcins E and F and methyl antcinates G and H) were isolated by Chemg et al. with the same analytic methods (Cherng, I. H., Wu, D. P., and Chiang, H. C. 1996. Triteroenoids from Antrodia cinnamomea . Phytochemistry. 41:263-267). And two ergostane related steroids, zhankuic acids D and E together with three lanosta related triterpenes, 15 alpha-acetyl-dehydrosulphurenic acid, dehydroeburicoic acid, dehydrosulphurenic acid were isolated by Yang et al. (Yang, S. W., Shen, Y. C., and Chen, C. H. 1996. Steroids and triterpenoids of Antrodia cinnamomea —a fungus parasitic on Cinnamomum micranthum . Phytochemistry. 41:1389-1392). Several compounds were continually found to play important roles for AMPK and TOR signal transduction pathway. Through activating AMPK and inhibiting mTOR translation pathway to reach a well control of G1 phase in tumor cells, and completely block development of tumor cells and cause a series of apoptosis.
SUMMARY OF THE INVENTION
Some extracts of Antrodia camphorata were proved to have the foregoing benefits, and their compounds were continually identified. However, for Antrodia camphorata extract, whether some compounds with anti-tumor bioactivity or medical use were existed needs further experiments to identify.
An object of the present invention is to provide a compound isolated from Antrodia camphorata , represented by formula I:
wherein R1 is a hydrogen atom or an acetyl group.
Preferably, R1 is a hydrogen atom, and the compound is represented by formula II:
Preferably, R1 is an acetyl group, and the compound is represented by formula III:
A further object of the present invention is to provide a method of inhibiting cancer cell growth by using the above compounds; the cancer is selected from the group consisting of lung cancer, colon cancer, prostate cancer, liver cancer and breast cancer.
A further object of the present invention is to provide an extract of Antrodia camphorata for inhibiting cancer cell growth, extracted by the following steps: extracting a fruiting body, mycelium, or the mixture thereof twice, with an ethanol solution with a ratio of 1:10 to obtain two ethanol extracts, concentrating the ethanol extracts to yield a crude extract, the crude extract being extracted three times with dichloromethane/water (1:1) to form a dichloromethane layer and a water layer, the dichloromethane layer being loaded to a layered silica gel column with hexane/dichloromethane (1:4), dichloromethane, and methanol/dichloromethane (5:95) to yield the extract.
Without further elaboration, it is believed that one skilled in the art can, based on the above description, utilize the present invention to its fullest extent. The following specific example is, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Antrodia camphorata Extract
Antrodia camphorata fruiting bodies, mycelium or their mixture were provided (1.0 kg) and then extracted twice with an 10-fold ethanol solution to obtain two ethanol extracts. The ethanol extracts were concentrated to yield 230 g crude extract (LE-E). The crude extract was extracted three times with dichloromethane/water (1:1) to form a dichloromethane layer (LT-E-D, 102.6 g) and a water layer (LT-E-W, 127.4 g). Dichloromethane layer (6.0 g) was loaded to a layered silica gel column with hexane/dichloromethane (1:4), dichloromethane, and methanol/dichloromethane (5:95) to yield four layers, respectively ANCA-E-D-1, ANCA-E-D-2, ANCA-E-D-3, and ANCA-E-D-4.
Anti Tumor Activity of Antrodia camphorata Extract
Cell proliferation of A549 cell line (lung cancer), CT26 cell line (colon cancer), DU145 cell line (prostate cancer), HepG2 cell line (liver cancer), MDCK cell line (kidney from canine), PC3 cell line (prostate cancer), MDA-MB-231 cell line (breast cancer) and MCF-7 cell line (breast cancer) was assessed by MTT cell viability assay. The results are shown in tables 1-8.
Above cell lines were cultured in determined medium for 24 hours. Proliferative cells were washed with PBS solution, treated with trypsin-EDTA (1×), centrifuged at 1,200 rpm for 5 min, precipitated the cells and discarded supernatant. The cells were resuspended with 10 ml of fresh medium, and then loaded to 96-well plate. While the assay initiated, 0.01˜200 μg/ml of Antrodia camphorata extract was added in each well, and the plate was incubated for 48 hours, at 37° C., 5% CO 2 . Each wall was added with 2.5 mg/ml MTT reagent in the dark. After 4 hours of reaction, 100 μl lysis buffer were added to each wall to terminate the reaction. Finally, absorbances were read with an ELISA reader in the wavelength of 570 nm, so as to calculate the cell viability and half maximal inhibitory concentration (IC50). The experiment data was represented by means±SD. All data was statistically analyzed by paired-t test, and a P-value less than 0.05 was considered significant.
TABLE 1
A549 cell line (lung cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
200
+++
+
+/−
+
+/−
+/−
+/−
+/−
++++
100
+++
+
+/−
+
++
+/−
+/−
+/−
++++
50
+++
+
++
+
++
+/−
+++
+++
+++
25
+++
+
++
+
++
+/−
+++
++
++++
10
+++
+
+
++
+++
+/−
+
+
1
+++
+++
+
+++
+++
+
+
++
0.1
+++
+++
+++
+++
+++
++
+
+++
0.01
+++
++++
+++
+++
++++
+++
+++
+++
100
TABLE 2
CT26 cell line (colon cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
200
+++
+/−
+/−
+/−
+/−
+/−
+/−
+/−
+++
100
+++
+/−
+/−
+/−
+
+/−
+/−
+/−
+++
50
+++
+/−
+/−
+/−
+
+/−
+/−
+
++++
25
++++
+/−
+
+
+
+/−
+
+
++++
10
+++
+
+
++
++
+/−
+
+
1
++++
+++
+
++++
++++
+/−
+
+
0.1
++++
++++
+++
++++
+++
++
+
+++
0.01
++++
+++
+++
+++
+++
+++
+++
+++
100
TABLE 3
DU145 cell line (prostate cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
200
+++
+/−
+/−
+/−
+/−
+/−
+/−
+/−
+++
100
+++
+/−
+/−
+/−
+
+/−
+/−
+/−
++++
50
++++
+/−
+
+/−
+
+/−
+
+
+++
25
+++
+/−
+
+/−
+/−
+/−
+
+
++++
10
++++
+/−
+/−
+/−
+/−
+/−
+/−
+/−
1
+++
+
+/−
++
+++
+/−
+/−
+/−
0.1
+++
+++
+
+++
+++
+/−
+/−
++
0.01
+++
+++
+++
+++
+++
++
++
+++
100
TABLE 4
HepG2 cell line (liver cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
200
+++
+/−
+/−
+/−
+/−
+/−
+/−
+/−
+++
100
+++
+/−
+/−
+/−
+
+/−
+/−
+/−
+++
50
+++
+/−
+/−
+/−
+
+/−
+/−
+
++++
25
+++
+/−
+
+
++
+/−
+
+
++++
10
+++
+
+
++
+++
+/−
+/−
+
1
+++
++
+
+++
++++
+/−
+
+
0.1
+++
+++
++
++++
+++
+
+
+++
0.01
+++
+++
++
++++
++++
++
++
+++
100
TABLE 5
MDCK cell line (kidney from canine)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
200
+++
+++
+/−
++
+
+/−
+/−
+/−
+++
100
+++
+++
+/−
+++
++++
+/−
+/−
+/−
++++
50
+++
+++
+++
+++
+++
+/−
+
++
+++
25
+++
+++
+++
+++
+++
+
+
+++
++++
10
+++
+++
+++
+++
+++
+
+++
+++
1
+++
+++
+++
+++
+++
+
+++
++
0.1
+++
+++
+++
+++
+++
+++
+++
+++
0.01
++++
+++
++++
+++
+++
++++
+++
++++
100
TABLE 6
PC3 cell line (prostate cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
200
+++
+/−
+/−
+/−
+/−
+/−
+/−
+/−
++++
100
++++
+/−
+/−
+/−
+
+/−
+/−
+/−
+++
50
++++
+/−
+
+/−
+
+/−
+
+
++++
25
++++
+/−
+
+/−
+/−
+/−
+/−
+/−
+++
10
+++
+/−
+/−
+
+/−
+/−
+/−
+/−
1
++++
+
+/−
+++
+++
+/−
+/−
+/−
0.1
++++
+++
+
+++
+++
+/−
+/−
+++
0.01
++++
++++
+++
++++
++++
++
++
+++
100
TABLE 7
MDA-MB-231 cell line (breast cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
100
++
++
+/−
+
+/−
+/−
+/−
+/−
+++
50
+++
+
+/−
+
++
+/−
+/−
++
+++
25
+++
+
++
++
++
+/−
++
++
++++
10
+++
++
++
++
++
+
++
++
++++
1
+++
++
++
+++
+++
+
+
++
0.1
+++
+++
+++
+++
+++
++
++
+++
0.01
+++
+++
+++
+++
+++
+++
+++
+++
0.001
+++
+++
+++
+++
+++
+++
+++
+++
100
TABLE 8
MCF-7 cell line (breast cancer)
Dose
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
ANCA-
3 days
μg/ml
DMSO
ANCA-E
E-D
E-W
E-D-1
E-D-2
E-D-3
E-D-4
Cell
Blank
100
++
++
+/−
++
+++
+/−
+/−
+/−
++++
50
++
++
++++
++
+++
+/−
++++
++++
++++
25
+++
++
+++
++
++
+++
++++
+++
+++
10
++++
+
++
++
+++
++
+++
+++
+++
1
+++
++
++
+++
+++
+
++
++
0.1
++++
+++
++
+++
+++
++
++
+++
0.01
++++
+++
+++
+++
+++
+++
++
+++
0.001
++++
++++
+++
++++
+++
+++
+++
+++
100
The symbols used in tables respectively represent: 0˜25% cell viability: +/−; 25˜50% cell viability: +; 50˜75% cell viability: ++, 75˜100% cell viability: +++, >100% cell viability: ++++. The solvent used herein is DMSO, whose IC50 value is 2.34%, which means when the drug is diluted to contain 2.34% of DMSO would cause 50% cell death. In this experiment, when the drug concentration was diluted to 100 μl/ml, DMSO concentration was 0.5%. ANCA-E, ANCA-E-D, ANCA-E-W, ANCA-E-D-1, ANCA-E-D-2, ANCA-E-D-3, and ANCA-E-D-4 are different extracts.
According to the results shown in above tables, ANCA-E-D-2, ANCA-E-D-3, ANCA-E-D-4 can preferably inhibit the survival of various tumor cells. For example, in comparison to the other extracts, ANCA-E-D-2 and ANCA-E-D-3 preferably inhibit survival of A549 cell line (lung cancer), CT26 cell line (colon cancer), DU145 cell line (prostate cancer), HepG2 cell line (liver cancer), MDCK cell line (kidney from canine), PC3 cell line (prostate cancer), MDA-MB-231 cell line (breast cancer) and MCF-7 cell line (breast cancer). Though the effect of ANCA-E-D-4 is lower than ANCA-E-D-2 and ANCA-E-D-3, it still has a moderate inhibition effect thereof. Accordingly, above extracts can be used for treating cancers, such as lung cancer, colon cancer, prostate cancer, liver cancer and breast cancer, and the effective compounds contained in those extracts also can be purified.
Purification of Antrocamol LT1 and Antrocamol LT2 from Antrodia camphorata Extracts
According to the above results, ANCA-E-D-2 and ANCA-E-D-3 were subjected to C18 reverse-phase HPLC columns for purification. For ANCA-E-D-3 purification, a fraction collected at 18.75 min (80% MeOH/H20) was concentrated to yield a novel compound “Antrocamol LT1” (150 mg). For ANCA-E-D-2 purification, a fraction collected at 25.10 min (80% MeOH/H20) was concentrated to yield another novel compound “Antrocamol LT2” (170 mg). The structures of the novel compounds were determined as follow.
Antrocamol LT1 was a transparent aqueous product, the molecular formula was determined as: C 24 H 38 O 5 ; 4-hydroxy-5-[9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyl]-2,3-dimethoxy-6-methyl-cyclohex-2-enone; molecular weight: 406.
1H-NMR Spectral Data of Antrocamol LT1: 1 H-NMR (400 MHz, CDCl 3 ): □ 1.12 (3H, d, J=7.2 Hz), 1.61 (3H, s), 1.64 (3H, s), 1.66 (3H, s), 1.68 (3H, s), 1.72 (1H, m), 1.98-2.30 (8H), 2.51 (1H, dq, J=11.6, 7.2 Hz), 3.62 (3H, s), 4.02 (3H, s), 4.33 (1H, d, J=2.8 Hz), 4.35 (1H, dt, J=9.2, 4.0 Hz), 5.09 (1H, d, J=8.4 Hz), 5.14 (1H, t, J=7.2 Hz), 5.15 (1H, t, J=7.2 Hz); 13 C-NMR (100 MHz, CDCl 3 ): □□ 012.17 (q), 15.95 (q), 16.19 (q), 18.13 (q), 25.72 (q), 25.93 (t), 26.78 (t), 39.41 (t), 39.98 (d), 43.29 (d), 47.94 (t), 58.81 (q), 60.48 (q), 65.35 (d), 67.24 (d), 121.64 (d), 127.64 (d), 128.42 (d), 132.03 (s), 134.99 (s), 135.97 (s), 137.42 (s), 160.82 (s), 197.15 (s).
Antrocamol LT2 was a transparent aqueous product, the molecular formula was determined as: C 26 H 40 O 6 ; 4-acetoxy-5-[9-hydroxy-3,7,11-trimethyldodeca-2,6,10-trienyl]-2,3-dimethoxy-6-methyl-cyclohex-2-enone; molecular weight: 448.
1H-NMR Spectral Data of Antrocamol LT2: 1 H-NMR (400 MHz, CDCl 3 ): □ 1.18 (3H, d, J=7.2 Hz), 1.54 (3H, s), 1.64 (3H, s), 1.67 (3H, s), 1.69 (3H, s), 1.72 (1H, m), 1.80-2.40 (8H), 2.50 (1H, dq, J=11.6, 7.2 Hz), 3.65 (3H, s), 3.98 (3H, s), 4.36 (1H, m), 5.10 (1H, t, J=6.8 Hz), 5.12 (1H, d, J=8.0 Hz), 5.20 (1H, t, J=6.4 Hz), 5.72 (1H, t, J=3.2 Hz); 13 C-NMR (100 MHz, CDCl 3 ): □□ 12.80 (q), 15.96 (q), 16.09 (q), 18.14 (q), 20.93 (q), 25.72 (q), 26.19 (t), 26.76 (t), 39.47 (t), 41.25 (d), 42.98 (d), 48.12 (t), 59.65 (q), 60.67 (q), 65.53 (d), 68.98 (d), 120.74 (d), 127.42 (d), 128.25 (d), 131.74 (s), 134.70 (s), 137.31 (s), 137.56 (s), 158.21 (s), 169.73 (s), 196.84 (s).
TABLE 9
MDA-
MB-
MDCK
CT26
A549
HepG2
PC3
DU-145
231
MCF-7
μg/ml
μg/ml
μg/ml
μg/ml
μg/ml
μg/ml
μg/ml
μg/ml
ANCA-E
>200
10
10
10
1
1
20.28 ± 1.21
>100
ANCA-E-D
100
1
1
1
0.1
0.1
30.72 ± 0.97
35.03 ± 4.32
ANCA-E-
25
0.1
0.1
0.1
0.1
0.1
26.53 ± 1.82
30.85 ± 1.19
D-3
Antrocamol
>10
0.070 ± 0.006
0.093 ± 0.003
0.014 ± 0.001
0.057 ± 0.002
0.057 ± 0.009
0.98 ± 0.05
0.99 ± 0.08
LT1
Antrocamol
>10
0.80 ± 0.03
1.06 ± 0.22
0.59 ± 0.02
0.69 ± 0.06
0.91 ± 0.08
1.03 ± 0.05
0.95 ± 0.11
LT2
The half maximal inhibitory concentration (IC50) is a measure of the effectiveness of a compound in inhibiting biological or biochemical function. This quantitative measure indicates how much of a particular drug or other substance (inhibitor) is needed to inhibit a given biological process (e.g. cell apoptosis-inducing activity of a compound) by half. As shown in table 9, novel compounds Antrocamol LT1, Antrocamol LT2, and extracts of ANCA-E, ANCA-E-D and ANCA-E-D-3 had a predominant anti cancer activity for various cancers, such as lung cancer, colon cancer, prostate cancer, liver cancer and breast cancer. In the future, based on the present invention, these novel compounds and extracts can be further developed to anti cancer drugs.
All of the references cited herein are incorporated by reference in their entirety.
The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.
The embodiments and examples were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present invention pertains without departing from its spirit and scope. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.
Some references, which may include patents, patent applications and various publications, are cited and discussed in the description of this invention. The citation and/or discussion of such references is provided merely to clarify the description of the present invention and is not an admission that any such reference is “prior art” to the invention described herein. All references cited and discussed in this specification are incorporated herein by reference in their entireties and to the same extent as if each reference was individually incorporated by reference. | Disclosed is a method for inhibiting cancer cell growth in a subject in need thereof, comprising administering to the subject an effective amount of a compound from Antrodia camphorata , wherein the compound is represented by formula (I):
wherein R1 is a hydrogen atom or an acetyl group; and a method of inhibiting cancer cell growth by using the compound, the cancer is selected from the group consisting of lung cancer, colon cancer, prostate cancer, liver cancer and breast cancer. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a Continuation-in-Part of PCT/DE/2008/001479 designating the United States for the National Phase, published Sep. 5, 2008, which claims priority from German Application Nos. 10 2007 048 897.3, filed Oct. 11, 2007 and 10 2007 063 095.8, filed on Dec. 28, 2007, the entire disclosures of which are hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention related to the field of medical technology and concerns a device for cleaning optic gauges, which have an eye surface contact area and in particular applanation tonometer gauges or ophthalmic contact lenses used for diagnostic purposes or laser treatment. The invention also concerns the method of operation of the same device.
[0004] 2. Description of the Prior Art
[0005] In eye treatment (opthalmology) today different devices and instruments are used for diagnosis and laser treatment. These include replaceable and reusable optic gauges, which come into direct contact with the eye surface (in other words with the outer cornea) during treatment.
[0006] For example, this is how glaucoma is diagnosed (green star) by examining the intraocular pressure (internal pressure of the eyes). This examination comprises identifying a number of intraocular pressures throughout the day, ideally to collate a 24-hour pressure profile, which is not only able to detect the increase of intraocular pressure, but also augmented fluctuations in intraocular pressure throughout the day in the development, or the progression, of glaucoma damage. The most reliable device to determine intraocular pressure used by ophthalmologists today is the so-called applanation tonometer by Goldmann. The Goldmann applanation tonometry is typically performed on a seated patient. For this a local anaesthetic is applied to the eye. FIG. 1 illustrates the measurement of intraocular pressure on a seated patient with a Goldmann applanation tonometer. FIG. 1 shows a view where an attached, replaceable and typically reusable optic gauge ( 6 ) (tonometer gauge) can be seen on the tonometer measuring arm, which is introduced from the left-hand side into the cornea of the patient's right eye. The cornea is then flattened by the tonometer gauge ( 6 ), with the eye surface contact area facing the eye, and pressure being applied to the eyeball accordingly. The necessary forced applied to flatten the cornea is directly proportional to the intraocular pressure, according to the Imbert-Fick law. The force used to flatten the cornea is transferred to the tonometer gauge and can be captured and recorded with the appropriate display or measuring equipment.
[0007] Furthermore, optic gauges, so-called ophthalmic contact lenses, are used for diagnostic purposes and laser treatment, on the retina or choroid, for example. Prior to the treatment, a local anaesthesia is also applied to the cornea and conjunctiva of the eye, to numb the eye, before the ophthalmic contact lens' eye surface contact area is placed on the cornea. FIG. 2 shows a view of diagnostic treatment of a female patient's left eye using an ophthalmic contact lens ( 6 ). The doctor holds the ophthalmic contact lens ( 6 ) with his hand and places the eye surface contact area of the ophthalmic contact lens onto the cornea of the patient's left eye. The eye specialist can thereby closely inspect the upper eye lid for diagnostic purposes through this ophthalmic contact lens ( 6 ). Furthermore, a laser beam can be guided into the upper eye lid through the ophthalmic contact lens, for example onto the retina, so as to prevent a dangerous retinal detachment. Moreover, laser treatments are possible for leaking or diseased proliferating choroid blood vessels, such as with diabetes.
[0008] In any case, reusable optic gauges must be cleaned of tear film residues after every treatment, at any rate the optic gauges' eye surface contact area must be cleaned, as, on the one hand, these residues can affect the optic properties of the optic gauges and therefore future measurement results; and, on the other hand, pathogenic germs and other exogenous carriers of infection, or damaging substances, contained in the lachrymal fluid may be transmitted to other patients' eyes by the optic gauge.
[0009] The cleaning of such optic gauges, which presently also includes disinfection, has to date been carried out manually. Typically, the optic gauges are thoroughly cleaned with water, for 30-60 seconds, for example. Then they are disinfected in aqueous solution, such as one containing 3% hydrogen peroxide, or 70% ethanol or 60 to 70% isopropanol or 2.5% sodium hypochlorite, for some 5-10 minutes. Afterwards, the optic gauges are rinsed once again with water for approx. 10 to a maximum of 60 minutes. Finally, the optic gauges are dried with a disposable towel, so that they can be subsequently re-used or safely stored away.
[0010] The current cleaning of optic gauges by hand requires the employment of personnel and is therefore expensive, on the one hand, and, due to human shortcomings, it is not always guaranteed that the above-mentioned cleaning process is properly carried out (such as mandatory disinfection or the exposure time to a cleaning fluid exactly followed according to the respective guidelines). In particular the interruptions or distractions of personnel in everyday practice can lead to deviations from the prescribed cleaning process. Often, the correct materials are not used for cleaning (such as alcohol cloths that have no disinfectant effect), which significantly reduces the durability of softer lenses in particular. Even with the prescribed cleaning, after two years of use there is noticeable wear and tear on the surfaces of a tonometer gauge, particularly on its eye surface contact area. FIGS. 3 a and 3 b , respectively, illustrate a vertical view from above of a part of the circular eye surface contact area of a tonometer gauge. FIG. 3 a shows the view of a new, unused tonometer gauge. FIG. 3 b shows the view of a tonometer gauge that has been used for 2 years and at all times cleaned following the method prescribed, and dried with a disposable towel. It is clearly visible in FIG. 3 b that the surfaces of the soft tonometer gauge material are frayed. This can affect both the optic properties and the measurement results, as well as causing mechanical injuries to the cornea. In addition the cleanability of the tonometer gauge deteriorates, as, for example, disinfectant or other residues become embedded in the roughened surfaces and it may be difficult to rinse them out. This fraying is caused to a great extent by the mechanical actions of drying the tonometer gauge with the disposable towel.
SUMMARY OF THE INVENTION
[0011] The present invention relates to a cleaning device for reusable optic gauges with an eye surface contact area, particularly applanation tonometer gauges or ophthalmic contact lenses used for diagnostic or laser treatment which provides a reliable, careful and cost-efficient cleaning of optic gauges.
[0012] According to the invention, the devices for cleaning optic gauges, which have an eye surface contact area, particularly applanation tonometer gauges or ophthalmic contact lenses used for diagnostic or laser treatment, comprise at least: a top-opening, cleaning unit which can be filled and emptied of liquid; one or more liquid reservoirs, which are connected to the cleaning unit to ensure that the appropriate liquid contained in the liquid reservoirs is introduced into the cleaning unit; a waste water repository, which is connected to the cleaning unit to ensure that liquid can be drained into the waste water repository from the cleaning unit; a receptacle to hold at least one optic gauge, which is positioned, or can be positioned in such a way that an optic gauge inserted, with the eye surface contact area inserted first in the receptacle from above, will at least partially extend into the cleaning unit; one or more switches, for influencing or shutting off of the liquid being dispensed from the liquid reservoirs into the cleaning unit and/or the liquid being drained from the cleaning unit; mechanisms providing a wash cycle; mechanisms providing a drying cycle; a control unit connected to the switches, the wash and drying cycle controls. These foregoing elements can be automatic and controlled by the control unit as per a fixed pre-set or specific cleaning program.
[0013] The device according to the invention enables an automatic cleaning of at least one optic gauge in the receptacle, after typical manual application, with a fixed pre-set or variable specific cleaning program. The word “clean” is hereby interpreted widely, and comprises, depending on the liquids being used in the device, for example the disinfecting or washing as well as the subsequent drying of the optic gauge.
[0014] Prior to describing the individual component parts of the device according to the invention in detail as follows, the control of the device and its working principle are first considered.
[0015] The present invention is controlled by a control unit, which executes or implements control commands in the pre-set or pre-determinable cleaning programs. The cleaning program can be software-based and therefore, in principle, can be variable or fixedly pre-set. The cleaning program preferably defines a sequence of so-called wash and dry cycles which will be implemented by the device of the invention. The wash cycle is understood to comprise each process that entails the filling of the cleaning unit with liquid from the liquid reservoir, then the partial immersion of at least one optic gauge, with its eye surface contact area inserted first, in this liquid for the specified duration of a cleaning program, and finally the emptying of liquid from the cleaning unit. Meanwhile, the drying cycle comprises each process during a cleaning program for a specified length of time, whereby the optic gauge is no longer immersed in liquid and the optic gauge is dried which typically follows a wash cycle.
[0016] The liquids required for the cleaning program, and the wash cycles, should be placed in the device's liquid reservoirs. One especially preferential design has two liquid reservoirs, with distilled water, preferably, being added to the first liquid reservoir for washing and a disinfectant liquid being added to the second, such as 3% hydrogen peroxide solution. Naturally, the number of required liquid reservoirs depends on the number of liquids needed for the cleaning program's wash cycles. The number of liquid reservoirs is less than or equal to the number of liquids required for the cleaning program, as by mixing liquids one or more additional mixed liquids can be produced. An advantage is that the liquid reservoirs have a lid, to avoid contamination or evaporation of the liquid; they can be easily refilled and/or easily replaced. In the latter case, the liquid reservoirs can also consist of standard commercial containers, such as disinfectant or cleaning liquid holders, in which the liquids are sold. The liquid reservoirs should also consist primarily of resistant, inert materials, which will not be damaged by the liquids and will not change the liquids chemically.
[0017] The receptacle in the present invention serves to hold at least one optic gauge to be washed. Typically, the optic gauges are manually inserted or placed into the receptacle. To remove the optic gauge from the receptacle, a wide variety of noted specialist devices and mechanisms can be used. An advantage is that the receptacle is appropriate for different forms of optic gauges. Alternatively, adapters can also be provided which can be integrated with the receptacle to make them suitable for inserting different shapes of optic gauges.
[0018] The receptacle is either installed relative to the cleaning unit, or it is at least positionable so that one optic gauge can be loaded from above, with the eye surface contact area inserted first, and at least partially being immersed in the cleaning unit. In the latter case, alternatively a propulsion mechanism can be provided as an added advantage, so that the receptacle and/or the cleaning unit can be positioned relative to each other, to ensure that an optic gauge can be loaded from above, with the eye surface contact area inserted first, to at least partially extend into the cleaning unit and then be removed upwards out of the cleaning unit. The propulsion mechanism can be a mechanical, manually operated lever unit or an electric motor, particularly a linear motor.
[0019] The basic provision of at least one cleaning unit, the liquid reservoirs and a waste water repository of the device of the invention can be made in a variety of different designs. These may result from the design of the device, from mechanical data or requirements when constructing the device, etc. The simplest design of the cleaning unit is to make it rotationally symmetrical, with a funnel-shaped floor, which has an opening at its deepest point, through which the liquid from the cleaning unit can be drained. This type of cleaning unit is simple to manufacture technically and allows for optimal emptying of the liquid from the cleaning unit. Liquid from the liquid reservoirs can be introduced into the cleaning unit via inlet openings provided in the wall or floor of the cleaning unit, via liquid feed lines directly above the cleaning unit or via one or the same opening(s) through which the liquids are emptied, or a combination is also possible. In a particularly preferential design, all the surfaces in the cleaning unit that the liquid comes into contact with have a “lotus effect”.
[0020] By “lotus effect” the low wettability of a surface is indicated, as can be observed in lotus plants. The cause of the lotus effect lies in a particular surface structure, which creates such a low adhesion force that the cohesion forces even within a liquid with a lower surface tension outweigh the adhesion forces and therefore no wetting of the surface results. Micro, nano-structured, superhydrophobic surfaces are required to reproduce this effect.
[0021] The planned waste water repository serves as a receptacle for the used fluids needed for the different wash cycles in the cleaning unit. The waste water repository has the advantage of being easily removable from the device, or at least easily emptied, and it is ideally designed so that it can hold the liquid contents that are produced during at least one day's use.
[0022] In a particularly preferential version of the invention, one initial liquid reservoir is provided for cleaning fluids, such as distilled water, and a second holder is provided for disinfectants, such as one containing H 2 O 2 , NaOH or NaOCl, whereby the volume from the first holder, from the second and the volume from the waste water repository corresponds to a ratio of 2:1:3. The volume the waste water repository can hold is preferably at least that of the cleaning and disinfectant liquids required per day.
[0023] As already explained above, in the liquid reservoirs the required liquids are provided for the individual wash cycles of the cleaning program. In principle, for a wash cycle only one liquid from the liquid reservoir fills the cleaning unit. For certain wash cycle applications it is however possible to fill the cleaning unit with a mix of liquids from more than one liquid reservoir. The liquid in the cleaning unit at the end of the wash cycle is typically emptied into the waste water repository. This means that the used liquid in the cleaning unit cannot be re-used for another wash.
[0024] To reduce liquid consumption, at least for one or more types of liquid, in another particularly beneficial design of the device according to the invention, one or more closed fluid circuits, each with a liquid filter system, are provided. With a closed fluid circuit of this type, the required liquid from the respective reservoir fills the cleaning unit for a wash cycle, and after its use in the cleaning unit it is fed via a liquid filter system back to the liquid reservoir. This makes it possible for used, soiled liquid in the cleaning unit to be salvaged and to be available for re-use in the corresponding liquid reservoir. The filter system is ideally designed to make it easily accessible and, therefore, easily replaceable.
[0025] The liquid reservoirs, the cleaning unit and the waste water repository are typically interconnected through the fluid conduits accordingly, for example, through hose lines or metal flumes. The liquid is conveyed through the fluid conduits, in the simplest case, by means of hydrostatic pressure applied to the fluids. For this purpose, the liquid reservoir's is situated above the cleaning unit and the waste water repository below. This ensures that the filling and emptying of the cleaning unit is feasible solely due to the hydrostatic pressure applied to the liquids. Alternatively, or additionally, one or more liquid pumps and/or compressors can be provided, which are connected to and controlled by the control unit. These at least ensure that liquid from the liquid reservoirs can be actively pumped into, or out of, the cleaning unit.
[0026] To control the liquid flow, the device according to the invention comprises one or more switches, which are connected to the control unit and allow a minimum control of the flow of liquid from the reservoirs into the cleaning unit, as well as the draining of liquid from the cleaning unit. Above all, these ensure that these filling and draining processes can be switched (shut off), if required. It is an added advantage if all switches are valves, in particular magnetic valves.
[0027] Moreover, the device of the invention comprises a support mechanism for the wash cycles as well as the drying cycles. These mechanisms improve the effectiveness, in other words the efficacy, and/or efficiency, or rather cost-optimization, of the respective processes. As a support mechanism for the wash cycle, fundamentally the appropriate mechanism is used to improve and/or optimize the outlay of the washing cycle. The same applies to the drying cycle support mechanism. Furthermore, it is conceivable to use a mechanism that can support both the wash and drying cycles.
[0028] One particularly advantageous design variant of the device of the invention provides a support mechanism for the wash cycle and/or the drying cycle, which is connected to the control unit. The control unit then controls a second propulsion means, preferably an electric motor, which can rotate along the longitudinal axis at least one of the optic gauges placed in the receptacle. By rotating, at least partially, an optic gauge immersed in the liquid of the cleaning unit along its longitudinal axis, the number of the optic gauge's immersed surfaces coming into contact with the liquid molecules per unit time is increased, and therefore the washing process is assisted. The results from analysis of different optic gauges suggest that rotational speeds of <500 rpm are particularly suitable, preferably 25-250 rpm. By rotating the optic gauges the liquid itself also rotates, which reduces the abovementioned supportive effect due to the lower relative speed of the liquid and the gauge's surfaces. As a result, the rotational direction of the gauge along its longitudinal axis is switched during the washing process at specific intervals, as an added advantage.
[0029] Moreover, the second propulsion means provides support for the drying process, as the optic gauges are rotated at such a rotational speed along their longitudinal axis to ensure that any remaining liquid residue (such as drops) are removed by the centrifugal force of the rotation from the optic gauge, and particularly from the eye surface contact area. Ideally, the optic gauges should have a rotation speed of >300 rpm, ideally 600-1000 rpm along their longitudinal axis.
[0030] An alternative, or additional, support mechanism for the wash cycle is the provision of at least one ultrasonic transducer, which is compatible with the control unit, where the liquid ultrasonic waves in the cleaning unit can be coupled. The existing ultrasonic fields in the liquid generate waves with high and low pressure. If such a low pressure wave hits the optic gauges being washed, they form small, air bubbles acting on germs with steam filled cavities. When the following high pressure wave strikes the cavity, the static pressure in the cavity increases through its compression once again over its saturated vapour pressure. Thus, the vapour bubbles condense abruptly with the speed of sound. The pressure peaks rise up to 100,000 bar. These cyclically rising and falling cavities work on the liquid-immersed surfaces of the optic gauge and clean them. Dirt and other adhesions are gently and mechanically removed.
[0031] A further alternative, or additional, support mechanism for the wash cycle can be provided in the form of a mixer in the cleaning unit, where the liquid in the cleaning unit is moved around. The support produced for the cleaning effect is explained, as above, by rotating the optic gauge along its longitudinal axis, through increasing the number of immersed surfaces of the optic gauge that come into contact with liquid molecules per unit time. In an advanced embodiment, the mixer is designed as a propeller, which is arranged in the bottom area of the cleaning unit. The propeller is rotatable supported around a horizontal axis of rotation, i.e. in case of a rotation-symmetrical cleaning unit the axis of rotation is aligned perpendicular to said axis of symmetry. For driving the propeller an electric motor is connected at one end of a shaft. The propeller is joined at the other end of the shaft. Due to propeller rotation, flow swirls are induced into the cleaning liquid which support the cleaning process and which further prevent air bubbles from accumulating at concave shaped surfaces of the optic gauge facing down.
[0032] A further alternative, or additional, support mechanism for the wash cycle and/or drying cycle can be provided in the form of a heating element in the cleaning unit, where the liquid or air in the cleaning unit is heated. Through heating, the temperature of the liquid in the cleaning unit is increased, which in turn increases the number of the immersed optic gauge's surfaces coming into contact with liquid molecules per unit time and thereby assists the wash process. During a drying cycle, the heating element can also warm the air inside the cleaning unit, which can lead to an increase in the evaporation rate of liquid residues present on the surfaces of the optic gauge inserted into the cleaning unit.
[0033] A further alternative, or additional, support mechanism for the drying cycle can be provided in the form of a fan, to ensure the optic gauge, and particularly its eye surface contact area, is dryable.
[0034] As stated above, a control unit is provided to control the whole cleaning process, which can at least be connected to the washing and drying support mechanisms. These mechanisms can be automatically controlled via the control unit, as per a fixed, pre-set or variable specific cleaning program. An advantage here is that the device can be provided with an input unit connected to the control unit, where the parameters concerning the cleaning program are specified. This input unit can, for example, be an external computer, which is connected to the control unit via a control unit interface. For recording the cleaning processes carried out, a module for setting up a cleaning cycle can be provided, as well as an output unit, via which at least the cleaning cycle can be output. The cleaning programme can be started ideally by manual entry or operation of a starting unit, such as a switch etc., connected to the control unit.
[0035] In addition, ideally at least one filling level probe is provided on the cleaning unit, connectable to the control unit, which allows determination of whether at least one minimum pre-set target filling level set for each cleaning unit has been reached. Moreover, one filling level probe is provided on the liquid reservoirs, which is connectable to the control unit, so that achievement of a minimum of at least one pre-set target filling level in each case can be determined. Furthermore, a minimum of one filling level probe can be provided on the waste water repository, connected to the control unit, which can monitor the achievement of at least one pre-set maximum liquid filling level in the waste water repository. In addition, a visual and/or acoustic alarm can be provided, where an alarm is triggered once a minimum or maximum level of liquid has been reached. Moreover, once this alarm has been triggered the program sequence can be stopped or actually not put into operation at all.
[0036] The following will indicate the operating method of the device, which comprises the following steps. Step one is allocating a cleaning program in the control unit, whereby the cleaning program determines a sequence of wash cycles and drying cycles. Step two manually places at least one optic gauge into the receptacle. Step three, if the receptacle is not fixed, makes sure that the optic gauge placed into the receptacle from above, with the eye surface contact area inserted first, extends into the cleaning unit at a depth, and that the corresponding positioning of the receptacle and/or the cleaning unit are relative to each other. Step four is starting the cleaning program. Step five automatically runs the wash and drying cycles according to the cleaning programme's sequence and cleaning parameters.
[0037] At the end of step five, the cleaning of the optic gauge is finished and the sixth step is to remove it from the receptacle. Alternatively, the clean optic gauges can remain in the device to be stored safely until they are next used.
[0038] A particularly favourable variation of this method is that the optic gauge projects out of the receptacle during the whole cleaning program, unaltered at the same target depth in the cleaning unit. This simplifies the construction technically. Alternatively, the procedure is adaptable by which the optic gauge during the drying process, for example, is removed from the cleaning unit.
[0039] In the cleaning program, each wash cycle is primarily defined by parameters, which determine the liquids to be used and/or the liquid reservoirs in which the liquid is stocked for the respective wash process, the target length of wash cycle, or during the wash cycle the means to be activated to support the wash process. Furthermore, primarily all drying cycles are defined by parameters in the cleaning program, which determine the target length of the drying cycle, for the particular drying cycles, and the support mechanism to be activated during the drying process.
[0040] Primarily, for every wash cycle, the following minimum steps will be followed. Step one, filling the cleaning unit up to the specified target level with the liquid from the liquid reservoir defined by the respective wash cycle in the cleaning program. After the unit is filled, the optic gauges with the eye surface contact area inserted first have a target immersion depth in the liquid contained in the cleaning unit. Step two, according to the respective definition in the cleaning program, one or more of the wash cycle support mechanisms is activated. Step three, after the cleaning program's specified target wash cycle has ended, the liquid shall be emptied from the cleaning unit into the waste water repository or it shall be transferred back to the liquid reservoirs via a filter system, from which the preceding filling of the cleaning unit occurs.
[0041] Primarily, for every drying process, the minimum following steps are followed. As set by the cleaning program, one or more of the support mechanisms for the drying cycles is activated for a target length of time specified by the cleaning program.
[0042] Primarily, the cleaning unit is filled with a liquid, which is identical in terms of immersion depth, regardless of the type of optic gauge being cleaned. This can technically be implemented so that every optic gauge inserted from above, with the eye surface contact area inserted first, sits at the same target depth in the cleaning unit, and the amount of liquid dispensed into the cleaning unit is measured out in such a way that a specified, target depth customized target filling level is reached in the cleaning unit. Reaching the target filling level can, in turn, be achieved using a filling level probe.
[0043] In principle, the sequence of the wash and drying cycles in the cleaning program is arbitrary. In this way, two wash cycles could follow one another with different liquids, before the drying cycle. However, it is particularly advantageous to provide a drying cycle at the end of the cleaning program's sequence.
[0044] All in all, the device of the invention permits a gentle, cost-effective, automatic and controlled cleaning of optic gauges, particularly tonometer gauges and ophthalmic contact lenses. To clean ophthalmic contact lenses, the cleaning program must include changeable times for wash cycles, to make sure that, depending on the liquid used, the ophthalmic contact lenses are not immersed for too long, as the putty sections of the ophthalmic contact lenses can be damaged. The device's liquid consumption can be reduced by means of a cleaning unit designed for a reduced volume to save on cleaning and disinfectant liquids. Standards-compliant cleaning programs can be simply implemented by means of a changeable, typically software-based cleaning program. The device of the invention can comprise suitable displays to ensure that the duration of the wash and drying cycles can be monitored. Furthermore, internal test and checking circuits can be arranged in the device, which constantly monitor the device's functionality and the correct running of the specific cleaning program. If problems should arise, this could generate a visual or acoustic alarm or lead to other specific remedial measures. The device also operates independently of a water supply through a water pipe. The device can also operate in a fully self-contained manner with battery power. Through the corresponding dimensions of the liquid reservoirs and the waste water repository, a daily amount of liquid (for example, approx. 20-30 cleanings of tonometer gauges in an optician's practice) can be held and processed in the device, without having to refill the liquid reservoirs or empty the waste water repository.
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] The invention will be described with examples as follows, without restriction on the general concepts of the invention and making reference to a design example.
[0046] FIG. 1 is a view of prior art applanation tonometry with a patient;
[0047] FIG. 2 is a view of the implementation of prior art diagnostic treatment with an ophthalmic contact lens;
[0048] FIG. 3 a is a microscopic picture of surfaces of a new prior art tonometer gauge;
[0049] FIG. 3 b is a microscopic picture of surfaces of a prior art tonometer gauge which has been used for two years and cleaned according to a specific cleaning procedure;
[0050] FIG. 4 is a schematized construction of the device according to the invention; and
[0051] FIGS. 5 a and b are longitudinal sectional views through the receptacle according to the invention containing the optical gauge and a mixer designed as a propeller.
DETAILED DESCRIPTION OF THE INVENTION
[0052] FIGS. 1-3 b illustrate the state of the art and have already been explained in the above and therefore, at this stage, reference will be made to FIG. 4 and FIGS. 5 a and b.
[0053] FIG. 4 shows a schematized construction of the device of the invention for cleaning optic gauges, which have an eye surface contact area. The optic gauge placed in the device's receptacle ( 5 ) to be cleaned is the tonometer gauge ( 6 ). The device is also suitable in particular for cleaning ophthalmic contact lenses, which can be placed in receptacle ( 5 ) instead of the tonometer gauge.
[0054] The device comprises two liquid reservoirs ( 1 , 2 ) which are connected to the cleaning unit ( 11 ) via hose lines ( 12 ), a waste water repository ( 3 ) connected to the cleaning unit ( 11 ) via hose lines, a receptacle ( 5 ) with the tonometer gauge ( 6 ) placed inside, as well as a second propulsion unit ( 4 ), which rotates the receptacle ( 5 ) holding the tonometer gauge ( 6 ) along a rotation axis which corresponds to the longitudinal axis of the tonometer gauge ( 6 ). The cleaning unit ( 11 ) is cylindrical, equipped with a downwardly tapered conical floor surface. At the deepest point of the floor surface there is an outlet opening, which connects to the waste water repository ( 3 ). The cleaning unit ( 11 ) is also coated with lotus effect surfaces, so that the liquid contained in the cleaning unit can be easily and completely emptied. The liquid reservoirs ( 1 , 2 ) are positioned above the cleaning unit ( 11 ), and this is, in turn, placed above the waste water repository ( 3 ). This allows for filling of the cleaning unit ( 11 ) with liquid from the liquid reservoirs ( 1 , 2 ) and emptying of the fluid in the cleaning unit ( 11 ) into the waste water repository ( 3 ) without additional pumps which is possible solely due to the hydrostatic pressure differences. The device has housing ( 13 ) with funnel-shaped openings (each marked with vertical arrows) intended to supply, or fill, the liquid reservoirs ( 1 , 2 ) with liquid and to empty the waste water repository. Switchable magnetic valves ( 8 ) are also provided to control the supply of liquids from the liquid reservoirs ( 1 , 2 ) to the cleaning unit ( 11 ), as well as emptying the cleaning unit ( 11 ). The device also includes two filling level probes ( 7 ), with one attached to the cleaning unit ( 11 ) to detect when the target filling level has been reached, and one filling level probe ( 7 ) attached to the waste water repository ( 3 ) to detect when the maximum level in the repository has been reached. The filling level probes used for this purpose are known to specialists. They can be based on visual, electric or mechanical operating principles, or a combination of the above. Finally, there are two light-emitting diodes (LEDs) ( 9 , 10 ) on the housing which display the device status. To display the device status almost all well-known specialist alternatives are feasible, therefore their description can be foregone here. In this case, an initial green light-emitting diode ( 9 ) is provided, which flashes during the automatic, uninterrupted running of the cleaning program and shines constantly at the end of the cleaning program. There is also a red light-emitting diode ( 10 ) present, which lights up if a fault is detected during the automatic cycle of a cleaning programme, or if the maximum filling level has been reached in the waste water repository.
[0055] The first propulsion means is not displayed here, which positions the receptacle ( 5 ) relative to the cleaning unit ( 11 ) so that a tonometer gauge ( 6 ) placed from above into the receptacle ( 5 ), with the eye surface contact area inserted first, can be at least partially immersed in the cleaning unit ( 11 ) and can be lifted upwards out of the cleaning unit ( 11 ). The insertion and removal of the tonometer gauge ( 6 ) into the receptacle ( 5 ) occurs with the receptacle ( 5 ) vertically positioned above the cleaning unit ( 11 ), to ensure that the tonometer gauge ( 6 ) can be easily inserted/removed manually in and out of the receptacle ( 5 ), without touching the eye surface contact area of the tonometer gauge ( 6 ).
[0056] The first propulsion means could be a manually operated lever mechanism or an electric motor, particularly a linear motor. Of course there are a vast number of alternative, specialist mechanisms that are possible, which allow for simple, manual insertion or removal of a tonometer gauge ( 6 ) into/out of the receptacle ( 5 ) as well as at least a partial insertion of the tonometer gauge in the receptacle ( 5 ) into the cleaning unit. For example, the receptacle could be mounted on a swivel arm that can be swiveled upwards for the insertion and removal of the tonometer gauge and moved into a position during cleaning to immerse the tonometer gauge in the cleaning unit.
[0057] In another alternative design, the receptacle ( 5 ) does not require the first propulsion means. In this design the receptacle ( 5 ) is in a fixed position relative to the cleaning unit ( 11 ), so that the tonometer gauge ( 6 ) is placed from above into the fixed receptacle and it then extends into the cleaning unit ( 11 ).
[0058] FIG. 4 also does not illustrate a control unit, which, as a minimum, is connected electrically to the valves ( 8 ), the first propulsion means (if applicable), the second propulsion means ( 4 ), the filling level probes ( 7 ) and the LEDs ( 9 , 10 ) and through which a specific cleaning program can be automatically operated. As stated above, the cleaning program determines a sequence of wash and drying cycles, where the specific characteristics of the individual wash and drying cycles are defined according to parameters of that cleaning program.
[0059] FIGS. 5 a and b show longitudinal section views through a tonometer gauge 6 , which is placed in a receptacle 5 being rotatable mounted at a bearing L around the vertical axis H. The bearing L is not connected with the illustrated cleaning unit. It is assumed that the tonometer gauge 6 is arranged inside the cleaning unit which is filled with cleaning liquid. A propeller P is arranged within the cleaning unit. The propeller P is connected to a shaft D which is driven by an electric motor M. The propeller is arranged directly below the concave shaped surface of the tonometer gauge 6 which is directed downwardly. Thus accumulation of air bubbles below this concave contour of the gauge 6 is avoided.
[0060] The present design example of the device of the invention for cleaning optic gauges will ideally operate with a cleaning program which has an initial wash cycle running sequence, with the following parameters:
Use of a cleansing fluid, such as distilled water, Length of wash cycle: >preferably 30-180 s, and Rotation of the optic gauge along its symmetrical axis at <500 rpm and turning in alternating directions,
A first drying cycle with the following parameters:
Length of the drying cycle: >5 s, preferably 10-60 s and Rotation of the optic gauge along its symmetrical axis at >300 rpm,
A second wash cycle with the following parameters:
Use of a disinfectant liquid, such as 3% hydrogen peroxide, Length of the wash cycle: >1 min, preferably 5-10 min and Rotation of the optic gauge along its symmetrical axis at <500 rpm and turning in alternating directions,
A second drying cycle with the following parameters:
Length of the drying cycle: >5 s, preferably 10-60 s and Rotation of the optic gauge along its symmetrical axis at >300 rpm,
A third wash cycle with the following parameters:
Use of a cleansing fluid, such as distilled water, Length of the wash cycle: >2 min, preferably 10-60 min and Rotation of the optic gauge along its symmetrical axis at <500 rpm and turning in alternating directions, and
A third drying cycle with the following parameters:
Length of the drying cycle: >5 s, preferably 10-60 s, and Rotation of the optic gauge along its symmetrical axis at >300 rpm.
KEY TO REFERENCE NUMBERS
[0000]
1 Liquid reservoir (such as for distilled water)
2 Liquid reservoir (such as for 3% hydrogen peroxide)
3 Waste water repository
4 , 4 a , 4 b Support mechanism for the wash cycle ( 4 a ) and support mechanism for the drying cycle ( 4 b ) are identical in the present design example: ( 4 )=( 4 a )=( 4 b ): propulsion means (such as an electric motor), mechanism to rotate the optic gauge along its longitudinal axis
5 Receptacle
6 Optic gauges, such as tonometer gauges, ophthalmic contact lenses
7 Filling level probe (visual, electric, etc.)
8 Switches, valve, magnetic valve
9 , 10 LED display
11 Cleaning unit
12 Hose lines
13 Housing | A device for cleaning optic gauges ( 6 ), which have an eye surface contact area, and in particular applanation tonometer gauges or ophthalmic contact lenses for diagnostic purposes or laser treatment is described. The device comprises: a liquid filling and emptying top-opening cleaning unit ( 11 ); one or more liquid reservoirs ( 1,2 ), connectable to the cleaning unit ( 11 ) so that fluids contained in the liquid reservoirs ( 1,2 ) can be dispensed into the cleaning unit ( 11 ); a waste water repository ( 3 ), connectable to the cleaning unit ( 11 ) so that liquid can be drained from the cleaning unit ( 11 ) into the waste water repository ( 3 ); a receptacle ( 5 ) to hold at least one optic gauge ( 6 ), that is either in a fixed position or positionable, so that an optic gauge ( 6 ) inserted into the receptacle ( 5 ) from above, eye surface contact area first, at least partially extends into the cleaning unit ( 11 ). | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates an anti-noise panel which can be used, for example, as a traffic noise barrier along roads, highways and/or railways. The panel according to the invention comprises a front shell and a rear shell, made of thermoplastic material, that are coupled together within which rubber elements of specifically designed shape and size are incorporated. Said panel can be advantageously obtained by using recycled, injected thermoplastic material, that allows the resulting panel to be conveniently used when the wind causes strong impact, for example, along railway lines where the compression waves generated by trains traveling at high speed over time tend to disassemble the riveted aluminum/steel sound barriers currently in use.
STATE OF THE ART
[0002] The construction features of the noise barriers currently in use do not satisfy today's requirements. Moreover, a great number of noise reduction solutions are produced with barriers that are very heavy and very expensive, but that nonetheless are not always suitable for a given area of application.
[0003] In order to establish the noise reduction efficiency of sound absorbing systems, reference should be made to the sound abatement performance parameters resulting from testing in free field conditions as set forth in the UNI 11022 standard which follows the same guidelines as the ISO 10847 standard, i.e. the noise in dB(A) measured at the receiving location with the barrier/noise absorption medium installed between the receiving location and the noise source. The unsuitability of certain barriers currently in use is due to the fact that several factors were considered marginal, or were not even taken into consideration, because they were not subjected to specific regulations until the new European Directives came into force. Said Directives in fact not only regulate noise pollution but also all types of environmental pollution, thus all barriers which are composed of materials that deteriorate rapidly must be replaced within a period estimated at around 2 to 3 years.
[0004] The types of barriers currently in use are typically made of the following materials: aggregate concrete, with vegetation or tire rubber granules there within; wood having a rock wool core; steel having a rock wool core; aluminum having a rock wool core; light alloy having a rock wool core; PMMA polymethylmethacrylate; polycarbonate; glass; fibre-reinforced polymer; composite materials/carbon fibre.
[0005] Different types of materials are used in function to market requirements, however it is not always possible to satisfy both aesthetic and noise reduction requirements. Most noise barriers currently in use belong to the following types: steel having a rock wool core; aluminum having a rock wool core; wood having a rock wool core; PMMA polymethylmethacrylate. Among the aforementioned types, steel having a rock wool core and aluminum having a rock wool core are the most commonly used. Noise barriers currently in use are generally composed of a metal or wood casing having perforations for the passage of sound waves and a rock wool core whose function is the absorption of the sound energy, or more precisely the energy present in sound waves of a range of frequencies and plainly not all the frequency spectrum.
[0006] The barriers currently in use are easy to manufacture but with a low level of automation; the technologies are known and the materials are easy to obtain but are getting increasingly costly; some can be customized in order to blend into the surrounding environment but only within certain limits.
[0007] However, the barriers currently in use indeed have many disadvantages that can be summarized as follows:
Disadvantages regarding performances:
[0009] They are extremely limited in terms of sound absorption efficiency as well as life cycle, which can be estimated at around 4 to 5 years; they require periodical maintenance; the installation is complicated and lengthy; the rock wool used is hazardous to health, and in fact is soon to be banned.
[0010] One of the main adverse point of said barriers is the fastening system because it must be specifically designed for each type of barrier.
[0011] Barriers currently in use are fitted into the cavity of the support structure but this is not sufficient to guarantee stability, therefore, bolts, anchors etc. are used on the side that does not face the noise source. The said barriers are made of different pieces, therefore their stiffness is insufficient, and moreover the fastening elements must be secured manually and this entails additional manufacturing costs. It is quite common to see a worker on a ladder or self-propelling platform carrying out maintenance, checking, tightening or replacing the fastening elements of barriers especially along railway lines where the compression wave generated by the passing of a train over time loosens the fastening elements, then often forces the barriers out of the support structure cavity and hurls them over the surrounding area, with all the risks entailed in the case of contact with persons because besides being heavy they also have sharp edges.
Disadvantages regarding maintenance over time:
[0013] Barriers currently in use require maintenance work, both in terms of cleaning to remove the dirt caused by atmospheric conditions and the dust caused by traffic, and accordingly periodical maintenance to ensure the efficiency of the fastening elements.
Disadvantages regarding the expected life cycle:
[0015] In addition to the fact that barriers that use rock wool on the inside are soon to be banned (in view of the Directives EN 1793-1, ISO/R 354-1985 and DIN 52212), such barriers also have a limited life cycle. Moreover, atmospheric conditions, and especially precipitation containing dust and pollutants seep into the rock wool causing deterioration of its physical/chemical properties and reducing its volume by more than 30%. Said deterioration reduces the useful life of the barriers to 4-5 years; firstly there a loss of sound adsorption efficiency, and then the rock wool dust, which is very hazardous to health, is released into the atmosphere.
[0016] It should be noted that most of the noise barriers are installed near cities and built-up areas and in many cases they are located practically alongside houses and residential apartment buildings.
Other disadvantages:
[0018] An additional disadvantage of the barriers currently in use regards their manufacturing process, which is not fully automated therefore the workers involved in the process are exposed to the dust that is continually released from the rock wool when it is fitted into the barriers. Said barriers are open at the ends and have many perforations, thus any type of handling causes the release of rock wool dust into the air.
[0019] Another negative aspect of barriers currently in use concerns dismantling and disposal. The fact that said barriers are made of metal parts that are very costly (steel or aluminum) implies the recovery of said parts, which is a very difficult and expensive process because it involves separating the metal from the rock wool, which must then be disposed off.
[0020] It is therefore an object of the present invention to provide noise barriers that allow to overcome the drawbacks of the prior art as above reported.
SUMMARY OF THE INVENTION
[0021] This object has been achieved by the anti-noise panel as set forth in claim 1 . The anti-noise panel of the present invention comprises a front shell and a rear shell, made of thermoplastic material, that are coupled together so as to form a sealed inner cavity, said panel incorporating dampers of specifically designed shape and size. By suitably joining the shells, the resulting panel has a one-piece structure that has been proved to be an extremely valid noise reduction solution, whereas being very cost effective as well as more efficient and longer lasting than the known noise barriers.
[0022] The present invention further relates to a process for the production of said anti-noise panel which comprises the steps of:
[0000] a) forming a front shell, optionally incorporating at least one damper, by injection moulding,
b) forming a rear shell, optionally incorporating at least one damper, by injection moulding, and
c) joining said front shell to said rear shell so that a inner cavity is formed, thus obtaining the anti-noise panel.
[0023] For the purposes of the present invention, by the phrase “front shell A” is meant a shell A exposed to the noise source.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The characteristics and advantages of the present invention will be apparent from the detailed description reported below and the annexed Figures, wherein:
[0025] FIG. 1 shows a view of the front shell (A) of an anti-noise panel according to a first embodiment of the invention;
[0026] FIG. 2 shows a view of a rear shell (C) of the anti-noise panel according to said first embodiment of the invention;
[0027] FIGS. 3 and 4 show a portion of the anti-noise panel as well as elements composing the same according to said first embodiment;
[0028] FIG. 5 shows a section view of the anti-noise panel of FIGS. 3 and 4 ;
[0029] FIG. 6 shows a view of the front shell (A) of an anti-noise panel according to a second embodiment of the invention;
[0030] FIG. 7 shows a view of a rear shell (C) of the anti-noise panel according to said second embodiment of the invention;
[0031] FIGS. 8 and 9 show a portion of the anti-noise panel as well as elements composing the same according to said second embodiment;
[0032] FIG. 10 shows a section view of the anti-noise panel of FIGS. 8 and 9 ;
[0033] FIG. 11 shows a diagram illustrating the phono-absorbing property of an anti-noise panel according to the invention over the frequency spectrum of the sound waves.
DETAILED DESCRIPTION OF THE INVENTION
[0034] The subject of the present invention is therefore an anti-noise panel comprising a structure incorporating at least one damper and comprising a front shell made of plastic material and a rear shell made by the same or different plastic material, said front shell being joined to said rear shell so as to form a sealed inner cavity.
[0035] FIG. 1 shows a first preferred embodiment of the present invention, wherein said panel 1 comprises a front shell A made of thermoplastic material and a rear shell C made by the same or different thermoplastic plastic material. According to the invention, the front shell A and the rear shell C are joined together so as to form a one-piece structure having a sealed inner cavity IC.
[0036] The internal and external configurations of the panel 1 are designed by making reference to features of an anechoic chamber. Preferably, the inner cavity IC has a labyrinth configuration.
[0037] In the present invention, by “thermoplastic material” is meant a material capable of softening or fusing when heated and of hardening again when cooled. Exemplary thermoplastic materials include organic synthetic polymers, elastomers and compounds thereof.
[0038] Front shell and rear shell are preferably made of thermoplastic organic polymers or compounds thereof, that are rigid once thermoformed, such as polymethylmethacrylate (PMMA), Acrylonitrile Butadiene Styrene (ABS), polystyrene (PS), High Density Polyolefins, Polyvinyl Chloride (PVC), Chlorinated Polyvinyl Chloride (CPVC), Polyvinylidene Fluoride (PVDF), Polycarbonate (PC), Polyammide (PA), Polybutylenethereftalate (PBT), Polyethylenethereftalate (PET) or compounds thereof. More preferred thermoplastic organic polymers are polymethylmethacrylate (PMMA), polypropylene (PP), mixtures thereof, or compounds of (ABS)-(PC).
[0039] Preferably, the at least one damper of the anti-noise panel 1 is made of thermoplastic elastomers or compounds thereof. Said elastomers are used as having three essential characteristics:
capability to be stretched to moderate elongations and, upon the removal of stress, return to something close to its original shape, processability as a melt at elevated temperature, and absence of significant creep.
[0043] Preferred thermoplastic elastomers are natural, semisynthetic or synthetic rubber or blends of said rubber with other thermoplastic elastomers, such as Styrene Ethylene Propylene Styrene (SEPS), Styrene Butadiene, Acrylonitrile Butadiene, or Styrene Isoprene Styrene (SIS).
[0044] More preferred elastomers are synthetic rubber, such as ethylene propylene diene monomer (EPDM) or blends of the same with other thermoplastic elastomers.
[0045] Advantageously, the shell A or the shell C or both can be made of recycled thermoplastic material. According to a preferred embodiment of the present invention, the shells A and C of the anti-noise panel 1 are made of 100% recycled thermoplastic material, thus being very low-cost and environmental-friendly. Actually, according to this embodiment, conveniently no aluminum or steel and/or ferrous materials are used.
[0046] Optionally, the above thermoplastic material can be blended with at least one inert filler. The inert filler can be chosen from talc, calcium carbonate, glass spheres, graphite, carbon black, carbon fiber, glass fiber, wollastonite, mica, alumina, silica, and silicon carbide.
[0047] The thermoplastic material according to the present invention can also include additives such as lubricants, flame retardants, heat and UV/Light stabilizers, dimensional stabilizers, waxes, colorants, foaming agents, impact modifiers, corrosion inhibitors, anti-static agents, plastic processing aids, anti-fog agents, anti-oxidants, anti-block, slip additives, mould release agents, or mould coating agents.
[0048] FIGS. 1 to 5 are relative to a first embodiment of the anti-noise panel 1 according to the invention having a plurality of dampers. With reference in particular to FIGS. 1 and 2 , the anti-noise panel 1 comprises a first plurality of dampers B on the said front shell A. Hereinafter this dampers B are also indicated with the expression “external dampers B” since they comprise an external part B 1 which actually protrudes outwards of the sealed inner cavity IC. FIG. 1 and the section view of FIG. 4 show a preferred shape of these dampers B according to which the external part B 1 has a pyramidal shape having a square base.
[0049] With reference in particular to the section view of FIG. 5 , the external dampers B comprises also an internal part B 2 which protrudes inwards of the inner cavity IC. The internal part B 2 of the dampers B comprises lamellae 8 having different thickness and length that advantageously allow to absorb the energy deriving from sound waves of the relevant frequencies. In fact, said lamellae 8 dissipate the energy absorbed by means of vibration at the tip 8 B of said lamellae 8 which is tapered from the base 8 C.
[0050] According to the first embodiment shown in FIGS. 1-5 , the anti noise-panel 1 also comprises a plurality of internal dampers D which are incorporated in the rear front shell C. Hereinafter, these dampers D are indicated with the phrase “internal dampers D” since they develop substantially inwards the sealed inner cavity IC as clearly shown, for example, in FIG. 5 . As illustrated, the shape and size of the internal dampers D are different from those of the external dampers B incorporated in the front shell A. The internal dampers D are inter-positioned between the external dampers B in such a way as to cover as much space as possible on the inside of the sealed inner cavity IC of the anti-noise panel 1 .
[0051] With reference to FIG. 5 , the internal dampers D are smaller than and have a different shape with respect to that of the external dampers B, because they are intended to absorb the energy deriving from sound waves of different ranges of frequencies. In particular, in the illustrated embodiment, the internal dampers D are formed as cylindrical coaxial bodies 9 which develop inward of the sealed inner cavity IC.
[0052] FIG. 11 is a diagram illustrating the phono-absorbing property Rw(dB) of the anti-noise panel 1 over the frequency spectrum of the sound waves. Said diagram has being plotted according to ISO 717-1 (in the range 100 to 3150 Hz) by detecting experimental measurements. In the diagram, the broken line identifies the standard of ISO 717-1, whereas the continuous line is the characteristic trend detected for the anti-noise panel 1 according to the invention. As shown by the diagram, the phono-absorbing property is advantageously greatly satisfactory over all the range of frequencies 100 up to 3150 Hz, being even conveniently higher than what required by the standard in the range of frequencies up to 300 Hz and in the range beyond 1600 Hz. In particular, it has been observed that the external dampers B, incorporated in the front shell A, are quite successfully effective in absorbing the energy deriving from sound waves on the range up to 1600 Hz, while the internal dampers D incorporated of the rear shell C, improve said absorption of energy deriving from sound waves beyond 3000 Hz.
[0053] With reference to FIG. 4 , the front shell A and the rear shell C comprise stiffening ribs 7 , in order to further improve the structural strength of the panel 1 especially against specially adverse circumstances of impacts or collisions. In particular, these stiffening ribs 7 develop inwards of the inner cavity IC and along one or more internal sides of corresponding shell A, C. The rear shell C also comprises cylindrical stiffening ribs 7 B which develop inward the inner cavity IC substantially around corresponding internal dampers D.
[0054] The outer surface of the front shell A comprise two parallel rest surface 4 defined at opposite ends which can be used to simplify the assembly of the panel on suitable support structure 6 like that shown in FIG. 5 . Analogously, also the outer surface of the rear shell C comprise two similar rest surface with the same purposes.
[0055] FIGS. 6 to 10 are relative to a second embodiment of the anti-noise panel 1 according to the present invention. As shown for example in FIG. 6 , in this case panel 1 comprises a first plurality of external dampers B incorporated on the front shell A and substantially equivalent to those relative to the first embodiment above describe. In this case the panel 1 comprises also a second plurality of external dampers BI always incorporated on the front shell A. The dampers B of the first plurality and those BI of the second plurality are reciprocally spaced according to orthogonal directions. FIGS. 8 and 9 show the configuration of these dampers BI of the second plurality which have a pyramid shape protruding inwards of the inner cavity IC. In particular, the dampers BI are preferably made of thermoplastic material which can be equivalent or different to the material used for the front shell A. In other words, according to this embodiment, the first plurality of dampers B is made of thermoplastic rubber and the second plurality of dampers BI is made of thermoplastic material.
[0056] In this second embodiment, the rear shell C does not incorporate any dampers. Experimental measurement have proved that the performances of the panel 1 according to the second embodiment, even if not so excellent as in the case of the first embodiment, however are highly satisfactory and conveniently effective in adsorbing noise, i.e. by only using the first plurality of dampers B and the second plurality of dampers BI both incorporated on the front shell A.
[0057] As illustrated in the section views of FIGS. 8 and 9 , the configuration of the shells A, C in the second embodiment is substantially equivalent to that of the first one. Consequently, common elements relative to both embodiments are indicated in FIGS. 6-10 by using the same references used in the FIGS. 1-5 . The one-piece structure of the anti-noise panel of the present invention and the successful sound absorption proved above allow to overcome the drawbacks of the prior art panels.
[0058] In a further aspect, the present invention relates to a process for manufacturing the anti-noise panel as above described, comprising the steps of
[0000] a) forming a front shell A, optionally incorporating at least one damper, by injection moulding,
b) forming a rear shell C, optionally incorporating at least one damper, by injection moulding, and
c) joining said front shell A to said rear shell C so that a sealed inner cavity is formed, thus obtaining the anti-noise panel.
[0059] The above process allows the at least one damper to be incorporated in the front shell A and/or in the rear shell C during the manufacturing of the shell themselves. In this regard, the shells A, C can be simultaneously manufactured by means of a bi-injection moulding.
[0060] As above indicated, the front shell A and the rear shell C form a sealed inner cavity IC, once said shells are joined. The shells A, C are preferably joined by fitting together the respective perimeter edge 11 , 21 . More precisely, the front shell A comprises a first perimeter edge 11 which is preferably welded to a second perimeter edge 21 of the rear shell C (see for example FIG. 5 ). Conveniently, the first perimeter edge 11 has the same configuration, in terms of shape and size, of the second edge 21 . In this manner, after joining the shell A to the shell C, the inner cavity IC directly results isolated and sealed and the resulting anti-noise panel is a one-piece structure.
[0061] The front shell A and the rear shell C are preferably joined by thermo-welding. In particular, the thermo-welding is preferably performed by means of a hot blade or alternatively by ultrasounds. According to a preferred embodiment, said at least one damper for intercepting the noise is not positioned after the said anti-noise panel is manufactured, thus being incorporating therein so as to form a one-piece anti-noise panel.
[0062] The said anti-noise panel is preferably produced in two automated stage. No screws nor rivets are preferably used for assembling the two shells, because assembly is conveniently achieved by means of an automated joining system. Preferably, no sound absorption materials are used, because noise reduction is successfully achieved by combining the anechoic chamber and the bi-injection moulding technology.
[0063] The technical solutions adopted for the anti-noise panel according to the present invention allow it to fully accomplish the object above indicated. The panel is reliable and is manufactured at competitive costs.
[0064] It will be apparent to the person skilled in the art that various modifications can be conceived and reduced to practice without departing from the scope of the invention. | It is disclosed an anti-noise panel comprising a front shell and a rear shell that are coupled together within which rubber elements of specifically designed shape and size are incorporated. Said panel can be advantageously obtained by using also recycled, injected thermoplastic material, that allows the resulting panel to be conveniently used when the wind causes strong impact, for example, along railway lines where the compression waves generated by trains traveling at high speed over time tend to disassemble the riveted aluminum/steel sound barriers currently in use. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to a wedged-base bulb socket for a motor vehicle light or the like, particularly to a wedged-base bulb socket in the body of which terminals are partially embedded integrally as the body of the socket is molded.
In is necessary to prevent molten resin from flowing into the contact portions (which pinch the wedged part of the bulb and come into contact with the lead wires of the bulb for making electrical connection thereto) of the bulb contact parts of the terminals as the body of a conventional bulb socket is molded from resin in such a manner that the terminals are partially embedded in the body of the bulb socket. The die used for molding the body of the conventional bulb socket from resin must be specially constituted to meet these requirements, and the constitution of the die is complicated. This significantly increases the costs of production of the conventional bulb socket.
SUMMARY OF THE INVENTION
The present invention has been made in order to solve the above-mentioned problems in the conventional bulb socket.
Accordingly, it is an object of the present invention to provide such a socket for a wedged-base bulb in which molten resin does not flow into the contact portions of the bulb contact parts of the terminals of the socket, although the die for molding the body of the socket is not specially constituted, and in which the resilience of the contact portions is maintained for long periods of time.
A further object of the present invention is to provide a socket for a wedged-base bulb in which molten resin does not flow into the contact portions of the bulb contact parts of the terminals, although the die for molding the body of the socket from the resin is not specially constituted, and in which the contact portions are less likely to be plastically deformed and can therefore maintain their resilience for a long period of time.
In the wedge-base bulb socket provided in accordance with the present invention, the terminals are partially embedded in the body of the socket as the body is molded from the resin. The bulb contact parts of the terminal are formed with a wall bent nearly in a U shape so as to surround the contact portions which pinch the wedged part of the wedged-base bulb.
In the socket provided in accordance with another aspect of the present invention, the terminals are partially embedded in the body of the socket as the body is molded from the resin. The bulb contact parts of the terminals have contact portions which pinch the wedged part of the wedged-base bulb, a wall having an approximately U shape so as to surround the contact portions as a whole, coupling portions joining the contact portions to the wall and having a relatively large width, and touch portions having nearly the same width as the coupling portions and extending from the contact portions toward the inside surface of the wall.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a plan view of a bulb socket constructed according to a first preferred embodiment of the invention;
FIG. 2 shows a sectional view of the bulb socket of FIG. 1 taken along a line (2)--(2) in FIG. 1;
FIG. 3 shows a front view of each terminal of the bulb socket;
FIG. 4 shows a side view of each terminal of the bulb socket;
FIG. 5 shows a plan view of the terminal;
FIG. 6 shows a plan view of a bulb socket constructed according to a second preferred embodiment of the invention;
FIG. 7 is a sectional view of the bulb socket of FIG. 6 taken along a line (7)--(7) in FIG. 6;
FIG. 8 shows a cut-away front view of each terminal of the bulb socket of FIG. 6;
FIG. 9 shows a cut-away side view of the terminal; and
FIG. 10 shows a cut-away plan view of the terminal.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred embodiments of the present invention will hereafter be described with reference to the attached drawings.
A first preferred embodiment of the invention will be described with reference to FIGS. 1 through 5 of the drawings.
A bulb insertion part A 1 for attaching a wedged-base bulb and a plug-in part A 2 for coupling a connector are molded together from resin to constitute the body A of a bulb socket. During the molding process, two terminals B are partially embedded in the body A of the bulb socket integrally therewith so that the bulb contact parts B 1 of the terminal are located in the internal opening of the bulb insertion part A 1 and the connector contact parts B 2 of the terminals are located in the internal opening of the plug-in part A 2 .
Each of the terminals B, which are made of a metal plate, integrally includes the bulb contact part B 1 , which is electrically coupled to the wedged-base bulb and the connector contact part B 2 ; , which is electrically coupled to the connector. The bulb contact part B 1 has contact portions 1 which elastically pinch the wedged part of the wedged-base bulb and are electrically coupled to the lead wires of the bulb, and a wall 2 formed nearly in a U shape so as to surround the contact portions. The contact portions 1 of the bulb contact part B 1 are formed in the same manner as a conventional bulb socket, but the wall 2, which extends above the contact portions and which is formed integrally therewith and has approximately a U shape so as to surround the contact portions, differs from the conventional bulb socket.
When the terminals B are to be partially embedded in the body A of the bulb socket when the body is molded from resin, the terminals are set in prescribed positions in a die for molding the socket body from the resin. At the time of molding, the openings inside the walls 2 of the bulb contact parts B 1 of the terminals B are closed by the core C of the die or the like so that molten resin does not flow into the contact portions 1 of the bulb contact parts.
According to the present invention, when terminals are partially embedded in the body of the bulb socket, molten resin does not flow into the contact portions of the bulb contact parts of the terminals, although the die for molding the body of the bulb socket from the resin need not be specially constituted as in a conventional bulb socket. The constitution of the die is thus simplified, reducing the cost of production of the bulb socket. Since the contact portions of the bulb contact parts of the terminals are surrounded by the walls of the bulb contact parts, the contact portions are prevented from being excessively spread when a bulb is inserted. For that reason, good resilience of the contact portions is maintained for a long period of time, reliably maintaining the electrical connection of the contact portions and the bulb for a long period of time.
A second embodiment of the invention will be described with reference to FIGS. 6 through 10 of the drawings.
A bulb insertion part A 1 for attaching a wedged-base bulb and a plug-in part A 2 for coupling a connector are molded together from resin to constitute the body A of the socket. During the molding process, two terminals B are partially embedded in the body A of the socket integrally therewith so that the bulb contact parts B 1 of the terminals are located in the internal opening of the bulb insertion part A 1 of the socket body, and the connector contact parts B 2 of the terminals are located in the internal opening of the plug-in part A 2 .
Each of the terminals B, which are made of a metal plate, integrally includes the bulb contact part B 1 , which is electrically coupled to the wedged-base bulb, and the connector contact part B 2 , which is electrically coupled to a connector. The bulb contact part B 1 has contact portions 1 which elastically pinch the wedged part of the bulb and are electrically coupled to the lead wires of the bulb, a wall 2 formed in approximately a U shape so as to surround the contact portions, coupling portions 3 joining the contact portions to the wall, and touch portions 4 located in contact with the inside surface of the wall. The contact portions 1 of the bulb contact parts B 1 have the same form as a conventional socket. The bulb socket of this embodiment, however, differs from the conventional socket in that coupling portions 3 of relatively large width H are provided continuously with the bottoms 1a of the contact portions and joining the contact portions to the wall 2, which extends above and surrounds the contact portions, and also in that the touch portions 4 of nearly the same width as the coupling portions are provided at the bottoms of the contact portions opposite the coupling portions and extending toward the inside surface of the wall in parallel with the coupling portions.
When the terminals B are to be partially embedded in the body A of the socket when the socket body is molded from resin, the terminals are set in prescribed positions in a molding die, and the openings inside the walls 2 of the bulb contact parts B 1 of the terminals are closed by a core C. As a result, the terminals are integrated with the body of the socket and the molten resin does not flow into the contact portions 1 of the bulb contact parts of the terminals when the socket is molded from resin.
According to the above-described second embodiment of the invention, when terminals are partially embedded in the body of the bulb socket in molding the socket body from resin, the molten resin does not flow into the contact portions of the bulb contact parts of the terminals, although the die for molding the socket body from the resin need not be specially constituted. The constitution of the die is thus simplified, reducing the costs of production of the bulb socket. Since the contact portions and the walls of the bulb contact parts of the terminals are joined to each other by coupling portions of relatively large width, molten resin is more surely prevented from flowing into the contact portions. Since the contact portions are surrounded by the walls and supported by the coupling portions and touch portions located in contact with the inside surfaces of the walls, plastic deformation and excessive spreading of the contact portions when a bulb is inserted are more surely prevented than in a conventional bulb socket, thereby maintaining good resilience of the contact portions for a long period of time and thus maintaining a reliable electrical connection of the socket and the bulb for a long period of time. | A bulb socket for a wedged-base bulb which can be manufactured at a low cost and yet which is capable of maintaining good resilience of its contact portions over a long period of time. The socket includes a molded-resin body and a plurality of terminals partially embedded in the body as the latter is being molded. Bulb contact parts of the terminals are formed with a wall having an approximately U shape so as to surround the contact portions which pinch the wedged parts of the bulb. The wall preferably extends above the contact portions. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
The present patent application claims the benefits of priority of Canadian Patent Application No. 2,559,471, filed on Aug. 31, 2007, at the Canadian Intellectual Property Office and entitled: “Underground communication network system for personnel tracking and HVAC control”.
FIELD OF THE INVENTION
The present invention generally relates to mining underground ventilation control and its optimization as a function of a dynamic demand related to the tracking of the machinery location and/or operating status and/or personnel location. More specifically it relates to the predictive modeling and simulation along with the optimization of the air distribution and fans energy consumption to physically control the operating setpoints for fans and air flow regulators.
BACKGROUND OF THE INVENTION
FIG. 1 represents a typical mine ventilation layout with airflow control equipment. The intent is not to generalize the FIG. 1 layout example to all mines, but to typically explain and associate the optimized mine ventilation system application to mining ventilation. The optimized mine ventilation system can be applied to an infinite variation of mine layout configurations.
As shown on FIG. 1 a mine is typically composed of the following elements:
One or more intake fans [ FIG. 1 , element ( 2 )] provide air from the surface atmosphere to the underground infrastructure via one or more downcast shafts [ FIG. 1 , element ( 3 )]. The fans speed is manually controlled by a local controller or by a basic control system with surface HMI (Human Machine Interface). The control system usually also includes startup and shutdown sequences and protection interlocks.
The downcast shaft(s) provides fresh air to working levels where production occurs on one or more extraction zones off each level [ FIG. 1 , elements ( 5 , 6 , 7 )]. Ramps with or without access doors will also divert some air from each levels to other levels [ FIG. 1 , elements ( 8 , 9 )]. Ramps provide a route for equipment to move from one level to another.
Ore and waste material is extracted from the production zones by diesel machinery and is dropped in ore or waste passes down to lower levels to be crushed and brought back to the surface by conveyors in shafts [ FIG. 1 , elements ( 26 , 27 )].
Air is forced from each level to the ore extraction zones or service areas [ FIG. 1 , elements ( 10 , 11 , 29 , 12 , 13 , 14 )] by auxiliary fans and ducting connected to the fans [ FIG. 1 , elements ( 15 , 16 , 30 , 17 , 18 , 19 )]. As per the surface fans, the auxiliary fans speed is manually controlled by a local controller or by a basic control system with surface HMI (Human Machine Interface). The diesel particulate emission contaminated air from the ore extraction zones comes back to the level via the ore extraction excavation.
Contaminated air is flowing to upcast shaft(s) [ FIG. 1 , element ( 4 )] through fixed opening bulkheads or bulkheads with variable air flow regulators [ FIG. 1 , elements ( 23 , 24 , 25 )]. The air flow regulators position is manually controlled by a local controller or by a basic control system with surface HMI (Human Machine Interface).
In some modern installations air flow measurement stations are found at the bulkhead [ FIG. 1 , elements ( 20 , 21 , 22 )].
Sometimes when the surface fans capacity is exceeded, lower levels will have additional booster fans used as in-line pressure enhancers [ FIG. 1 , element ( 28 )]. The fans speed is manually controlled by a local controller or by a basic control system with surface HMI (Human Machine Interface). The control system usually also includes startup and shutdown sequences and protection interlocks.
One or more exhaust fans [ FIG. 1 , element ( 1 )] draw air from one or more upcast shafts [ FIG. 1 , element ( 4 )] out to the surface atmosphere. The fans speed is manually controlled by a local controller or by a basic control system with surface HMI (Human Machine Interface). The control system usually also includes startup and shutdown sequences and protection interlocks.
Traditionally the calculation of required setpoints for fans speed and bulkheads surface area opening or air flow regulator opening position has been achieved by manual survey results of air flows and regulatory requirements for maximum diesel equipment presence in one work zone. In addition, numerous mine operators use the calculation assistance of commercially available ventilation network steady state non real-time simulators designed to simulate existing ventilation networks. Fan operating points, airflow quantities, and frictional pressure drops are obtained from those calculations to assist derive physical operating setpoints.
There are several drawbacks and deficiencies in those fans speed and bulkhead opening setpoint calculations:
Surveys are spontaneous measurements and are not representative of the changing operating environment of a live mine. Therefore, maximum safe setpoint values have to be used to be representative of the worst case scenarios.
Commercially available simulators lack one or more of the following capabilities rendering them unfit for live real-time control. They are either non real-time calculation engines unfit for live control. Their pressure and flow calculations may also omit the depth air column compensation for air density and pressure calculation which creates significant errors in the results also rendering them unfit for live real-time control. Their flow calculations may not be compensated for natural ventilation pressure flows from temperature differences. This also renders them unfit for live real-time control.
The aforementioned control equipment setpoint calculation methods are therefore used with limits and safety factors that cannot dynamically adjust to accommodate a live diesel machinery ventilation presence often wasting valuable air therefore not available to other work zones. Hence, those setpoint calculations do not offer a live dynamic optimization of the air flow routing and distribution. In conclusion, those production ventilation setpoint calculation methods often prohibits mine operators to access deep remote ore body sectors due to the lack of available air.
The optimized mine ventilation system has been engineered to circumvent those previously mentioned setpoint calculation deficiencies. The optimized mine ventilation system permits on-demand ventilation as per dynamic personnel location and dynamic diesel machinery location and operating status. An optimized zonal ventilation demand is calculated and the optimized mine ventilation system assures optimal air routing and distribution at minimum energy cost.
The optimized mine ventilation system does not require costly air flow sensors which typically have proven problem prone installations due to the harsh mine air environment. Routine maintenance of those sensors is therefore eliminated. Only a few sensors will be required to keep a live correlation check with the model.
OBJECTS OF THE INVENTION
The objectives of this optimized mine ventilation system invention are to assist mine operators with:
A real-time production enhancement tool which optimizes the underground air distribution to reach ore body sectors which could not be reached with the current ventilation routing procedures; A real-time energy management tool that contributes in diminishing the energy required to ventilate underground work zones while maintaining target flow rates; A real-time environmental management tool that contributes to diminish the electrical power generation CO emission footprint while also maintaining target flow rates. A system that installs easily to existing or new control infrastructure based on “Open Architecture” that connects transparently, without programmatic developmental efforts to any OPC (Ole for Process Control, see www.opcfoundation.org) based control system.
Other and further objects and advantages of the present invention will be obvious upon an understanding of the illustrative embodiments about to be described or will be indicated in the appended claims, and various advantages not referred to herein will occur to one skilled in the art upon employment of the invention in practice.
SUMMARY OF THE INVENTION
The aforesaid and other objectives of the present invention are realized by a proper ventilation layout and related equipment parametric information configuration and installation of an optimized mine ventilation system in accordance with this invention along with a basic control system which modulates fans speed and air flow regulator position and which read few critical air flow measurements to correlate in real-time the results of the optimized mine ventilation system modeling and optimizer calculations.
FIG. 2 is a summary block diagram of the optimized mine ventilation system connection to external third party components.
The optimized mine ventilation system [ FIG. 2 , item ( 33 )], requires the following directly connected third party systems:
A tracking system providing data on the dynamic location and operating status of the machinery [ FIG. 2 , item ( 34 )]. A basic control system (such as PLCs or a DCS to execute local control and to route fan speed setpoints to fans and regulator opening setpoints to air flow regulators [ FIG. 2 , items ( 30 , 31 , 32 )].
The optimized mine ventilation system [ FIG. 2 , item ( 33 )] performs the following general tasks:
Perform a dynamic air mass flow balance for the entire mine ventilation network inclusive of all fans and air flow regulators or fixed opening bulkheads. From the dynamic tracking data, calculate each machinery ventilation demand and personnel ventilation demand. Perform a total ventilation demand for all machinery and/or personnel present in each of the mine defined work zones (ore extraction zones, service areas and levels). Calculate the aggregate demand for each zone parent-child relationship. For example, the total demand for a level is equal to the total demand for all related ore extraction zones and service areas plus the total demand related to machinery and personnel directly tracked on the level. Provide the demand to each of the zone related controllers: auxiliary fans and air flow regulators. Fans and airflow regulators can be controlled in manual or semi-automatic mode directly by the operator. A VOD control mode uses tracking data to automatically modulate the fans and air flow regulators as per the dynamic demand calculation. When in VOD control mode, the controllers regulates the flow for each zone as per the tracking and safety limits settings. In VOD control mode, the surface fans cascade controller will modulate the optimum air flow distribution and the lowest fan operating cost as per the cascade controllers set limits. In VOD control mode, the setpoints are filtered for stability, minimum time between up and down changes, ramp-up, ramp-down and deadband before they are sent to the basic control system via OPC connection. Critical air flow measurements are monitored and correlated to the modeled flows and when a discrepancy exists, the optimized mine ventilation system calls for a survey and calibration.
The features of the present invention which are believed to be novel are set forth with particularity in the appended claims.
As a first aspect of the invention, there is provided a method of optimizing mine ventilation, the method comprising:
calculation of a ventilation demand of a zone of interest; as a function of machinery location and operating status and personnel location monitoring, determining an optimal quantity of ventilation required for the zone of interest; and remotely controlling a ventilation flow in the zone of interest as a function of the determined optimal quantity of ventilation required.
Preferably, the step of determining an optimal quantity of ventilation comprises calculation of monitoring data using a ventilation system model adapted to determine an optimal quantity of ventilation required in the zone of interest.
Preferably, the steps of monitoring the zone of interest, of determining an optimal quantity of ventilation and of remotely controlling the ventilation equipment are carried out in real-time.
Preferably, the step of monitoring comprises monitoring presence of operating machinery and personnel inside the zone of interest and the monitoring data comprises machinery-and-personnel related data.
Preferably, the step of monitoring presence of operating machinery and personnel comprises gathering the machinery-and-personnel related data using a monitoring and communication system covering the zone of interest, where the machinery-and-personnel related data comprises an indication of a quantity of operating machinery and personnel present inside the zone of interest.
Preferably, the machinery-and-personnel related data further comprises, if operating machinery is present in the zone of interest, an indication if the machinery is diesel operated, and if it is the case, an engine or hydraulic-electric operating status of the machinery.
Preferably, the machinery-and-personnel related data further comprises, if operating machinery is present in the zone of interest and the machinery is diesel operated, engine-characteristics related data allowing for determining a total amount of horse power of the machinery.
Preferably, the step of controlling a ventilation flow in the zone of interest is carried out automatically.
Preferably, the presence of machinery is detected using a wireless communication system.
Preferably, the presence of personnel is detected using a wireless communication system.
The presence of machinery can also be detected using a radio frequency identification system.
The presence of personnel can also be detected using a radio frequency identification system.
The step of controlling a ventilation flow in the zone of interest is optionally manually controlled by an operator.
Preferably, the triggering is carried out by the operator using a graphical Human-Machine-Interface allowing graphical visualization of a ventilation status as per simulation model calculations of the zone of interest.
Preferably, the process of remotely controlling a ventilation flow in the zone of interest comprises adjusting speed of fans and/or regulators position.
As a further aspect of the invention, there is provided a system for optimizing ventilation equipment, the system comprising:
a real-time simulation model based control system which calculates air flow data in real-time for a zone of interest; a real-time simulation model that calculates flow and pressure as a function of the density and temperature variation which is a function of depth; a real-time simulation model that accounts for natural ventilation pressure flows; an optimizer for air flow distribution and fan energy consumption connected to the simulation model unit, as a function of an optimal quantity of ventilation required for the zone of interest; a real-time simulation model that will correlate physical air flow measurements to modeled air flow calculations and in case of discrepancies will have the capability to automatically calibrate system components k factor resistance to match physical measurements; and a ventilation equipment controlling unit connected to the optimal ventilation simulating unit and adapted to be connected to a communication system for remotely controlling performance of ventilation equipment as a function of the determined optimal quantity of ventilation required.
Preferably, the remote controlling of ventilation equipment is triggered automatically upon reception, by the ventilation equipment controlling unit, of the determined optimal quantity of ventilation required.
The system preferably further comprises a graphical image generating module connected to the monitoring unit for generating, as a function of the calculated by modeling and received monitoring data, a graphical image of a current ventilation status of the zone of interest.
Preferably, the graphical image generating module is further connected to the optimal ventilation simulating unit for generating, as a function of the determined optimal quantity of ventilation required, a graphical image of an optimal ventilation status of the zone of interest.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects, features and advantages of the invention will become more readily apparent from the following description, reference being made to the accompanying drawings in which:
FIG. 1 is background information on a mine ventilation typical layout and related air flow modulation equipment such as fans and airflow regulators within bulkheads. The optimized mine ventilation system invention models the ventilation air flow of the network and controls physical air flow modulation equipment.
FIG. 2 is a block diagram summary of all ventilation control components inclusive of an optimized mine ventilation system.
FIG. 3 is a detailed block diagram of the optimized mine ventilation system invention components and links to external elements. Dashed components are external elements to the optimized mine ventilation system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A novel optimized mine ventilation system will be described hereinafter. Although the invention is described in terms of specific illustrative embodiment(s), it is to be understood that the embodiment(s) described herein are by way of example only and that the scope of the invention is not intended to be limited thereby.
An embodiment of the optimized mine ventilation system according to the present invention will be described below in detail with reference to the drawings.
The following describes a summary of the optimized mine ventilation system functionality and links to external systems with references to FIG. 3 .
A third party machinery and personnel tracking system provides real-time data on the machinery location and operating status and on personnel location [ FIG. 3 , item ( 55 )].
From the dynamic tracking status of each machinery a ventilation demand is calculated for each defined mine work zones as per the following [ FIG. 3 , items ( 56 , 57 )]:
CFM or m3/s per diesel hp when diesel is “On”. CFM or m3/s per diesel hp when diesel is “Off”. This permits operations to have air available for machinery stopped at a location with personnel around. CFM or m3/s per diesel hp when the diesel is “Off” and its hydraulic-electric is “On”.
Those three parameters are configurable per machinery by the surface or underground operators.
The system calculates the aggregate demand for each zone parent-child relationship from the zone definition database [ FIG. 3 , item ( 57 )]. For example, the total demand for a level is equal to the total demand for all related ore extraction zones and service areas plus the total demand related to machinery and personnel directly tracked on the level.
The system sets to a minimum the personnel ventilation demand requirement per zone and overrules the machinery calculation if the personnel demand is higher.
If the calculated personnel and machinery total demand while on VOD control mode, the VOD controller will set the zone flow to a minimum air flow as defined by the ventilation engineer.
The mine ventilation layout, fans and air flow regulators are created in the form of an electronic process and instrumentation diagram using the Simsmart™ Engineering Suite modeling and simulation tool. Parametric information for all layout and control elements present on the diagram is configured in the diagram database [ FIG. 3 , item ( 52 )]. The diagram is compiled into a run-time engine execution environment [ FIG. 3 , item ( 51 )]. The run-time engine environment executes in real-time all physics, characteristic, mathematics and logic based equations.
The Simsmart™ Engineering Suite run-time engine is responsible for the following tasks:
As described above, to calculate the dynamic ventilation air flow demand and summarized per defined mine area such as an ore extraction zone, a level, a service area and other workplaces. To model the ventilation network and establish an air flow mass balance. The air density, pressure and temperature are preferably compensated for depth. The real-time model execute real-time calculations for pressure, fluid velocity, flow, temperature, several other fluid properties, fan speed and regulator position [ FIG. 3 , items ( 53 )]. To execute controls in manual, semi-automatic and VOD mode to optimize the air distribution and fan energy consumption based on the calculated dynamic air flow demand [ FIG. 3 , item ( 54 )]. To provide the required logic for fans and air flow regulators setpoint scheduling [ FIG. 3 , items ( 63 )]. To declare and handle alarm and special event conditions.
The following physics calculation assumptions describe the basic concepts and equations used for the simulation model components and the real-time resolution of the differential equations matrix [ FIG. 3 , item ( 51 )]:
The simulation model uses compressible air flow with a polytropic process. This is a process which occurs with an interchange of both heat and work between the system and its surroundings. The nonadiabatic expansion or compression of a fluid is an example of a polytropic process. The interrelationship between the pressure (P) and volume (V) and pressure and temperature (T) for a gas undergoing a polytropic process are given by Eqs. (1) and (2),
PV
a
=
c
(
1
)
P
b
T
=
c
(
2
)
where a and b are the polytropic constants for the process of interest. These constants, determined from mine surveys. Once these constants are known, Eqs. (1) and (2) can be used with the initial-state conditions (P 1 and T 1 or V 1 ) and one final-state condition (for example, T 2 , obtained from physical measurement) to determine the pressure or specific volume of the final state.
Because density varies significantly, the air weight effect is not negligible. In this case there is an auto compression effect. Pressure variation not only causes density variation but also causes temperature variation accordingly based on the polytropic index.
The calculations account for Natural Ventilation Pressure (NVP). NVP is the pressure created in a ventilation network due to the density difference between air at the top and bottom of the downcast and upcast shafts. In deep hot mines there is usually a large difference between surface and underground temperatures—there is a difference in density between air on surface and underground and this causes air to move from high to low density. The NVP will either assist or retard fans in the system. When NVP assists a fan, it tends to move air in the same direction as the fan. The NVP can be the to lower the system resistance curve against which the fan operates. This means the fan will handle more air at lower pressure.
The actual tunnel air resistance is calculated using the entered standardized Atkinson resistance or the standardized Atkinson friction factor.
The air pressure, air velocity, flow resistance and air flow rate are calculated at all points in the system.
The pressure and density calculation accounts for air weight (air potential pressure) and the Bernoulli Equation accounts for potential energy.
Correction of fan specification curves with the density variation effect.
Calculation of variable speed fan flow, pressure, power and efficiency curves.
Ducting junctions, dovetails or transitions can calculate process pressure and flow resistance for each port.
Transitions, junctions and fan calculation accounts for positive and negative flow resistance.
All components calculate air properties: temperature, pressure, viscosity, humidity, dew point temperature, particles, and contaminant concentrations.
An iteration convergence method is used for transient simulation modes.
Latent heat calculation is not available.
The ventilation demand calculation commands controllers to modulate fans and air flow regulators [ FIG. 3 , item ( 54 )].
There are four types of regulatory controls for fans and air flow regulators in the optimized mine ventilation system:
Auxiliary fans control. From the air mass flow balance calculations, the auxiliary fans speed is modulated so the output flow at the exit of the ducting section meets the calculated target demand flow for each work zone. Air flow regulator controls for levels. From the air mass flow balance calculations, the air flow regulator opening position is modulated so the regulator output flow meets the calculated target demand flow for each work zone. If an air flow regulator is in manual mode or if the regulator is a fixed bulkhead opening, an intake compensation cascade controller will modulate the surface fans in order to meet the calculated target demand flow. Surface fans controls. The surface fan controller is a cascade controller [ FIG. 3 , items ( 58 , 59 )] that optimizes the surface fan speeds in order to minimize energy consumption while assuring all levels to obtain their calculated target demand flow and maintaining a set maximum regulator opening. This maximum regulator opening is the cascade controller setpoint. It is assumed that all surface fans are driven by a variable frequency drive. As an example, if the surface fans cascade controller setpoint is set at 80% opening maximum for any air flow regulator, the surface fans will be modulated in order to assure that any level air flow regulator will be at and not exceed this 80% maximum opening. The surface fans cascade controller calculates a common modulated fan speed for all fans. This speed is then split by a ratio to intake fans and to another ratio to exhausts fans. Booster fans controls. The booster fan controller is a cascade controller over the air flow regulator controller. It will modulate the booster fan speed based on set maximum air flow regulator opening. For example if the cascade controller setpoint is set at 70%, this means that when the booster fan will be modulated upward when the regulator position exceeds 70%.
The optimized mine ventilation system has the following control modes [ FIG. 3 , item ( 54 )]:
Surface Operating Mode:
MAN: A fixed fan speed or regulator position setpoint is entered by the surface operator. The fan speed and/or regulator position not modulated automatically. The simulation model does not modulate the fan speed or the airflow regulator position to meet a CFM value. The machinery tracking has no effect on the control. The local underground controller requires to be in “Surface” mode.
AUT: This mode activates the selected VOD or CFM modes.
a. VOD: The CFM setpoint is calculated from the dynamic machinery tracking results. The fan speed and/or regulator position is automatically modulated to meet the CFM demand setpoint as per the calculated actual flow by the simulation model. The modulated fan speed or airflow regulator position setpoint is sent to the underground physical device. The controller also needs to be in AUT mode for the VOD mode to be active. The controller also requires to be in “Surface” mode. A minimum flow setting is available for the VOD mode. Therefore, a dynamic tracking ventilation demand setpoint may never be lower than a defined pre-set. The minimum flow presets are defined in a purpose built HMI page. b. CFM: The CFM setpoint is a fixed value and is entered by the surface operator for fans or airflow regulator. The fan speed and/or regulator position is automatically modulated to meet the fixed value CFM setpoint as per the calculated actual flow by the simulation model. The simulation model will modulate the fan speed or the airflow regulator position to meet the desired CFM value. The equipment tracking has no effect on the control. The controller also needs to be in AUT mode for the CFM mode to be active. The controller requires to be in “Surface” mode.
Underground Operating Mode:
Control is normally achieved from the surface, but an underground operator via a tablet PC may acquire a control mode called “Underground”. When he acquires control he can operate the selected controller in Manual mode.
The surface operator receives an alarm when control is acquired by the underground operator. The surface operator is requested to acknowledge the alarm. When the alarm is acknowledged, the alarm condition disappears.
When the underground operator releases control back to the surface operator, an alarm is displayed to the surface operator. The surface operator is requested to acknowledge the alarm. When the alarm is acknowledged, the alarm condition disappears.
When the control is released by the underground operator, the selected controller goes back to the previous mode in use before he acquired control.
The following describes each mode:
SUR: A fan speed and/or regulator position is set by the surface operator in MAN, AUT (VOD/CFM) modes (see above). UND: When a controller is set to UND, a fan speed and/or regulator position is manually set by an underground operator via a WIFI tablet PC HMI control page.
The VOD control mode setpoints are filtered [ FIG. 3 , item ( 65 )] for stability, minimum time between up and down changes, ramp-up, ramp-down and deadband before they are sent to the basic control system and physical fans and air flow regulators via OPC connection [ FIG. 3 , items ( 66 , 67 )].
Since not all mine ventilation operating procedures call for work zone flow setpoints being calculated on machinery location, operating status and personnel location, controller modes and setpoints are also subject to scheduled or ad-hoc events [ FIG. 3 , item ( 63 )]. Therefore, presets for each controller modes and setpoints can be configured for an array of user definable events [ FIG. 3 , item ( 64 )]. Optionally, an autoswitch to tracking based ventilation (VOD mode) can be enabled when a minimum ventilation demand has been detected by the dynamic tracking. Likewise, another autoswitch to tracking based ventilation can be enabled when a defined period of time has elapsed.
Scheduling presets can also cover specific events such as pre-blast and post-blast events. The optimized mine ventilation system will warn the operator if pre-blast event is set with remaining personnel and machinery activity in the mine.
The optimized mine ventilation system monitors critical key air flow measurements [ FIG. 3 , item ( 60 )] and will alarm when a correlation deviation to the measurements calculated by the model [ FIG. 3 , item ( 61 )]. The optimized mine ventilation system will call for a flow survey to verify if the measurement instrument or the calculated flow are in error. If it is concluded that the calculated flow must be calibrated, the ventilation engineer will set the related flow controller in calibration mode. Then, it will automatically adjust the related system portion calculated k factor to match the survey data.
While illustrative and presently preferred embodiment(s) of the invention have been described in detail hereinabove, it is to be understood that the inventive concepts may be otherwise variously embodied and employed and that the appended claims are intended to be construed to include such variations except insofar as limited by the prior art. Indeed, the system of the invention can be used in any confined environment where there is a need for ventilation as a function of the presence of humans, animals and/or equipment, for example: tunnels. | The optimized mine ventilation system of this invention supplements mine ventilation basic control systems composed of PLCs (Programmable Logic Controllers with human machine interfaces from vendors such as Allen-Bradley™, Modicon™ and others) or DCSs (Distributed Control System from vendors such as ABB™ and others) with supervisory control establishing a dynamic ventilation demand as a function of real-time tracking of machinery and/or personnel location and where this demand is optimally distributed in the work zones via the mine ventilation network and where the energy required to ventilate is minimized while totally satisfying the demand for each work zones. The optimized mine ventilation system operates on the basis of a predictive dynamic simulation model of the mine ventilation network along with emulated control equipment such as fans and air flow regulators. The model always reaches an air mass flow balance where the pressure and density is preferably compensated for depth and accounts for the natural ventilation pressure flows due to temperature differences. Model setpoints are checked for safety bounds and sent to real physical control equipment via the basic control system. | 4 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a buttonhole sewing machine for the production of a group of buttonholes on a workpiece, the group having at least two buttonholes of varying design and/or size, the buttonhole sewing machine comprising a needle, which is mounted in an arm, and which is drivable to reciprocate in a Z direction by means of a driving motor, and which is drivable by a jogging drive for the production of a zigzag seam by a motion of the needle relative to the workpiece, and which is drivable to pivot about an axis by means of a pivot drive; a hook bearing, which is disposed in a base plate, and which is drivable by a pivot drive to pivot synchronously and equiangularly of the needle about a pivot axis which extends in the Z direction; a hook, which is disposed in the hook bearing; a stitch hole, which is allocated to the needle and the hook; a holder for the workpiece, which holder is displaceable by drives in an X direction and a Y direction; and an operating and control unit.
2. Background Art
In a buttonhole sewing machine of the generic type known from U.S. Ser. No. 09/063,965, U.S. Pat. No. 6,006,685 the workpiece holder in the form of an X-Y table is actuated by two stepper motors. Furthermore, the needle bar and the hook bearing are driven synchronously and equiangularly by a stepper motor so that the sewing tools are rotatable about the axis of the needle, which helps attain a constant position of the sewing tools relative to the direction of sewing and thus considerable flexibility of the machine as regards the geometry of the seam.
SUMMARY OF THE INVENTION
It is an object of the invention to embody the buttonhole sewing machine of the generic type such that a group of buttonholes of varying design and/or dimensions can be sewn by it successively, there being no need of manual adjustment of the machine.
According to the invention, this object is attained by devices for the entry, storage and processing of information about the varying design and/or size of the group of buttonholes; and by a device for triggering the drives for the successive production of the buttonholes on the workpiece. The measures according to the invention help attain that all the relevant parameters of buttonholes that are to be produced successively at a single work place, i.e. by one and the same buttonhole sewing machine, are entered in advance and that the buttonholes are then sewn one after the other. The buttonholes can be cut if a cutter is provided for the production of an incision in the zigzag seam; if the operating and control unit comprises means for the entry, storage and processing of information about the execution and non-execution and the type of the incision; and if the device for triggering the drives also comprises means for triggering the cutter. In this case it is of no importance whether cutting the buttonholes takes place in the pre- or after-cutting mode.
Provision is made for a gimp thread feeder, which is very often desired, automatic feeding and cutting of the gimp thread being provided within the scope of automation of the sewing operation of the varying buttonholes. Of course, this design of the gimp thread feeder can also be employed when buttonholes are sewn successively which are identical in design and size and/or when no automation is provided.
Details of the invention will become apparent from the ensuing description of an exemplary embodiment, taken in conjunction with the drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is an elevation of a buttonhole sewing machine;
FIG. 2 is a front view of an X-Y table according to the arrow II of FIG. 1;
FIG. 3 is a diagrammatic illustration of a vertical section of a gimp thread feeder according to the arrow II of FIG. 1 during a sewing job;
FIG. 4 is an illustration of the gimp thread feeder according to FIG. 3 during the cutting of a gimp thread;
FIG. 5 is an illustration of the gimp thread feeder according to FIG. 3 during the feed of a gimp thread prior to the start of a sewing job;
FIG. 6 is a view of a cutter on an enlarged scale as compared to FIG. 1;
FIG. 7 is a view of a workpiece in the form of a jacket forepart comprising four buttonholes of three different types which are to be sewn;
FIG. 8 is a diagrammatic illustration of a straight buttonhole;
FIG. 9 is an illustration of an eye type buttonhole;
FIG. 10 is an illustration of an eye type buttonhole with a stitched transverse lock;
FIG. 11 is a diagrammatic illustration of an operating and control unit of the sewing machine; and
FIG. 12 is an input diagram for illustration of the entry of buttonhole parameters.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The single/double thread chain stitch sewing machine seen in FIG. 1 comprises a housing 1 , which substantially consists of a so-called base plate 2 , a standard 3 and an upper arm 4 . An arm shaft 5 is rotatably run in the arm 4 and can be driven in rotation by means of a driving motor 6 via a belt drive 7 .
Mounted in the arm 4 in bearings 9 , 10 is a substantially vertical needle bar 8 , which can be driven to reciprocate by the arm shaft 5 via a crank drive 11 . At its lower end, the needle bar 8 is provided with a needle 12 .
Underneath the needle bar 8 , a hook bearing 13 , which comprises a chain stitch hook 14 (FIG. 3 ), is mounted in bearings 15 , 16 for rotation by approximately 400° about a vertical pivot axis 17 which extends in the Z direction. Rotary actuation of the hook bearing 13 takes place via two belt drives 19 , 20 by means of a stepper motor which serves as a pivot drive 18 . The needle bar 8 is mounted in the bearings 9 , 10 not only for displacement in the longitudinal direction, but also for rotation about the pivot axis 17 . Via a setting shaft 21 , which is drivable by the belt drive 19 and extends in the Z direction, and via a further belt drive 22 , it is driven synchronously and equiangularly of the hook bearing 13 by the pivot drive 18 so that the needle 12 and the hook bearing 13 are synchronously and equiangularly pivoted about the pivot axis 17 .
The needle bar 8 and the needle 12 are drivable to jog laterally, i.e. to swing, by means of a needle jogging drive 23 . The lateral jogging motion is accompanied with a deflection of the needle bar 8 relative to the pivot axis 17 . Due to the rotatability of the needle bar 8 , the jogging plane of the needle bar 8 with the needle 12 is displaceable synchronously and equiangularly of the position of rotation of the hook bearing 13 . A stepper motor 25 is provided for the lateral jogging of the needle bar 8 , this stepper motor 25 acting on the needle bar 8 by way of a jogging shaft 28 , which is run in bearings 26 , 27 . To this end, provision is made for a transmission 29 (not shown in detail), which is known from U.S. Pat. No. 1,991,627 and U.S. patent application Ser. No. 09/256,853, U.S. Pat. No. 6,095,066.
An X-Y table 30 (seen in detail in FIG. 2) is disposed on the base plate 2 ; it is mounted on guide rods 31 which extend in the X direction and it is displaceable in this direction. By means of connecting rods 32 , the guide rods 31 are supported on rods 33 which are mounted in the base plate 2 and extend in the X direction. The connecting rods 32 cooperate with the rods 33 and the guide rods 31 and the table 30 to form a parallel rod guide, by means of which the table 30 can be displaced parallel to itself in the Y direction. In doing so, it makes slight motions in the Z direction which are however negligible because of their minor significance. The described motion of displacement of the table in the Y direction takes place by means of a stepper motor 34 which is coupled with one of the rods 33 via a pinion 35 and a segment gear 36 . Displacement of the table 30 in the X direction takes place by means of a stepper motor 37 and a spindle drive 38 (roughly outlined). The described design and the actuation of the table 30 are also known from U.S. Ser. No. 09/256,853, U.S. Pat. No. 6,095,066. A clamp 39 is disposed on the table 30 , fixing the workpiece 40 . A workpiece cutter 41 for cutting a buttonhole is customarily provided beside the needle bar 8 on the arm 4 above the table 30 .
As seen in FIGS. 3 to 5 , the chain stitch hook 14 is disposed in the hook bearing 13 ; a looper thread 45 is fed to the hook 14 through an opening 44 formed in the bottom 43 of the hook bearing 13 concentrically of the pivot axis 17 . Disposed on the base plate 2 above the hook bearing 13 and in the plane of the table 30 is a stitch plate 46 with a stitch hole 47 , through which passes the needle 12 with a needle thread 48 , the needle thread 48 being seized by the jogging hook 14 and a double thread chain stitch being formed in the workpiece 40 .
Further provided in the hook bearing 13 is a feeder 49 , feeding a gimp thread 50 to the workpiece 40 through the stitch hole 47 . This feeder 49 comprises a pivotal guide 51 for the gimp thread 50 . This guide 51 has a curved guide tube 52 which is mounted on a two-armed pivoted lever 53 . The lever 53 is mounted in a bearing 54 pivotally about a horizontal axis 55 which extends in the X direction; the bearing 54 is disposed in the hook bearing 13 . At the end, turned away from the guide tube 52 , of the pivoted lever 53 , a pivot drive 56 acts thereon, which is formed by a pneumatically actuated double action piston-cylinder drive articulated to the bottom 43 of the hook bearing 13 . A clamping device 57 is provided on the pivoted lever 53 in a manner allocated to guide tube 52 ; the clamping device 57 comprises a clamping surface 58 , which is formed on the guide tube 52 , a clamping jaw 59 , which cooperates therewith, and a clamping jaw drive 60 of linear action. The drive 60 is also formed by a pneumatically actuated double action piston-cylinder drive.
Provided on an inside wall 61 of the base plate 2 , which also carries the upper bearing 15 of the hook bearing 13 , is a gimp thread cutter 62 , which comprises scissors 63 , which are moved by means of a linear displacement drive 64 into a position of rest (seen in FIGS. 3 and 5) outside the hook bearing 13 , or which are moved into the wall 66 of the hook bearing 13 through an opening 65 thereof, into a position of work (seen in FIG. 4) located in the path of the gimp thread 50 . Also the displacement drive 64 is formed by a pneumatically actuated double action piston-cylinder drive.
The gimp thread 50 is supplied in the same way as the looper thread 45 through the opening 44 in the bottom 43 of the hook bearing 13 and piloted through a gimp thread guide 67 which is stationary in the hook bearing 13 and disposed on the path between the opening 44 and the guide tube 52 . The pivot drive 56 and the clamping jaw drive 60 are provided with compressed air via compressed air lines 68 , 69 , 70 , 71 , which are flexible hose lines, leading through the opening 44 in the bottom 43 of the hook bearing 13 . Since the hook bearing 13 only performs a non-revolving pivotal motion, flexible plastic hoses are able to participate in this motion without being damaged. The displacement drive 64 is supplied with compressed air via compressed air lines 72 , 73 . The scissors 63 are designed in known manner to perform a cutting motion upon advance into its position of cutting. A feed channel 74 for the gimp thread is formed in the stitch plate 46 and opens laterally into the stitch hole 47 ; it is located in the feed path of the guide 51 .
The cutter 41 is known partially from U.S. Ser. No. 09/063,965, U.S. Pat. No. 6,006,685. It comprises a lower knife 75 , which is located in the plane of the stitch plate 46 and is stationary in the base plate 2 , and a cutting block 76 located on the arm 4 beside the needle bar 8 and vertically above the knife 75 . The cutting block 76 comprises a carrier 77 , on which are disposed several knife abutments 78 , 79 , only two of which are illustrated. The carrier 77 is rotatably mounted in a holder 80 , which is designed as a downwardly open bow, and it is drivable to rotate about an axis of rotation 82 by means of a rotary actuator 81 so that one knife abutment 78 and 79 at a time moves into a position allocated to the knife 75 . The holder 80 is non-rotatably, but axially displaceably arranged on a rod 80 a , the lower end of which rests on the carrier 77 . The rod 80 a is displaceable in the Z direction, but is mounted non-rotatably in a bearing 83 . A lifting mechanism 84 of vertical action, i.e. which acts in the Z direction and is designed in the form of a pneumatically actuated double action piston-cylinder drive, acts on the upper end of the rod 80 a. Further, a cutting drive arrangement 85 acts on the rod 80 a ; it comprises a lever 86 of substantially horizontal arrangement, one end 87 of which is articulated to the holder 80 and the other end of which is mounted in the arm 4 pivotally about a horizontal axis by means of a pivot bearing 88 . A roll 89 is attached to the lever 86 and can be engaged with a cam 91 formed on an operating lever. This operating lever 90 is mounted pivotally in a pivot bearing 92 in the arm 4 , pivoting about an axis that is parallel to the axis of the pivot bearing 88 . A cutting drive 93 in the form of a pneumatically actuated piston-cylinder drive acts on the end of the operating lever 90 that is opposite the pivot bearing 92 , the piston rod 94 of this drive 93 being articulated to the end of the operating lever 90 that is opposite the pivot bearing 92 . The cylinder 95 of the cutting drive is articulated by means of a bearing 96 in the arm 4 . The cam 91 on the operating lever 90 is formed in such a way that it engages with the roll 89 only after a certain motion of extraction of the cutting drive 93 and then forces the cutting drive 93 downwards and thus also the holder 80 together with the carrier 77 and the knife abutments 78 , 79 , the downward knife abutment 78 , which is located above the cutting block 76 , bearing there-against. When the piston rod 94 is completely retracted into the cylinder 95 —as seen in FIG. 6 —then the holder 80 together with the knife abutments 78 can be lifted further upwards by means of the lifting mechanism 84 against the force of a spring 97 which is located between the holder 80 and the rod 80 a. Only strokes in the order of magnitude of 5 mm and with a path of approximately 1 mm for the actual cutting job are performed at high forces by means of the cutting drive arrangement 85 .
The knife 75 has the shape of the longest possible incision to be carried out in a buttonhole, in particular in an eye type buttonhole. The knife abutments 78 only extend over the length along which an incision will really be performed in an eye type buttonhole. Wherever no knife abutment is available for the knife 75 when an incision is made, the workpiece 40 will yield laterally so that a shorter incision is made.
The feeding device 49 cooperates with the sewing tools, i.e. the needle 12 and the hook 14 , and with the cutter 41 , as follows:
The basis from which to proceed is a sewing operation illustrated in FIG. 3, in which zigzag stitches are made for the production of a buttonhole seam. The zigzagging configuration is produced exclusively by the needle jogging drive 23 . The gimp thread 50 is fed in a known manner into the buttonhole seam. In this case, the guide 51 together with the guide tube 52 is in its position of guidance, in which it is pivoted away from the stitch plate 46 and in which the gimp thread 50 is piloted through the opening 44 , the guide 67 , the guide tube 52 and the feed channel 74 , which discharges laterally into the stitch hole 47 , and in which the gimp thread 50 is fed out of the stitch hole 47 into the zigzag seam. The clamping device 57 is opened in this case. The cutter 62 is in its retracted position of rest so that the hook bearing 13 can be rotated together with the needle 12 freely about the pivot axis 17 , corresponding to the course of the seam that is to be produced. The double thread chain stitch seam is produced by cooperation of the needle 12 and the hook 14 in known manner. The course of the seam results from the displacement of the table 30 combined with the joint pivoting of the needle 12 and the hook bearing 13 .
Before the end of the seam is reached, the hook bearing 13 is in a position of rest, in which the opening 65 is located in front of the scissors 63 . Now the clamping jaw drive 60 is actuated such that the clamping jaw 59 is pressed against the clamping surface 58 , clamping the gimp thread 50 . Simultaneously the displacement drive 64 is actuated so that the scissors 63 are moved through the opening 65 into the hook bearing 13 where they cut the gimp thread 50 at a distance from the guide tube 52 . Immediately afterwards, the scissors 63 are moved out of the hook bearing by corresponding reverse actuation of the displacement drive 64 ; the gimp thread 50 remains clamped in the clamping device 57 . The moment when the gimp thread 50 is cut through is selected such that the part of the gimp thread that leads to the workpiece 40 is taken up entirely in the finished buttonhole seam, i.e. is used up. With the subsequent start of another gimp thread 50 zigzag seam, the end 75 of the gimp thread 50 which stands out from the guide tube 52 is automatically supplied to the feed channel 74 and thus to the stitch hole 47 by the pivot drive 56 being actuated in the way seen in FIG. 5 . In this way, the guide tube 52 moves as far as to the stitch plate 46 and pushes the free end 100 of the gimp thread 50 upwards through the feed channel 74 and the stitch hole 47 . During this feed motion, the gimp thread 50 is still clamped between the clamping jaw 59 and the clamping surface 58 . When another sewing job starts, the end 100 is clamped in the zigzag seam; the clamping arrest between the clamping jaw 59 and the clamping surface 58 is released, to which end the clamping jaw drive 60 is actuated counter to the clamping motion. Then the pivot drive 56 is again actuated in such a way that the guide tube 52 is pivoted back into its initial position illustrated in FIGS. 3 and 4.
FIG. 7 illustrates a jacket as a workpiece 40 , in which three different buttonholes are to be made, namely a lapel buttonhole A, two identical forepart buttonholes B and a sleeve buttonhole C. FIGS. 8, 9 , 10 illustrate some buttonholes and the corresponding buttonhole seams only by way of example. FIG. 8 shows a simple button hole 101 without an eye, having a straight incision 102 and a rectangular zigzag seam 103 . FIG. 9 illustrates a buttonhole 104 with a so-called eye 105 and a straight incision 102 and a so-called eye type incision 106 in the eye 105 . In the vicinity of the eye 105 , the zigzag seam 107 extends on an arc of a circle. The buttonhole 108 of FIG. 10 corresponds to that of FIG. 9, a stitched transverse lock 109 being provided in addition to the zigzag seam 107 at the end opposite the eye 105 . Of course, there are lots of other forms of buttonhole seams, the illustration of which is however not necessary for the understanding of the invention. As described, the buttonholes 101 , 104 and 108 are provided with different incisions 102 , 102 and 106 . They are produced by varying triggering/activation of the cutter 41 . Of course, it is possible also to produce buttonholes without any incision as a decorative seam pattern by putting the cutter 41 out of operation in accordance with the program.
The sequence of the program can be seen from FIGS. 11 and 12. The sewing machine is provided with an operating and control unit 110 , into which to enter, via a keyboard, the parameters of a buttonhole 101 , 104 , 108 , for instance the length l thereof, and the decision of whether the buttonhole is to have an eye 105 and a gimp thread 50 . It is further entered whether the buttonhole is to have a straight incision 102 and an eye incision 106 . Further entries involve the question whether the buttonhole is to have a stitched transverse lock 109 and what will be the width a of this transverse lock. The width b of the stitches of the respective zigzag seams 103 and 107 can also be entered. The entered data can be checked by a display 112 . Further parameters of the buttonhole seams to be produced are programmable as well.
The freely selectable data are filed in working-storage sections 113 of the unit 110 , whereas data relevant to the machine are filed in the main storage 114 .
All the drive systems described inclusive of the drive system for the cutter 41 are triggered by the operating and control unit 110 . This is roughly outlined in FIG. 11 by correspondingly encircled reference numerals. FIG. 12 diagrammatically reflects the program entry PRG described above, use being made therein of the reference numerals introduced above. The type of the workpiece 40 is entered under PRG. This is followed by the entry of the buttonholes 101 , 104 , 108 , namely the lapel buttonhole A, the two forepart buttonholes B, B and the sleeve buttonhole C. Subsequently the respective lengths l are entered and then whether or not an eye 105 is to be sewn. In FIG. 12, the circle is marked with a diagonal cross for the corresponding feature. Then it is entered whether or not a gimp thread 50 is to be sewn in. Then it is decided whether a straight incision 102 or an eye incision 106 is to be made. Finally, it is decided whether a stitched transverse lock 109 is to be sewn and what will be the width. Finally, the width b of the zigzag seam 103 and 107 must still be entered. | A buttonhole sewing machine for the production of a group of at least two buttonholes of varying design and/or size comprises devices for the entry, storage and processing of information on the varying design and/or size of the group of buttonholes and a device for triggering the drives for the successive production of buttonholes on the workpiece. | 3 |
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to the fabrication of ultra large scale integrated circuits and, more particularly, to an improved method for depositing a flow fill intermetallic dielectric on a wafer bearing these circuits.
The latest ultra large scale integrated circuits include features as small as about 0.5 microns and smaller. To effect contact with these features, the metallic contacts in the chip that contains the circuits must be stacked in three or more levels. These contacts are formed by a process that includes lithography and etch, and are separated by an intermetallic dielectric, typically SiO 2 . For successful lithography and etch in the formation of a second or subsequent level of metal, the substrate above which they are deposited must be substantially flat.
A process for depositing an SiO 2 intermetallic dielectric with a substantially flat upper surface is described in C. D. Dobson, A. Kiermasz, K. Beekman and R. J. Wilby, Advanced SiO 2 planarization using silane and H 2 O 2 , Semiconductor International, December 1994, pp. 85-88; in M. Matsuura, Y. Hayashide, H. Kotani, T. Nishimura, H. Iuchi, C. D. Dobson, A. Kiermasz, K. Beekmann and R. Wilby,; and in A. Kiermasz, C. D. Dobson, K. Beekmann and A. H. Bar-Ilan, Planarization for sub-micron devices utilizing a new chemistry, DUMIC Conference, Feb. 21-22, 1995, pp. 94-100. These references are incorporated by reference for all purposes as if fully set forth herein. The FIGURE schematically shows the "flow fill layer" 30 thus deposited between and around metallic contacts 22. Flow fill layer 30 includes a base layer 32, a flowlayer 34, and a cap layer 36. The essence of the process is the deposition of flowlayer 34, by reacting SiH 4 and H 2 O 2 at 0° C. to form a liquid layer, believed to be primarily Si(OH) 4 in composition. The liquid flows around and above metallic contacts 22, providing a dielectric layer with a substantially flat top surface. Base layer 32 of SiO 2 is deposited, prior to the deposition of flowlayer 34, by plasma enhanced chemical vapor deposition (PECVD), to provide a surface to which flowlayer 34 adheres well. Cap layer 36 of SiO 2 is deposited over flowlayer 34, also by PECVD, to protect flowlayer 34 in the final step: baking the wafer at a temperature of between 400° C. and 450° C. to transform flowlayer 34 from Si(OH) 4 to SiO 2 .
It is important that flowlayer 34 not have cracks. The transformation of Si(OH) 4 to SiO 2 involves the evaporation of water as steam, which may induce the formation of cracks in flowlayer 34 as flowlayer 34 is transformed from a liquid to a solid. One of the purposes of cap layer 36 is to prevent the formation of these cracks. Cap layers 36 deposited by the processes known in the art have not been entirely successful in preventing crack formation.
There is thus a widely recognized need for, and it would be highly advantageous to have, a method of depositing a cap layer of a flow fill layer that protects the flowlayer of the flow fill layer against crack formation to a greater extent than the processes known in the art.
SUMMARY OF THE INVENTION
According to the present invention there is provided, in a process for depositing a flow fill layer on an integrated circuit wafer, the flow fill layer including a cap layer for preventing crack formation during the evaporation of water, an improved method for depositing the cap layer to a final thickness, comprising the steps of: (a) depositing a first thickness of the cap layer on the wafer; (b) evaporating at least a portion of the water via the first thickness of the cap layer; and (c) subsequent to the evaporation, depositing a second thickness of the cap layer on the wafer.
In the conventional process for depositing cap layer 36, the wafer is warmed to a temperature of about 300° C. and the entire cap layer 36 is deposited in one PECVD step. The innovation of the present invention is to deposit cap layer 36 in two or more PECVD steps. In each PECVD step, a different partial thickness of cap layer 36 is deposited.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention is herein described, by way of example only, with reference to the accompanying drawings, wherein:
The sole FIGURE (prior art) is a schematic cross-section through a flow fill layer.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is of a method for depositing a cap layer of a flow fill layer. Specifically, the present invention can be used to inhibit crack formation in the flowlayer of the flow fill layer.
The principles of cap layer deposition according to the present invention may be better understood with reference to the following description. The process parameters described herein are specific to the manufacture of a flow fill layer whose base layer 32 is 2000 Å thick, whose flowlayer 34 is 9000 Å thick, and whose cap layer is 3000 Å thick, using a Planar 200 multi-chamber cluster tool manufactured by Electrotech of Bristol, UK; but it will be readily apparent to one ordinarily skilled in the art how to adjust the parameters for flow fill layers of other geometries and for other integrated circuit manufacturing devices.
The process parameters recommended by Electrotech are as follows:
______________________________________Base Layer:pressure 1400 mTNitrogen 1500 sccmNitrous Oxide 3500 sccmSiH.sub.4 150 sccmRF power 100 Wtime 38 secondsFlowlayer:pressure 850 mTNitrogen 300 sccmSiH.sub.4 120 sccm60% H.sub.2 O.sub.2 0.65 g/sectime 62 secondsCap Layer: Warm-up Step:final temperature 300° C.time 90 secondsCap Layer: Deposition:pressure 750 mTNitrogen 1000 sccmNitrous Oxide 2000 sccmSiH.sub.4 100 sccmRF power 500 Wtime 36 seconds______________________________________
In the Electrotech warm-up step, the wafer is maintained at a temperature of 300° C. for about 90 seconds in order to start the evaporation water from flowlayer 34 before the actual deposition of the cap layer.
According to the present invention, cap layer 36 preferably is deposited in only two PECVD steps. In the first step, approximately the first 1000 Å of cap layer 36 is deposited. The wafer then is maintained at a temperature of between 300° C. and 350° C. for between 90 seconds and 180 seconds to start the evaporation of water from flowlayer 34 through this first portion of the cap layer. In the second step, the remaining 2000 Å of cap layer 36 is deposited.
______________________________________Cap Layer: First Step: Warm-up:final temperature 300° C.-350° C.time up to 10 secondsCap Layer: First step: Deposition:pressure 750 mTNitrogen 1000 sccmNitrous Oxide 2000 sccmSiH.sub.4 100 sccmRF power 500 Wtime 12 secondsCap Layer: Second Step: Warm-up:final temperature 300° C.-350° C.time 90-180 secondsCap Layer: Second Step: Deposition:pressure 750 mTNitrogen 1000 sccmNitrous Oxide 2000 sccmSiH.sub.4 100 sccmRF power 500 Wtime 24 seconds______________________________________
It is to be understood that these parameters are illustrative only. The essence of the present invention is the deposition of cap layer 36 in several steps, rather than all at once, with partial evaporation of water from flowlayer 34 in between the several steps. It will be apparent, to one ordinarily skilled in the art, how to adapt these parameter values for other applications.
While the invention has been described with respect to a limited number of embodiments, it will be appreciated that many variations, modifications and other applications of the invention may be made. | An improved method for depositing the cap layer of a flow fill layer of an integrated circuit. The cap layer is deposited in at least two steps, instead of all at once. | 8 |
BACKGROUND OF THE INVENTION
This invention relates to a toy construction kit for building wet sand structures. The toy construction kit includes sets of building modules for casting supportable sand components in making large and elaborate sand structures.
Children enjoy playing in the sand at the beach, or in a playground or home "sandbox." Particular enjoyment is derived from building sand castles and other sand structures from wet or damp sand. Building large or complex sand structures often requires an artistic talent and dexterity not possessed by young children. In fact, such structures are frequently built by young adults, often in teams, during competitions. As the wet sand begins to dry, the sand structure crumbles under its own weight, often before the entire structure is completed.
To provide younger children with the means to produce large, imposing structures in a short period of time, casting pails are frequently used. By packing sand in a sand pail, and inverting the pail at the desired location, elements of a structure can be completed quickly before appreciable drying occurs. While this method is popular with young children, the inability to construct tall and complex structures leads to disinterest and boredom.
In order to provide young children and enthusiastic adults with a challenge in building cast sand structures, the toy construction kit of this invention was devised. The primary problem with the use of existing pail cast structures is the inability to stack castings or span between castings. The toy construction kit of this invention solves the problems of existing sand casting kits that merely provide a series of different molds, and provides structural elements to greatly expand the type and size of structures buildable using the toy construction kit.
The toy construction kit is designed as an educational tool to both develop motor skills and conceptualization. Building integrated structures from a set of modules requires a gradual increase in dexterity as the structures increase in complexity.
The toy construction kit was primarily designed for use with wet sand, but any compactible material, such as snow can be used with the construction kit. In summer or winter, hours of enjoyment can be provided with the toy construction kit of this invention.
SUMMARY OF THE INVENTION
The toy construction kit of this invention relates to a system for building wet sand structures. The system includes, not only a set of sand molds, but additional structural elements that enables the cast sand modules to be stacked and spanned in a variety of different composite structures.
It is contemplated that the toy construction kit can be marketed as a simple starter kit with one or more different mold configurations, and also in more elaborate sets including a variety of different molds. The construction kit includes at least one support plate, a support post connectable to the support plate, and a forming mold into which sand is packed around the support post. The mold may be a simple container similar to the shape of a sand bucket with a post recess for positioning the support post prior to filling with sand. Once sand is filled in the mold, the support plate having a similar post recess is connected to the distal end of the support post which has a length equal to the depth of the container. With the support plate engaged on the support post, the mold is inverted and the support disengaged from the recess in the mold to assist in maintaining the integrity of the sand module which may be lifted by the support plate and located as desired in the structure being built.
In addition to the three basic components, small connecting clips are provided to interconnect a plurality of sand modules by interconnecting the support plates supporting the sand casting. The support clips comprise a small tab with a plurality of short projecting posts that selectively engage one of a series of complementary post recesses in the perimeter of the support plate. In some embodiments an interconnecting plate may be employed to substitute for one or more support clips.
It can be appreciated that although only a single mold need be provided for each casting shape, a plurality of complimentary support plates and support posts are provided to enable the casting mold to produce a plurality of sand modules.
In the preferred embodiments, a plurality of different mold configurations is shown as examples of the type of variety of geometrically-shaped, mold configurations that may be provided with the construction kit, and is not intended to limit the invention to the specific mold configurations shown. As it is intended that a number of sand cast modules be stacked in a spanning fashion, the construction kit in general includes both a support plate for the top as well as the bottom of the cast sand module. In this manner, the weight of the sand module is directed from the base plate of one module to the top plate of the underlying module and hence to the centrally positioned support post. This prevents the weight of other modules from crumbling the sand casting of the lower modules. These and other features will become clear from a consideration of the Detailed Description of the Preferred Embodiments that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a sand structure constructed with the sand casting kit of this invention.
FIG. 2 is a partially exploded view of a kit module with a pyramid-shaped mold for making mold castings used in the structure of FIG. 1.
FIG. 3 is an enlarged, partial cross-sectional view of the pyramid-shaped mold of FIG. 2, taken on the lines 3--3 in FIG. 3.
FIG. 4 is an exploded perspective view of a kit module with a bucket-shaped mold.
FIG. 5 is an exploded perspective view of a kit module with a cylinder-shaped mold.
FIG. 6 is an exploded cross-sectional view of a kit module with a hemispherical-shaped mold.
FIG. 7 is an exploded cross-sectional view of a kit module with a truncated pyramid-shaped mold.
FIG. 8 is an exploded cross-sectional view of a kit module with a hanger-like mold.
FIG. 9 is an exploded cross-sectional view of an alternate post and plate arrangement.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The toy construction kit for sand structures of this invention may take many different configurations. FIG. 1 shows an example of one type of structure that can be built by one of the molds in the construction kit. The multi-tier pyramid structure, designated generally by the reference numeral 10, is made with a four-sided, truncated pyramid module set 12 as shown in FIG. 2. With reference to FIGS. 1-3, the pyramid module set 12 includes a sand mold 14, a plurality of square support plates 16, a plurality of support posts 18 and a plurality of caps 20. For convenience, only one support plate, post and cap is shown in FIG. 2. A sufficient number of these elements should be provided to construct complex structures as shown in FIG. 1. It is to be understood that different sand castings made from molds of different configurations can be combined into an integrated structure. For simplicity of description, the structure 10 of FIG. 1 incorporates a plurality of pyramid sand castings 22 that are formed by casting with the mold 14 shown in FIG. 2.
The pyramid mold 14 in FIG. 2 has an apex 24 with an internal construction as shown in FIG. 3. The pyramid mold 14 is fabricated with four substantially triangular plates 26 that are interconnected along opposed edges with a small inside projection 28 positioned in each corner at the apex 24. The projection 28 seats a cap 20 and support post 18 when inverted for filling with sand when the casting is intended to support other castings. The top casting 22a is made without the cap 20.
In fabricating a sand casting from the pyramid module set 12 of FIG. 2, the pyramid mold 14 is inverted and the post 18 and cap 20 are positioned on the apex projections 28. Wet or damp sand is then packed in the inverted mold around the support post 18 flush with the perimeter edges 34 of the open pyramid mold 14. It is to be understood that other compactible materials such as snow may be utilized. The support plate 16 has a centrally positioned socket member 36 with a recess 38 to receive the distal end 40 of the support post 18. While the filled mold 14 is inverted, the support plate 16 is oriented to direct the recess 38 of the socket member 36 at the distal end 40 of the installed support post 18. While orienting the edges 42 of the support plate 16 in alignment with the perimeter edges 34 of the pyramid mold 14 that define the opening of the mold, the support plate 16 is pressed against the support post 18 to engage the distal end 40 of the support post 18 with the socket member 36 of the support plate.
When the sand-packed mold 14 is returned to a right-side position and the mold 14 removed from the support plate 16, the support post 18 and cap 20 form an integral part of the sand casting. The support plate 16 is sufficiently rigid to support the sand casting and enable the casting to be lifted and moved to a desired location by the builder. It is to be understood that the opening for release of the sand casting is equal or greater than the internal cross dimension to enable release of the casting.
When the builder constructs a multi-tiered structure as shown in FIG. 1, the top cap 20 remains installed on the distal end 40 of the support post 18. The top cap 20 has a socket portion 44 and a plate portion 46. The plate portion 46 has four short corner pegs 48 that are sized to engage one of the corner holes or dimples 50 in each of a group of plates, enabling the structure 10 as shown in FIG. 1 to be constructed with substantial stability. The top casting 22a is made without using the cap 20 by filling the apex portion above the projections 28 with sand. The post 18 is positioned on the sand and centered while the rest of the mold is filled with sand as described above. As noted, the structure of FIG. 1 is constructed using a single mold and a plurality of plate, post and cap members. Other configurations of a mold are shown with reference to FIGS. 4-8, and the sand castings can be combined and integrated into a variety of different sand structures.
Referring to FIG. 5, a mold 54 having the traditional configuration of a common sand pail, is in the form of a truncated cone. In a similar manner, the module set 12 has a circular base plate 56 and a circular top plate 58. Both the base plate 56 and top plate 58 have a centrally positioned socket member 36 which engages a support post 18, as previously described. Again, in use, the conical mold 54 is inverted and the top plate 58 deposited in the bottom 59 of the mold. The support post 18 is installed in the socket member 36 in the top plate 58. Sand is packed into the mold around the post 18 and the base plate 56 pressed against the sand to engage the socket member 36 with the distal end 40 of the post. The mold is then inverted and the casting drops from the mold with the top plate 58 for placement in a desired structure.
Small interconnector members 60, similar in construction to the caps 20, but without a socket member, are provided for interconnecting multiple castings. The interconnection member 60 is square in configuration with a small projecting corner peg 48 in the four topside and bottom side corners. The corner pegs engage holes or dimples 62 spaced around the perimeter of the base plate 56 and the top plate 58.
As a further variation in a module set, the cylindrical module set 12 of FIG. 5 includes a cylindrical open end mold 64. Identical circular end plates 66 each have a central socket member 36 that engages the end of a support post 18. The inside circumference of the cylindrical mold 64 encompasses the perimeter of one of the circular plates 66 with a centrally mounted post 18. Sand is then packed into the cylindrical mold around the support post until filled. When filled, the opposite end plate 66 is centered and the socket member 36 pressed into engagement with the end of the support post 18. Holding the second attached end plate 66, the mold is drawn upward over the mold plate to expose the cylindrical plug-type casting. The end plates 66 have holes 68 for engaging the interconnector members 60 when composite structures are built.
Referring to the cross sectional views of FIGS. 6-8, various other configurations of mold structures can form the basis of a module set 12. In FIG. 6, a hemispherical mold 70 has a internal socket 72 for temporarily retaining a support post 18 when packing sand in the mold 70. A circular base plate 74 has a standard socket 36 that engages the post 18 after the mold 70 has been filled with sand and inverted. In return to the placement position, the mold 70 can be removed and a cap 20 with a socket 44 as disclosed with reference to FIG. 2 may be installed on the post 18 for coupling other mold castings. Similarly, in FIG. 7, a truncated pyramidal mold 78 has a bottom 80 with a socket 82 for temporarily and loosely engaging the post 18 when the mold is inverted and filled with sand. A square base plate 84 having a socket 36 that engages post 18 for supporting the casting when the mold is returned to the casting position and removed from the sand casting. A square top plate 86 with a socket 36 engageable with the post 18 may be installed for support of other castings.
Additionally, in FIG. 8 an elongated hangar-like mold 90 having two internal sockets 92 for temporarily holding posts 18 while the mold is inverted and packed with sand. Again, a bottom plate 94 having semi-circular ends 96 with sockets 36 is pressed against the sand filled mold to engage the sockets 36 with the posts 18 for supporting the sand casting. When inverted and the mold 90 is removed, a pair of caps 20 may be installed on the ends of the posts 18 for interconnection of auxiliary castings in the formation of a composite structure.
It is to be understood that if desired, that the socket and post construction can be altered, for example as shown in FIG. 9, wherein the post 100 has ends 102 with a bore 104 that receive a pin 106 mounted on top and bottom support plates 108.
While, in the foregoing, embodiments of the present invention have been set forth in considerable detail for the purposes of making a complete disclosure of the invention, it may be apparent to those of skill in the art that numerous changes may be made in such detail without departing from the spirit and principles of the invention. | A toy construction kit for constructing sand cast structures using a set of different casting molds, support posts installed in the molds during filling and compacting the sand, and support plates that encompass the open part of the mold and that include a socket to engage the post, the support plate and post supporting the sand casting when the mold is removed the kit including interconnection clips to interconnect the support plates of multiple casting when constructing a multi-tier structure. | 0 |
This application is a continuation of application Ser. No. 07/929,958 filed Aug. 14, 1992, now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to a temperature sensing device that is provided on a fixing device of an image forming apparatus for controlling the fixing temperature.
Temperature sensing in a fixing device is done by measuring the temperature on the circumferential surface of a fixing roller. In order for temperature sensing to be done accurately, temperature sensing devices which are in a type of direct pressure contact with the fixing roller are used.
The temperature sensing device mentioned above is one that is kept in contact with a rotating fixing roller with an optimum pressure. It is, for example, a temperature sensing device wherein a thermistor temperature sensing element is supported by a supporting member formed of an elastic substance such as foamed silicone or the like, all of which are covered by a protective sheet such as a polyimide film. This temperature sensing device is kept in pressure-contact with a circumferential surface of a fixing roller, through the protective sheet, with a load of 50-150 GMF, thereby the temperature on the roller surface is measured directly, and a heater built in the fixing roller is turned on or turned off by the measured temperature. Thus, the temperature may be controlled.
When a temperature sensing element is supported directly by a supporting member, the temperature on the side of the temperature sensing element where it is in contact with a fixing roller is the same as that on the fixing roller surface, but the temperature on the other side being in contact with the supporting member is different because heat in the temperature sensing element is lost through the supporting member. For example, a temperature difference of 30° C. to 40° C. has been created for the measured temperature of about 190° C., making it impossible to measure accurately the temperature on the fixing roller surface. When setting the fixing temperature to 190° C., the actual controlled temperature on the fixing roller surface can be 200° C.-210° C., far higher than the temperature at which the apparatus is set.
In addition to the above, the temperature difference has tended to be increased by the change of pressure-contact condition of the supporting member caused by friction and vibration caused by on the rotation of the fixing roller.
As one means to overcome the temperature difference, there has been proposed a method wherein a thin metal sheet having a high thermal conductivity such as an aluminum foil is inserted between a temperature sensing element and a supporting member to take advantage of the heat-transfer thereby it is possible to measure and control accurately the temperature on the fixing roller surface.
With regard to the method mentioned above, there has been proposed methods in Japanese Utility Model Examined Publication No. 21315/1989 and Japanese Patent Examined Publication No. 51765/1989. In both cases, however, due to the structure wherein a temperature sensing element is embedded in a cutout and recess having a certain depth provided in advance on a supporting member, the top surface of the temperature sensing element does not always protruded above the supporting member because of the variation of the depth of the cutout and recess of the embedded position, resulting in occasional inability of accurate measurement of temperature on the fixing roller surface, despite transfer the thin metal sheet.
The method suggested in Japanese Utility Model Publication Open to Public Inspection No. 63731/1988, likewise, is not common because it is expensive due to a specific thermistor used therein.
The method suggested in Japanese Utility Model Examined Publication No. 19612/1982 is one wherein a temperature sensing element is attached on a flexible thin layer to be in close-contact therewith and the thin layer is provided with a superficial layer having a lower coefficient of friction. The method, however, is not satisfactory on the point of thermal responding properties.
SUMMARY OF THE INVENTION
An object of the invention is to provide a temperature sensing device capable of coming in pressure-contact with a fixing roller constantly without being influenced by the accuracy of processing and assembling thereof and capable of measuring temperature on the surface of the fixing roller accurately.
In the first constitution of a fixing device with a temperature sensing device for achieving the object mentioned above, the above-mentioned temperature sensing device comprises a temperature sensing element, a supporting member made of elastic material and a heat-conductive thin metal sheet which is inserted between the temperature sensing element and the supporting member, so that a part thereof protrudes around the back of the temperature sensing element, in a device for sensing temperature on a fixing roller of a fixing device that heats and fixes a toner image on an image-transfer material.
In such a device, when the temperature sensing device mentioned above is in pressure-contact with the fixing roller, the top of the temperature sensing element is kept in contact with the circumferential surface of the fixing roller through a protective sheet, while the bottom of the temperature sensing element is partially buried in the supporting member.
With regard to a second embodiment of a fixing device with a temperature sensing device, in a fixing device with a temperature sensing device comprising a temperature sensing element, a supporting member which is made of elastic material and supports the temperature sensing element and a protective sheet that covers the temperature sensing element and the supporting member, heat-conductive materials are coated on the supporting member including a portion where the supporting member is in contact with the temperature sensing element.
With regard to a third embodiment, in a fixing device with a temperature sensing element comprising a supporting member which is made of elastic material and supports the temperature sensing element and a protective sheet that covers the temperature sensing element and the supporting member, the supporting member is of a two-layer composition consisting of a heat-conductive elastic member and an adiabatic elastic member, and the temperature sensing element is held by the heat-conductive elastic member mentioned above.
With regard to the fourth embodiment, in a fixing device with a temperature sensing device comprising a temperature sensing element, a supporting member which is made of elastic material and supports the temperature sensing element, and a protective sheet that covers the temperature sensing element and the supporting member, the above-mentioned supporting member is kept in pressure-contact with the circumferential surface of the fixing roller at two points of the supporting member which are positioned at an upstream side and a downstream side in the direction of rotation of the fixing roller.
In a fifth embodiment of a fixing device with a temperature sensing device, it comprises a temperature sensing element, a supporting member which is made of elastic material and supports the temperature sensing element, and a protective sheet that covers the temperature sensing element and the supporting member, and the surface of a heat-sensing area of the temperature sensing element is formed to be a layer having high thermal conductivity.
In a sixth embodiment of a fixing device with a temperature sensing device, it comprises a temperature sensing element, a supporting member which is made of elastic material and supports the temperature sensing element, and a protective sheet that covers the temperature sensing element and the supporting member, and a sheet having high thermal conductivity is inserted respectively between the supporting member and the temperature sensing element and between the temperature sensing element and the protective sheet.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1(a), 1(b) and 1(c) are sectional views showing a first example of a temperature sensing device of the invention,
FIG. 2 is a graph showing the results of measurement conducted by the above-mentioned temperature sensing device,
FIG. 3 is a perspective view showing how the above-mentioned temperature sensing device is mounted,
FIGS. 4(a), 4(b), 4(c) and 4(d) are sectional views showing a second example of a temperature sensing device of the invention,
FIGS. 5(a), (b), (c) and (d) are sectional views showing a third example of a temperature sensing device of the invention,
FIG. 6 is a sectional view showing a fourth example of a temperature sensing device of the invention,
FIGS. 7(a), 7(b) and 7(c) are sectional views showing a fifth example of a temperature sensing device of the invention, and
FIGS. 8(a), 8(b) and 8(c) are sectional views showing a sixth example of a temperature sensing device of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The first example of invention will be shown in FIGS. 1(a)-1(c) and in FIG. 3.
The basic constitution of a temperature sensing device of the invention is shown in FIG. 1(a) wherein numeral 1 represents a thermistor temperature sensing element, numeral 2 represents a flat and thin metal sheet that is heat-conductive, 3 is an elastic supporting member whose top is flat and 4 is a metallic holder that holds supporting member 3.
Thin metal sheets having a heat conductivity of λ=100 W/m° C. or more are acceptable as thin metal sheet 2, and aluminum foil, copper foil, berylium foil, and magnesium foil are preferable; the thickness of an aluminum foil to be used is 20-30 μm.
For supporting member 3, foamed silicone which has a broad elastic area and high thermal resistance is used.
Both thermistor 1 and the supporting member 3 having thin metal sheet 2 between them as shown in the figure and metallic holder 4 are wrapped with heat-resisting protective sheet 5 such as a polyimide film. As shown in FIG. 1(b) and FIG. 1(c) showing a sectional view taken on arrowed line A--A in FIG. 1(b), therefore, thermistor 1 is caused by the tension based on wrapping of the protective sheet 5 to be buried partly in supporting member 3, forming a hemispherical concave surface on top face of the supporting member 3.
Due to the foregoing, part of thin metal sheet 2, in a foil shape, is transformed automatically into a hemispherical shape following the shape of the thermistor 1, and other parts of the thin metal sheet remain at the top surface and come in contact, through protective sheet 5 with fixing roller 10 under a pressure-contact condition.
Further, since thermistor 1 is held so that a part thereof protrudes from the top surface of supporting member 3 by the elasticity of supporting member 3, thermistor 1 can be kept in pressure-contact with the surface of fixing roller 10, through protective sheet 5 maintaining firm contact despite dispersion of thermistor 1 itself and erroneous positioning thereof.
In FIG. 2, results of experiments show the relation between temperatures (shown with solid lines) on the surface of a fixing roller controlled by a conventional temperature sensing device wherein no thin metal sheet or no heat-conductive coated layer 102 shown in the second example described later is used or no sheet-shaped cover 202 is used for wrapping the temperature sensing device and temperatures (shown with broken lines) controlled by the temperature sensing device of the invention. According to the results of experiments, when the temperature was controlled by the former temperature sensing device for the temperature on a fixing roller set to 190° C.±5° C., the temperature on the surface of an experimental roller was 230° C.-240° C. for overshooting and 200° C.-210° C. for the controlled temperature, showing the controlled temperature exceeding by far the set temperature, while when the temperature was controlled by the latter, the temperature was 200° C.±5° C. for overshooting and 194° C.±5° C. for the controlled temperature, showing the controlled temperature extremely close to the above-mentioned set temperature.
The temperature sensing device of the invention may be attached rotatably by connecting metallic holder 4 to bracket 6 fixed in fixing device through a through type shaft 7. The metallic holder 4 supported on bracket 6 is urged clockwise by torsion spring 8 with a fulcrum of through type shaft 7 so that it may bring thermistor 1 in pressure-contact with the surface of fixing roller 10.
The urging force of torsion spring 8 is adjusted so that the load for pressure-contact of thermistor 1 on fixing roller 10 may be within a range of 50 gf to 100 gf. When fixing roller 10 is removed on the occasion such as a maintenance, stopper 4A united with metallic holder 4 hits bracket 6 to avoid rotation of the temperature sensing device exceeding the necessary amount.
Other examples of the invention will be explained as follows, referring to FIGS. 4(a)-4(d), FIGS. 5(a)-5(d) and FIG. 6.
FIGS. 4(a) through 4(d) show basic embodiments of a second example of a temperature sensing device, and numeral 1 represents a thermistor temperature sensing element, 3 represents an elastic supporting member, 102 represents a coated layer of heat-conductive material coated on the portion where thermistor 1 is in contact with supporting member 3, and 4 represents a metallic holder that holds supporting member 3.
For supporting member 3, foamed silicone material having a broad elastic area and high thermal resistance is used, and as the heat-conductive material, on the other hand, Dotite (trade name) is appropriate, and is coated to be a thin layer as shown in FIG. 4(a), or is coated in a layer shape on supporting member 3 including the portion where temperature sensing element 1 is in partial contact with supporting member 3 as shown in FIG. 4(b).
Both thermistor 1 and supporting member 3 having heat-conductive coated layer 102 between them as shown in the figure and the metallic holder 4 are wrapped with heat-resisting protective sheet 5 such as a polyimide film. As shown in FIG. 4(c) and FIG. 4(d) showing a sectional view taken on arrowed line A--A in FIG. 1(b), therefore, the thermistor 1 is caused by the tension based on wrapping by protective sheet 5 to be buried partly in supporting member 3, forming a hemispherical concave surface on the top face of supporting member 3.
Due to the foregoing, part of the heat-conductive coated layer 102 is transformed automatically into a hemispherical shape following the shape of thermistor 1 when positioned behind the thermistor, and other parts of the thin metal sheet remain at the top surface and come in contact with the fixing roller 10, through protective sheet 5, under the pressure-contact condition.
Further, since thermistor 1 is held so that a part thereof protrudes from the top surface of supporting member 3 by reaction force caused by elasticity of supporting member 3, thermistor 1 can be kept in pressure-contact, through protective sheet 5 with the surface of fixing roller 10 maintaining the firm contact condition despite dispersion of thermistor 1 itself and erroneous positioning thereof.
FIGS. 5(a)-5(d) show a third example of a temperature sensing device wherein supporting member 12 that supports thermistor 1 is of a two-layer composition including elastic member 12A and elastic member 12B both of which are cemented to be one unit.
For elastic member 12A which is in contact with thermistor 1, foamed material having a high thermal conductivity is used, and for the elastic member 12B, on the other hand, foamed material being highly adiabatic is used, and they are united into one in a flat layer form as shown in FIG. 5(a) or in an embedded type as shown in FIG. 5(b).
Even in the present example, therefore, when being brought into contact with the surface of fixing roller 10, through protective layer 5, thermistor 1 is embedded in the elastic member 12A as shown in FIG. 5(c) and FIG. 5(d) showing a sectional view taken on arrowed line BB in FIG. 5(c).
FIG. 6 shows a fourth example of a temperature sensing device wherein metallic holder 14 holding supporting member 12 has recessed portion 14A at the central part on the bottom of the metallic holder, and a slight clearance is formed between recessed portion and the bottom of supporting member 12.
Due to the foregoing, when metallic holder 14 is urged clockwise by the action of torsion spring 8 and thereby the supporting member 12 is brought into pressure-contact with the circumferential surface of the fixing roller 10, through protective layer 5, an upstream side and downstream side of supporting member 12 in the direction of rotation of the fixing roller, namely edge portions at right and left sides of the supporting member 12 are brought into pressure-contact strongly, while thermistor 1 is brought into pressure-contact moderately owing to the elasticity of the supporting member 12. Therefore, a stable temperature sensing attitude can be maintained constantly without any change thereof and without any generation of vibrations even when friction resistance caused by sliding of the fixing roller 10 is applied thereon.
Still other examples of the invention will be explained as follows, referring to FIGS. 7(a)-7(c) and FIGS. 8(a)-8(c).
FIGS. 7(a)-7(c) show a basic embodiment of the fifth examples of a temperature sensing device wherein numeral 1 represents a thermistor temperature sensing element, numeral 3 is an elastic supporting men, her, 202 represents a highly heat-conductive film-shaped sheet that covers the surface of thermistor 1, and 4 is a metallic holder that holds supporting member 3.
For the supporting member 3 mentioned above, foamed silicone material that has a broad elastic area and is highly heat-resisting is used, and one side of supporting member 3 is provided with thermistor 1 and film-shaped sheet 202 which is highly heat-conductive is formed on the surface of a temperature-sensing portion of an thermistor 1 through the evaporating means or the like to cover the thermistor. Incidentally, the film-shaped sheet 202 may also be formed through means such as glueing, spattering or coating. As is shown in FIG. 7(a), both thermistor 1 and supporting member 3 covered by highly heat-conductive film-shaped sheet 202 are wrapped with heat-resisting protective sheet 5 such as a polyimide film together with metallic holder 4. A lead wire of thermistor 1 is welded with an electric cable through means such as welding in supporting member 3 and electric cable is led out of supporting member 3. As shown in FIG. 7(b) and FIG. 7(c) that shows a sectional view taken on arrowed line AA in FIG. 7(b), therefore, thermistor 1 is caused by tension based on wrapping protective sheet 5 to be buried partly in the supporting member 3, forming a hemispherical concave surface on the top face of supporting member 3.
As a result of the above construction, when thermistor 1 is in contact with fixing roller 10, a temperature sensing portion of thermistor 1 is totally reads the temperature of fixing roller 10 that is an item to be measured, thereby it is possible to enhance the temperature sensing ability and heat responding ability fixing roller 10.
Further, since thermistor 1 is held so that a part thereof protrudes from the top surface of the supporting member 3 by reaction force caused by elasticity of the supporting member 3, thermistor 1 can be kept in pressure-contact, through protective layer 5, with the surface of fixing roller 10 maintaining the firm contact condition despite dispersion of thermistor 1 itself and erroneous positioning thereof.
FIGS. 8(a)-8(c) show a sixth examples of a temperature sensing device wherein thermistor 1 is sandwiched vertically between two equally-shaped highly heat-conductive sheets 112 and is placed on supporting member 3 held by metallic holder 4 to be wrapped with protective sheet 5 so that they may be united solidly. With regard to thermistor 1, supporting member 3, metallic holder 4 and protective sheet 5, those having the same specific characteristics as in the fifth example may be used. As heat-conductive sheet 112 having high thermal conductivity, a metal foil such as aluminum foil is preferably used.
FIG. 8(a) shows how thermistor 1 sandwiched by heat-conductive sheets 112 is placed on supporting member 3, FIG. 8(b) shows how a portion of thermistor 1 wrapped with protective sheet 5 which protrudes in a shape of a semicircle is brought into contact with the circumferential surface of fixing roller 10, and FIG. 8(c) shows a sectional view taken on arrowed line BB in FIG. 8(b). In present example, again, the thermistor 1 is in the state that it is sandwiched by heat-conductive sheets 112 which represent a heat-absorbing member and thereby, both the top surface and the bottom surface of the thermistor 1 are mostly at the same temperature as the circumferential surface of the fixing roller 10. Therefore, it has been confirmed that temperature sensing with a small temperature gradient for thermistor 1 and an excellent responding ability can be conducted.
In example mentioned above, the thermistor 1 is sandwiched between two heat-conductive sheets 112. However, thermistor 1 may be inserted in twice-folded heat-conductive sheet 112 or may be put in bag-shaped heat-conductive sheet 112 and placed on the supporting member 3. This may contribute to easy assembling work.
Owing to the present invention, it has become possible to provide a fixing device with a temperature sensing device that is suitable for mass production because of its merits of easy processing and mounting thereof and is capable of measuring and controlling the fixing temperature accurately with its advantages of firm contact with a fixing roller. | In a device for sensing a temperature of a fixing roller, a thermistor is provided on a flat upper surface of a support member made of a foamed silicone material, with a heat conductive material provided between them. A heatproof protective sheet is wrapped around so that the thermistor is partially sunk into the support member by the tightness of the wrapping. The heat conductive material is thereby deformed to the thermistor's shape. At the same time, the top part of the thermistor is always protruded from the upper part of the support member. A holder keeps this construction in contact with the circumferential surface of the fixing roller. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to the construction of a wall including, for example, glass blocks and separator strips.
Walls, both interior and exterior, are typically made of elements, such as stone, bricks, and blocks of cinder or glass. These wall elements are typically laid up with a hardenable material between the individual elements, such hardenable material being, for example, mortar, cement, or grout. These materials have in common that they are moldable at room temperature or ambient temperature and become hard and rigid after being put in place. These materials are typically made from mixtures of dry materials and a liquid such as water, which are mixed as needed to make the moldable cement, mortar or grout, the stone, bricks or blocks being laid upon a bed of such material, with the ends and top and bottom in engagement with a layer of such material. In some cases, grouting material, which is extrudable or moldable at room temperature or ambient temperature, is used, but usually for waterproofing, rather than as a load-bearing component of the erected wall.
Glass blocks have been used as components of walls in more recent times, glass blocks having gained substantial popularity and comparatively extensive use in the fourth and fifth decades of the Twentieth Century. Glass blocks were used as components of walls for either decorative purposes, or to permit the passage of light therethrough, or both. Typically, glass block walls were constructed using mortar, but glass blocks not requiring mortar have been suggested.
Hohl 2,141,000 discloses a wall which is made of glass blocks, and without mortar, grout, cement or other material which is moldable at room temperature or ambient temperature and which becomes hardened. The glass blocks are separated by elongate plates or strips which extend horizontally between rows, being of substantial length: vertical strips extend between adjacent blocks in a row, and between the separator strips at the top and bottom of each row. The strips have webs which are provided at their sides with flanges having curved surfaces which match the curvature of the shoulders of the glass blocks. These flanges are somewhat bell-shaped in cross-section, and when the wall is viewed in elevation, the end faces of the flanges occupy substantially the same space which would be occupied by conventional mortar. The strips are extruded metal, or may be of formed sheet metal. The strips which extend horizontally have tongues at their ends, which extend through openings in vertical side strips, and are held by nails which extend through the holes in these tongues. As a consequence, the distance between the vertical strips at each side of the wall is a predetermined, fixed distance, and the construction inherently assumes a constant, unvarying size of the blocks used, whereas in fact the glass blocks exhibit some small but significant variation in size from the norm; this variation is not accommodated by the construction of Hohl 2,141,000. This construction entails some difficulty in assembling the horizontal strips to the vertical side strips, since only a narrow space is provided, between the strips and the space or opening in which the glass block wall is constructed for the insertion of the nails. Further, the construction requires a facing strip to cover the extending tongues and holding nails.
There has been suggested, in addition, in Nichols 2,326,245 a similar construction, in which a wall of glass blocks and strips as shown in Hohl 2,141,000 is provided in panels, each panel comprising a perimeter frame, in addition to the rows of glass blocks with the horizontal and vertical separator strips.
SUMMARY OF THE INVENTION
The present invention is directed to a wall made of blocks, such as glass blocks, and of separator strips of solid material, such as metal, wood or plastic, such material being substantially rigid and non-moldable at ambient and room temperature. The separator strips comprise webs having flanges at their sides, the flanges having inner surfaces which are in spaced, parallel relationship, and which are substantially perpendicular to the web. These inner surfaces adjoin a portion of the side faces of each of said glass blocks, so that a perimeter portion of each of the side faces is covered and concealed by the flanges of the horizontal separator strips. Vertical separator strips of substantially the same cross-sectional shape are provided, the inner surfaces of the flanges of the vertical strips adjoining a marginal portion of the faces of the adjacent blocks, and the flanges of the horizontal and vertical strips adjoin portions of the faces of the glass blocks. The vertical separator strips which are provided between adjacent glass blocks in a row have their webs of slightly greater length than the flanges, so that an extension of the webs of the vertical separator strips extend into the channel provided between the flanges of the horizontal separator strips, the ends of the flanges of the vertical separator strips engaging the flanges of the horizontal separator strips.
A shim or shims is provided at one or both ends of each row as needed in order to provide for firm engagement of the vertical separator strips and blocks in a row, so as to provide rigidity to the wall: these shims or other means for forcing the blocks and vertical separator strips together accommodate the variations in the sizes of the glass blocks from the norm. Side strips are provided of simple channel shaped configuration, with the flanges thereof adjoining the faces of the adjacent glass blocks, and with the webs secured to a wall and to the floor which together partly define the opening in which the glass wall is constructed.
Among the objects of the present invention are to provide a glass block wall construction made without settable material and which provides a rigid and secure wall.
Another object of the present invention is to provide a glass block wall construction having enhanced appearance.
Still another object of the present invention is to provide a glass wall construction in which the appearance thereof is enhanced by a partial covering of the faces of glass blocks by flanges of separator strips used in the construction of the wall.
Still another object of the present invention is to provide a mortarless glass block wall which is rigid and secure against dislocation under conventional forces.
A still further objection of the present invention is to provide a glass block wall in which accommodation is provided for the variation in size of the glass blocks from the norm.
Still another object of the present invention is to provide a glass block wall of the mortarless type in which separator strips of inexpensive construction are provided.
Yet another object of the present invention is the provision of a glass block wall which may be readily assembled and disassembled by unskilled persons.
Other objects and many of the attendant advantages of the present invention will be readily understood from consideration of the following specification, claims and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view, with parts broken away, of a portion of a glass block wall in accordance with the portion.
FIG. 2. is a perspective view, with parts broken away, of a portion of a glass block wall in accordance with the present invention.
FIG. 3 is a cross-sectional view taken on the line 3--3 of FIG. 1.
FIG. 4 is a cross-sectional view taken on the line 4--4 of FIG. 1.
FIG. 5 is a cross-sectional view taken on the line 5--5 of FIG. 2.
FIG. 6 is a perspective view of a corner element forming a component of a further embodiment of a glass block wall in accordance with the present invention.
FIG. 7 is a perspective view of still another corner element, for forming two perpendicular glass block walls in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, wherein like or corresponding reference numerals are used for like or corresponding parts throughout the several views, there is shown in FIG. 1 a glass block wall 10 in accordance with the present invention. Other block material may be used instead of glass. Glass block wall 10 is constructed without mortar, cement or grout, or other material of similar nature which is normally moldable or pliant at ambient temperature and which sets or hardens into a rigid state after it has been applied. As disclosed herein, glass block wall 10 is made without putty, mastic or other non-load bearing material which is used for the prevention of entry of water, since as shown the glass block wall construction is for interior use. As will be understood, however, when used for exterior purposes, such materials may be used.
The glass block wall 10 comprises rows of conventional glass blocks 12 having two substantially parallel faces, each nominally square, and four edges substantially transverse to them. Such glass blocks are made in standard or normal sizes, such as 6"×6", 8"×8", 91/2"×9 1/2", and 12"×12". These are the normal size designations, although these are not the actual or intended normal dimensions of the glass blocks. For example, each of the edges of the 8"×8" glass block is actually a nominal 73/4" long. The widths of the edges of the glass blocks are standardized; the 6" size block has a width of 31/8" (approximately) and 8" size block has a width of 3 7/8" approximately. It has been found that while the glass blocks have a normal or standard size, for example, 73/4" for the 8"×8" block, in actuality the size of the glass blocks of a particular nominal size actually vary, and a particular block may depart by about 1/16" from the normal or designated size. As a consequence, a row of just ten glass blocks may vary from the normal in horizontal extent of something over 1/2" if all of the blocks in that row happen to be undersized, as is possible.
Referring again to FIG. 1, between each row of the blocks 12 are horizontal separator strips 20, and between the glass blocks 12 in a row are vertical separator strips 40. A bottom base strip 60 is provided, and a pair of side strips 70 and 80 are also provided. A top strip (not shown) may be provided for the top of the glass wall construction 10 and may be a simple strip of rectangular cross-section to which a facing strip or flange may be nailed, after assembly, or may be a strip like the strip 60.
Referring to FIG. 2, there is shown a lower corner of the glass block wall 10, including the bottom base strip 60, which comprises a web 62 with flanges 64 and 66 at the sides thereof, these flanges having inner faces 65 and 67, respectively, which are spaced apart, are substantially parallel, and are substantially perpendicular to the plane of the web 62., The inner surfaces 65 and 67 adjoin the marginal portions 14' and 16' of the faces 14 and 16 of glass block 12: by adjoining these portions of the faces 14 and 16, these inner surfaces 65 and 67 are either adjacent to or in contact with these portions of these faces. The bottom strip 60 is mounted upon and secured to a spacer strip 68 which is secured to the floor F. The spacer strip 68 is shown extending to a wall W which, together with the floor F, partly define the opening into which the glass block wall 10 is constructed.
Extending above the first row of glass blocks 12 is the horizontal separator strip 20 which comprises a web 22 of generally rectangular shape, having a lower planar surface 24 and an upper planar surface 26, these surfaces being substantially parallel. At the sides of the web 22, there are provided a pair of flanges 28 and 30, having inner faces 29 and 31 which are parallel, and substantially perpendicular to the web 22. The inner faces 29 and 31 adjoin the glass block 12 above the flange 22 in the same manner as the inner faces 65 and 67 of the flanges 64 and 66. The flanges 28 and 30 extend over the lower marginal portions of the faces 14 and 16 of the glass block 12, the flanges 28 and 30 having a height substantially above the upper surface of web 22, and therefore of the bottom edge of the glass block 12. The flanges 28 and 30 also extend downwardly a substantial distance, covering the upper marginal portions of the side faces 14 and 16 of the glass block 12 beneath the separator strip 20.
In FIG. 3, there is shown the wall W, adjacent to which is the side strip 70, which is comprised of a web 72 and flanges 74 and 76. Side strip 70 may be secured in known manner to the wall W. There is also shown in FIG. 3 the glass block 12 which is in the lower corner of the glass block wall 10, and the flanges 64 and 66 of the bottom base strip 60. A shim 75 is shown in position between the end of the glass block 12 and the web 72 of the side strip 70. The shim 75 is placed in position after the entire bottom row of blocks 12 see FIG. 1) is placed in position, extending between the side strips 70 and 80, and after the vertical separator strips 40 have been put in place. As will be apparent, construction of the glass block wall 10 will begin with the securing in position of the bottom base strip 60 and the side strips 70 and 80, and the bottom spacer 68, if used. Then the bottom row of glass blocks is put in position by placing, alternately, glass blocks 12 and vertical separator strips 40 until the bottom row of glass blocks is complete. After that, a shim or shims 75, of the size required, is utilized, preferably at the end of the row of glass blocks 12, in order to accommodate any differences in the actual sizes of the glass blocks 12 forming the bottom row.
FIG. 4 shows the corner glass block 12, a vertical separator strip 40, the bottom base strip 60, and the spacer 68, the latter in place on the floor F. As shown, the bottom base strip 60 is secured by a nail to the spacer strip 68. Also, the flanges 64 and 66 will be seen in adjoining relationship to the lower margins of the faces 14 and 16 of glass block 12, and extending over a substantial part of those faces.
In FIG. 5, there is shown a portion of a vertical separator strip 40, the bottom base strip 60, and the spacer strip 68 on the floor F. Spacer strip 40 is not longer than the edge of a glass block 12, and has substantially the same size and substantially the same cross-sectional shape as the horizontal spacer strip 20: it has a web 22 at the sides of which, as indicated by the dashed lines, are a pair of flanges 44 and 46 which adjoin marginal portions of glass blocks 12 in the same manner as the flanges of the horizontal separator strip 20. The flanges 44 and 46 have a lesser extent in the longitudinal direction than does the web 42, extending to the top surface of flanges 64 and 66. The web 42 has an extension 43 which extends into the space between the flanges 64 and 66 of the bottom base strip 60. The upper end of the separator strip 40 is of identical configuration, having an extension of the web 42 beyond the flanges 44 and 46, so as to extend into the space between the flanges 28 and 30 of the horizontal separator strip 20 above the two glass blocks 12 which are on either side of the vertical separator strip 40. The provision of the extension 43 assists in the assemblage of the glass block wall 10, providing guidance and support for the various elements as they are being assembled. As shown in FIGS. 1 and 2, the upper and lower ends of the flanges 44 of vertical separator strips 40 substantially engage the flanges of the horizontal separator strips 20.
The provision of the various flanges on the bottom base strip 60, the side strips 70 and 80, the horizontal separator strips 20 and the vertical separator strips 40, provides a distinctive and attractive appearance, the strips significantly contributing to the appearance of the glass block wall 10 by covering marginal portions of the faces 14 and 16 each glass block. The various strips may be made of wood, which may be colored so as to coordinate or contrast with the decor of the room, or may be of plastic or even metal, of any desired color and/or surface ornamentation. In addition, the flanges, since they adjoin the glass blocks, hold them securely in position against movement. The various shims 75, used as necessary in each row, provides for a locking engagement of the glass blocks and separator strips in each row. Thus, each row is securely locked, and the rows in vertical array are securely locked so that there results a glass block wall which is of rigid construction, being durable and not subject to inadvertent disassembly. The glass block wall 10 is constructed so as to accommodate actual size variations between glass blocks of the same nominal size, so that a secure and attractive glass block wall may be erected in accordance with the present invention, by unskilled persons. The glass block wall 10 may be readily disassembled, if desired.
The various strips are of an inexpensive construction. For example, they may be readily manufactured from wood, or from plastic, and may also be manufactured from metal. Consequently, because of the simple cross-sectional configurations of all of the strips and because of the regularity thereof, even of the vertical separator strips 40, these strips are inexpensive to produce.
In FIG. 6, there is shown a corner element 90 which includes a hollow vertical side column 92 comprising opposed side plates 93 and 94. A back wall 95 extends between the side plates 93 and 94 and a front wall 96 also extends between them, but spaced inwardly from the edges to provide flanges 97 and 98, respectively, to receive between them an adjoining glass block 12 , face 14 and parts of marginal portion 14' thereof being shown. Forming a part of the corner element 90 is a horizontal beam 101 and as shown in FIG. 7, the horizontal beam 101 is constructed in a manner similar to the column 92, having side plates 102 and 103, a bottom wall 104, and a top wall 105 which lies beneath the edges thereof and provides flanges 106 and 107, respectively, so as to provide flanges which receive the adjoining glass block 12 (not shown in FIG. 7.) Thus, the corner glass block 12 may be placed in position on the corner element 90, with the flanges of the walls 102 and 103 and the flanges of the walls 93 and 94 adjoining lower and a side marginal portions of the glass block 12.
There is shown in FIG. 7, a base corner element 120 which may be used at the intersection of two perpendicular glass block walls. Thus, there is provided a column 121 comprising a back wall 122, a side wall 123 which is configured so as to provide outstanding flanges 124 and 125. A third wall 126 extends between the back and side walls 122 and 123, and a fourth wall 127 also extends between the back and side walls 122 and 123, respectively, being positioned so as to provide flanges 128 and 129. A second base beam 110 is shown, extending perpendicular to the base beam 101 and to the column 121. Base beam 110 is substantially identical in construction to the base beam 101. Thereby, it has upstanding flanges 111 and 112, to receive in adjoining relationship a glass block (not shown), which glass block will also be in adjoining relationship to the flanges 128 and 129.
The corner elements 90 and 120 may be utilized in certain installations where it is not desirable to have a spacer, such as the spacer 68, and where it is desirable also to have the bottom row of glass blocks 12 at a higher elevation than can be obtained through the use of the bottom base strip 60. These corner elements may be utilized in locations where the floor and wall are in substantially perpendicular relationship, whereas the embodiments of the inventions shown in FIGS. 1-5 may be utilized where such relationship is not provided.
The claims and the specification describe the invention presented, and the terms that are employed in the claims draw their meaning from the use of such terms in the specification. Some terms employed in the prior art may be broader in meaning than specifically employed herein. Whenever there is a question between the broader definition of such term as used in the prior art and the more specific use of the term herein, the more specific meaning is meant. | A glass block wall is provided, and includes rows of glass blocks without mortar, mastic or grout. The blocks rest upon horizontal strips of simple, readily made shape, such as channels and I-sections, and are separated by vertical strips of I-section, preferably having their webs slightly longer than their flanges. A perimeter frame is provided, at least parts of which are secured to the floor and a wall defining the opening for the glass block wall. Wedges are provided at the end of each row of glass blocks as required to accommodate the variation in the size of individual glass blocks from the normal or established size. Corner elements are provided. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2007-13740 filed on Jan. 24, 2007, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a method for suppressing radiation of electromagnetic wave noise in portable electric apparatuses.
[0004] 2. Description of the Related Art
[0005] FIG. 1 is a block diagram showing the configuration of a conventional electric apparatus. The electric apparatus comprises a plurality of circuit blocks 10 - 1 through 10 - 3 . The plurality of circuit blocks 10 - 1 through 10 - 3 receive power from a power circuit 300 through power line 320 . The power circuit 300 is a constant voltage source which regulates voltage supplied to the circuit blocks 10 - 1 through 10 - 3 to a constant voltage. The high current supplied to the circuit block from the power circuit flows to a power supply line. As a result, the power supply line requires expansive wiring space in order to reduce line impedance. In turn, this expansive wiring space becomes an impediment to the miniaturization of portable apparatuses. Additionally high frequency current, generated by circuit block operations, flows in the power supply line. As a result, the problem occurs that the power supply line acts as an antenna, radiating electromagnetic wave noise into the air.
[0006] A known method for preventing the high frequency current noise generated by operations of the circuit blocks from flowing to a shared power supply line 320 is to suppress input voltage fluctuations from passing to a power supply line. The input voltage fluctuations may be suppressed by adding a voltage follower circuit to a power input portion of the circuit block, as disclosed in Japanese Unexamined Patent Application No. H11-103014. Additionally, Japanese Unexamined Patent Application No. H11-235018 discloses a distributed power supply system in which power circuits are provided on each circuit block in place of voltage follower circuits.
SUMMARY
[0007] According to an aspect of an embodiment, an electric apparatus includes a plurality of circuit blocks, a plurality of power sources, and a plurality of input portions receiving power in one-to-one correspondence with the plurality of circuit blocks, wherein the power sources are located in proximity to the power input portions and are connected to the power input portions.
[0008] The above-described embodiments of the present invention are intended as examples, and all embodiments of the present invention are not limited to including the features described above.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 shows a conventional example.
[0010] FIG. 2 shows a first embodiment of the present invention.
[0011] FIG. 3 shows a second embodiment of the present invention.
[0012] FIG. 4 shows a third embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] Reference may now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout.
[0014] The best embodiments of the present invention are described referring to the drawings. The following embodiments are described referring to the drawings. The following embodiments are illustrations, and the present invention is not limited to these embodiments.
[0015] FIG. 2 is a configuration diagram of an electric apparatus 1200 which is a first embodiment of the present invention. The electric apparatus 1200 internally has a plurality of circuit blocks 10 - 1 , 10 - 2 , and 10 - 3 made up of large scale integrated circuits (LSI) or the like. Circuit blocks are connected with a signal lines (not shown in figure), and processing determined based on content of signals transmitted by the signal line is carried out.
[0016] The circuit blocks 10 - 1 through 10 - 3 are provided with a power input portion which receives supplied power. Also, batteries 20 - 1 through 20 - 3 , which are power sources, are installed in proximity to the power input portion. The circuit blocks 10 - 1 through 10 - 3 receive power supplied from the batteries 20 - 1 through 20 - 3 via the power input portion. The circuit blocks 10 - 1 through 10 - 3 are, for example, complementary metal oxide semiconductor (CMOS) logic LSIs, and perform on-off logic operations in synchronization with a clock signal.
[0017] A CMOS logic circuit charges a metal oxide semiconductor (MOS) transistor gate with an electric load supplied from the power input portion to perform an ON operation and discharges the gate load to perform an OFF operation. As the charging and discharging operations of the MOS transistor gate are synchronous with the clock signal, the inflow of the gate charge current of the MOS transistor is generated at the frequency of the clock signal.
[0018] A high frequency current generated by the on-off operation of the CMOS logic circuit flows between the power source and the CMOS logic circuit. When the power source and a load, which is the CMOS logic circuit, are separated, the high frequency current flows in a power supply line which connects them and the power supply line acts as an antenna which radiates electromagnetic wave noise.
[0019] In contrast, an electric apparatus 1200 of the first embodiment has a battery installed for, and in proximity to, each CMOS logic circuit LSI. Therefore, the high frequency current flows in an extremely short loop and radiation of electromagnetic noise into the air is suppressed.
[0020] Next, an electric apparatus 1300 of a second embodiment will be explained with reference to FIG. 3 .
[0021] In the first embodiment, a power supply installed in proximity and connected to the power source of the circuit block, such as an LSI, is a replaceable primary battery or charged secondary battery. When the battery dies it must be replaced with a new primary battery or charged secondary battery. It is possible to use a rechargeable secondary battery or a capacitor as the battery connected to the power input portion in order to avoid the nuisance of having to replace batteries. The rechargeable secondary battery or capacitor is installed in proximity to the circuit block, thereby making it possible to recharge without replacing batteries.
[0022] In addition to the configuration of the electric apparatus 1200 of the first embodiment, the electric apparatus 1300 of the second embodiment is further provided with a power supply line 320 for supplying charging current for charging the secondary batteries or capacitors installed as the batteries 20 - 1 through 20 - 3 , a charging circuit 310 which charges the batteries 20 - 1 through 20 - 3 via the power supply line 320 , and a power receiving terminal 200 for supplying power from an external power source to the charging circuit 310 . Note that an external power source 100 is the external power source for supplying external power to the electric apparatus 1300 .
[0023] In order to supply charging power to the secondary battery or capacitor, the charging circuit 310 has a DC-DC converter which outputs a constant current or constant voltage/constant current.
[0024] Problems such as heat generation and rapid deterioration in operating life may occur when charging the secondary battery or capacitor, unless the charging current is controlled to within the allowable levels. Therefore, the constant current output DC-DC converter controls the charging current depending on battery voltage to ensure that the charging current does not fluctuate and a constant current is achieved.
[0025] Additionally, when a lithium battery is used as the secondary battery, explosion, combustion, or rapid deterioration in operating life may result if charging is not performed within the allowable voltage for charging. Therefore, it is preferable to perform charging using a constant voltage/constant current output DC-DC converter.
[0026] In order to prevent heat generation or deterioration in operating life, the maximum current value of the charging current, which charges the secondary battery or capacitor, is restricted, but the minimum value is not restricted. When charged at 1 C, secondary batteries which charge using constant current such as NiCd batteries and NiMH batteries take approximately one hour to complete charging. However, when charged at 0.5 C, these batteries take approximately two hours to complete charging. The only difference when the current value of the charging current is lowered is that more time is required to charge.
[0027] When a lithium secondary battery is charged at 1 C, charging is completed in approximately two hours, and when charged at 0.5 C charging is completed in approximately 2.7 hours. Just as in the NiCd batteries and NiMH batteries, when the current value of the charging current is reduced, the time required to charge increases by a corresponding amount.
[0028] When supplying power to load logic circuits such as LSIs, unless the current required by the load is supplied, the load voltage will drop and the circuit (load) will perform maloperations. Therefore, the maximum current required by the load must flow to in power supply line.
[0029] Additionally, it is necessary to lower the impedance of the power supply line in order to suppress a voltage drop in the power supply line when maximum current is flowing. The line impedance of the power supply line is proportional to the length of the power supply line and inversely proportional to the cross-sectional area. The thickness of a copper wiring pattern of a multi-layer printed circuit board is approximately 17 μm, and is approximately 35 μm even if using a surface layer for the power supply-use line. The thickness of the copper wiring pattern is never more than 50 μm.
[0030] Conventionally, a width of 10 mm is necessary to realize 1 mΩ using a copper wiring pattern 17 μm thick and 10 mm long. In order to accommodate high currents a wide wiring space is necessary and this was an impediment to the miniaturization of portable apparatuses.
[0031] However, as stated above, the second embodiment lowers the current value for supplying charging current to the secondary batteries 20 - 1 through 20 - 3 from the charging circuit 310 . As a result, a pattern width of the power supply line 320 can be narrowed and the electric apparatus 1 can be provided using a smaller wiring space.
[0032] Additionally, as the current flowing from the charging circuit 310 to the secondary batteries 20 - 1 through 20 - 3 is a constant current, only a magnetostatic field is generated at the power supply line 320 and electromagnetic wave noise is not radiated into the air from the power supply line 320 .
[0033] Furthermore, it is preferable that the charging circuit 310 charges the secondary batteries 20 - 1 through 20 - 3 when the electric apparatus 1 is not operating.
[0034] The following describes a third embodiment with reference to FIG. 4 .
[0035] In the second embodiment, when a battery is installed as a power source at each CMOS logic circuit LSI forming an electric apparatus 1300 and any battery of the plurality of batteries is completely discharged, the electric apparatus 1300 can not operate even if there is sufficient power remaining in the other batteries. In order to eliminate this inconvenience, the remaining power of the batteries with sufficient power should be used to supplement the power of the batteries with little remaining power.
[0036] In addition to the electric apparatus 1300 of the second embodiment, the electric apparatus 1400 of the third embodiment is further provided with first switch circuits 401 - 1 through 401 - 3 installed on the wiring between the batteries or capacitors 20 - 1 through 20 - 3 and the charging circuit 310 , second switch circuits 402 - 1 through 402 - 3 installed on the wiring between the batteries or capacitors 20 - 1 through 20 - 3 and the circuit blocks 10 - 1 through 10 - 3 , and switch controllers 500 - 1 through 500 - 3 . Energy saving for the electric apparatus 1400 can be realized by the third embodiment.
[0037] The switch controllers 500 - 1 through 500 - 3 are controllers which control the on-off state of the first switch circuits 401 - 1 through 401 - 3 and the second switch circuits 402 - 1 through 402 - 3 . When an external power supply 100 is connected to a power receiving terminal 200 of the electric apparatus 1400 , and the charging circuit 300 is operating, the switch controllers 500 - 1 through 500 - 3 operate so that the first switch circuits 401 - 1 through 401 - 3 are in the on state and the batteries 20 - 1 through 20 - 3 are charged.
[0038] The switch controllers 500 - 1 though 500 - 3 can detect, by the signal line (not shown in figure), if power is being supplied to the power receiving terminal 200 from external power supply 100 and if the charging circuit 310 is in operation. When the charging circuit 310 is in operation and any of the batteries 20 - 1 through 20 - 3 are fully charged (100% charged state) the switch controllers 500 - 1 through 500 - 3 switch off a first switch circuit corresponding to the fully charged battery, and in addition to stopping charging, cut off the power supply line 320 from the battery.
[0039] When the external power supply 100 is not connected to the power receiving terminal 200 of the electric apparatus 1400 , or when the external power supply 100 is connected but the charging circuit 310 is not operating, the switch controllers 500 - 1 through 500 - 3 switch off the first switch circuits 401 - 1 through 401 - 3 and cut off the power supply line 320 from the batteries 20 - 1 through 20 - 3 .
[0040] Hence, the first switch circuits 401 - 1 through 401 - 3 are installed between the batteries or capacitors 20 - 1 through 20 - 3 and the charging circuit 310 , and, by using the first switch circuit to cut off the power supply line 320 from the batteries, the flow of high frequency current to the power supply line from the circuit block and resulting radiation of high frequency noise are prevented.
[0041] When the circuit blocks 10 - 1 through 10 - 3 of the electric apparatus 1400 are in an operating state, the switch controllers 500 - 1 through 500 - 3 switch on second switch circuits 402 - 1 through 402 - 3 and supply power to the circuit blocks 10 - 1 through 10 - 3 . When any of the circuit blocks 10 - 1 through 10 - 3 of the electric apparatus 1400 are in a non-operating state, the switch controllers 500 - 1 through 500 - 3 switch off the second switch circuit of that non-operating circuit block, thereby reducing power consumption.
[0042] When the power of a battery corresponding to a circuit block is insufficient and the electric apparatus 1400 cannot continue operation, power from a battery with extra power is used to compensate. This is achieved by the switch controller switching on the first switch circuit corresponding to the battery with insufficient power and the first switch circuit of the battery with sufficient power so as to share the batteries.
[0043] As an example of this, a situation will be explained in which the circuit block 10 - 1 is in a non-operating state, the circuit blocks 10 - 2 and 10 - 3 are in an operating state, the power source 20 - 2 has insufficient power, and the power source 20 - 1 has extra power.
[0044] In a situation of this nature, the switch controllers 500 - 1 and 500 - 2 switch on the first switch circuits 401 - 1 and 401 - 2 , the switch controller 500 - 3 switches off the first switch circuit 401 - 3 , and the power source 20 - 1 compensates for power source 20 - 2 .
[0045] At this point, since the circuit block 10 - 1 is in a non-operating state, the switch controller 500 - 1 switches off the second switch circuit 402 - 1 and, since the circuit blocks 10 - 2 and 10 - 3 are in an operating state, the switch controllers 500 - 2 and 500 - 3 switch on the second switch circuits 402 - 2 and 402 - 3 .
[0046] As detailed above, when a battery is installed as a power source in each CMOS LSI that makes up an electric apparatus 1400 and any battery of the plurality of batteries is partially or even completely discharged, it is still possible to cause the electric apparatus 1400 to operate by utilizing other batteries with sufficient remaining power to compensate for the batteries with little remaining power.
[0047] Although a few preferred embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents. | An electric apparatus includes a plurality of circuit blocks, a plurality of power sources; and a plurality of power input portions receiving power in one-to-one correspondence with the plurality of circuit blocks, wherein the power sources are located in proximity to the power input portions and are connected to the power input portions. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to an improvement in fluid fuel combustion, more particularly to a method of effectively burning fluid fuel by applying a magnetic field to the fuel and optionally to steam or air to be fed to combustion devices.
With the increased attention to pollution problems and resource saving problems, it has become important to reduce the dust, residual oxygen and nitrogen oxide contents in exhaust gases from burners and boilers.
SUMMARY OF THE INVENTION
The inventor has found that the combustion of fluid fuel, for example, fuel oil in burners can be effectively improved by applying a magnetic field to the fuel to be fed to burners.
A primary object of this invention is to improve the combustion of fluid fuel in combustion devices, for example, fuel oil in boilers.
Another object of this invention is to provide a method of effectively performing the combustion of fluid fuel so that boilers can be operated with a lower content of residual oxygen in exhaust gas.
Still another object of this invention is to reduce the dust loading in exhaust gas from combustion devices.
A further object of this invention is to provide a magnetizing apparatus of a simple construction for applying a magnetic field to fuel to be fed to combustion devices to ensure more complete combustion.
The above and other objects of the invention will appear more fully from the following description.
According to this invention, there is provided a method of effectively performing the combustion of fluid fuel comprising the steps of feeding fluid fuel and oxygen-containing gas to a combustion device, applying a magnetic field having a magnetic flux density of at least 10 gauss to the fuel at a point upstream of said combustion device, and adjusting the flux density to reduce the dust and residual oxygen contents in exhaust gas to a minimum.
The magnetic flux density to be imparted to fuel widely varies depending upon fuel, air or steam, and combustion equipment and conditions. In general, the preferred range of magnetic flux density is from 1000 to 3500 gauss, and the most preferred range is from 1400 to 1800 gauss when fuel oil is used in combination with conventional heat power boilers. However, these preferred ranges are merely illustrative since preferred ranges will shift to lower or higher value if one or more of the above-described factors are changed. The optimum range will be determined through experimental runs.
In the preferred embodiment of this invention, a magnetic flux density of at least 500 gauss may additionally be imparted to air which is supplied to burners together with fuel. A magnetic flux density of 500 to 2000 gauss may be imparted when steam is used.
This invention also provides a magnetizing apparatus in combination with pipes for feeding fluid fuel and air-containing gas to combustion devices, which comprises a casing which has suitable means for securing the casing on the pipe so that the pipe penetrates the casing substantially at the center thereof, a pair of connecting yokes fixedly disposed in the casing at the top and bottom thereof, a plurality of permanent magnets placed in two rows between the connecting yokes, a pair of movable yokes sandwiched between the magnets in each row and facing the pipe, and adjusting means for moving the movable yokes toward and away from the pipe, wherein a variable flux density of at least 10 gauss traversing the pipe is produced by the arrangement of the magnets and yokes.
Electromagnet assemblies are also included in this invention.
The method and the magnetizing apparatus of this invention can be applied to any desired combustion system comprising a fuel tank, a pump, a combustion device, for example, a burner, and a pipe for connecting them in fluid communication. The magnetizing apparatus should be located between the pump and the burner because it is unnecessary for any other parts to be magnetized.
The fluid fuel which may be used in this invention includes liquid and gaseous fuel, for example, fuel oil such as Diesel, bunker and burner fuel oils and those known as "A", "B" or "C" fuel oil classified according to the Japanese Industrial Standard; light fuel oil; burning kerosene and light oil; fuel gas or the like.
The combustion devices used herein include general burners and boilers covering from home appliance boilers to heat power boilers, various combustion furnaces, and internal combustion engines, for example, Diesel and gasoline engines for automobile and ships. Any burner or nozzle may be equipped, for example, pressure spraying, air or steam spraying, or rotary type.
According to this invention, the magnitude of magnetic field to be applied to the fuel is adjusted to reduce the dust loading in the exhaust gas to a minimum level. At the optimum range of magnetic flux density, an oxygen supply can be throttled so that the content of residual or non-consumed oxygen in the exhaust gas may be minimized. Operating boilers at a lower residual oxygen content in exhaust gas is advantageous in cost and pollution control since dust is also reduced through the magnetizing treatment of fuel.
The principle of magnetization of fuel does not form a part of this invention, but will be explained as follows. Fuel carriers magnetism. This is confirmed by the fact that a burner made of magnetizable material and located downstream of the magnetizing apparatus is magnetized. Fuel mainly consists of hydrocarbons. Groupings of hydrocarbons, when flowing through a magnetic field or between opposite magnetic poles, change their orientation of magnetization in a direction opposite to that of the magnetic field. The molecules of hydrocarbons shift from a certain configuration to another. At the same time, intermolecular force (van der Waals force) is considerably reduced or depressed. These mechanisms are believed to help to disperse oil particles and to become finely divided. In addition, hydrogen ions in fuel and oxygen ions in air or steam are magnetized to form magnetic domains which are believed to assist in atomizing fuel into finer particles.
Dust in exhaust gas from a boiler was measured by both weight and concentration methods. It was found that at the same weight of dust contained in exhaust gas, the exhaust gas generated after the magnetizing treatment according to this invention exhibited a higher value in concentration than that generated without magnetization. This fact means that dust particles after magnetization are finer than those usually found, which in turn, means that oil particles are made finer by the magnetizing treatment of this invention.
This invention may be applied to compact boilers as well as large-scale boilers exemplified by heat power boilers. Generally, compact boilers suffer from shortcomings that a comparatively large proportion of fuel fed is not consumed, flame is red, spark is generated and vibrating combustion occurs. Combustion conditions are improved by applying magnetism to fuel according to this invention. (1) The flame becomes brighter and turns from red to white orange. A high temperature bright flame is observed. (2) The flame is reduced in vertical length and extended laterally. The rate of combustion becomes higher. (3) Spark in the flame is reduced or eliminated. (4) Vibrating combustion is prevented. (5) Pollution material content in exhaust gas is reduced.
The combustion mechanisms due to the magnetization of fuel according to this invention will be summarized as follows:
(1) After passing a magnetic field, fuel carrying magnetism is atomized from nozzles.
(2) Groupings of hydrocarbons are made repulsive under an influence of a high magnetic field and thus dispersed effectively, resulting in more finely divided fuel particles.
(3) Hydrocarbons are pyrolyzed to generate atomic carbon and hydrogen which combine with oxygen atoms supplied from air or steam to provide explosion reaction, resulting in a high temperature bright flame. A non-combusted carbon value, otherwise appearing as soot, is diminished to a considerable extent.
(4) Fineness of atomized fuel particles accelerates the oxidation rate so that combustion may be carried out at a lower oxygen concentration.
(5) The degree of dilution of the fuel stream by low temperature air is thus reduced, resulting in an increase in flame temperature.
(6) Combustion reaction with atomic carbon prevails. As a result, CO 2 is increased in quantity, formation of CO is prevented, and dust is reduced in quantity.
(7) An increase in flame temperature causes a slight increase of nitrogen oxide formation (which can be compensated by other known methods).
(8) A reduction in oxygen concentration and an increase in radiation heat due to high temperature bright flame result in an increase of combustion efficiency.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Other features and advantages of the invention will be apparent from the following description taken in connection with the accompanying drawings, wherein:
FIG. 1 is a side view showing one example of a magnetizing apparatus mounted on a fuel pipe according to this invention;
FIG. 2 is a transverse cross section of the magnetizing apparatus taken on line II--II of FIG. 1;
FIG. 3 is a block diagram of a fuel combustion system of this invention;
FIG. 4a is a diagram showing the relationship of magnetic flux density to dust loading in Example 1;
FIG. 4b is an enlarged diagram of FIG. 4a;
FIG. 5 is a diagram showing the relationship of dust loading to magnetic flux density imparted to steam in Example 2;
FIG. 6 is a diagram showing the relationship of dust loading to magnetic flux density imparted to air in Example 3;
FIGS. 7 and 8 are diagrams showing the relationships of residual oxygen content to dust loading and nitrogen oxide content in Example 3; and
FIGS. 9 and 10 are diagrams showing the relationships of residual oxygen content to dust loading and nitrogen oxide content in Example 4.
Referring to FIGS. 1 and 2, a magnetizing apparatus of this invention generally designated by numeral 10 comprises a rectangular casing 1. Numeral 11 designates a pipe for feeding fuel to a burner (15 in FIG. 3 as described later). The casing 1 has suitable openings and fixtures (not shown) for mounting and centering the casing 1 on the pipe 11. The casing 1 accommodates a plurality of permanent magnets 2 for example ferrite magnet, arrayed in two rows with one on top of the other in each row, and connecting yokes 3 are fixedly placed at the top and bottom of the casing 1. Two movable yokes 4 are located on opposite sides of the interior of the casing 1 so as to sandwich the pipe 11. The movable yoke 4 is slidable relative to the adjoining magnets 2. The arrangements of magnets 2, connecting yokes 3 and movable yokes 4 at the right and left sides in FIG. 2 are substantially symmetrical with respect to the fuel pipe 11 located at the center of the casing 1. A screw 5 penetrates the side wall of the casing 1 and is threaded in a bore in the yoke 4 so that the yoke 4 may be moved toward and away from the pipe 11 by turning a knob 5a of the screw 5.
More particularly, the magnets 2 each having N and S poles at opposite main sides are arranged alternately in each unit as shown in FIG. 2. Such an arrangement of magnets produces a magnetic field represented by magnetic lines of force 6. With orientation of magnetic poles as shown, the magnetic force flows along loops connecting the right-hand magnets 2, connecting yoke 3, left-hand magnets 2, left-hand movable yoke 4, fuel pipe 11, and right-hand movable yoke 4 in a direction shown by the arrows. In other words, the magnets 2 and connecting yokes 3 provide the same repulsive poles in the proximity of the pipe 11 on each side thereof. The screws 5 and hence the movable yokes 4 serve to adjust the magnetic field applied to the pipe 11 from the magnets 2. Therefore, a variable magnetic flux traversing the pipe 11 is produced by the arrangement of magnets and yokes.
With the above arrangement, a compact magnetizing apparatus is provided which can effectively apply magnetic field to the pipe 11 and hence to the fuel. In addition, the magnetic field can readily be adjusted by turning the knobs 5a to move the yokes 4 toward and away from the pipe 11. The knobs 5a can easily be calibrated through simple experimental measurements to show the magnitude of any magnetic field produced.
The magnetizing apparatus of this invention can be applied to a conventional fuel feeding system depicted in FIG. 3. The fuel feeding system comprises a tank 12 from which fuel is fed via a valve 13 and a pump 14 to a burner 15. Between the pump 14 and the burner 15 is located a magnetizing apparatus 10 like that shown in FIG. 1 and 2. The fuel pumped from the tank flows through the magnetic field generated by the magnetizing apparatus 10 and then to the burner 15 through the pipe 11. Typically, the magnetizing apparatus 10 is adapted to impart to fuel a magnetic energy as high as 1000 gauss or more in flux density.
At the initial state of operation of the magnetizing apparatus, most of the magnetism imparted is absorbed or consumed by the pipe 11 if a pipe is made of magnetisable material. This absorption continues until the pipe 11 is magnetized to saturation. The magnetization of pipes is confirmed by the fact that it takes 72 hours or more until dust reduction comes into effect after the magnetizing apparatus is actuated, and that the pipes have residual magnetism after the magnetizing effect or apparatus is removed. The magnetization of associated parts also constitutes a reason why the magnetizing apparatus of this invention should be located downstream of pumps, valves or the like.
When it is desired to avoid such a delay, pipes made of non-magnetic material such as non-magnetic steel (e.g. SUS 316) may preferably be used. A portion of the fuel feeding system extending from a point downstream of the magnetizing apparatus to the burner may be made of non-magnetic material. In this case, magnetized fuel is directly fed to burners or atomizing nozzles with a minimum reduction of magnetism.
Although the magnetizing apparatus is combined with the pipe for feeding fuel in the above-illustrated embodiment, it may also be combined with pipes for feeding air and steam for assisting the combustion of fuel. Such applications are similar to that shown in FIG. 3 and may easily be designed by those skilled in the art.
The following examples illustrate certain applications according to the invention. These are merely illustrative and are not to be construed to limit the claims in any manner whatsoever.
EXAMPLE 1
A fuel feeding system as shown in FIG. 3 was employed. The magnetizing apparatus of this invention was set on a pipe for feeding fuel to a medium-type combustion furnace equipped with six burners. Fuel oil classified as "C" fuel oil according to JIS K 2205 and having sulfur and nitrogen contents of 2.7% and 0.3%, respectively, was fed at a flow rate of 8.9 tons/hour. Magnetic flux density was varied from 0 to 5000 gauss at internals of 100 gauss. The dust content in exhaust gas from the furnace was measured according to JIS Z 8808.
The results are shown in FIG. 4a, in which the dust content expressed in terms of mg per Nm 3 (normal cubic meters) is plotted as ordinate and the flux density in gauss is plotted as abscissa. As seen from FIG. 4a, a reduction of dust content appears in the range of about 500 to 600 gauss. The dust content is reduced to a minimum in the ranges of 2000±200 gauss, 3000±200 gauss, and about 4400 gauss.
It should be noted that such optimum flux density ensuring a significant dust content reduction in exhaust gas varies depending on fuel, air or steam and combustion equipment.
The relationship of dust content to flux density in the proximity of 2000 gauss is shown in FIG. 4b on an enlarged scale. The dust content is reduced to a minimum at a flux density of 2000 gauss and gradually increases as the flux density deviates from the optimum value. The magnetizing apparatus of this invention permits adjustment of the flux density to the optimum range, for example, of 2000±100 gauss simply by turning the knobs to move the slide yokes in relation to the pipe through which fuel flows.
EXAMPLE 2
A general heat power boiler having a steam capacity of 130 tons/hour was used. In this example, not only fuel fed to the boiler, but also steam for assisting combustion were subjected to magnetizing treatment. Operating conditions were as follows.
Fuel oil: "C" fuel oil
Fuel pipe: Magnetization to a flux density of 2000 gauss
Steam pipe: Magnetization to a flux density varying from 0 to 2000 gauss
Period: 10 days
The content of residual oxygen in exhaust gas from the boiler was adjusted to 2.0%, 1.2%, or 1.0% by volume in each test run. The dust loading in exhaust gas was measured according to ASTM D2156-65 "Standard Test Method for Smoke Density in Flue Gases from Burning Distillate Fuels." A smake tester from Bacharach Industrial Instrument Co. was used and the dust loading was expressed in terms of Smoke Tester Number.
The results obtained by varying the flux density from 0 to 2000 gauss in the steam feeding pipe are shown in FIG. 5. As seen from FIG. 5, dust loading is reduced to a minimum when the flux density in steam is in the range between 1400 and 1800 gauss.
At a flux density of 1500 gauss in steam, the dust loading in exhaust gas was measured according to JIS Z 8808 and the content of nitrogen oxides (NO x ) was also determined. The results are tabulated in Table I.
Table I______________________________________ Dust loading Smoke O.sub.2 NO.sub.x tester JIS Z 8808 (vol %) (ppm) (NO.) (mg/Nm.sup.3)______________________________________Magnetized fuel 2.0 155 2.0 40 1.2 130 3.5 120Magnetized fuel + 2.0 160 1.0 20magnetized steam 1.2 135 2.5 60 1.0 125 3.0 80______________________________________
EXAMPLE 3
Example 2 was repeated except that air was used instead of steam and subjected to magnetizing treatment.
The results obtained by varying the flux density from 0 to 2000 gauss in the air feeding pipe are shown in FIG. 6. As seen from the relationship of dust content to flux density shown in FIG. 6, the dust content is lowest at 1500 gauss.
At a flux density of 1500 gauss in air, the dust and nitrogen oxide (NO x ) contents in exhaust gas were determined. The results are tabulated in Table II.
Table II______________________________________ Dust loading Smoke O.sub.2 NO.sub.x tester JIS Z 8808 (vol %) (ppm) (NO.) (mg/Nm.sup.3)______________________________________Magnetized fuel 2.0 160 1.0 20 1.2 135 2.5 60Magnetized fuel + 2.0 165 0.5 10magnetized air 1.2 140 1.5 30 0.8 120 3.5 120______________________________________
In order to show how the magnetizing treatment according to this invention can influence the relationships of residual oxygen to dust and NO x contents in exhaust gas, the data obtained are plotted in diagrams of FIGS. 7 and 8. In these diagrams, line 21 (appearing as triangle 21 in FIG. 8) is a reference test run conducted under usual conditions without magnetization. Line 22 corresponds to a test run where only fuel was subjected to magnetizing treatment and line 23 corresponds to a run where both fuel and air were subjected to magnetizing treatment as described above. It should be noted that a usual NO x reducing technique was used in the latter two test runs.
It was found that the boiler can be operated at a comparatively low oxygen content of 1.3 to 1.5% by volume in the flux density range of 1400 to 1800 gauss. A maximum reduction of dust loading according to this invention was 67% in comparison with the usual run.
EXAMPLE 4
A heat power boiler having a steam capacity of 135 tons/hour was used. "C 5 " gasoline series fuel oil was used and the flux density was varied from 0 to 3000 gauss to magnetize the fuel. It was found that the preferred range was 1600 to 2300 gauss and the most preferred was 2150 gauss.
The results are shown in FIGS. 9 and 10. Line 31 is a reference test run conducted under usual conditions without magnetization. Line 22 corresponds to a test run where fuel is magnetized to 1600 gauss and line 33 corresponds to a test run where fuel is magnetized to 2150 gauss.
As apparent from FIG. 9, according to the magnetizing treatment of this invention, the dust loading can be reduced by 90% at the same oxygen content of 2.5% as shown by line a. The oxygen content can be reduced from 2.5% to 1.7% at the same dust loading of 34 mg/Nm 3 as shown by line b. As seen from FIG. 10, for example, the content of residual oxygen in exhaust gas can be reduced from 2.5 vol% of the reference run to 2.1 vol% at the same nitrogen oxide content of 60 ppm.
In another test run, air was subjected to magnetizing treatment. An additional substantially uniform effect was found over the range from 1000 to 2000 gauss.
After the magnetizing apparatus was removed, an effect due to residual magnetism was observed.
EXAMPLE 5
A 90 tons/hour heat power boiler was used. "C" fuel oil having a sulfur content of 2.7% was fed and subjected to magnetizing treatment to impart a flux density of 1800 gauss. Steam fed to the boiler was also subjected to magnetizing treatment to impart a flux density of 1200 gauss. When only fuel was magnetized, the oxygen content was reduced from 3.8% of usual run to 3.3%. When steam was further magnetized, the oxygen content was reduced to 2.3%. | The combustion of fluid fuel, typically fuel oil in burners or boilers is improved by applying a magnetic field to the fuel at the point upstream of the burner to impart a magnetic flux density of at least 10 gauss to the fuel, and adjusting the magnetic field to reduce to a minimum the dust and residual oxygen contents in an exhaust gas. A magnetizing apparatus is also disclosed which comprises permanent magnets and movable yokes for adjusting a magnetic flux density traversing a pipe for feeding fuel. The magnetizing apparatus is located on the pipe between pumping means and the burner. | 5 |
FIELD OF THE INVENTION
The present invention relates to data backup and replication.
BACKGROUND OF THE INVENTION
Data backup and replication systems create copies of enterprise data at local or remote sites. Some conventional backup and replication systems operate by tracking I/O write commands from physical or virtual servers to storage devices such as storage area network (SAN), network attached storage (NAS) and direct attached storage (DAS). Other conventional systems operate by creating clones or snapshots of enterprise data. Such systems generally save only the last snapshot or clone on disk, or several last snapshots or clones. Recent systems provide continuous data protection (CDP) by journaling write commands so as so provide any point in time data recovery.
Conventional systems limit CDP capability based on disk space available to maintain a journal. Service providers define their objectives and service level agreements (SLAB) in terms of time. For CDP, the SLA generally relates to the window of time history that can be recovered.
As such, a drawback with conventional data backup and replication systems is that an IT professional must be able to correctly estimate the disk space that will be required in order to maintain a desired time frame, and reserve this amount of disk space. Generally, the estimation is inaccurate and the reserved disk space is wasted. Specifically, during off-peak periods, the reserved disk space is unused, and during peak periods the disk space is not able to accommodate all of the changes and maintain the entire SLA history window.
Today, enterprise infrastructures are evolving as pools of resources for on-demand use, instead of reserved pre-allocated resources. Thus it would be of advantage to provide a data backup and replication system that is flexibly adaptable to journal size requirements.
SUMMARY OF THE DESCRIPTION
Aspects of the present invention overcome drawbacks with conventional data backup and replication systems, by leveraging a resource pool of enterprise storage units available for journaling and data replication, to adjust the size of a CDP journal on demand. Data backup and replication systems of the present invention flexibly accommodate disk space required for journaling, allocating more storage units during peak periods, and releasing storage units during off-peak periods.
Further aspects of the present invention enable test journaling in parallel with production journaling, by allocating storage units devoted to test data. The storage units devoted to test data are allocated as required during a test, and are released upon completion of the test. Production data replication and protection continue in parallel with test journaling, without disruption.
There is thus provided in accordance with an embodiment of the present invention a data center for data backup and replication, including a pool of multiple storage units for storing a journal of I/O write commands issued at respective times, wherein the journal spans a history window of a pre-specified time length, and a journal manager for dynamically allocating more storage units for storing the journal as the journal size increases, and for dynamically releasing storage units as the journal size decreases.
There is additionally provided in accordance with an embodiment of the present invention a computer-based method for a data center, including receiving, by a computer at a sequence of times, new data to add to a journal, the journal including one or more allocated storage resources from a pool of resources, and wherein journal data is stored in the allocated storage resources and promoted from time to time to a recovery disk, determining, by the computer, if the journal already contains data for an entire pre-designated time history, additionally determining, by the computer, if the addition of the new data to the journal would cause the journal to exceed a pre-designated maximum size, further determining, by the computer, if the additional of the new data to the journal requires allocating an additional storage resource to the journal, when the further determining is affirmative, then yet further determining, by the computer, if the pool of resources has a free storage resource available, when the determining or the additionally determining or the yet further determining is affirmative, then promoting, by the computer, old time data to a recovery disk, removing, by the computer, old time data from the journal, and releasing, by the computer, one or more of the storage resources from the journal, if all of the data from the one or more storage resources was promoted to the recovery disk, when the further determining is affirmative, then allocating, by the computer, an additional storage resource to the journal, and adding, by the computer, the new data to the journal.
There is further provided in accordance with an embodiment of the present invention a method for data backup and replication, including accessing a pool of multiple storage units for storing a journal of I/O write commands issued at respective times, wherein the journal spans a history window of a pre-specified time length, dynamically allocating more storage units for storing the journal as the journal size increases, and dynamically releasing storage units as the journal size decreases.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be more fully understood and appreciated from the following detailed description, taken in conjunction with the drawings in which:
FIG. 1 is a first simplified diagram of a data center with enhanced data replication journaling, in accordance with an embodiment of the present invention;
FIG. 2 is an administrative user interface screenshot for setting data replication journal parameters, in accordance with an embodiment of the present invention;
FIG. 3 is a subsequent simplified diagram of the data center, vis-à-vis the diagram shown in FIG. 1 , in accordance with an embodiment of the present invention; and
FIG. 4 is a simplified flowchart of a method for a data center, in accordance with an embodiment of the present invention.
DETAILED DESCRIPTION
Aspects of the present invention relate to data backup and replication systems that flexibly allocate and release storage units required for journaling, from a resource pool of storage units, allocating more storage units during peak periods, and releasing storage units during off-peak periods.
Reference is made to FIG. 1 , which is a first simplified diagram of a data center 100 with enhanced data replication journaling, in accordance with an embodiment of the present invention. Data center 100 is used to replicate data from a protected site to a recovery site. The replicated data may be used for a failover, to ensure business continuity when the protected site is not fully functional.
As shown in FIG. 1 , protection is configured individually for different server groups, such as server group 110 A and server group 1108 . Each server group 110 A and 1108 includes one or more physical or virtual servers. Each server group 110 A and 1108 reads and writes data in one or more respective physical or virtual disks 120 A and 120 B.
The recovery site includes a journal 130 and one or more recovery disks 140 . Data transfer between the protected site and the recovery site is via a wide area network (WAN) 150 .
Data center 100 replicates data by intercepting write requests between server groups 110 A and 1108 and their respective disks 120 A and 120 B, transmitting the write requests to journal 130 via WAN 150 , storing the write requests as journal entries in journal 130 , and periodically promoting the write requests to recovery disk 140 by applying them to the data in recovery disk 140 and thereby updating recovery disk 140 to a more recent time.
In accordance with an embodiment of the present invention, journal 130 uses a pool of storage resources as necessary, instead of using dedicated storage. The journal shown in FIG. 1 stores a history window of 12 hours' worth of data, each hour's worth of data being numbered chronologically “1”-“12” from oldest to newest. I.e., the first hour's data is labeled “1”, and the 12 th hour's data is labeled “12”. The various individual hours' worth of data are of varying sizes, as different amounts of data activity occur during different hours of the day. At the stage shown in FIG. 1 , the data in recovery disk 140 corresponds to the zero-hour data (TIME=0).
Moreover, journal 130 stores its history in data chunks 135 , each data chunk being stored in a different resource from the pool of storage resources. Data chunks 135 are labeled “A”-“E” for reference. Data chunks 135 are also of varying sizes, as the resources from the pool of resources are generally of different sizes. In general, an hour's worth of data may fit within a single data chunk 135 , or may require more than one data chunk 135 .
Journal 130 is configured by an administrator to store a specified time history window of data, irrespective of space required. Journal 130 allocates and de-allocates resources from the pool of storage resources, to dynamically expand when more data chunks 135 are required and to dynamically contract when fewer data chunks 135 are required. As such, resources are freed for other applications when journal 130 requires less storage space, instead of being dedicated to the journal as in conventional journaling systems.
Reference is made to FIG. 2 , which is a screenshot of an administrative user interface 200 for setting data replication journal parameters for a protection group, such as server group 110 A, in accordance with an embodiment of the present invention. Shown in FIG. 2 are settings 201 - 210 for specifying various protection group parameters. Setting 201 is for specifying a priority, used for determining priority for transferring data from the protection group to the recovery site, when WAN 150 has limited bandwidth and when there is more than one protection group at the protected site. Setting 202 is for specifying a recovery point objective (RPO) threshold, which is the maximum desired time lag between the latest data written at the protected site and the latest data safely replicated at the recovery site. Setting 203 is for specifying a maintenance history, which is the time window for which write commands are saved in journal 130 . E.g., if the specified maintenance history is 12 hours, as in FIG. 1 , then data may be recovered to any checkpoint within the past 12 hours. Setting 204 is for specifying a maximum journal size. When journal 130 reaches its maximum size, older journal entries are promoted to recovery disk 140 and removed from journal 130 . Setting 205 is for specifying a test period, which is a time between tests for checking integrity of the protection group. Setting 206 is for specifying WAN compression; i.e., whether or not data is compressed at the protected site prior to being transferred via WAN 150 to the recovery site. Setting 207 is for specifying a host at the recovery site that handles the replicated data. Setting 208 is for specifying a datastore at the recovery site for storing the replicated data. Setting 209 is for specifying a test network for use during a test failover. Setting 210 is for specifying a failover network for use during an actual failover. Generally, the failover network is a network suitable for the recovery site deployment architecture.
Reference is made to FIG. 3 , which is a subsequent simplified diagram of data center 100 , vis-à-vis the diagram shown in FIG. 1 , in accordance with an embodiment of the present invention. FIG. 3 shows that when the journal stores a full window history of data, such as 12 hours' worth of data, and newer data arrives, the oldest hour's worth of data is promoted to recovery disk 140 prior to adding the newest data. Specifically, the data labeled “1”, which is the oldest time data in journal 130 , is promoted to recovery disk 140 . I.e., the write requests in data “1” are applied to recovery disk 140 , thereby updating the contents of disk 140 from being current for TIME=0 to being current for TIME=1. Data “1” is then removed from journal 130 . Moreover, removal of data “1” frees data chunk A, which is then de-allocated so that it can be used by other applications, or reused by journal 130 . Thereafter, the new data labeled “13” is added to journal 130 , which now stores data “2” to 13″.
FIG. 3 shows that that data “13” is smaller than data “1” and, as such, the space required for storing data “2” to “13” is less than the space required for storing data “1” to “12”. Moreover, journal 130 does not require as many data chunks at TIME=13 than it did at TIME=12, and non-used resources are freed at TIME=13 for use by other applications. Specifically, data chunks “B”-“E” suffice for storing data “2” to “13”, and data chunk “A” is freed up.
As shown in FIG. 2 , setting 204 enables an administrator to specify a maximum journal size. When storage of new data would cause journal 130 to exceed its maximum size, the oldest data is promoted to recovery disk 140 and removed from journal 130 , until journal 130 is able to store the new data within its size limit. In such case, journal 130 may store less than 12 hours' worth of data; i.e., less than the history specified by setting 203 .
Reference is made to FIG. 4 , which is a simplified flowchart of a method 300 for a data center, in accordance with an embodiment of the present invention. At operation 310 , new data is available for journaling. At operation 320 a determination is made whether or not journal 130 already contains a complete time window history of data, such as 12 hours' worth of data. If so, then at operation 330 the currently oldest time data in journal 130 is promoted to recovery disk 140 and removed from the journal. At operation 340 the oldest data chunk 135 is freed from the journal if all of the data that it stored was promoted to recovery disk 140 , and processing advances to operation 350 . If is determined at operation 320 that journal 130 does not contain a complete time window history of data, then processing advances directly from operation 320 to operation 350 .
At operation 350 a determination is made whether or not addition of the new data would cause journal 130 to exceed its maximum size. If so, then processing returns to operation 330 . Otherwise, processing advance to operation 360 where a determination is made whether or not addition of the new data requires allocation of an additional data chunk 135 . If allocation of an additional data chunk is required, then at operation 370 a determination is made whether or not an additional data chunk is available from the resource pool. If an additional data chunk is not available, the processing returns to operation 330 . If an additional data chunk is available, then at operation 380 an additional data chunk is allocated to the journal and processing returns to step 370 . If it is determined at operation 360 that allocation of an additional data chunk is not required, then processing advances to operation 390 where the new data is added to the data chunks allocated to the journal.
Whenever operation 340 is performed, any unused resources by journal 130 are de-allocated and freed for use by other applications. Whenever operation 380 is performed, additional resources are allocated to journal 130 .
In accordance with an alternate embodiment of the present invention, allocation and de-allocation of resources for journal 130 is performed asynchronously with the actual journaling. Specifically, promotion of data from journal 130 to recovery disk 140 , allocation of resources 135 , and de-allocation of resources 135 are performed periodically, irrespective of whether or not new data has arrived for journaling. As a result, the speed of journaling new data is increased, since operations 320 - 380 of FIG. 4 are not performed at the time of journaling the new data. In this alternate embodiment, the maximum size constraint is not enforced at all times, and instead is exceeded for short durations.
The above description relates to production journaling. However, the present invention also applies to test journaling, for testing integrity of data recovery during a failover. In this regard, it is noted that prior art systems generally stop replication of production data while a test is being performed. As such, new production data is not being protected during the test.
Using the present invention, journal testing is performed in parallel with production journaling, in order to avoid disruption of production replication and protection.
For test journaling, data chunks 135 devoted to testing are allocated to the journal, as required for storing test data, in addition to the production data chunks 135 described hereinabove. During a test, journal test data is stored in data chunks devoted to testing and, in parallel, journal production data is stored in production data chunks. The data chunks devoted to testing are not promoted to recovery disk 140 .
Upon completion of a journal test, the data chunks devoted to testing are released, and the production data continues to be journaled.
In the foregoing specification, the invention has been described with reference to specific exemplary embodiments thereof. It will, however, be evident that various modifications and changes may be made to the specific exemplary embodiments without departing from the broader spirit and scope of the invention as set forth in the appended claims. Accordingly, the specification and drawings are to be regarded in an illustrative rather than a restrictive sense. | A data center for data backup and replication, including a pool of multiple storage units for storing a journal of I/O write commands issued at respective times, wherein the journal spans a history window of a pre-specified time length, and a journal manager for dynamically allocating more storage units for storing the journal as the journal size increases, and for dynamically releasing storage units as the journal size decreases. | 6 |
FIELD OF THE INVENTION
The present invention relates to the preparation of a supported catalyst for the asymmetric cyanohydrination of m-phenoxybenzaldehyde (m-PBA), and to a process for carrying out the asymmetric cyanohydrination.
THE PRIOR ART
The compound (s)-m-phenoxybenzaldehyde cyanohydrin (m-PBAC) is an important intermediate in the synthesis of insecticidal pyrethroids. The existing industrial methods therefor are impractical and expensive, and thus the art has struggled for a long time in the attempt to provide convenient and industrially practical syntheses for this compound. The asymmetric synthesis of these cyanohydrins by the addition of hydrogen cyanide to the corresponding benzaldehyde has been attempted by Oku et al., in the presence of a synthetic dipeptide catalyst (J.C.S. Chem. Com., pp. 229-230 [1981], Oku et al., Makromol. Chem. 183, 579-586 [1982], and other publications). The preparation and use of different catalysts has been addressed in various other publications and patents, such as U.S. Pat. No. 4,569,793, U.S. Pat. No. 4,594,196, U.S. Pat. No. 4,681,947, and GB 2 143 823. All these methods, however, suffer from different drawbacks. First of all, the reaction as carried out according to the art is very slow, and the methods employed are inconvenient from the industrial point of view. Furthermore, the requirements for purity of the product are extremely high, and according to the known art obtaining a very pure product is difficult.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a catalyst by means of which the asymmetric cyanohydrination of m-PBA can be carried out easily, cheaply, and on an industrial scale. It is another object of the invention to provide a method employing such a catalyst, by means of which a highly pure product can be obtained.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst according to the invention comprises an enantiomeric cyclo (phenylalanyl-histidine) (CPH) on a solid support, the solid support being a non-ionic polymer resin. The said resins preferably comprise styrenic-divinylbenzene copolymers.
Examples of some commonly employed styrenic-divinylbenzene copolymers useful for carrying out the invention are the XAD resins, the Diaion HP resins and Sepabeads SP207. The XAD resins, also called Amberlite Polymeric Adsorbants, are described in detail in several technical bulletins of the Rohm and Haas Company, e.g., the bulletin dated 1978, and in the related patents granted to Rohm and Haas. Amberlite Polymeric Adsorbants are hard insoluble spheres of high surface, porous polymer. They usually provide a nominal mesh size of 20-60 and are available in a variety of polarities and surface characteristics. Among their various uses, Amberlite XAD-2 and XAD-4 are used, e.g., in sensitive analytical procedures to detect, identify and measure the presence of pesticides and other organics in the environment. They are also used to detect narcotics in blood and urine. XAD-4 is also used for treating "drug overdose" victims throughout the world, by passing the blood of the person being treated through a cartridge containing the resin. The physical properties of the Amberlite Adsorbants are summarized in Table I as taken from the mentioned 1978 Rohm and Haas bulletin. Among the various XAD resins, XAD-4 is considered the most convenient, since it provides conversions up to 96% with enantiomeric excesses of up to 98.5%. Other XAD resins, such as XAD-7, XAD-16, XAD-1180, are suitable for carrying out the invention, although, as said, XAD-4 is preferred.
TABLE I__________________________________________________________________________Typical properties of Amberlite polymeric adsorbents True Wet Surface Average Skeletal NominalChemical Porosity Density Area Pore Dia. Density MeshNature Vol. % gr/cc sqm/gr Angstrom gr/cc Sizes__________________________________________________________________________ NonpolarXAD-1 Polystyrene 37 1.02 100 100 1.07 20 to 60XAD-2 Polystyrene 42 1.02 300 90 1.07 20 to 60XAD-4 Polystyrene 45 1.02 725 40 1.08 20 to 60__________________________________________________________________________
Sepabeads SP207, as well as the Diaion HP resins, such as HP-20, HP-30 and HP-40 polymers (Mitsubishi Chemical Industries Ltd.), are useful in similar applications, e.g., for recovering amino acids from mixtures thereof (U.S. Pat. No. 4,740,615).
Surprisingly, it has been found that preparing a CPH on solid supports which are conventionally employed for catalyst preparation, such as activated carbon, alumina and so on, results in a catalyst which is not active or very slightly active.
Another object of the invention is to carry out the asymmetric cyanohydrination of m-PBA, catalysed by (L,L) or (D,D)-CPH. Some important factors which should be taken into account, when carrying out this reaction, are: (a) the concentration of the catalyst, (b) the concentration of m-PBA, and (c) the temperature at which the reaction takes place. Other factors of importance are the order of addition of reactants, the excess of HCN, the solvent of the reaction, and the mode of operation (batch operation or loop operation, viz., recirculation over a stationary catalyst). The typical chemical and optical EE yields of m-PBAC obtained according to the process of the invention, are in the range of at least 82 to at least 98%, and the dominating configuration obtained is opposite to that of the enantiomeric CPH used in the reaction. The molar excess of HCN should preferably be in the range of 1.7 to 2.57, but lower excesses are also possible.
The quantity of the enantiomeric catalyst, expressed in mole % CPH relative to m-PBA used in the reaction, should preferably be in the range of 0.75 to 2. Concentrations below 0.75 do not afford high enough conversions, even under prolonged reaction periods such as 8 hours. Under these conditions the conversion usually will not exceed 90%, while higher values of CPH result in practically complete conversion. High enantiomeric excesses, however, are obtained both at low and high catalyst concentration. Higher catalyst concentrations, on the other hand, may adversely affect the enantiomeric excess, due to competing racemization.
The concentration of m-PBA in the reaction mixture affects the rate of reaction, as well as the conversion and the enantiomeric excess. Concentrations of m-PBA below 15 volume % result in conversions lower than 90% and EE higher than 90%, between 15 vol. % and 23 vol. % conversions of 95-100% are obtained, with EE greater than about 95-98%, and between 34-84 vol. % the conversion is about 100%, and the EE drops to 85-26%.
High conversions are obtained in the reaction according to the invention at virtually all practical temperatures. The reaction proceeds to high conversions at -5° C. as well as +25° C. However, the lower the temperature, the higher the enantiomeric excess. At room temperature, the obtainable enantiomeric excess is in the order of 74-75%, at 10° C. EE values are around 90%, and at 0° C. and below, 95% or higher values are obtained. This, as will be apparent to a person skilled in the art, is due also to the undesired reaction of the product in the presence of the catalyst, which is promoted by higher temperatures.
The preferred solvent for the reaction is toluene. However, other solvents can be employed as well, as is apparent to a person skilled in the art, such as benzene, ethers, e.g., diethyl or disopropyl ether, and their mixtures with toluene. Hydrocarbon solvents such as petrol ether give very high conversions, but very low EE. Halogenated hydrocarbons, such CCl 4 , can also be employed, but they mostly result in unsatisfactory conversions and EE.
The catalysts can be prepared, in a way known to the man of the art, by adsorbing the cyclic dipeptide (CPH), from an appropriate solution, on the XAD. A preferred way of doing so is to pass the solution of CPH through a column containing the solid support. Very low concentration solutions (e.g., 0.1% CPH in water) can be employed. After the required amount of CPH has been adsorbed on the XAD, the column can be washed with a non-reactive solution, in order to remove non-adsorbed material, and then dried. The temperature at which the column is dried should not exceed 100° C. and the catalyst obtained is ready and immobilized in the column. For further details on these standard procedures, reference is made to the Rohm and Haas Summary Bulletin referred to above.
It should be noted that in the catalytic systems obtained, the CPH supported on solid support, consists of a molecular layer of cyclo(phenylalanylhistidine) on the solid support. It is believed that this adsorption provides an activated monolayer of single molecules, and that this is responsible for the high efficiency and selectivity of the solid supported catalyst. Furthermore, the catalyst so prepared has a great advantage over the prior art catalysts. The catalysts known in the prior art provide an inconsistent performance, possibly due to a physical change during the reaction. Thus, it is difficult to control a reaction in which the catalyst activity substantially changes with time. In contrast, the solid supported catalyst of the invention is 100% active from the very beginning, does not undergo physical changes to any appreciable extent, and is therefore substantially constant in performance.
It has further surprisingly been found that the overall reaction times obtained with the catalyst of the invention are substantially shorter than those known in the art, which permits to carry out continuous or semi-continuous reactions, in which the catalyst is immobilized rather than suspended. As will be appreciated from the following examples, operating according to the invention, with recirculation, results in 95-96.5% conversions after 2.5 hours at 0° C., with an EE of 97.6-86.7%. These indicative results can be compared, e.g., with U.S. Pat. No. 4,611,076, Table 2, which reports results obtained at 25° C. In Experiment 1, after 2 hours, a 95.9% conversion is obtained with an EE of 80%. This, in view of the difference in reaction temperatures, represents a considerable difference in reaction rates.
The reaction can be carried out in a batch mode, by dispersing the solid catalyst in the reaction mixture, in which case at the completion of the reaction the catalyst can be filtered out, recovered and reused. On the other hand, the nature of the catalyst of the invention is such as to permit continuous reactions with or without recirculation to be carried out. This practically means that the reaction can be effected by passing the reaction mixture through the column containing the catalyst, either by recirculating the mixture several passes through the same column (semi-batch operation), or by providing a cascade of a number of such columns (continuous operation).
The above and other characteristics and advantages of the invention will be better understood through the following illustrative and non-limitative examples thereof.
EXAMPLE 1
Preparation of CPH on Solid Support Catalysts--General Procedure
The following catalysts, composed of enantiomeric cyclo (phenylalanylhistidine), (CPH), on solid supports, were prepared by passing a solution of cyclic dipeptide (CPH) in water (0.1%) through a column containing the solid support. After the prescribed amount of CPH was charged on the support, the column was washed with water to remove any traces of non-adsorbed CPH, and dried in vacuum oven (80° C.).
The efficiencies of the catalysts, thus obtained, were tested by a batchwise cyanohydrination of m-phenoxybenzaldehyde with hydrocyanic acid in toluene. The specific catalysts, conversions, and enantiomeric excess are listed in the Table II below.
TABLE II______________________________________Asymmetric addition of hydrogen cyanide tom-Phenoxybenzoldehyde catalysed byL,L or D,D CPH on solid supports. L,L-/DD-CPH/Solid Conver- EnantiomericSolid Support Support (%) sion (%) Excess (%)______________________________________XAD-7 (L,L) 2.1 76 18.8XAD-4 (D,D) 5.85 96 98.5Kieselgel 60 0.0 -- --Chromosorb 0.0 -- --Charcoal (L,L) 5.0 48 33.2(Chromatog.)Charcoal (L,L) 6.5 95.2 1.0(Powder)XE 305 0.0 -- --XAD-16 (D,D) 6.46 81.6 87.5XAD-1180 (D,D) 5.0 70.5 87.8Charcoal (D,D) 4.93 -- --(3 mm)______________________________________
EXAMPLE 2
Preparation of (s)-m-Phenoxybenzaldehyde cyanohydrin
m-Phenoxybenzaldehyde (105 g, 530 mmole) was added to the catalyst (D,D-CPH/XAD-4; 45.3 g contains 2.65 g D,D-CPH) and left for 5 min. Consequently toluene (520 ml) and HCN (1 ml) were added and left overnight at +5° C. under nitrogen. Hydrogen cyanide (34 ml) was added and the mixture was mechanically stirred for 4 hrs. in an ice bath. The catalyst was filtered off and washed with toluene (100 ml). The combined filtrate and washings were twice extracted with HCl (1M, 50 ml) and with water to neutrality. Dodecylbenzene sulfonic acid (240 mg) was added as stabilizer. Similarly, Et 3 NH+HSO 4 - was also employed in some cases for the same purpose.
Evaporation of the solution under water pump and then under high vacuum gave the product, 115 gr.
______________________________________Analysis: m-PBAC 89.77% free CN 92 ppm % H.sub.2 O 461 ppm (Karl Fisher) [α].sub.D = -24.43° (466 mg, 10 ml CHCl.sub.3) Enantiomeric 98.5% excessD,D-CPH: cyclo-D-phenylalanyl- D-histidinem-PBAC: m-Phenoxybenzaldehyde cyanohydrin______________________________________
EXAMPLE 3
Example 2 was repeated, but using different reaction conditions, and either (D,D) or (L,L)-CPH. The results of 25 runs are detailed in Table III, together with the reaction conditions for each run. The m-PBA concentration in the table is defined as: ##EQU1##
EXAMPLE 4
Example 2 was repeated, with the exception that the solvent was replaced with different solvents. Six experimental runs were carried out, each with a different solvent.
All experiments were carried out at 20° C. and stopped after 4 hours. The results are detailed in Table IV. PG,14
TABLE III______________________________________Asymmetric Cyanohydrination of m-PBACharacteristic Conditions and Results CPH.sup.a / Reaction Con-Reaction m-PBA m-PBA Temp. Time version eeNo. mole % conc. °C. hr % %______________________________________ 1 (L,L) 1.89 8.0 r.t. 3.5 78 44 2 (L,L) 1.50 8.0 0 4.3 91.7 92.6 3 (L,L) 0.50 14.8 r.t. 4.3 61.2 74.7 4 (L,L) 1.55 8.0 0 4.5 89.6 93 5 (L,L) 1.49 8.0 0 4.5 88.2 92.7 6 (D,D) 1.52 14.9 0 4.0 94.7 89.2 7 (D,D) 0.75 14.9 -40 13.0 82 86 8 (D,D) 0.76 14.9 0 7.0 89.5 82.4 9 (D,D) 1.52 20.8 0 4.0 97.4 89.210 (D,D) 1.50 21.2 -2 4.0 93.7 85.911 (D,D) 1.28 22.5 -5 5.0 93.7 89.912 (D,D) 1.53 22.7 -3 4.0 98.0 98.213 (L,L) 1.94 15.0 0 4.0 98.0 93.414 (L,L) 1.0 14.8 0 4.0 88.3 93.615 (L,L) 1.89 15.5 +10 4.0 98.4 92.916 (L,L) 1.85 15.8 0 4.0 98.6 94.717 (D,D) 2.0 14.8 0 4.5 99.4 8618 (L,L) 2.0 14.8 0 4.5 100 9119 (L,L) 2.0 34.0 0 4.5 100 8520 (L,L) 1.0 34.2 +10 7.0 86.7 6321 (L,L) 2.0 84.0 +10 4.0 100 26.622 (L,L) 1.0 84.0 +10 4.0 100 20.223.sup.b (D,D) 1.0 15.0 0 8.0 81.6 87.524.sup.c (D,D) 1.0 15.0 0 8.0 70.5 87.825 (D,D) 1.73 15.0 0 4.0 95.8 92.3______________________________________ .sup.a CPH/XAD4; .sup.b CPH/XAD16; .sup.c CPH/XAD1180 (D,D) = D,DCPH; (L,L) = L,LCPH
TABLE IV______________________________________Asymmetric cyanohydrination in different solvents ConversionSolvent % ee %______________________________________t-BuOCH.sub.3 85.0 40.6i-Pr.sub.2 O 72.3 78.225% i-Pr.sub.2 O/Tol. 85.9 72.6Et.sub.2 O 88.4 61.4CCl.sub.4 70 51.4Petrol ether 60-80% 98.4 9.1______________________________________
EXAMPLE 5
Preparation of Optically Active m-PBAC-Cyanohydrination of m-PBA by recirculation
The catalyst (6.8 g, 5.85% D,D-CPH/XAD-4) packed in a short column equipped with a cooling jacket was charged with m-PBA (3.47 g) and toluene (17.5 ml), and left overnight at +5° C. The column was connected at the bottom to a three neck flask containing the rest of the reactant m-PBA (10.4 g) in toluene (49 ml), and the solution was circulated through the top of the column by a metering pump. The system was cooled in ice/water bath and then hydrocyanic acid (4.6 ml) was added to the flask. The reaction mixture was recycled at a rate of 60 ml/min. through the column. After 2.5 hrs, the circulation was stopped and the content of the column was washed with toluene (60 ml). The reaction mixture was extracted with phosphoric acid (0.1M, 2×50 ml) and with water (3×50 ml) to neutrality, to remove all the cyclic peptide D,D-CPH without any damage. The extractions and washings were combined and brought to 380 ml and pH 8.15 with ammonium hydroxide, α D =+0.103° (estimated 301 mg D,D-CPH--Solution A). The organic phase, after evaporation of the toluene has a conversion of 96.5% and an assay of 89.1% m-PBAC, α D =0.722° (0.396 g, 10 ml CHCl 3 ) corresponding to an enantiomeric excess of 87.6%. The catalyst in the column was washed with methanol (200 ml) to remove the rest of the adsorbed D,D-CPH. Evaporation of the methanol extract to dryness and washing the residue with toluene (20 ml) left clean D,D-CPH which was redissolved in water (250 ml) containing phosphoric acid (10 ml 0.1M). This filtered solution has α D =+0.045° (estimated D,D-CPH--90 mg, solution B). The pH was adjusted to 8.15 with ammonium hydroxide.
The resin in the column was prepared for recharge with the extracted D,D-CPH for the next operation by washing with methanol/water and water. D,D-CPH solutions A and B above, were passed through the column. All the D,D-CPH was adsorbed. Passing additional water (100 ml) through the column proves that no leak of the D,D-CPH took place.
The catalyst thus recharged was dried in a vacuum oven (80° C.) and was ready for the next cyanohydrination reaction. The catalyst was so recycled five times, without any appreciable loss of the cyclic dipeptide. Conversions and assays were determined by NMR method. The results are listed in Table V below. The EE values of Table V were calculated on the basis of results obtained by NMR techniques. Results of potentiometric assays normally indicate higher EE values.
TABLE V______________________________________Asymmetric addition of HCN to m-PBA catalysed by D,D-CPH/XAD-4 in a circulation processCycle No. Conversion % ee %______________________________________1 96.5 87.62 95.7 93.33 93.2 86.74 95.3 93.55 95.0 97.6______________________________________
The above description and examples have been given for the purpose of illustration and are not intended to be limitative. The skilled chemist will be able to effect many changes in the materials and methods employed herein, which are within the skill of the routineer, and which do not exceed the scope of the invention. | A catalyst for the asymmetric cyanohydrination of m-phenoxybenzaldehyde, comprises a catalytically effective amount of enantiomeric cyclo (phenylalanyl-histidine) adsorbed on a solid support comprising a non-ionic polymer resin.
The catalyst is particularly useful as a catalyst in a process for the preparation of (s)-m-phenoxybenzaldehyde cyanohydrin, in which m-phenoxybenzaldehyde is reacted in a cyanohydrination solvent. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This is a divisional application of U.S. patent application Ser. No. 09/275,346, filed Mar. 24, 1999 and entitled “Method and Apparatus for Drilling an Offshore Underwater Well,” which claims the benefit of 35 U.S.C. 119(a) of EP Serial No. 98302386.2 filed Mar. 27, 1998, and entitled “Method And Apparatus For Drilling An Offshore Underwater Well”, both hereby incorporated herein by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
[0002] None.
BACKGROUND OF THE INVENTION
[0003] The present invention relates to a method and apparatus for drilling an offshore underwater well.
[0004] Two conventional methods exist for drilling an offshore underwater well. The first of these is to drill and set a conductor pipe between a surface platform and the sea bed followed by drilling a surface well using a platform wellhead. The BOP is located on the surface wellhead. Subsequent casing strings are landed in the surface wellhead. The well is completed by suspending completion tubing from the wellhead and installing a platform tree. A second method is to drill and set a conductor pipe into the seabed using a floating drilling vessel with the wellhead located on the seabed. A subsea drilling BOP has to run on a drilling riser down to the seabed and is connected to the subsea wellhead. A subsea well is drilled with subsequent casing hangers landed in the subsea wellhead. The well is completed by placing a conventional tree on the seabed wellhead. An alternative subsea option is to use a horizontal tree and then run the tubing.
[0005] As the industry moves further offshore and beyond the continental shelf, the water depths being considered are drastically increasing as reservoirs down the flank of the continental shelf and on the ocean floors are discovered. These water depths rule out the use of conventional platforms and their low cost drilling techniques. Floating or tension production platform systems can be used but their drilling footprint into the reservoir is limited, requiring peripheral seabed subsea production support wells. Subsea fields involve considerable complex subsea architecture and require extensive high cost rig intervention.
[0006] One way in which an attempt has been made to increase the footprint of a production platform is the provision of a slanted conductor. In such an arrangement, the conductor is supported at an angle by the platform so that it can be run in at an angle thereby increasing the lateral distance between the base of the platform and the location where the conductor meets the seabed. However, such an arrangement is awkward and costly as it requires a specially made structure to support the conductor at an angle. Further, the system will not work in deep water without some support for the conductor at various locations between the surface and the seabed, which is not available from a floating platform.
SUMMARY OF THE INVENTION
[0007] According to the present invention, a method of drilling an offshore underwater well comprises the steps of installing a riser conduit so that it is substantially vertically supported at a production deck situated substantially at the sea surface and deviates progressively further from the vertical with increasing sea depth, fixing the riser conduit at the seabed in a non-vertical orientation, and drilling the well into the seabed at an angle to the vertical.
[0008] As the riser conduit is substantially vertically supported at the production deck, it is possible to use conventional platform drilling and production techniques which help keep the costs to a minimum. Further, because the riser conduit is supported at the surface and at the seabed, and deviates progressively further from the vertical in between, intermediate support is not required but can be provided if necessary by buoyancy modules.
[0009] In some fields, the reservoir could be relatively close to the seabed. In such a case, there is insufficient depth for a conventional subsea well which starts vertically at the seabed to be deviated to a sufficient angle to access reservoir formations not already being drained by nearby vertical or deviated wells. Therefore only a limited reservoir acreage can be accessed. With the present invention, some of this deviation from the vertical is already provided before reaching the seabed, so that less deviation is required underground which allows higher angle or horizontal wells to be drilled far along the reservoir. This allows better access to reservoirs which are close to the seabed. However, the most important benefit of the present invention arises when the water is sufficiently deep that the riser conduit can be deviated to be horizontal at the seabed. Once the riser conduit becomes horizontal, it is possible to extend it some considerable distance along the seabed before drilling into the seabed so that the drilling footprint of a platform can be greatly increased without drilling.
[0010] There are a number of different ways in which the riser conduit can be installed. According to a first method, the riser conduit is run from an installation vessel with a skid attached, installed vertically and pivotally connected at the seabed, the installation vessel is moved horizontally to the production installation while the riser conduit is fed out from the installation vessel, and the riser conduit is transferred to the production installation. According to a second method, the production deck is offset from the location where the riser conduit is connected to a skid and is to be fixed at the seabed, the riser conduit is connected to a skid and is fed down from the production deck and is maneuvered out to the end target location at the seabed. According to a third method the riser conduit is pre-made and towed to the appropriate location before being fixed at the production deck and fixed at the seabed. In this third case, the pipe may be towed out just off the seabed, and one end raised to the production deck. Alternatively, the pipe may be towed out and hung off at the platform before being lowered to the seabed and fixed.
[0011] According to a second aspect of the present invention, an offshore wellhead assembly comprises a production deck at which a riser conduit is vertically suspended, the riser conduit deviating progressively further from the vertical with increasing sea depth, the riser conduit being fixed at an angle to the vertical at the seabed by a fixture, and a cased well extending into the seabed from the fixture.
[0012] This arrangement provides the same advantages of being able to access reservoirs areas close to the seabed, and increase the drilling footprint of the production installation as referred to above.
[0013] The riser conduit may be rigidly locked to the fixture. However, in order to provide ease of installation and a fixture which can accommodate the riser at any angle it is preferable for the riser conduit to be pivotally attached to the fixture.
[0014] The fixture is preferably in the form of a skid having a gravity base or piles to secure it to the seabed. The skid is readily able to be transported to the correct location and can be simply secured to the seabed by the base or the piles.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Examples of methods and assemblies in accordance with the present invention will now be described with reference to the accompanying drawings, in which:
[0016] [0016]FIG. 1 is a schematic view of an assembly according to a first example;
[0017] [0017]FIG. 2 shows the assembly of FIG. 1 in greater detail;
[0018] FIGS. 3 A- 3 D show details of elements of FIG. 2; and
[0019] [0019]FIG. 4 is a schematic view of a second example.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] [0020]FIG. 1 shows an example of a tension leg production installation 1 which is shown at the sea surface and is anchored to an optional gravity storage base 3 by mooring legs 4 . From the production installation a number of riser conduits 5 A, 5 B are suspended initially vertically, but deviating progressively from the vertical with increasing sea depth. The conduit 5 A has sufficient curvature that by the time it reaches the seabed 6 it is horizontal and can extend a significant horizontal distance along the seabed. At the desired location, the conduit 5 A terminates at a skid 7 from which a cased well 8 extends towards the production reservoir 9 where a liner or screen 10 can be positioned. The conduit 5 B is of similar construction, with the one exception that it is not horizontal at the seabed. Instead, it is fastened at an oblique angle to the skid 7 and the cased well 8 extends at the same angle into the seabed.
[0021] The details of the horizontally extending arrangement of conduit 5 A are shown in more detail in FIG. 2 and FIGS. 3 A- 3 D and installation of the wellhead assembly will be described with reference to these drawings.
[0022] The first stage of the installation is to install the riser conduit which is in this particular example a well riser conduit, from the production installation 1 to the skid 7 , and connected to the skid secured to the seabed. This can be done in a number of ways. Firstly, the skid 7 can be fixed to the end section of the riser conduit at the production platform. The riser conduit is then run vertically from the production platform and is maneuvered out towards the seabed target zone. When correctly positioned the skid 7 is fixed to the seabed. As a second method, instead of running the riser conduit vertically from the production installation, the riser conduit can be pre-made and can be horizontally towed to the desired location, where it is attached at one end to the production deck 1 . The riser conduit is then positioned on the seabed and the skid 7 is fixed to the seabed. A third alternative which can be used with a installation vessel instead of a tension leg production installation deck is to position the installation vessel: Immediately above the skid 7 and run the drilling riser conduit vertically to attach it to the skid 7 as shown in FIG. 3D which is preinstalled on the seabed as previously described. The installation vessel can then be moved across to the production platform. The end of the riser conduit is transferred from the installation vessel and secured to the production platform.
[0023] In order to attach the riser conduit to the skid 7 , the riser conduit 5 is connected to a wellhead 12 , which is held vertically and is pivotally attached to the skid 7 , as shown in FIG. 2 and FIG. 3B, about an axis 13 so as to be movable through an angle of 90°, as demonstrated by the arrow 14 . The wellhead has a swivel telescopic section 12 A, which is locked during the installation process at mid-stroke and is unlocked once the system is installed to allow for riser conduit twist and thermal expansion. This allows not only for the third installation method described. above where the wellhead 12 will initially have to be vertical, but also allows for the oblique riser conduit SE, as illustrated in FIG. 1. The riser conduit 5 is landed within the wellhead 7 and is sealed by pressure seals 15 .
[0024] The next stage is to drill from the wellhead 12 into the seabed 6 and to install a conductor. Depending on the surface formation a hole can be drilled and a conductor can be installed, or the conductor 16 can be run with an internal shoe bit rotated by a drill string turbine. This latter arrangement can be used in order to drill through unconsolidated formations close to the surface of the seabed so that the conductor 16 supports the formation where a drilled hole would collapse during drilling. In the case of the riser conduit 5 B, the conductor 16 will follow the angle of the riser conduit into the seabed, while for the horizontal arrangement, as shown in FIGS. 2 and 3B, the conductor will initially be horizontal but will drop angle under gravity so that it continues obliquely downwardly through the seabed to the desired depth. The conductor 16 is provided with a stop which lands in the wellhead 12 at which point the internal shoe bit is removed and conventional drilling techniques can be used to install a intermediate string 17 , a production casing string 18 , both of which are landed and sealed within the wellhead 12 , and a liner or screens 10 .
[0025] The drilling elements can be provided with a system of rollers which may be driven in order to facilitate their rotation and passage down the riser conduit. It may even be useful to provide hydraulic force to the drilling or to the casing running systems to provide movement along the riser conduit S, particularly where the riser conduit has a long horizontal portion.
[0026] The appropriate tie back casings 19 , 20 are hung off at the production deck and landed within the wellhead 12 in a similar manner as for conventional vertical tieback wellheads.
[0027] The well completion tubing 21 is now run from the production installation all the way to the production formation. Alternatively, the completion tubing can be hung off in the wellhead 12 . The completion tubing can be provided with two surface control safety valves 22 , 23 .
[0028] By using the tie back strings and landing the production tubing in the wellhead 12 , it is possible to perform a disconnect operation above the wellhead 12 after the well is made safe. To facilitate reconnection, the skid can have a horizontal pipeline pull in system. Alternatively if it is envisaged that the conductor will never need to be disconnected the intermediate casing string and the production casing string can be run directly up to the production platform without landing in the skid wellhead 12 .
[0029] At the production deck, a BOP (not shown) is removed and a tree 24 of known construction is installed for production. In this case, a horizontal tree is shown which has the tubing run through it and landed in it.
[0030] A second example of an assembly is shown in FIG. 4. The only difference between this assembly and that shown in FIG. 1 relates to the nature of the production installation. Instead of a tension leg production installation at the surface as shown in FIG. 1, the example of FIG. 4 has a tension leg subsurface platform 25 which is positioned at a relatively short distance below the surface 2 and connected to a mobile drilling vessel 26 by a short drilling riser 27 . The mobile drilling vessel can be moved between wellheads 28 together with a drilling BOP 29 and can thus be used to drill a number of wells. In this case, the drilling riser is vertical at the subsurface platform 25 . | A method of drilling an offshore underwater well comprising the steps of installing a riser conduit so that it is substantially vertically supported at a production deck. The riser conduit deviates progressively further from the vertical with increasing sea depth, so that its end can be anchored at the seabed by a skid either at an oblique angle so that drilling into the seabed can be carried out at the oblique angle, or horizontally, so that the riser conduit can extend some considerable distance across the seabed before drilling is carried out. | 4 |
FIELD OF THE INVENTION
[0001] The present invention belongs to the high-energy electrochemistry field, and relates particularly to a method for preparing a spherical doped nickelous hydroxide and a multi-metal oxide, and a lithium ion battery.
BACKGROUND OF THE INVENTION
[0002] Currently a lithium ion battery has an extensive application in such electronic devices as mobile telephones, portable computers, and portable audio-visual equipment. However, price of its anode material, lithium cobalt oxide (LiCoO 2 ), is going up continuously because of resource problems, which limits development of the lithium ion battery. Therefore, people have been working hard to look for a suitable substitute material. The material recently studied most is such composite anode materials as cobalt nickel manganese. The most widely used method reported in literature is a codeposition method. According to this method, prepare a metal salt solution according to a certain proportion; add such additives as ammonia water to control crystallization velocity of a hydroxide; and then react with an alkali to produce a deposit. In accordance with this method, add ammonia water into a base solution; after the salt solution is dripped into the base solution, first such metallic ions as Ni 2+ and Co 2+ have a complexation with ammonia (NH 3 ) to produce a complex ion of X(NH 3 ) n 2+ (n=1˜6, X=Ni, Co), concentration of the metallic ion being lowered; then amount of Ni 2+ and Co 2+ is dramatically reduced due to their reaction with OH − to produce a hydroxide deposit; and then M(NH 3 )n 2+ releases the complex metallic ions to keep a certain concentration of the metallic ions in the solution. However, this method has the following shortcoming: After the salt solution is added into the base solution, ammonia (NH 3 ) and OH − coexist with the metallic ions, resulting in a competitive behavior; and it is very difficult for ammonia (NH 3 ) to control crystallization due to the fact that it is easier for OH − than NH 3 to react with such ions as Ni 2+ and Co 2+ , which makes the intermediate particles have an irregular microstructure and a wider size distribution.
[0003] Umicore, Belgium thinks that the material with a bigger particle size has a poorer cycling performance. According to the research done by Guoliang Wu et al., particle size distribution of the material has a remarkable influence on the discharge capacity, especially on the charge-discharge cycling performance; and the wider the particle size distribution, the poorer the cycling performance. The reason is that, the material with a wider particle size distribution will have a poor porosity, which affects its capillarity with an electrolyte and thus makes the impedance show higher; and when the battery is charged to an extreme potential, Li + on surface of a big particle will deintercalate excessively, which will damage its layered structure and is to the disadvantage of the cycling performance.
SUMMARY OF THE INVENTION
[0004] Aiming at the shortcoming of the above method, a purpose of the present invention is to provide a method for preparing the spherical doped nickelous hydroxide, by which the spherical doped nickelous hydroxide has a regular structure and a narrow particle size distribution, the particle size is easy to be controlled, and an industrialized production is made possible.
[0005] Another purpose of the present invention is to provide a multi-metal oxide with high electrical conductivity and good cycling performances as well as its preparation method.
[0006] Still another purpose of the present invention is to provide an anode material of the lithium ion battery with high electrical conductivity and good cycling performance as well as a lithium ion secondary battery.
[0007] The technical solution for realizing the above-mentioned purposes is as below:
[0008] A method for synthesizing the spherical doped nickelous hydroxide is provided, including the following steps:
[0009] 1) First mix a bivalent nickel salt and a bivalent cobalt salt with ammonia water and an ammonium salt to produce a complex solution; and
[0010] 2) then add the complex solution produced in Step 1) and a mixed solution of a metal salt and an alkali solution into a reaction vessel in parallel flow, stir to produce deposit of the spherical doped nickelous hydroxide, and wash away impurity ions.
[0011] It is preferred that the metal salt is chosen from an aluminum salt, a magnesium salt, or a mixture of the two. The aluminum salt and the magnesium salt are preferred to be a nitrate or an acetate.
[0012] It is preferred that, concentration of ammonia water in Step 1) is 0.1˜1 mol/L, and concentration of the ammonium salt 0.02˜0.25 mol/L. The molar ratio of ammonia water to the ammonium salt is 4:1˜5:1, the acid group of the ammonium salt being the same to that of the nickel salt and the cobalt salt.
[0013] It is preferred that, the nickel salt and the cobalt salt are a sulfate, a nitrate, a chloride or an acetate, while the alkali solution is NaOH or KOH; and the molar ratio of total of the nickel salt, the cobalt salt, and the dopant metal salt to the alkali solution is 1:2.1˜1:2.4.
[0014] It is preferred that, there is further a base solution in the reaction vessel; the base solution is a mixed buffer solution of ammonia water and the ammonium salt, with concentration of ammonia water in the base solution being lower than that in Step 1); and amount of the base solution is such that lower end of a stirring paddle can just be stretched into the base solution on bottom of the vessel and stir the base solution. Concentration of ammonia water in the base solution is preferred to be half of that in Step 1). The stirring velocity is preferred to be 100˜600 r/min.
[0015] A method for preparing the multi-metal oxide is also provided for the purposes of the present invention. That is, dry deposit of the spherical doped nickelous hydroxide prepared by the above-mentioned method, mix it uniformly with lithium hydroxide, and obtain the finished product by high-temperature sintering.
[0016] It is preferred that, the molar ratio of total of the nickel salt, the cobalt salt, and the metal salt to the single-water lithium hydroxide is 1:1.02˜1:1.07; when the metal salt is chosen from an aluminum salt, a magnesium salt, or a mixture of the two, total of the metal salt is the total of Ni, Co and Al, or the total of Ni, Co and Mg, or the total of Ni, Co, Al and Mg.
[0017] It is preferred that, the stirring velocity for mixing is 100˜600 r/min, and the drying temperature 150˜200° C.; the high-temperature sintering is performed at 700˜800° C., and the sintering duration is 12˜24 hours.
[0018] The present invention further provides a lithium ion secondary battery, whose anode active material contains the multi-metal oxide prepared by the above-mentioned method.
[0019] And the present invention still further provides a multi-metal oxide with an expression of LiCo a Ni b M 1−a−b O 2 , where M stands for aluminum or magnesium, a=0.03˜0.15, and b=0.6˜0.82.
[0020] The above-mentioned multi-metal oxide is suitable as anode material of the lithium ion battery.
[0021] By adopting the above technical solution, the beneficial technical effects of the present invention are as below with reference to the following embodiments to be illustrated in detail:
[0022] 1) Dope with the metallic ions when producing a spherical nickel intermediate, making the dopant metallic ions produce a more uniform mixed hydroxide intermediate material in liquid phase with cobalt and nickel; during the high-temperature sintering process of this intermediate, the dopant ions can better go into a void among unit cells of the material, which improves stability of the layered deintercalation structure, and restrains or decelerates phase transition during the charge-discharge process;
[0023] 2) while preparing the spherical doped nickelous hydroxide, since before codeposition mix the bivalent nickel salt and cobalt salt with ammonia water and the ammonium salt to produce the complex solution (a buffer solution around pH=7 can be produced with the ammonium salt and ammonia water; there will appear no deposit in the complex solution, whose main purpose is to prevent cobalt from depositing), and then add the complex solution and the mixed solution of the dopant metal salt and the alkali solution into the reaction vessel in parallel flow to produce deposit of the spherical doped nickelous hydroxide, this method effectively prevents the problem that particles are difficult to grow up into a sphere due to direct addition of the alkali solution;
[0024] 3) in view of the fact that the complex solution and the mixture of the salt and the alkali solution are added into the reaction vessel in parallel flow to produce deposit of the spherical doped nickelous hydroxide, as long as the flow velocity is kept constant, pH value in the reaction vessel can be kept constant without the problem that the pH value rises; therefore, by the method of the present invention, the velocity at which the spherical doped nickelous hydroxide is prepared in the reaction vessel and the uniform particle size can be guaranteed, size of the intermediate effectively controlled, and a narrow particle size distribution of the synthesized intermediate obtained;
[0025] 4) because the reaction vessel is added with the mixed buffer base solution of ammonia water and the ammonium salt, it is guaranteed that right from the beginning of feeding, the complex solution and the alkali solution can be stirred uniformly; and presence of the buffer base solution can guarantee that fluctuation of the pH value is very small when the reaction begins;
[0026] 5) it can be seen with reference to embodiments and data to be described in detail below that, the multi-metal oxide (LiCo a Ni b M 1−a−b O 2 ) prepared by the method of the present invention has a uniform particle size distribution, with the particle size being about 6˜10 μm, the first charge-discharge specific capacity up to 170 mAh/g, the first charge-discharge efficiency close to 80%, and a tap density 2.4 g/cm 3 , keeping both a higher specific capacity and a higher tap density; according to an experiment with a button battery, the multi-metal oxide shows good cycling performance, with a specific capacity of 120 mAh/g remaining after 100 cycling times; it has high-voltage resistance and can be charged up to 4.5 V, with good safety performance; and
[0027] 6) because the above-mentioned controlled crystallization method is adopted for preparing the spherical doped nickelous hydroxide, the process is simple and easy to be controlled, there is no need for “emptying” the reaction vessel, a continuous production is possible with a high production efficiency, and a large-scale production is feasible.
[0028] The present invention will be further described below in detail with reference to drawings and embodiments.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] FIG. 1 is a particle size analysis diagram of the spherical doped nickelous hydroxide (hereinafter referred to as “the product”).
[0030] FIG. 2 is an XRD spectrogram of the product particle phase obtained by an X Ray Diffractometer (XRD).
[0031] FIG. 3 is an SEM photograph of the product particle taken by a Scanning Electron Microscope (SEM).
[0032] FIG. 4 is a first charge-discharge curve of a battery made from the multi-metal oxide prepared with the product.
[0033] FIG. 5 is a cycling performance curve of a battery made from the multi-metal oxide prepared with the product.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0034] The present invention provides a method for synthesizing the spherical doped nickelous hydroxide, including the following steps: 1) First mix a bivalent nickel salt and a bivalent cobalt salt with ammonia water and an ammonium salt to form a complex solution; and 2) add the complex solution produced in Step 1) and a mixed solution of a metal salt and an alkali solution into a reaction vessel in parallel flow, stir to produce deposit of the spherical doped nickelous hydroxide, and wash away impurity ions. The produced spherical doped nickelous hydroxide (hereinafter referred to as “the doped spherical nickel”) can be expressed by the chemical formula, Ni b Co a M (1−a−b) (OH) n , where M stands for metal element in the dopant metal salt that can be Al, Mg or their mixture. The produced spherical doped nickelous hydroxide, as an intermediate, can be used to produce the multi-metal oxide, LiCo a Ni b M 1−a−b O 2 . That is, dry deposit of the doped spherical nickel prepared by the above-mentioned method, mix it uniformly with lithium hydroxide, and obtain the finished product by high-temperature sintering. The produced multi-metal oxide can be used for preparing an anode active material of the lithium ion battery. The implementation and effects of the present invention are explained in detail below with reference to embodiments.
Embodiment 1
Doped Spherical Nickel Intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n
[0035] Method for preparing the above-mentioned doped spherical nickel intermediate: Add a complex salt solution of nickel sulfate and cobalt sulfate with ammonia water and ammonium sulfate, as well as NaOH added with aluminum sulfate into a 40 L reaction kettle in parallel flow, the molar ratio of Ni 2+ to Co 2+ being 0.75:0.10, total concentration of the salts 0.85 mol/L, concentration of ammonia 0.8 mol/L, concentration of ammonium sulfate 0.18 mol/L, concentration of NaOH 2.3 mol/L, concentration of aluminum sulfate 0.15 mol/L. The base solution is a mixed solution of ammonia and ammonium sulfate, concentration of ammonia being 0.4 mol/L, concentration of the ammonium salt 0.09 mol/L. Amount of the base solution is such that a stirring paddle can just stir the base solution. The feeding velocity is controlled at 1 L/h, the reaction temperature 50° C., the pH value 11.5, and the stirring velocity 600 r/min. The dark green spherical nickel intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n can be obtained by codeposition. Age for 2 h, wash away SO 4 2− with distilled water for 5˜7 times, dry for 12 hours in an oven at 60° C., mill with a ball mill, sift, and obtain a precursor material.
[0036] Structure and properties of the product prepared in this embodiment can be characterized through the following means: Use an X Ray Diffractometer (XRD) to determine physical phase of the particle, and a Scanning Electron Microscope (SEM) to directly observe shape and size of the product.
[0037] As shown in FIG. 1 , this product has a narrower particle size distribution with the particle diameter at 10 μm, which shows that the particle has a more uniform particle diameter.
[0038] In view of position and number of a diffraction peak on the XRD spectrogram of particle phase of the product as shown in FIG. 2 , there is no impurity peak, showing that no other impurity phase is resulted from doping and the product has a regular layered structure.
[0039] It can be seen from the SEM photograph of the product particle as shown in FIG. 3 that particles of the product are nearly spherical, a spherical shape being advantageous for full usage of the capacity.
Embodiment 2
Doped Spherical Nickel Intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n
[0040] The method of this embodiment is basically the same with that of Embodiment 1, except that the nickel salt, the cobalt salt, the ammonium salt and the aluminum salt of this embodiment are an acetate, the alkali is KOH, and the stirring velocity 300 r/min. Other conditions and preparation methods are the same with those in Embodiment 1. The dark green spherical nickel intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n can be obtained by codeposition. Age for 2 h, wash away the acetate ion with distilled water for 5˜7 times, dry for 12 hours in the oven at 60° C., mill with the ball mill, sift, and obtain the precursor material.
Embodiment 3
Doped Spherical Nickel Intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n
[0041] The method of this embodiment is basically the same with that of Embodiment 1, except that concentration of ammonia in this embodiment is 1 mol/L, concentration of ammonium sulfate 0.25 mol/L, and concentration of ammonia in the base solution 0.5 mol/L. Other conditions and preparation methods are the same with those in Embodiment 1. The dark green spherical nickel intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n can be obtained by codeposition.
Embodiment 4
Doped Spherical Nickel Intermediate Ni 0.75 Co 0.10 Al 0.15 (OH) n
[0042] The method of this embodiment is basically the same with that of Embodiment 1, except that concentration of ammonia in this embodiment is 0.1 mol/L, concentration of ammonium sulfate 0.02 mol/L, concentration of ammonia in the base solution 0.05 mol/L, and the stirring velocity 100 r/min. Other conditions and preparation methods are the same with those in Embodiment 1. The dark green spherical nickel intermediate Ni 0.75 CO 0.10 Al 0.15 (OH) n can be obtained by codeposition.
Embodiment 5
Doped Spherical Nickel Intermediate Ni 0.6 Co 0.03 Al 0.37 (OH) n
[0043] Method for preparing the above-mentioned doped spherical nickel intermediate: This embodiment is different from Embodiment 1 in that a=0.03 and b=0.6, that is, the molar ratio of Ni 2+ to Co 2+ is 0.6:0.03, total concentration of the salts 0.97 mol/L, and the molar ratio of nickel and cobalt to aluminum 0.63:0.37. Other conditions and preparation methods are the same with those in Embodiment 1.
Embodiment 6
Doped Spherical Nickel Intermediate Ni 0.82 Co 0.15 Mg 0.03 (OH) 2
[0044] Method for preparing the above-mentioned doped spherical nickel intermediate: Add a complex salt solution of nickel sulfate, cobalt sulfate and magnesium nitrate with ammonia water and ammonium sulfate, and NaOH into a 40 L reaction kettle in parallel flow, the molar ratio of Ni 2+ to Co 2+ to Mg 2+ being 0.82:0.15:0.03, total concentration of the salts 1 mol/L, concentration of ammonia 0.8 mol/L, concentration of ammonium sulfate 0.4 mol/L, concentration of NaOH 2.4 mol/L. The base solution is a mixed solution of ammonia and ammonium sulfate, concentration of ammonia being 0.4 mol/L, concentration of the ammonium salt 0.09 mol/L. Amount of the base solution is such that the stirring paddle can just stir the base solution. The feeding velocity is controlled at 1 L/h, the reaction temperature 50° C., the pH value 11.5, and the stirring velocity 600 r/min. A dark green spherical doped polyoxide Ni 0.82 Co 0.15 Mg 0.03 (OH) 2 can be obtained by codeposition.
Embodiment 7
Doped Spherical Nickel Intermediate Ni 0.82 Co 0.15 Al 0.02 Mg 0.01 (OH) n
[0045] Method for preparing the above-mentioned intermediate: This embodiment is different from Embodiment 6 in that the dopant metal magnesium is replaced with aluminum and magnesium, the molar ratio of Ni 2+ to Co 2+ to Al 3+ to Mg 2+ n the mixed salt solution is 0.82:0.15:0.02:0.01, total concentration of the salts 1 mol/L, concentration of ammonia 0.4 mol/L, and concentration of ammonium sulfate 0.72 mol/L. The salt solution and NaOH are added into the 40 L reaction kettle in parallel flow, concentration of NaOH being 2.3˜2.4 mol/L. The base solution is a mixed solution of ammonia and ammonium sulfate, concentration of ammonia being 0.2 mol/L, concentration of the ammonium salt 0.09 mol/L. Amount of the base solution is such that the stirring paddle can just stir the base solution. The feeding velocity is controlled at 1 L/h, the reaction temperature 50° C., the pH value 11.5, and the stirring velocity 600 r/min. A dark green spherical doped polyoxide Ni 0.82 Co 0.15 Al 0.02 Mg 0.01 (OH) n can be obtained by codeposition. Age for 2 h, wash away SO 4 2− with distilled water for 5˜7 times, dry for 12 hours in the oven at 60° C., mill with the ball mill, sift, and obtain the precursor material. Measure its humidity accurately. Mill with the ball mill and mix uniformly according to the molar ratio of Ni 0.82 CO 0.15 Al 0.02 Mg 0.01 (OH) n to LiOH at 1:1.06, put into a crucible, place into an electric resistance furnace, heat up to 250° C. at a temperature rising velocity of 5° C./ min, keep the temperature for 2 h, then continue to heat up to 700° C. and keep constant for 12 h, take out of the crucible when the temperature declines below 200° C., grind with the ball, and then obtain the anode material of the lithium ion battery with high capacity, high-voltage resistance, and good cycling performance.
Embodiment 8
Synthesis of the Multi-Metal Oxide LiCo 0.10 Ni 0.75 Al 0.15 O 2
[0046] Mill the material synthesized in Embodiment 1 with the ball mill and mix uniformly according to the molar ratio of Ni 0.82 Co 0.015 Al 0.02 Mg 0.01 (OH) n to LiOH at 1:1.06, put into the crucible, place into the electric resistance furnace, heat up to 250° C. at the temperature rising velocity of 5° C./ min, keep the temperature for 2 h, then continue to heat up to 700° C. and keep constant for 12 h, take out of the crucible when the temperature declines below 200° C., grind with the ball, and then obtain the multi-metal oxide with high capacity, high-voltage resistance, and good cycling performance.
[0047] Manufacture a button lithium ion battery with this multi-metal oxide according to normal processes, and test its electrochemical performance.
[0048] It can be seen from the first charge-discharge curve as shown in FIG. 4 that, the manufactured product has high-voltage resistance, and can be charged up to 4.5 V, with good safety performance. The specific capacity of the first charge is 210 mAh/g, the specific capacity of discharge 170 mAh/g, with a charge-discharge efficiency at 81%.
[0049] According to the cycling performance curve of the product as shown in FIG. 5 , there is a greater capacity attenuation from the first to the second cycle, which however also provides a sufficient lithium source for forming an SEI film on the cathode surface. The capacity retention rate in a following cycle is all above 99%, and the specific capacity still remains above 120 mAh/g after cycling for 100 times. It can thus be seen that, the multi-metal oxide of the present invention is an anode material of the lithium ion battery with high electrical conductivity and good cycling performance. | The invention relates to a method for preparing multiple metal oxides and intermediate compound, i.e. spherical nickelous hydroxide which is lopped. The said intermediate compound is prepared by two steps: mixing bivalent nickel salt, cobalt salt, ammonia water and ammonium salt to form solution containing complex; then adding the said solution containing complex with the mixture solution of metal salt(s) and alkali into reaction vessel in parallel flow, stirring to form precipitate of spherical nickelous hydroxide which is dopped, and washing to remove the impurities. The resulting spherical nickelous hydroxide which is dopped, as an intermediate compound, can be used to produce multiple metal oxides. The resulting multiple metal oxides can be used as anode active material. The spherical nickelous hydroxide which is dopped, according to present invention, has advantages of uniform size and narrow size distribution. And the multiple metal oxides has high electric conductivity and cycle performance, particularly, is suitable to be used as anode material. | 2 |
BACKGROUND OF THE INVENTION
This invention relates to a device for controlling the balloon and tension in the thread from a storing and distributing apparatus to an operating machine.
As is well known in the art, many operating machines, such as weaving machines, are not directly supplied with yarn from a bobbin, cop or the like, but such a yarn from the bobbin reaches the operating machine after being previously wound on an apparatus, where a magazine or supply yarn is formed. The yarn is then supplied to utilization with constant controlled tension.
One being drawn from these storing apparatus, the yarn unwinds at a very high speed at the periphery of a drum, on which it is wound in turns. Many types of devices have been proposed for imparting a predetermined rate of tension to the yarn unwinding from the drum. However, it was found that, although being effective in imparting a predetermined rate of tension to the yarn unwinding from the drum, these devices are not versatile. Thus, they do not allow adjusting the tension to rates that vary with time.
Furthermore, the risk very often occurs that the thread unwinding from the drum would form balloons due to centrifugal force, or would tend to be moved away from the drum to a high extent, thus preventing any control of outlet speed and yarn tension.
It is the primary object of the present invention to provide a device of simple structure and low cost of production, which is readily applicable to known type of thread storing apparatus. The device is to enable controlling the balloon of the thread unwinding from the apparatus to which such a device is applied, and also to enable controlling the tension of the yarn supplied to an operating machine at a constant rate and extent that can be easily and readily varied.
SUMMARY OF THE INVENTION
These and other objects are accomplished by a device comprising a bell having a base wall, from which a substantially cylindrical peripheral wall extends. The bell has an inner diameter larger than the outer diameter of the storing apparatus to which the device is applicable. An element is provided for supporting and spacing the base wall on the top of a yarn storing apparatus. The element comprises a plurality of thin elongated flexible fingers having a free end thereof. The flexible fingers are inclined in the yarn movement direction during the unwinding of the storing apparatus and are distributed according to a circular crown or sector.
BRIEF DESCRIPTION OF THE DRAWING
In order that the structures and features of the device be more clearly understood, a preferred embodiment thereof will now be described, as given by mere way of example, reference being had to the accompanying DRAWING, in which the single FIGURE shows the device mounted on a yarn storing apparatus.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In a front elevational view, the FIGURE of the drawing shows a yarn storing and distributing apparatus comprising a cylindrical drum 1, on which a rotating distributor 2 forms a number of turns by means of a yarn 3 arriving, for example, from a bobbin or cop. In a conventional manner, these turns are upward axially displaced along drum 1. Yarn 4, which is supplied to the operating machine (for example a textile machine), passes through a hole provided along the axis of drum 1 and unwinds from the top of the drum, as clearly shown in the FIGURE of the drawing. During this unwinding step of the yarn from the drum, the yarn fastly rotates all about the drum, while moving at the same time from the periphery of the center of the drum.
As mentioned above, many types of these apparatus are known and are extensively used in the art and therefore will not be herein described in detail. For example, some embodiments of these apparatus are described in U.S. Pat. No. 3,796,386, while another embodiment is described in the U.S. Pat. Application No. 565,607 filed on Apr. 7, 1975, by the same applicants of this invention.
The device according to the present invention comprises a bell, outlined in the drawing, and having a base wall 5, from which a cylindrical peripheral wall 6 extends with inner diameter larger than the outer diameter of drum 1, to which the device is applied. In addition to the bell, the device comprises a base 7 bearing at the top of drum 1. From this base a plurality of thin flexible elongated fingers 8 extend upwardly, the upper ends of which are free. The fingers are distributed according to a circular crown or sector coaxial with drum 1. These fingers, for example, are made of plastics material, and are inclined in the thread movement direction. They are preferably inclined both in the direction of rotation for the thread about the upper end of the drum during the unwinding step, and are slightly inclined to the center.
An important feature of the above described device is that the base wall 5, that is the whole bell, simply rests on the free ends of the fingers 8, so that as the yarn is unwound from drum 1, the yarn passes between the upper ends of fingers 8 and the underside of base wall 5. As apparent, the yarn will cause the deflection of these fingers one at a time, so that the braking action exerted by the fingers on the yarn will be substantially due only to the action, or pressure, of one of these fingers at a time.
The combined action of fingers 8 and base wall 5 is that of controlling the tension in the thread unwinding from drum 1. The cylindrical wall 6 accomplishes the function of controlling the balloon tending to be formed by the unwinding yarn due to centrifugal effect, and prevents such a balloon from taking undue and no longer controllable dimensions.
As it will be seen from the FIGURE of the drawing, a pin 9 projects from the upper surface of base wall 5. The pin in this case may be hollow for allowing the yarn unwound from the drum to exit therethrough. The pin is exactly positioned at the center of the base wall 5 and on which rings 10 of an exactly predetermined weight can be slipped.
Evidently, should only one ring 10 weigh on the bell, such a weight will be distributed on fingers 8. These will exert a predetermined pressure on the surface of wall 5, and accordingly will cause a predetermined braking action on the drum unwinding thread. If two or more rings weigh on or rest on the bell, the braking action to be exerted by flexible fingers 8 on the unwinding yarn can be very simply and exactly adjusted to a predetermined rate.
Finally, it should be noted that the underside of wall 5 can be easily shaped so that fingers 8 by acting on the surface will assure the bell centering on drum 1.
As apparent, instead of being fast with and projecting from a base 7, the fingers 8 can be fast with and project from from the underside of wall 5 or project from the cylindrical peripheral wall 6. In such cases, the flexible fingers would have the free ends thereof bearing on the upper surface of drum 1.
The device described has been proven to be perfectly efficient in assuring a correct control of tension and elimination of balloons when unwinding all types of yarn, elastomer yarns excluded. | Device for controlling the balloon and tension in the thread from a thread storing and distributing apparatus to textile machines. Such a device comprises a bell superimposed to the storing apparatus and supported thereon by flexible fingers which are deflected by the thread unwinding from the apparatus. | 3 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to image processing systems, and in particular to an image processing system that can transmit image data to an external information processing system.
[0003] 2. Description of the Related Art
[0004] Digital cameras for recording captured image data on a memory card are known, as described in Japanese Patent Laid-Open No. 2003-111002. In such digital cameras, image data recorded in a memory card is often transmitted to a computer to save and/or process the image data therein. For this purpose, a digital camera is generally connected to a computer, where host application software is started up to import an image recorded on the memory card to the computer.
[0005] The digital camera connected to a computer (hereinafter, referred to as a PC) has two principal modes.
[0006] In one mode, a user interface (hereinafter, referred to as a UI) of the digital camera is enabled. In this mode, the UI of the digital camera is operated to, for example, transfer images to the computer.
[0007] In the other mode, the UI of the digital camera is disabled. In this mode, the digital camera is accessed with an application running on the computer and the UI of the application is operated to import images from the digital camera to the computer.
[0008] In the mode where the UI of the digital camera is enabled, if, for example, an image is deleted by operating the camera or by accessing the digital camera with the host application running on the computer, processing for preventing data inconsistency, that is, processing for data synchronization or exclusive processing on data, is required. Because the operation by the digital camera and the operation by the computer are available in parallel in this case.
[0009] On the other hand, the mode where the UI of the digital camera is disabled is problematic in that a useful feature such as the ability to transfer an image specified after the image has been confirmed on the screen of the digital camera is not available due to the disabled UI of the digital camera. In this case, once the mode of the disabled camera UI is selected, there is no way of easily switching to the other mode as described above with satisfying the data synchronization or the exclusive processing.
SUMMARY OF THE INVENTION
[0010] The present invention is directed to solve the above-described problems.
[0011] Among other advantages, the present invention can enable image data to be transmitted by a simple UI operation, and to prevent image data inconsistency between the camera and the computer.
[0012] According to an aspect of the present invention, an image processing system includes a playback unit for playing back an image recorded on a recording medium; a communication unit for transmitting the image played back by the playback unit to an external information processing system via a transmission pathway; an operation unit including a plurality of operation keys; and a control unit for switching a transmission mode among a plurality of modes including a first mode in which transmission of the image according to an operation of the operation unit is enabled and a second mode in which transmission of the image according to an operation of the operation unit is disabled. The control unit changes the transmission mode to the first mode according to a predetermined operation of the operation unit in the second mode.
[0013] According to another aspect of the present invention, an image processing system includes an imaging system having a first mode in which transmission of an image recorded on a recording medium by an operation of an operation unit is enabled and a second mode in which transmission of the image by an operation of the operation unit is disabled, and capable of transmitting an image recorded on the recording medium via a transmission pathway; and a computer connected to the imaging system via the transmission pathway, the computer receiving the transmitted image to display the transmitted image on a display device and the computer having a first status in which processing of the image recorded on the recording medium by operating a user interface is enabled and a second status in which processing of the image by operating the user interface is disabled. If a predetermined operation is performed by the operation unit while the imaging system is in the second mode and the computer is in the first status, the imaging system switches from the second mode to the first mode and the computer switches from the first status to the second status.
[0014] According to still another aspect of the present invention, a data processing system includes a communication unit for receiving an image on a recording medium via a transmission pathway, the image being played back by an external image processing system having a first mode in which transmission of the image according to an operation of an operation unit is enabled and a second mode in which transmission of the image according to an operation of the operation unit is disabled; a display unit for displaying the image on a display device, the image being received via the communication unit; a user interface for specifying processing of the image recorded on the recording medium; and a control unit for switching an operation status between a first status in which processing of the image recorded on the recording medium by an operation of the user interface is enabled and a second status in which processing of the image according to an operation of the user interface is disabled. The control unit sets the image processing system to the second mode by transmitting a control command via the communication unit if the operation status is the first status, and the control unit switches the operation status from the first status to the second status and changes the image processing system to the first mode by outputting a control command to the image processing system via the communication unit if a predetermined operation is performed on the user interface in the first status.
[0015] According to still another aspect of the present invention, a data processing method includes the steps of displaying an image on a display device, the image being received by a communication unit for receiving the image on a recording medium via a transmission pathway, the image being played back by an external image processing system having a first mode in which transmission of the image according to an operation of an operation unit is enabled and a second mode in which transmission of the image according to an operation of the operation unit is disabled; and switching an operation status between a first status in which processing of the image recorded on the recording medium by an operation of a user interface for specifying processing of the image recorded on the recording medium is enabled and a second status in which processing of the image according to an operation of the user interface is disabled. In the switching step, the image processing system is set to the second mode by receiving a control command via the communication unit if the operation status is the first status, and if a predetermined operation is performed on the user interface in the first status, the operation status is switched from the first status to the second status and the image processing system is changed to the first mode by receiving a control command via the communication unit.
[0016] Further features and advantages of the present invention will become apparent from the following description of the embodiments (with reference to the attached drawings).
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a diagram of a system to which the present invention is applied.
[0018] FIG. 2 is a functional block diagram of a computer in a system to which the present invention is applied.
[0019] FIG. 3 is a diagram showing a display screen of a digital camera when the camera is in the camera-operation mode according to an embodiment of the present invention.
[0020] FIG. 4 is a functional block diagram of a digital camera.
[0021] FIG. 5 is a diagram showing a display screen of an application.
[0022] FIG. 6 is a diagram showing a display screen of an application.
[0023] FIG. 7 is a flowchart showing the operation of a digital camera.
[0024] FIG. 8 is a flowchart showing the operation of an application.
[0025] FIG. 9 is a diagram showing a transfer image list.
[0026] FIG. 10 is a flowchart showing the operation of an application.
[0027] FIG. 11 is a flowchart showing the operation of an application.
[0028] FIG. 12 is a flowchart showing the operation of an application.
[0029] FIG. 13 is a flowchart showing the operation of a digital camera.
[0030] FIG. 14 is a flowchart showing the operation of an application.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0031] Embodiments according to the present invention will now be described in detail with reference to the drawings.
[0032] FIG. 1 is a diagram showing the structure of a system to which the present invention is applied.
[0033] Referring to FIG. 1 , a computer 10 , functioning as a host device, is connected to a monitor 12 for displaying an output from the computer 10 as an image, a mouse 14 including mouse buttons 16 , and a keyboard 18 . A digital camera 20 is connected to the computer 10 via a USB data transfer cable 22 .
[0034] FIG. 2 is a functional block diagram of the computer 10 shown in FIG. 1 .
[0035] As known to persons of ordinary skill in the art, the computer 10 has an operating system (OS) in the hardware, and application software 50 runs under the control of the operating system. Elements not required to understand the structure of the embodiment, such as the CPU and the memory management system of the operating system, are omitted.
[0036] The computer 10 includes a hard disk drive (HDD) 30 , functioning as an auxiliary storage device. The operating system includes a file system 32 having a function for enabling files to be input/output without directly controlling the hardware by the application software 50 . For the file system 32 , a known structure can be used. The file system 32 reads and writes data from and to the hard disk 30 via a disk input/output interface 34 .
[0037] The operating system further includes a drawing management system 36 having a function for generating an image without directly controlling the hardware by the application software 50 . A video interface 38 converts image data generated in the drawing management system 36 into a video signal adapted for the monitor 12 .
[0038] The operating system further includes an imaging device management system 40 . The imaging device management system 40 manages a device for manipulating image data, such as a digital camera and a scanner. The imaging device management system 40 automatically allocates a device driver appropriate for a connected device, and furthermore, provides a mechanism for managing input to and output from the device without direct control of the device by the application software 50 . In addition, the application software 50 can be started up at the request of the connected device.
[0039] The keyboard 18 is connected to a keyboard interface 42 and the mouse 14 is connected to a mouse interface 44 . External devices, including the digital camera 20 , are connected to a USB interface 46 .
[0040] As described above, the digital camera 20 is connected to the USB interface 46 via the USB cable 22 , and interchanges control commands, status signals, and image data with the application software 50 for the digital camera via a digital camera device driver 37 and the imaging device management system 40 .
[0041] The application software 50 acquires images from the digital camera 20 and controls the digital camera 20 . The application software 50 according to this embodiment includes a communication management unit 52 for communicating with the digital camera 20 by accessing the imaging device management system 40 ; an image transfer management unit 53 for acquiring an image captured in the digital camera 20 by using the communication management unit 52 ; a camera UI control unit 54 for sending a control command to the digital camera 20 , setting the mode of the display screen of the digital camera 20 , and turning the UI ON/OFF by using the communication management unit 52 ; a data display unit 56 for displaying on the monitor 12 an image and other information transferred from the digital camera 20 ; and a file management unit 58 for storing image data transferred from the digital camera 20 in the hard disk 30 for data management. Elements not required to understand the structure of the embodiment are omitted.
[0042] FIG. 3 is an external view of the digital camera 20 .
[0043] A liquid crystal screen 209 displays various menus for specifying settings of the digital camera 20 . The liquid crystal screen 209 is also used as a viewfinder for photography. Also, previously captured images can be played back on the liquid crystal screen 209 from the memory card.
[0044] A power button 2101 turns ON/OFF the power of the digital camera 20 , and a photography/playback switching button 2106 switches between the photography mode and the playback mode of the digital camera 20 . A shutter button 2102 is used to take a picture. A menu button 2103 is used to display a menu screen for setting the camera operation. When the menu button 2103 is operated, various menus are displayed on the liquid crystal screen 209 . Items to be displayed in the menu differ depending on the mode of the digital camera 20 . A set button 2104 and a move button 2105 are used to operate menus. More specifically, the move button 2105 is used to move from one selectable item to another and the set button 2104 is used to set the selected item. As described later, the menu button 2103 also has a function for switching to a camera operation mode while the digital camera 20 is connected to a PC.
[0045] FIG. 4 is a functional block diagram of the digital camera 20 .
[0046] Elements not required to understand the structure of the embodiment, such as the CPU and elements related to image playback, are omitted.
[0047] A photography unit 201 includes elements related to photography, such as a lens, an aperture, a CCD, and an image processor. A file management unit 202 manages access to a memory card 208 , functioning as a storage device. According to this embodiment, a Compact Flash® (CF) card is used as the memory card 208 . Image data generated by the photography unit 201 is stored in the memory card 208 as a file.
[0048] A communication management unit 203 communicates with the computer 10 via a USB interface 205 .
[0049] The UI management unit 204 controls the UI of the digital camera 20 to manage display items on the liquid crystal screen 209 . The UI management unit 204 also controls the UI of the digital camera 20 to manage inputs from operation buttons 210 . The operation buttons 210 include the buttons 2101 to 2105 shown in FIG. 3 .
[0050] FIGS. 5 and 6 show a graphical user interface displayed on the monitor 12 by the application software 50 shown in FIG. 2 .
[0051] The UI of the application 50 includes tabs for selecting functions, as shown in FIGS. 5 and 6 , so that the UI changes by switching between the tabs.
[0052] The tabs include a camera-operation-information tab 501 and an image list tab 502 . If the application 50 according to this embodiment is started up by the imaging device management system 40 , the camera-operation-information tab 501 is selected initially, so that the screen shown in FIG. 6 appears. As described later, the startup of the application 50 by the imaging device management system 40 is automatically performed when the imaging device management system 40 senses that the digital camera 20 is connected to the PC 10 .
[0053] In contrast, when the application 50 is started up by the user, the image list tab 502 is initially displayed, so that the screen shown in FIG. 5 appears.
[0054] When the camera-operation-information tab 501 in FIG. 6 is selected, a message indicating that the UI of the digital camera 20 is enabled is displayed in a camera mode display area 505 . In this mode, the operation that can be performed with the application 50 is to specify an image transfer destination. An image transfer destination is a location in the computer, i.e., the location where an image file transferred from the digital camera 20 by operating the UI on the digital camera 20 is to be saved.
[0055] When the image list tab 502 shown in FIG. 5 is selected, reduced versions of images stored in the memory card 208 placed in the digital camera 20 are listed in an image list display area 5011 .
[0056] While the application 50 is in this mode, the UI of the digital camera 20 is disabled, that is, the digital camera 20 cannot be operated. Thus, a message indicating that the UI of the digital camera 20 is disabled is displayed in the camera mode display area 505 . In this mode, image data in the memory card 208 placed in the digital camera 20 can be transferred to the PC 10 by operating the application 50 .
[0057] When image data stored in the memory card 208 is to be imported to the hard disk 30 of the PC 10 , a desired image is selected from the reduced versions of images displayed in the image list display area 5011 and a [TRANSFER] button 5012 is then pressed. A transfer destination in the hard disk 30 can be specified with a [SELECT DESTINATION] button 5014 . Furthermore, pressing a [DELETE] button 5013 causes the image file corresponding to the selected image to be deleted from the memory card 208 placed in the digital camera 20 .
[0058] The digital camera 20 according to this embodiment has two modes of communication with the PC 10 .
[0059] One mode is an application mode, in which the UI of the digital camera 20 is disabled; more specifically, nothing is displayed on the liquid crystal screen 209 of the camera 20 , and the operation buttons 210 on the camera 20 , except for the power button 2101 and the menu key 2103 , are disabled.
[0060] The other of the two communication modes is a camera operation mode, in which the UI of the digital camera 20 is enabled; more specifically, a menu as shown in FIG. 3 is displayed on the liquid crystal screen 209 and the menu can be operated with the operation buttons 210 .
[0061] According to this embodiment, while the digital camera 20 is in the camera operation mode, a camera-operation image-transfer menu, as shown in FIG. 3 , is displayed on the liquid crystal screen 209 to allow the user to select one of the following three menu items.
[0062] A first menu item is a [TRANSFER ALL IMAGES] item 2091 . When this item is selected, image data stored in the memory card 208 placed in the digital camera 20 can be all transferred to the host application 50 .
[0063] A second menu item is a [TRANSFER SELECTED IMAGES] item 2092 . When this item is selected, pre-selected image data is transferred to the computer 10 .
[0064] A third menu item is a [SELECT AND TRANSFER IMAGES] item 2093 . When this item is selected, image data stored in the memory card 208 are sequentially played back for display on the liquid crystal screen 209 , so that desired images to be transferred to the computer 10 are selected from among the displayed images.
[0065] When the application 50 is running and the image list tab 502 is selected to list images stored in the memory card 208 placed in the digital camera 20 , as shown in FIG. 5 , the digital camera 20 is placed in the application mode, i.e., the mode in which the UI of the digital camera 20 is disabled. As a result, the digital camera 20 cannot be used to operate image data in the CF card 208 . This prevents images displayed with the application 50 from differing from the images in the CF card 208 placed in the digital camera 20 .
[0066] In other words, it is not necessary to perform processing for matching the information displayed by the application 50 to the content of the memory card 208 placed in the digital camera 20 .
[0067] In contrast, when the digital camera 20 is in the camera-operation mode, the display screen of the application 50 appears as when the camera-operation-information tab 501 is selected, as shown in FIG. 6 ; in short, the content of the memory card 208 placed in the digital camera 20 is not displayed.
[0068] Therefore, the content of the memory card 208 placed in the camera 20 is prevented from being changed using the application 50 during image transfer in the camera-operation mode. More specifically, the problem of, for example, attempting to delete image data being transferred using a command from the PC 10 is eliminated.
[0069] Processing by the camera 20 and the application 50 for these operations will now be described with reference to flowcharts.
[0070] According to this embodiment, when the digital camera 20 is connected to the PC 10 , the digital camera 20 is automatically placed into the camera-operation mode, displaying the menu shown in FIG. 3 on the liquid crystal screen 209 . Furthermore, the digital camera 20 can be placed into the camera-operation mode by operating the menu button 2103 on the digital camera 20 and issuing an event indicating operation of the menu button 2103 to the PC 10 while the digital camera 20 is connected to the PC 10 in the above-described application mode. To perform desired processing, the user operates the move button 2105 on the digital camera 20 to move selection to the desired menu item and presses the set button 2104 .
[0071] Furthermore, in this case, the imaging device management system 40 senses that the digital camera 20 is connected to the PC 10 to automatically startup the application 50 . As a result of the application 50 being started up, the initial screen of the monitor 12 appears as when the camera-operation-information tab 501 is selected, as shown in FIG. 6 . If the application 50 has already been started up, the screen of the camera information tab 501 being selected automatically appears.
[0072] FIG. 7 is a flowchart for describing the operation of the command message processing routine for processing commands from the PC 10 in the digital camera 20 .
[0073] First in step S 701 , a determination is made as to whether a command for entering the camera-operation mode has been issued as a result of the camera 20 being connected to the PC 10 or the menu button 2103 being operated while the digital camera 20 connected to the PC 10 is in the application mode. If a command for entering the camera-operation mode has been issued, in step S 705 the camera buttons and the liquid crystal screen 209 are enabled by the UI management unit 204 . Subsequently, in step S 706 , the menu screen shown in FIG. 3 is displayed on the liquid crystal screen 209 .
[0074] If a command for entering the camera-operation mode has not been issued, then in step S 702 it is determined whether a command for entering the application-mode has been issued. If a command for entering the application-mode has been issued, in steps S 703 and S 704 the camera buttons and the liquid crystal screen 209 are disabled by the UI management unit 204 .
[0075] If neither a command for entering the camera-operation mode nor a command for entering the application-mode has been issued, in step S 707 appropriate command processing is carried out. This processing includes, for example, transferring a transfer image list, to be described later, to the PC 10 .
[0076] FIG. 8 is a flowchart showing the operation of the digital camera 20 when the set button 2104 is pressed to select one menu item while the digital camera 20 is in the camera-operation mode.
[0077] First, in step S 801 , a transfer image list which is a list of images to be transferred is generated. Images to be transferred differ depending on the item selected in the camera-operation image-transfer menu shown in FIG. 3 . When the [TRANSFER ALL IMAGES] item 2091 is selected, a transfer image list containing all images stored in the memory card 208 is generated. When the [TRANSFER SELECTED IMAGES] item 2092 is selected, a transfer image list is generated according to a pre-generated image transfer list.
[0078] The image transfer list used in this specification is based on the Digital Print Order Format (DPOF) commonly used in digital cameras. The content of the list and how to select the list are not directly related to the present invention, and will not be described.
[0079] When the [SELECT AND TRANSFER IMAGES] item 2093 is selected, images stored in the memory card 208 are sequentially read and displayed on the liquid crystal screen 209 , so that the user can select images to be transferred from among those sequentially displayed images.
[0080] The image display method is not directly related to the present invention, and thus will not be described. Regardless of which item has been selected, the generated transfer image list contains paths to image files in the memory card 208 , as shown in FIG. 9 . The format of the list is not directly related to the present invention, and any format can be employed for the list.
[0081] Next in step S 802 , a transfer-image-list generation event is issued to the application 50 . This informs the application 50 that a transfer image list has been generated. At this point, the application 50 will request the transfer image list from the camera. Thus, a command from the application 50 that requests the transfer image list is awaited in step S 803 . On receiving the transfer-image-list generation event, the application 50 then issues the command to the camera 20 to acquire the list. In this manner, this list can by synchronized or compared with images currently stored on the PC 10 to maintain data consistency as further described with reference to FIG. 11 .
[0082] When a request is made for the transfer image list, in step S 804 the transfer image list generated in step S 801 is transferred to the application 50 .
[0083] The operation of the application software 50 will now be described.
[0084] FIG. 10 is a flowchart for describing the processing when the application software 50 is started up.
[0085] First in step S 1001 , it is determined whether the application 50 has been started up by the user or by the imaging device management system 40 .
[0086] If a determination is made that the application 50 has been started up from the imaging device management system 40 , it means that the digital camera 20 has been connected to the PC 10 or the menu button 2103 on the digital camera 20 has been pressed, and the process proceeds to step S 1002 .
[0087] In step S 1002 , image data is acquired in the camera-operation mode. Image acquisition in the camera-operation mode will be described later.
[0088] On the other hand, if a determination is made that the application 50 has not been started up from the imaging device management system 40 , in step S 1003 a command for entering the application mode is issued to the camera 20 to disable the UI of the camera 20 . Then in step S 1004 , image data is acquired from the camera 20 to display the image data in the format shown in FIG. 5 . The image acquisition method is not directly related to the present invention, and thus will not be described.
[0089] FIG. 11 shows a flowchart for describing the operation for image acquisition by the application 50 in the camera-operation mode. First in step S 1101 , the screen appearing when the camera-operation-information-tab 501 is selected, as shown in FIG. 6 , is displayed on the monitor 12 . Then in step S 1102 , a transfer-image-list generation event from the camera 20 is awaited.
[0090] On receiving a transfer image generation event, in step S 1103 a command for requesting a transfer image list is issued to the camera 20 to acquire the transfer image list. The description of processing for acquiring one image data item at a time from the transfer image list follows.
[0091] In step S 1104 , the acquired transfer image list is analyzed to determine whether an image that has not yet been acquired exists in the list. If the list contains an image that has not yet been acquired, in step S 1105 one image file contained in the transfer image list is acquired from the digital camera 20 . The acquisition method is not directly related to the present invention, and will not be described. The acquired image data is then saved in a predetermined location in the hard disk 30 . The saving destination can be changed with the [SELECT DESTINATION] button 5014 on the camera operation information screen shown in FIG. 6 .
[0092] On the other hand, if a determination is made that the list does not contain an image to be acquired, i.e., that all images described in the transfer image list have been acquired, the processing ends. In this manner, data consistency is maintained between the camera 20 and the PC 10 since images that were previously acquired are not reacquired and unnecessary duplication of images is avoided.
[0093] The operation triggered as a result of the camera-operation-information tab 501 being selected after the image list tab 502 has been selected (after start up of application 50 ) will be described with reference to the flowchart of FIG. 12 .
[0094] First in step S 1201 , a command for entering the camera operation mode is issued to the digital camera 20 . As described above, the camera 20 enables its UI on receiving this command. Then in step S 1202 , the screen appearing when the camera-operation-information tab 501 is selected, as shown in FIG. 6 , is displayed on the monitor 12 .
[0095] The operation triggered as a result of the image list tab 502 being selected after the camera-operation-information tab 501 has been selected will be described with reference to the flowchart of FIG. 13 .
[0096] In step S 1301 , a command for entering the application mode is issued to the camera 20 . As described above, on receiving this command, the camera 20 disables its UI to reject camera operation by the user. Then in step S 1302 , the display screen of the monitor 12 changes to the screen appearing when the image list tab 502 is selected, as shown in FIG. 5 . To display the image list tab 502 , images need to have been acquired in the camera 20 . This operation is not directly related to the present invention, and will not be described.
[0097] The processing for quitting the application 50 will now be described with reference to the flowchart in FIG. 14 .
[0098] First in step S 1401 , a command for entering the application mode is issued to the camera 20 . This is performed because processing in the camera-operation mode cannot be performed after the application 50 is terminated. Finally, in step S 1402 the application 50 ends.
[0099] As described above, according to this embodiment, the two modes of the digital camera are switched in conjunction with the mode of the host application. Thus, when the application on the PC is used to display images stored in the memory card placed in the digital camera, the UI of the camera is disabled to prevent images from being deleted unintentionally by operating the digital camera.
[0100] In addition, when the digital camera is used to operate images stored in the memory card, the images are not displayed with the application to prevent the images from being operated with the application. This eliminates the need for tracking the result of image processing on the PC.
[0101] Furthermore, when the camera is in the application mode, both the camera and the PC can be placed into the camera-operation mode by operating the menu key, so that a simple procedure for transferring images by using the camera is provided. Thus, the user does not need to switch the PC mode each time the user attempts to transfer images via camera operation.
[0102] While the present invention has been described with reference to what are presently considered to be the embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
[0103] This application claims priority from Japanese Patent Application No. 2003-419360 filed Dec. 17, 2003, which is hereby incorporated by reference herein. | An image processing system includes a playback unit for playing back an image recorded on a recording medium, a communication unit for transmitting the image played back by the playback unit to an external information processing system via a transmission pathway, an operation unit including a plurality of operation keys, and a control unit for switching a transmission mode among a plurality of modes including a first mode in which transmission of the image according to an operation of the operation unit is enabled and a second mode in which transmission of the image according to an operation of the operation unit is disabled. The control unit changes the transmission mode to the first mode according to a predetermined operation of the operation unit in the second mode. | 7 |
REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 12/931,394 filed Jan. 31, 2011 now abandoned, and the benefit of this earlier filing date is claimed for all matter common therewith.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to exercise structures and more particularly to structures focused on exercising the upper torso and abdominal musculature of a person by simulating the rowing motions of a kayak at enhanced effort levels associated with stabilizing a resiliently supported body alignment of the user by simulating the rowing movements of a kayak.
2. Description of the Prior Art
The exponential growth of automation has long surpassed nature's ability to adjust our habits, committing virtually all of us to a sedentary lifestyle both in the course of our work and also at home where we engage in our repose the various entertainment modalities. As a consequence obesity is now a significant health hazard exacerbated by increases in heart disease, diabetes and similar conditions that reduce both the quality and also the expected length of human life. Simply, these lifestyle changes are occurring at a rate that cannot be accommodated by evolutionary response and as we each perceive this state the impetus to exercise is now driving all of us.
These widely perceived observations along with the persistent nature that brought us all here has also resulted in all sorts of exercise mechanisms that singularly and/or in various groupings allow us to focus on one or more aspects of our musculature along with other processes including those entailed in our cardiovascular function, metabolic processes and the like. Concurrently, our attention to correct exercise is now also perceived as an effective mechanism for managing stress and has therefore pervaded our whole lifestyle with various exercise mechanisms that are not just suitable for large exercise facilities like gymnasiums, but also for use in ones home.
One physical activity that is universally associated with robust health is that of kayaking. The image of navigating down the rapids of a mountain stream as we balance the kayak by our mid torso musculatures is seen as good for one's health and as result various kayaking simulators have been devised which in one manner or another seek to duplicate this activity, as exemplified by the teachings of U.S. Pat. No. 6,328,677 issued on Dec. 11, 2001 to Drapeau; U.S. Pat. No. 6,106,436 issued on Aug. 22, 2000 to Lundahl; U.S. Pat. No. 5,803,876 issued on Sep. 8, 1998 to Hickman; U.S. Pat. No. 5,624,357 issued on Apr. 27, 1997 to Englehart et al.; U.S. Pat. No. 4,687,197 issued on Aug. 18, 1987 to this inventor and Bengt Swesson, and others.
Each of the foregoing examples, and similar others, while suitable for the purposes intended, describe a kayak simulating structure in which the user is well supported on a stationary seat and from that vantage moves a kayak paddle against weights or other force inducing resistance. Thus while providing a simple and compact exercise structure the foregoing examples confine the major exercise efforts to the arms, shoulders and the upper torso while the abdomen and the lower back are left unattended.
An exercise structure that takes benefit of the simplicity of a kayak and that fully and completely involves the mid torso musculature of the user is therefore extensively desired and it is one such structure that is disclosed herein.
SUMMARY OF THE INVENTION
Accordingly, it is the general purpose and object of the present invention to provide a kayak simulating exercise structure in which only the user's lower legs are securely restrained while the remaining body portions are all free for involvement in the simulated paddle motion.
Other objects of the invention are to provide a resiliently mounted kayak simulating exercise structure in which the torso movements of the user are compelled in the course of stabilizing the alignment thereof on a resiliently mounted seat.
Yet additional, further and other objects of the invention shall become apparent from the examination of the teachings that follow in conjunction with the illustrations appended.
Briefly, these and other objects are accomplished within the first form of the present invention by providing a generally elongate longitudinal seat supported on a transverse, cushion mounted, pedestals at its front and rear ends with each of the pedestals adjustably extendable to select the desired seat inclination from horizontal. The seat itself may be formed as a generally U-sectioned structure defined by two lateral walls on the sides of a supporting panel covered by a cushioning pad on which an exercising user may sit with his or her lower back supported by an adjustably mounted lower back support pillow while the user's legs extend over the front edge of the seat.
At the front end this elongate seat structure is adjustably engaged to a generally vertical bearing assembly pivotally mounted between the walls of a U-sectioned mounting bracket to support at various inclinations therein a bearing yoke engaged to the exterior of a telescoping shaft assembly that at its free upper end includes a U-joint that is engaged to the midpoint of the kayak paddle shaft. The lower end of the telescoping shaft assembly, in turn, extends beyond the bearing yoke within the hollow interior of the seat structure to engage at the ends of two radially opposed bellcranks mounted thereon the respective ends of a pair of gas filled, orifice restricted struts which then provide the resistance to the paddle movement at the upper end.
The deployment of the foregoing articulated paddle mount at the front edge of the seat results in a split seat surface on the sides thereof on which the thigh portions of the user's legs are positioned with the lower leg portions then extending onto a pair of foot rests on the adjustably engaged front support pedestal. This arrangement provides an interlocking engagement between the user's legs and the seat structure while the remaining body portions including the torso of the user are supported by the narrow seat surface restrained against rearward motion by the lower back support pillow. In this manner most of the user's body is effectively unrestrained as he or she reaches upwards and forwards to articulate the paddle from the rearward weight biased inclined alignment set by the adjustment of the cushion mounted support pedestals, with the resulting upper torso weight creating unbalances that are fully analogous to that of a kayak which then need to be stabilized by the extent and vigor of the paddle movement.
In accordance with the second form of the present invention these same unbalanced states that inherently drive the user to even higher efforts are even more emphasized by supporting on a resilient mounting of the seat itself where this further level of added resilience then emphasized by added seat height which is then enhanced even more by resilient restraints provided at each of the foot supports, thus compelling even higher mid-torso efforts in the course of use. Consequently the whole focus of this exercise structure is further enhanced with the resiliently mounted support structure compelling the user to achieve a balance state solely by his or her sheer vigor.
It will be appreciated that in both instances this resilient mounting is stabilized only by the inertia and resistance associated with the articulation of the paddle enhanced both by the mass inertia on the paddle ends and by the selectively connected restricted orifice struts opposing the lower end of the paddle shaft within the interior cavity formed by the seat structure. In this manner an exercise assembly is provided in which various levels of resistance can be set and which effectively modifies the levels of involvement of the whole torso musculature by the simple inclination adjustment of the frame. All this is achieved without the joint degrading consequences associated with walking or jogging or the tendon damage that sometimes results from lifting weights.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective illustration of a first embodiment of the inventive kayak simulating exercise structure conformed for use in its inclined alignment;
FIG. 2 . is a sectional view of the first embodiment of the inventive exercise structure taken along line 2 - 2 of FIG. 1 ;
FIG. 3 is yet another sectional view of the first embodiment of the inventive exercise structure taken along line 3 - 3 of FIG. 1 ;
FIG. 4 is a further perspective illustration of a second embodiment of the inventive kayak simulating exercise structure deployed for use;
FIG. 5 is a further sectional view illustrating the spring restrained seat engagement in accordance with the second implementation of the inventive kayak simulating exercise structure useful to expand the level of the exercise vigor by the expansion of the range of torso imbalance; and
FIG. 6 is a perspective detail, in partial section, of a spring opposed foot restraint useful with the invention herein.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIGS. 1 through 3 the first embodiment of the inventive kayak simulating exercise structure, generally designated by the numeral 10 , comprises an elongate seat assembly 11 defined by a generally U-sectioned elongate spine piece 12 defined by two opposed lateral wall surfaces 12 - 1 and 12 - 2 bridged by a top surface 12 T that is then covered by a padding layer 12 P. The interior cavity in the spine piece 12 that is thus formed receives in a selectively adjustable engagement the top of a transverse rear pedestal 14 , the adjustable connection thereof to the side walls 12 - 1 and 12 - 2 being effected by pivot posts 14 P spaced from a row of openings 14 o one of which is then selectively fixed by a bolt 14 B to determine the rear edge of the seat height above a set of resilient support pads SP supporting the pedestal bottom on the ground.
A similarly constructed front pedestal assembly 24 , again pinned by pivot posts 24 P and aligned by them capture of bolt 24 B in one of the plural openings 24 o , provides the front support for the assembly, again cushioned by the resilient pads SP. This front support, however, extends subjacent the front edge of the seat over which the legs of the user are draped and therefore includes a foot rest panel 25 again adjustably mounted relative the front pedestal 24 by selective engagement of attachment bolts 25 B within one of the several openings 25 o . Also adjustably mounted to the front end 12 E of the seat structure is a generally vertical U-sectioned support bracket 15 extending through the top surface 12 T to pivotally mount a bearing yoke or collar 16 in which a tubular exterior sleeve 17 E of a telescoping mount 17 is received for rotation while axially restrained within the bearing yoke by an upper and lower retaining ring 17 U and 17 L.
With the feet now supported on the foot rest panel 25 and aligned on either side of the front edge 12 E of the resulting seat structure, as bisected by the U-shaped support bracket 15 , the axial telescoping extension of the inner shaft 17 I may be fixed to the desired height by inserting a pin 17 P through the common interior of a set of openings 17 o in the exterior sleeve 17 E and one of several drillings 17 D in the inner shaft. The shaft inclination, in turn, is concurrently fixed by selective engagement of pins 15 P in one of several openings 15 o in the walls of bracket 15 and a corresponding opening 18 O in an adjustment fixture 18 on shaft assembly 17 . Of course, the pivotal articulation of the bearing yoke 16 may also be left unrestrained for expanded exercise use in the manner of symmetrical rowing as in rowing a boat.
The lower portion of the exterior sleeve 17 E forming the telescoping shaft assembly 17 that extends into the interior cavity within the seat structure includes a set of opposed, radially projecting bellcranks 17 B each engaging at its free end a corresponding end of one of a pair of conventional gas filled, orifice restricted, struts 19 such as those sold under part no. 171BEQ by Magnus Mobility Systems, Inc., 1912 West Business Center Dr., Orange, Calif. 92867 which at their other ends are each respectively pinned to one of a plurality of openings 19 o in a transverse bracket 19 B spanning between the side walls 12 W. In this manner the torsional forces about the rotary axis of the shaft assembly 17 or the resistive forces opposing the pivotal movement of the bearing yoke 16 are conveniently adjusted to match the level of effort desired.
Once thus adjusted the a paddle assembly 30 engaged to a U-joint 37 at the free end of the interior shaft 17 I provides the necessary exercise forces to the user sitting on seat pad 12 P with the legs straddling the mount assembly 15 . From this relatively unrestrained position the user, while sitting on seat pad 12 P restraining only his or her legs over the seat edge and in the foot rests providing positional control, reaches to extend his or her arms to grasp the paddle 30 on each side of the U-joint 37 and only through that connection obtains any force resistance. To provide some positional reference a seat back cushion 36 may be adjustably mounted, again by bolts 36 B engaging one of several openings 36 o , on the seat pad 12 P.
Those skilled in the art will appreciate that the elongate form of the spine piece 12 and the also the seat pad 12 P mounted thereon provide little lateral support to the user, thus confining all position control to the leg engagement between the seat edge and the foot rests 25 . With this limited body engagement virtually all of the abdominal musculature, the musculature of the lower back and also the musculature of the chest and upper back are all involved in maintaining a proper seated position as the paddle 30 is cyclically articulated. This muscular involvement becomes even more exacerbated by the resistance of the struts 19 and the resilience of the support pads SP.
By particular reference to FIGS. 4-6 a second embodiment of the present invention, generally designated by the numeral 110 , further enhances the torso balancing exercise effort by inserting a further resilient structure between a modified seat structure 112 P and the spine structure 12 . Like numbered parts functioning in a like manner to that previously described, the top bridging surface 12 T of the spine assembly 12 is provided with a set of longitudinally aligned pillow blocks 112 B while the lower side of the seat structure 112 P itself is bridged by a transverse panel 112 T on which a corresponding longitudinally aligned set of pivot mounts 112 M is mounted spaced to straddle the pillow blocks 112 B so that a conforming cylindrical pivot shaft 114 can be passed can be received through their common interior.
The inherent lateral instability obtained by the foregoing pivotally supported seat spacing is then partly resiliently stabilized by a set of helical springs 115 captured in compression between the lateral edges of the lower seat panel 112 T and the spine panel 12 T, compelling the user to provide the remainder of the balancing forces by articulating the paddle. Of course, similar to the previous example, this compelled balancing activity is longitudinally fixed by the selective engagement of the pillow assembly 136 by fasteners 136 B in one of several lateral openings 136 L formed in the sides of seat 136 with further control over the level of effort then determined by the inclination obtained through the selective engagements of the front and/or rear pedestals.
This adjustable resilient supporting structure is then further enhanced by providing spring biased pedal assemblies 125 pivotally mounted on pivots 126 formed on each of the foot rests 25 , each of the pedal assemblies then opposed in its pivotal motion by a captured spring 127 . In consequence the whole of the body engagement contact is either through the resiliently mounted seat 136 and/or pedals 125 , thereby fully simulating the balancing needs of a water supported kayak.
In each instance the desired muscular involvement levels obtained by the adjustment of the seat inclination from the horizontal, the alignment of the pivot axis, the bellcrank moment arm selection and/or the masses mounted on the oar all interact with resilient compliance of the body support structures to simulate the interactive dynamics of this torso-kayak combination. As these inclinations from horizontal are effected the resulting rearward movement of the body center of mass a lower back support pillow 36 or 136 may be once again adjustably engaged to the spine piece 12 by the mechanisms previously described. In this manner the rearward sliding of the user's lower back is limited without any significant lateral restraint.
It will be appreciated that the foregoing arrangements accommodate various body types and levels of exercise by the repeated application of a simple adjustment selection to produce a structure that effectively retains the general attributes of kayaking in which most of the user's body are laterally unconstrained while vigorous movements are carried out both against various (enhanced) levels of resistance and inclinations that themselves enhance the exercise levels. To further extend these enhancements the paddle 30 may be provided with weights 30 W and may include offset handles 30 H to allow the exercising of biceps which is particularly effective when the pivotal motion of the yoke is unrestrained. In each instance, like in the course of rowing a kayak, small muscular adjustments are continuously made, thus closely imitating the real event. As result an interest to perfect the movements is developed, promoting the usefulness of the exercise structure which inherently is simple and inexpensive to produce.
Obviously many modifications and variations of the instant invention can be effected without departing from the spirit of the teachings herein. It is therefore intended that the scope of the invention be determined solely by the claims appended hereto. | An exercise assembly simulating the muscular movements of a kayaker includes an elongate seat resiliently mounted on an elongate spine structure supported on adjustable pedestals that are each further resiliently mounted. At the front end an adjustably aligned pivot engages through a U-joint a simulated kayak paddle with the motion of the pivot resisted by restricted orifice cylinders mounted in the spine structure. A generally uniform adjustment arrangement is utilized to conform the assembly to the various users and/or various exercise levels. | 0 |
CLAIM TO PRIORITY
[0001] The present invention claims priority under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 60/362,360, filed Mar. 6, 2002, the entire disclosure of which is herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention provides a direct feed fuel cell for producing electrical energy by electrochemical oxidation/reduction of an organic fuel, and in particular to a direct feed methanol fuel cell system with integrated gas separation.
[0004] 2. The Prior Art
[0005] Fuel cells are devices in which an electrochemical reaction is used to generate electricity. A variety of materials may be suitable for use as a fuel depending upon the materials chosen for the components of the cell and the intended application for which the fuel cell will provide electric power.
[0006] Fuel cell systems that utilize carbonaceous fuels may be divided into “reformer-based” systems (i.e., those in which the fuel is processed in some fashion to extract hydrogen from the fuel before it is introduced into the fuel cell system) or “direct oxidation” systems in which the fuel is fed directly into the cell without the need for separate internal or external processing. Most stationary fuel cells are reformer-based fuel cell systems. However, because fuel processing is expensive and requires significant volume, reformer-based systems are presently limited to comparatively high power applications. Because of their ability to provide sustained electrical energy, fuel cells have increasingly been considered as a power source for smaller devices including consumer electronics such as portable computers and mobile phones. Accordingly, designs for both reformer based and direct oxidation fuel cells have been investigated for use in portable electronic devices. Reformer based systems are not generally considered a viable power source for small devices due in part to the size, expense, and technical complexity of present fuel reformers.
[0007] Thus, significant research has focused on designing direct oxidation fuel cell systems for small applications, and in particular, direct systems using carbonaceous fuels including but not limited to methanol, ethanol and aqueous solutions thereof. One example of a direct oxidation fuel cell system is a direct methanol fuel cell system. There are several reasons why a direct methanol fuel cell (DMFC) power system is advantageous for providing power for smaller applications. First, methanol has a high energy content, thus providing a compact means of storing energy. In addition, methanol can be stored and handled with relative ease, and because the reactions necessary to generate electricity in an DMFC system occur under ambient conditions.
[0008] DMFC power systems are also particularly advantageous since they are environmentally friendly. The chemical reaction in a DMFC power system yields carbon dioxide and water as by products (in addition to the electricity produced). Moreover, a constant supply of methanol and oxygen (preferably from ambient air) can continuously generate electrical energy to maintain a continuous, specific power output. Thus, mobile phones, portable computers, and other portable electronic devices can be powered for extended periods of time while substantially reducing or eliminating at least some of the environmental hazards and costs associated with recycling and disposal of alkaline, Ni-MH and Li-Ion batteries.
[0009] The electrochemical reaction in a DMFC power system is a conversion of methanol and water to CO 2 and water. More specifically, in a DMFC, methanol, which may be in an aqueous solution, is introduced to the anode face of a protonically-conductive, electronically non-conductive membrane in the presence of a catalyst. When the fuel contacts the catalyst, hydrogen atoms from the fuel are separated from the other components of the fuel molecule. Upon closing of a circuit connecting a flow field plate of the anode chamber to a flow field plate of the cathode chamber through an external electrical load, the protons and electrons from the hydrogen atoms are separated, resulting in the protons passing through the membrane electrolyte and the electrons traveling through an external load. The protons and electrons then combine in the cathode chamber with oxygen producing water. Within the anode chamber, the carbon component of the fuel is converted by combination with water into CO 2 , generating additional protons and electrons.
[0000] The principal electrochemical processes in a DMFC are:
Anode Reaction: CH 3 OH+H 2 O=CO 2 +6H + +6 e
Cathode Reaction: 3/2O 2 +6H + 6 e − =2H 2 O
Net Reaction: CH 3 OH+3/2O 2 =CO 2 +H 2 O
[0010] The methanol in a DMFC is preferably used in an aqueous solution to reduce the effect of “methanol crossover”. Methanol crossover is a phenomenon whereby methanol molecules pass from the anode side of the membrane electrolyte, through the membrane electrolyte, to the cathode side without generating electricity. Heat is also generated when the “crossed over” methanol is oxidized in the cathode chamber. Methanol crossover occurs because present membrane electrolytes are permeable (to some degree) to methanol and water.
[0011] The voltage output of a single fuel cell may not be sufficient to provide appropriate power to the desired application. Given the strict form factor limitations and increasingly demanding power requirements of portable electronic equipment, most applications require much higher voltages than what a single, typical DMFC can provide—which is on the order of 1.5 volts. For example, effective voltage for a laptop computer can be as high as 24 volts. To obtain such voltages using fuel cell technology, individual fuel cells are connected in series, typically forming a fuel cell stack.
[0012] Current fuel cell stack designs utilize a bipolar plate to decrease the size, and increase the efficiency of said assembly. Instead of two current collectors, only one plate is used with a flow field cut into each side of the plate. That is, one side of the plate is used in the anode chamber of one fuel cell, while the other side is used in the cathode chamber of an adjacent fuel cell. The single plate may also serve to assist in the distribution of fuel on one side of the plate and an oxidant preferably from ambient air on the other side of the plate.
[0013] Bipolar plates are typically made of a gas-impermeable material, to prevent intermixing among the fuel on the anode side and the oxidant on the cathode side. Introduction of oxygen into the anode chamber of a fuel cell typically diminishes the performance of the cell, and may cause the methanol to oxidize completely, without contributing to the generation of electricity within the fuel cell system.
[0014] The bipolar plate is electronically conductive such that the electrons produced at the anode on one side of the bipolar plate can be conducted through the plate where they enter the cathode on the other side of the bipolar plate. Two end-plates, one at each end of the complete stack of cells, are connected via the external circuit.
[0015] One of the problems associated with fuel cell stacks using bipolar plates is that of eliminating gaseous effluent from the anode chamber. Prior art DMFC systems address this problem via a recirculation configuration system. In such a system, a gas separator incorporated in an effluent return line is used to remove gases from anode effluent fluids. The gas separator separates carbon dioxide from the unused fuel solution and exhausts carbon dioxide.
[0016] Although prior art recirculation configurations address some of the problems of handling anode effluent (conserving unused methanol fuel and rendering the fuel supply impervious to rapid changes in power demands of the fuel cell) these systems typically incorporate discrete auxiliary equipment to do so, including but not limited to gas separators and other components that separate liquids from gases. This auxiliary equipment consumes volume and adds to the overall materials and assembly costs, rendering re-circulating DMFC systems less feasible for portable power and electronics applications. Moreover, in fuel cell stack systems, gas separators must be used to ensure the performance of the stack and the system as a whole. Thus, the cost of the fuel cell stack increases dramatically in view of such additional requirements.
[0017] Therefore, it would be desirable to provide an apparatus and method for removing anode effluent gas from a fuel cell of a fuel cell stack where liquids may be separated from gases within the stack without adding additional volume or components.
SUMMARY OF THE INVENTION
[0018] The present invention addresses the concern outlined above and presents a novel device and method for venting anode effluent gas without the use of external gas separators.
[0019] In one embodiment of the present invention, a bi-polar plate for a fuel cell stack having at least two individual fuel cells, includes an anode portion in a first fuel cell, where the anode portion includes a fuel flow field, a gas permeable membrane positioned away from the anode aspect of a membrane electrolyte of the first fuel cell and a gaseous effluent vent channel positioned adjacent the gas permeable membrane. The vent channel communicates gaseous effluent from the anode aspect of the membrane electrolyte via an outlet. The bipolar plate also includes a cathode portion in a second fuel cell, and having a flow field by which oxygen is introduced to the cathode of the fuel cell.
[0020] In another embodiment of the present invention, a fuel cell of a fuel cell stack includes an anode chamber, a cathode chamber, a proton conducting membrane electrolyte positioned between the chambers and a bi-polar plate. The bi-polar plate includes an anode portion disposed on the anode aspect of the membrane electrolyte in the anode chamber of the fuel cell. The anode portion includes a fuel flow field, a gas permeable membrane positioned away from the membrane electrolyte of the first fuel cell, and a gaseous effluent vent channel positioned immediately adjacent the gas permeable membrane. The vent channel communicates gaseous effluent from the anode side of the fuel cell to an outlet.
[0021] In another embodiment of the present invention, a fuel cell system includes a fuel cell stack including at least two fuel cells and a fuel delivery means. Each fuel cell includes an anode chamber, a cathode chamber and a membrane electrolyte positioned between the anode chamber and the cathode chamber. The system further includes a bi-polar plate. The bi-polar plate includes an anode portion disposed on the anode aspect of the membrane electrolyte in the anode chamber of a first fuel cell. The anode portion including a fuel flow field, a gas permeable membrane positioned away from an anode backing layer of a membrane electrolyte of the first fuel cell and a gaseous effluent vent channel positioned immediately adjacent the gas permeable membrane. The vent channel communicates gaseous effluent from the anode side of the fuel cell via an outlet. The bipolar plate also includes a cathode portion for functioning as a cathode in a cathode chamber of an adjacent fuel cell having a flow field by which oxygen is introduced to the cathode of the fuel cell.
[0022] In yet another embodiment of the present invention, a fuel cell stack includes at least two individual fuel cells, where adjacent fuel cells include a shared bi-polar plate shared between adjacent fuel cells and an anode side of the bi-polar plate includes a vent channel for venting gaseous effluent from the anode.
[0023] In another embodiment of the present invention, an anode plate for a fuel cell, which includes a membrane electrolyte is provided. The anode plate includes a fuel flow field having a portion thereof positioned substantially opposite the membrane electrolyte. The fuel flow field comprises a gas permeable membrane and a gaseous effluent vent channel positioned immediately adjacent the gas permeable membrane. The vent channel communicates gaseous effluent from the fuel flow field via an outlet.
[0024] In yet another embodiment, a fuel cell is provided which includes a membrane electrolyte, an anode backing layer positioned proximate the membrane electrolyte, a cathode plate forming a cathode chamber and a cathode backing layer positioned proximate the cathode plate. The cathode plate includes a flow field by which oxygen is introduced to the cathode plate. The fuel cell also includes an anode plate which forms an anode chamber. The anode plate includes a fuel flow field and a gas permeable membrane positioned away from an anode backing layer of a membrane electrolyte. The anode plate also includes a gaseous effluent vent channel positioned immediately adjacent the gas permeable membrane, for communicating gaseous effluent from the anode side of the fuel cell to an outlet.
[0025] In another embodiment of the invention, a method of removing gaseous effluents from the anode aspect of a fuel cell system is provided. The fuel cell system for this embodiment includes a membrane electrolyte, an anode chamber having a fuel flow field, a fuel delivery means, a gas permeable membrane and an outlet in communication with the gas permeable membrane. The method includes collecting the gaseous effluent at the anode chamber and communicating the collected gaseous effluent to the outlet.
[0026] The embodiments of the invention may also be sued with one or more of the following features:
having the gas permeable membrane made of a first material for substantially blocking gaseous communication through the membrane and a second material for allowing gaseous communication through the membrane. The first material may include a first field of the membrane and the second material may include a second field of the membrane; the first and second materials as outlined above may be bonded together; the first and second materials may be mechanically affixed to one another; the first material may include a plurality of openings, and the second material may be positioned within each of the plurality of openings; the second material may include Zintex®; the second material may include expanded PTFE; the first and the second materials may be combined to substantially form a single structure; the second material may be divided into a plurality of portions which are spaced apart along the first material; the plurality of portions may extend substantially the width of the fuel flow field; the plurality of portions may extend substantially the length of the fuel flow field; the second material may include a web of micromesh, and the first material may include a plurality of strips positioned intermittently along the second material; and the first material may be separated from the second material.
[0039] The embodiments and features of the present invention will become even clearer with reference to drawings which accompany this application (briefly described below) and with reference to the detailed description of the invention which follows thereafter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0040] FIG. 1 illustrates a cross-sectional view of a prior art fuel cell stack, where fuel flow through the fuel channels is normal to the page.
[0041] FIG. 2 illustrates the novel anode plate according to one embodiment of the present invention in a multi-fuel cell arrangement.
[0042] FIGS. 3A-3C illustrate various arrangements of a gas permeable membrane for use with the present invention.
[0043] FIGS. 4 A-B illustrate a portion of an exemplary anode flow field channel formed by either the anode plate of a single fuel cell, an anode-cathode (bi-polar) plate assembly for a fuel cell stack or a bipolar plate for use with a fuel cell stack according to the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0044] Illustrative embodiments of the present invention described below provide a direct feed fuel cell system for producing electrical energy through an electrochemical oxidation/reduction of an organic fuel reactant and an oxidizing agent. More particularly, the invention may be directed to a direct feed methanol fuel cell system for producing electrical energy through the electrochemical oxidation of an organic fuel, such as methanol, and reduction of an oxidizing agent, such as air.
[0045] Those skilled in the art will appreciate, however, that embodiments in accordance with the invention are not limited to a direct feed methanol fuel cell, but, rather, may also be used in other fuel cell systems that generate electrical energy from the electrochemical oxidation/reduction of organic fuel reactants and oxidizing agents. Those skilled in the art will also recognize that the inventions disclosed herein will also may be used in a variety of systems and architectures.
[0046] Embodiments of the invention will be described with reference to FIGS. 1-4 which are presented for the purpose of illustrating embodiments and are not intended to limit the scope of the claims.
[0047] FIG. 1 illustrates a prior art fuel cell stack 100 . As shown, a plurality of fuel cells are arranged together, and include bipolar plates 110 between them. Specifically, each fuel cell of the prior art stack includes a cathode end plate 108 on one end of the fuel cell stack, and an anode plate 106 on the other end of the stack. As stated, bipolar plates are positioned between adjacent fuel cells. Each bipolar plate includes an anode side having a fuel flow field 102 and a cathode side including an air flow field 104 . Each fuel cell also includes membrane electrolyte 112 is positioned between the anode plate (chamber) and the cathode plate (chamber). Diffusion layers 114 are positioned on either side of the membrane electrolyte (adjacent the anode chamber and cathode chamber) so that the membrane is adequately exposed to the fuel mixture and air. Other than the fuel and air flow fields, the fluidic management system of this stack is not shown, and may include necessary pumps, and in the prior art, would also include a means by which fuel is supplied to the stack and by which gases are separated from the anode aspect of each cell of the fuel cell stack. The fuel cell stack 100 produces electrical energy (e − ) for connection to an electrical load (light bulb 101 ).
[0048] As shown in FIGS. 2-4 , the present invention, for example, includes a direct oxidation fuel cell stack 2 which may include a plurality of fuel cells each having a membrane electrolyte assembly 4 with a proton-conducting, electronically non-conductive membrane electrolyte 6 disposed between an anode side 8 and a cathode side 10 of a corresponding fuel cell. The exact shape of the anode chamber and cathode chamber may be defined by a “flow field” which is generally integrated into the anode plate (fuel flow field) and the cathode plate (air flow field), respectively. The flow fields aid in distributing the fuel and the oxidizing agent to the membrane electrolyte. Although FIG. 2 is illustrated as a stack comprised of only two cells, any number of fuel cells can be stacked in order to achieve the desired voltage and current requirements. A fuel supply 3 , which may comprise any one or more of a fuel source, a fuel cartridge, a mixing and/or storage chamber (for creating and/or storing an aqueous, for example, fuel mixture) and a pump, or any combination thereof, delivers fuel (preferably in a mixture form; e.g., aqueous solution) to the fuel flow fields. The fuel mixture may be supplied to the fuel flow fields of each fuel cell via a conduit 5 or channel, or any other means to fluid communicate the fuel mixture to the fuel flow fields.
[0049] Each surface of the membrane electrolyte 6 may be coated with electrocatalysts which may serve as anode reactive sites 12 on the anode aspect of the membrane and cathode reactive sites 14 on the cathode aspect of the membrane. The anode and cathode reactive sites facilitate the electrochemical reactions of the DMFC.
[0050] It is worth noting that the electrocatalysts may be provided in other areas within the anode and cathode chambers, and thus, the invention is not limited to fuel cells where the catalysts are provided on the membrane electrolyte.
[0051] Diffusion layers 16 and 18 , may be included and positioned on either side of the membrane. These layers provide a more uniform, effective supply of methanol solution (anode diffusion layer 16 ) to the anode reactive sites and a more uniform, effective supply of oxidizing agent (cathode diffusion layer 18 ) to the cathode reactive sites. Diffusion layers 16 and 18 on each of the anode and cathode sides of the membrane electrolyte may also assist in maintaining appropriate humidification of the membrane electrolyte by assisting in the distribution and removal of water to and from the membrane electrolyte at rates that maintain a proper water balance in the DMFC power system. Moreover, each layer may be used with the fuel and air flow fields, to further aid in distributing fuel and oxidant to the respective reactive sites.
[0052] Between adjacent fuel cells in the interior of the fuel cell stack, a bipolar plate assembly 25 is provided, with an anode side 8 of the plate functioning as the anode in one fuel cell 24 and a cathode side 10 of the plate functioning as a cathode in an adjacent fuel cell 28 . The bipolar plate assembly is constructed of an electrically conductive material, such as, although not limited to, a carbon composite, graphite or a number of metals, including, although not limited to, stainless steel, so that electrons can be conducted between adjacent fuel cells for connection in series.
[0053] The bipolar assembly includes a fuel flow field 30 channeled into the anode side and an oxidant flow field 32 channeled into the cathode side of the plate. The base of each channel of the fuel flow field includes a first side 34 of a gas permeable, liquid impermeable membrane 36 , with the other side 38 of the membrane being in communication with a venting channel 40 . The venting channel includes at least one end connected to a port 42 located on the outside of the bipolar plate. This port may be exposed to ambient air, or may be connected to another conduit which allows gases to pass from the channel, to the port, to the ambient environment, or to perform work within the fuel cell system. Those skilled in the art will recognize that the components of the bipolar plate assembly may be integrated into a single component, using molding and fabrication techniques known to those skilled in the art. It will also be appreciated by those of ordinary skill in the art that the gas-permeable membrane 36 may fill venting channel 40 up to an including port 42 .
[0054] Although the novel bipolar assembly is shown as used with a compact fuel cell stack, the present invention may also be directed to a single anode plate of a first fuel cell electrically coupled to a cathode plate of a second fuel cell of a fuel cell stack, with the anode plate including a fuel flow field in association with the gas permeable, liquid impermeable membrane and the venting channel/port. Moreover, this novel arrangement of the anode plate or assembly is also appropriately used with a single fuel cell system.
[0055] Thus, the gaseous effluent produced in the fuel flow field on the anode side (or anode plate of separate or single fuel cells) of the bipolar plate pass into the channel and escape out of the fuel cell stack via the port.
[0056] The gas permeable membrane of the fuel cell system may be comprised substantially of a gas permeable, preferably liquid impermeable material such as an expanded polyfluoroethylene or other selected expanded polymer, provided that sufficient electrical contacts with the diffusion layer are maintained. Alternatively, the membrane may be comprised of a first material, which does not communicate gas, where a second gas diffusing material is placed in predetermined patterns among the first material. Those skilled in the art will recognize that the exact pattern of the flow field plates may also contribute to the determination of the optimal pattern of gas permeable, liquid impermeable membrane in the bipolar plate or assembly, since the flow field plates are, due to the materials used to fabricate the flow field plates. Accordingly, examples of such patterns are illustrated in FIGS. 3A-3C . In FIG. 3A , “vertical” strips of gas permeable material 36 are placed in specific locations on a gas-blocking material 37 . FIG. 3B illustrates a similar embodiment, but the strips 36 are positioned “horizontally” or in an irregular manner (e.g., diagonally) which allows for the substantially uniform removal of gas from each anode chamber. Patches 36 of the gas-permeable material may be patterned as that shown in FIG. 3C . Thus, using such patterns of gas permeable material, the entire area of each channel of the fuel flow field need not exposed to the membrane. With regard to the venting channel, it need only be formed such that it is in communication with a predetermined amount of the membrane for properly ridding the anode side of gaseous effluent.
[0057] Alternatively, the gas permeable, liquid impermeable material may be in direct communication with the ambient environment, or a vent which is in communication with the ambient environment. By way of example, and not limitation, FIG. 4A illustrates a top, semi-cross-sectional view (i.e., looking normal to the fuel flow field) of an anode flow field plate 402 wherein the gas permeable material 404 (cross hatching) extends from the an edge of the plate, which is directly or indirectly in communication with the ambient environment. Accordingly, the fuel solution that is passing through (arrows) the flow field channel is comprised of the fuel mixture, unreacted fuel, and gases created by the anodic half reaction. When these gasses come into contact with the gas permeable membrane, they are removed from the liquid in the flow field channel, and vented to the ambient environment.
[0058] FIG. 4B shows a semi-cross sectional view of the end of the fuel flow field 402 , illustrating how only a portion of the fuel flow field need be exposed to the gas permeable membrane 404 (cross hatching). In this embodiment, the gas permeable membrane is included with an effluent conduit 406 , which leads the effluent to a vent 408 . The fuel flow is shown with a + and − signs: flow of the fuel mixture out of the page (+) and flow of the fuel mixture into the page (−). A further advantage of such a design is that it allows adequate contact between the bipolar plate or assembly and the adjacent MEA, thus improving the performance of the stack and fuel cell system.
[0059] A novel feature of this embodiment of the invention, is the ability to customize the rate and/or profile at which anodically generated gas is removed from the flow field by altering the configuration of the gas permeable membrane with the other components of the anode plate. Specifically, the number of outlets to the ambient environment, as well as their size, shape, and pattern arrangement may be designed to allow gases to escape at varying rates and/or profiles. In addition, the design and operation of this embodiment avoids or minimizes the coalescence and/or accumulation of CO 2 bubbles in the anode chamber (which sometimes limit the reactions and/or the efficiency of the fuel cell). Moreover, the gas separation properties may be further customized by selecting materials for the gas permeable membrane that allow anodic gasses to escape from the system at a desired rate, and/or may allow certain gasses to pass selectively.
[0060] The gas separating second material is constructed of, although not limited to, a hydrophobic polymer having a high capacity to remove carbon dioxide from anode chamber of each fuel cell. The hydrophobic polymer of the second material may include, although is not limited to, ZINTEX®, available from W.L. Gore & Associates of Newark, Del. In some instances it may be desirable to use a material that will preferentially allow carbon dioxide to pass through it and limiting the amount of oxygen that passes through the membrane. One example of a material that preferentially allows carbon dioxide to pass while limiting the passage of oxygen, is Teflon AF, available from Biogeneral Inc., San Diego, Calif.
[0061] The gas permeable, liquid impermeable membrane may be manufactured via co-extrusion, or using other methods well known to those skilled in the art. Alternatively, the apertures may be punched out of the first material with a die, and the second material added using an appropriate adhesive, or mechanically fastened or otherwise attached.
[0062] Exposing the liquid in the anode chamber with the gas permeable, liquid impermeable membrane according to the present invention limits the extent to which ambient oxygen may migrate into the anode chamber. Alternatively, other designs and profiles may be used to limit the diffusion of other ambient gases to the anode chamber from the vent and gas permeable membrane. The gas permeable portion may, regardless of the method used to manufacture, be designed to increase the ability to remove CO 2 .
[0063] Accordingly, having thus described some of the embodiments of the invention, various alterations, modifications and improvements may readily occur to those skilled in the art. Such alterations, modifications and improvements are intended to be within the scope and spirit of the invention. Accordingly, the foregoing description is by way of example only and is not intended as limiting. | The present invention is directed to a novel anode plate forming an anode chamber of a fuel cell. The anode plate includes an anode fuel flow field, a substantially gas permeable membrane, and a channel coupled to an outlet positioned immediately adjacent said membrane. The channel directs gaseous effluents produced in the anode chamber out of the fuel cell via the outlet. This novel anode plate may be used in a single fuel cell, electrically and mechanically coupled to a cathode plate in a multi-fuel cell arrangement, or combined with a cathode plate producing a bi-polar plate for a fuel cell stack. Alternatively, the features of the anode plate and cathode plate may be integrated into a single component, thus improving performance and limiting the size of a stack and system implementing said stack. | 7 |
This is a continuation-in-part of co-pending application Ser. No. 249,862 filed on Sept. 27, 1988, now abandoned.
BACKGROUND OF THE INVENTION
This invention relates to a bubble bath assembly which generates a multiplicity of minute bubbles in the water in a bathtub, and, in particular, relates to a bubble bath assembly which floats on the water in a bathtub.
In the related art, International Application No. PCT/JP 84/00409 filed Aug. 24, 1984 (U.S. patent application Ser. No. 855,628, now abandoned, discloses a health bath structure having a water-jetting nozzle which is retained above the water in a bathtub. This health bath structure has a pump-encasing housing which must be fixedly mounted on a wall of a bathroom, and therefore installation work is necessary in order to use this structure. Moreover, since this structure is fixed at a specific position, an auxiliary equipment is required to transfer the nozzle to a desired position.
U.S. Pat. No. 3,842,823 discloses a portable hydromassage unit designed to straddle the side wall of a bathtub. This unit has a clamping bracket which is movable along a bridge portion of the housing, which is adapted to rest on the side wall of the bathtub. By adjusting the position of the clamping bracket, the clamping bracket is capable of clamping the side wall in cooperation with a power unit housing which is adapted to be disposed outside the bathtub, and whereby the hydromassage unit is removably installed on the side wall of the bathtub. However, when the side wall of a bathtub has a thickness exceeding the range of the movement of the clamping bracket, it is not possible to mount the hydromassage unit on the bathtub. In particular to a bathtub of a dugout type, a hydromassage unit of the above-mentioned type can not be applied.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a bubble bath assembly which is applicable to any type of bathtub.
Another object of the present invention is to provide a bubble bath assembly for which there is no need of installation work, and thus it is easy to handle.
A further object of the present invention is to provide a bubble bath assembly which can easily be transferred to the desired position in a bathtub.
With these and other objects in view, the present invention provides a bubble bath assembly including: a housing having an inlet and an outlet; pump means, encased within the housing, for drawing water into the housing through the inlet and for discharging water under pressure from the outlet; and water-jetting means, communicatively connected to the outlet of the housing, for discharging water in a jet therefrom. This assembly is characterized in that the housing comprises float means for floating the bubble bath assembly on bath water. When the assembly is on the bath water, the float means causes the water-jetting means to be held over the bath water and allows the inlet of the housing to be held under the bath water. The assembly is also characterized in that the water-jetting means has an outlet port which directly confronts the bath water when the assembly floats on the bath water. Because of the outlet port, water to be discharged from the water-jetting means is to be directed to the surface of the bath water.
It is preferred that the center axis of the housing is disposed substantially vertically when the assembly floats on the bath water. The housing may have upper and lower portions such that, when the assembly is on the bath water, the upper portion is held over the bath water, and the lower portion is held under the bath water. The water-jetting means may be a plurality of substantially tubular nozzles, and the outlet port may be a plurality of openings formed on the nozzles so that each of the nozzles has one of the openings. In this case, the nozzles are disposed on the upper portion of the housing so that the openings are arranged at equal angular intervals about the center axis of the housing, and the distances between the center axis and the respective openings are equal. It is preferred that each of the openings has an axis parallel to the center axis of the housing, and the inlet of the housing is disposed on the lower portion of the housing.
The housing may include an inner partition wall dividing the interior space of the housing into an air chamber and a pump chamber. In this case, the pump chamber receives the pump means and is in fluid communication with the inlet and outlet of the housing. The float means may be the air chamber.
The housing may have a plurality of hollow protrusions disposed thereon at equal angular intervals about the center axis of the housing. In this case, the air chamber is defined by the inner faces of the hollow protrusions and the inner partition wall.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a side-elevational view of a bubble bath assembly according to the present invention;
FIG. 2 is a plan view of the bubble bath assembly shown in FIG. 1;
FIG. 3 is a view taken along the line III--III in FIG. 2, in which a part of a pump mechanism is shown in elevation; and
FIG. 4 is a perspective view of the bubble bath assembly in FIG. 1, showing the assembly floating on water in a bathtub.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, like reference characters designate corresponding parts throughout several views, and descriptions of the corresponding parts are omitted once given.
FIGS. 1 to 4 show a bubble bath assembly of a free-floating type, embodying the principle of the present invention. Reference numeral 10 designates a housing made of a plastic. This housing 10 is constituted of a hollow lower member 12 of a substantially truncated trigonal pyramidal configuration with larger and smaller open ends, a lid-like upper member 14 of a rounded-angled triangular configuration, hermetically closing the larger open end of the lower member 12, and a filter cap 16 of a flat sieve-like structure covering the smaller open end of the lower member 12.
The upper member 14 has a hollow semispherical central projection 18 and three hollow semispherical peripheral projections 19, 20 and 21. The central projection 18 is centrally disposed on the outer face of the upper member 14 while the peripheral projections 19, 20 and 21 are disposed respectively at the three corners of the upper member 14 to form the rounded angles. That is, the peripheral projections 19, 20 and 21 are disposed on the outer face of the upper member 14 at equal angular intervals around the central projection 18. The upper member 14 also has a tubular inner wall 17 disposed on that portion of the upper member's inner face along the circumference of the central projection 18.
The lower member 12 has three hollow hemisphere-like portions 22, 23 and 24 projecting outward respectively from the three corners at the open larger end thereof. A tubular inner wall 25 is disposed within the lower member 12, and is joined at its lower end coaxially to the smaller end of the lower member 12. As best shown in FIG. 3, the upper member 14 is secured to the open larger end of the lower member 12 by screws 26 in such a manner that the peripheral projections 19, 20 and 21 of the upper member 14 are mated respectively with the hemisphere-like portions 22, 23 and 24 of the lower member, and the respective inner walls 17 and 25 are coaxially connected at their free ends with each other. That is, when the upper and lower members 14 and 12 are secured to each other, the inner walls 17 and 25 form a resultant tubular partition wall 28 disposed coaxially within the housing 10, and the hemisphere-like portions 22, 23 and 24 and the semispherical projections 19, 20 and 21 form three identical hollow spherical protrusions 34, 35 and 36 which are disposed on the housing 10 at equal angular intervals about the center axis X of the housing 10.
The partition wall 28 hermetically divides the interior space of the housing 10 into two principal chambers, namely, a pump chamber 30 and an air chamber 32 surrounding the pump chamber 30. The pump chamber 30 is defined by the inner face of the tubular partition wall 28 and the respective inner faces of the filter cap 16 and the central projection 18, while the air chamber 32 is defined by the outer face of the partition wall 28 and the inner peripheral face of the housing 10. The air chamber 32 includes three main sections, i.e., the respective internal spaces of the three spherical protrusions 34, 35 and 36, and three passages, each communicatively interconnecting the corresponding two main sections. A pump mechanism 38 is fixedly received in the pump chamber 30, while air at an atmosphere is filled in the air chamber 32. That is, the air chamber 32, particularly the three spherical protrusions 34, 35 and 36 of the housing 10, serve as float means for floating this bubble bath assembly on water. When this assembly floats on water with its upper member 14 facing upward, the assembly is subjected to a buoyancy such that the waterline comes up to the seam 78 between the upper member 14 and the lower member 12. In other words, the assembly can float on water with its lower member 12 under the water and its upper member 14 over the water. In this embodiment, since the three spherical protrusions 34, 35 and 36 are arranged around the larger end of the lower member 12, the distance between the center of buoyancy of the assembly and the filter cap 16 is longer than that between the center of gravity of the assembly and the filter cap 16. Consequently, when this bubble bath assembly is placed on water with its upper member 14 facing upward, it floats on the water considerably stably. In addition, both the center of buoyancy and the center of gravity of the assembly are disposed on the center axis X.
An outlet of the pump chamber 30 in the form of three threaded through holes 76 (only one shown in FIG. 3) are disposed on the central projection 18 of the housing at equal angular intervals about the center axis X. As best shown in FIG. 2, three identical tubular nozzles 40, 41 and 42 are screwed at their threaded proximal ends into the through holes 76, and extend perpendicularly to the center axis X from the central projection. More specifically, the positions of the nozzles 40, 41 and 42 on the housing 10 are such that, when the nozzles are viewed from a plane perpendicular to the axis X, each nozzle is disposed between the corresponding two spherical protrusions. Each of the nozzles is provided at its distal end with an outlet opening 44 open down ward as viewed FIG. 3. That is, the axis of each opening 44 is parallel to the center axis X of the housing. The length of each nozzle is such that, when the bubble bath assembly is viewed from a plane perpendicular to the axis X, the distal end of the nozzle project outward over the outer face of the housing 10. In other words, the distance between the center axis X and the axis Y of each opening 44 is longer than that between the center axis X and the outer face of that portion of the housing 10 excluding the spherical protrusions.
The pump mechanism 38 include a electric motor 46, impeller 48 and other members. To describe the pump mechanism 38 more specifically, a substantially annular guide tube 50 is fitted in the smaller end of the lower member 12 to form an inlet of the pump chamber 30, and is secured by screws 52 to the lower member 12. The motor 46 is hermetically enclosed by a motor container 54, and is secured through a spacer 56 to the guide tube 50 by means of bolts 58 so that the output shaft 60 of the motor 46 is arranged coaxially with the housing 10. The impeller 48 is operatively connected to the output shaft 60 and is disposed within the guide tube 50. Water paths in the form of gaps 62 are formed between the spacer 56 and the guide tube 50 so as to allow water in the guide tube 50 to flow into the pump chamber 30. The filter cap 16 is threadedly engaged with the guide tube 50 to cover the inlet, that is, the smaller end of the lower member 12. A filter medium 64 is interposed between the filter cap 16 and the guide tube 50 to filtrate water to go through the inlet.
As best shown in FIG. 4, an electric cord 66 is disposed on the assembly in order to connect the motor 46 of the pump mechanism 38 to an electric power box (not shown) which is to be separately installed from the bubble bath assembly. This electric cord 66 extends from the motor 46 to the central projection 18, and passes out of the housing 10 through the summit of the central projection 18. A waterproof off/on switch 68 for the motor 46 is disposed at an intermediate portion of the cord 66. The electric power box is, for example, a converter for converting a current of AC 100 V into a current of DC 12 V and for supplying the motor 46 with the current of DC 12 V. Otherwise, the power box is a battery charger able to continuously supply a current of DC 12 V for approximately 1.5 hours without the charging of electric power and able to be charged from a electric power source supplying a current of AC 100 V. A waterproof connector 80 (see FIG. 2) is used for electrically connecting the cord 66 to the power box. A plurality of suction cups (not shown) are attached to the cord 66 to fasten the cord 66 to a bathroom wall or a side wall of a bathtub. Fastening the cord 66 to such walls helps the assembly to be steady on the water in a bathtub. It is preferred that these suction cups are connected to the cord 66 for sliding movement along the cord 66. Reference numeral 70 designates a cord protector for protecting the cord 66 from an external force.
The operation of the bubble bath assembly thus constructed will now be described. Upon using the bubble bath assembly, the entire assembly except for the power box is brought into a bathroom in which a bathtub is installed, while the electric power box is left outside the bathroom. Then, as shown in FIG. 4, the assembly is floated on water 74 in the bathtub 72 with its upper member 14 facing upward. That is all preoperation which should be accomplished before the switch 68 is turned on, and thus no more work for installing the assembly is required. When the assembly is on the bath water 74, the axis X is vertically disposed, the lower member 12 is held under the bath water 74, and the upper member 14 is held over the bath water 74. Therefore, the nozzles 40, 41 and 42 are retained above the bath water 74, and the inlet of the pump chamber 30 is held under the bath water.
Subsequently, the switch 68 is turned on to actuate the motor 46. Due to the actuation of the motor 46, the bath water 74 is drawn into the guide tube 50 through the filter cap 16 and filter medium 64, and then is led into the pump chamber 30. The water drawn into the pump chamber 30 is, then, pressurized and is sent to the nozzles 40, 41 and 42. The water is, subsequently, discharged in a jet from the outlet openings 44 of the nozzles 40, 41 and 42, and is directed vertically against the surface of the bath water 74.
When water is sucked into the pump chamber 30 through the filter cap 16 and the like, a reaction force to the suction is exerted on the assembly so as to urge the assembly downward. However, since another reaction force due to the jetted water discharged from the nozzles, counteracts the reaction force due to the suction, the level of the waterline on the housing 10 does not move during the operation. Also, the reaction force due to the jet of water, which is exerted on the assembly, is directed parallel to the axis X of the housing 10 because the outlet openings 44 are disposed at equal angular intervals about the center axis X, and the distances between the center axis X and the respective outlet openings 44 are equal, and further because the axis Y of each outlet 44 is parallel to the center axis X. Therefore, the bubble bath assembly is kept steady on the bath water during its operation.
When the jet of water impinges on the surface of the bath water 74, it introduces oxygen in atmosphere into the bath water 74. This results in the generation of a multiplicity of minute bubbles suspended throughout the water 74. When these innumerable bubbles in the water 74 contact the human body immersed in the bath water 74, they break instantly, and generate ultrasonic waves throughout the bathtub 72. These ultrasonic waves enhance the heat transfer rate between the bath water 74 and the human body, massage the human body and promote the removal of dirt and oils from the skin of the human body, which help in the prevention of skin diseases and muscular pains which can afflict the human body.
In addition, when it is not necessary or not required to keep the aforementioned assembly in the bathtub, the assembly can easily be removed from the bathtub 72. Also, when the impact of the jetted water is required on a specific part of the human body, the whole assembly can easily be moved to locate the nozzles 40, 41 and 42 to the exact position where the nozzles can affect the specific part.
EXAMPLE
A test bubble bath assembly equivalent to the assembly shown in FIGS. 1 to 4 was prepared. This assembly's housing including the cord protector had a height of about 39 cm and a maximum transverse outer size of about 33 cm. The weight of the assembly was about 3.5 kg. A pump motor contained in the housing was such that it was able to cause water to be discharged from three nozzles at the maximum flow rate of 80 lit./min.
The bubble bath assembly described above was floated on water in a bathtub, and the assembly was operated. Then, the position of the waterline on the housing was checked. The result was that the distance between the waterline and the filter cap was 16 cm, and the waterline was substantially coincidental with the seam between upper and lower members. Also, the frequency of ultrasonic waves generated due to the burst of the minute bubbles was measured. The result was that it was about 20,000 to 80,000 Hz. | There is disclosed a bubble bath assembly including a housing, a pump mechanism and a water-jetting mechanism. The housing has an inlet and an outlet. The pump means is encased within the housing in order to draw water into the housing through the inlet and to discharge water under pressure from the outlet. The water-jetting mechanism is communicatively connected to the outlet of the housing to discharge water in a jet therefrom. This assembly is characterized in that the housing includes a float for floating the bubble bath assembly on bath water in such a manner that the water-jetting mechanism is held over the bath water and the inlet of the housing is held under the bath water. The assembly is also characterized in that the water-jetting mechanism has an outlet port which directly confronts the bath water when the assembly floats on the bath water, so that water to be discharged from the water-jetting mechanism is directed to the surface of the bath water. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application claims priority from U.S. Provisional Application No. 61/854,159, filed Apr. 18, 2013, which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a combination of one or more female RJ connector(s) and a female flash card connector in a common housing that can be mounted to a PCB. The female RJ connector(s) and the female flash card connector can be mounted one atop of the other or side by side in the common housing which can include shielding.
[0004] 2. Description of Related Art
[0005] Modular connectors are commonly used for telephone systems, data networks, and low-speed serial connections. These connectors are inexpensive, relatively simple to terminate, and easy to plug and unplug. A modular connector typically has a clear, plastic body with the male plug including a tab for locking the male plug and female jack together when connected. In the vernacular used by the technology industry, these modular connectors are called “RJ” connectors. This is technically inaccurate, but the naming convention is widely used. RJ is an acronym for Registered Jack, which is part of a coding system developed in the 1970s by AT&T to classify telephone services and equipment. The coding system, called the Universal Service Order Code (USOC), used designations that began with the letters RJ to denote the capabilities of jacks in a building, and how they should be wired in order to connect to the public phone network.
[0006] A registered jack (RJ) is a standardized physical network interface, both jack construction and wiring pattern, for connecting telecommunications or data equipment to a service provided by a local exchange carrier or long distance carrier. The standard designs for these connectors and their wiring are named RJ11, RJ14, RJ21, RJ45, RJ48, etc. Many of these interface standards are commonly used in North America, though some interfaces are used world-wide.
[0007] A typical RJ connector includes an RJ socket housing (a.k.a. a female RJ electrical connector or jack) for insertion of an RJ male plug (a.k.a. a male RJ electrical connector) to form an electrical connection. RJ socket housings are available in many configurations including one port, multiple ports in a horizontal row, and stacked rows of RJ connectors.
[0008] MicroSD is a small removable flash memory card used mostly with mobile phones, tablets, laptop computers, and desktop computers to store data. It is the smallest flash memory card currently on the market. It measures just 5 mm×11 mm×0.7 mm making it ideal for mobile phone and tablet computer use. When users want to insert a MicroSD card into a MicroSD card connector they simply slide the MicroSD card into the MicroSD female flash card connector opening where the MicroSD card locks into place.
[0009] Although MicroSD cards are actually very small they can store large amounts of data. MicroSD cards are available with storage capacities ranging from 128 MB up to 8 GB, using a storage density of 34 GB/cm 3 . There are different formats on Micro SD cards to store data, including an SDHC format.
[0010] SDHC stands for Secure Digital High Capacity. MicroSD cards formatted in the SDHC format provide higher storage capacity versus the same form factor as a normal Micro SD (or Secured Digital (SD)) card. SDHC cards first appeared in 2006. SDHC cards are generally formatted with the Fat32 file system. SDHC cards have a fixed sector size of 512 bytes.
[0011] The SD Card Association (SDA) has placed a limit of 32 GB on SDHC capacity, while technically speaking SDHC cards could support up to 2 terabytes (TB) of storage. SDHC cards emerging onto the market created considerable consumer confusion as normal SD cards, such as MicroSD cards, are used for many portable devices including digital cameras, camcorders, game systems, MP3 players and other electronic devices. SDHC cards are also graded by speed in three classes. Generally speaking, Class 2 offers 2 MB/s, Class 4 offers 4 MB/s and Class 6 offers 6 MB/s.
SUMMARY OF THE INVENTION
[0012] This invention combines a MicroSD card connector with a female RJ connector in a common housing. When the MicroSD card connector is combined with the female RJ connector in a common housing there is a saving of space on a substrate, e.g., printed circuit board (PCB), where the common housing is installed as a single unit verses installing a MicroSD card connector and a female RJ connector separately on the substrate.
[0013] The combination female MicroSD card connector and female RJ connector in a common housing disclosed herein can be mounted to a PCB in different manners depending on how contact pins from each connector are positioned in the common housing. The contact pins can extend at right angle and through a bottom wall of the common housing for insertion into through-holes in a PCB. Optionally the contact pins can be positioned horizontally to extend through a back or rear wall of the common housing for insertion into through-holes in a PCB. Conventional female RJ connectors and conventional MicroSD card connectors can be mounted in these different arrangements as well. The contact pins of these conventional connectors generally have symmetric orientation which minimizes the size of each connector. The symmetric orientation of the connectors in the common housing disclosed herein permits the smallest size possible to conserve space.
[0014] More specifically, disclosed herein is a female RJ connector and a female MicroSD card connector combined into a single (common) connector housing that can be attached to a PCB to save space and provide for the storage of data within a MicroSD card which can be inserted into the Micro SD card connector. The common housing can have shielding surrounding all or part of the female RJ Connector and the female MicroSD card connector. The female RJ connector and the female MicroSD card connector combine data storage with networking connectivity.
[0015] The female RJ connector and the female MicroSD card connector in a common housing combine the capabilities of the RJ connector for networking connectivity with that of the MicroSD card connector's storage of data on a MicroSD card. One application of this data storage in combination with the RJ connector is the accumulation of data pertaining to the status of the RJ connection when an RJ male plug is seated in the female RJ connector and data is being conveyed via this connection. This status data can include activity on the RJ connection including number of transmissions and number of Ethernet networking collisions. MicroSD cards are capable of holding large amounts of data which can be used to store files, folders, and any other information a user may want to store.
[0016] MicroSD cards which insert into the female MicroSD card connector are smaller than the dimensions of a standard female RJ connector opening and therefore the common housing can have a width and height and depth not much larger than the female RJ connector. Also or alternatively to a MicroSD card connector, standard USB, HDMI, and/or SATA connectors could be included in the common housing while maintaining the same height and size of the common housing.
[0017] The female RJ connector and any other connector described herein can be stacked one atop of each other in the housing, side by side within the housing, or, in the case where the housing encloses three or more connectors, the connectors can be stacked one atop of each other and side by side.
[0018] Also disclosed herein is a combination connector comprising: a plurality of walls defining a housing; a female RJ connector and a female flash card connector inside the housing; contact pins extending from contacts of the female RJ connector and contacts of the female flash card connector through at least one wall of the housing for connection to a PCB; and electromagnetic interference (EMI) shielding on one or more of the walls.
[0019] The walls can include top and bottom walls, right and left side walls extending between the top and bottom walls, a rear wall, and, optionally a front wall.
[0020] The female RJ connector and the female flash card connector can be positioned adjacent each other vertically or horizontally within the housing.
[0021] The housing can include in one of the plurality of walls, e.g., a front wall, a first opening configured to facilitate insertion of a male RJ connector into an opening of the female RJ connector, and a second opening configured to facilitate insertion of a flash card into an opening of the female flash card connector.
[0022] The combination connector can further include an integrated circuit (IC) chip in the housing. The IC chip can be operative for analyzing network transmission data on one or more contact pins of the female RJ connector and for storing said data in a memory of a flash card inserted in the female flash card connector.
[0023] The combination connector can further include an integrated circuit (IC) chip in the housing that can be operative for facilitating electrical connectivity between contacts of a male RJ connector and contacts of the female RJ connector when the male RJ connector is inserted into the female RJ connector. The IC chip can be further operative for collecting and storing connectivity data in a memory of a flash card inserted in the female flash card connector.
[0024] The female flash card connector can be a MicroSD connector and the flash card can be a MicroSD card.
[0025] The combination connector can further include a female USB connector in the housing and contact pins extending from contacts of the female USB connector through at least one wall of the housing for connection to a PCB.
[0026] The housing can include in one of the plurality of walls, e.g., a front wall, a first opening configured to facilitate insertion of a male RJ connector into the female RJ connector, a second opening configured to facilitate insertion of a flash card into the female flash card connector, and a third opening configured to facilitate insertion of a male USB connector into the female USB connector.
[0027] The female RJ connector, the female USB connector, and the female flash card connector can be positioned adjacent each other vertically, horizontally, or some combination of vertically and horizontally within the housing.
[0028] The combination connector can further include an integrated circuit (IC) chip in the housing. The IC chip can be operative for analyzing network transmission data on one or more contacts of the female USB connector, or on one or more contacts of the RJ connector, or on one or more contacts of the female USB connector and the female RJ connector. The IC chip can be further operative for storing said transmission data in a memory of a flash card inserted in the female flash card connector.
[0029] The combination connector can further include an integrated circuit (IC) chip in the housing. The IC chip can be operative for facilitating electrical connectivity between at least one of the following: contacts of a male USB connector and the contacts of the female USB connector when the male USB connector is inserted into the female USB connector; and contacts of a male RJ connector and the contacts of the female RJ connector when the male RJ connector is inserted into the female RJ connector.
[0030] The IC chip can be further operative for collecting and storing connectivity data in a memory of a flash card inserted in the female flash card connector.
[0031] The combination connector can further include a second female RJ connector in the housing and contact pins extending from contacts of the second female RJ connector and through at least one wall of the housing for connection to a PCB.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 is a perspective view of a combination female RJ connector and a female MicroSD card (reader/writer) connector in a common housing, including, in operative plug-in relation, a male RJ connector and a MicroSD flash memory card;
[0033] FIG. 2 is a partial cross-sectional perspective view of the combination female RJ connector and the female MicroSD card connector in the common housing of FIG. 1 that also houses magnetic components, a smart logic integrated circuit (IC) chip, and/or one or more LEDs;
[0034] FIG. 3 is a perspective view of a combination female RJ connector, a female MicroSD card connector, and a female USB connector in a common housing including, in operative plug-in relation, a male RJ connector, a MicroSD card, and male USB connector;
[0035] FIG. 4 is a partial cross-section of the combination female RJ connector, female MicroSD card connector, and female RJ connector in the common housing of FIG. 3 that also houses magnetic components, a smart logic integrated circuit (IC) chip, and one or more LEDs; and
[0036] FIG. 5 is a partial cross-section of a combination first female RJ connector, second female RJ connector, and a female MicroSD card connector in a common housing.
DETAILED DESCRIPTION OF THE INVENTION
[0037] The present invention will be described with reference to the accompanying figures where like reference numbers correspond to like or similar elements.
[0038] With reference to FIGS. 1 and 2 , a combination connector 1 includes a female RJ connector 2 and a MicroSD (flash) card (reader/writer) connector 3 in a common housing that includes a top wall 21 , a right side wall 22 , a left side wall 23 , a bottom wall 24 , a back wall 25 , and a front wall 26 . The female RJ connector 2 and the female MicroSD card connector 3 are located and contained within these walls. These walls optionally can be expanded to house other one or more additional connectors such as, without limitation, a USB connector, an HDMI connector, SATA connectors, and one or more additional RI Connectors 2 .
[0039] FIG. 1 shows a male RJ connector 30 positioned to be plugged into female RJ connector 2 when moved in the direction of line 32 and a MicroSD flash card 34 positioned to be plugged into female MicroSD card connector 3 when moved in the direction of line 36 . FIG. 1 also shows one or more optional LEDs 7 a and 7 b in the common housing, contacts 9 of female RJ connector 2 , contacts 11 of MicroSD card connector 3 , shielding 6 (e.g., on the outside of walls 21 , 22 , 23 , 25 , and, optionally, 24 ) and a shielding tab 5 coupled to shielding 6 for connection to a PCB. Shielding 6 can be made of any of a variety of conductive (e.g., metal) materials. Female RJ connector 2 and female MicroSD card connector 3 can be made from a variety of materials, such as, without limitation, plastic or metal. Under the control of IC chip 16 (discussed hereinafter) and/or an external controller (not shown), female MicroSD card connector 3 can be configured to write data to MicroSD card 34 , read data from MicroSD card 34 , or both, when MicroSD card 34 is inserted and seated in female MicroSD card connector 3 .
[0040] The contacts 9 of RJ connector 2 connect to contact pins 10 which extend from female RJ connector 2 through one of the walls 21 , 22 , 23 , 24 , 25 , e.g., bottom wall 24 , to be mounted to a substrate, e.g., a PCB, by soldering, surface mount technology, press fitting, or other means of mounting connectors known in the art. Similarly, contacts 11 of MicroSD card connector 3 connect with contact pins 12 which extend from female MicroSD card connector 3 through one of the walls 21 , 22 , 23 , 24 , 25 , e.g., bottom wall 24 , to be mounted to the substrate by soldering, surface mount technology, press fitting, or other means of mounting connectors known in the art.
[0041] FIG. 2 shows a partial cross-section of the combination female RJ connector and female MicroSD card connector 1 in a common housing with optional integrated magnetic components 14 , a smart logic integrated circuit (IC) chip 16 for data collection of connectivity status information, LEDs 7 a and 7 b , LED contact pins 8 connected to LED 7 b , magnetic coils 15 , and PCB 13 . MicroSD contact pins 10 are in electrical contact with MicroSD internal contacts 11 which make contact with contacts (not shown) on MicroSD card 34 once it is completely inserted into the opening 18 of MicroSD connector 3 . RJ connector cavity opening 20 of female RJ connector 2 includes RJ connector contacts 9 with spring function which are in electrical contact with contact pins 12 . RJ connector internal contacts 9 make contact with contacts 42 of male RJ connector 30 when it is completely inserted into the RJ connector cavity opening 20 of female RJ connector 2 .
[0042] The optional smart logic IC chip 16 facilitates the evaluation of network traffic on the contacts 9 of female RJ connector 2 when male RJ connector 30 with networking cable 40 attached thereto is inserted into female RJ connector 2 . While a single smart logic IC chip 16 is described, the number of such IC chips is not to be construed as limiting the invention.
[0043] In an embodiment, IC chip 16 can be operative for analyzing network transmission data on one or more contacts 9 of female RJ connector 2 and for storing said analysis and any related data in a memory of MicroSD card 34 seated in female MicroSD card connector 3 .
[0044] In another embodiment, IC chip 16 can be operative for facilitating electrical connectivity between contacts 42 of male RJ connector 30 and contacts 9 of female RJ connector 2 . IC chip 16 can further be operative for collecting and storing connectivity data in a memory of MicroSD card 34 inserted into MicroSD card connector 3 .
[0045] With reference to FIGS. 3 and 4 and with continuing reference to FIGS. 1 and 2 , with some exceptions, another embodiment combination connector 100 is similar in many respects to combination connector 1 shown in FIG. 1 . Some of these exceptions include connector 100 including a female USB connector 19 in addition to RJ connector 2 and MicroSD card connector 3 . In order to facilitate the addition of female USB connector 19 , the heights of walls 22 , 23 , 25 , and 26 are increased (made taller) over like numbered walls of combination connector 1 shown in FIGS. 1 and 2 .
[0046] Female USB connector 19 includes internal contacts 46 disposed on a PCB 48 which is positioned in the cavity 44 of female USB connector 19 to facilitate connection with mating contacts (not shown) of a male USB connector 38 when the male USB connector 38 is plugged into female USB connector 19 when moved in the direction of line 50 . The internal contacts 46 of female USB connector 19 are in electrical contact with contact pins 52 which extend through female USB connector 19 through one of the walls 21 , 22 , 23 , 24 , 25 , e.g., bottom wall 24 , to be mounted to a substrate, e.g., a PCB, by soldering, surface mount technology, press fitting, or other means of mounting connectors known in the art.
[0047] The combination connector 100 in a common housing shown in FIGS. 3 and 4 can include optional integrated magnetic components 14 , one or more magnetic coils 15 , and/or a smart logic integrated circuit (IC) chip 16 .
[0048] In the embodiment of combination connector 1 shown in FIGS. 1 and 2 , magnetic components 14 and magnetic coils 15 are connected and operative for buffering electrical signals impressed on one or more contacts 9 . In the embodiment of combination connector 100 shown in FIGS. 3 and 4 , magnetic components 14 and magnetic coils 15 are connected to and operative for buffering electrical signals appearing on one or more contacts 9 , one or more contacts 46 , and/or some combination thereof.
[0049] In the embodiment of combination connector 1 shown in FIGS. 1 and 2 , smart logic (IC) chip 16 facilitates the collection and, optionally, the analysis of data transfer occurring on one or more contacts 9 when male RJ connector 30 is inserted in female RJ connector 2 , and for storing said analysis and/or collected data on MicroSD card 34 inserted in MicroSD card connector 3 . In a similar manner, smart logic (IC) chip 16 in the combination connector 100 shown in FIGS. 3 and 4 facilitates the collection and, optionally, the analysis of data transfer occurring on one or more contacts 9 and/or one or more contacts 46 , and the storage of said analysis and/or collected data on MicroSD card 34 inserted in MicroSD card connector 3 of combination connector 100 .
[0050] With reference to FIG. 5 and with continuing reference to FIGS. 3 and 4 , with some exceptions, another embodiment combination connector 200 is similar in many respects to combination connector 100 shown in FIGS. 3 and 4 . Some of these exceptions include connector 200 including a second female RJ connector 2 ′ in replacement of the female USB connector 19 in combination connector 100 . This second RJ connector 2 ′ is in addition to RJ connector 2 and MicroSD card connector 3 . Female RJ connector 2 ′ includes internal contacts 9 ′ with spring function which are in electrical contact with contact pins 12 ′ which extend from the female cavity of female RJ connector 2 ′ through one of the walls 21 , 22 , 23 , 24 , 25 , e.g., bottom wall 24 , to be mounted to a substrate in any manner known in the art.
[0051] In the combination connector 200 shown in FIG. 5 , magnetic components 14 and/or magnetic coils 15 are connected to and operative for buffering electrical signals appearing on one or more contact pins 9 and/or 9 ′. Smart logic IC chip 16 facilitates the collection and, optionally, the analysis of data transfer occurring on one or more contacts 9 and/or 9 ′, and the storage of said analyzed and/or collected data on MicroSD card 34 inserted in MicroSD card 3 of combination connector 200 .
[0052] The present invention has been described with reference to the accompanying figures. Obvious 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. | A combination connector includes a number of walls defining a housing and a female RJ connector and a female flash card connector inside the housing. Contact pins extend from contacts of the female RJ connector and contacts of the female flash card connector through at least one wall of the housing for connection to a PCB. The walls include electromagnetic interference (EMI) shielding. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the manufacture of glass fiber mats by the wet-laid process and, more particularly, it is concerned with a method of improving the tensile strength of such mats upon being subjected to severe wet conditions.
2. Description of the Prior Art
Glass fiber mats are composed of glass fibers held together by a binder material. Typical binders used in the industry are urea-formaldehyde resins, phenolic resins, bone glue, polyvinyl alcohols, and latexes. These binder materials are impregnated directly into the fibrous mat and set or cured to provide the desired integrity for the glass fibers. The most widely used binder is urea-formaldehyde because it is inexpensive. Unfortunately, urea-formaldehyde binder is deficient in one or more respects for glass fiber mats. In particular, the tensile strengths of mats bound with urea-formaldehyde deteriorate appreciably when the mats are subjected to wet conditions, which are normally encountered in their use in roofing products. Such roofs may fail if their wet tensile strength is much lower than its dry tensile strength.
Accordingly, it is an object of this invention to provide glass fiber mat roofing shingles and built-up roofing products which retain a substantial portion of their dry tensile strength even under severe wet conditions.
SUMMARY OF THE INVENTION
The above stated objects and features of the invention are accomplished herein by providing a glass fiber mat composed of a plurality of sized glass fibers held together by an improved binder composition consisting essentially of a urea-formaldehyde resin and about 0.01 to 5%, preferably about 0.5%, by weight of a surfactant which is highly water soluble and which wets the surfaces of the sized glass fibers. Preferred surfactants having these physical characteristics are anionic surfactants such as sodium dodecylbenzene sulfonate.
The glass mats of the invention preferably are made by applying the binder composition directly to the wet glass mat, drying and curing the binder at elevated temperatures. The finished glass mat product contains about 60% to 90% by weight glass fibers and about 10% to 40% by weight of binder.
The glass mats made thereby retain up to 79% of their dry tensile strength when subjected to severe wet conditions.
DETAILED DESCRIPTION OF THE INVENTION
The following detailed description of the invention will be made with particular reference to a wet-laid process for preparing glass fiber mats, although it will be understood that other processes known in the art, such as a dry-laid process, may be used as well. Furthermore, the description is made using chopped bundles of sized glass fibers, although other forms of glass fibers such as continuous strands, also may be used.
The process of forming glass fiber mats according to the invention begins with chopped bundles of sized glass fibers of suitable length and diameter. Generally, fibers having a length of about 6 mm to 75 mm and a diameter of about 3 to 20 microns are used. Each bundle may contain from about 20 to 300, or more, of such fibers, which may be wet or dry, as long as they can be suitably dispersed in an aqueous dispersant medium. The bundles are added to the dispersant medium to form an aqueous slurry. Any suitable dispersant known in the art may be used. The fiber slurry then is agitated to form a workable dispersion at a suitable consistency. The dispersion then is passed to the screen of a mat-forming machine. En route to the screen, the dispersion usually is diluted with water to a lower fiber concentration.
The fibers are collected at the wire screen in the form of a wet fiber mat and the excess water is removed by vacuum in the usual manner. The wet mat now is ready for application of the binder composition thereto, which is accomplished by soaking the mat in an excess of binder solution and removing excess binder under vacuum. The mat then is dried and the binder composition is cured in an oven at elevated temperatures, generally at least about 200° C. This heat treatment alone will effect curing; alternatively, but less desirable, catalytic curing may be used, such as with an acid catalyst, e.g. ammonium chloride or p-toluene sulfonic acid.
The binder composition of the invention is prepared by blending a urea-formaldehyde resin with about 0.01 to 5% by weight of a suitable surfactant which is highly water soluble and which wets the surfaces of the sized glass fibers.
The urea-formaldehyde resins of the binder composition are commercially available materials; for example, urea-formaldehyde resins such as "S-3701-C" sold by Pacific Resins and Chemicals, Inc., Tacoma, Washington, and "PR-913-23", sold by Borden Chemical, Columbus, Ohio, may be used. These resins generally are modified with methylol groups which upon curing form methylene or ether linkages. Such methylols may include N,N'-dimethylol; dihydroxymethylolethylene; N,N'-bis(methoxymethyl), N,N'-dimethylolpropylene; 5,5-dimethyl-N,N'-dimethylolpropylene; N,N'-dimethylolethylene and the like.
The surfactants having the desired physical properties of being highly water soluble and of wetting the surfaces of the sized glass fibers are found most suitably among anionic surfactants, although cationic and nonionic surfactants may be used with lesser benefit on improving the wet tensile strength property of the glass mat.
The molecular structures of the anionic surfactants that are used to improve wet tensile strength in the current invention contain two essential segments:
(a) a hydrophobic segment containing from 8 to 30 carbon atoms, and
(b) an anionic segment selected from among carboxy, sulfate ester, phosphate ester, sulfonic acid and phosphonic acid groups, generally in the form of their alkali metal, ammonium or alkylammonium salts. Optionally, the molecule may also contain a polyalkyleneoxy chain, but the number of alkyleneoxy units per molecule preferably should not exceed 10. The preferred alkyleneoxy unit is the ethyleneoxy unit.
The hydrophobic segment may be alkyl, aryl, alkaryl, substituted alkyl, substituted aryl or substituted alkaryl radicals. Furthermore, the alkyl groups can either be straight or branched chain and saturated or unsaturated. Suitable substituent groups, when present, include hydroxy, alkoxy, acyloxy, carboxy lower alkyls, thio, alkylthio, acylamide and halogen groups.
Examples of such anionic organic surfactant compounds are the water soluble alkali metal salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 30 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals). Important examples of the synthetic surfactants which form a part of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 carbon atoms), sodium or potassium alkyl benzene-sulfonates, such as are described in U.S. Pat. Nos. 2,220,009 and 2,477,383, in which the alkyl group contains from about 9 to about 15 carbon atoms; other examples of alkali metal alkylbenzene sulfonates are those in which the alkyl radical is a straight or branched chain aliphatic radical containing from about 10 to about 20 carbon atoms for instance, in the straight chain variety 2-phenyl-dodecane-sulfonate and 3-phenyl-dodecane-sulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g. tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts or alkylphenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 20 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and others known in the art.
Other useful anionic surfactants are described in U.S. Pat. Nos. 3,844,952 and 3,976,586 and these are included by reference for use in the process of this invention.
Anionic surfactants, which perform best as additives for urea-formaldehyde, include Siponate DS-10, sodium dodecylbenzene sulfonate (Alcolac Chemical); Igepon TC-42, N-methyl-N-acyl-taurine, (GAF Corp.); Nekal WS-25, sodium bis(2,6-dimethyl 4heptyl)sulfosuccinate (GAF Corp.); Igepon TK-32, sodium N-methyl-N-tall oil and taurate (GAF Corp.) and Alipal CO-433, sodium nonylphenoxy polyethyleneoxy ether sulfate (GAF Corp.). Glass mats made from urea-formaldehyde and such surfactants retain up to 79% of the dry tensile strength under wet conditions. On the other hand, cationic and non-ionic surfactants which do not possess the required water solubility and ability to wet the sized glass fibers, provide mats which can retain much less of its dry tensile strength under wet conditions.
The following experimental examples will more fully describe the invention.
EXAMPLE 1
The Control
7.2 g. of 32 mm. length OCF 670 M sized glass fibers were dispersed by stirring in 12 l. of a 40 ppm solution of dimethylhydrogenated tallow amine oxide (DMHT-Armak Co.), a 0.06% by weight consistency. The dispersion was diluted to a 0.015% consistency en route to a dewatering screen where a wet web was formed. The wet web then was dipped into an aqueous binder solution of urea-formaldehyde (20% solids by weight). Thereafter excess binder was removed by vacuum and the mat was dried. The basis weight of the mat was about 110 g/m 2 ; the caliper was 1.0 mm; the urea-formaldehyde constituted about 23% by weight of the mat.
EXAMPLES 2-6
The Invention
The procedure of Example 1 was repeated except that the following surfactants were added in the given amounts per 497.5 g. of the binder solution (0.5% addition). A mat of similar physical parameters were obtained.
______________________________________ Amount ActivityEx. No. Surfactant (g.) (%)______________________________________2 Siponate DS-10 0.51 98 (Alcolac-sodium dodecylbenzene sulfonate)3 Nekal WS-25 1.04 48 (GAF-sodium bis(2,6-dimethyl- 4-heptyl)sulfosuccinate4 Igepon TC-42 2.00 25 (GAF-sodium N--coconut acid- N--methyl taurate)5 Igepon TK-32 2.50 20 (GAF-sodium N--methyl-N--tall oil acid taurate)6 Alipal CO-433 1.67 30 (GAF-sodium nonylphenoxy polyethyleneoxy ether sulfate)______________________________________
EXAMPLES 7-10
The Comparison
______________________________________7 Gafac RE-610 0.50 100 (GAF-nonylphenoxy polyethyleneoxy phosphate)8 Nekal BX-78 0.67 75 (GAF-sodium dibutyl naphthalene sulfonate)9 Blancol N 0.58 86 (GAF-sodium salt of sulfonated naphthalene formaldehyde condensate)10 Darvan No. 1 0.50 100 (R.T. Vanderbilt-sodium naphthalene sulfonic acid formaldehyde condensate)______________________________________
The glass mats of Examples 1-10 were tested for their tensile strengths under dry conditions (dry tensile) and after thorough soaking in water for 10 minutes at 25° C., (wet tensile 25° C.) and for 10 minutes at 82° C. (wet tensile 82° C.). The tensile strengths were tested in accordance with GMFT-08 test using mat specimens 50 mm×200 mm in the machine direction (MD). The results were recorded as N/50 mm for the average of 5 samples. The samples had a tear strength of about 7 N. The results are given in the Table below.
TABLE______________________________________ Tensile Reten- Tensile Strengths tion Strengths Wet % of Wet Retention (25° Dry (82° % of DryEx. No. Dry C.) Tensile Dry C.) Tensile______________________________________1-Control 204 32 16 204 14 72-Invention 388 224 57 388 48 133-Invention 312 212 68 312 64 214-Invention 316 168 53 316 64 205-Invention 282 224 79 282 112 406-Invention 252 122 48 252 50 207-Comparison 100 16 16 100 6 68-Comparison 126 14 11 126 -- --9-Comparison 225 63 28 225 28 1210-Comparison 197 44 22 197 22 11______________________________________
The results in the Table above demonstrate that the addition to the urea-formaldehyde binder of a surfactant which is highly soluble in water and which wets the surfaces of the sized glass fibers (the anionic surfactants of Examples 2-6) result in a pronounced increase in percent retention of dry tensile strength under wet conditions at both room and elevated temperatures, whereas those relatively non-water soluble surfactants which do not wet the sized glass fibers (Examples 7-10) do not improve upon the wet tensile strength properties of the control. | What is described herein is a method of improving the wet tensile strength of sized glass fiber mats characterized by forming the mat from a plurality of glass fibers and a binder composition therefor which consists essentially of a urea-formaldehyde resin and about 0.01 to 5% by weight of a surfactant which is both highly water soluble and which wets the surfaces of sized glass fibers. The preferred surfactant is an anionic surfactant such as a sodium dodecylbenzene sulfonate. The glass mats thus made retained up to 79% of their tensile strength upon being subjected to severe wet conditions. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to athletic apparel and more particularly to an improved shoulder pad device for football players and other atheletes involved in contact sports that will afford protection for the shoulders, collar bone, biceps, sternum, ribs, clavicle, pectoral muscles, lateral aspects of the scapula and the humerous bone. Also, the invention contemplated herein is not bulky, is not cumbersome, but is lightweight and capable of receiving high intensity blows without breaking and also capable of absorbing a major portion of the energy created by the blow and distributing this energy over a wide area, thus protecting the football player from injury. Further, the football shoulder pad device contemplated herein is assembled without the use of even one rivet. Any element comprising the shoulder pad may be removed from the completed assembly simply by the disengagement of a Velcro strap, no special tools are needed. Elements may be added to the assembly as needed depending on the requirements of the user.
Further, the invention contemplated herein does not limit the body movements of the player, thereby permitting this invention to be used by linemen, backfield men, and quarterbacks. Each player on the team requires a certain kind of protection because of his position, e.g. linemen, and some less, e.g. quarterbacks. The ease with which the shoulder pads can be assembled, since there are no rivets nor screws used, enables the shoulder pad assembly to be assembled for the player depending on his position. In fact, to carry this premise to the extreme, the shoulder pads contemplated here can be repaired, assembled or modified during a ball game, quickly and efficiently.
2. Description of the Prior Art
The prior art is replete with shoulder pads and the like. For example, back in 1900, U.S. Pat. No. 653,544 discloses a shoulder pad comprising two halves formed out of heavy leather. Generally speaking, all shoulder pads have the same construction, i.e., they are formed of two half sections that are rigid or semi-rigid tied together at the back and at the chest. Also attached to the inside surface of the two half sections will be some kind of padding which is usually stitched or riveted to the half sections. From 1900 to the present, improvements have been made to the shoulder pads by the addition of additional shoulder cups, rib protection, hip protection and improved armor type materials and padding. The shoulder pads manufactured are held together by rivets or other similar type retaining means. Modern type shoulder pads are usually the cantilever type shoulder pads which allow the player increased mobility without loss of protection.
Not only is it important to provide a shoulder pad that gives the player the ultimate in protection and mobility, but it is also important to the entity that provides the shoulder pads and other equipment that the shoulder pads be economical in price and easy to maintain. All of the prior art shoulder pads require dozens of rivets in the manufacture of same. This makes the manufacture of the shoulder pads very costly. Also, in order to make repairs to the shoulder pads, it is necessary to have special tools in order to remove the rivets and make the necessary repairs.
Looking at 1981 U.S. Pat. No. 4,295,227, which discloses a modern day shoulder pad, it can be seen that it is constructed of a multiplicity of members, moveable and non-moveable. It is held together by rivets and/or straps which in turn are affixed to the armor material with rivets.
The present invention provides a great improvement over the prior art by providing an improved shoulder pad which is economical to manufacture, simple to repair without any tools, easy and comfortable to wear, and which is, to a great extent, lighter in weight compared to the prior art devices. The present invention is an improved shoulder pad completely assembled without the need of any mechanical fasteners.
SUMMARY OF THE INVENTION
The complications described in the prior art are overcome by the present invention, i.e., it is no longer necessary to manufacture shoulder pads using mechanical fasteners such as rivets. The padding utilized herein provides a more complete protection than the prior art. In the prior art, protection is provided by assembling a shoulder pad utilizing hard surface materials to which are riveted padded materials. Once the shoulder pad is assembled, it cannot be disassembled or repaired without the use of special tools. Also, since the assembly is more or less permanent, cleaning the shoulder pad assembly is cumbersome and expensive.
The present invention, an improved shoulder pad, is assembled about a vest-like padded jacket which is only open at the front. It is not necessary to tie the back portions together since the back portion is now an integral unit. The vest jacket is adapted to receive all the necessary elements which may be epaulettes, padded cups, back plates, shoulder plates, and breast plates necessary to make a complete assembly.
As in all shoulder pads, there are two U-shaped members which form a good part of the shoulder pad assembly and, as the prior art teaches, padding is stitched to the U-shaped members. In this invention, the U-shaped members are simply fit over the padded vest jacket and held there by straps which in this instance are equipped with opposing strips of VELCRO® material, a fastener which is very easy to work with. All the other elements which make up the rest of the shoulder pad assembly are then affixed to the combination of the two U-shaped members and the vest jacket. It can therefore can be seen that the present invention offers a novel shoulder pad which is very easily assembled and which offers increased body protection.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevation view of the improved shoulder pad.
FIG. 2 is a back elevation view of the improved shoulder pad.
FIG. 3 is a side elevation view of the improved shoulder pad, taken at line 3--3 of FIG. 1.
FIG. 4 is a top elevation view of the improved shoulder pad taken along line 4--4 of FIG. 1.
FIG. 5 is a disassembled partial view of the improved shoulder pad.
FIG. 6 is a partial cross-sectional view of the shoulder pad taken at line 6--6 of FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring initially to FIG. 1, the improved shoulder pad is indicated generally at 10. Referring now to FIGS. 1 and 5, the construction of the invention can better be understood. FIG. 5 illustrates the invention in an unassembled condition. The invention includes a semi-rigid right-handed member generally indicated at 12 which fits over the right shoulder and a semi-rigid left-handed member 112 which fits over the left shoulder. The members 12 and 112 are U-shaped in design as viewed from the side and member 12 consists of a chest plate 14, backplate 16 and an arch 18. U-shaped member 112 consists of a chest plate 114, backplate 116 and an arch 118. The arches 18 and 118, when the shoulder pad 10 is completely assembled, provide an opening for the wearer of the shoulder pad 10. The arches 18 and 118 are spaced such that an opening is provided for the neck of the wearer and with the spacing such that the arches 18 and 118 are adjacent and relatively close to the neck. The U-shaped member 12 is provided with openings or apertures 48, 50, 52, 60, 62, 228, 230, 232 and 234. Similarly, U-shaped member 112 is provided with identical apertures. As mentioned previously, U-shaped member 112 is identical to U-shaped member 12. Simply put, U-shaped member 12 is for the right shoulder and U-shaped member 112 is for the left shoulder.
A vest-type jacket member 20 having an interior surface 22 and front portion 24a and 24b. The configuration of the jacket 20 is that of a sleeveless vest without buttons. The inside surface 22 of the jacket 20 is a padded material comprised of a plurality of swells 25 which form a plurality of elongated air pockets 26 throughout the jacket 20. The swells 25 which are really air cushions for distributing a force or blow applied to the jacket 20. The jacket 20 is provided with elongated openings on the chest portion 24a and 24b at 28, 30, 128 and 130. Other elongated openings or elongated apertures are provided on the shoulder portion of the jacket 20 at 32, 34, 132 and 134. Again referring to the upper front portion of the jacket 20, there are provided elongated openings at 36, 136, 38, 40, 138 and 140. Located on the interior surface 22 there is provided an elongated opening 39. The padding may comprise closed cell elastomeric vinyl foam in a stretch fabric cover. The vest jacket is provided with reinforced stitch ribbing 23 at all exterior edges. Referring now to FIG. 2, the back section of the jacket 20 is provided with openings at 42, 44, 142 and 144.
Referring to FIG. 5 there is disclosed a right shoulder epaulette 46 or floppet as it is sometimes referred to. The floppet 146 for the left shoulder is identical to the right shoulder cap 46. The right shoulder epaulette 46 is provided with apertures at 250, 252, 260 and 334. Apertures are provided on the left shoulder epaulette 146 which are identical to those on the right shoulder epaulette 46. The reason for the apertures will soon become apparent.
There is also provided a right outer shoulder pad 64 and left outer shoulder pad 66. Members 64 and 66 are preformed padded cloth members with an interior configuration complementary to the contours of a human shoulder and are also designed to absorb all exterior forces and blows delivered to the shoulder. The members 64 and 66 are provided with reinforced stitch ribbing 68 at all exterior edges. Shoulder member 64 is provided with an aperture 70, shoulder member 164 is also provided with a similar aperture but is not shown. For purposes of brevity only a detailed description of the right side member 12 is being provided since the construction and assembly of the left side member 112 is identical to that of the right side member 12.
The shoulder pad assembly 10 is further provided with a pair of right and left outer shoulder and bicep pad members 72 and 172. The outer shoulder pad 72 is provided with an aperture 76. Likewise, outer shoulder pad member 172 is provided with an aperture, but is not shown on the drawings. The outer shoulder pad members 72 and 172 consist of two integral parts 78 and 80 and 178 and 180 respectively. Members 78 and 178 have a cup-like configuration and are designed to fit the shoulders. Members 80 and 180 are flexible in design and on the outside surface at 82 and 182 there is provided a VELCRO® surface fastening material on members 80 and 180. The strap 84 and 184 is also provided with VELCRO® fastening material and holds the member 72 and 172 onto the right and left arm respectively of the player. Member 72 and 172 is also provided with a reinforced ribbing 86 and 186 at all exterior edges.
Also shown on FIG. 5 is a semi-rigid chest plate member 88 having apertures 330, 328, 428 and 430. Another member comprising a part of the improved shoulder pad is a neckroll 90 provided with apertures 538, 539 and 540. The neckroll 90 is provided at its terminating ends with well-known fastening means VELCRO® such that the neckroll can be adjusted to the wearer's satisfaction. Yet another element of the improved shoulder pad are padded right and left rib protection member 92 and 192.
All of the elements and members of the improved shoulder pad have now been described and assembly of the elements and members will now be illustrated. The assembly of the shoulder pad 10 is done with the use of straps such as the strap shown at 94 in FIG. 5. All the straps used in the assembly are furnished with the well-known fastening means VELCRO®. The length and width of the straps to be used are dictated by where and how they are being utilized.
It is again emphasized that only the assembly of the right side member 12 will be described since the left hand assembly is identical. Shoulder bicep member 72 is connected to the right side U-shaped member 12 by looping a VELCRO® equipped strap through the aperture 232 and up and around the edge of the arch 18 and through aperture 76 and finally closing upon itself. Naturally, the adjustment is determined by the size of the individual. Outer shoulder member 64 is affixed to the right side member 12 by running a VELCRO® equipped strap through aperture 70, 232 and 234, and finally closing upon itself. Right shoulder cap member 46 is affixed to U-shaped right side member 12 by running a VELCRO® equipped strap through apertures 232, 234 and 334. For added strength, cap member 46 is also attached to U-shaped right side member 12 by running a VELCRO® equipped strap through apertures 50, 52, 250 and 252, and finally closing upon itself, and through apertures 60, 62, 260 and 262, and finally closing upon itself. Right hand member 12 fits over the jacket portion 24a and is connected thereto by running a VELCRO® equipped strap through apertures 32 and 34. Any of the straps used to connect member 46, 64 or 72 may be used for this purpose. No extra strap is necessary; however, the strap connecting member 62 is the preferable one to use.
The shoulder pad 10 is also provided with a neckroll 90 which can be worn around a player's neck to reduce injuries. The possibility of neck injuries is due primarily to extreme flexing of the cervical spine and because of exterior blows which may be directed to a player's neck. The neckroll 90 is connected to the shoulder pad 10 by looping straps, having VELRO® fasteners, through apertures 38, 40 and 538, 39 and 539, 138, 140 and 540. All the straps close upon themselves. The terminating ends of the neckroll 90 are provided with VELCRO® fasteners and thus can be adjusted to whatever size the player wants. The neckroll 90 may be a shaped roll of sponge rubber and serves as a restraint, i.e., it prevents the flexing or stretching of the neck beyond a predetermined position thus reducing the possibility of neck injuries. The neckroll 90 may also be used for training purposes and is easily removed.
The improved shoulder pad 10 is also provided with a semi-rigid plastic chest plate 88 which offers additional frontal protection to the players. A strap 96 provided with VELCRO® fasteners is looped through the apertures 42, 44, 142 and 144 located at the back portion of members 12 and 112. The strap 96 is then looped through the apertures 98 and 198 located on the right and left rib protection members 92 and 192 respectively. Now coming to the frontal portion the terminating end of strap 96, which is looped through aperture 98, is inserted into the aperture 430, 230 and 30 and looped through aperture 28, 228 and 428. The strap 96 is then looped back on itself becoming locked in place because of the VELCRO® fasteners on said strap. The left side of the strap 96 is similarly connected.
U-shaped right hand member 12 is provided with an aperture 48 and left hand member 112 is provided with apertures 148 and 149 (see FIG. 1). In the final assembly of the shoulder pad 10, the top portion of right hand member 12 and left hand member 112 is held together by looping a strap 151 through apertures 48, 148 and 149, said strap 151 being equipped with VELCRO® fastening means.
Epaulette members 46 and 146, U-shaped members 12 and 112, and chest plate member 88 are all a dense semi-rigid type material such as a light-weight molded plastic. One material could be a high density polyethylene, which provides high impact resistance to blows. The padding used in members 64, 164, 72, 172, 80 and 180, and on the interior surface of the jacket member 20, may be an elastomeric vinyl foam which may be covered by a stretch knit fabric. The padding may also be formed from closed cell vinyl rubber. These types of padding have the ability to absorb most of the energy delivered by blows thus offering enhanced protection to the player.
The shoulder pad 10 described herein, because of its inherent construction, may have any number of pads, caps, or epaulettes added very simply because no rivets or stitching of any kind are required in the construction, and assembly. The prior art shoulder pads all use stitching or riveting or both in their construction. The shoulder pad 10 described does not require such type of construction. The entire assembly is performed with straps thus obviating the need for any special type of tooling. Further, the shoulder pad 10 can be easily modified for any player depending on his position. Also, the shoulder pad 10 can be easily repaired right on the field in a relatively short period of time. The vest member 24 described herein, because of its inherent design, provides more protection for the shoulder blades and provides extra frontal protection. It is again noted that all prior art devices require the padding material to be stitched or riveted to the plastic shell. Also, it can be seen that none of the plastic material used here can come in contact with the user's body.
Thus, although a preferred embodiment of the shoulder pad has been disclosed and described in detail herein, it should be understood that this invention is in no sense limited thereby and its scope is to be determined by the appended claims. | A protective gear assembly includes cantilever-type protective pads to be used by those athletes engaged in contact sports such as football, hockey, etc. The pads are releasably attached to a one piece padded vest type jacket by strap like members which pass through apertures thereon. The vest jacket is designed to receive all the necessary elements in the protective gear assembly such as epaulettes, padded cups, back plates shoulder plates and breast plates. | 0 |
This application is a continuation of Ser. No. 651,170, filed Sept. 17, 1984 now abandoned.
FIELD OF THE INVENTION
This invention relates to wellhead connectors. More particularly, the present invention pertains to an improved downhole and surface electrical connector assembly.
BACKGROUND OF THE INVENTION
Various approaches are known in the art for passing cable through a wellhead into the interior of the well head casing. Cugini, et al, U.S. Pat. No. 3,437,149 and Sipowicz U.S. Pat. No. 4,041,240, disclose pressure-sensitive cable feed-thru means which extend from the exterior of a wellhead construction through a pressure zone in the wellhead into the interior of a wellhead casing. Therein, coupling means are provided at both ends of the cable feed-thru means. Conductors are embedded in a dielectric material which is moulded within, and protected by, a rigid metal casing or shell.
One problem facing the art today resides in the fact that the potting compounds holding the conductors in place are invariably attacked by the hot oil and hot fluids used to facilitate the pumping of individual oil wells. These fluids attack externally by penetrating the coupling which attaches the lower connector to the feed-thru mandrel, and internally by capillary action of the conductors within the downhole electrical cable. Both actions may result in an electrical failure by means of an electrical shorting action.
In addition, the high pressure differentials cause minute cracks in the rigid bonding materials used, thereby leading to leaks in the system which if not detected may have the effect of causing blow outs in the well whenever a conductor, or pair of conductors is broken loose from the bonding material.
Thus, a basic problem with some prior art techniques resides in the maintenance of the integrity of the dielectric material which encases the conductors, and which passes from a low pressure environment to a high pressure environment. Yet another problem facing the art today is the difficulty and often troublesome process of installing the wellhead conductor in the various types of casing heads in use throughout the petroleum producing industry.
The principal prior art cited in the parent application are U.S. Pat. No. 3,945,700, No. 4,154,302 and No. 4,426,124. Also, an accumulated listing of related patents appears in the parent application.
In view of the foregoing, it is an object of the present invention to provide a new and improved downhole and surface electrical feed-thru connector assembly which will maintain the dielectric strength of the materials which encase the electrical conductors and simultaneously prevent any pressure leaks from developing within and around the electrical conductor.
It is another object of the present invention to provide an improved downhole and surface electrical feed-thru connector assembly wherein the dielectric material is capable of expansion and contraction while ensuring a rigid seal around the electrical conductors and within the mandrel and connector shells within which they are housed or encased.
It is still another object of the present invention to provide an improved downhole and surface electrical feed-thru connector assembly which characterizes a mandrel connector capable of variations in length and which is readily adaptable to accommodate specific wellhead requirements.
It is still another object of the present invention to provide the capability of adapting the improved electric feed-thru connector assembly on a variety of wellhead configurations.
These and other objects of the present invention will be best understood from a consideration of the following detailed description taken in connection with the accompanying drawings which form part of the specification, with the understanding, however, that the invention is not confined to a strict conformity with the drawings but may be changed or modified so long as such changes or modifications make no material departure from the salient features of the invention as expressed in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional view of the complete electric feed-thru connector assembly of the present invention.
FIG. 2 is a cross-sectional view of the electric feed-thru mandrel assembly of the present invention.
FIG. 3 is a cross-sectional view of a conductor for the mandrel assembly of FIG. 2.
FIG. 4 is a partial cross-sectional view of a type GT universal adaptor configuration with a electrical feed-thru completion as described herein.
FIG. 5 is a pictorial view of the flanged adaptor of FIG. 4 installed on a tubing head with a threaded valve connection to a production nipple.
FIG. 6 is a partial cross-sectional view of a threaded tubing head with an electrical feed-thru completion as described herein.
FIG. 7 is a partial cross-sectional view of a tubing head with a clamp connection at its lower end.
FIG. 8 is a partial cross-sectional view of an adjustable toadstool flange assembly with a electrical feed-thru completion as described herein.
FIG. 9 is a partial cross-sectional view of an electric feed-thru connector assembly installed in a unitized wellhead.
SUMMARY OF THE INVENTION
In summary, this invention includes an elongated mandrel sleeve having an internal sleeve shoulder formed therein and facing the high pressure end of the sleeve with the sleeve being externally adapted for field mechanical connection into high pressure wellhead equipment. An elongated pre-formed rigid high mechanical strength dielectric insulator having an external insulator shoulder is installed within the mandrel sleeve with the insulator shoulder in abutment with the internal shoulder of the sleeve. The insulator support means is mounted and sealed in physically bonded relation within the interior of the mandrel sleeve by means of a dielectric potting material disposed as an insulator sleeve or film in the surface areas between the insulator and the mandrel sleeve. The insulator support has a plurality of holes extending axially in parallel and laterally spaced apart relation through the insulator with each hole having an internal hole shoulder formed therein to face the high pressure end of the sleeve. An elongated rigid electrical conductor having an external conductor shoulder and electrical connectors at either end is installed within each hole with the conductor shoulder in abutment with the hole shoulder. Each electrical conductor is mounted and sealed in physically bonded relation within the interior of the hole by a dielectric potting material as a conductor sleeve or film in the surface areas between the conductor and the side of each hole. A designated integral body made of the dielectric potting material is disposed and sealed in physically bonded relation within the mandrel sleeve and between the electrical conductors at the high pressure end of the mandrel sleeve. The dielectric potting may be an epoxy which may be pliable as cured into place. As provided, the insulator support, the conductors, and the integral body serves to seal off fluids from flow through the mandrel sleeves, limited only by a fluid pressure level sufficiently high to cause physical failure of the material of the insulators. The connector is provided in an embodiment adapted for connection through a wellhead hanger and also as a cable connector adapted for connection to the bottom and the top of a cable and of the bottom and top of the connector as installed in a hanger. Thus, the connector may be used in series as later described.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 depicts a complete electric feed-thru connector assembly 10. The main functions of the connector assembly 10 are to provide coupling to electric feed cables at opposite ends of the mandrel shell 7, to conduct high voltage and high current from a surface power source to a downhole pumping system, and to seal off any pressure, gas, or moisture that may tend to enter the feed-thru assembly means 10.
The connector 10 is constructed with various components to ensure a current leakage of no more than twenty micro-amps. It consists of three conductors 12 arranged parallel to each other (one shown) surrounded by an improved insulator 13 of extremely high dielectric strength. On both ends of the insulator 13 is a special potted dielectric material 18 which when completely cured forms a pressure-tight seal throughout the connector 10. Located at the lower end of the connector is a clamp connection 14 secured by four screws 15 when assembled. This clamp 14 is constructed of rigid steel and serves as a locking device with a preferred cable 19. On the opposite ends of the connector 10 is a threaded coupling nut 16 which is a means of sealingly securing the connector 10 to the mandrel shell or sleeve 7, thereby forming a seal which will eliminate any pressure, gas or moisture from entering the feed-thru connector assembly.
The three conductors 12 (one shown) are designed with various special characteristics. Their primary function, however, is to deliver high voltage and high current through the connector 10. The sealing means 21 of the conductor 12 (FIG. 2) forms a back-up seal designed to incorporate long life to the connector 12. Further, it acts to ensure a pressure-tight seal when installed into the insulator 13. These sealing means also protect each individual conductor 12 from any moisture or gas that may escape from the annulus.
The conductors 12 are preferably constructed of a copper alloy, specifically designed to conduct maximum voltage and amperage requirements. The large diameter end of the conductor 12 is designed to have a maximum bearing surface between the conductor 12 and the insulator 13 in case of a well blow-out. The cable insert or socket 23, located at the large diameter and of the conductor 12, is designed to accommodate any prepared cable requirement. Preferably, silver solder is used as a bonding material to ensure a clean positive connection upon the insertion of the cable 19 into the cable insert 23. In some applications, the insert 23 may be bonded to the cable 19 by high pressure mechanical crimping.
The small diameter end of the conductor is also disposed with inserts 24. These inserts or sockets accommodate the other set of conductors 71 located in the mandrel shell 7 (FIG. 2). The inserts or sockets 24 are designed with four slots 25, each being 90° apart, which run their full length. The conductors 71 in the mandrel shell 7 are slightly larger in diameter than the inside diameter of the connector insert 24, thus allowing the insert to expand when assembled and contract when disassembled.
When the connector 10 is fully plugged into the mandrel shell 7 and secured by the threaded coupling nuts 16, a complete connection is incorporated, thus ensuring 100% conductivity. The three conductors 12 are positioned parallel to each other and are affixed in position with a special potted dielectric material forming a body 18 which withstands constant annulus pressures and insulates the conductors from crossing currents.
The insulator 13 provides a means for completely insulating the internal components of the connector 10 and the mandrel shell 7. It also provides high compression strength so as to withstand maximum working pressure, and a extremely high dielectric strength to minimize possible current leakage.
The insulator 13 is a universal component designed to fit the connector 10 and the mandrel shell 7. A secondary sealing means 31 illustrated as an O-ring may be disposed on its exterior surface to provide a secondary seal. The lower end of its outer surface is designed specifically to provide a maximum bonding surface for the potting material which is formed as a thin sleeve or film between the insulator 13 and the shell 7, making possible operation under maximim working pressures. The three conductors 12, which are axially disposed within longitudinal holes within this unit, have their own sealing means which seal on the insulator 13. The inside diameters 33 (one shown) of the longitudinal holes within which the conductors 12 are disposed run parallel to each other and have a special finish contained therein to ensure a 100% sealing surface for the conductors. The outside diameter 34 of the insulator 13 defines a vertical taper which allows a special potted dielectric material to form a seal between the inside diameter of the shell 17 and the insulator 13. The inside diameters 33 of the longitudinal holes of the insulator are tapered vertically to allow the special potted dielectric material 18 to form a seal around the conductor 12 and within such inside diameters. After complete assembly of the connector 10 and mandrel 7, a special potted dielectric material is injected from both ends, thus sealing and bonding the insulator 13 in its fixed position and eliminating any possible fluid leakage.
The clamp connection 14 serves as a universal means for tightly clamping the preferred cable 19 to the connector 10. It is preferably constructed of a rigid steel and may be adapted to fit any required cable size. The clamp 14 has a two-piece configuration and is adapted such that four screws 15 will secure if together. A cable locking means 41 is machined within the inside diameter of the lower end of the clamp, and is designed to accomodate to the armor of the preferred cable 19. Once installed it is virtually impossible to dislodge the cable 19 from the connector 10 without first removing the four screws 15.
The clamp connection 14 is secured to the connector shell 7 by a groove locking means 42. The connector shell 17 details a groove design which operates in the same manner as the cable locking means. A lug 43 mates with the groove to ensure proper location of the clamp connection 14 from the connector shell 17. Injection ports 44, located 180° apart, are used to inject special dielectric potting material into the completed assembly. This special dielectric potting material forms a body 18 which completely seals all internal gaps designed into the clamp connection for extra protection in critical areas, thus making it one integral unit upon installation. The clamp connection 14 acts to protect the feed-thru means from hostile environments, moisture, constant high annulus pressures and from any well fluids that may attack the feed-thru system.
The connector shell 17 functions primarily as a casing or shell to protect the high voltage and high current internal components from being attacked by any type of hostile environment, constant annulus pressures and well fluids. A groove locking means 51 disposed upon the lower end of the exterior surface of the connector shell 17 is designed to mate with the clamp connection 14. The lug 43 incorporated on the clamp connection 14 mates precisely with the groove 51, thereby making it virtually impossible to dislodge the clamp connection from the connector shell.
The inside diameter of the connector shell 17 details a shoulder 52 which acts as a stop means for the insulator 13. This shoulder gives the insulator a maximum bearing surface upon which to rest, thereby securing it in place and protecting it from any annulus pressures which could possibly cause failure. The inside diameter of the connector sleeve 17 is provided with a special surface finish to insure a positive seal and bond for the special potting dielectric material 18 and the insulator 13. With reference to FIGS. 1 and 2, it is to be noted that the insulator support member 13 of FIG. 1 and the insulator support member 72 of FIG. 2, may be identical and interchangeable. Also, the dielectric potting material 18 shown below and above the insulator member 13 in FIG. 1, may be the same and serve the same function as the unnumbered materials shown in FIG. 2.
As shown in FIGS. 1 and 2, the lower ends of the structures 7 and 10 are seen to be the high pressure ends which are designed to withstand well pressures of the upper end of mandrel 10 and will normally encounter atmoshperic pressures only. When these structures 7 and 10 are utilized in tandem, as shown in FIGS. 4-9, the sealing effectiveness is thereby greatly increased against fluid pressure impressed at the lower end of the structure 10.
The high pressure resistant structure shown as assembly 10 in FIG. 1 is the same as connectors 112 in FIG. 4, connectors 132 in FIG. 6, connectors 142 in FIG. 7, connectors 155 in FIG. 8, and the unnumbered connections in FIGS. 5 and 9. Likewise, the central mandrel sleeve shown unnumbered and as 7, 113, 133 and 143 in FIGS. 4-9, are the same except for individual length. The upper connector as shown in FIGS. 4-9, such as the upper connector 112 in FIG. 4, are making connection at atmospheric pressure and are not usually needed for pressure resistance since no leakage from the wellhead is previously assured by the series connection of connectors 112 and 113.
Located at the male end (top) of the connector shell 17 is and O-ring groove 53 for use in sealing the mandrel shell 7 to the connector shell 17 when mated for operation. The male end of the connector shell 17 has a specially designed axial alignment groove (not shown) disposed therein to ensure that both the upper connector and the lower connector are in appropriate registry.
The coupling nut 16 appropriately fits over the connector shell 17 at the male end. A groove 55 is disposed on the connector shell 17, and is used to secure the coupling nut 16 with music wire by supplying the wire through the coupling nut 16 into the groove 55, thus allowing the coupling nut to rotate on the connector shell 17 for fast and easy connection and disconnection.
The coupling nut is preferably constructed of a rigid steel. The exterior 61 of the coupling nut 16 is preferably diamond knurled for fast make-up. A groove 62 located on the interior of the coupling nut 16 is specifically designed in reference to the connector shell 17 for easy access to the replaceable seal on the shell. Further, a hole 63 is appropriately disposed on the outside diameter of the coupling nut 16 for feeding in music wire to secure it in place, thereby making it virtually impossible to remove, but ensuring full and complete rotation of the piece.
FIG. 2 details an electric feed-thru mandrel assembly which consists of three two-piece conductors 71 (one shown), one or more insulators 72, a shell 73, special potted dielectric material 74, and a plurality of sealing mechanisms. Its primary function is to isolate constant high annulus pressures and hostile environments from the atmosphere while preventing any moisture or corrosive well fluids from attacking its internal components.
The mandrel assembly of FIG. 2 is preferably fabricated in two basic lengths, depending on the configuration of the wellhead. The short, or mini, mandrel is readily applicable in relatively simple operations. The longer mandrel is used in more complex well completions and can be readily adapted to accommodate specific requirements. Herein, the conductor 71 functions as a means of conducting extremely high voltage and high current from a surface power source to various electrical pumping systems located downhole.
The mandrel shell 7 is preferably constructed of a rigid steel material and is designed with two sealing mechanisms appropriately located on the upper external portion of the shell. In operation, the mandrel shell is axially threaded into the hanger portion of the wellhead with a special thread to withstand any type of force that might occur.
The main function of the insulator 72 is to ensure a maximum compression strength of 50,000 psi, for example, while holding a dielectric strength of no more than 20 micro-amps. It also acts to insulate the conductors 71 from any crossing currents and to ensure a back stop for a flexible potted dielectric material 74 which is injected into both ends of the insulator 72. The special potted dielectric material 74 actually seeps into specially designed areas of the insulator and act as a secondary sealing agent while bonding the insulator into its fixed position.
The mandrel conductors 71 have a two-piece configuration and run parallel to each other throughout the mandrel. As can be seen more clearly in FIG. 3, the lower conductors 81 can be adapted to fit any mandrel length while the upper conductors 82 can be universally used in the short mandrel, the long mandrel, or the connector. A sealing means 83 is incorporated on the upper conductor 82 and functions as a permanent fixture when installed into the insulator. Female threads 84 are disposed on the upper conductor 82 and are designed to accept the male threads 85 on a lower conductor 81, thus making the conductor means a universal component by simply lengthening the lower conductor 81 for various mandrel lengths.
In operation, upon installation of the three two-piece conductors, a special potted dielectric material is injected into the mandrel. This material actually forms a permanent seal around each conductor and bonds them in their fixed positions, allowing no room for vertical movement. It also fills all special design areas on the exterior surface of the conductor to ensure stability and proper conductivity.
The conductors 71 are preferably made of a solid copper material and perform the task of conducting high voltage and high current from a power source through a wellhead into a high pressure zone within the well bore of a well. In prior art disclosures, high pressure and hostile environments cause the conductors to become dislodged, thus leaving room for short circuiting and well blow-outs.
The insulator 72 of the mandrel asembly 7 is a universal component constructed to be accommodated within the mandrel shell or connector shell. Its basic function is primarily to serve as an insulation means to insulate critical areas of the conductors from crossing currents, to accomplish a dielectric strength of less than 20 micro-amps, and to ensure a maximum compression strength of 30,000 psi, for example.
Unlike prior art feed-thru systems, the presently disclosed invention is disposed with multiple sealing means which in fact perform secondary sealing operations. For example, the outside diameter 91 of the insulator 72 for the mandrel assembly 7 have optional tapers (not shown) which allow epoxy material, when injected, form a thin sleeve or film and thereby to bond the insulators to the shell for stability. Further, it incorporates a seal around these critical areas. The O-ring groove 92 ensures a back-up sealing means for use in holding maximum pressures upon expansion and contraction of the flexible epoxy material for testing and field use. The inside diameter 93 (one shown) also have tapers incorporated within for the potting material to form a thin film or sleeve and thereby to bond the conductors upon the injection process, and to seal them completely from moisture and the escape of corrosive gases. The insulator 72 has three inside diameters 93 which are precisely spaced parallel to each other to accommodate the conductor 74 which run the total length of the component. Within the inside diameters 93 is a back stop or bearing shoulder surface 94 facing the high pressure end as shown which acts to ensure against possible movement or blow-out of the conductors.
The mandrel shell or sleeve 73, identified in FIG. 2 functions as an embodiment for the conductors 71, insulators 72, and special dielectric material 74. Its main purpose is to protect all internal components from high annulus pressures, corrosive gases, high temperatures, deteriorating well fluids, and possible intrusion of moisture which could possibly cause electrical or mechanical failure. The mandrel shown may be adapted quickly and easily to any preferred length depending upon the wellhead configuration. In prior art feed-thru devices, particularly Cugini, et al, the mandrel shell does not lend itself to variations in length. Further, they are molded as one complete unit and the entire unit must be replaced when such means wears out or failure occurs.
The mandrel shell 7 of the present disclosure is disposed with threads 101 located at both ends so as to receive coupling nuts thereupon. Upon proper torquing of the coupling nuts 16, the conductors 71 are fully engaged into the connector 10, thereby ensuring 100% conductivity.
The inside diameter 102 of the mandrel shell 7 is disposed with specially designed grooves. The special potted dielectric material 74 engages these grooves and thereby incorporates a rigid bond throughout the interior of the mandrel shell upon completion of the injection process. Located on the middle of the exterior surface of the mandrel shell 7 are male threads 103 which are utilized to secure the complete electric feed-thru means assembly. When fully engaged into the wellhead hanger means two seals 104 are engaged to ensure absolutely no leakage.
FIG. 4 details a partial cross-sectional view of one embodiment of the invention. This flanged adaption comprises a dual tubing hanger 111, upper and lower connectors 112, a mandrel 113, an adaptor flange 114, a heavy duty knock-off cap 115, special O-ring sealing means. The upper portion 116 of the adaptor flange is threaded to accommodate a heavy duty knock-off cap 115 which basically functions to secure the dual tubing hanger into its position. The dual tubing hanger 111 rests on the taper located on the inner circumferential surface of the adaptor flange 114 which activates a positive o-ring seal in this pressure zone. The o-rings eliminate any possibility of pressure, gas or fluids escaping into the atmosphere.
Production tubing 118 is threaded into the lower end of the dual tubing hanger 111. It functions as a means of transporting fluids and gases through the annulus of the inner string of casing to the desired depth for production operations. The upper connection, or production nipple 119, is also threaded into the dual tubing hanger 111. Its primary function is for production outside of the well where threaded valves may be attached.
The electric feed-thru assembly, located adjacent to the production tubing 120, is also threaded into the dual tubing hanger 111. The mandrel shell (see FIG. 2) has male threads on the external portion to accommodate within the dual tubing hanger 111. The two o-rings are activated when the mandrel is threaded into the dual tubing hanger 111. The inner circumference 121 of the adaptor flange 114 as an internal taper to support the dual tubing hanger 111 on its completion as shown. It also functions as a means of incorporating a metal to metal seal between the outer circumference of the dual tubing hanger 111 and the inner circumference of the adaptor flange 114, thereby eliminating any possible pressure, gas or well fluids from escaping into the atmosphere.
Unlike prior art feed-thru assemblies, this electric feed-thru adaptor assembly provides a simple and unique method for adapting a high voltage and high current electrical conduit into a well assembly when completion needs require electrically driven submersible pumps, subsurface monitoring equipment, and similar devices. During landing and completion operations, the dual tubing hanger 111, feed-thru mandrel 113, and production string 118 may be run through a blow-out preventer and landed in place while maintaining complete control over the well. Further, it is well suited for use where standard tubing hangers can not be used.
FIG. 5 depicts the embodiment of FIG. 4 installed on a tubing head with a threaded valve connection to a production nipple 129.
Another embodiment of this invention is delineated in Fig. 6, and may be adapted to accommodate any existing casing. This embodiment details a dual tubing hanger 131, upper and lower connectors 132, electric feed-thru mandrel 133, and special o-ring sealing devices. These components are essentially universal since they can be accommodated within the flanged, as well as the threaded adaptations--the essential difference being the connection on the bottom. Threaded connections are furnished with a tubing head for applications where only casing is existing. Two outlets 134 are basically used for circulation and pressure monitoring in the annulus of the inner string of casing, or production casing. This assembly provides a simple and unique method for adapting high voltage and high current electrical conduits into a wellhead assembly when completion needs require the presence of electrically driven submersible pumps, subsurface monitoring equipment, and similar devices.
FIG. 7 illustrates a cross-sectional view of yet another embodiment of the present invention wherein a tubing head 144 with a clamp connection 145 at the lower end may be adapted to fit any clamp connection. Its basic components are a dual tubing hanger 141, upper and lower connectors 142 and electrical feed-thru mandrel 143, and special o-ring sealing devices. This assembly also provides a simple and unique method for adapting high voltage and high current electrical conduits into a wellhead assembly when required for completion.
Still another embodiment of this invention is depicted in FIG. 8. It comprises a toadstool adaptor 151, a tubing head adaptor 152, an adjustable hold down flange 153, an electric feed-thru long mandrel 154, an upper connector 155, a lower connector 156, a dual tubing hanger 157, lock screws 158, a seal hub 159, and special o-ring sealing devices. The casing 160 is suspended and packed into an existing wellhead (not shown).
The inner circumference of the tubing head adaptor 152 is specially designed to maintain the tubing head 157 in its position while accomplishing a premium seal and maintaining complete suspension of the production tubing 161 and electric feed-thru assembly. During landing operations, the dual tubing hanger 157 is lowered into the bowl of the tubing head adaptor 152. It sits on a 45° shoulder 164 thereby allowing the production tubing 161 and the electric flow-thru assembly to be suspended. Locking screws 158 are then horizontally threaded in through the top flange of the inner circumference of the tubing head adaptor 152. These screws have tapers on their ends which ride on the taper of the dual tubing hanger 157, thereby permitting no movement once set into position.
The outer circumference of the dual tubing hanger 157 has two o-rings 163 which seal on the inner circumference of the tubing head adaptor 152 so as to prevent the escape of pressure, gas, or well fluids. A special taper on the top of tubing hanger 157 allows the locking screws 158 to secure it into its operating position. Two ports located within the dual tubing hanger 157 have a precise facing to accommodate the production tubing 161 and the electric feed-thru connector assembly. Tubing hanger 157 also has a special pocket designed within it to accommodate the seal sub 159 which functions as an external extension linking the dual tubing hanger 157 to the toadstool adaptor 151. It has o-ring seals 164 at each end which fit into specially designed seal pockets. These o-rings 164 make it possible to perform a test on the upper ring gaskets 165 before the valves are attached to the toadstool flange 166. The production tubing 161 is threaded into the upstream end of the dual tubing hanger 167 and is suspended downhole to a desired depth for production purposes. Female threads located on the downstream end of the dual tubing hanger 157, just beneath the seal sub 159, are prepared to accept the tubing joints for landing the dual tubing hanger 157 inside the tubing head adaptor 152.
Located adjacent to the production tubing 161 is an electric feed-thru connector assembly which consists of a long mandrel 154, an upper connector 155, a lower connector 156, and special o-ring sealing means. The long mandrel 154 is equipped with two sets of o-rings 167. The purpose of this double sealing means is to seal two components, the dual tubing hanger 157 and the toadstool adaptor 151 for testing of the upper ring gasket 165, and to eliminate any annulus pressure, gas, or well fluids from escaping into the atmosphere. During landing and completion operations, the long mandrel 154, lower connector 156 (with cable), dual tubing hanger 157 and production tubing 161 may be run through a blow-out preventer, while maintaining complete control of the well.
The toadstool adaptor 151 is preferably constructed of a rigid material and functions primarily as a cap for this particular embodiment. It is disposed with a ring groove 165 and special seal pockets to perform premium sealing tasks. The toadstool flange 166 is constructed to accommodate any desired connection.
The adjustable hold-down flange 153 fits around the lower exterior circumference of the toadstool adaptor 151 and is adjustable to facilitate alignment. Once the toadstool adaptor 151 is installed, the adjustable hold-down flange 153 is lowered to fit on the mating taper 168, thus making it possible to align the bolt pattern of the tubing head adaptor 152 with the bolt pattern of the adjustable hold-down flange 153 before tightening. Unlike prior art electric feed-thru assemblies, this embodiment provides a simple and unique method for adapting a high voltage and high current electric conduit through a preferred wellhead arrangement when required for completion operations.
FIG. 9 details a partial cross-sectional view of another embodiment of the present invention wherein an electric feed-thru connector assembly is installed in a unitized wellhead. The components utilized herein are similar to those mentioned in FIG. 8--the obvious differences being the clamp connection 171, the sealing means on the dual tubing hanger 172, and the toadstool adaptor 173. This wellhead is useful to suspend various casing programs in the offshore industry. In some instances, completion will require electrically driven submersible pumps, subsurface monitoring equipment, and similar devices for production purposes. In this instance, the electric conduit must be installed from the outside of the wellhead, through the wellhead to the desired location. It is critical that no annulus pressures, gases or well fluids be allowed to escape through the wellhead into the atmosphere, or attack the feed-thru means. This unitized embodiment completely deletes any possible leakage of internal or external components, and further, is equipped with a sanitary feed-thru device capable of conducting high voltage and high current through a completion with constant high annulus pressures, corrosive gases and deteriorating well fluids.
From the foregoing it can be seen that this invention is one well-adapted to attain all of the ends and objects hereinabove set forth, together with other advantages which are obvious and which are inherent thereto.
It is to be understood that certain features and subcombination are of utility and may be employed with reference to other features and subcombinations. This is contemplated by and is within the scope of the claims.
As many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matters herein set forth or shown in the accompanying drawings are to be interpreted as illustrative and not in a limiting sense. | Wellhead electrical connection apparatus for feeding electricity into a well under fluid pressure, includes a mandrel sleeve having an internal sleeve shoulder formed to face high pressure end of sleeve. A performed rigid high mechanical strength dielectric insulator support having an external insulator shoulder is installed within the sleeve with the insulator shoulder in abutment with the internal shoulder of sleeve. Insulator support means is mounted and sealed in physically bonded relation within the interior of the sleeve by means of dielectric potting material disposed as an insulator film or sleeve in surface areas between insulator support and sleeve. Insulator support has a plurality of holes extending in parallel and laterally spaced apart relation through the insulator with each hole having an internal hole shoulder formed to face high pressure end of sleeve. An elongated rigid electrical conductor member having an external conductor shoulder and electrical connectors on each end is installed within each hole with conductor shoulder in abutment with hole shoulder. Each electrical conductor is mounted and sealed in physically bonded relation with interior of hole by a dielectric potting material disposed as a conductor sleeve or film in surface areas between conductor member and side of hole. | 7 |
BACKGROUND
[0001] Computer systems consist of one or more processors, each of which executes a collection of machine instructions. The processors may be physical components implemented in semiconductor chips or may be virtual, implemented by operations on one or more physical processors.
[0002] Some of the instructions executed by a processor may be performed entirely within the processor. Though, other instructions may entail interaction between the processor and other components of the computer system. Frequently, computer systems will contain separate devices with which the processors will interact as the computer operates. For example, memory operations may entail interactions with a hard disk and network communication operations may entail interaction with a network interface card.
[0003] To facilitate these interactions, a computer system may have a bus that supports communication between a processor and other devices. One common type of bus is known as the PCI (Peripheral Component Interconnect) bus. In addition to allowing data to be exchanged, some buses support messages that can signal an interrupt. A device may use such a message to signal to a processor that it has completed an operation requested by the processor or that it has otherwise performed some action or detected a condition that requires service from a processor. In this way, a processor can assign an operation to a device and perform other functions while the device is performing the operation.
[0004] Once the device finishes the operation, a processor is notified by the interrupt and may perform completion processing on the operation. The nature of completion processing may vary based on the device or operation performed. However, examples of completion processing include reading data from the device or delivering retrieved data to an application that requested the data.
[0005] Buses implemented according to the PCI, PCI-X, or PCI Express standard support the message signaled interrupt (MSI) and the message signaled interrupt extended (MSI-X) protocols. Devices that use these protocols may request service by writing a system specified data value to the system specified address using a PCI memory write transaction. System software initializes the message address and message data during device configuration. The message address encodes information on the target processors and delivery mode. The device performs a memory write for a pre-configured MSI message to interrupt the processor.
SUMMARY OF INVENTION
[0006] Interrupt servicing and overall computer system operation may be improved by appropriately defining and selecting messages for use by devices to interrupt processors in a multi-processor system. The messages may be defined using groups of processors based on proximity of the processors within each group. Groups may be distinct sets of processors or may overlap or may be contained within other groups. A desirable approach to interrupt servicing may be achieved by defining messages for each device such that the device has messages targeting processors distributed across the processor groups. If the most efficient processor is not a target of a message for a device, a message targeting a processor within the same group as the most efficient processor or a processor in a group in close proximity to the group containing the most efficient processor may be selected. By defining messages with processors distributed across proximity-based groups, the likelihood is increased that a device will have a message targeting the most efficient processor or a processor in close proximity to the most efficient processor.
[0007] Appropriate definition of messages may also improve overall efficiency of computer system operation. By defining messages that contain target processors distributed across the processors within each group, processing load is more efficiently distributed.
[0008] Accordingly, in one aspect, the invention relates to a method of operating a computer to define messages for the devices for use in issuing interrupts. The method may result in maximizing a number of groups within a plurality of proximity-based processor groups targeted by messages created for each device of the plurality of devices. The method may minimize a number of messages targeting each group.
[0009] In another aspect, the invention relates to a computer with a plurality of processors coupled to a plurality of devices over a bus. The computer may be programmed to define bus messages based on an ordering of processor groups and processors within the groups. Using this ordering, a desired distribution of messages across processors and processor groups may be achieved.
[0010] In a further aspect, the invention relates to a method of operating a computer to store messages in each of the devices for use in interrupting a targeted processor, send a request to a device to perform a function, and suggest which interrupt message the device should use upon completion of the function. The suggested message is selected by identifying an efficient processor to service the specific device interrupt and then selecting as the suggested message one which targets a processor based on its proximity to the efficient processor.
[0011] The foregoing is a non-limiting summary of the invention, which is defined by the attached claims.
BRIEF DESCRIPTION OF DRAWINGS
[0012] The accompanying drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures is represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. In the drawings:
[0013] FIG. 1 is sketch illustrating a high-level overview of a prior-art multi-processor computer system;
[0014] FIG. 2 is a block diagram showing the processing of an input/output (I/O) operation in a prior-art multi-processor computer system;
[0015] FIG. 3 is a flowchart of a process in which interrupt messages are defined and assigned to devices according to embodiments of the invention; and
[0016] FIG. 4 is a flowchart of a process of assigning an operation to a device according to embodiments of the invention.
DETAILED DESCRIPTION
[0017] The inventors have appreciated that for some interrupts in a multi-processor computer, such as those signaling completion of an input/output (I/O) operation assigned to a device, the efficiency of processing the interrupt may vary from processor to processor. Further, the efficiency with which each processor performs an operation may be proximity-based. Accordingly, in embodiments of the inventions, processors may be grouped based on proximity for the purpose of defining interrupt messages. A proximity-based grouping may consist of processors that have a close physical proximity to other processors in that grouping, and/or that have a proximity which facilitates efficient communication among the grouped processors.
[0018] For example, in completion processing performed following an I/O operation, a processor that initiated the I/O operation may be able to more efficiently access information or instructions necessary to complete the processing. Such a situation can arise because the processor initiating an operation may have information or instructions used in completing the I/O operation or subsequent related processing stored in a local cache or other memory locations to which that processor has preferential access. As a result, that processor may be capable of more efficiently performing processing that completes the operation or related processing than other processors.
[0019] For another processor to perform the same operation, there may be a loss of efficiency associated with processor-to-processor communication as the processor that initiated the I/O operation supplies information to the processor performing the completion processing. This loss of efficiency may be less for other processors within the same processor group as the processor initiating the interrupt because processor-to-processor communications for processors within proximity-based groups may be more efficient than processor-to-processor communications between processors in different groups. Moreover, the loss of efficiency may be based on proximity between the groups. As an example, processors implemented as cores physically in the same semiconductor chip may communicate using on-chip circuitry, which is likely faster than chip-to-chip communication circuitry. Accordingly, the cores on a single semiconductor chip may form a proximity-based group of processors. Likewise, processors in chips mounted on the same printed circuit board (PCB) likely can communicate more efficiently than processors on different PCBs that communicate across a bus.
[0020] Differences in efficiency based on proximity is not a phenomenon limited to physical processors. In a system with virtual processors, virtual processors hosted on the same physical processor may perform processor-to-processor interactions more efficiently than virtual processors hosted on different physical processors. Accordingly, the processors in a multi-processor computer system may form groups, and processors in some groups may perform certain operations more efficiently than others.
[0021] The inventors have appreciated that proximity-based groupings can be used to increase efficiency in computers signaling interrupts based on bus messages, such as occurs in computers operating according to the MSI-X protocol over a PCI bus. Each device in such a system that issues interrupts may have a limited number of messages available and therefore be limited in the number of processors that can be targeted by an interrupt. As a result, a device may not have a message available to target the most efficient processor to perform processing triggered by the interrupt. However, by appropriately defining messages for the devices, the likelihood can be increased that the device will have a message that targets a processor in close proximity to the most efficient processor.
[0022] With messages defined in this way, upon completion of an operation, a device may issue an interrupt to a processor using a message that targets an efficient processor. If the most efficient processor is not among the target processors of messages defined for the device, another processor may be selected as the target processor from the same group as the most efficient processor or in a group in close proximity to the group containing the most efficient processor. Thus, by appropriately defining messages for the device to use, the average processing per interrupt is reduced.
[0023] The inventors have appreciated that distributing messages evenly across processers within a proximity-based processor group can further contribute to an increase in computing efficiency by avoiding overloading any particular processor. For example, if multiple devices are connected to the computer, an unfavorable (inefficient) assignment of messages could result in messages simultaneously targeting the same processer. The invention reduces the likelihood that an unbalanced queue would accumulate at any one processor. Even if an imbalance is not so great as to cause a large queue, constant interrupts of a processor may preclude it from performing other functions. Accordingly, in some embodiments, definition of messages may also distribute the processing load evenly across all processors in each group and throughout the computer system. Though in other systems, efficiency may be increased by concentrating interrupts in one or a few processors and embodiments may be constructed that concentrate messages on one or a few processors.
[0024] FIG. 1 depicts a computer system 100 in which embodiments of the invention may be used. System 100 consists of multiple processors, both physical and virtual. In the example of FIG. 1 , processors 122 1 , . . . , 122 4 , 124 1 , . . . , 124 4 , and 126 1 , . . . , 126 4 are shown. Each of the processors may be implemented on one or more semiconductor chips, with each semiconductor chip supporting one or more processors. System 100 is shown with semiconductor chips, 120 1 , 120 2 , and 120 3 . Twelve processors and three semiconductor chips are shown for simplicity, but the number of processors and semiconductor chips is not a limitation on the invention and any suitable number may be used.
[0025] Each of the semiconductor chips may be implemented as is known in the art. In the example of FIG. 1 , semiconductor chips 120 1 and 120 2 are quad-core semiconductor chips, with each core being usable as a processor. Semiconductor chip 120 3 is a single core chip. Such semiconductor chips are commercially available from sources such as Intel Corporation.
[0026] FIG. 1 illustrates that each processor need not correspond to separate physical circuitry. One or more of the processors may be virtual processors. In the example of FIG. 1 , processors 126 1 . . . 126 3 are implemented as virtual processors. Virtual processors 126 1 . . . 126 3 may be implemented using known virtualization software executing within an operating system of computer 100 . However, in embodiments of the invention, semiconductor chips and either physical or virtual processors may be implemented in any suitable way or may be obtained from any suitable source.
[0027] Chips 120 1 and 120 2 are mounted on printed circuit board (PCB) 110 1 , and chip 120 3 is mounted on PCB 110 2 . Though two PCBs are shown, the number of PCBs is not a limitation of the invention and any suitable number may be used.
[0028] Components on different PCBs or on different parts of the computer system 100 may communicate over one or more buses. Processors may communicate over one bus, while I/O devices may communicate over another. In the example of FIG. 1 , only a single bus is illustrated for simplicity. In such an embodiment, the processors on chip 120 1 may communicate with the processors on chip 120 3 using bus 130 . Bus 130 may be a standardized bus as is known in the art. For example, bus 130 may be a PCI bus. However, the construction and protocol of bus 130 are not critical to the invention and any suitable bus or buses may be used in embodiments of the invention.
[0029] In operation, the processors may execute software such as application software or operating system software that performs functions based on the desired functionality of computer 100 . Some functions may involve operations performed solely within the processors. Other functions may involve operations assigned to devices 140 1 . . . 140 3 . Processors in FIG. 1 may communicate with devices 140 1 , 140 2 , 140 3 over bus 130 , including assigning operations to the devices 140 1 . . . 140 3 .
[0030] Each device may process an operation assigned to it as a result of communication with one or more of the processors. In embodiments of the invention, the devices may perform I/O operations or any other suitable type of operation. Such devices may include hard disks, sound and video capture cards, network cards, or any other suitable device. Three devices are shown in system 100 for simplicity, but the number of devices is not a limitation on the invention and any suitable number may be used.
[0031] From time to time, a device may issue an interrupt to be serviced by a processor. Such interrupts may include a request for a processor to perform completion processing. In the embodiment illustrated, the devices use bus messages to signal interrupts to processors. Each device has a fixed number of messages available with which to transmit an interrupt to a targeted processor. For example, device 140 1 has three messages 142 1 , 142 2 , 142 3 , which may target any three processors in the computer system 100 . In embodiments of the invention, such messages may be formatted according to a suitable protocol for the bus over which they are transmitted. For example, PCI devices may utilize messages which operate according to the MSI-X protocol. Although FIG. 1 limits devices 140 1 , 140 2 , and 140 3 to three, two, and three messages respectively, the number of messages available to a device is not a limitation of the invention and any appropriate number may be used.
[0032] In operation, each of the messages, 142 1 . . . 142 3 , 144 1 , 144 2 , 146 1 . . . 146 3 , may be defined by operating system software executing on one or more of the processors. However, in accordance with embodiments of the invention, the messages may be defined in any suitable way. In the example illustrated, each of the messages is addressed to target an interrupt handler in a physical or virtual processor within computer system 100 . The message is also formatted to indicate to that interrupt handler that an interrupt represented by the message signals that a specific device has completed an assigned operation.
[0033] The defined messages may be used as part of a process of operating computer system 100 that includes assigning operations to devices 140 1 . . . 140 3 . For example, FIG. 2 is a block diagram illustrating the initiation and completion of an input/output (I/O) operation in a prior-art multi-processor computer system 100 . This I/O operation process 200 consists of subprocess 210 , which comprises initial actions taken by a processor. Namely, in block 212 , a processor receives a request for an I/O operation from an application program or other software being executed. In block 214 , that processor assigns the I/O operation to a particular device and then, at block 216 , returns to performing other tasks.
[0034] Meanwhile, the device performs the I/O operation assigned to it at block 220 . In block 230 , the device informs the computer that the I/O operation is complete by generating an interrupt using a message. The message sent may be selected from a set of predefined messages for the device, such as messages 142 1 . . . 142 3 , 144 1 , 144 2 , 146 1 . . . 146 3 . The receiving processor (not necessarily the same processor that initiated the operation in block 210 ) then processes the interrupt at block 240 , thereby completing the I/O operation. Such completion processing may be as known in the art. However, in embodiments of the invention, any suitable completion processing may be performed.
[0035] The inventors have appreciated that the efficiency of assigning an operation to a device may be improved by proper definition of messages used to signal completion of an assigned operation. Some processors may more efficiently service some interrupts than other processors, and by defining messages to increase the likelihood that an efficient processor is a target of a predefined message, overall efficiency may be improved. One reason for variations from processor to processor in the efficiency of performing completion processing is that processors implemented in the same chip may communicate using on-chip circuitry, which is likely faster than chip-to-chip circuitry that may be used to communicate between processors on different chips on the same PCB. In contrast, processor-to-processor communication over a bus connecting the PCBs is likely slower than communication between processors on the same PCB or on the same chip. Because completion processing may require communication between processors, the efficiency with which processor-to-processor communication is performed may impact the overall efficiency with which completion processing is performed.
[0036] For example, the efficiency with which an I/O operation is performed may be improved if the initiating processor and the completion processor are either the same or at least in close physical proximity to one another such that processor-to-processor communication is efficient. The same processor that initiated an operation may have favorable access to information or instructions needed to complete the operation. As a result, that processor may perform the completion processing more efficiently than other processors. Alternatively, if the same initiating processor is not available for completion, a processor grouped in close physical proximity of the initiating processor may be a more efficient choice than a processor located outside of that grouping.
[0037] In embodiments of the invention, processors may be designated as being part of a particular proximity-based group so that all processors have a close physical proximity to other processors in their group, and/or have a proximity that facilitates efficient communication among the grouped processors. Groups may consist of distinct sets of processors or may overlap and thus result in multiple groups containing the same processor or processors. The defined processor groups may then be used in establishing messages for use by devices, such as devices 140 1 . . . 140 3 , to use when signaling interrupts for completion processing of an assigned operation. Target processors in a set of messages for each device may be defined in a way that increases the likelihood that a processor that may efficiently perform completion processing is a target of a message defined for that device.
[0038] In a system as illustrated in FIG. 1 , for example, an embodiment of the invention may designate that those processors lying on a single semiconductor chip 120 1 , 120 2 , or 120 3 form a proximity-based processor group. Chips 120 1 and 120 2 lie on printed circuit board (PCB) 110 1 , and chip 120 3 lies on PCB 110 2 . Because processors in chips mounted on the same PCB are likely to communicate more efficiently than processors on different PCBs that communicate through a bus, an embodiment of the invention may describe the processors on PCB 110 1 as being in one group and those on PCB 110 2 in a second group. Alternatively, cores within one semiconductor chip may be in closer proximity to each other than they are to cores in a separate semiconductor chip. In the example of FIG. 1 , cores 122 1 . . . 122 4 may be regarded to form one group. Cores 124 1 . . . 124 4 within semiconductor chip 120 2 may be regarded as a second group. Both physical and virtual processors within semiconductor chip 120 3 may be regarded as a third proximity-based group. Furthermore, there is nothing preventing multiple proximity group definitions, such as those given above, from being used in a single implementation of this invention.
[0039] To facilitate efficiency improvements arising from the utilization of such proximity-based processor groupings, an example embodiment of the invention shown in FIG. 3 uses a process by which interrupt messages are defined and assigned to devices to increase the likelihood that a device will have available a message that can target an efficient processor. For example, in FIG. 1 , device 140 1 has three messages 142 1 , 142 2 , 142 3 which may target any three processors in the computer system 100 . In a prior-art system, these messages could potentially be targeted to a single processor or perhaps to processors on the same chip. Instead, the process illustrated in the embodiment in FIG. 3 would ensure an even distribution of these messages across proximity-based processor groups, with each message targeting a processor on a different chip.
[0040] As a specific example, each of the three message 142 1 . . . 142 3 that device 140 1 is capable of storing may target a processor within a different one of the proximity-based groups created through the use of different semiconductor chips 120 1 . . . 120 3 . As a specific example, message 142 1 may target core 122 1 , message 142 2 may target core 124 1 and message 142 3 may target virtual processor 126 1 .
[0041] Each of the three messages 146 1 , 146 2 , 146 3 available for use by device 140 3 may likewise target a processor in each of the three proximity-based groups that exist in computer system 100 ( FIG. 1 ). The messages in device 140 3 could target the same three processors that are targeted by the messages in device 140 1 . However, the inventors have appreciated that efficiency of operation of computer system 100 may also be improved if message targets are distributed across all of the processors, such that no processor is interrupted so frequently that other operations are not performed efficiently by that processor. Accordingly, in some embodiments, it may be desirable for the messages 146 1 . . . 146 3 created for device 140 3 to target different processors than the messages 142 1 . . . 142 3 created for device 140 1 . For example, while message 142 1 may target core 122 1 , message 146 1 may target core 122 3 . Message 142 2 may target core 124 1 , and message 146 2 may target core 124 2 . Likewise, message 142 3 may target virtual processor 126 1 , and message 146 3 may target virtual processor 126 3 . This pattern of distributing messages across the processors may be used in assigning messages for all devices. For example, message 144 1 for device 140 2 may target core 122 2 and message 144 2 may target virtual processor 126 2 . In this way, the messages defined for any one of the devices may be distributed across the proximity-based groups, and the messages collectively defined for all of the devices may be distributed across the processors in system 100 . In other embodiments, it may be more efficient for all devices targeting processors in a given proximity-based group to have their messages go to the same processor or a subset of the total set of processors in the group.
[0042] FIG. 3 illustrates a process by which such a distribution may be achieved in some embodiments of the invention. The process of FIG. 3 may be performed by the operating system of a computer or by any other suitable component. The process may be performed when the computer begins operation or when a device is detected during operation. Specifically, process 300 may start at block 310 with a computer system 100 discovering what devices are connected to it.
[0043] Processing at block 316 establishes the maximum number, N, of proximity-based processor groupings that are in the system and the maximum number M i of processors in group i, where i belongs to the set {1, 2 . . . N}. Processor groups may be defined based on the architecture of the computer system 100 on which the process 300 is being executed. Any suitable definition of proximity may be used for defining groups. For example, in the embodiment of FIG. 1 , processors were segregated into groups based on the specific semiconductor chip on which they were implemented. In other embodiments, the groups may be defined based on the specific PCB in which the processors are physically implemented. In other instances, a measure of time required for processor-to-processor communication may be used to define processors within the same proximity based groups. In other embodiments, combinations of these factors may be used to define groups, or groups may be nested to form a hierarchy. For example, a socket representing a physical chip may have multiple cores, each of which may in turn have multiple virtual processors. These processors could be grouped or nested at any level. While the embodiment of FIG. 3 only operates on a single level of groups, other embodiments may iterate through each level of the hierarchy to select a message target to assign. Regardless of how the groups are defined, processing at block 316 determines the number of groups and the number of processors within each group.
[0044] The process of FIG. 3 is shown to be an iterative process. The process iterates over each device for which messages are to be defined and iterates over each message to be defined for each device. In the embodiment illustrated, state information is maintained between iterations. In the example of FIG. 3 , the state information is maintained in counters, but any suitable mechanism may be used to maintain state information. Accordingly, the beginning portion of process 300 involves initializing counters that maintain state information. In block 320 , counter variables n and P 1 . . . N are initialized. Variable n denotes the current group being considered and can range in value from 0 to N−1. Variable P i denotes the current processor being considered in group i, where i belongs to the set {1, 2 . . . N−1} and P i ranges in value from 0 to M i −1. Consequently, according to this embodiment, n and P i are all initialized to the value 0, indicating that the first group and first processor in that group will be considered first. The groups and processors within those groups can be ordered in any suitable way and is not a limitation on the invention.
[0045] In block 330 , on the first time it is executed, a first device is considered, and in block 340 , on the first time it is executed, a first message to be assigned to that device is considered. In block 350 , on the first time it is executed, this first message is defined to target the first processor in the first group, as denoted by the current state of counter variables n and P i .
[0046] In the interest of evenly distributing messages across groups and processors within groups, blocks 360 and 370 increment the counter variables such that the next group and first processor within that group are considered next. Incrementing the counters at blocks 360 and 370 is done using modular arithmetic. Modular arithmetic causes the counters to wrap around when their maximum values are reached. For example, at block 360 , counter P n tracks the most recently assigned processor within group n. Counter P n should not equal or exceed the value, M n , indicating the number of processors within group n. Accordingly, if the increment operation at block 360 would cause P n to equal the value M n , the value of P n returns to zero. Likewise, processing at block 370 is performed as a modular increment. The value n incremented at block 370 represents the current group being processed. Because, in the embodiment illustrated, there are N groups, the value of n should not equal or exceed N. When the value of n is incremented to equal N, the value wraps around and n is set to zero.
[0047] If the first device has more messages that need to be assigned to it, the process branches from decision block 380 to block 340 where the next message is identified. That message is subsequently defined to target that second group and first processor within that group.
[0048] The process of assigning targets to messages for the first device will continue iteratively in this fashion. For each new message to be created for the first device, the process will move from group to group, returning to the first group when a processor from the last group has been assigned as a target of a message. Within each group, the target processor will be rotated and will return to the first processor in a group when the last one has been allocated.
[0049] This process may continue until sufficient messages for the first device have been defined. The process is then repeated from block 330 for each remaining device (block 390 ). Processing may loop back to block 330 at any suitable time. For example, process 300 may continue to loop back to block 330 until all of the devices detected upon start-up of a computer have been processed. If at some later time a new device is detected, process 300 may resume with processing at block 330 . By resuming at block 330 , the process may resume without re-initializing counters at block 320 . In this way, the iterative process of distributing messages across processor groups may continue even for devices discovered after initial start-up. Such a capability, for example, may be employed with a computer configured with a “plug and play” architecture. A plug and play architecture may allow a computer to detect a newly added device. However, regardless of how devices are discovered, process 300 may be used to efficiently assign targets to messages used by each device.
[0050] As a specific example of the embodiment of FIG. 3 , processors within each of the process 300 could be applied to the computer system 100 of FIG. 1 . In doing so, chips 120 1 , 120 2 , 120 3 could comprise the N=3 groups of interest. Messages 142 1 , 142 2 , and 142 3 would be defined to target processors 122 1 , 124 1 , and 126 1 respectively. Messages 144 1 and 144 2 would be defined to target processors 122 2 and 124 2 respectively. And, messages 146 1 , 146 2 , and 146 3 would be defined to target processors 126 2 , 122 3 , and 124 3 , respectively. In this way, a balanced distribution of these messages across groups, and processors within these groups, has been achieved.
[0051] Once the messages have been defined, they may be used as part of ongoing processing within the computer. FIG. 4 illustrates one embodiment of a process by which the defined messages may be used. Namely, process 400 demonstrates that a processor may suggest a message to a device when assigning an operation to the device according to embodiments of the invention. In particular, in block 410 , a processor selects a device to service a request. Such a request may be any suitable request (such as a request for an I/O operation) received from an application program or other software being executed.
[0052] However, regardless of how the request is initiated, a processor responding to the request may identify a device that performs an operation used in completing the request. As an example, a processor processing a request for information from a disk drive may identify that a disk drive needs to perform a read operation in order for the processor to complete the request. In that example, the device selected at block 410 may be the disk drive.
[0053] Regardless of how the device to service a request is identified at block 410 , the process continues to block 420 . The processor determines what interrupt messages are available to the selected device (block 420 ). The processor identifies an efficient processor to service the anticipated completion interrupt (block 430 ). Such an efficient processor may be identified in any suitable way and may depend on the nature of the operation to be performed by the device. For example, based on the nature of the request received at block 410 , a processor may determine that it will utilize data made available as a result of completion processing for the request. In that scenario, the processor may select itself as the most efficient processor. In other scenarios, a processor may identify that, as a result of completion processing, data will be communicated to a different processor. In that scenario, the processor to receive the data may be identified as the most efficient processor to execute completion processing. However, the specific criteria used to identify the most efficient processor are not a limitation on the invention.
[0054] If the list of interrupt messages available to the device (as determined in block 420 ) includes one that targets the identified efficient processor, then the process branches from decision block 440 to block 460 . At block 460 , a suggestion is sent to the device to use the message targeting the identified process when sending its service completion interrupt upon completion of the requested operation. The suggestion for which message a device should use to signal that it has completed an assigned operation is not critical to the invention. The suggested message may be sent as part of assigning the operation to the device or in any other suitable way.
[0055] On the other hand, if the efficient processor is not targeted by any of the available messages identified in block 420 , then the process branches from decision block 440 to block 450 . The next closest processor may be identified at block 450 . The next closest processor can be identified in any suitable way. In the embodiment illustrated, proximity-based groupings of processors which have a close physical proximity to other processors in that grouping, and/or which have a proximity which facilitates efficient communication among the grouped processors are used to identify relative closeness of processors.
[0056] Regardless of how the next closest processor is identified at block 450 , the process loops back to decision block 440 . At decision block 440 , a check is again made as to whether the identified processor is a target of a message for the device to process the operation. If the identified processor is not a target of a message, the process again loops back to block 450 where a next closest processor is identified. The process may continue in this fashion until a processor is identified that is a target of a message available to the device to perform the operation. Once a message is found to have a matching targeted processor, that message is chosen as the one the processor will suggest be used by the selected device to send its service completion interrupt (block 460 )
[0057] The inventors have appreciated that the process 400 is likely to improve the efficiency of assigning an operation to a device as compared to the prior art due to the initial defining and assigning of messages to devices (such as the embodiment illustrated in FIG. 3 ) which ensures a distribution of these messages that is balanced across proximity-based processor groups, and is further balanced across processors within groups.
[0058] Having thus described several aspects of at least one embodiment of this invention, it is to be appreciated that various alterations, modifications, and improvements will readily occur to those skilled in the art.
[0059] Such alterations, modifications, and improvements are intended to be part of this disclosure, and are intended to be within the spirit and scope of the invention. Accordingly, the foregoing description and drawings are by way of example only.
[0060] The above-described embodiments of the present invention can be implemented in any of numerous ways. For example, the embodiments may be implemented using hardware, software or a combination thereof. When implemented in software, the software code can be executed on any suitable processor or collection of processors, whether provided in a single computer or distributed among multiple computers.
[0061] Further, it should be appreciated that a computer may be embodied in any of a number of forms, such as a rack-mounted computer, a desktop computer, a laptop computer, or a tablet computer. Additionally, a computer may be embedded in a device not generally regarded as a computer but with suitable processing capabilities, including a Personal Digital Assistant (PDA), a smart phone or any other suitable portable or fixed electronic device.
[0062] Also, a computer may have one or more input and output devices. These devices can be used, among other things, to present a user interface. Examples of output devices that can be used to provide a user interface include printers or display screens for visual presentation of output and speakers or other sound generating devices for audible presentation of output. Examples of input devices that can be used for a user interface include keyboards, and pointing devices, such as mice, touch pads, and digitizing tablets. As another example, a computer may receive input information through speech recognition or in other audible format.
[0063] Such computers may be interconnected by one or more networks in any suitable form, including as a local area network or a wide area network, such as an enterprise network or the Internet. Such networks may be based on any suitable technology and may operate according to any suitable protocol and may include wireless networks, wired networks or fiber optic networks.
[0064] Also, the various methods or processes outlined herein may be coded as software that is executable on one or more processors that employ any one of a variety of operating systems or platforms. Additionally, such software may be written using any of a number of suitable programming languages and/or programming or scripting tools, and also may be compiled as executable machine language code or intermediate code that is executed on a framework or virtual machine.
[0065] In this respect, the invention may be embodied as a computer readable medium (or multiple computer readable media) (e.g., a computer memory, one or more floppy discs, compact discs, optical discs, magnetic tapes, flash memories, circuit configurations in Field Programmable Gate Arrays or other semiconductor devices, or other tangible computer storage medium) encoded with one or more programs that, when executed on one or more computers or other processors, perform methods that implement the various embodiments of the invention discussed above. The computer readable medium or media can be transportable, such that the program or programs stored thereon can be loaded onto one or more different computers or other processors to implement various aspects of the present invention as discussed above.
[0066] The terms “program” or “software” are used herein in a generic sense to refer to any type of computer code or set of computer-executable instructions that can be employed to program a computer or other processor to implement various aspects of the present invention as discussed above. Additionally, it should be appreciated that according to one aspect of this embodiment, one or more computer programs that when executed perform methods of the present invention need not reside on a single computer or processor, but may be distributed in a modular fashion amongst a number of different computers or processors to implement various aspects of the present invention.
[0067] Computer-executable instructions may be in many forms, such as program modules, executed by one or more computers or other devices. Generally, program modules include routines, programs, objects, components, data structures, etc. that perform particular tasks or implement particular abstract data types. Typically the functionality of the program modules may be combined or distributed as desired in various embodiments.
[0068] Also, data structures may be stored in computer-readable media in any suitable form. For simplicity of illustration, data structures may be shown to have fields that are related through location in the data structure. Such relationships may likewise be achieved by assigning storage for the fields with locations in a computer-readable medium that conveys relationship between the fields. However, any suitable mechanism may be used to establish a relationship between information in fields of a data structure, including through the use of pointers, tags or other mechanisms that establish relationship between data elements.
[0069] Various aspects of the present invention may be used alone, in combination, or in a variety of arrangements not specifically discussed in the embodiments described in the foregoing and is therefore not limited in its application to the details and arrangement of components set forth in the foregoing description or illustrated in the drawings. For example, aspects described in one embodiment may be combined in any manner with aspects described in other embodiments.
[0070] Also, the invention may be embodied as a method, of which an example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.
[0071] Use of ordinal terms such as “first,” “second,” “third,” etc., in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.
[0072] Also, the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including,” “comprising,” or “having,” “containing,” “involving,” and variations thereof herein, is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. | An efficient interrupt system for a multi-processor computer. Devices interrupt a processor or group of processors using pre-defined message address and data payload communicated with a memory write transaction over a PCI, PCI-X, or PCI Express bus. The devices are configured with messages that each targets a processor. Upon receiving a command to perform an operation, the device may receive an indication of a preferred message to use to interrupt a processor upon completion of that operation. The efficiency with which each interrupt is handled and the overall efficiency of operation of the computer is increased by defining messages for the devices within the computer so that each device contains messages targeting processors distributed across groups of processors, with each group representing processors in close proximity. In selecting target processors for messages, processors are selected to spread processing across the processor groups and across processors within each group. | 6 |
The present invention relates to protective devices for hypodermic syringes to prevent the needle of the syringe from repuncturing the skin of the patient or health care professional after the intended use of the syringe, and more particularly to an automatically operated needle guard assembly which embeds the syringe needle into a protective cap to prevent repuncture after each use of the needle.
BACKGROUND OF THE INVENTION
Because of the possibility of spreading infectious disease, hypodermic needles used in the health care industry are generally disposed of after a single use. The need to prevent repuncture with used hypodermic needles has become of paramount importance in view of the AIDS epidemic. Patients, doctors, nurses, lab personnel, and hospital laundry workers have become accidentally infected with the AIDS HIV virus by puncturing themselves with hypodermic needles previously used on AIDS infected patients. Although provisions are made for the safe disposal of hypodermic needles in the medical workplace, the difficult and sometimes chaotic environment of some medical situations can cause even the best trained medical personnel to misplace a used hypodermic needle.
Because the hypodermic needle is frequently used during times of high stress, it would be of great benefit to provide a needle that automatically shields itself after a single use without the necessity of any conscious effort or thought by the attendant using the needle.
Many different protective cap-type, or sheath-type devices for protecting hypodermic needles against accidental needle sticks have been advanced. While many of these devices are workable, they either require manual deployment of a protective cap or sheath, (and thus a conscious effort by the attendant) or they involve a mechanism that obstructs the attendant's view of the needle as it is advanced into the patient's skin. Other shielding devices that are available involve complex mechanisms which would be costly to manufacture. U.S. Pat. No. 4,915,696 to Feimer, U.S. Pat. No. 4,725,267 to Vaillancourt, U.S. Pat. No. 4,986,819 to Sobel, U.S. Pat. No. 4,892,521 to Laico, U.S. Pat. No. 4,846,809 to Sims U.S. Pat. No. 4,943,284 to Erlich, U.S. Pat. No. 4,911,694 to Dolan, and U.S. Pat. No. 5,015,240 to Soproni are representative of devices which require manual deployment of a trigger, or of a protective cap or sheath by the attendant. These devices do not address the need for automatic actuation of the cap to eliminate the element of human error in deployment of the protective device.
Some prior inventions obstruct the vision of a substantial portion of the needle when entering the patient's skin, and require a specific amount of insertion into the skin to effect the triggering of the protective device, (e.g. U.S. Pat. No. 4,795,432 to Karczmer and U.S. Pat. No. 5,059,180 to McLees). These type of devices would be inconvenient to use and deploy, and possibly dangerous.
It is an object, therefore, of the present invention to provide a needle tip protective guard for a hypodermic needle that operates automatically and that requires no additional action by the operator.
It is another object of the invention to provide a needle guard having a short, unobtrusive profile in the retracted, inactivated position.
It is a further object of the invention to provide a needle tip guard which includes a propellent system for placing the guard, which propellent system becomes activated when the operator presses the plunger on the hypodermic syringe to complete the injection. Thus, the act of using the syringe causes the guard to operate.
It is another object to provide a needle guard that will close itself off to prohibit the needle from reemerging once it has been enclosed by the guard.
Another object is to provide a needle guard that is made integral with the needle, so that the needle and guard are mounted to the syringe simultaneously.
A still further object of the invention is to provide such a guard mechanism that is constructed of simple plastic parts to minimize material and production costs.
SUMMARY OF THE INVENTION
These and other objects of the invention are achieved by a mechanism that uses gas pressure produced by the combining of two chemicals to propel a protective cap along the needle shaft and over the needle tip. The two chemicals are combined when the attendant pushes the syringe to inject medication into the patient, and, in a first embodiment, simultaneously squeezes a small bellows located under the plunger. The bellows pumps a liquid chemical through a tube and into contact with another chemical located in a chamber at the hub of the needle. In a second embodiment, the attendant depresses a circular disc and push rod assembly simultaneously with the syringe plunger to cause communication between the two chemicals in the chamber. The chamber in both embodiments is connected to a flexible sheath that is in an initially collapsed configuration. A plastic cap with a small aperture through which the needle protrudes is connected to the other end of the flexible sheath. A slow progressive gas pressure results from the chemical reaction in the chamber causing the flexible sheath to elongate and push the protective cap down the needle shaft and over into contact with the tip. The protective cap contains a plastic wafer with a small moveable tab member in its center that is elastically biased toward the center, but held aside by the needle. When the needle tip is withdrawn from the aperture in the cap, the moveable tab member returns to center, blocks the aperture, and prohibits the needle from reemerging from the protective cap.
Other objects and features of the invention will become apparent from the following detailed description of the preferred embodiments when taken in conjunction with the drawings wherein reference to specific parts is made.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevation view of a hypodermic needle equipped with the automatic needle guard.
FIG. 2 is a partial cross section elevation view of the needle guard assembly of FIG. 1 before being attached to the syringe.
FIG. 3 is a side cross section view of the hypodermic needle with the automatic needle guard ready to draw medication into the syringe.
FIG. 4 is a side cross section view of the hypodermic needle with the automatic needle guard, wherein the needle is ready to inject medication into the patient.
FIG. 5 is a cut-away side view of the top portion of the needle guard assembly of FIG. 2 showing the bellows pump.
FIG. 6 is a cut-away, cross section view of the bottom portion of the needle guard assembly of FIG. 2, showing the hypodermic needle and the automatic needle guard. I FIG. 7 illustrates the needle guard of FIG. 6 fully expanded with the needle enclosed within the protective cap.
FIG. 8 is a top view of the bellows pump and its mounting element, taken along line 8--8 of FIG. 5.
FIGS. 9 & 10 are end views of the plastic wafer forming part of the needle guard assembly, showing the position of the moveable member before and after the needle is enclosed within the protective cap.
FIG. 11 is an elevation view of an alternate embodiment of the present invention.
FIG. 12 is an elevational cross section view of the embodiment of FIG. 11 showing the needle guard assembly attached to the syringe.
FIG. 13 is a detail, cross section view of the embodiment of FIG. 11 showing the hypodermic needle and the interior structure of the automatic needle guard.
FIG. 14 is an elevation cross section view of the needle guard of the embodiment of FIG. 11 shown in the fully extended position with the needle enclosed within the protective cap.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
For the sake of brevity, like components shall have the same designation throughout the description of the figures.
Referring to FIG. 1, a plastic needle guard chamber assembly 10 is attached to the needle end of hypodermic syringe 12 by the twist-on method used on conventional needles. A liquid carrying tube 16 is made integrally with, and shown connected to a guard housing 11 at one end, and at the other end tube 16 is connected to a bellows type pump 14 located under the syringe plunger 17. The hypodermic needle 20 is made integrally with the needle guard housing 11 and is shown in a fully exposed position with a moveable protective cap 18 in an unactivated position.
In FIG. 2, the needle guard chamber assembly 10 described above is shown in condition for attachment to the syringe 12. A conventional needle 20 and internally threaded hub 22 are shown relative to the other needle guard chamber assembly components. The protective cap 18 is shown secured to the needle guard housing 11 by a friction hold created between flanges 23 of cap 18 and the inside of a shallow socket 24 depending from housing 11. The cap 18 may also be secured by adhesive, or other suitable means. The protective cap 18 has contained within it an expandable sheath 26 made of a resilient material such as latex or plastic. The sheath 26 is connected to the protective cap 18 at one end and to the needle guard chamber 11 at the other end.
In FIG. 3, the assembly depicted in FIG. 2 is shown connected to a hypodermic syringe 12 which is ready to draw medication. The syringe plunger 17, which can be freely rotated axially within the syringe, is shown with ratchet type serration 28 along the length of the syringe stem 30 and extending half way around the circumference of stem 30. The bellows pump 14 is shown with a molded step 31 which acts as a pawl in conjunction with the serration 28 on the syringe plunger stem 30. Also on the syringe stem 30 is a low profile, cantilevered radial extension 32 which encircles 180 degrees of the stem opposite to the extension of the serration 28. Extension 32 provides a bellows pump contact between the bellows 14 and the stem 30. The serrations 28 allow for retraction of the plunger when drawing medication from a vial, but prohibit advancement of the plunger. After the attendant fills the syringe, the plunger is rotated 180 degrees to simultaneously disengage the serration 28 from the pawl 31 and to place the extension 32 directly over the bellows pump 14.
In FIG. 4, the plunger 17 has been rotated 180 degrees from its previous position shown in FIG. 3 and lifted upward, whereby the device is ready to inject medication into the patient. As plunger 17 is lowered, the bellows pump conductor or extension 32 begins to depress the bellows pump 14 in the final 1/8 to 1/4 inch of travel as the syringe plunger 17 is pushed by the attendant to inject medication through hollow tube 20. After injection, the bellows pump 14 will have forced a quantity of liquid material or chemical contained therein to travel into tube 16 and then into guard housing 11, as will be described.
In FIGS. 5 & 8, the bellows pump 14 is shown with a rounded bead 34 at its lower end which snaps into a mating groove 36 (shown in FIG. 3) in the top of the syringe housing. These mating parts provide for quick and simple snap-on mounting of the bellows pump 14 to the syringe 12. Also shown is the pawl 31 encircling 180 degrees of the inside of the bellows pump.
FIG. 6 shows the tube 16 connected to the guard housing 11. The housing 11 includes a hollow portion 40 in which a first chemical propellent is disposed. A second liquid chemical is disposed in bellows pump 14 and tube 16. The first and second chemicals in hollow portion 40 and tube 16, respectively, are reactants relative to each other, whereby when the two chemicals come into contact, a reaction results, producing a gaseous product of reaction and an increase in the pressure in hollow portion 40 of housing 11. To prevent premature contact of the two chemical reactants, a small amount of viscous fluid 38 such as petroleum jelly or similar thick material acts as a plug in tube 16 at its entrance to the housing 11. The gas producing reactants may be any compounds or combination or solutions of compounds that when combined, will produce emission of gas. Such compounds could be water plus a mixture of citric acid and sodium carbonate, hydrogen peroxide and manganese dioxide, acetic acid and sodium bicarbonate, or similar known materials.
The gas produced by combining the chemical reactants will cause an increase in pressure within the hollow portion 40 of guard housing 11. This pressure acts upon the upper surface of protective cap 18, dislodging the protective cap and flange 23 from socket 24, and forcing the protective cap downward along the length of needle 20. As shown in FIG. 7, expandable sheath 26 extends downward along protective cap 18, forming an extension of pressurized chamber portion 40, thereby maintaining the gaseous pressure against protective cap 18.
FIG. 7 shows the sheath 26 fully expanded with the protective cap 18 moved to a position beyond the tip of the hypodermic needle 20. Also shown in FIG. 7 is a thin wafer 42 lodged in protective cap 18. The wafer 42 includes a flexible tab 44 (FIGS. 9 & 10) which, in one position covers the aperture 43 in the protective cap. The tab 44 seals the aperture 43 in the protective cap 18 to prevent the needle 20 from reemerging from the cap.
FIGS. 9 & 10 are detailed illustrations of the thin plastic wafer 42, shown in FIG. 9 with the needle 20 holding the wafer's moveable member 44 to the side. When protective cap 18 is extended by gas pressure beyond the tip of needle 20, the needle is withdrawn from the aperture 43 in the protective cap 18, the moveable tab member 44 is allowed to return to center by its own resiliency (as shown in FIG. 10) and the tab blocks the needle 20 from reemerging from the protective cap 18 through aperture 43.
In operation, the medical professional attaches the needle guard assembly 10 (as shown in FIG. 2) to the hypodermic syringe 12 by threading the needle guard housing 11 onto the hypodermic syringe. The bellows pump 14 is then snapped onto the top of the syringe and held in place by a snap-fit of the rounded bead 34 on the bellows 14 and the mating groove 36 on the syringe 12. The attendant then inserts the hypodermic needle 20 into a vial of medication, and lifts the plunger 17 until the required amount of medication has entered the syringe 12. The needle is then removed from the vial and the plunger 17 is rotated 180 degrees to simultaneously disengage the serration 28 from the pawl 31, and to place the conductor extension 32 over the bellows pump 14.
The attendant then inserts the needle 20 into the patient's skin and presses the plunger 17 to inject the medication. In the final 1/8 to 1/4 inch of travel of the plunger 17, the conductor 32 compresses the bellows pump 14 and displaces a quantity of liquid Chemical down through tube 16 and into chamber 40, dislodging viscous liquid 38 whereby the first liquid in tube 16 comes into contact with the second chemical in chamber 40. After completion of the injection, the needle 20 is withdrawn from the patient as the chemical reaction continues inside the chamber 40. A steadily increasing pressure develops as the chemical reaction inside the chamber 40 produces gas. The gas pressure causes the protective cap 18 to be propelled down the needle 20 and expandable sheath 26 to elongate under the force of the gas pressure. When the protective cap 18 has moved completely over the end of the needle 20, the tab member 44 (FIG. 10) closes off the aperture 43 in the protective cap 18 to prevent reemergence of the hypodermic needle 20 through the aperture 43.
The needle guard assembly 10' constructed according to a second embodiment of the invention will now be described with reference to FIGS. 11-14. In this embodiment, the mechanism for triggering the chemical reaction to propel the protective cap 18 is different from the embodiment of FIGS. 1-10.
In FIG. 11 the hypodermic syringe 12 is shown connected to the needle guard assembly housing 45. A push rod 46 slidably extends through a bracket 60 which is mounted alongside of the syringe 12. The push rod 46 has a circular disc 47 at the upper end that extends over the top of the syringe plunger 17.
FIG. 12 shows the device of the second embodiment in condition to inject medication into the patient. The attendant presses the circular disc 47 and the syringe plunger 17 downward simultaneously to administer the injection. The end 48 of push rod 46 moves downward and contacts a flange 49 on the protective cap 18 in the final 1/8 inch of travel of the syringe plunger 17. In this embodiment, the side of the protective cap 18 extends upward alongside hub 22, and is releasably and frictionally held to hub 22 at 61 (FIG. 13). When the injection is completed, the push rod will have advanced the protective cap 18 approximately 1/8 of an inch downward and the chemicals located within the protective cap 18, as will be described, will combine and produce gas, applying a downward pressure on cap 18.
FIG. 13 is a detail view of the interior of protective cap 18, and shows the threaded hub 22 for mounting the needle 20 to the syringe 12. The expandable sheath 26 is shown connected to the hub 22 at the top and to the protective cap 18 at the bottom. Two chemical reactants 50 and 53 are located within the protective cap 18, and are initially separated by a cylindrically shaped flange 51 that extends downwardly from hub 22. Flange 51 is in mating contact with a corresponding flange 52 which extends upward from the bottom interior of protective cap 18. When the protective cap 18 has been advanced slightly by the downward movement of push rod 46 after completion of the injection, the mating flanges 51 and 52 separate to allow communication between the two chemical reactants 50 and 53. The gas produced by the chemical reaction will cause an increase in pressure inside the protective cap 18, and an elongation of the expandable sheath 26 along with downward movement of protective cap 18. FIG. 14 shows the sheath 26 fully expanded with the protective cap 18 covering the tip of the hypodermic needle 20. Also shown is tab 42 covering the aperture 43 in the protective cap as described in conjunction with the first embodiment. As in the first embodiment, the tab 42 prevents the needle 20 from reemerging from the protective cap 18.
In operation, the medical professional attaches the needle guard assembly 45 to the hypodermic syringe 12 by threading the needle guard chamber hub 22 onto the mating thread on the hypodermic syringe. The attendant then inserts the hypodermic needle 20 into a vial of medication and retracts the plunger 17 until the required amount of medication has entered the syringe 12. The needle 20 is then removed from the vial, and the syringe is ready to inject medication. The attendant inserts the needle 20 into the patient's skin and presses downward on the circular disc 47 and the syringe plunger 17 simultaneously. In the final 1/8 to 1/4 inch of travel of the syringe plunger 17, the push rod 46, which is connected to the circular disc 47, contacts flange 49 on the protective cap 18, and moves the protective cap a short distance down the needle 20. The short displacement of the protective cap 18 separates flanges 51 and 52 (FIG. 13), which allows communication between chemicals 50 and 53. This starts a chemical reaction within the protective cap 18 just as the injection is completed and the needle is removed from the patient's skin.
The chemical reaction described above is started when the protective cap 18 is displaced a short distance causing separation of the downward extending flange 51 from a mating upwardly extending flange 52. This separation of flanges 51 and 52 causes the liquid chemical reactant 53 to come into contact with the other chemical reactant 50. A few seconds after the injection is completed, an increasing gas pressure develops inside the protective cap 18 as the chemical reaction progresses. The gas causes the expandable sheath 26 to elongate and the protective cap 18 to move down the needle 20. When the protective cap 18 has moved completely over the end of the needle 20, the tab member 42 closes off the aperture 43 in the protective cap 18 to prevent reemergence of the needle 20.
Specific embodiments of the novel Automatic Self-Protecting Hypodermic Needle Assembly according to the present invention have been described for the purpose of illustrating the manner in which the invention may be made and used. It should be understood that implementation of other variations and modifications of the invention in its various aspects will be apparent to those skilled in the art and that the invention is not limited by the specific embodiments described. It is therefore contemplated to cover by the present invention any and all modifications, variations, or equivalents that fall within the true spirit and scope of the basic underlying principles encompassed by the claims set forth hereinbelow. | An automatic self-protecting hypodermic needle assembly comprising a hypodermic syringe having a housing, a moveable plunger in the housing, a medicant chamber formed between the housing and the plunger, and a hollow needle extending from the housing in communication with the medicant chamber. A needle guard assembly is attached to the syringe housing and includes a guard housing adjacent the needle, a protective cap removably attached to the guard housing and an aperture through which the needle extends. A propellant is located in the guard housing in communication with the protective cap. When activated by an activating element, the propellant expands from a liquid to a gas, applies a pressure to the protective cap, and drives the protective cap along the length of the needle until the cap extends beyond the tip of the needle and the needle tip becomes embedded in the protective cap. Control means are provided under the operation of the medical attendant using the hypodermic syringe to automatically activate the propellant upon completion of the use of the syringe, and to embed the needle tip into the protective cap. | 0 |
INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS
Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57.
BACKGROUND
Field
The present disclose relates to a dispensing pump, and more particularly, to a dispensing pump that may be used in a process of manufacturing an electronic product and may dispense an accurate amount of a liquid, such as a liquid synthetic resin, at high speed.
Discussion of Related Technology
Pumps for dispensing liquid are used in various technical fields, such as processes of manufacturing electronic products by using semiconductor chips, and the like.
In particular, dispensing pumps are widely used in an underfill process of a semiconductor process. The underfill process is usually used in a surface mounting technique, such as a flip chip in which a plurality of metal balls are formed on a surface facing a substrate and which electrically connects the substrate and a semiconductor chip via the plurality of metal balls. If a liquid synthetic resin is applied onto a circumference of the semiconductor chip, the resin is dispersed into a space between the semiconductor chip and the substrate by a capillary phenomenon and is filled in a space between the metal balls. The resin that fills the space between the semiconductor chip and the substrate is hardened so that adhesive strength between the semiconductor chip and the substrate can be improved. In addition, the hardened resin serves as a shock absorber and dissipates heat generated in the semiconductor chip.
A function of dispensing a liquid at high speed of such dispensing pumps becomes significant. Korean Patent Laid-open Publication Nos. 10-2005-0093935 and 10-2010-0045678 disclose a structure of a pump for dispensing a resin by ascending/descending a valve due to interaction between a cam and a cam follower. Such dispensing pumps according to the related art have excellent performance but have a limitation in speed at which a valve rod descends due to a structure of cam protrusions of a cam member and a structure of a roller. Thus, there are some difficulties in dispensing the liquid at high speed, and in particular, it is difficult to dispense a liquid with high viscosity at high speed.
SUMMARY
One aspect of the present invention provides a valve accelerating type dispensing pump that may descend a valve rod at high speed and thus may dispense a liquid with high viscosity at high speed.
Another aspect of the present invention provides a valve accelerating type dispensing pump including: a pump body; a valve body including an inlet path on which a liquid from an outside is supplied, a reservoir in which the liquid supplied via the inlet path is stored, and a discharge path on which the liquid stored in the reservoir is discharged, the valve body being installed at the pump body; a valve rod pressurizing the liquid stored in the reservoir of the valve body and inserted in the reservoir of the valve body so that the liquid is discharged via the discharge path; an operating rod connected to the valve rod and allowing the valve rod to move relative to the valve body; a cam member including a through hole through which the operating rod passes and cam protrusions formed along a circumferential direction of the cam member based on the through hole and having inclined surfaces formed so that a height of the cam protrusions increases, the cam member being installed at the pump body so that the cam member rotates around the through hole; a rotating unit rotating the cam member; a cam follower including rollers that roll on the inclined surfaces of the cam protrusions when the cam member rotates, the cam follower coupled to the operating rod and allowing the valve rod to move relative to the valve body; an accelerating member assembled with the cam follower to allow relative rotation of the cam follower within a predetermined angle range and installed at the pump body so as to make a linear motion approaching the cam member; and an elastic member installed between the pump body and the accelerating member and providing an elastic force to the accelerating member so that the accelerating member approaches the cam member.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other features and advantages of the present invention will become more apparent by describing in detail embodiments thereof with reference to the attached drawings in which:
FIG. 1 is a perspective view of a valve accelerating type dispensing pump according to an embodiment of the present invention;
FIG. 2 is an exploded perspective view of main elements of the valve accelerating type dispensing pump illustrated in FIG. 1 ;
FIG. 3 is a cross-sectional view taken along a line III-III of the valve accelerating type dispensing pump of FIG. 1 ;
FIG. 4 is a cross-sectional view taken along a line IV-IV of the valve accelerating type dispensing pump of FIG. 1 ;
FIGS. 5A, 5B, 6A, 6B, 7A, and 7B are schematic views for explaining an operation of the valve accelerating type dispensing pump of FIG. 1 ; and
FIG. 8 is an exploded perspective view of main elements of a valve accelerating type dispensing pump according to another embodiment of the present invention.
DETAILED DESCRIPTION OF EMBODIMENTS
Embodiments of the present invention will now be described more fully with reference to the accompanying drawings in which embodiments of the invention are shown.
FIG. 1 is a perspective view of a valve accelerating type dispensing pump according to an embodiment of the present invention, FIG. 2 is an exploded perspective view of main elements of the valve accelerating type dispensing pump illustrated in FIG. 1 , and FIG. 3 is a cross-sectional view taken along a line III-III of the valve accelerating type dispensing pump of FIG. 1 .
Referring to FIGS. 1 through 3 , the valve accelerating type dispensing pump according to the present embodiment includes a pump body 100 , a valve body 110 , a valve rod 210 , an operating rod 220 , a cam member 300 , and a cam follower 400 .
The pump body 100 serves as a housing that supports the entire structure of the valve accelerating type dispensing pump. The pump body 100 is installed at a transfer device and is moved by the transfer device to allow a liquid to be dispensed.
The valve body 110 is installed at the pump body 100 . The valve body 110 includes an inlet path 111 , a reservoir 112 , and a discharge path 113 . The liquid stored in an external syringe (not shown) flows to the reservoir 112 via the inlet path 111 . The liquid stored in the reservoir 112 is discharged via the discharge path 113 due to an operation of the valve rod 210 that ascends/descends with respect to the reservoir 112 . A nozzle 120 is connected to the discharge path 113 so as to adjust dispensing characteristics of the liquid.
The valve rod 210 is inserted in the reservoir 112 and pressurizes the liquid stored in the reservoir 112 so as to discharge the liquid via the discharge path 113 .
The cam member 300 is disposed above the valve body 110 and the valve rod 210 and is installed at the pump body 100 . The cam member 300 is installed at the pump body 100 so as to rotate around a virtual central axis that extends in a lengthwise direction of the valve rod 210 . A bearing 130 is installed between the cam member 300 and the pump body 100 so that the cam member 300 may rotate with respect to the pump body 100 .
The cam member 300 rotates by a rotating unit 900 . The rotating unit 900 includes a motor 910 , a driving pulley 920 , a timing belt 930 , and a driven pulley 940 . The motor 910 is installed at the pump body 100 , and the driven pulley 940 is installed at the cam member 300 . The timing belt 930 connects the driving pulley 920 and the driven pulley 940 . If the motor 910 allows the driving pulley 920 to rotate, the driven pulley 940 rotates due to the timing belt 930 . As a result, the cam member 300 rotates.
The cam member 300 includes a through hole 320 and a plurality of cam protrusions 310 . The through hole 320 is formed to penetrate the center of the disc-shaped cam member 300 in a vertical direction. The plurality of cam protrusions 310 are arranged in a circumferential direction of the cam member 300 so that eight cam protrusions 310 are at the same angle intervals (i.e., at intervals of 45 degrees). The cam protrusions 310 are inclined in the same rotation direction along the circumferential direction of the cam member 300 . That is, the cam protrusions 310 include inclined surfaces 311 that are inclined so that the height of the cam protrusions 310 may increase gradually clockwise, as illustrated in FIG. 2 . Cross-sections of the cam protrusions 310 may be formed so that the inclined surfaces 311 are steeply bent from their tops to lower portions. In the present embodiment, the inclined surfaces 311 of the cam protrusions 310 are formed to be bent from their tops in the vertical direction, as illustrated in FIGS. 2, 5A, and 5B .
The operating rod 220 is disposed in the through hole 320 of the cam member 300 and is coupled to the valve rod 210 . The operating rod 220 is coupled to the cam follower 400 and ascends or descends and allows the valve rod 210 to be moved up and down relative to the valve body 110 .
The cam follower 400 faces a surface on which the cam protrusions 310 of the cam member 300 are formed and ascends/descends with respect to the cam member 300 due to interaction between the cam protrusions 310 and the cam follower 400 . The cam follower 400 includes two rollers 420 that roll on the inclined surfaces 311 of the cam protrusions 310 . Two rollers 420 of the cam follower 400 are disposed at intervals of 180 degrees.
The cam follower 400 is assembled with an accelerating member 500 and is installed at the pump body 100 . The accelerating member 500 includes a spline boss 530 and is coupled to the pump body 100 via a spline shaft 520 so as to make a linear motion (ascending/descending motion in the present embodiment) approaching the cam member 400 and not to allow relative rotation of the cam follower 400 . An elastic member 600 is disposed between the accelerating member 500 and the pump body 100 and provides an elastic force so that the elastic member 600 may be moved relative to the accelerating member 500 to approach the cam member 300 . In the present embodiment, the elastic member 600 having a shape of a spring 600 is used. The cam follower 400 that is disposed between the accelerating member 500 and the cam member 300 , receives the elastic force of the elastic member 600 from the accelerating member 500 and is maintained to be closely adhered to the cam member 300 .
The accelerating member 500 and the cam follower 400 are assembled with each other so that they may rotate relative to each other within a predetermined angle range. Due to interaction between accelerating protrusions 410 formed on the cam follower 400 and angle limiting portions 510 formed on the accelerating member 500 , the accelerating member 500 and the cam follower 400 may be rotated relative to each other within the predetermined angle range. In the present embodiment, the angle limiting portions 510 are long holes that extend in the circumferential direction of the accelerating member 500 . Two angle limiting portions 510 having a shape of long holes face each other in a state where a central axis (operating rod 220 ) of the cam follower 400 is interposed between two angle limiting portions 510 . The accelerating protrusions 410 of the cam follower 400 are formed in the form of rods that extend in a radial direction of the cam follower 400 and protrude from the cam follower 400 . Like the angle limiting portions 510 , two accelerating protrusions 410 are disposed and face each other in a state where the central axis of the cam follower 400 is interposed between two accelerating protrusions 410 . The accelerating protrusions 410 are respectively inserted in the angle limiting portions 510 of the accelerating member 500 . Since the accelerating protrusions 410 are caught in inner walls of the angle limiting portions 510 , the cam follower 400 rotates with respect to the accelerating member 500 within an angle range that is allowed by the angle limiting portions 510 . That is, a relative rotational angle of the cam follower 400 with respect to the accelerating member 500 is limited by interference between the accelerating protrusions 410 and the angle limiting portions 510 . A range of the relative rotational angle of the cam follower 400 with respect to the accelerating member 500 that is limited by interaction between the accelerating protrusions 410 and the angle limiting portions 510 may be greater than 0 degree and less than angle intervals between the cam protrusions 310 . In the present embodiment, a rotatable angle of the cam follower 400 may be greater than 0 degree and less than 90 degrees. The rollers 420 are installed at ends of the accelerating protrusions 410 according to the present embodiment and roll on the inclined surfaces 311 of the cam protrusions 310 of the cam member 300 .
Hereinafter, an operation of the valve accelerating type dispensing pump having the above structure of FIGS. 1 through 3 will be described.
FIG. 4 is a cross-sectional view taken along a line IV-IV of the valve accelerating type dispensing pump of FIG. 1 , and FIGS. 5A, 5B, 6A, 6B, 7A, and 7B are schematic views for explaining an operation of the valve accelerating type dispensing pump of FIG. 1
Referring to FIG. 4 , the liquid stored in the external syringe flows to the reservoir 112 of the valve body 110 via the inlet path 111 under uniform pressure.
If the motor 910 operates in this state, the motor 910 rotates with the driving pulley 920 , and the driven pulley 940 that is connected to the driving pulley 920 via the timing belt 930 , also rotates. The cam member 300 that is coupled to the driven pulley 940 rotates with the driven pulley 940 .
If the cam member 300 rotates, the rollers 420 of the cam follower 400 roll along the inclined surfaces 311 of the cam protrusions 310 , and the cam follower 400 ascends. Since the accelerating member 500 is spline-coupled to the pump body 100 via the spline shaft 520 , the accelerating member 500 does not rotate but the rollers 420 roll along the inclined surfaces 311 of the cam protrusions 310 so that the accelerating member 500 and the cam follower 400 ascend. When the accelerating member 500 ascends, the elastic member 600 is pressurized while applying the elastic force to the accelerating member 500 in a downward direction. Due to the elastic force of the elastic member 600 , the rollers 420 of the cam follower 400 are maintained in contact with a top surface of the cam member 300 . The operating rod 220 that is coupled to the cam follower 400 , ascends with the valve rod 210 . When the valve rod 210 ascends, the liquid flows in a space formed in the reservoir 112 , and the space is filled with the liquid.
Referring to FIGS. 1, 5A, and 5B , when the cam member 300 rotates, the accelerating protrusions 410 of the cam follower 400 are slid along the angle limiting portions 510 of the accelerating member 500 and are caught in left walls of the angle limiting portions 500 based on FIGS. 5A and 5B . Thus, rotation of the cam follower 400 does not proceed any more. That is, even when the cam member 300 rotates, the cam follower 400 does not rotate with respect to the accelerating member 500 . A concept of a state of force balance between the cam follower 400 and the cam member 300 is as shown in FIGS. 5A and 5B . A vertical resistance F R applied to the rollers 420 on the inclined surfaces 311 of the cam protrusions 310 is balanced with a horizontal component force F H and a vertical component force F V that are applied to the rollers 420 . The vertical component force F V is provided by the elastic member 600 and is transferred to the rollers 420 via the accelerating member 500 . The horizontal component force F H is transferred to the rollers 420 via the pump body 100 —the accelerating member 500 —the cam follower 400 , because the accelerating protrusions 410 are caught in the angle limiting portions 510 .
If the rollers 420 roll up to tops of the inclined surfaces 311 of the cam protrusions 310 and ascend, the horizontal component of the vertical resistance F R that is balanced with the horizontal component force F H applied to the rollers 420 becomes extinct, as illustrated in FIGS. 6A and 6B . That is, on the inclined surfaces 311 of the cam protrusions 310 , a force is applied to the rollers 420 in the horizontal direction, and any force other than a frictional force is not applied to the rollers 420 in the vertical direction. As a result, due to the horizontal component force F H applied by the angle limiting portions 510 to the accelerating protrusions 410 , the rollers 420 bounce off the cam protrusions 310 in the circumferential direction (right direction in FIGS. 5A, 5B, 6A, 6B, 7A, and 7B ) of the cam member 300 , as illustrated in FIGS. 7A and 7B . As described above, since the cam follower 400 may rotate with respect to the accelerating member 500 within the angle range that is allowed by the angle limiting portions 510 , the cam follower 400 rotates with respect to the accelerating member 500 that does not rotate, in an opposite direction to a rotation direction of the cam member 300 , and the rollers 420 escape from the tops of the cam protrusions 310 at high speed. In this case, due to the elastic force of the elastic member 600 , the accelerating member 500 , the cam follower 400 , the operating rod 220 , and the valve rod 210 descend. As a result, the liquid filled in the reservoir 112 is pressurized by the valve rod 210 and is discharged via the discharge path 113 .
If the cam member 300 rotates consecutively and the rollers 420 ascend and descend along the cam protrusions 310 repeatedly, the valve rod 210 ascends and descends consecutively so that the liquid may be discharged via the discharge path 113 .
In the above liquid-pumping mechanism, the descending speed of the valve rod 210 greatly affects the discharge amount and discharge speed of the liquid. In order to adjust an accurate discharge amount, an inner diameter of the discharge path 113 may be relatively small. As the descending speed of the valve rod 210 increases, the liquid having high viscosity may be quickly dispensed via the discharge path 113 having a small inner diameter. In particular, when the viscosity of the liquid is high, if the descending speed of the valve rod 210 is not sufficiently high, due to resistance caused by viscosity and resistance of the discharge path 113 , the liquid may not be discharged. However, like in embodiments of the present invention, the accelerating member 500 is used so that a liquid having high viscosity may be dispensed. In this way, by using the valve accelerating type dispensing pump according to embodiments of the present invention, the range of the liquid that may be dispersed, may be greatly increased.
When there is no interaction between the accelerating protrusions 410 and the angle limiting portions 510 as described above, the descending speed of the valve rod 210 is determined by a rotational speed of the cam member 300 . As illustrated in FIGS. 6A and 6B , the rollers 420 should roll toward the cam member 300 by a distance D indicated in FIG. 7A so that the rollers 420 may be moved from the tops of the cam protrusions 310 to the lowermost portion of the top surface of the cam member 300 , as illustrated in FIGS. 7A and 7B . In a valve dispensing pump having no accelerating member including angle limiting portions according to the related art, since a cam member should rotate in a state where a cam follower is fixed and rollers should roll up to a bottom surface of the cam member, the descending speed of the valve rod is determined by the rotational speed of the cam member. Even when an elastic member that provides a strong elastic force is used, the descending speed of the valve rod is substantially determined by the rotational speed of the cam member rather than the elastic force of the elastic member. In particular, when an outer diameter of each roller increases, a distance that is required for the rollers to contact the lowermost portion of the top surface of the cam member, increases so that the descending speed of the valve rod is also decreased by the distance.
However, in the valve accelerating type dispensing pump according to the present embodiment, when the rollers 420 roll along the inclined surfaces 311 of the cam protrusions 310 , the angle limiting portions 510 push the accelerating protrusions 410 in an opposite direction to the rotation direction of the cam member 300 by using the horizontal component force F H applied to the rollers 420 , as illustrated in FIGS. 6A and 6B . The cam follower 400 rotates with respect to the accelerating member 500 due to a force applied by the angle limiting portions 510 to the accelerating protrusions 410 and rotates instantaneously in an opposite direction to the rotation direction of the cam member 300 , as illustrated in FIGS. 7A and 7B . As a result, the rollers 420 and the cam member 300 are moved in opposite directions, and the rollers 420 roll at much higher speed compared to the related art by the distance D at which the rollers 420 contact the lowermost portion of the top surface of the cam member 300 . Even when the rollers 420 having a relatively large outer diameter are used, due to interaction between the accelerating protrusions 410 and the angle limiting portions 510 , the rollers 420 may be moved relative to the cam member 300 at high speed, and the valve rods 210 may descend due to the elastic member 600 at very high speed. Since the momentum and kinetic energy of the valve rod 210 are proportional to a descending speed of the valve rod 210 and a square of the descending speed, the liquid may be dispensed at much higher speed compared to the related art. In particular, a liquid having high viscosity may be dispensed by a sufficient force via the discharge path 113 having a relatively small inner diameter.
If the rollers 420 contact next cam protrusion 310 , the cam follower 400 that rotates with respect to the accelerating member 500 in an opposite direction to the cam member 300 , rotates in the same direction as the rotation direction of the cam protrusions 310 due to the vertical resistance F R of the cam protrusions 310 , and the accelerating protrusions 410 are caught in the angle limiting portions 510 in a progressive direction. When the angle range of the angle limiting portions 510 is less than the angle range between the cam protrusions 310 , the accelerating protrusions 410 are first caught in inner walls of the angle limiting portions 510 , and rotation of the cam follower 400 with respect to the accelerating member 500 stops. If the rollers 420 contact next cam protrusion 310 , the cam follower 400 rotates in the same direction as the cam member 300 so that the accelerating protrusions 410 are caught in opposite inner walls of the angle limiting portions 510 and rotation of the cam follower 400 stops.
To sum up, in the related art, even when an elastic force of an elastic member is strong, the descending speed of the valve rod is determined by the size of an outer diameter of a roller and a rotational speed of a cam member. However, in the valve accelerating type dispensing pump according to embodiments of the present invention, due to interaction between the angle limiting portions 510 and the accelerating protrusions 410 , the descending speed of the valve rod 210 may be increased using a sufficient elastic force of the elastic member 600 .
Although embodiments of the present invention have been described as above, the scope of the present invention is not limited to the above-described embodiments.
For example, the accelerating protrusions 410 are formed on the cam follower 400 , and the angle limiting portions 510 are formed on the accelerating member 500 . However, the accelerating protrusions 410 may be formed on the accelerating member 500 , and the angle limiting portions 510 may be formed on the cam follower 400 .
Also, a bearing that rolls along the inner walls of the angle limiting portion 510 may be installed at the accelerating protrusions 410 so as to reduce friction between the accelerating protrusion 410 and the angle limiting portion 510 .
In addition, the angle limiting portions 510 have the shape of long holes, as described above. However, the angle limiting portions 510 may also be formed in the form of long grooves. The accelerating protrusions 410 and the angle limiting portions 510 may be formed in various shapes in which the accelerating member 500 and the cam follower 400 may rotate relative to each other within a predetermined angle range due to interference between the accelerating protrusions 410 and the angle limiting portions 510 .
Furthermore, the rollers 420 are installed at the accelerating protrusions 410 , as described above. However, the rollers 420 may be configured in different ways. The accelerating protrusions 410 interfere with the angle limiting portions 510 independently from the rollers 420 so that the rotational angle of the cam follower 400 may be limited, and the rollers 420 may be configured to be coupled to the cam follower 400 separately from the accelerating protrusions 410 .
FIG. 8 illustrates another example of accelerating protrusions 551 and angle limiting portions 452 .
The accelerating protrusions 551 are formed on an accelerating member 550 , and the angle limiting portions 452 are formed on a cam follower 450 . The angle limiting portions 452 of the cam follower 450 are formed in the form of long grooves having a circular arc shape on a surface that faces the accelerating member 550 along a circumferential direction of the accelerating member 550 . The accelerating protrusions 551 of the accelerating member 550 are formed in the form of rods that extend in a bottom surface of the accelerating member 550 and are inserted in the angle limiting portions 452 of the cam follower 450 . The cam follower 450 rotates with respect to the accelerating member 550 slightly, and the accelerating protrusions 551 are caught in the inner walls of the angle limiting portions 452 such that the cam follower 450 does not rotate any more. The remaining configuration of the accelerating protrusions 551 and the angle limiting portions 452 excluding the above configuration is the same as FIGS. 1 through 7A and 7B . If rollers 451 of the cam follower 450 roll along cam protrusions 310 in a state where the angle limiting portions 452 are caught in the accelerating protrusions 551 and the cam follower 450 cannot rotate, the angle limiting portions 452 are pushed by the accelerating protrusions 551 so that the cam follower 450 rotates with respect to the accelerating member 550 . As such, the relative speed between the rollers 451 and the cam member 300 increases, and the valve rod 210 may descend at high speed.
In the present embodiment, eight cam protrusions 310 and two rollers 420 are disposed. However, the number of cam protrusions 310 and the number of rollers 420 may be diverse. The shape of the cam protrusions 310 may vary according to their inclined angles and curvatures of inclined surfaces.
As described above, in a valve accelerating type dispensing pump according to embodiments of the present invention, an accurate amount of a liquid may be dispensed at high speed.
Also, the valve accelerating type dispensing pump according to embodiments of the present invention may dispense a liquid having high viscosity at high speed due to a fast descending speed of a valve rod.
While embodiments of the present invention have been particularly shown and described, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. | A dispensing pump, and more particularly, a valve accelerating type dispensing pump that may be used in a process of manufacturing an electronic product and may dispense an accurate amount of a liquid, such as a liquid synthetic resin, at high speed. The valve accelerating type dispensing pump can descend a valve rod at high speed and thus can dispense a liquid with high viscosity at high speed. The valve accelerating type dispensing pump can dispense an accurate amount of a liquid at high speed. Also, the valve accelerating type dispensing pump can dispense a liquid having high viscosity at high speed due to a fast descending speed of a valve rod. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to the use of tertiary amine catalysts for producing polyurethanes, especially polyurethane foam.
Polyurethane foams are widely known and used in automotive, housing and other industries. Such foams are produced by reaction of a polyisocyanate with a polyol in the presence of various additives. One such additive is a chlorofluorocarbon (CFC) blowing agent which vaporizes as a result of the reaction exotherm, causing the polymerizing mass to form a foam. The discovery that CFCs deplete ozone in the stratosphere has resulted in mandates diminishing CFC use. Production of water-blown foams, in which blowing is performed with CO 2 generated by the reaction of water with the polyisocyanate, has therefore become increasingly important. Tertiary amine catalysts are typically used to accelerate blowing (reaction of water with isocyanate to generate CO 2 ) and gelling (reaction of polyol with isocyanate).
The ability of the tertiary amine catalyst to selectively promote either blowing or gelling is an important consideration in selecting a catalyst for the production of a particular polyurethane foam. If a catalyst promotes the blowing reaction to a too high degree, much of the CO 2 will be evolved before sufficient reaction of isocyanate with polyol has occurred, and the CO 2 will bubble out of the formulation, resulting in collapse of the foam. A foam of poor quality will be produced. On the other hand, if a catalyst too strongly promotes the gelling reaction, a substantial portion of the CO 2 will be evolved after a significant degree of polymerization has occurred. Again, a poor quality foam, this time characterized by high density, broken or poorly defined cells, or other undesirable features, will be produced.
Tertiary amine catalysts generally are malodorous and offensive and many have high volatility due to low molecular weight. Release of tertiary amines during foam processing may present significant safety and toxicity problems, and release of residual amines from consumer products is generally undesirable.
Amine catalysts which contain ureido functionality (e.g., CONH 2 ) have an increase in molecular weight and hydrogen bonding and reduced volatility and odor when compared to related structures which lack this functionality. Furthermore, catalysts which contain ureido functionality chemically bond into the urethane during the reaction and are not released from the finished product. Catalyst structures which embody this concept are typically of low to moderate activity and promote both the blowing (water-isocyanate) and the gelling (polyol-isocyanate) reactions to varying extents.
U.S. Pat. No. 4,644,017 discloses the use of certain diffusion stable amino alkyl ureas having tertiary amino groups in the production of a polyisocyanate addition product which do not discolor or change the constitution of surrounding materials such as PVC.
U.S. Pat. No. 4,007,140 discloses the use of N,N'-bis(3-dimethylaminopropyl)urea as a low odor catalyst for the manufacture of polyurethanes.
U.S. Pat. No. 4,194,069 discloses the use of N-(3-dimethylaminopropyl)-N'-(3-morpholinopropyl)urea, N,N'-bis(3-dimethylaminopropyl)urea and N,N'-bis(3-morpholinopropyl)urea as catalysts for producing polyurethanes.
U.S. Pat. No. 4,094,827 discloses the use of certain alkyl substituted ureas which provide lower odor and a delay in the foaming reaction that aids in the production of polyurethane foam.
U.S. Pat. No. 4,330,656 discloses the use of N-alkyl ureas as catalysts for the reaction of 1,5-napthylene diisocyanate with polyols or for the chain extension of prepolymers based upon 1,5-napthylene diisocyanate without accelerating atmospheric oxidation.
DE 30 27 796 A1 discloses the use of higher molecular weight dialkyl aminoalkyl ureas as reduced odor catalysts for the production of polyurethane foam.
SUMMARY OF THE INVENTION
The present invention provides a composition for catalyzing the trimerization of an isocyanate and/or the reaction between an isocyanate and a compound containing a reactive hydrogen, e.g., the blowing reaction and the urethane reaction for making polyurethane. The catalyst composition comprises an N,N,N'-trimethylbis(aminoethyl)-ether substituted urea represented by formula I or II: ##STR2## The catalyst composition may comprise compound I, compound II, or a blend of compounds I and II in any weight ratio.
The advantage of these catalyst compounds is their high activity and blowing selectivity. Additionally, they contain a ureido group which will react with isocyanate and chemically bond into the urethane during the reaction; therefore, the catalyst composition is not released from the finished product. The compositions are somewhat viscous and have minimal odor.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst compositions according to the invention can catalyze (1) the reaction between an isocyanate functionality and an active hydrogen-containing compound, i.e. an alcohol, a polyol, an amine or water, especially the urethane (gelling) reaction of polyol hydroxyls with isocyanate to make polyurethanes and the blowing reaction of water with isocyanate to release carbon dioxide for making foamed polyurethanes, and/or (2) the trimerization of the isocyanate functionality to form polyisocyanurates.
The polyurethane products are prepared using any suitable organic polyisocyanates well known in the art including, for example, hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate ("TDI") and 4,4'-diphenylmethane diisocyanate ("MDI"). Especially suitable are the 2,4- and 2,6-TDI's individually or together as their commercially available mixtures. Other suitable isocyanates are mixtures of diisocyanates known commercially as "crude MDI", also known as PAPI, which contain about 60% of 4,4'-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates. Also suitable are "prepolymers" of these polyisocyanates comprising a partially prereacted mixture of a polyisocyanate and a polyether or polyester polyol.
Illustrative of suitable polyols as a component of the polyurethane composition are the polyalkylene ether and polyester polyols. The polyalkylene ether polyols include the poly(alkylene oxide) polymers such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, among others, ethylene glycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and like low molecular weight polyols.
In the practice of this invention, a single high molecular weight polyether polyol may be used. Also, mixtures of high molecular weight polyether polyols such as mixtures of di- and trifunctional materials and/or different molecular weight or different chemical composition materials may be used.
Useful polyester polyols include those produced by reacting a dicarboxylic acid with an excess of a diol, for example, adipic acid with ethylene glycol or butanediol, or reacting a lactone with an excess of a diol such as caprolactone with propylene glycol.
In addition to the polyether and polyester polyols, the masterbatches, or premix compositions, frequently contain a polymer polyol. Polymer polyols are used in polyurethane foam to increase the foam's resistance to deformation, i.e. to increase the load-bearing properties of the foam. Currently, two different types of polymer polyols are used to achieve load-bearing improvement. The first type, described as a graft polyol, consists of a triol in which vinyl monomers are graft copolymerized. Styrene and acrylonitrile are the usual monomers of choice. The second type, a polyurea modified polyol, is a polyol containing a polyurea dispersion formed by the reaction of a diamine and TDI. Since TDI is used in excess, some of the TDI may react with both the polyol and polyurea. This second type of polymer polyol has a variant called PIPA polyol which is formed by the in-situ polymerization of TDI and alkanolamine in the polyol. Depending on the load-bearing requirements, polymer polyols may comprise 20-80% of the polyol portion of the masterbatch.
Other typical agents found in the polyurethane foam formulations include chain extenders such as ethylene glycol and butanediol; crosslinkers such as diethanolamine, diisopropanolamine, triethanolamine and tripropanolamine; blowing agents such as water, CFCs, HCFCs, HFCs, pentane, and the like; and cell stabilizers such as silicones.
A general polyurethane flexible foam formulation having a 1-3 lb/ft 3 (16-48 kg/m 3 ) density (e.g., automotive seating) containing a gelling catalyst such as triethylenediamine (TEDA) and a blowing catalyst such as the catalyst composition according to the invention would comprise the following components in parts by weight (pbw):
______________________________________Flexible Foam Formulation pbw______________________________________Polyol 20-100Polymer Polyol 80-0Silicone Surfactant 1-2.5Blowing Agent 2-4.5Crosslinker 0.5-2Catalyst 0.2-2Isocyanate Index 70-115______________________________________
Any gelling catalyst known in the polyurethane art may be used with the catalyst compounds of the invention. Illustrative of suitable gelling catalysts are TEDA and tin urethane catalysts.
The blowing catalyst composition comprises the compounds represented by the following formulas I and II, and any wt % combination of compounds I and II. Mixtures of compounds I and II may comprise 50 to 95 wt % compound I and 5 to 50 wt % compound II. As a result of the preparation procedure the catalyst composition may also contain up to 20 wt % unreacted urea III. ##STR3##
Compounds I and II are prepared by reacting urea and 4,10-diaza-4,10,10-trimethyl-7-oxa-undecanamine in the appropriate molar ratios under an inert atmosphere at elevated temperatures. Compounds I and II can be isolated individually by chromatography.
A catalytically effective amount of the catalyst composition is used in the polyurethane formulation. More specifically, suitable amounts of the catalyst composition may range from about 0.01 to 10 parts by wt per 100 parts polyol (phpp) in the polyurethane formulation, preferably 0.05 to 0.5 phpp.
The catalyst composition may be used in combination with, or also comprise, other tertiary amine, organotin or carboxylate urethane catalysts (gelling and/or blowing) well known in the urethane art.
EXAMPLE 1
Blend of 4,10-Diaza-4,10,10-trimethyl-7-oxa-undecane urea and N,N'-Bis-(4,10-diaza-4,10,10-trimethyl-7-oxa-undecane)urea
A one liter 3 neck round bottom flask was fitted with the following: mechanical stirrer, reflux condenser, nitrogen sparger, and a temperature controlled heating mantle. The flask was charged with 138.31 g of urea (CH 4 N 2 O) and 467.49 g of 4,10-diaza-4,10,10-trimethyl-7-oxa-undecanamine (IV) (C 10 H 25 N 3 O). (Compound IV can be prepared according to following Examples 5-7.) ##STR4## The mixture was stirred at a constant rate while being slowly heated to 120° C. The reaction was controlled at 120° C. until all signs of NH 3 evolution had ceased (as evidenced by bubbling in the N 2 pressure relief device). The pale yellow liquid was cooled to 80° C. and the flask containing the liquid was evacuated via vacuum pump and refilled with N 2 three time to remove any volatiles still present. Table 1 presents quantitative 13 C NMR analysis of the reaction.
TABLE 1______________________________________Reaction Product Example 1 mole %______________________________________4,10-Diaza-4,10,10-trimethyl-7-oxa-undecane urea 85.27N,N'-Bis-(4,10-diaza-4,10,10-trimethyl-7-oxa-undecane) urea 4.65Urea 10.08______________________________________
EXAMPLE 2
4,10-Diaza-4,10,10-trimethyl-7-oxa-undecane urea
The mixture from Example 1 was dissolved in ether and filtered through silica gel. The silica gel was washed with methanol and the extract was concentrated using a rotary evaporator. Quantitative 13 C NMR analysis of the methanol extract is shown in Table
TABLE 2______________________________________Reaction Product Example 2 mole %______________________________________4,10-Diaza-4,10,10-trimethyl-7-oxa-undecane urea 89.32N,N'-Bis-(4,10-diaza-4,10,10-trimethyl-7-oxa-undecane) urea 2.91Urea 7.77______________________________________
EXAMPLE 3
N,N'-Bis-(4,10-diaza-4,10,10-trimethyl-7-oxa-undecane)urea
A one liter 3 neck round bottom flask was fitted with the following: mechanical stirrer, reflux condenser, nitrogen sparger, and a temperature controlled heating mantle. The flask was charged with 8.88 g of urea (CH 4 N 2 O) and 63.03 g of 4,10-diaza-4,10,10-trimethyl-7-oxa-undecanamine (IV) (C 10 H 25 N 3 O). The mixture was stirred at a constant rate while being slowly heated to 120° C. The reaction was controlled at 120° C. until all signs of NH 3 evolution had ceased (as evidenced by bubbling in the N 2 pressure relief device). The temperature was increased to 140° C., 160° C., and 180° C., allowing bubbling to subside between temperature increases. The yellow liquid was cooled to 80° C. and the flask containing the liquid was evacuated via vacuum pump and refilled with N 2 three times to remove any volatiles still present. Quantitative 13 C NMR results of the reaction product are presented in Table
TABLE 3______________________________________Reaction Product Example 3 mole %______________________________________4,10-Diaza-4,10,10-trimethyl-7-oxa-undecane urea 4.76N,N'-Bis-(4,10-diaza-4,10,10-trimethyl-7-oxa-undecane) urea 95.24Urea 0______________________________________
EXAMPLE 4
In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in parts by weight (pbw):
______________________________________COMPONENT PARTS______________________________________E-648 60E-519 40DC-5043 1.5Diethanolamine 1.49Water 3.5TDI 80 105 Index______________________________________ E-648 a conventional, ethylene oxide tipped polyether polyol marketed by Arco Chemical Co. E519 a styreneacrylonitrile copolymer filled polyether polyol marketed b Arco Chemical Co. DABCO ® DC5043 silicone surfactant marketed by Air Products and Chemicals, Inc. TDI 80 a mixture of 80 wt % 2,4TDI and 20 wt % 2,6TDI
For each foam, the catalyst (Table 4) was added to 202 g of the above premix in a 32 oz (951 ml) paper cup and the formulation was mixed for 20 seconds at 5000 RPM using an overhead stirrer fitted with a 2 in (5.1 cm) diameter stirring paddle. Sufficient TDI 80 was added to make a 105 index foam index=(mole NCO/mole active hydrogen)×100! and the formulation was mixed well for 5 seconds using the same overhead stirrer. The 32 oz (951 ml) cup was dropped through a hole in the bottom of a 128 oz (3804 ml) paper cup placed on a stand. The hole was sized to catch the lip of the smaller cup. The total volume of the foam container was 160 oz (4755 ml). Foams approximated this volume at the end of the foam forming process. Maximum foam height and time to reach the top of the mixing cup (TOC1) and the top of the 128 oz. cup (TOC2) were recorded (see Table 4).
TABLE 4______________________________________ Full Foam TOC1 TOC 2 Height HeightCATALYSTS (sec) (sec) (sec) (mm)______________________________________0.25 pphp DABCO 33LV/0.10 13.39 41.13 130.04 418.87pphp DABCO BL-110.25 pphp DABCO 33LV 20.54 72.94 192.77 403.100.25 pphp DABCO 33LV/0.18 13.75 39.68 117.49 422.92pphp Ex 1 catalyst______________________________________ DABCO 33LV ® catalyst 33 wt % TEDA in dipropylene glycol from Air Products and Chemicals, Inc. DABCO BL11 catalyst 70 wt % bisdimethylaminoethyl ether in dipropylene glycol from Air Products and Chemicals, Inc..
The data in Table 4 show that the use of the Example 1 catalyst composition afforded an initial reactivity profile as measured by TOC1 and TOC2 comparable to that of the control catalyst BL-11, with the added advantage that full foam height was reached more rapidly. The 33LV only control demonstrated that both the control blowing catalyst BL-11 and the Example 1 blowing catalyst contributed observable catalytic activity at the chosen use levels.
EXAMPLE 5
N,N,N'-Trimethylbis(aminoethyl)ether (TMAEE)
A 2-liter stainless steel autoclave was charged with 499.4 g (3.75 moles) of dimethylaminoethoxyethanol (DMAEE) and 37.9 g of Cu/ZnO/Al 2 O 3 catalyst. After purging the reactor with N 2 and H 2 , the catalyst was reduced in situ under 56 bar of H 2 at a temperature of 195° C. for 9 hr. The reactor was then cooled to 25° C. and vented to ambient pressure. From a sample cylinder connected to a port in the reactor head, 177 g (5.7 moles) of monomethylamine (MMA) was charged using a 6.5 bar N 2 head to assist in the transfer. After resealing the reactor and pressurizing it to 14.8 bar with H 2 , the reactor was heated to 195° C. and kept at that temperature for 23.3 hr. The reactor was then cooled to 25° C. and 600.1 g of reaction product was recovered after filtration to remove the catalyst particles. Gas chromatographic analysis showed that 65% of the DMAEE was converted and the reaction product contained:
______________________________________Reaction Product wt %______________________________________N,N,N'-trimethylbis(aminoethyl)ether 38.2Dimethylaminoethoxyethanol 29.4Water 7.1Monomethyl amine 5.8Other amines 19.5______________________________________
The reaction product was heated under vacuum to remove the low boiling components. A short path distillation was then done to remove heavies and any traces of Cu/ZnO/Al 2 O 3 catalyst. The overhead product from the short-path distillation (325.6 g) contained:
______________________________________Overhead Product from Short-Path Distillation wt %______________________________________N,N,N'-trimethylbis(aminoethyl)ether 57.2Dimethylaminoethoxyethanol 37.4Other amines 5.4______________________________________
This overhead product was used in the preparation of TMCEAEE in Example 6 below.
EXAMPLE 6
N,N,N'-Trimethyl-N'-2-cyanoethylbis(aminoethyl)ether (TMCEAEE)
Into a three necked round bottom flask equipped with a teflon coated magnetic stir bar, reflux condenser, pressure equalizing dropping funnel, and thermometer was placed 325 g of the mixture from Example 1 (1.27 moles of contained N,N,N'-trimethylbis(aminoethyl)ether). The mixture was heated to 55° C. and 71 g (1.34 moles) of acrylonitrile was added over a period of two hours. The reaction was allowed to proceed an additional five hours until less than 1% of unreacted N,N',N'-trimethylbis(aminoethyl)ether remained. The crude product was used without purification in Example 7.
EXAMPLE 7
4,10-Diaza-4,10,10-trimethyl-7-oxa-undecanamine
N,N,N'-Trimethyl-N'-3-aminopropylbis(aminoethyl)ether (TMAPAEE)!
Into a 1 liter stainless steel autoclave was placed 20 g of chromium promoted sponge nickel and 150 g of 28% aqueous ammonium hydroxide. The reaction vessel was sealed and purged with nitrogen then hydrogen. The contents of the reaction vessel were then heated to 90° C. and the pressure adjusted to 82 bars with hydrogen. Then 426 g of the mixture from Example 2 was pumped into the reaction vessel over a period of 3.5 hours. The reaction was allowed to proceed an additional 50 minutes during which time less than 1% of the total hydrogen used was consumed. The hydrogen pressure was maintained at 82 bars throughout the reaction by admission of hydrogen from a 3.79 liter ballast on demand from a dome regulator. The reaction vessel was then cooled and vented and the contents filtered through a 0.45 micron fritted stainless steel filter.
The crude product was placed into a one liter flask and distilled through a 91.4 cm×2.54 cm i.d. packed column to afford 184.5 g of 97.5% pure 4,10-diaza-4,10,10-trimethyl-7-oxa-undecanamine (IV) collected at 124° to 133° C. at 13 millibar.
STATEMENT OF INDUSTRIAL APPLICATION
The present invention provides a catalyst composition for preparing polyurethane products, especially polyurethane foams. | A method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of a blowing agent, a cell stabilizer and a catalyst composition consisting essentially of the compound represented by the following formula I or II, or any blend of I and II. ##STR1## | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of the following patent applications:
1. Chinese patent application number 200810000936.9 titled “Thienopyridazine Compounds, Their Preparations, Pharmaceutical Compositions And Uses”, filed on 8 Jan. 2008 in the State Intellectual Property Office of the People's Republic Of China. 2. Chinese patent application number 200910000337.1 titled “Thienopyridazine Compounds, Their Preparations, Pharmaceutical Compositions And Uses”, filed on 6 Jan. 2009 in the State Intellectual Property Office of the People's Republic Of China. 3. PCT application number PCT/CN2009/000021 titled “Thienopyridazine Compounds, Their Preparations, Pharmaceutical Compositions And Uses”, filed on 7 Jan. 2009 in the State Intellectual Property Office of the People's Republic Of China.
The specifications of the above referenced applications are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
The present invention relates to pharmaceutical chemistry, in particular, relates to thienopyridazine compounds, their preparations, and pharmaceutical compositions containing them and uses thereof.
BACKGROUND OF THE INVENTION
Cancer is a major threat to human health, and a majority of cancers in human are caused by external environmental factors. Every year at least 5 million persons died of cancer around the world. The cure rate is still low although some treatment methods of cancers are currently available to cure patients, such as surgery, radiotherapy, chemotherapy and so on. Using chemical pharmaceuticals for preventing and treating cancers is currently one of the most effective methods.
Thienopyridazine compounds or compounds of their thieno analogues have been found to have anti-tumor activities.
F. Hoffman-La Roche AG discloses a thienopyridazine as an IKK inhibitor in WO2005105808.
Amgen Inc. of USA discloses a thienopyridazine compound as a p38 protease inhibitor of tyrosine kinase in WO2007124181.
Smithkline Beecham Corporation discloses a 2-ureidothiophene compound in WO03029241 and a 3-ureidothiophene compound in WO03028731, which are similar to thienopyridazine compounds as CHK1 inhibitors. AstraZeneca AB discloses a 3-ureidothiophene modified compound as a CHK1 inhibitor in WO 2005066163.
Chemical pharmaceuticals for preventing and treating cancers currently include inhibitors of receptors of tyrosine kinases and non-receptors of tyrosine kinases, and their targets include VEGFR, EGFR, HER2, SRC, JAK and TEK; and also include inhibitors of threonine-serine kinases and their targets include MEK, JNK, c-MET, AKT, PIM, TIE, PLK and so on. The compounds of the present invention are inhibitors of cancers and protein kinases including Checkpoint Kinase CHK1/CHK2 of cell cycles.
It has been found from researches for regulations of checkpoints of cell cycle that closing expression of CHK1 can reverse drug resistance of cancer cells, thereby increase sensitivities of tumor cells to DNA damage therapy, and dramatically increase activities of anti-cancer pharmaceuticals. In addition, it may obtain tumors selective pharmaceuticals through majorities of tumors having mutations features in p53 of eliminating G1/S checkpoint. The present invention provides a novel thienopyridazine compound as inhibitors of protein kinases of novel tumors associated with growth factors (including CHK1, CHK2), which not only have anti-tumor actions but also can enhance anti-tumor effectiveness of other anti-tumor pharmaceuticals.
SUMMARY OF THE INVENTION
According to the present invention, the applicant found novel compounds having anti-proliferative activities (e.g. anti-cancer activities), and thereby used for treatment of human and animal. The present invention also relates to methods for preparation of said compounds, pharmaceutical compositions comprising them, and their uses in the preparation of pharmaceuticals for use in the production of anti-proliferative effects in worm-blooded animals such as human.
The present invention includes pharmaceutically acceptable salts or prodrugs of such compounds, and the applicant also provides pharmaceutical compositions and methods of using such compounds for treatment of cancer according to the present invention.
Such properties of compounds of the present invention are expected to be of useful values for treatments of diseases associated with cell cycle stagnation and cell proliferation as follows: cancer (solid tumor and leukemia), fibroproliferative and differentiative diseases, psoriasis, rheumatoid arthritis, Kaposi's sarcoma, acute and chronic nephropathies, atheroma, atherosclerosis, arterial restenosis, autoimmune diseases, acute and chronic inflammation, bone diseases and ocular diseases with retinal vessel proliferation.
According to one aspect of the present invention, the compounds of formula (I) or their pharmaceutically acceptable salts or hydrates are provided,
Wherein, R1 and R2 are independently H or C 1-4 alkyl;
R3 is a saturated or unsaturated 5- or 6-membered ring containing N, S or O, and optical isomers thereof;
R4 is a halophenyl mono substituted or disubstituted at any position.
Preferably, R1═R2═H.
Preferably, R3 is a saturated 6-membered ring containing N, S or O, and its optical isomers.
Preferably, R3 is hexahydropyridyl, tetrahydropyranyl, tetrahydrothiopyranyl, tetrahydropyrrolidinyl, tetrahydrofuranyl, or tetrahydrothienyl, and its optical isomers.
Preferably, R3 is hexahydropyridinyl, and its optical isomers.
Preferably, R4 is a monosubstituted halophenyl.
Preferably, R4 is
wherein, X represents F, Cl, Br, I.
More preferably, the compounds of formula (I) are selected from as follows:
2-(4-fluorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-tetrahydrothiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrothiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-tetrahydrothiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(S-3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(R-3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrothiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrothiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-fluorophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-tetrahydrothiophenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrothiophenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-tetrahydrothiophenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(S-3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(R-3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrothiophenemethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrothiophenemethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
Preferably, R3 is pyridinyl, α-pyranyl, γ-pyranyl, α-thiopyranyl, γ-thiopyranyl, pyrrolidinyl, furanyl, or thienyl, and its optical isomers.
More preferably, the compounds of formula (I) are selected from as follows:
2-(4-fluorophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-α-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-α-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-α-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-α-thiopyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-α-thiopyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-α-thiopyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(2-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(4-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-thiopyranmethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-thiopyranmethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-fluorophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-fluorophenyl)-4-(3-thiaphenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-thiaphenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-bromophenyl)-4-(3-thiaphenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(2-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
2-(4-chlorophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-thiaphenemethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-thiaphenemethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(4-chlorophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-N-methyl formamide;
2-(4-chlorophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-N,N-dimethyl formamide;
2-(3,5-dichlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide;
In accordance with another aspect of the present invention, a pharmaceutical composition is provided, including compounds of formula (I) having a therapeutically effective amount and its pharmaceutically acceptable salts or hydrates, and pharmaceutically acceptable carriers.
The pharmaceutical compositions of the present invention can be locally administered such as at lung, head, colon and so on in the form of solution, suspension, aerosol or dry power and so on; or systematically administered such as oral administration in the form of tablets, power, or parenterally administered in the form of solution or suspension, or subcutaneous administration, or rectal administration in the form of suppository, or percutaneous administration.
In accordance with another aspect of the present invention, uses of the compounds of formula (I) or pharmaceutically acceptable salts or hydrates thereof in the preparation for medicaments of treatment or prophylaxis of tumor diseases are provided. Wherein said tumor diseases include cervical tumor, tumor of head and neck, carcinoma of breast, ovary, lung (non small cell), pancreas, colon, prostate or other tissues, as well as leukemias and lymphomas, tumors of central and peripheral nervous system and other tumors such as melanoma, fibrosarcoma and osteosarcoma.
In accordance with further aspect of the present invention, uses of the compounds of formula (I) or pharmaceutically acceptable salts or hydrates thereof in preparation for medicaments of treatment or prophylaxis of proliferative diseases are provided. Wherein said proliferative diseases include autoimmune, inflammatory, neurological and cardiovascular diseases.
In accordance with one aspect of the present invention, uses of the compounds of formula (I) or pharmaceutically acceptable salts or hydrates thereof in the preparation for medicaments of limiting cell proliferation of human or animals are provided.
In accordance with still another aspect of the present invention, uses of the compounds of formula (I) or pharmaceutically acceptable salts or hydrates thereof in the preparation for medicaments of inhibiting the tumors or kinases associated with growth factors are provided.
For the above mentioned uses, the dosage depends on compounds used, administration approaches, required treatment diseases.
In accordance with last aspect of the present invention, methods of the compounds of formula (I) or pharmaceutically acceptable salts or hydrates thereof are provided, and the method includes the following steps:
In the presence of alkali, the compound of formula A is treated with dialkyl oxalates:
then is treated with hydrazine, to produce the compound of formula B:
the compound of formula B is treated with phosphorus oxychloride, to produce the compound of formula C:
and the compound of formula C is reacted with the compound R 3 CH 2 , to produce the compound of formula D,
and then the compound of formula D is reacted with NHR1R2, the protecting group on R3 is then removed and treated with an alkaline, to produce the compounds of formula (I) or pharmaceutically acceptable salts or hydrates thereof,
wherein R is a C 1-4 alkyl, and R1 and R2 are independently H or C 1-4 alkyl respectively; R3 is a saturated or unsaturated 6- or 5-membered ring containing N, S or O, and its optical isomers; R4 is a halophenyl monosubstituted or disubstituted at any position.
The synthesis process of the present invention is described below:
The synthesis process of 2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide.
Wherein, the compound of formula A may be prepared by conventional chemical methods in the field or purchased commercially. After being obtained, the compound of formula A is condensed with dialkyl oxalates, e.g. diethyl oxalate, in the presence of alkali such as common alkali LDA (lithium diisopropylamide) and common organic solvents such as tetrahydrofuran, to produce the compound Y. The condensation reaction should be proceeded at a low temperature due to the presence of LDA. It is easy for persons skilled in the art to obtain LDA which is generally fresh prepared at a low temperature.
Then, compound Y is reacted with hydrazine such as H 2 NNH 2 in alcoholic solvent to produce the compound of formula B.
The compound of formula B is treated with phosphorus oxychloride for an acylation reaction to produce the compound of formula C.
The above three steps refer to a synthesis method of intermediate of thienopyridazine compound produced by F. Hoffman-La Roche AG. in WO2005105808.
The compounds of R3CH 2 with a Boc protecting group are prepared by conventional methods in the field, and heated at the reaction temperature of 80˜90° C. in the presence of catalysts such as PdCl 2 (dppf) and solvents such as phosphates/1,4-dioxane, the compound of formula C is reacted with R3CH 2 containing a Boc protecting group for overnight to produce the compound of formula D. In the above reactions, the compounds of R3CH 2 should be pretreated with 9-BBN, please refer to the coupling reaction of “Suzuki-Miyaura”, p 6125-6128, Tetrahedron Letters 45(2004).
The compoundS of formula D and HNR1R2 are ammonolyzed in a sealed container using conventional methods with the reaction solvents of 1,4-dioxane, under heating at temperature of 80° C. for overnight, then the Boc protecting group on R3 is removed under acidic conditions to obtain the acid salts of formula (I), and adjust pH with alkali to produce the compounds of formula (I).
The raw materials of the above mentioned preparations are either obtained by commercial suppliers or are prepared by conventional methods in the field.
DETAILED DESCRIPTION OF THE INVENTION
Hereafter, the present invention will be described specifically with reference to examples. The examples are given only for illustration of the technical solution of the present invention and should not be construed to limit the present invention.
Where, the structure of the compounds of formula (I) is determined by nuclear magnetic resonance (NMR) and mass-spectrometric techniques; the proton NMR chemical shifts are measured using δ scale, and the peak multiplicity is represented as follows: s, single peak; m, multiple peak. The intermediate is generally represented by mass spectrometry and NMR.
EXAMPLE 1
2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1: Synthesis of 5-bromo-thiophene-3-formic acid
Thiophene-3-formic acid (12.6 g) and AcOH (96 ml) are added to a reaction flask (250 ml), to dissolved after stirred at room temperature, HBr solution (8 ml) is then added to the reaction flask, and the reaction is rapidly changed to a light yellow. Pyridinium bromide perbromide (27 g) is then added to the flask in batches at room temperature. After addition, the reaction is stirred at room temperature, and the reaction is tracked by HPLC. The above mixture is poured into ice-water after reaction, stirred for about 30 minutes, filtered to form a white powder solid, the white powder solid is crystallized with hot water, filtered and dried to obtain a crystal of 5-bromo-thiophene-3-formic acid (10.8 g), content of 92% measured by HPLC.
Thiophene-3-formic acid (12.5 g), AcOH (83 ml) are added to a reaction flask (500 ml), stirred at room temperature and dissolved to obtain a colorless transparent liquid. A solution of Br 2 (5.4 ml) in AcOH (100 ml) is placed in a constant pressure funnel and dropped to the reaction flask at room temperature and kept at a temperature below 25° C. After addition, the reaction is carried out at room temperature overnight. The reaction mixture is poured into ice-water next day, stirred for about 30 minutes, filtered to form a white powder solid. The white powder solid is crystallized with hot water, filtered and dried to obtain a white crystal of 5-bromo-thiophene-3-formic acid (10 g), content of 92% measured by HPLC.
Step 2: Synthesis of 5-bromo-thiophene-3-ethyl formate
5-bromo-thiophene-3-formic acid (18.5 g) obtained by the above step, absolute ethanol (150 ml) and concentrated sulfuric acid (5 ml) are added into a three mouth flask (500 ml) and heated under reflux, and vaporized under reduced pressure to remove solvent after reaction. Then ethyl acetate (100 ml) and saturated brine (200 ml) are added, and stirred, placed for layer separation. The aqueous layer is reextracted with ethyl acetate (25 ml×2) twice. The organic phase is combined together and transferred to a separatory funnel. Sodium carbonate solution (10%) is added to the separatory funnel to adjust pH≈8 and then separated, and a organic phase is washed with a saturated brine to pH=7, and dried with anhydrous magnesium sulfate over night, and filtered next day, and vaporized under reduced pressure to remove solvent to obtain a light yellow oil-liquid of 5-bromo-thiophene-3-ethyl formate (15 g).
Step 3: Synthesis of 4-chlorophenylboric acid
4-Bromochlorobenzene (70.6 g) is added into a four mouth flask connecting with a mechanical stirring apparatus, two constant pressure funnels and a temperature probe. Toluene (588.3 ml) and tetrahydrofuran (THF) (147 ml) are added under stiffing at room temperature under argon, and dissolved to obtain a colorless transparent liquid. Then triisopropyl borate (109.2 ml) and n-butyllithium (176.4 ml, 2.5M in hexane) are respectively added into two constant pressure funnels, and cooled the inner temperature to below −78° C., then n-butyllithium solution is dropped to the flask under controlling a dropping speed to keep the inner temperature below −78° C. After addition, the mixture is kept at the temperature for 1 hour, then triisopropyl borate is dropped into the mixture under the temperature below −78° C., and kept at the temperature for 1 hour after addition, and then the cooling system is removed to naturally warm up to −20° C. HCl solution (360.4 ml, 2.2M) is added to the mixture to warm up to about 10° C., and then placed for layer separation. The aqueous phase is reextracted with toluene (58.8 ml, 2 times). The organic phase is combined together and washed with saturated brine to pH=7 to obtain a colorless transparent liquid, dried with anhydrous sodium sulfate, filtered, and evaporated under reduced pressure to remove most of solvents and the white solid is finally precipitated, filtered to obtain a crystal of 4-chlorophenylboric acid (48 g).
Step 4: Synthesis of 5-(4-chlorophenyl)-thiophene-3-ethyl formate
5-(4-chlorophenyl)-thiophene 3-ethyl formate (10.5 g), 4-chlorophenylboronic acid (6 g), Pd[P(Ph) 3 ] 4 (1.5 g), sodium carbonate (7.5 g) and a solvent mixture of toluene:water:EtOH (4:2:1, v/v) are in turn added to a three mouth flask (500 ml) and heated at reflux for 3 hours, the reaction is tracked by TLC. The reaction mixture is cooled to a room temperature after reaction, and placed for layer separation. The aqueous phase is reextracted with toluene (35 ml, 2 times). The organic phase is combined together and washed with saturated brine to pH=7, dried with anhydrous sodium sulfate over night and filtered next day, and then evaporated under reduced pressure to remove solvents to obtain a light yellow viscous fluid, and placed to obtain a clotted solid, and recrystallized with absolute EtOH to obtain a crystal of 5-(4-chlorophenyl)-thiophene-3-ethyl formate (8.6 g).
1 HNMR (500 MHz, DMSO), δ 8.30 (sc, 1H), 7.81 (s, 1H), 7.72 (m, 2H), 7.46 (m, 2H), 4.27 (m, 2H), 1.30 (m, 3H).
Step 5: Synthesis of 5-(4-chlorophenyl)-2-ethoxyoxalyl-thiophene-3-ethyl formate
Preparation of LDA: THF (252.6 ml) and N,N-diisopropylamine (79 ml) are added into a three mouth flask (1000 ml) under argon, and n-butyllithium (302.8 ml, 1.6M in hexane) is placed to a constant pressure funnel (500 ml) and dropped into the flask when the inner temperature is below −20° C. with an intensely exothermic reaction, and kept −20° C.˜−30° C. of the inner temperature under controlling an adding speed; after addition, the above mixture naturally is warmed up to a room temperature directly used for the following condensation reaction.
Condensation reaction: 5-(4-chlorophenyl)-3-thiophene-ethyl formate (28.7 g), THF (1084 ml) and diethyl oxalate (29.7 ml) are added into a four mouth flask (2000 ml) connecting with the mechanical stirring apparatus, two constant pressure funnels and a temperature probe. The mixture is stirred at room temperature and dissolved to obtain a light yellow transparent liquid. LDA solution prepared by the above step is transferred into a constant pressure funnel and cooled to a temperature below −78° C., and LDA is dropped to the flash under argon at the temperature below −78° C. under controlling a dropping speed, after addition, the reaction is tracked by TLC. HCl solution (2.2M) is added to the flash after reaction and adjusted to pH≈3, and a color of the reaction liquid is changed from reddish brown into orange. The temperature is warmed up to about 0° C., a solid NaCl is then added, and stirred to desolve, and placed for layer separation. The aqueous phase is reextracted with THF (143.5 ml, 2 times). The organic phase is combined together and washed with saturated brine for two times, and then adjusted to pH≈8 with diluted sodium carbonate solution; finally, washed with saturated brine to pH=7, dried with anhydrous sodium sulfate, filtered and evaporated under reduced pressure to remove solvent to obtain a light yellow viscous fluid, and placed at room temperature to gradually become a solid, and recrystallized with EtOH to obtain a pure product of 5-(4-chlorophenyl)-2-ethoxyoxalyl-thiophene-3-ethyl formate (orange crystal, 25.5 g).
1 HNMR (500 MHz, CD 3 Cl), δ 7.61 (s, 1H), 7.59 (m, 2H), 7.42 (m, 2H), 4.37 (m, 4H), 1.39 (m, 6H).
Step 6: Synthesis of 2-(4-chlorophenyl)-4-oxo-4,5-dihydro-thiero[2,3-d]pyridazinyl-7-ethyl formate
A crystal of 5-(4-chlorophenyl)-2-ethoxyoxalyl-thiophene-3-ethyl formate (3.0 g), absolute ethanol (45 ml) are added into a reaction flask (100 ml), stirred at room temperature to obtain a yellow suspension. Hydrazine hydrate (0.75 ml) is added into a constant pressure funnel, stirred for 10 minutes and then dropped to the reaction flask. The yellow suspension is dissolved to a transparent liquid, and the above mixture is heated at 70° C. and a yellow solid in the flask is gradually precipitated with rise of the temperature, and the reaction liquid became increasingly viscous. The reaction mixture is kept for 1 h and then cooled to a room temperature, and filtered to obtain a pistachio solid, and the pistachio solid is respectively washed with a mixture of hexane/dichloromethane (1:1)(15 ml, 2 times) and methanol/dichloromethane (1:1)(15 ml, 2 times) and dried under reduced pressures to obtain 2-(4-chlorophenyl)-4-oxo-4,5-dihydro-thiero[2,3-d]pyridazinyl-7-ethyl formate (2.75 g).
Step 7: Synthesis of 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate
2-(4-chlorophenyl)-4-oxo-4,5-dihydro-thiero[2,3-d]pyridazinyl-7-ethyl formate (1.5 g), phosphorous oxychloride (22.5 ml) are added to a three mouth flask (100 ml), heated at 95° C. for 3 h, and dissolved to obtain a dark red brown solution. After reaction, the solution is cooled to a room temperature and evaporated under reduced pressures to remove solvent to obtain a chocolate brown viscous fluid. Tetrahydrofuran and a saturated brine are added to the fluid and stirred, and many yellow solids are precipitated, then filtered, placed for layer separation and reextracted; adjusted to pH≈9 with a diluted sodium carbonate solution after the organic phase is combined together; finally, washed with a saturated brine to pH=7, and dried with anhydrous sodium sulfate, filtered, decolourised with active carbon at reflux to obtain a light yellow green liquid; and the fluid is evaporated under reduced pressure to remove solvent to obtain 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (light green flocculent solid, 1.0 g).
1 HNMR (500 MHz, CD 3 Cl), δ 7.74 (m, 3H), 7.59 (m, 2H), 4.65 (m, 2H), 1.55 (m, 3H). HRMS (high resolution MS) MW=351.98.
Step 8: Synthesis of N-Boc-3-methylene piperidine
Triphenylmethyl phosphonium iodide (22.14 g) and toluene (135 ml) are added into a three mouth flask (500 ml), stirred at room temperature to obtain a milky white suspension and quickly changed to orange after potassium tert-butanolate (5.31 g) is added. Then N-Boc-3-piperidone (6.0 g) in toluene (66 ml) is added into a constant pressure funnel and dropped into the flask under argon with obvious exothermic phenomenon, and kept at the temperature of 30° C. and the reaction is tracked by TLC after addition. After reaction, the mixture is filtered and washed with a saturated brine (200 ml, 2 times) and then adjusted to pH≈3 with diluted HCl (1M), and then washed with a saturated brine to pH=7, dried with anhydrous sodium sulfate, and filtered to obtain a yellow transparent liquid. The yellow transparent liquid is purified together with silica gel by chromatography (elution liquid: petroleum ether:ethyl acetate=15:1) to obtain a yellow oil-liquid of N-Boc-3-methylene piperidine (4.2 g).
1 HNMR (400 MHz, CD 3 Cl), δ 4.83 (s, 1H), 4.76 (s, 1H), 3.89 (s, 2H), 3.45 (m, 2H), 2.26 (m, 2H) 1.64 (s, 2H), 1.51 (s, 9H).
Step 9: Synthesis of 4-(1-Boc-3-piperidinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate
N-Boc-3-methylene pyrazdine (0.4 g) is added into a three mouth flask under argon and cooled to 0° C. 9-BBN solution (12 ml, 0.5M in THF) is injected into the reaction flask with a syringe and kept for 30 min, and then warmed up to room temperature for 2 h, and evaporated to remove solvent under a reduced pressure (25° C.). 1,4-dioxane (20 ml), PdCl 2 (dppf) (0.05 g), potassium phosphate (0.32 g) and 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate are added to the reaction flask and heated at 90° C. over night. The reaction mixture is cooled to room temperature next day, then addition of ice water (50 ml) and ethyl acetate (50 ml), and then stirred for about 15 min, and placed for layer separation. The water layer is reextracted with ethyl acetate for 3 times, the organic phase is combined together and washed with a saturated brine to pH=7, dried with anhydrous magnesium sulfate and filtered. The filtered liquid is purified with silica gel by chromatography (ethyl acetate:petroleum ether=1:5) to obtain an orange viscous fluid (0.6 g), and ethanol (2 ml) is added to the fluid and crystallized in refrigerator to obtain a solid of 4-(1-Boc-3-piperidinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (0.3 g).
1 HNMR (400 MHz, DMSO), δ 8.90 (s, 1H), 8.03 (m, 2H), 7.63 (m, 2H), 4.54 (m, 2H), 3.73 (s, 2H), 3.32 (m, 2H), 3.28 (m, 1H), 2.82 (m, 2H), 2.09 (s, 1H), 1.78 (s, 1H), 1.64 (s, 1H), 1.44 (m, 3H), 1.39 (s, 1H), 1.32 (s, 9H).
MS (EI): 515 (M+), 486, 458, 442, 414, 334, 332, 306, 304, 149, 57.
Step 10: Synthesis of 4-(1-Boc-3-piperidinemethyl)-2(4-chlorophenyl)-7-aminocarbonyl-thieno[2,3-d]pyrida-zine
4-(1-Boc-3-piperidinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (0.3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred into a separating funnel next day, and addition of ethyl acetate, vibrated, and placed for layer separation. The water layer is reextracted with ethyl acetate for 2 times, the organic phase is combined together and adjusted to pH≈3 with 1M HCl solution, and then washed with saturated brine to pH=7, dried with anhydrous magnesium sulfate and filtered. The filtered liquid is purified with silica gel by chromatography (ethyl acetate:petroleum ether=1:5) to obtain a solid of 4-(1-Boc-3-piperidinemethyl)-2(4-chlorophenyl)-7-aminocarbonyl-thieno[2,3-d]pyridazine (0.22 g)
1 HNMR (500 MHz, CDCl 3 ), δ 8.10 (s, 1H), 7.77 (m, 2H), 7.66 (s, 1H), 7.48 (m, 2H), 5.90 (s, 1H), 4.05 (s, 1H), 3.88 (m, 1H), 3.31 (m, 1H), 3.21 (m, 1H), 2.81 (m, 2H), 2.28 (s, 1H), 1.81 (s, 1H), 1.67 (s, 3H), 1.39 (s, 9H).
MS (ESI): 487 (M+1).
Step 11: Synthesis of 2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride
4-(1-Boc-3-piperidinemethyl)-2(4-chlorophenyl)-7-aminocarbonyl-thieno[2,3-d]pyridazine (200 g) and ethyl acetate (4 ml) are added to a single mouth flask (25 ml) and dissolved to a light yellow transparent solution, addition of HCl (4 ml, 3M) and the solution is quickly changed to a white suspension, heated at 30° C. for 1 h, and the suspension is changed to transparent and the reaction is tracked by plate; after reaction, the above mixture is evaporated under reduced pressure to remove solvent to obtain a solid of 2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg).
1 HNMR (500 MHz, DMSO), δ9.51 (m, 1H), 9.09 (m, 1H), 8.79 (s, 1H), 8.66 (s, 1H), 8.29 (s, 1H), 8.08 (m, 2H), 7.62 (m, 2H), 3.45 (m, 2H), 3.4 (m, 1H), 3.17 (m, 1H), 2.79 (m, 2H), 2.52 (m, 1H), 1.81 (m, 2H), 1.77 (m, 1H), 1.42 (m, 1H).
MS (ESI): 387 (M+1).
Step 12:
Synthesis of 2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg) is added to a single mouth flask, then addition of water (5 ml) and the sodium carbonate is dropped to pH=9˜10, stirred for 30 min. The above mixture is extracted by ethyl acetate, washed with water, and evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (70 mg).
EXAMPLE 2
2-(4-chlorophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethyltetrahydropyran (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then addition of the zinc-reagent to the THF solution and reacted at 45° C. for 4 hours. The above mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 and evaporated under reduced pressure to remove solvent to obtain 4-(3-tetrahydropyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 417 (M+1)
Step 2:
4-(3-tetrahydropyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night, cooled to room temperature over night and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-tetrahydropyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 388 (M+1)
EXAMPLE 3
2-(4-chlorophenyl)-4-(3-tetrahydrothiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethyl tetrahydrothiapyran (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly added at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 hours. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 and evaporated under reduced pressure to remove solvent to obtain 4-(3-tetrahydropyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 433 (M+1)
Step 2:
4-(3-tetrahydropyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night, and cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-tetrahydropyranmethy)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 404 (M+1)
EXAMPLE 4
2-(4-chlorophenyl)-4-(2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to N-Boc-2-bromomethyl piperidine (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly added at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is added to the THF solution at 45° C. for 4 hours. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 and evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(N-Boc-2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 516 (M+1)
Step 2:
2-(4-chlorophenyl)-4-(N-Boc-2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred into a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The water layer is reextracted with ethyl acetate for 2 times, the organic phase is combined together and adjusted to pH≈3 with 1M HCl solution, and then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2(4-chlorophenyl)-4-(N-Boc-2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 487 (M+1)
Step 3:
4-(N-Boc-2-piperidinemethyl)-2(4-chlorophenyl)-7-aminocarbonyl-thieno[2,3-d]pyridazine (200 mg) and ethyl acetate (4 ml) are added to a single mouth flask (25 ml) and dissolved to a light yellow transparent solution. HCl solution (4 ml, 3M) is added and changed to a white suspension, heated at 30° C. for 1 h and the white suspension is changed to transparent. The reaction is tracked by plate. After reaction, the solvent is evaporated under reduced pressure to remove solvent to obtain a solid of 2-(4-chlorophenyl)-4-(N-Boc-2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg).
MS (ESI): 423 (M+1)
Step 4:
2-(4-chlorophenyl)-4-(N-Boc-2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg) is added to a single mouth flask, then addition of water (5 ml) and the sodium carbonate is dropped to pH=9˜10, stirred for 30 min. The above mixture is extracted by ethyl acetate, washed, and evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(2-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (70 mg).
MS (ESI): 387 (M+1)
EXAMPLE 5
2-(4-chlorophenyl)-4-(4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to N-Boc-4-bromomethylpiperidine (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(N-Boc-4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 515 (M+1)
Step 2:
2-(4-chlorophenyl)-4-(N-Boc-4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred into a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The water layer is reextracted with ethyl acetate for 2 times, the organic phase is combined together and adjusted to pH≈3 with 1M HCl solution, and then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2(4-chlorophenyl)-4-(N-Boc-4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 487 (M+1)
Step 3:
4-(N-Boc-4-piperidinemethyl)-2-(4-chlorophenyl)-7-aminocarbonyl-thieno[2,3-d]pyridazine (200 mg) and ethyl acetate (4 ml) are added to a single mouth flask (25 ml) and dissolved to a light yellow transparent solution. HCl solution (4 ml, 3M) is added and changed to a white suspension, heated at 30° C. for 1 h and the white suspension is changed to transparent. The reaction is tracked by plate. After reaction, the mixture is evaporated under reduced pressure to remove to obtain a solid of 2-(4-chlorophenyl)-4-(4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg).
MS (ESI): 423 (M+1)
Step 4:
2-(4-chlorophenyl)-4-(4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride is added to a single mouth flask (25 ml), then water (5 ml) is added and the sodium carbonate is dropped to pH=9˜10 stirred for 30 min. The above mixture is extracted by ethyl acetate, washed, and evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(4-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (70 mg).
MS (ESI): 387 (M+1)
EXAMPLE 6
2-(4-chlorophenyl)-4-(3-pyrrolidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to N-Boc-3-bromomethylpyrrole (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is added to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , ands evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(N-Boc-3-tetrahydropyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 502 (M+1)
Step 2:
2-(4-chlorophenyl)-4-(N-Boc-3-tetrahydropyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction liquid is cooled to room temperature and transferred into a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The water layer is reextracted with ethyl acetate for 2 times, the organic phase is combined together and adjusted to pH≈3 with 1M HCl solution, and then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2(4-chlorophenyl)-4-(N-Boc-3-tetrahydropyrrole methyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 473 (M+1)
Step 3:
4-(N-Boc-3-tetrahydropyrrolemethyl)-2(4-chlorophenyl)-7-aminocarbonyl-thieno[2,3-d]pyridazine (200 mg) and ethyl acetate (4 ml) are added to a single mouth flask (25 ml) and dissolved to a light yellow transparent solution. HCl solution (4 ml, 3M) is added and changed to a white suspension, heated at 30° C. for 1 h and changed to transparent. The reaction is tracked by plate. After reaction, the solution is evaporated under reduced pressure to remove solvent to obtain a solid of 2-(4-chlorophenyl)-4-(3-tetrahydropyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg).
MS (ESI): 409 (M+1)
Step 4:
2-(4-chlorophenyl)-4-(3-tetrahydropyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride is added to a single mouth flask (25 ml), then water (5 ml) is added and sodium carbonate is dropped to pH=9˜10 and stirred for 30 min. The mixture is extracted by ethyl acetate, washed, and evaporated under reduced pressure to remove solvent to obtain 2-(4-chlorophenyl)-4-(3-tetrahydropyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (70 mg).
MS (ESI): 373 (M+1)
EXAMPLE 7
2-(4-chlorophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethyltetrahydrofuran (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-tetrahydropyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 403 (M+1)
Step 2:
4-(3-tetrahydrofuranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-tetrahydrofuranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 374 (M+1)
EXAMPLE 8
2-(4-chlorophenyl)-4-(3-tetrahydrothiophenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethyl tetrahydrothiophene (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added, and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-tetrahydrothiophenemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 419 (M+1)
Step 2:
4-(3-tetrahydrothiophenemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-tetrahydrothiophene methyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 389 (M+1)
EXAMPLE 9
2-(4-chlorophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethylpyridine (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtered after stiffing for 15 minutes and placed for liquid separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-pyridinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 410 (M+1)
Step 2:
4-(3-pyridinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH3.H2O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na2SO4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 381 (M+1)
EXAMPLE 10
2-(4-chlorophenyl)-4-(3-α-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethylpyran (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-α-pyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 412 (M+1)
Step 2:
4-(3-α-pyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-α-pyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 383 (M+1)
EXAMPLE 11
2-(4-chlorophenyl)-4-(3-α-thiapyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethylthiopyran (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-α-thiopyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 428 (M+1)
Step 2:
4-(3-α-thiopyranmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-α-thiopyranmethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 399 (M+1)
EXAMPLE 12
2-(4-chlorophenyl)-4-(2-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 2-bromomethylpyridine (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 hours. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes, and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(2-pyridinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 410 (M+1)
Step 2:
4-(2-pyridinemethy)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na2SO4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(2-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 381 (M+1)
EXAMPLE 13
2-(4-chlorophenyl)-4-(4-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 4-bromomethylpyridine (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , ands evaporated under reduced pressure to remove solvent to obtain 4-(4-pyridinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 410 (M+1)
Step 2:
4-(4-pyridinemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(4-pyridinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 381 (M+1)
EXAMPLE 14
2-(4-chlorophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethylpyrrole (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-pyrrolemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 398 (M+1)
Step 2:
4-(3-pyrrolemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 369 (M+1)
EXAMPLE 15
2-(4-chlorophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethylfuran (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is added dropwise to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and place for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-furanmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 399 (M+1)
Step 2:
4-(3-furanmethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-furanmethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 370 (M+1)
EXAMPLE 16
2-(4-chlorophenyl)-4-(3-thiaphenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 3-bromomethylthiophene (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(3-thiophenemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 415 (M+1)
Step 2:
4-(3-thiophenemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(3-thiophenemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 386 (M+1)
EXAMPLE 17
2-(4-chlorophenyl)-4-(2-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
DMPU (225 ml), FeCl 3 (0.75 g) and CuCl (0.3 g) are added to 2-bromomethylpyrrole (24.75 g, 0.138 mol), and then Et 2 Zn (106.8 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (810 ml) and PdCl 2 (dppf) (5.09 g) are added to 4-chloro-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stiffing for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (500 ml, 2 times). The organic phase is combined together, washed with a saturated brine (500 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 4-(2-pyrrolemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (25 g).
MS (ESI): 398 (M+1)
Step 2:
4-(2-pyrrolemethyl)-2-(4-chlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (3 g), 1,4-dioxane (5 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (25 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred to a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The aqueous layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted with 1M HCl solution to pH≈3, then washed with a saturated brine to pH=7, dried with anhydrous Na 2 SO 4 and filtered. The filtered liquid is purified with silica gel by chromatography to obtain a solid of 2-(4-chlorophenyl)-4-(2-pyrrolemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (2 g).
MS (ESI): 369 (M+1)
EXAMPLE 18
2-(3,5-dichlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide
Step 1:
5-bromo-thiophene-3-ethyl formate (10.5 g), 3,5-dichlorobenzene boronic acid (6 g), Pd[P(Ph) 3 ] 4 (1.5 g), sodium carbonate (7.5 g) and a mixture (347 ml) of toluene:water:EtOH (4:2:1, v/v) are in turn added to a three mouth flask (500 ml) and heated at reflux for 3 h. The reaction is tracked by TLC. The reaction mixture is cooled to room temperature after reaction, and placed for layer separation. The aqueous phase is extracted with toluene (35 ml, 2 times). The organic phase is combined together and washed with a saturated brine to pH=7, dried with anhydrous sodium sulfate over night and filtered next day, and evaporated under reduced pressure to remove solvent to obtain a light yellow viscous fluid, placed for solid condensation, and recrystallized with absolute EtOH to obtain a crystal of 5-(3,5-dichlorophenyl)-3-thiophene-ethyl formate (8.6 g).
Step 2:
Preparation of LDA: THF (252.6 ml) and N,N-diisopropylamine (79 ml) are added into a three mouth flask (1000 ml) under argon, and n-Buli (302.8 ml, 1.6M in hexane) is added into a constant pressure funnel (500 ml) and is dropped when the inner temperature is below −20° C. with an intensely exothermic reaction, and kept the inner temperature between −20° C.˜−30° C. by controlling a adding speed. After addition, the reaction mixture is naturally warmed up to room temperature, and then directly used for the following condensation reaction.
Condensation Reaction: 5-(3,5-dichlorophenyl)thiophene-3-ethyl formate (28.7 g), THF (1084 ml) and diethyloxalate (29.7 ml) are added into a four mouth flask (2000 ml) connecting with a mechanical stiffing apparatus, a 500 ml constant pressure funnel and a temperature probe. The above mixture is stirred at room temperature and dissolved to obtain a light yellow transparent liquid. The LDA solution prepared is transferred into a constant pressure funnel under argon, cooled, and then the LDA is dropped to the flask when the inner temperature is below −78° C., and kept the inner temperature below −78° C. by controlling the adding speed. After addition, the reaction is tracked by TLC. HCl solution (2.2M) is added to adjust pH≈3 after reaction, and the color of the reaction mixture is changed from reddish brown into orange. The temperature is warmed up to about 0° C., a solid NaCl is then added, and desolved under stirring, and then placed for layer separation. The aqueous phase is reextracted with THF (143.5 ml, 2 times). The organic phase is combined together and washed with a saturated brine for two times, and then adjusted pH≈8 with diluted sodium carbonate solution; finally, washed with a saturated brine to pH=7, dried with anhydrous sodium sulfate, filtered and evaporated under reduced pressure to remove solvent to obtain a light yellow viscous fluid, placed at room temperature and gradually condensated to solid, recrystallized by EtOH to obtain a pure product of 5-(3,5-dichlorophenyl)-2-ethoxyoxalyl-thiophene-3-ethyl formate (orange crystal, 25.5 g).
Step 3:
A crystal of 5-(3,5-dichlorophenyl)-2-ethoxyoxalyl-thiophene-3-ethyl formate (3.0 g), and absolute ethanol (45 ml) are added into a reaction flask (100 ml), stirred at room temperature to obtain a yellow suspension. The hydrazine hydrate (0.75 ml) is added into a constant pressure funnel under stiffing for 10 minutes and then dropped to the flask. The yellow suspension is dissolved to a transparent liquid, and heated at 70° C. to gradually precipitate yellow solids in the flask with rise of the temperature, and the reaction liquid increasingly becomes viscous, and kept for 1 h and then cooled to room temperature, and filtered to obtain a pistachio solid, the solid is respectively washed with a mixture of hexane/dichloromethane (1:1)(15 ml, 2 times) and methanol/dichloromethane (1:1)(15 ml, 2 times) and dried under a reduced pressure to obtain 2-(3,5-dichlorophenyl)-4-oxo-4,5-dihydro-thiero[2,3-d]pyridazine-7-ethyl formate (2.75 g).
Step 4:
2-(3,5-dichlorophenyl)-4-oxo-4,5-dihydro-thiero[2,3-d]pyridazine-7-ethyl formate (1.5 g) and phosphorous oxychloride (22.5 ml) are added to a three mouth flask (100 ml), heated at 90° C. for 3 h, and gradually dissolved to obtain a dark red brown solution. After reaction, the solution is cooled to room temperature and evaporated under reduced pressure to remove solvent to obtain a chocolate brown viscous fluid. THF and a saturated brine are added under stirring, then yellow solids are precipitated, filtered, placed for layer separation, and reextracted and adjusted to pH≈9 with diluted sodium carbonate solution after the organic phase is combined, and then washed with a saturated brine to pH=7, and dried with anhydrous sodium sulfate, filtered, decolourised with active carbons at reflux to obtain a light yellow green liquid, the liquid is evaporated under reduced pressure to remove solvent to obtain 4-chloro-2-(3,5-dichlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (light green flocculent solid, 1.0 g).
Step 5:
DMPU (5 ml), FeCl 3 (0.017 g) and CuCl (0.007 g) are added to N-Boc-3-bromomethylpiperidine (0.55 g), and then Et 2 Zn (2.5 ml) is slowly dropped at 40˜45° C. for 45 minutes to obtain a zinc-reagent.
THF (18 ml) and PdCl 2 (dppf) (0.12 g) are added to 4-chloro-2-(3,5-dichlorophenyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (30 g), and then the zinc-reagent is dropped to the THF solution at 45° C. for 4 h. The reaction mixture is poured into a saturated brine, filtrated after stirring for 15 minutes and placed for layer separation. The aqueous phase is extracted with THF (80 ml, 2 times). The organic phase is combined together, washed with a saturated brine (80 ml, 3 times) and dried with anhydrous Na 2 SO 4 , and evaporated under reduced pressure to remove solvent to obtain 2-(3,5-dichlorophenyl)-4-(N-Boc-3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (0.5 g).
Step 6:
2-(3,5-dichlorophenyl)-4-(N-Boc-3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-ethyl formate (0.5 g), 1,4-dioxane (1.0 ml) and NH 3 .H 2 O (5 ml) are added to a sealed tube (5 ml) and heated at 80° C. over night. The reaction mixture is cooled to room temperature and transferred into a separating funnel next day, and addition of ethyl acetate, vibrated, placed for layer separation. The water layer is reextracted with ethyl acetate for 2 times. The organic phase is combined together and adjusted to pH≈3 with 1M HCl solution, and then washed with saturated brine to pH=7, dried with anhydrous sodium sulfate and filtered. The filtered liquid was purified together with silica gel by flash chromatography to obtain a solid of 2(3,5-dichlorophenyl)-4-(N-Boc-3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (0.3 g).
Step 7:
2(3,5-dichlorophenyl)-4-(N-Boc-3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (200 g) and ethyl acetate (4 ml) are added to a single mouth flask (25 ml) and dissolved to a light yellow transparent solution. HCl solution (4 ml, 3M) is added and changed to a white suspension, and heated at 30° C. for 1 h and the white suspension is changed to transparent. The reaction is tracked by plate; and evaporated under reduced pressure after reaction to remove solvent to obtain a solid of 2-(3,5-dichlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg).
Step 8:
2-(3,5-dichlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide hydrochloride (100 mg) is added to a single mouth flask (25 ml), then addition of water (5 ml) and the sodium carbonate is dropped to pH=9˜10 under stirring for 30 min. The mixture is extracted by ethyl acetate, washed with water, and evaporated under reduced pressure to remove solvent to obtain 2-(3,5-dichlorophenyl)-4-(3-piperidinemethyl)-thieno[2,3-d]pyridazinyl-7-formamide (70 mg).
MS (ESI): 421 (M+1)
EXAMPLE 19
Preparation of Pharmaceutical Formulations
1. Injection
(1) Formulation
Compound II 50 g Sodium chloride 2250 g Water for injection 250,000 ml To make 1,000 bottles
(2) Preparation
The compound II is added into a tank according to the formulation, and water for injection (about 200,000 ml) is added and dissolved completely. Sodium chloride is then added according to the formation, and then continue to add sufficient quantity sodium chloride after completely dissolved. pH is adjusted to 4.0˜5.0. Activated carbon (250 g) is added for 30 minutes before being removed with filter decarbonization. The mixture is then bottled in 250 ml/bottle after precision filtration with Titanium Rod. The injection is prepared after water sterilization at 115° C. for 30 minutes.
2. Tablets
(1) Formulation
Compound XXXIII 50 g Starch 160 g Hydroxypropyl cellulose 39 g Polyvidone K30 (5%) q.s. Sodium carboxy methyl starch 10.4 g Magnesium stearate 1.3 g To make 1000 tablets
(2) Preparation
Compound XXXIII, starch and hydroxypropyl cellulose are added into a hopper of fluidbedgranulator, and warmed up to 38° C.˜45° C. by opening the main air to premix the material for 5 minutes. Suitable polyvidone K30 (5%) water solution is nebulized to granulate, the material is controlled to 55° C.˜60° C. and dried for 10 minutes, mixed with sodium carboxy methyl starch and magnesium stearate to tablet after granulation. 3. Capsules
(1) Formulation
Compound XXXXIV 50 g Lactose 194.4 g Sodium carboxy methyl starch 7.8 g Colloidal silicon dioxide 5.2 g Magnesium stearate 2.6 g To make 1000 capsules
(2) Preparation
Compound XXXXIV, lactose, sodium carboxy methyl starch and colloidal silicon dioxide are added into a mixer according to the formulation and mixed for 60 minutes to make it homogeneous. Magnesium stearate is then added according to the formulation and mixed for 10 minutes, filled in a general Gelatin plastic shell.
Some of the above compounds are tested in vitro and in vivo for their antitumor activities. Among these tests, the cytotoxicity is tested in vitro using SRB and MTT methods for 72 h. The specific activity data is summarized in Table 1. The growth inhibition effect of the compound on mouse S180 sarcoma is summarized in Table 2. The efficacy of the compounds on treating transplanted tumor of human colon cancer HT-99 on nude mice is summarized in Table 3.
TABLE 1
Anti-cancer Activity of the Compound IC50(μM) In vitro
Human poorly
Human
differentiated gastric
colon cancer
Mouse lung
Human ovarian
Order No.
Compound No.
adenocarcinoma (BGC-823)
HT-29
cancer (3LL)
cancer (A2780)
1
I
3.35
4.22
1.40
6.40
2
II
4.47
7.4
3.32
6.20
3
VI
5.86
7.53
2.55
1.54
4
XI
9.24
10.70
8.43
11.85
5
XIII
2.62
0.73
1.24
1.18
6
XIV
30.46
16.76
8.59
6.01
7
XV
2.25
804
8
XXI
8.68
9
XXIII
>100
5.57
>100
>100
10
XXVI
24.58
>100
>100
>100
11
XXXIV
74.50
>100
50.64
>100
12
XXXVIII
8.17
1.33
3.13
3.13
13
XXXXVI
11.11
>100
>100
30.29
14
XXXXXVIII
16.4
21.8
21.4
13.9
15
XXXXXXIX
17.02
9.48
3.31
7.11
16
XXXXXXX
5.45
>100
>100
>100
TABLE 2
The growth inhibition effects of the compounds on mouse S180 colon cancer
N = 7 −X ± SD
Compound
Dosage
Adimin
Starting
Ending
Tumor
Body Weight
Rate of
No.
mg/kg
Route
Body Weight(g)
Body Weight(g)
Weight (g)
without Tumor (g)
inhibition (%)
II
50
ip
19.70 ± 0.76
20.03 ± 1.11
1.41 ± 0.30
18.63 ± 0.93
52.62
XX
50
ip.
19.50 ± 0.89
21.19 ± 1.40
1.86 ± 0.26
19.33 ± 1.60
37.23
XII
50
ip.
19.50 ± 0.73
20.79 ± 1.83
1.48 ± 0.16
19.31 ± 1.79
50.02
XXIV
50
ip
19.39 ± 0.60
23.18 ± 1.66
1.62 ± 0.26
21.56 ± 1.48
45.45
Negative
19.49 ± 0.76
26.21 ± 2.38
2.97 ± 0.63
23.24 ± 2.18
Control
Note:
ip: administration of intraperitoneal injection.
TABLE 3
The efficacy of the compound on treating transplanted
tumor of human colon cancer HT-99 on nude mice
No. of
Compound
Dosage
Adimin.
Animals
TV(X + SD, mm 3 )
RTV
No.
mg/kg
Route
d0/dn
d0
dn
X ± SD
T/C (%)
II
60
ip, d0, 1
6/3
146 ± 13
690 ± 271
4.64 ± 1.65
70
V
60
ip, d0, 1
6/3
150 ± 16
910 ± 0
6.40 ± 0
96.5
XI
60
ip, d0, 1
6/1
150 ± 15
1224 ± 440
7.52 ± 0.26
113.4
XIX
60
ip, d0, 1
6/3
147 ± 9
663 ± 86
4.53 ± 0.82
68.3
XXII
60
ip, d0, 1
6/3
151 ± 11
714 ± 127
4.69 ± 0.71
70.7
XXX
60
ip, d0, 1
6/3
144 ± 23
482 ± 83
3.78 ± 1.09
57.0
XXXI
60
ip, d0, 1
6/3
145 ± 13
785 ± 300
5.36 ± 1.94
80.8
GCT + II
20 + 25
ip + iv, d0, 1
6/6
183 ± 7
409 ± 81
1.58 ± 0.27
30
GCT + XI
20 + 25
ip + iv, d0, 1
6/6
196 ± 15
399 ± 89
1.55 ± 0.22
27
GCT
20
ip, d0, 1
6/6
184 ± 17
463 ± 74
1.64 ± 0.44
37
CPT-11 + II
20 + 25
ip + iv, d0, 1
6/4
193 ± 15
619 ± 115
3.80 ± 1.01
57
CPT-11 + XI
20 + 25
ip + iv, d0, 1
6/5
207 ± 13
601 ± 36
1.61 ± 0.57
33
ADR + II
4 + 25
ip + iv, d0, 1
6/3
195 ± 19
573 ± 80
3.63 ± 1.09
50
ADR + XI
4 + 25
ip + iv, d0, 1
6/3
180 ± 21
697 ± 64
4.60 ± 1.52
69
ADR
4
ip, d0, 1
6/3
183 ± 13
667 ± 67
4.38 ± 1.38
64
Control
Solvent
ip, d0, 1
10/8
154 ± 12
1022 ± 276
6.63 ± 1.62
Notes:
d0: administration time for the first time;
dn: the 17 th day after administration;
RTV: relative tumor volume;
Control group: n = 10;
Treatment group: n = 6;
ip: administration of intraperitoneal injection
iv: administration of intravenous injection
GCT is a control drug: Gemcitabine
ADR is a control drug: Adriamycin
CPT-11 is a control drug: Irinotecan
It may be shown from the above tables that the compounds of the present invention not only have certain antitumor effects, and can also enhance the antitumor efficacy of the cytotoxic antitumor agents such as Gemcitabine, CPT-11, ADR and so on.
Although the present invention has been described in connection with the above embodiments, it should be understood that the present invention is not limited to such preferred embodiments and procedures set forth above. The embodiments and procedures were chosen and described in order to best explain the principles of the invention and its practical application, to thereby enable others skilled in the art to best utilize the invention. It will be apparent to those skilled in the art that various substitution, modifications and changes may be thereto without departing from the scope and spirit of the invention. Therefore, the intention is intended to cover all alternative constructions and equivalents falling within the spirit and scope of the invention as defined only by the appended claims and equivalents thereto. | The present invention relates to thienopyridazine compounds of formula (I), their pharmaceutically acceptable salts or hydrates, wherein R1 and R2 are independently H or C1-4 alkyl, R3 is a saturated or unsaturated 5- or 6-membered ring containing N, S or O, or its optical isomers, R4 is a halophenyl monosubstituted or disubstituted at any position. The present invention provides the preparation methods of these compounds, pharmaceutical compositions containing these compounds and the uses of these compounds, particularly in treating cancer. | 0 |
BACKGROUND OF THE INVENTION
There is a considerable body of prior art in the design of fan-type snowmaking apparatus wherein a high velocity stream of subfreezing ambient air is forced through a tubular housing from an open inlet to a coaxial outlet where water is sprayed into the air stream. This mixture of water and air propelled from the outlet end of the tubular housing is especially effective in making artificial snow if a nucleating device is provided in the tubular housing upstream of the water injection at the outlet end. A nucleating device sprays a mixture of fine droplets of water and pressurized air into the main air stream flowing through the tubular housing by air displacement means such as a motor-driven fan. The minute droplets of water generated by the nucleator attract moisture to form larger crystals more closely comparable to natural snow.
The most common conventional location for a nucleator nozzle is on the central axis of the tubular housing downstream of the fan, as exemplified by the designs in U.S. Pat. Nos. 3,733,029, 3,945,567 and 4,813,598. The fan or other air displacement means in such a configuration typically includes a drive motor coaxial with the fan axis, usually with some form of cowling over the motor, and a nucleator disposed coaxially downstream of that apparatus is necessarily in its lee so that the nucleator is not directly in the highest velocity air stream flow where its seeding of ice crystal nuclei can be most effective.
In U.S. Pat. No. 5,167,367 a design is disclosed wherein a multiple-orifice nucleator is located at a six o'clock position upstream of the water injection means instead of on the axis of the tubular housing, but even in that design the nucleator orifices are on the leeward side of a reservoir component tilted at an angle facing downstream, and hence are not directly in the air stream flow. A circular array of nucleator nozzles concentric with and spaced radially from the tubular housing axis is shown in U.S. Pat. No. 5,180,106 but they are completely shielded from the air stream flow by a fixed central cylindrical shroud.
To locate nucleator nozzles radially away from the axis of the tubular housing directly in the subfreezing air stream flow, and not in the protective lee of the coaxial fan and motor or some shroud such as that required in U.S. Pat. No. 5,180,516, can create serious icing problems. When compressed air mixes with water in the nucleator nozzle a subfreezing air stream impinging directly upon the nucleator may very well cause the water component in the nucleator to form rime ice which can clog the nucleator nozzle.
It is a principal purpose of the present invention to provide a nucleator assembly which will be located at a region of maximum effectiveness directly within the cold air stream flow through the tubular housing, and not in the lee of any upstream fan motor or shroud, and which enhances the mixing of air and water in the nucleator while preventing freezing of the water as it mixes with the air. Motionless mixers are well known for enhancing the mixing of certain viscous fluids, as taught for example in U.S. Pat. Nos. 4,840,903 and 4,850,705, but those devices generally are applicable to the mixing of viscous fluids in plastic injection molding processes or epoxy and resin static mixers. Motionless mixers of that form have not previously been utilized for water and air mixing in nucleators for snowmaking equipment.
SUMMARY OF THE INVENTION
The invention provides a nucleator assembly for snowmaking apparatus wherein an extended tubular housing has opposite coaxial inlet and outlet ends with air displacement means mounted within the housing remote from its outlet end for forcing an air stream through the housing and with water injection means downstream from the air displacement means for ejecting water into the air stream. The nucleator assembly includes at least one body element downstream from the air displacement means fixed radially with respect to the housing axis and having upstream and downstream portions. This body element defines at least one internal mixing chamber and respective air and water supply bores adapted to communicate said chamber with external sources of pressurized air and water respectively. On the downstream portion of the body element is a nozzle spaced radially from the housing axis to be directly in the air stream flow and communicating with the mixing chamber for ejecting an admixture of pressurized air and water into the air stream. Turbulence-creating mixing means are included within the mixing chamber for enhancing the mixing of the air and water ejected through the nozzle. Means are provided for preventing freezing of the water mixed with the air within and adjacent to the nozzle.
The body element is preferably radially disposed with respect to the housing axis and is upstream of the water injection means. The body element may be fixed at one end to the inside of the housing and at the other end to an axial diffuser extending downstream from the air displacement means. A plurality of body elements may be included spaced equally angularly apart radially around the housing axis.
In a preferred form of the invention the mixing chamber is elongated and the turbulence-creating mixing means is a removable elongated twisted motionless mixer unit inserted within the mixing chamber to enhance the mixing of the air and water ejected through the associated nozzle. For the freeze prevention means, a removable electrical heating cartridge may be mounted within a cartridge-receiving bore within the body element.
The body element is preferably in the form of a flat vane having upstream and downstream edge portions. The vane may have flat sides disposed parallel to the direction of the air stream flow and its upstream and downstream edges may be substantially narrower than said flat sides and tapered to present minimal resistance to the air stream flow. A thermal barrier slot may extend into the vane from its downstream edge portion between its mixing chamber and the housing axis to prevent heat conduction beyond that portion of the vane which includes the mixing chamber and nozzle.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a longitudinal elevation of snowmaking apparatus equipped with the nucleator assembly of the invention with the tubular housing in half section to show the internal components of the apparatus;
FIG. 2 is an end view of the outlet end of the apparatus of FIG. 1;
FIG. 3 is a lateral section taken along the line 3--3 of FIG. 1;
FIG. 4is an enlarged side elevation of one of the body elements or vanes of the nucleator assembly of the invention;
FIG. 5 is a top plan view of the body element or vane of FIG. 4; and
FIG. 6 is an end elevation of the downstream edge portion of the vane of FIG. 4.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring first to FIGS. 1 to 3 the snowmaking apparatus of the invention includes an extended tubular housing 10 having an inlet end 11 and an opposite coaxial outlet end 12. The housing 10 may be formed in three sections joined at flanges 13 and 14 to include an upstream converging inlet section 15, a relatively short cylindrical central section 16 and a somewhat longer outlet section 17. Suitable grating means may be provided across the inlet end 11 to prevent entry of foreign objects into the tubular housing 10.
Mounted coaxially principally within the inlet section 15 of the housing 10 is a fixed conical inlet diffuser 19 supported in place by appropriate radial ribs 20 and 21. Coaxially mounted by suitable radial supports (not shown) between the central section 16 and the outlet section 17 of the tubular housing 10 is an electric motor 23 which drives a fan 24 adapted to force a stream of sub-freezing ambient air through the tubular housing 10 from the inlet end 11 through the outlet end 12. It is known in the design of fan-type snowmaking apparatus to remove some blades of the fan 24 to render it asymmetrical and then balance the fan by appropriate weights applied elsewhere to rotating parts, all for the purpose of reducing noise emitted during operation. Conventional flow control fins 25 may be provided immediately downstream of the fan 24.
Extending coaxially from the downstream end of the motor 23 is a downstream conical diffuser 26 which ends approximately at the outlet end 12 of the housing 10. Encircling that outlet end of the housing 10 are water ejection means for ejecting water into the air stream forced through the housing 10. This may comprise two complete circular tubular headers 28 and 29 and one smaller header 30 describing a half circle. The headers 28 to 30 are supplied with water, under pressure from a source mentioned hereinafter, which is ejected through a multiplicity of nozzles 32 spaced equally angularly apart around the respective headers. Some of those nozzles 32 are shown in FIG. 2.
In accordance with the invention a nucleator assembly is included for introducing a spray of water into the cold air stream to provide nuclei for the formation of ice crystals when mixed with the water ejected at the nozzles 32. This nucleator assembly includes four radially disposed vanes 35, 36, 37 and 38, preferably of aluminum, shown in FIGS. 1 to 3. These four vanes are spaced equally angularly apart around the housing axis downstream from the air displacement means. One end of each vane is fixed to the inside of the outlet section 17 of the tubular housing 10 and the other end is fixed to and supports the downstream diffuser 26. As shown in FIG. 4 that edge of each vane 35 to 38 closest to the axis of the housing 10 is angled to conform to the conical shape of the downstream diffuser 26.
Turning now to FIGS. 4 to 6 the vane 35 is shown in more detail. The edge 40 is the aforementioned angled edge and it is opposite edge 41 which is affixed to the inside of the outlet section 17 of the housing 10. The vane 35 also includes an upstream edge portion 42 and a downstream edge portion 43.
The vane 35, like the vanes 36 to 38, has formed in its edge 41 a pair of threaded bores 45 and 46 for receiving fastening screws attaching it to the housing 10. Similarly its angled edge 40 is formed with threaded bores 47 and 48 for receiving fastening screws to secure it to the downstream diffuser 26.
Each vane defines an elongated interior mixing chamber 50 which is a blind hole opening at the downstream edge 43 of the vane. Transverse to the mixing chamber 50 is a water supply bore 51 communicating with the inner end of the mixing chamber 50 and opening on the edge portion 41 of the vane 35. Also, there is formed in the vane 35 a transverse air supply bore 52 which also communicates with the mixing chamber 50 and opens on the edge portion 41 of the vane 35. The bores 51 and 52 are connected by means not shown to a valving unit 54 on the underside of the outlet section 17 of the tubular housing 10 and thence by respective water and air lines 55 and 56 shown in FIG. 2 to appropriate external sources of pressurized water and air. Typical air flow may be at about 70 psig and water flow at about 400 psig. By means of a valve control 57 the flow of water may be varied to vary the ratio of water to air in the mix entering the mixing chamber 50 of the various vanes. Triple water supply nipples 58 are associated with the valving unit 54 for conduit connection to the three headers 28 to 30.
The mixture of water and air created in the mixing chamber 50 is ejected forcibly through a nozzle 59 on the downstream edge portion 43 of each vane. The orifice of the nozzle 59 is spaced radially from the central axis of the tubular housing 10 to be directly in the annular airstream flowing around the motor 23 and the downstream diffuser 26. The nozzle 59 is threaded into a socket formed in the downstream end of the mixing chamber 50. Before it is threaded in place an elongated turbulence-creating removable twisted motionless mixer unit 60 is inserted within the mixing chamber 50 for enhancing the mixing of the air and water. A preferred form of such a twisted motionless mixer unit is that shown and described in detail in the aforementioned U.S. Pat. Nos. 4,840,493 and 4,850,705 and it is commercially available. Its use heretofore has not extended to the mixing of water and air in snowmaking apparatus.
Each of the vanes has flat sides 62 and 63 disposed parallel to the direction of the air stream flow, the upstream and downstream edge portions 42 and 43 being substantially narrower than the flat sides 62 and 63. Also, the flat sides 62 and 63 include a tapered upstream edge portion 65 and a tapered downstream edge portion 66 to present minimal resistance to the air stream flow.
As noted previously, formation of rime ice adjacent the nozzles 59 is possible from the sub-freezing temperature of ambient air forced through the tubular housing 10 unless measures are taken to prevent such freezing. In accordance with the invention a removable electric cartridge 67 of a type which is commercially available is mounted in a cartridge-receiving bore 68 within the vane 35 generally adjacent the mixing chamber 50. The cartridge heats the region of the chamber 35 around the mixing chamber and adjacent the nozzle 59 to prevent that formation of rime ice. Also, to confine the heating effect to the desired area in the vane 35 a thermal barrier slot 70 extends into the vane 35 from its downstream edge portion 33 between the mixing chamber 50 and the housing axis. This prevents heat conduction beyond that portion of the vane 35 which includes the mixing chamber 50 and the nozzle 59.
In operation the motor 23 drives the fan 24 to force a high-velocity stream of air through the housing 10 into which water is sprayed from the nozzles 32 at the outlet end of the housing. The air stream proceeds in an annular flow over the motor 23 and the downstream diffuser 26 and passes directly over the nucleator vanes 35 to 38. Air and water under pressure are thoroughly mixed by the twisted motionless mixing unit 60 in the mixing chamber 50 and emerge from the nozzle 59 in a particularly fine spray to provide optimum nucleation for formation of large ice crystals closely resembling natural snow. In doing so, notwithstanding exposure to sub-freezing ambient air, no rime ice forms on the nozzles 59 because of the heating affect of the cartridge heater 67.
Various modifications can be made in the foregoing structure and embody the inventive concept. For example, the vanes 35 to 38 need not be radially disposed since it is necessary only that their nozzles 59 be spaced radially from the axis of the housing 10 directly within the air stream. Also there may be more than one array of the vanes 35 longitudinally spaced along the housing axis. The vanes need not be joined to the downstream diffuser 26 but could be joined together at the axis of the housing 10. While the flat shape of the vanes described hereinbefore is certainly preferred, their cross section could be varied.
The scope of the invention is to be determined from the following claims rather than from the foregoing description of a preferred embodiment. | A nucleator assembly for snowmaking apparatus wherein body elements or vanes are disposed in a tubular housing, preferably radially, downstream from an air displacement mechanism and define mixing chambers in which air and water are mixed and then ejected from nozzles on the body elements or vanes radially spaced from the housing axis directly in the air stream flow, and portions of the body elements or vanes are heated to prevent freezing of the water in and adjacent to the mixing chambers and nozzles. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a sewing machine, and more particularly, to a needle receiving assembly for a sewing machine.
2. Description of the Related Art
A full-turn shuttle hook and a half-turn shuttle hook are two examples of available shuttle bodies in sewing machines. In one type of the half-turn shuttle hook (hereinafter referred to as a "DBS shuttle hook"), the needle comes between an upper thread loop and the bobbin. The needle drop position is between the bobbin thread lead-out point of the bobbin and the beak of the shuttle body. In another type of the half-turn shuttle hook (hereinafter referred to as a "DPS shuttle hook"), the upper thread loop comes between the needle and the bobbin. Here, the beak of the shuttle body is between the needle drop position and the bobbin thread lead-out point of the bobbin.
A sewing machine incorporating a DBS shuttle hook forms perfect stitches in a forward feeding direction in which a fabric is fed in a right-to-left direction as viewed from the operator, and forms hitch stitches in a reverse feeding operation (in which a fabric is fed in a left-to-right direction as viewed from the operator). Hence, the sewing machine of this type is extensively employed for lock stitching.
In general, in lock stitching, perfect stitching should be employed to form straight stitches from the view point of the quality of stitches, and in order to eliminate the difficulty of a thread getting loose at both ends of a line of stitches, the latter should be ended by hitch stitching. In order to meet these requirements, a DBS shuttle hook is employed. However, a sewing machine having a DBS shuttle hook is not suitable for omnidirectional stitching.
A sewing machine incorporating a DPS shuttle hook is also known in the art (see, e.g., Japanese Patent No. 99353). This type of sewing machine is capable of forming perfect stitches in both the forward feeding direction and the reverse feeding direction and is thus suitable for omnidirectional stitching. However, this type of sewing machine is not popularly employed in the art yet. Additionally, it should be noted that the DPS shuttle hook responds well to the variation in thickness of a fabric, and is thus suitable for sewing a heavy weight fabric and for use with a thread large in yarn number count.
FIG. 6 shows a conventional bobbin case 100 used with a half-turn shuttle. As shown in FIG. 6, the bobbin case 100 has an engaging member 101, in which a thread hole 102 is formed. A bobbin thread 104 supplied from a bobbin 103 accommodated in the bobbin case 100 is passed through the thread hole 102 of the horn 101 of the bobbin case 100. The bobbin case is set in the sewing machine (not shown) such that it faces forward so that it is conveniently handled by an operator when it is set in or removed from the sewing machine.
The direction of rotation of the shuttle body should be determined so that the upper thread on the needle side is twistable because a sewing thread for a sewing machine is fundamentally of Z-twist. Thus, in the case of a DBS shuttle hook, the direction of rotation of the shuttle body is clockwise as viewed from the operator side. However, in the case of a DPS shuttle hook, the direction of rotation of the shuttle body is counterclockwise.
FIG. 7 shows a conventional shuttle race body 121 and a conventional shuttle race ring 125. The shuttle race body 121 has a recess 122 which is opened upwardly and in its joining surface which is brought into contact with the shuttle race ring 125. The shuttle race ring 125 has a needle receiving section (or rear loop receiving section) 126 in its joining surface which is brought into contact with the joining surface of the shuttle race body 121 in such a manner that the needle receiving section 126 confronts with the recess 122 of the shuttle race body 121. In FIG. 7, reference numeral 127 designates an engaging groove with which the horn 101 (FIG. 6) is engaged.
FIG. 8 shows the needle receiving section (or rear loop receiving section) 126 with the shuttle race ring 125 coupled to the shuttle race body 121. As shown in FIG. 9, when a DBS shuttle hook is employed, the needle receiving section 126 of the shuttle race ring 125 is capable of regulating a rear limb 114r on one side of the needle 113 and securing a front limb 114R on the other side. The front limb 114R is scooped up with the beak 112 of the DBS shuttle hook.
A sewing machine incorporating a DBS shuttle hook and a sewing machine incorporating a DPS shuttle hook will now be compared with reference to FIGS. 10(a) and 10(b).
In FIG. 10(a), reference numeral 111 designates the DBS shuttle hook; 112, the beak of the DPS shuttle hook 111; 113, the needle; 114, the upper thread; and R, the upper thread loop. In FIG. 10(b), reference numeral 115 designates the DPS shuttle hook; and 116, the beak of the DPS shuttle hook 115.
In the case where the DBS shuttle hook 111 is employed, the distance (1) between the needle drop point and the bobbin thread lead-out point is as shown in FIG. 10(a). In the case where the DPS shuttle hook 115 is employed, the distance (2) between the needle drop point and the bobbin thread lead-out point is as shown in FIG. 10(b). As shown in FIGS. 10(a) and 10(b), the distance (2) is larger than the distance (1).
In the case where the DPS shuttle hook 115 is employed, the distance (2) between the needle drop point and the bobbin thread lead-out point must be shifted laterally as much as (the width of the lace of the shuttle body+α (alpha)) when compared with the distance (1) between the needle drop point and the bobbin thread lead-out point in the case where the DBS shuttle hook 11 is employed.
In the case where the DPS shuttle hook 115 is employed, the beak 116 comes between the needle receiving groove (or rear loop receiving section) 126 of the shuttle race ring 125, and the loop R of the upper thread 114 is positioned on the side of the needle receiving section 126. Hence, in this case, unlike the case where the DBS shuttle hook is employed, the needle receiving groove 126 cannot regulate the rear limb.
However, if, in the case where the DPS shuttle hook 115 is employed, the rear limb cannot be regulated as was described above, then it is impossible to obtain the front limb sufficiently, and accordingly it may be impossible to scoop it up with the beak.
Heretofore, the shuttle race ring 125 has been integral with the needle receiving section (or rear loop receiving section) 126. Hence, it was impossible to adjust the position of the needle receiving section 126. This is another problem accompanying the employment of the DPS shuttle hook 115.
SUMMARY OF THE INVENTION
The present invention has been made in view of the above circumstances and has as an object to provide a needle receiving assembly for a sewing machine using the DPS shuttle hook which is capable of positively regulating the rear limb and which can be adjusted in position.
Additional objects and advantages of the invention will be set forth in part in the description which follows and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the appended claims.
To achieve the objects and in accordance with the purpose of the invention, as embodied and broadly described herein, a needle receiving assembly for a sewing machine is provided, comprising a throat plate through which a sewing needle can pass and a needle collar for regulating a rear loop of an upper thread passing through the sewing needle, the needle collar being adjustable in position relative to the sewing needle.
To further achieve the objects and in accordance with the purpose of the invention, as embodied and broadly described herein, a sewing machine is also provided, comprising means for driving a sewing needle, and a needle assembly, the needle assembly including a throat plate through which the sewing needle passes when driven by the driving means and a needle collar for regulating a rear loop of an upper thread passing through the sewing needle, the needle collar being adjustable in position relative to the sewing needle.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the written the drawings:
FIG. 1 is an exploded perspective view of a shuttle driving device in a sewing machine according to one embodiment of the invention;
FIG. 2 is a perspective view of a bobbin case;
FIG. 3 is a plan view of a shuttle race cap according to the invention;
FIG. 4 is a side view of the shuttle race cap of FIG. 3;
FIG. 5 is a plan view of the shuttle race cap showing how to scoop up a front limb with a beak of a DPS shuttle hook in a sewing machine with the needle receiving assembly according to the invention;
FIG. 6 is a perspective view of a conventional bobbin case provided for a half-turn shuttle;
FIG. 7 is an exploded perspective view of a conventional shuttle race body and a conventional shuttle race ring in a sewing machine;
FIG. 8 is an enlarged plan view of a needle receiving section with the shuttle body coupled to the shuttle race body;
FIG. 9 is a plan view showing how the rear limb is regulated by the needle receiving section of the shuttle race ring in the sewing machine using the DPS shuttle hook;
FIG. 10(a) is a cut-away side view of a DBS shuttle hook showing the distance between the needle drop point and the bobbin thread lead-out point; and
FIG. 10(b) is a cut-away side view of a DPS shuttle hook showing the distance between the needle drop point and the bobbin thread lead-out point.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The needle collar of the present invention is adjustable in position. Hence, even in a sewing machine using the DPS shuttle hook, the rear loop of the upper thread can be positively regulated. In addition, by changing the position of the needle collar, the amount of regulation of the rear loop of the upper thread can be suitably adjusted.
The needle collar is mounted on the thread control panel having the thread control hole in such a manner that it is adjustable in position. Hence, in the sewing machine using the DPS shuttle hook, the needle collar adapted to regulate the rear loop of the upper thread can be arranged by use of the thread control panel, and the needle collar can be readily adjusted in position.
A needle receiving assembly for a sewing machine according to the invention will now be described with reference to FIGS. 1 through 5.
As shown in FIG. 1, a shuttle driving device according to the invention comprises a spindle (or arm shaft) 1, a crank section 2, a crank rod 3, an oscillating rock shaft 4, gears 5 and 6, a lower shaft 7, a shuttle race body 8, a driver 9, a shuttle body (or DPS shuttle hook) 10, a shuttle race ring 11, a bobbin 12, a bobbin case 13, a horn of the bobbin case 14, a arm shaft counter balance 21, a throat plate 31, a thread cutting device 32, a thread control panel (or shuttle race cap) 41, a thread control hole 42, and a needle collar (or rear loop receiving member) 45.
The arm shaft 1 has a pulley (not shown) at the right end to which the torque of the electric motor is applied through an endless belt. The arm shaft 1 is couple to the crank rod 3 via the crank section 2. The lower end portion of the crank rod 3 is eccentrically coupled to the oscillating rock shaft 4. The gears 5 and 6 are mounted on the oscillating rock shaft 4 and the lower shaft 7, respectively, such that they are engaged with each other. Near the left end of the lower shaft 7, the shuttle race body 8 is fixed to the sewing machine body.
The driver 9 is coupled to the left end of the lower shaft 7, and rotatably provided inside the shuttle race body 8. In addition, the shuttle body driven by the driver 9, namely, the DPS shuttle hook 10, is also rotatably provided inside the shuttle race body 8. More specifically, a race 10a formed along the outer periphery of the DPS shuttle hook 10 is slidably fitted in a race 8a which is also formed along the outer periphery of the shuttle race body 8. The prolongation of the race 10a is formed into a beak 10b (See FIG. 5). The DPS shuttle hook 10 is turned counter-clockwise by the driver 9.
The shuttle race ring 11 is fixed to the shuttle race body 8. The bobbin case 13 accommodating the bobbin 12 is set in the shuttle race body 8 through the opening of the shuttle race ring 11.
The engaging member 14 protrudes outwardly from the bobbin case 13. The shuttle race ring 11 has an engaging groove 11a with which the horn 14 is engaged.
As shown in FIG. 2, the amount by which the horn 14 of the present invention protrudes from bobbin case 13 is less than that of the conventional horn 101 of FIG. 6. Also, unlike the conventional horn 101, horn 14 of the present invention has no thread hole. Hence, the bobbin thread 15 wound on the bobbin 12 is merely led out of the bobbin case 13 irrespective of the horn 14.
The length of the horn 14 is determined from the position of the driver 9 (FIG. 1). That is, the horn 14 of the bobbin case 13 is designed such that the upper end of the horn 14 comes below the upper surface of the driver 9 when the angle of rotation of the arm shaft 1 is in a range of 5° to 35° with the top dead point of the needle bar as a reference (0°).
The counter balance 21 is coupled to the left end of the arm shaft 1. In front of the counter balance 21, a thread take-up lever, needle bar crank, needle bar crank rod, needle bar, and needle are provided.
The throat plate 31 is provided above the shuttle race body 8. The thread cutting device 32 and the thread control panel (or shuttle race cap) 41 are provided between the throat plate 31 and the shuttle race body 8 in such a manner that the thread control panel 41 is located below the thread cutting device 32.
The sewing machine thus designed operates as follows. First, the torque of the motor is applied through the endless belt to the pulley, so that the arm shaft 1 is rotated to drive the needle, while the full turn motion of the arm shaft 1 is converted into a swing motion with the aid of the crank section 2 and the crank rod 3, so that the oscillating rock shaft 4 swings.
The swinging motion of the oscillating rock shaft 4 is transmitted through the gears 5 and 6 to the lower shaft 7. That is, it is converted into the half turn motion of the lower shaft 7. Hence, the DPS shuttle hook 10, being driven by the driver 9 integral with the lower shaft 7, performs a half turn motion in the counterclockwise direction.
In the sewing machine with the above-described DPS shuttle hook 10, as shown in FIGS. 3 and 4, the needle collar (or rear loop receiving member) 45 adapted to regulate the rear loop 17r of the upper thread 17 passed through the needle hole of the needle 16 is mounted on the shuttle race cap 41 which is the thread control panel having the thread control hole 42, such that the position of the needle collar 45 is adjustable. That is, in the case where the DPS shuttle hook 10 is employed, as shown in FIG. 5, the beak 10b comes between the shuttle race ring 11 and the sewing needle 16, and the front loop 17R of the upper thread 17 is on the side of the shuttle race ring 11. Hence, in this case, unlike the case where the DBS shuttle hook is employed, the rear loop 17r on the opposite side cannot be regulated with the needle receiving section (or rear loop receiving section) 11b of the shuttle race ring 11.
Hence, in the embodiment of the invention, as shown in FIGS. 3 and 4, the needle collar (or rear loop receiving member) 45 is arranged on the lower surface of the shuttle race cap 41 such that it appears partially in the thread control hole 42. Further, two fixing screws 46 are screwed into the needle collar (or rear loop receiving member) 45 through adjusting elongated holes 43 formed therein, so that the position of the needle collar (or rear loop receiving member) 45 is adjustable.
The thread control hole 42 receives the upper thread 17 and the bobbin thread 15, and, especially when a thread cutting operation is carried out by the thread cutting device 32, slings the upper thread 17 towards the needle and the fabric and slings the bobbin thread 15. The thread control hole 42 is suitably shaped as shown in FIG. 3, wherein reference character O designates the needle drop point.
As was described above, the needle collar (or rear loop receiving member) 45 is mounted on the lower surface of the shuttle race cap 41 such that its position can be adjusted with the fixing screws 46 set in the adjusting elongated holes 43. Hence, in the sewing machine employing the DPS shuttle hook 10, as shown in FIG. 4, the rear loop 17r of the upper thread below the thread control hole 42 is regulated with the needle collar (or rear loop receiving member) 45, and the front loop 17R can be sufficiently obtained on the side of the shuttle race ring 11.
The position of the needle collar (or rear loop receiving member) 45 can be adjusted by shifting the fixing screws 46 along the adjusting elongated holes 43, which makes it possible to suitably adjust the amount of regulation of the rear limb 17r.
As was described above, the DPS shuttle hook 10 performs the half turn motion in the counterclockwise direction. Hence, the front limb 17R can be positively scooped up with the beak 10b which is moved to the left in FIG. 5. Thus, high quality stitches can be formed with the sewing machine using the DPS shuttle hook.
In the above-described embodiment, the bobbin case for the DPS shuttle hook has a short horn having no thread hole. However, the invention is not limited this embodiment. That is, it may be a conventional bobbin with a long horn having a thread hole.
In the above-described embodiment, the needle collar is mounted on the shuttle race cap. However, the needle collar can alternatively be mounted on the sewing machine body.
Furthermore, the configuration of the needle collar is not always limited to that which has been described above. In addition, the needle collar may be suitably changed or modified in structure without departing from the spirit of the invention.
As is apparent from the above description, the needle receiving assembly according to the invention has the following benefits. The needle collar, which is adjustable in position, regulates the rear loop of the upper thread passed through the needle. Hence, especially in a sewing machine using a DPS shuttle hook, the rear limb can be positively regulated, and the front limb can be positively scooped up with the beak.
In addition, since the position of the needle collar can be adjusted, the amount of regulation of the rear limb can be suitably adjusted.
Furthermore, the needle collar (or rear loop receiving member) can be mounted on the thread control panel having the thread control hole such that its position is adjustable. Hence, in the sewing machine using a DPS shuttle hook, the needle collar adapted to regulate the rear loop of the upper thread can be arranged by use of the thread control panel, and the position of the needle collar can be readily adjusted.
The foregoing description of the preferred embodiments of the invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed, and modifications and variations are possible in light of the above teachings or may be acquired from practice of the invention. The embodiments were chosen and described in order to explain the principles of the invention and its practical application to enable one skilled in the art to utilize the invention in various embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims appended hereto, and their equivalents. | A needle receiving assembly for a sewing machine comprising a throat plate through which a sewing needle can pass and a needle collar for regulating a rear loop of an upper thread passing through the sewing needle. The position of the needle collar relative to the sewing needle is adjustable. | 3 |
CROSS REFERENCE TO RELATED APPLICATION
The present invention is related to commonly assigned and co-pending U.S. application entitled, "Write Input Transaction Apparatus and Method", filed Aug. 30, 1990, invented by Allgeier et al., and having a Ser. No. 07/575,096.
BACKGROUND OF THE INVENTION
The present invention relates to signature capture devices and more specifically to a handwriting capture device.
Today, retailers are burdened with having to store and retrieve large amounts of paper records from credit and check transactions. Normally, these records are produced at a retail terminal as master copies of sales receipts, and which are removed from the terminal at the end of the business day for balancing and entry into accounting journals and shipment to processing and storage facilities. Allgeier et al. discloses a write input device employing a display underneath a transparent digitizer to capture signature information. The display gives a customer feedback for stylus input.
While the Allgeier et al. device works well, having a liquid crystal display makes it expensive. Therefore, it would be desirable to eliminate the display and reduce the cost by using a low-cost resistive membrane digitizer. The low-cost resistive membrane must function in response to minimal signing force applied by an ordinary writing instrument such as a pen.
The use of pressure-sensitive resistive membrane digitizers is subject to false actuations, including those caused by finger contact. If the digitizer is shorted by finger contact during signing, the digitized points representing the signature will be obscured by the finger points, resulting in random scribbling in place of the signature.
The sensitivity of a pressure-sensitive digitizer is determined by the density of the spacer dot pattern, which maintains separation between the top and bottom sheets of the digitizer. The more dense the pattern is, the more resistant the digitizer is to finger actuation. However, a high pattern density requires more writing force to capture a signature. In systems without displays or other sources of immediate feedback, it is essential that the digitizer be sensitive to writing force.
Therefore, it would be desirable to provide a handwriting capture device without a display, but having a digitizer sensitive to minimal writing force.
SUMMARY OF THE INVENTION
In accordance with the teachings of the present invention, a handwriting capture device is provided. The handwriting capture device includes a housing having a top surface, a pressure-sensitive digitizer having a low pattern density and mounted in the top surface, circuitry for sensing the presence of a receipt and activating the digitizer, circuitry for processing signature information from the digitizer, and a clamp for retaining the receipt in place over the digitizer. In the preferred embodiment, the clamp also serves to minimize finger contact with the digitizer.
It is accordingly an object of the present invention to provide a handwriting capture device.
It is another object of the present invention to provide a handwriting capture device, which is less expensive than a handwriting capture device employing a liquid crystal display mounted beneath a transparent digitizer.
It is another object of the present invention to provide a handwriting capture device which employs a highly sensitive low-cost digitizer which can capture signatures entered using minimal force from an ordinary writing instrument, such as a ballpoint pen.
It is another object of the present invention to provide a handwriting capture device which employs a clamp for holding a pre-printed receipt in place over the digitizer for signature.
It is another object of the present invention to provide a handwriting capture device which employs a clamp for holding a pre-printed receipt in place over the digitizer for signature and which minimizes finger contact with the digitizer.
It is another object of the present invention to provide a handwriting capture device which is lightweight, hand-held, and portable.
BRIEF DESCRIPTION OF THE DRAWINGS
Additional benefits and advantages of the present invention will become apparent to those skilled in the art to which this invention relates from the subsequent, description of the preferred embodiments and the appended claims, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a perspective view of a first embodiment of the handwriting capture device of the present invention;
FIG. 2 is a sectional view of the handwriting capture device taken along line 2--2 of FIG. 1.
FIG. 3 is a sectional view of the handwriting capture device of the present invention taken along lines 3--3 of FIG. 1;
FIG. 4 is a perspective view of a second embodiment of the handwriting capture device of the present invention; and
FIG. 5 is a sectional view of the handwriting capture device of the present invention taken along line 5--5 of FIG. 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now to FIGS. 1 and 2, a first embodiment of the handwriting capture device 10 of the present invention is shown. The handwriting capture device 10 includes a housing 12 having a bottom supporting surface 14 and a top surface 16. In this embodiment, the housing 12 is generally rectangular in shape. The handwriting capture device 10 is lightweight and portable. The left end of the housing 12 is sufficient in width and depth to facilitate grasping of the housing 12.
Within the top surface 16 is a pressure-sensitive digitizer 18, although other types of digitizers are also envisioned. The digitizer 18 is sensitive to signing forces greater than or equal to a predetermined minimum signing force, which is no more than about 10 to 15 grams. When a pen is used, the digitizer has a sensitivity sufficient to capture a handwriting that produces a legible ink impression on the receipt. In this embodiment, a digitizer manufactured by W. H. Brady & Co. and having a part number 2500044089 is used. This digitizer has a near separation between dots of 0.2 inches. Dot separations higher than 0.2 are not recommended because spurious digitizer readings are more likely to occur. Digitizers having dot separations as low as 0.16 inches may be used in the present invention to achieve valid handwriting capture.
A thin layer of urethane rubber 19 is affixed to the top surface of the digitizer 18. The urethane rubber 19 provides a high friction surface for keeping the receipt 22 in place. A signature line 20 on the upper surface 16 and to the left of the digitizer acts as a guide for lining up a receipt 22 having a signature line 21.
Also within the housing 12 is the electronic processing circuitry 24 for operating the digitizer 18 and for controlling information flow from the digitizer 18 to a point-of-service (POS) terminal (not shown). The digitizer 18 is coupled to the electronic circuitry 24 by a wire connector 27 and the electronic circuitry 24 is coupled to the POS terminal by a wire cable 26. The housing may also include circuitry 25 for sensing the presence of the receipt 22 and activating the digitizer 18. In this embodiment, circuitry 25 includes a commercially available optical switch having an emitting side and a receiving side, both on opposite sides of the receipt. The sensing circuit 25 activates data capture by the digitizer 18 when the receipt 22 is in position under a clamp 30 so as to minimize acceptance of false actuations.
The paper receipt 22 from the POS terminal is properly aligned and held in place during movement of the device 10 by the clamp 30 which is integrally located on the top surface 16 at the right end of the housing 12. The clamp 30 includes an inverted, generally L-shaped member 32 having an inner surface 34. A vertical portion 36 of the inner surface 34 provides a stop against which the receipt 22 is aligned. A horizontal portion 38 of the inner surface 34 holds the receipt 22 in contact with the top surface 16 of the housing 12. The distance from the horizontal surface 38 to the top surface 16 is sufficient to allow a receipt 22 to pass between the two surfaces. The clamp 30 also includes an upwardly flared portion 40 at one end to facilitate insertion of the receipt 22 into the clamp 30.
Referring now to FIG. 3, the horizontal portion 38 of the inner surface 34 includes downwardly facing protrusions 42 which are generally hemispherical in shape in order to fixedly retain the receipt 22 in place. Correspondingly shaped receptacles or dimples 44 are located in the top surface 16 below the protrusions 42. In combination, the dimples 44 and protrusions 42 act to increase the frictional force between the top surface 16 and the receipt 22, thereby effectively retarding movement of the receipt 22 out of the clamp 30.
In operation, a POS operator inserts the right edge of the receipt into the clamp 30, starting at the upwardly flared portion 40. The receipt 22 is further inserted until the signature line 21 is properly aligned with the signature line 20 on the top surface 16 of the housing 12. In this position, the receipt 22 will also be properly aligned with the vertical surface 36 of the clamp 30 and properly engaged between the dimples 44 and the protrusions 42. The sensing circuitry 25 activates data capture by the digitizer 18. A customer then signs his name with a writing device, such as a pen, on the signature line 21. Advantageously, the handwriting capture device 10 is lightweight and can be easily transferred from person to person without dropping the receipt 22.
Referring now to FIGS. 4 and 5, a second and preferred embodiment 50 of the handwriting capture device of the present invention is shown. Like the first embodiment, the preferred embodiment 50 includes a housing 52 having a top surface 54, electronic processing circuitry 56 within the housing 52, sensing circuitry 57 within the clamp 30, and a digitizer 18 within the top surface 54. The same considerations as in the first embodiment regarding digitizer choices apply in this embodiment. A thin layer of urethane rubber 19 is affixed to the top surface of the digitizer 18 to provide a high friction surface for keeping the receipt 22 in place. The electronic processing circuitry 56 is coupled to the digitizer 18 through a wire connector 60 and to a POS terminal (not shown) through a wire cable 62.
In addition, the housing 52 includes a top member 63 and a base member 64 which is inclined to facilitate writing. In order to properly align a receipt 22 for signature, the housing 52 includes a guide member 66 on the top surface 54 at one end of the housing 52. The guide member 66 has a vertical guide surface 68 against which the receipt 22 is aligned. The housing 52 is sufficient in width and depth to facilitate grasping of the housing 52.
The preferred embodiment also includes a clamp 70 for retaining the receipt 22 in place during movement of the device 50. The clamp 70 includes a frame member 72 which is generally rectangular in shape and which is made of transparent plastic to allow a customer to view the itemized information on the receipt 22 while signing. The clamp 70 is anchored at its left end and its right end is biased against the top surface 54 of the housing 52. Centrally located within the clamp 70 is a rectangular window 76 exposing the digitizer 18 below. The window 76 facilitates proper installation of the receipt 22 over the digitizer 18 and serves to quickly orient a customer with the correct location 78 for signing. The clamp 70 may also include an upwardly flared portion 74 for facilitating insertion of the receipt 22 under the clamp.
Advantageously, the clamp 70 also serves to minimize finger contact with the digitizer 18. The clamp 70 includes a vertical rib 80 extending across the clamp 70 for guarding the digitizer 18 from the thumb of the left hand of a customer writing with his right hand and also restricts access to the digitizer 18 by a customer writing with his left hand. The frame member 72 blocks contact with the digitizer 18 by the right hand. In addition, the window 76 provides insufficient room for finger placement, forcing finger placement on the pen to be a predetermined distance upwards from the pen tip for both right and left-handed customers.
In operation, a POS operator holds the device 50 in one hand and inserts the receipt using the other hand by slipping the receipt 22 under the upwardly flared portion 74 until the receipt 22 rests against the vertical guide surface 68 and the signature line 78 or box 79 is within the window 76. A customer then signs his name with a writing device, such as a pen, on the signature line 78. Advantageously, the clamp design facilitates one-handed insertion of the receipt 22. Also, the handwriting capture device 50 is lightweight and can be easily transferred from person to person without dropping the receipt 22.
Although the invention has been described with particular reference to certain preferred embodiments thereof, variations and modifications of the present invention can be effected within the spirit and scope of the following claims. | A handwriting capture device which employs a highly sensitive digitizer to accurately capture signature information entered using a writing force greater than or equal to a predetermined writing force. The handwriting capture device includes a housing having a top surface, a resistive membrane digitizer mounted in the top surface and having a low pattern density, a layer of urethane rubber for frictionally holding the receipt in place, circuitry for processing digitizer information, a clamp for retaining a receipt in place over the digitizer during movement of the device, and circuitry for sensing the presence of the receipt and for activating data capture by the digitizer when the receipt is positioned under the clamp. In the preferred embodiment, the clamp also serves to minimize finger contact with the digitizer. | 6 |
This is a division of application Ser. No. 575,602, filed Jan. 31, 1984, U.S. Pat. No. 4,481,097 11-6-84.
FIELD OF THE INVENTION
This invention relates to an electrode for use in electrolysis, and more particularly to an electrolytic electrode which exhibits outstanding durability in the electrolysis of an aqueous solution such as is liable to entail generation of oxygen at the anode.
BACKGROUND OF THE INVENTION
Heretofore, electrolytic electrodes using substrates of valve metals such as titanium (Ti) have found recognition as outstanding insoluble metal electrodes and have found utility as such in various fields of electochemistry. Particularly in the industry specializing in electrolysis of common salt, these electrodes have been found extremely useful as anodes for the generation of chlorine. As valve metals, tantalum (Ta), niobium (Nb), zirconium (Zr), hafnium (Hf), vanadium (V), molybdenum (Mo), tungsten (W), etc. have been known to the art besides Ti mentioned above.
These metal electrodes are generally obtained by coating substrates of the metal Ti with various electrochemically active substances represented by platinum-group metals or oxides thereof. Such electrodes disclosed by U.S. Pat. Nos. 3,632,498 and 3,711,385 are familiar examples. These electrodes, particularly when used for the generation of chlorine, are capable of retaining a low chlorine overvoltage for a long time.
When such a metal electrode as described above is adopted as an anode in electrolysis intended for or entailing generation of oxygen, the overvoltage of the anode is gradually raised. In an extreme case, this rise of overvoltage may induce a severe problem in that the anode will be passivated and prevented from continuing electrolysis any further. This phenomenon of the passivation of the electrode is believed to be best explained by a postulate that the Ti substrate is oxidized by the oxygen issuing from the oxide coat itself of the electrode or by the reaction of the substrate with the oxygen or the electrolyte permeating the coat and reaching the substrate. Consequently, a non-conducting Ti oxide coating forms on the substrate. Also, since the non-conducting oxide is formed in the interface between the substrate and the coat of the electrode, a further disadvantage may arise in that the oxide interface possibly could cause the electrode coat to separate from the substrate and eventually render the electrode completely unserviceable.
Electrolytic processes in which the anode product is oxygen, or in which oxygen is generated at the anode as a side reaction, include: (1) electrolysis using a sulfuric acid bath, a nitric acid bath, alkali baths, or the like; (2) electrolytic separation of Cr, Cu, Zn, or the like; (3) various forms of electroplating; (4) electrolysis of dilute brackish water, brine water, hydrochloric acid, or the like; and (5) electrolysis for the production of chlorates, and so forth.
To date, however, the problem mentioned above has been a serious obstacle to the effective use of metal electrodes in these industrial fields.
As a solution to this problem, a technique of preventing the electrode from being passivated due to the permeation of oxygen is described in U.S. Pat. No. 3,775,284. This technique involves interposing between the conducting substrate and the coat of the electrode a barrier layer formed of a Pt-Ir alloy or an oxide of cobalt (Co), manganese (Mn), palladium (Pd), lead (Pb), or platinum (Pt). The substances which constitute the interposed barrier layer, to some extent, prevent oxygen from being dispersed into the substrate during electrolysis. Nevertheless, the substances of the barrier layer possess a fair degree of electrochemical activity and, therefore, react with the electrolyte permeating the coat of the electrode and produce electrolytic products, e.g., gas, on the surface of the interposed barrier layer. Thus, there ensues the possibility that the physical and chemical actions of the electrolytic product will impair the tight adhesion of the coat of the electrode to the substrate and cause separation of the coat of the electrode from the substrate before the service life of the substance constituting the coat of the electrode is exhausted. Additionally, the barrier layer itself causes problems in that it prevents the electrode from being sufficiently corrosionproof. Thus, the solution produces a new problem and fails to provide lasting protection for the electrode.
U.S. Pat. No. 3,773,555 discloses an electrode which is coated with a laminate composed of a layer of an oxide, such as of Ti, and a layer of a platinum-group metal or an oxide thereof. This electrode nevertheless has the disadvantage in that the electrode undergoes passivasion when used in electrolysis in which oxygen is liberated.
SUMMARY OF THE INVENTION
The present invention is intended to overcome the above-described problems.
Accordingly, an object of the present invention is to provide an electrolytic electrode resistant to passivation, amply durable, and, therefore, particularly suitable for use in the aforementioned various electrolytic processes involving liberation of oxygen.
Another object of the present invention is a process for the production of an electrode having the above-mentioned characteristics.
The above-described objects have been met by an electrolytic electrode having a conducting metal such as Ti as the substrate and an outer coating of an electrode active substance, characterized by having interposed between the substrate and the electrode coat an intermediate layer having Pt dispersed in a mixed oxide consisting of an oxide of at least one metal selected from the group consisting of Ti and Sn, both having a valence of 4, and an oxide of at least one metal selected from the group consisting of Ta and Nb, both having a valence of 5.
This invention also relates to a process for the production of the electrolytic electrode.
The aforementioned intermediate layer of this invention is highly corrosionproof and possesses extremely low electrochemical activity and fulfills a main function of protecting the electrode substrate, such as of Ti, and preventing the electrode from passivation. In conjunction with the main function, the intermediate layer fulfils an auxiliary function of conferring good conductivity upon the electrode and producing a powerful union between the substrate and the coat of the electrode.
In accordance with this invention, therefore, there is provided an electrode which can be used as an electrode with ample durability in an electrolytic process which is adopted for the generation of oxygen or which entails a secondary reaction liberating oxygen.
DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described in more detail.
The substrate of the electrode in the present invention may be made of a conducting corrosionproof metal such as Ti, Ta, Nb, or Zr or an alloy based on such a metal. The metal Ti and the Ti-based alloys such as Ti-Ta-Nb and Ti-Pd which have found widespread acceptance to date are suitable for use in the preparation of the substrate.
This substrate may be formed in the shape of a plate, a perforated plate, a bar, or a net or in any other desired shape. Additionally, this substrate may be coated in advance with a platinum-group metal such as Pt or a valve metal such as Ta or Nb for the purpose of making the electrode more corrosionproof or providing improved adhesiveness with the intermediate layer.
Onto this substrate there is superposed an intermediate layer having Pt dispersed in a mixed oxide consisting of an oxide of Ti and/or Sn, each having a valence of 4, and an oxide of Ta and/or Nb, each having a valence of 5. This invention has been perfected based on a new knowledge that the interposition of this intermediate layer between the substrate and the coat of the electrode enables production of an electrode which excels in conductivity and proves perfectly useful as an amply durable anode particularly in an electrolytic process which proceeds with liberation of oxygen.
The inventors formerly perfected an electrolytic electrode which uses a conducting metal such as Ti as the substrate therefor and coats this substrate with a metal oxide, which electrolytic electrode is characterized by interposing between the substrate and the coat of the electrode an intermediate layer formed of a mixed oxide consisting of an oxide of Ti and/or Sn and an oxide of Ta and/or Nb. This electrolytic electrode is disclosed in commonly assigned pending U.S. patent application Ser. No. 521,764, now U.S. Pat. No. 4,484,999, filed on Aug. 9, 1983. This electrode possesses resistance to passivation and excels in durability. The intermediate layer used in the electrode exhibits good conductivity as an N-type semiconductor. However, since the intermediate layer has a limited carrier concentration, the opportunity existed for further improvement with respect to conductivity.
Owing to the conception of an idea of providing an intermediate layer possessing much higher conductivity than the intermediate layer of the former invention, the present invention has made it possible to produce an electrode which eliminates the drawback suffered by the former invention and offers still higher conductivity and durability.
As the substance to make up the intermediate layer contemplated by this invention, a composite having Pt dispersed in a mixed oxide consisting of an oxide of Ti and/or Sn and an oxide of Ta and/or Nb has been demonstrated to suit the purpose of this invention and manifest an outstanding effect. The substance of the intermediate layer offers excellent resistance to corrosion, exhibits no electrochemical activity, and possesses ample conductivity. The term "mixed oxide" is meant to embrace metal oxides which are nonstoichiometric or have lattice defects. As used in this invention, the term "mixed oxide" embraces those metal oxides represented by TiO 2 , SnO 2 , Ta 2 O 5 , etc., for the sake of convenience.
The substance of the intermediate layer, as described above, is substantially a combination of Pt in a metallic form, an oxide of a metal (Ti or Sn) having a valence of 4, and an oxide of a metal (Ta or Nb) having a valence of 5.
Specifically, any of the mixed oxides TiO 2 --Ta 2 O 5 , TiO 2 --Nb 2 O 5 , SnO 2 --Ta 2 O 5 , SnO 2 --Nb 2 O 5 , TiO 2 --SnO 2 --Ta 2 O 5 , TiO 2 --SnO 2 --Nb 2 O 5 , TiO 2 --Ta 2 O 5 --Nb 2 O 5 , SnO 2 --Ta 2 O 5 --Nb 2 O 5 and TiO 2 --SnO 2 --Ta 2 O 5 --Nb 2 O 5 can be used advantageously to manifest an ample effect when combined with Pt dispersed therein.
The proportions of the component oxides of the mixed oxide are not specifically defined and may be fixed in a wide range. For protracted retention of the durability and conductivity of the electrode, it is desirable to fix the ratio of the oxide of the tetravalent metal to the oxide of the pentavalent metal in the range of 95:5 to 10:90 by metal mole. The amount of Pt to be dispersed in the mixed oxide desirably falls in the range of 1 to 50 mol% based on the total amount of the substance making up the intermediate layer.
The formation of the intermediate layer in the electrode is advantageously effected by the thermal decomposition method which comprises the steps of applying a mixed solution containing chlorides or other salts of component metals destined to make up the aforementioned intermediate layer to the metal substrate and then heating the coated substrate under a blanket of oxidizing gas at temperatures of about 350° to 600° C. thereby producing a mixed oxide having Pt dispersed therein. Any other method may be adopted instead insofar as the method is capable of forming a homogeneous, compact coat having Pt dispersed in a conducting mixed oxide. By the aforementioned thermal decomposition method, Ti, Sn, Ta, and Nb are readily converted into corresponding oxides while Pt is merely decomposed thermally into metallic platinum and is not converted into an oxide at all. The amount of the substance of the intermediate layer to be applied to the substrate is desired to exceed about 0.1×10 -2 mol/m 2 calculated as metal. If the amount is less than the lower limit mentioned above, the intermediate layer consequently formed will fail to manifest its effect sufficiently.
Subsequently, an electrode active substance possessing electrochemical activity is superposed on the intermediate layer which has been formed on the substrate as described above, to complete an electrode. As the substance to form the coat of the electrode, a metal, a metal oxide, or a mixture thereof which excels in electrochemical properties and in durability can be advantageously used. From among the various substances which fulfill this requirement, a suitable substance may be selected in due consideration of the electrolytic reaction for which the electrode is desired to be used. Particularly suitable for the aforementioned electrolytic process which proceeds with liberation of oxygen are oxides of platinum-group metals or mixed oxides of such oxides with oxides of a valve metal. As typical examples of such oxides, there may be cited Ir oxide, Ir oxide-Ru oxide, Ir oxide-Ti oxide, Ir oxide-Ta oxide, Ru oxide-Ti oxide, Ir oxide-Ru oxide-Ta oxide, and Ru oxide-Ir oxide-Ti oxide. Of course, these substances, similar or dissimilar, may be applied as superposed in two or more layers.
The method for forming the coat of electrode is not specifically defined. Any of the various known methods such as the thermal decomposition method, the electrochemical oxidation method, and the powder sintering method may be suitably adopted. Particularly desirable is the thermal decomposition method which is disclosed in detail in U.S. Pat. Nos. 3,711,385 and 3,632,498.
No definite theory has yet been established to account for the aforementioned outstanding effect of this invention which is brought about when the intermediate layer having Pt dispersed in a mixed oxide of metals having the valencies of 4 and 5 is interposed between the substrate of metal and the active coat of the electrode. One logical explanation may reside in the following postulate:
Since the intermediate layer of a compact mixed oxide of metals incorporating therein dispersed Pt covers the metal surface of the substrate and consequently protects it against oxidation, the substrate is prevented from otherwise possible passivation. The substrate of the intermediate layer itself has Pt dispersed in the mixed oxide of a tetravalent metal and a pentavalent metal. In accordance with the generally recognized principle of valence control, this mixed oxide itself constitutes an N-type semiconductor and possesses high conductivity. Moreover, the Pt incorporated as dispersed in the mixed oxide confers high electron conductivity to the mixed oxide.
Also, since Pt is a substance which offers extremely high resistance to corrosion and has very high potential for the generation of oxygen, it is deficient in eletrochemical activity and generally does not react with the electrode and, thus, functions to heighten the durability of the electrode. If the substrate made of Ti, for example, permits formation of a non-conducting Ti oxide on the surface of the electrode during the manufacture of the electrode or during the use of the electrode in the electrolytic process, the pentavalent metal in the intermediate layer is dispersed to convert the oxide similarly into semiconductors. Thus, the electrode as a whole is allowed to retain its conductivity intact and preclude otherwise possible progress of passivation.
Better still, the substance of the intermediate layer has an ability to adhere intimately to the metal of the substrate such as Ti and to the active coat of the electrode such as of an oxide of a platinum-group metal or an oxide of a valve metal and, therefore, forms a tight union between the substrate and the coat. Thus, the intermediate layer is effective in enhancing the durability of the electrode.
EXAMPLES
The present invention will now be described more specifically below with reference to working examples. This invention is not limited in any way by these working examples:
EXAMPLE 1
A commercially available titanium plate 1.5 mm in thickness was defatted with acetone and then subjected to an etching treatment in an aqueous 20% hydrochloric acid solution at 105° C. to produce a substrate for the electrode. Subsequently, a solution obtained by mixing a 10% hydrochloric acid solution of tantalum titanium chloride containing Ta at a concentration of 10 g/liter (computed as metal, the same applies hereinafter) and titanium chloride containing Ti at a concentration of 10.4 g/liter with a 10% hydrochloric acid solution of chloroplatinic acid containing Pt at a concentration of 10 g/liter was applied to the upper side of the substrate and dried, and the coated substrate was burnt in a muffle furnace kept at 500° C. for 10 minutes. This procedure was repeated twice more. Consequently, on the substrate of Ti, an intermediate layer of a mixed oxide TiO 2 --Ta 2 O 5 (Ti80:Ta20 by metal mole ratio) having Pt dispersed therein in a ratio of 1.3 g/m 2 was superposed.
Subsequently, a hydrochloric acid solution of iridium chloride containing Ir at a concentration of 50 g/liter was applied to the intermediate layer. The coated layers were burnt in a muffle furnace kept at 500° C. for 10 minutes. This procedure was repeated three more times. Consequently, there was obtained an electrode having an Ir oxide containing Ir at a ratio of 3.0 g/m 2 as an electrode active substance.
In an electrolyte of 150 g of sulfuric acid solution per liter kept at 60° C., this electrode was used as an anode with a graphite plate used as a cathode and tested for accelerated electrolysis at a current density of 100 A/dm 2 . The anode served the electrolysis stably for 360 hours. For the purpose of comparison, an electrode was prepared by faithfully following the procedure described above, except that the incorporation of Pt in the aforementioned intermediate layer was omitted. In the same electrolysis, this electrode was passivated after 150 hours of electrolysis and could not be used any longer.
EXAMPLE 2
Electrodes were prepared by following the procedure of Example 1, except that the substance for the intermediate layer and that for the active coat of electrode were varied as indicated in Table 1. The thus prepared electrodes were subjected to accelerated electrolysis by way of test for performance. The electrolysis was conducted in an aqueous 150 g/liter sulfuric acid solution as the electrolyte under the conditions of 80° C., and 250 A/dm 2 of current density, with a platinum plate as the cathode. The results are shown in Table 1.
TABLE 1______________________________________ ServiceRun Sub- Intermediate Electrode Active LifeNo. strate Layer Substance (hrs)______________________________________1 Ti Pt--TiO.sub.2 --Ta.sub.2 O.sub.5 IrO.sub.2 75 (75:25)2 Ti Pt--TiO.sub.2 --Nb.sub.2 O.sub.5 IrO.sub.2 80 (80:20)3 Ti Pt--TiO.sub.2 --Ta.sub.2 O.sub.5 -- IrO.sub.2 65 SnO.sub.2 (70:20:10)4 Ti Pt--TiO.sub.2 --Ta.sub.2 O.sub.5 -- RuO.sub.2 --IrO.sub.2 45 Nb.sub.2 O.sub.5 (50:50) (80:10:10)5 Ti Pt--TiO.sub.2 --Ta.sub.2 O.sub.5 RuO.sub.2 --IrO.sub.2 38 (40:60) (50:50)6 Ti Pt--TiO.sub.2 --Ta.sub.2 O.sub.5 -- RuO.sub.2 --IrO.sub.2 55 Nb.sub.2 O.sub.5 (30:70) (30:40:30)7 Ti TiO.sub.2 --Ta.sub.2 O.sub.5 RuO.sub.2 --IrO.sub.2 10(Comparison) (80:20) (50:50)______________________________________ Note: The numerical values given in parentheses represent mole ratios of component metals excluding Pt. The amount of Pt in the intermediate layer was invariably 1.3 g/m.sup.2. The amount of the electrode active substanc was invariably 3 g/m.sup.2 as metal component.
From Table 1, it is noted that the electrodes of this invention incorporating a Pt-containing intermediate layer had decisively longer service life and exhibited higher durability than the electrode (comparison) incorporating an intermediate layer containing no Pt.
EXAMPLE 3
An electrode was prepared by following the procedure of Example 1, except that a mixed oxide of SnO 2 --Ta 2 O 5 having Pt dispersed therein (Sn80:Ta20 by metal mole ratio, with Pt dispersed at a ratio of 1.3 g/m 2 ) was used as the intermediate layer and it was similarly tested. The test for electrolysis was carried out in an aqueous 12N NaOH solution under the conditions of 95° C. and 250 A/dm 2 of current density, with a platinum plate used as the cathode.
This electrode had a service life of 46 hours. Another electrode was prepared for comparison by repeating the same procedure, except that the inclusion of Pt in the intermediate layer was omitted. This electrode for comparison had a service life of 16 hours. Thus, the electrode of this invention was demonstrated to enjoy very high durability as compared with the other electrode. | An electrode comprising a substrate of a conducting metal, a coat of an electrode active substrate, and a layer interposed between the substrate and the coat to serve as a protective barrier for the substrate acquires improved durability by using, as the intermediate layer, a layer having platinum dispersed in a mixed oxide consisting of an oxide of at least one metal selected from the group consisting of titanium and tin, each having a valence of 4, and an oxide of at least one metal selected from the group consisting of tantalum and niobium, each having a valence of 5. The electrode of improved durability is produced by a process which comprises the steps of preparing a substrate of a conducting metal, depositing a solution containing salts of Ti and/or Sn, Ta and/or Nb, and Pt on the substrate, heating the resultant coated substrate under the blanket of an oxidizing gas thereby forming an intermediate layer on the substrate, and subsequently coating the intermediate layer with a layer of an electrode active substance. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to a spinning plant machine with drafting equipment for the coupling and drafting of fiber slivers. In these spinning plant machines, e.g. spinning machines, combing machines or draw frames, the distances between the drafting rollers must be adjusted so that different fiber materials may be processed optimally on the same machine. To adjust the bearing blocks in which at least the lower roller of a pair of rollers is supported, DE 33 01 239 A1 discloses that in the drafting equipment of a draw frame the bearing blocks can be shifted following loosening of their attachments. For this, either one of the two bearing blocks which are part of the drafting equipment rollers must be detached separately from the guide rail and must then be displaced parallel and together with the second bearing block of the roller. The bearing blocks must then be aligned very exactly again before being secured. The greatest disadvantage here is the fact that the rollers must be newly adjusted each time. In addition to this, the locking screw by means of which the bearing blocks are held on the guide rail are accessible only from below. All of this renders the adjustment of the distances of the drafting rollers complicated and time-consuming.
DE 29 41 612 C2 discloses a method by which the drafting equipment rollers in a draw frame are placed on a sled which is moved in a straight line, whereby a toothed rod is attached to each sled and meshes with a pinion gear driven by an electrical motor. This arrangement is not only expensive because of its adjusting drive, but the parallel movement of the sleds requires an expensive configuration of their gliding surfaces.
The German utility model 1 821 627 discloses a method in drafting equipment for a twisting or spinning machine by which the bearing blocks of the drafting equipment rollers are provided with a threaded bore interacting with an adjusting spindle. By rotating the adjusting spindle, this bearing block can be adjusted. However this has the disadvantage that the replacement of the bearing blocks is rendered more difficult because the spindle must be unscrewed from the bearing block.
OBJECTS AND SUMMARY OF THE INVENTION
It is a principal object of the present invention to design a spinning plant machine with a drafting equipment having an adjusting device for the drafting rollers such that the disadvantages of the state of the art can be avoided. The adjusting device or the spinning plant machine is low cost and the adjustment of the distances between the drafting rollers can be carried out easily and rapidly. 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 practice of the invention.
The objects are attained by the present invention. By using a push rod which also serves as a guide for the bearing as a means to adjust the support, the drafting equipment rollers are easily adjustable within the drafting equipment and the entire drafting equipment is nevertheless simple in its construction. Due to the fact that the means for the adjustment of the bearing, i.e. the push rod, assumes at the same time the guiding function for the support, the drafting rollers become easily adjustable and the entire drafting equipment is nevertheless simple in its design. As a result of this, the reception or guidance for support can be made especially simple on the basic body of the drafting equipment. Furthermore, no measures are needed to prevent jamming of the support during adjustment. Long guidance surfaces through which jamming is reliably avoided can be obtained easily thanks to the push rod. This results in an advantage for the support itself, i.e. the fact that the bearing blocks can be made so bearing blocks of the drafting equipment roller seats can be at a right angle to the roller axis and can be short. Small distances from one pair of drafting rollers to the other can thus be advantageously realized.
It is especially advantageous if the support of the lower roller is made in two parts, so that the two ends of the lower roller are held by their sliding or roller bearings by a separate bearing arrangement. This has the advantage that each end of the roller can be adjusted by its own push rod, so that the adjustment is especially precise and the lower rollers are certain to be parallel to each other. It is especially advantageous for the push rod to be guided via stops at a right angle to its direction of movement. As a result, the precise positioning of the drafting equipment rollers is ensured even when the bearing arrangement is adjusted. The placement of the stop for the guidance of the push rod, directly at the basic body of the drafting equipment, is advantageous in that case. It is especially advantageous for the stop for the guidance of the push rod to be installed at a bearing of a lower roller. This simplifies manufacturer of the basic drafting equipment body. If the stop for the guidance of the push rod is constituted by another push rod, these can support each other mutually and thereby their stability of form and quality of guidance is mutually improved. In addition, the device becomes simpler in this manner and fewer finishing steps are required. It is especially advantageous to make the stop in such manner that its surface is perpendicular parallel to the axis of the lower rollers so that the guidance is parallel to the direction of movement of the push rod and lateral escape of the push rods is prevented. If a stop is provided in a plane which is parallel with the plane in which the axes of the drafting equipment rollers are installed, the result is that an unwanted movement of the push rods and therefore also of the bearing arrangement at a right angle to this plane is prevented. It is especially advantageous here to provide the stop on a bearing for a lower roller, whereby the bearing of the output roller of the drafting equipment is advantageously used for this, since it is not movable and attached to the basic body of the drafting equipment. As a result the guidance does not change its position relative to the basic body of the drafting equipment, so that a guidance of the push rod remaining in the same position can be obtained in a simple manner.
For simple operation of the drafting equipment, and thereby also of the spinning plant machine, in particular for the replacement of the lower rollers, it is especially advantageous if the bearing arrangement is connected in a detachable manner to the push rod which moves it. To replace the bearing arrangement, the latter is simply detached from the push rod which moves it and is taken out of the machine. It is equally simple to install a new bearing arrangement. In order to be able to position the bearing arrangement with precision when it is again installed, it is especially advantageous for the push rod to be provided with a receiving device which receives the bearing arrangement on the push rod exactly as before, i.e. that the newly mounted bearing arrangement is again in precisely the same position. This ensures that the axes of the drafting equipment are parallel and that the distance between the pairs of drafting rollers always remains the same. It is advantageous to provide a clamping device which clamps the push rod in a fixed position relative to the basic body of the drafting equipment. In this manner, the drafting equipment rollers are securely held in one and the same position during operation. Furthermore, in this way, the bearing arrangement itself need not be attached to the basic body of the drafting equipment. This makes it possible to detach and shift the drafting equipment rollers rapidly, since all movable bearing arrangements are fixed at only one or two clamping points. At the same time, the clamping device can also advantageously incorporate stops for guidance of a push rod, and if several push rods are used, all can be guided by the clamping device holding them.
To adjust the drafting equipment rollers easily, it is advantageous for the basic body of the drafting equipment to be provided with a gliding surface on which the bearing arrangement to be adjusted can be shifted. The adjustment of the bearing arrangement, and thereby of the distances between the drafting equipment rollers, is thereby made possible with little force expenditure. The gliding surface is advantageously made so as to be pressure-stable, so that it is able to accept the pressure forces exerted by the upper roller on the lower roller. These forces then need not be borne by the push rods. Their guidance task only consists in maintaining the bearing arrangement at the exact place on the gliding surface.
The movement of the push rod is caused very simply by connecting it via a coupling element to a threaded spindle. Rotation at the spindle makes an especially finely tuned, axial movement of the push rod possible. The axial length of the push rod reaches advantageously from the coupling element over the bearing arrangement to be adjusted up to a guidance following it in the axial direction. Guiding the push rod becomes especially simple and advantageous. If two push rods are used to adjust the bearing arrangement of a lower roller, it is especially advantageous for them to be coupled together so that both push rods can only be moved together in the same direction. In this manner the parallelism of the axes of the lower roller and of the other drafting equipment roller pairs is always preserved, also when adjustments are made. For this, the two push rods are advantageously connected via a coupling each to a threaded spindle and the latter in turn to each other via a chain or belt wheel with appertaining driving belt. It is especially advantageous if this is done by means of a toothed belt which interacts with corresponding belt wheels at the threaded spindles.
The invention is explained below through drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a spinning plant machine, e.g. a draw frame, in a side view;
FIG. 2 shows a side view of a draw-frame, partially in a section;
FIG. 3 shows the draw frame of FIG. 1 with adjusted input cylinders and central cylinders;
FIGS. 4a to 4c show the draw frame cylinders with bearing arrangement and push rod as well as parts of the base draw-frame body, in a section; and
FIG. 5 shows a partially left side view of the draw frame of FIGS. 2 and 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Reference will now be made in detail to one or more 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. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the invention without departing from the scope and spirit of the invention. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
FIG. 1 schematically shows a draw frame 1 in a side view. A fiber sliver 91 is taken out of several presentation cans 9 and is conveyed to the drafting equipment 2 of the draw frame. The drafting equipment 2 is shown by a point-dotted line. The individual fiber slivers are drafted together in the draw frame and leave the draw frame in the form of a newly drafted fiber sliver 92. Following this it is deposited by means of a rotating depositing plate 93 in a can 9. The drafting equipment 2 of the draw frame 1 may be an autolevelled or a non-autolevelled draw frame. The drafting equipment 2 of draw frame 1 consists of three roller pairs, each consisting of a lower roller 21 and an upper roller 22. However, the number of roller pairs can very well be more than three, and similarly several upper rollers can be attributed to one lower roller.
FIG. 2 shows the side view of a drafting equipment 2 for three pairs of drafting rollers pairs which are contained in a basic drafting equipment body 23. The drafting roller pairs, consisting of one upper roller 22 and one lower roller 21 (see FIG. 1) are seated at their ends in bearings 3. Upper and lower rollers are not shown in FIG. 2. Only a bore 210 which receives the bearing of the appertaining lower roller in the bearing arrangements 3 is visible, as well as grooves 220 in which the upper rollers are supported. The upper rollers may remain in the bearing arrangements after opening of the pressure arms (not shown) of the draw frame, or may swivel together with the pressure arm during opening. In the latter case, the upper rollers are detached from the pressure arm once the bearing arrangements have been adjusted, so that they are able to adapt to the bearing arrangement as the pressure arms close. Thereupon they are again attached to the pressure arm. The upper rollers are aligned precisely with the lower rollers by means of grooves 220. Since the fiber sliver enters the draw frame from the left, the left bearing arrangement 3 is the one of the input cylinder of the draw frame, the central bearing arrangement 3 the one of the central cylinder and the right-side bearing arrangement 3 the one of the output cylinder of the drafting equipment 2. The bearing arrangements 3 rest upon the basic drafting equipment body 23 as shown by broken line 10 in FIG. 2. The side of the basic drafting equipment body 23 towards the viewer is shown in a section in order to show the push rod 4. The bearing arrangement 3 of the input cylinder is attached to the push rod 4 by means of two screws 41. By loosening these screws, the bearing arrangement 3 can be taken out of the draw frame. The bearing arrangement 3 is merely held on the push rod 4 and its movement downward in direction of the basic drafting equipment body 23 is limited through the fact that the bearing 3 rests here on the basic drafting equipment body 23. On its side away from the output cylinder, the push rod 4 is provided with a coupling element 8 to which it is screwed. The coupling element 8 has a bore with a thread through which it interacts with a threaded spindle 81. The threaded spindle 81 is mounted in a holding device 24 of the basic drafting equipment body 23 and cannot be displaced axially. Through rotation at the threaded spindle 81, and due to the translation of the rotational movement into a longitudinal movement by the coupling element 8, the bearing arrangement 3 of the input cylinder can be pulled in the direction of the threaded spindle 81. At the same time the bearing arrangement 3 glides in plane 10 on the gliding surface 25 of the basic drafting equipment body 23.
The push rod 4 is provided with a seat 42 which is here made in the form of bores. The seat could however also be made in the form of journals. The corresponding part is in the bearing arrangement 3. When a bearing arrangement is removed from the push rod and then reinstalled on it, the seat 42 makes it possible to mount the bearing arrangement at exactly the same location again, e.g. by screwing it on. Adjustments after changing a bearing arrangement are not necessary. To fix the bearing arrangement within the drafting equipment, a clamping device 7 is provided which uses a locking screw 71 to fix the push rod 4 for the adjustment of the input cylinder as well as (not visible) the push rod for the adjustment of the central cylinder on the basic drafting equipment body 23. As a result, accidental displacement or changing of the distances between the drafting rollers during operation is impossible. The clamping device is the only device, with the exception of the self-inhibiting function of the threaded spindle 81, to fix the bearing arrangement 3 within the drafting equipment. The bearing arrangements themselves are not attached to the basic drafting equipment body 23. They are only attached to the push rod 4 via screw 41. The push rod 4 is moved in the area of the clamping device 7 and in the area of the bearing arrangement of the output cylinder 33. In addition the push rod 4 is moved in the area of the central cylinder 32 by its bearing arrangement 3.
FIG. 3 shows the drafting equipment 2 of FIG. 2, whereby the bearing arrangement 3 of the input cylinder 31 is shown in its two possible adjustment position. Here the push rod 4 is moved into the position closest to the holding device 24. Positions A of the input cylinder 31 (not visible) is reached when its bearing arrangement is mounted on the left one of the two seats 42 (see FIGS. 2 and 3). Position B is reached when the bearing arrangement of the input cylinder 31 is mounted on the right one of the two seats 42 (see FIGS. 2 and 3). As a rule only one seat 42 is available on its assigned push rod for the central cylinder 32 which is also shown in its position closest to the holding device 24. The output cylinder 33 cannot be displaced within the draw frame. The push rod which adjusts the central cylinder 32 cannot be seen in the drawing of FIG. 3, since it is the same as the shown push rod 4 of the input cylinder 31. The appertaining coupling element is not shown and would be in contact with the lower threaded spindle 81.
The guidance of the two push rods 4 on either side takes place at the clamping device 7 as well as at the output cylinder 33. The push rods 4 glide here with their tops along the underside of the output cylinder 33. Downward, in the direction of the basic drafting equipment body 23, the push rods have a clearance between it and themselves. Additional guidance of the push rods 4 is provided at the clamping device, where the push rod is located below a stop 43 on the basic drafting equipment body.
This stop is an even surface which is perpendicular to the plane of the drawing and extends horizontally in the draw frame. The top 401 of the push rod is guided at the clamping device 7 by an adjustable stop 43. This stop can be fixed by means of the locking screw 71 in direction of the basic drafting equipment body 23 so that it can be moved around the push rods. By being attached to their respectively assigned bearing arrangements 3, the push rods also bear indirectly, via the underside of the bearing arrangement 3, upon the gliding surface 25 of the basic drafting equipment body 23. The push rod lies directly on the basic drafting equipment body 23 only at the clamping device 7 such that a space 100 is defined between the body 23 and the bottom of the push rods. The gliding surface 25 is horizontal in this case exactly as in FIG. 2, and is represented by line 10. The support of the push rod 4 for its movement in vertical direction is provided therefore via stops 43, at the clamping device 7 and at the output cylinder 33. At the stops 43 of the clamping device 7, the push rod is supported upward as well as downward. Otherwise the push rod 4 is also guided by the threaded spindles 81 together with the coupling element 8, in particular during the adjusting process. The essential guiding task is however assumed by the stops 43 at the clamping device 7 and at the bearing arrangements of the output cylinders 33, here however only in the upward direction.
FIGS. 4a to 4c show a section through the drafting equipment cylinder, in principle as the right-hand side view of FIGS. 2 and 3, whereby input, central and output cylinders are shown one above the other in the drawing for greater clarity. FIG. 4a shows the input cylinder 31, FIG. 4b the central cylinder 32 and FIG. 4c the output cylinder 33. The input cylinder 31 consists of a lower roller 310 which is supported via bearing 311 in the bearing arrangement 3. All three bearing arrangements of FIGS. 4a to 4c have a recess 300 in which the push rods 4 extend in part. On both sides of the push rods, each bearing arrangement is provided with a supporting surface 250 by means of which they bear upon the gliding surface 25 of the basic drafting equipment body 23. The input cylinder 31 and the central cylinder 32 are here capable of displacement on the gliding surface, while the output cylinder 33 is attached on the basic drafting equipment body by means of fasteners (not shown). The input, central and output cylinders are understood to be the pairs consisting of upper and lower rollers.
The bearing arrangement 3 of the input and central cylinder is made in two parts so that two push rods 4 are also required to adjust the bearing arrangement 3. To adjust the input rollers 31, a push rod 4a is provided on the right hand bearing arrangement 3 and a push rod 4a on the left hand bearing arrangement 3. The left hand and right hand bearing arrangements 3 of the input cylinder are connected by screws to the appertaining push rods 4a.
The lateral guidance at the push rods 4a assigned to the input cylinder 31 is effected by the bearing arrangement 3 of central and output cylinder, as well as by the clamping device 7. The push rods 4a for the adjustment of the input cylinder 31 are attached to the bearing arrangements 3 of the input cylinder 31 by means of screws 41. In the recess 300 of the bearing arrangement 3 of the central cylinder 32 of FIG. 4b, the push rod 4a is provided in addition to the push rods 4b which adjust the bearing arrangement of the central cylinder 32, and are required to adjust the bearing arrangement 3 of the input cylinder 31 (see also FIG. 4a). In the recess 300 of the bearing arrangement 3 of the output cylinder 33 of FIG. 4c, the two push rods 4a and 4b are placed. The push rods 4a and 4b are guided laterally in such manner that they bear either against one of the two lateral walls 301 or in opposite direction against the other push rod. The push rods are also laterally supported against the lateral walls of the clamping device 7.
FIG. 5 shows a left lateral view of the drafting equipment of FIGS. 2 and 3 with the components visible in this view that are essential for the movement of the push rods for the adjustment of the drafting rollers. On the basic drafting equipment body 23, for the left as well as for the right side, holding devices 24 are provided to receive the threaded spindle 81 (see FIGS. 2, 3). The threaded spindles 81 extend via a bearing arrangement through he holding device 24 and are there connected to a toothed belt wheel 82. Since the drafting rollers are adjusted by two push rods on each side, four threaded spindles are accordingly provided, each with a toothed belt wheel 82. Two toothed belt wheels 82 at a time are connected to each other by means of a toothed belt 83. The toothed belt wheels 82 have a drive rod 84 on which a drive wheel (not shown) can be set, so that the rotation of the threaded spindle can be produced. It is sufficient here if, as in FIG. 5 for example, only the two toothed belt wheels 82 of the right side are equipped with a drive rod 84, since the rotation of a toothed belt wheel 82 on the right side via toothed belt 83 is transmitted to the toothed belt wheel on the left side. The utilization of a toothed belt ensures that the right-hand toothed belt wheel is given the same rotation as the left one, so that the threaded spindles on both sides move over the exactly same path. As is clearly shown in FIGS. 2 and 4, the two upper toothed belt wheels 82 adjust the input cylinder 31 of the drafting equipment and the two lower ones the central cylinder of the drafting equipment. Instead of a manually operated adjusting wheel, it is also possible to install and electrical motor on the drive rod 84 or to connect it via a gearing, so that the adjustment of the drafting rollers can be electrical and possibly also automatic. It is also advantageously possible to operate the clamping device 7 also automatically for adjustment, e.g. by means of a pneumatic or hydraulic clamping device, so that the entire adjusting process can be automated. Due to the fact that the parallelism of the drafting rollers is always ensured as described earlier during adjustment, it is also possible to make an adjustment also during operation, e.g. by means of an automatic adjusting device, whereby the means to influence the upper rollers must be designed accordingly.
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 cover such modifications and variations as come within the scope of the appended claims and their equivalents. | A spinning plant machine has a basic drafting equipment body to receive drafting equipment which has at least two pairs of rollers, whereby each pair is constituted by an upper roller and a lower roller. A device for the adjustment of the distance between the pairs of rollers is in the form of a push rod which is coupled to the bearing arrangement of the lower rollers as well as to fix the support of the lower rollers on the basic drafting equipment body. The push rods can be adjusted with precise parallelism and position. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of prior U.S. Provisional Patent Application Ser. No. 61/448,375, filed Mar. 2, 2011.
BACKGROUND OF THE INVENTION
The present invention is directed toward a towel washing and drying appliance and more particularly, toward such an appliance that washes, sanitizes, dries and warms one towel at a time and which is located at or near the bathroom.
Existing standard washers and dryers for towels use a large amount of energy and water. Energy is used in the hot water heater, the washer motor and pump, the dryer fan, motor and heating element. Also the air exhausted by the dryer is made-up from outdoors causing heating or cooling energy use by the building. A washer using an electric water heater and an electric dryer uses about 5 kilowatt-hours and about $0.50 per cycle. For 10 towels in a cycle this is ½ kWh or 5 cents per towel. A typical front load washer uses about 24 gallons per cycle. For 10 towels in a cycle this is 2.4 gallons of water per towel. Although the stated cost and water use may seem to be small amounts per towel, the frequency of towel usage per person results in large amounts for households and society as a whole. For households without access to in home washers and dryers the use of a compact, efficient and cost effective bathroom appliance to wash towels can save significantly more cost by reducing external laundry charges. For commercial applications (i.e. the hospitality industry) in addition to saving the cost of energy and water use, the appliance would save significant labor cost by removing towels from the laundry workload.
Prior inventions have been proposed to wash and dry towels in a single machine in an apparent effort to save time and money. U.S. Pat. No. 2,655,022 to Wells, for example, is directed toward a system for washing individual towels wherein the towel is first brought through a washing tank and then a rinsing tank before it passes by and electric heater for drying the same. A similar arrangement is shown in prior U.S. Pat. No. 3,110,974 to Paullus et al. which further includes an ultraviolet light for sanitizing the towels.
While both Wells and Paullus et al. present individual towels to a user, the towels are not actually removable from the apparatus. Rather, the towels are secured to a rod or the like that conveys them through the machine. The towel is merely exposed so that the user can dry his or hands or face. In neither system can the towel be removed so that a person can utilize the same to dry his or her entire body after a bath or shower.
There is, therefore, a need for an appliance that washes, sanitizes, dries and warms one towel at a time and allows the user to remove the towel from the apparatus to be used as a bath towel to dry his or her entire body.
SUMMARY OF THE INVENTION
The present invention is designed to overcome the deficiencies of the prior art discussed above. It is an object of the present invention to provide a towel washing and drying appliance and more particularly, toward such an appliance that washes, sanitizes, dries and warms one towel at a time.
It is another object of the present invention to provide a towel washing and drying appliance that washes, sanitizes, dries and warms one towel at a time and makes it available to be used as a bath towel.
In accordance with the illustrative embodiments demonstrating features and advantages of the present invention, there is provided a towel washing and drying appliance that washes, sanitizes, dries and warms one towel at a time in a linear progression. The unit includes a towel transport system then runs through the unit from a feeder to the towel storage receptor. Manual feeding with sensors to determine proper alignment is first, then washing/sanitizing with wash boxes positioned on either side, then extraction with wringers, followed by drying and then storage of the clean warm towels. The towel transport mechanism may change direction so that the towel is initially directed downward through the unit then up through washing and extraction then down again for drying. This allows for a compact appliance design. After two minutes the towel is ejected into an insulated basket or towel receptor where it is stored, fresh, warm and ready for use.
Other objects, features, and advantages of the invention will be readily apparent from the following detailed description of the preferred embodiments thereof taken in conjunction with the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
For the purpose of illustrating the invention, there is shown in the accompanying drawings forms which are presently preferred; it being understood that the invention is not intended to be limited to the precise arrangements and instrumentalities shown.
FIG. 1 is a perspective view shown somewhat schematically an illustrating the general arrangement of the invention;
FIG. 2 is a front elevational view of the towel washing and drying invention shown in FIG. 1 , and
FIG. 3 is a cross-sectional view of FIG. 2 illustrating the operation of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings in detail wherein like reference numerals have been used throughout the various figures to designate like elements, there is shown in FIGS. 1-3 a towel washing and drying appliance constructed in accordance with the principles of the present invention and designated generally as 1 .
The towel washing and drying appliance 1 includes a number of component parts. The number shown in the drawings identifying each part along with a brief description of the parts is as follows:
2 laundry processing unit
4 is a manual feed table
6 washer section
8 dryer section
10 towel path
12 insulated towel receptor
14 support unit
16 user interface
18 make-up water tank
20 waste water tank
22 drying fan
24 air-to-air heat exchanger
26 lint filter
28 feed-catch roller
30 support web with rollers
32 wash box
34 water seal rollers or wipers
36 water sump in the wash box
38 wash nozzles
40 wringer and water seal wipers
42 air seal rollers or wipers
44 drying air supply duct
46 drying air return/exhaust duct
48 electric heaters with insulated glass facing and insulation backing
50 optional ultra-violet lights with reflectors and lenses
52 access door to towel storage.
The unit 1 can be floor standing or wall mounted. In either case, it consists essentially of the laundry processing unit 2 and the attached support unit 14 . The laundry processing unit 2 includes a number of components including the manual feed table 4 which is where the operator feeds the towel into the unit. A towel transport captures the towel at the feed-catch roller 28 which also contains a support “web” with rollers 30 to support the towel through the machine.
Washing and sanitizing is performed in the wash-box 32 which is a 5 sided box with the open side facing the towel. Preferably, two wash boxes 32 are used, one on each side of the towel. The wash boxes 32 contain a volume of ozone infused cold water at the water sump 36 of the wash box. Compressed air provided the high velocity wash nozzles 38 sends pressurized wash water flow to and through the towel. This wash water flow is cycled in rapid succession and sequenced so that only one side of the towel is pressurized at a time. This dislodges any foreign objects not physically attached to the towel. A water extractor 40 in the form of a wringer consisting of two rollers with resilient surfaces, squeezes the towel tightly to force water from the fibers of the towel and back into the wash box.
Also included is a dryer comprised of electric heaters 48 positioned on each side of the towel and which focus heat directly on the towel to evaporate the remaining water. A stream of room air from the drying air supply duct 44 then carries the evaporated water from the system through the drying air return/exhaust duct 48 . Air seal rollers or wipers 42 contain the supply and return/exhaust air and direct the air in the proper direction within the dryer section 8 . An air-to-air heat exchanger 24 pre-warms the room air and cools the exhaust air to contain the heat in the system.
The towel receptor 12 is an insulated detachable box that contains one or more towels ready for use. An access door 52 to the towel receptor 12 allows access to the towels while containing the heat of the warmed towel.
The support unit 14 is also comprised of a number of components including a user interface 16 that provides an led readout and function keys for the user to operate the unit 1 . In addition, a make-up water tank 18 is located at the top to contain make-up water. Alternately this could be a water line connection. Waste water tank 20 is located at the bottom to contain used waste water. In lieu of a waste water tank, a drain could be connected to the unit.
An air compressor and air tanks can be used to provide the driving force for the wash nozzles 38 . An oxygen concentrator in the form of a small oxygen generator provides oxygen to the inlet of the ozone generator which makes ozone (o 3 ) for use as the cleaning agent for the machine. Ozone and clean water are introduced and mixed into a pressure tank providing ozone infused water ready for introduction to the wash boxes 32 .
After the towels are washed, the drying fan 22 provides room air to the dryer section 8 . A lint filter 26 captures any lint given off from the towel before the drying air is released back into the room and the air to air heat exchanger 24 exchanges heat between air from the dryer section 8 and incoming air. Since condensation may occur in the cooled return/exhaust air, a drain is also provided.
In addition to the above, it is also possible to provide the unit 1 with a detergent tank and dispenser, if desired. Also desirable is the inclusion of ultra-violet lights 50 with reflectors and protective lenses for sterilizing if needed. These two alternate features replace the need for the oxygen concentrator and ozone generator yet maintain the ability to wash with cold water and still provide a sanitized towel. This however may affect the wash cycle as there then needs to be a rinse cycle to eliminate the residual detergent from the towel before extraction and drying.
The necessary elements of the invention are the towel transport mechanism, the wash box 32 with water extraction wringers 40 , the drying heater 48 and drying fan 22 . Optional features of the invention are ozone washing versus typical detergent wash/rinse with a U-V light 50 for sanitizing.
A basic concept of the invention is linear/full-area laundry processing. As the name implies there is a linear progression of the towel through the laundry processing unit 1 . The towel transport system then runs through the unit from the feeder to the towel receptor. Manual feeding with sensors to determine proper alignment is first, then washing/sanitizing with the wash boxes 32 positioned on either side, then extraction with the wringers 40 , followed by drying and then storage of the clean warm towel in the towel receptor 12 . The towel transport mechanism may change direction so that, for example the towel is initially directed downward through the unit then up through washing and extraction then down again for drying. This allows for a compact appliance design.
The support unit 14 needs to be positioned attached to the laundry processing unit. The user interface 16 needs to be at a convenient and accessible location for the user. Due to the influence of gravity the make-up water tank 18 or connection needs to be at the top and the waste water tank 20 or connection needs to be at the bottom.
The oxygen generator is a device which makes an ozone generator more efficient. The ozone gas is infused into water in a preparation tank to produce a saturated solution of ozone in water. This provides for a very effective cleaning solution that acts on dirt, oil, grease and bacteria. Because ozone is highly reactive it breaks down completely after use into oxygen and water. This provides for effective cold water washing without detergent and eliminates the need for a rinse operation. The ozone system then feeds the wash boxes 32 and would need to be located in proximity to the washing/sanitizing station in the laundry processing unit 2 .
The drying fan 22 needs to be located in proximity to the dryer section 8 in the laundry processing unit 2 . Air is pulled in through the air-to-air exchanger 24 then through the fan then to the dryer section 8 . From the dryer section 8 the air is exhausted first through a small lint filter 26 then through the other side of the air-to-air heat exchanger 24 . A drain line is connected to the inlet air side of the exchanger 24 for any condensed water. The support unit 14 also has a cord and plug for connection to an electrical wall outlet.
The user would initially press a “FEED/WASH” or similar button. The user would then manually feed the top edge of the towel into the machine. Alignment sensors will detect if the towel is mis-aligned and then create an alarm for the user to re-align the towel into the unit. When properly fed with a towel the towel transport mechanism with the feed-catch roller 28 will change position to catch the towel and transport it to the first wash position in the washing station 6 . At the same time the ozone system starts to generate ozone, water is dumped into the preparation tank and the air compressor starts to fill a pressurized receiver with compressed air. When sufficient ozone is generated it infuses into the water preparation tank. This wash water is then dumped into each wash box 32 . The compressed air is released into the wash nozzles 38 in the wash box 32 and the washing starts for the full width of the towel and the height of the wash box 32 .
When this first wash location is complete the towel transport engages and positions the towel to the second wash location while at the same time wringing residual water from the towel using the wringer 40 . This then progresses for the full height of the towel. At some point after the first two wash locations are completed the leading edge of the towel reaches the dryer section 8 location. This triggers the start of the electric heaters 48 . When the heat has reached a certain level the drying fan 22 starts. A moisture sensor detects when drying is sufficient and releases the mechanism to advance once the next wash location has completed. This then repeats for the full height of the towel. If the alternate U-V lights 50 are employed in the design, they are activated when the first section of towel reaches the light station and deactivated when the towel is complete. Safety sensors and devices prevent overheating of the towel in the dryer section 8 . When the towel has completely processed an alarm signals the user. The user can then retrieve the washed, sanitized, dried and warmed towel.
An alternate process would be the warming of a clean towel. In this case the user would press a “FEED/WARM” or similar button and all the above processes would engage except for the wash, wash support features and the dryer fan 22 . Instead of a moisture indicator triggering the advance of the towel a simple timer or thermal sensor would be used. The same safety features would be used to prevent overheating of the towel.
The operation of the towel washing and drying unit 1 would involve a person feeding a dirty towel into the machine before the start of a bath or shower. The machine washes, sanitizes, dries and therefore warms the towel. After two minutes the towel is ejected into an insulated basket or towel receptor 12 where it is stored, fresh, warm and ready for use.
As should be readily apparent to those skilled in the art, the invention is different from typical washing and drying. The geometry of the bath towel is unique to other pieces in the laundry. A bath towel is a single ply textile with a consistent width of about 27 inches. This allows for a compact sheet-fed laundry machine to wash, sanitize and dry towels in a linear process which exposes the full surface area of each side of the towel to the workings of the machine. This linear/full-area processing is completely different that the normal laundry process and allows for a dramatic reduction in energy and water use. Because bath towels make up a high percentage of total washing loads the result is a significant savings to overall laundry cost. Because warming of the towel is integral to the drying process and because the automated appliance is located in proximity to the bath, shower or pool, no additional energy is needed to provide the user with the luxury of a warm bath towel with every bath or shower.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof and accordingly, reference should be made to the appended claims rather than to the foregoing specification as indicating the scope of the invention. | The high energy usage and high water usage of conventional washing and drying, specifically for towels, is addressed with the present invention. The “towel-station” of the invention is a single-piece sheet-fed appliance to be located at or near the bathroom, shower or pool to efficiently wash, sanitize, dry and warm a towel. Dramatic savings of energy and water result over that of conventional washing and drying. An additional benefit is the availability to the user of a warm towel after bathing without the use of additional energy since warming is performed as part of the drying process. | 3 |
[0001] This is a National Phase Application in the United States of International Patent Application No. PCT/JP2013/002542 filed Apr. 15, 2013, which claims priority on Japanese Patent Application No. JP2012-124339, filed May 31, 2012. The entire disclosures of the above patent applications are hereby incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to an improvement in a flow control system with flow monitoring, and specifically, to a flow control system with build-down system flow monitoring that can monitor in real time a controlled flow rate of a flow control system being operated by organically combining a build-down system flow monitor with a thermal type flow control system with supply pressure fluctuation resistance characteristics or a pressure type flow control system using an orifice.
BACKGROUND OF THE INVENTION
[0003] Conventionally, a thermal type flow control system MFC and a pressure type flow control system FCS are widely used in a gas supplying apparatus for a semiconductor control device, and in recent years, a thermal type flow control system with improved supply pressure fluctuation resistance characteristics is increasingly used.
[0004] FIG. 33 shows the arrangement of a pressure type flow control system FCS. This pressure type flow control system FCS includes a control valve CV, a temperature detector T, a pressure detector P, an orifice OL, and an arithmetic and control unit CD, etc. The arithmetic and control unit CD includes a temperature correction/flow rate arithmetic circuit CDa, a comparison circuit CDb, an input-output circuit CDc and an output circuit CDd, etc., and has excellent characteristics keeping stable flow control characteristics against fluctuation of a primary side supply pressure.
[0005] Referring to FIG. 33 , detection values from the pressure detector P and the temperature detector T are converted into digital signals and input into the temperature correction/flow rate arithmetic circuit CDa, and here, temperature correction of the detected pressure and flow rate computation are performed, and then the computed flow rate value Qt is input into the comparison circuit CDb. In addition, an input signal Qs of a set flow rate is input from a terminal In, and converted into a digital value by the input-output circuit CDc, and then input into the comparison circuit CDb, and, thereafter, compared with the computed flow rate value Qt from the temperature correction/flow rate arithmetic circuit CDa. As a result of the comparison, when the computed flow rate value Qt is larger than the set flow rate input signal Qs, a control signal Pd is output to the drive unit of the control valve CV. Accordingly, the control valve CV is driven in a closing direction, and is driven in the valve closing direction until the difference (Qs−Qt) between the set flow rate input signal Qs and the computed flow rate value Qt becomes zero.
[0006] The pressure type flow control system FCS has excellent characteristics in which when the relationship of P 1 /P 2 ≧approximately 2 (herein referred to as the critical expansion condition) is kept between the downstream side pressure P 2 of the orifice OL (that is, the pressure P 2 on the process chamber side) and the upstream side pressure P 1 of the orifice OL (that is, the pressure P 1 on the outlet side of the control valve CV), the flow rate Q of the gas G 0 distributed through the orifice OL is Q=KP 1 (here, K is a constant), the flow rate Q can be controlled with high accuracy by controlling the pressure P 1 , and even when the pressure of the gas G 0 on the upstream side of the control valve CV greatly changes, the controlled flow rate value hardly changes.
[0007] The pressure type flow control system FCS and the thermal type flow control system with pressure fluctuation resistance characteristics are known, therefore, detailed descriptions thereof are omitted here.
[0008] However, for example, in the pressure type flow control system FCS, an orifice OL with a minute hole diameter is used, so that the hole diameter of the orifice OL changes over time due to corrosion caused by a halogen-based gas and precipitation of a reactant gas, etc. As a result, the controlled flow rate value of the pressure type flow control system FCS and the actual flow rate value of the gas G 0 actually distributed become different from each other, and to detect this difference, so-called flow monitoring has to be frequently performed, and this greatly affects the operability of the semiconductor manufacturing equipment and the quality of a manufactured semiconductor.
[0009] Therefore, in the field of pressure type flow control systems, conventionally, a method is widely used for preventing the controlled flow rate value of the pressure type flow control system FCS and the actual flow rate value of the gas G 0 actually distributed from becoming different from each other by detecting a change in hole diameter of the orifice OL as early as possible, and, in order to detect the change in hole diameter of the orifice OL, a gas flow rate measuring method using a so-called build-up system or build-down system is adopted in many cases.
[0010] However, in the conventional gas flow rate measurement using a so-called build-up system or build-down system, actual gas supply has to be temporarily stopped, and as a result, the operation rate of the semiconductor manufacturing equipment is lowered, or the quality, etc., of a manufactured semiconductor is greatly affected.
[0011] Therefore, in recent years, in the field of thermal type flow control systems and pressure type flow control systems, a flow control system with flow monitoring that can easily monitor in real time whether supply gas flow control is being properly performed without temporarily stopping actual gas supply has been developed.
[0012] For example, FIG. 34 shows an example. A flow control system 20 with flow monitoring, being a thermal type mass flow control system (mass flow controller), includes a flow passage 23 , a first pressure sensor 27 a for an upstream side pressure, a control valve 24 , a thermal type mass flow sensor 25 provided on the downstream side of the control valve 24 , a second pressure sensor 27 b provided on the downstream side of the thermal type mass flow sensor 25 , a throttle unit (sonic nozzle) 26 provided on the downstream side of the second pressure sensor 27 b , an arithmetic and control unit 28 a , and an input-output circuit 28 b , etc.
[0013] The thermal type mass flow sensor 25 includes a rectifier body 25 a inserted into the flow passage 23 , a branched flow passage 25 b branched by a flow rate of a predetermined proportion of F/A from the flow passage 23 , and a sensor main body 25 c provided on the branched flow passage 25 b , and outputs a flow rate signal Sf showing a total flow rate F.
[0014] The throttle unit 26 is a sonic nozzle that provides a fluid at a flow rate corresponding to a primary side pressure when a pressure difference between the primary side and the secondary side of the throttle unit is greater than or equal to a predetermined value. In FIG. 34 , the reference symbols SPa and SPb denote pressure signals, Pa and Pb denote pressures, F denotes a total flow rate, Sf denotes a flow rate signal, and Cp denotes a valve opening degree control signal.
[0015] The arithmetic and control unit 28 a feed-back controls the control valve 24 by feeding-back pressure signals Spa and Spb from the pressure sensors 27 a and 27 b and a flow rate control signal Sf from the flow sensor 25 and outputting a valve opening degree control signal Cp. That is, a flow rate setting signal Fs is input into the arithmetic and control unit 28 a via the input-output circuit 28 b , and the flow rate F of the fluid flowing in the mass flow control system 20 is adjusted so as to match the flow rate setting signal Fs.
[0016] In detail, by controlling the opening and closing of the control valve 24 by feed-back controlling the control valve 24 by the arithmetic and control unit 28 a by using the output (pressure signal Spb) of the second pressure sensor 27 b , the flow rate F of the fluid flowing in the sonic nozzle 26 is controlled, and by using an output (flow rate signal Sf) of the thermal type flow sensor 25 at this time, the flow rate F of the actual flow is measured, and, by comparing the measured value of this flow rate F and the controlled value of the flow rate F, the operation of the mass flow control system 20 is confirmed.
[0017] Thus, in the flow control system 20 with flow monitoring shown in FIG. 34 , two measuring systems of pressure type flow rate measurement using the second pressure sensor 27 b for performing flow control and flow rate measurement using the thermal type flow sensor 25 for monitoring the flow rate are installed in the arithmetic and control unit 28 a , so that, whether or not the fluid at the controlled flow rate (set flow rate Fs) is actually flowing, that is, whether or not the controlled flow rate and the actual flow rate are different from each other can be easily and reliably monitored in real time, so that a high practical effect is obtained.
[0018] However, many problems that should be solved still remain in the flow control system 20 with flow monitoring shown in FIG. 34 .
[0019] A first problem is that since two different flow rate measuring systems of pressure type flow rate measurement using the second pressure sensor 27 b for performing flow control and flow rate measurement using the thermal type flow sensor 25 for monitoring the flow rate are utilized, the structure of the flow control system 20 with flow monitoring becomes complicated, and the system cannot be downsized and reduced in manufacturing cost.
[0020] A second problem is that the arithmetic and control unit 28 a is arranged to control the opening and closing of the control valve 24 by using the signals of both of an output SPb of the second pressure sensor 27 b and a flow rate output Sf of the thermal type flow sensor 25 , and correct the flow rate output Sf of the thermal type flow sensor 25 by using an output SPa of the first pressure sensor 27 a , and opening and closing of the control valve 24 are controlled by using three signals of the two pressure signals SPa and SPb of the first pressure sensor 27 a and the second pressure sensor 27 b and the flow rate signal Sf from the thermal type flow sensor 25 . Therefore, not only does the make up of the arithmetic and control unit 28 become complicated, but also the stable flow control characteristics and excellent high responsiveness of the pressure type flow control system FCS are lessened adversely.
CITATION LIST
Patent Documents
[0000]
Patent Document 1: Japanese Patent No. 2635929
Patent Document 2: Japanese Patent No. 2982003
Patent Document 3: Japanese Patent No. 4308350
Patent Document 4: Japanese Patent No. 4137666
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0025] A main object of the present invention is to solve the problem (a) in which in a conventional flow control system with flow monitoring using a build-down system or build-up system flow rate measuring method, actual gas supply has to be temporarily stopped at the time of flow monitoring, so that deterioration of the operation rate of the semiconductor manufacturing equipment and quality fluctuation of a manufactured semiconductor, etc., are caused, and the problem (b) in which in a conventional flow control system with flow monitoring having a combined structure of a thermal type flow meter and a pressure type flow control system as shown in FIG. 34 , the flow control system itself cannot be structurally simplified and downsized, and excellent response characteristics and stable flow control characteristics of the pressure type flow control system are lessened, etc. These problems are solved by various embodiments of the present invention, by integrally combining the pressure type flow control system FCS or supply pressure fluctuation resistant thermal type flow control system MFC and a build-down system flow rate measuring unit provided on the upstream side of the pressure type flow control system FCS or supply pressure fluctuation resistant thermal type flow control system MFC, operating the build-down system flow rate measuring unit within a pressure fluctuation range allowable for the upstream side pressure (input side pressure) of the flow control system, and transmitting a flow monitoring signal from the build-down system flow rate measuring unit at least once per second (preferably, a plurality of times per second). Thereby, flow monitoring in close approximation to real-time monitoring can be performed by the build-down system flow rate measuring unit simultaneously with flow control by the flow control system.
[0026] With the above-described structure, a flow control system with build-down system flow monitoring can be provided that can perform flow monitoring by the build-down system flow monitoring unit in close approximation to real-time (at least once per second) by fully utilizing the flow rate characteristics of the pressure type flow control system or supply pressure fluctuation resistant thermal type flow control system the flow control characteristics of which is hardly influenced by pressure fluctuation on the input side, and enables simplification of the arithmetic and control unit, significant downsizing of the system main body, and an improvement in gas replaceability, etc.
Means for Solving the Problems
[0027] The inventors of the present application have constructed test equipment shown in FIG. 1 first by using the pressure type flow control system FCS using an orifice, and conducted various basic tests relating to flow rate measurement by using a build-down system in which the flow rate was calculated from the gradient of a pressure drop between the pressure type flow control system FCS and the upstream side (primary side) valve AV.
[0028] That is, in FIG. 1 , the reference symbol N 2 denotes a gas supply source, RG denotes a pressure regulator, ECV denotes an electromagnetic drive unit, AV denotes an upstream side valve, FCS denotes a pressure type flow control system, VP denotes a vacuum pump, BC denotes a build-down capacity, T denotes a temperature detection sensor, P 0 denotes a pressure sensor output from a pressure sensor provided inside the pressure type flow control system FCS, E 1 denotes a power supply for a pressure type flow control system, E 2 denotes a power supply for an arithmetic and control unit, E 3 denotes a power supply for an upstream side valve, S denotes a signal generator, CP denotes an arithmetic and control unit, CPa denotes a pressure type flow rate arithmetic and control unit, CPb denotes a build-down monitoring flow rate arithmetic and control unit, PC denotes an arithmetic and display unit, and NR denotes a data logger.
[0029] The build-down capacity BC is equivalent to a pipe passage spatial volume between the outlet side of the upstream side valve AV and the inlet side of the control valve (not illustrated) of the pressure type flow control system FCS, and the build-down capacity BC can be adjusted to switch to 1.78 cc and 9.91 cc, 4.6 to 11.6 cc, and 1.58 cc to 15.31 cc by adjusting the length and inner diameter, etc., of the pipe passage or adjusting the internal volume of a build-down chamber (not illustrated) interposed in this pipe passage.
[0030] When the build-down chamber is used, as described later in an illustrative example, the inner diameter of the flow passage between the outlet of the upstream side valve AV and the inlet of the control valve CV is set to 1.8 mm, and the build-down capacity BC is selected to be 1.58 cc to 15.31 cc.
[0031] In the build-down monitoring flow rate arithmetic and control unit CPb inside the arithmetic and control unit CP, as described later, a necessary monitoring flow rate is computed by using a pressure drop rate of the build-down capacity BC portion, and further, in the pressure type flow rate arithmetic and control unit CPa, computation of the flow rate distributed through the orifice (not illustrated) and opening/closing control of the control valve (not illustrated), etc., are performed in the same manner as in the arithmetic and control unit of the conventional pressure type flow control system FCS.
[0032] The pressure type flow control system FCS, the upstream side valve AV, the pressure regulator RG, and other devices are all known, therefore, descriptions thereof are omitted here.
[0033] The pressure type flow rate arithmetic and control unit CPa is generally installed inside the arithmetic and control unit CP, however, in FIG. 1 , for convenience of description, the pressure type flow rate arithmetic and control unit CPa is shown in a state where it is separated from the arithmetic and control unit CP. Further, the upstream side valve AV has to perform opening and closing in a short time, so that a direct-operated solenoid valve is preferably used, however, an air-operated valve provided with a pilot solenoid valve may also be used as a matter of course.
[0034] The flow control system is hardly influenced by gas supply pressure fluctuation, and is specifically a pressure type flow control system FCS using an orifice, so that the build-down system flow rate measuring unit can be disposed on the upstream side of the flow control system. It is generally known that highly accurate flow rate measurement can be made by flow rate measurement using the build-down system.
[0035] That is, in the build-down system, the flow rate Q distributed inside the build-down capacity BC can be calculated by the following equation (1).
[0000]
Q
(
sccm
)
=
1
(
atm
)
760
(
Torr
)
×
1000
(
cc
/
l
)
×
60
(
sec
/
min
)
×
273
(
K
)
(
273
+
T
)
(
K
)
×
V
(
l
)
×
Δ
p
(
Torr
)
Δ
t
(
sec
)
[
Numerical
Equation
1
]
[0036] Here, V is the volume (I) of the build-down capacity BC, ΔP/Δt is a pressure drop rate in the build-down capacity BC, and T is a gas temperature (° C.).
[0037] First, in the test equipment shown in FIG. 1 , the upstream side pressure of the pressure type flow control system FCS was set to 400 kPa abs, the pressure difference ΔP was set to 50 kPa abs or more, the build-down capacity BC was set to 4.6 to 11.6 cc, and flow rate measurement using the build-down system was performed. FIG. 2 shows a pressure drop state at this time, and it was found that the flow rate itself could be measured with comparatively high accuracy, however, the pressure recovery time (a) was necessary, therefore, the output of the measured flow rate became discontinuous, and the time required for one cycle was several seconds or longer. As a result, it was found that under this measurement condition, the flow monitoring became significantly different from so-called real-time flow monitoring.
[0038] That is, when the time until the pressure reaches a prescribed value or more after the upstream side valve AV is opened is defined as a pressure recovery time (a), and the time until the pressure reaches the prescribed value or less after the upstream side valve AV is closed is defined as a flow rate output enabling time (b), according to the ratio of (a) and (b), the percentage of time during which flow rate output is possible is determined. This flow rate output enabling time (b) is determined according to the controlled flow rate of FCS, the build-down capacity BC, and a pressure drop range ΔP, therefore, it was found that unless the controlled flow rate of FCS, the build-down capacity BC, and the pressure drop range ΔP were more strictly examined and set to appropriate values, respectively, flow rate measurement using the build-down system cannot be made closer to real-time flow monitoring.
[0039] On the other hand, as real-time flow monitoring, ideally, continuous flow rate output is necessary, however, in actual operation of the semiconductor manufacturing equipment, etc., flow monitoring almost closer to real-time monitoring is possible as long as a flow rate output can be obtained at least once or more per second.
[0040] Therefore, in flow rate measurement using the build-down system, to realize flow monitoring close to real-time monitoring by obtaining a flow rate output at least once or more per second, the inventors of the present application conceived that the time necessary for gas refilling (pressure recovery time (a)) is made shorter by making smaller the pressure drop range (pressure difference) ΔP and build-down capacity BC. Based on this idea, the inventors considered whether or not the real-time performance could be secured by reducing the build-down capacity BC and the pressure drop range (pressure difference) ΔP of the upstream side in the flow control system to be used in semiconductor manufacturing equipment, and conducted various tests relating to the flow monitoring accuracy and reproducibility, etc.
[0041] [Test 1]
[0042] First, in the test equipment shown in FIG. 1 , as the pressure type flow control system FCS, three types of FCSs the rated flow rates of which were F20, F200, and F600 (sccm) were prepared.
[0043] The build-down capacity BC was set to two values of approximately 1.78 cc and approximately 9.91 cc. The build-down capacity BC of 9.91 cc was adjusted by adjusting the pipe length and pipe inner diameter.
[0044] Further, 0.5 sec (0.25 ms×2000 points) was set as a target flow rate output detection enabling time (b), and the test environment temperature was set to 25° C.±1° C.
[0045] Next, the FCS upstream side pressure was set to 370 kPa abs , the pressure difference was set to ΔP=20 kPa abs , the flow rate N 2 =100 sccm was set (set on the FCS side), and the pressure recovery characteristic (pressure recovery time (a)) at the time of build-down system flow rate measurement was measured.
[0046] FIG. 3 shows results of measurement of the pressure recovery characteristic, and FIG. 4 is an enlarged view thereof.
[0047] Further, FIG. 5 shows the pressure drop characteristic at this time.
[0048] As is clear from FIG. 4 , in FIG. 3 , it was confirmed that by reducing the build-down capacity BC to 1.78 cc and the pressure drop range ΔP to 20 kPa abs , the refilling time (pressure recovery time (a)) could be significantly shortened even at the N 2 flow rate of 100 sccm, and as shown in FIG. 5 , the measured flow rate output could be performed at intervals of at least 1 second or less.
[0049] In relation to Test 1, it was found that the opening and closing speed of the upstream side valve AV had a great influence in making the pressure recovery time (a) shorter than the flow rate output enabling time (b). Therefore, it was found that a direct-mounting type solenoid valve was preferably used as the upstream side valve AV.
[0050] It was also found that shortening of the pressure recovery time (a) by reducing the pressure drop range ΔP and the volume V of the build-down capacity BC led to shortening of the pressure drop time (flow rate output enabling time (b)), so that the relationship among the measured flow rate, the build-down capacity BC, and the pressure drop time (b) was especially important.
[0000]
TABLE 1
Gas flow rate and drop time per one cycle
when the build-down capacity is 1.78 cc
Flow rate (sccm)
Drop time (s)
5
4.22
10
2.11
50
0.42
100
0.21
[0051] Table 1 shows the relationship between the measured flow rate (sccm)(standard cubic centimeters per second) and the pressure drop time (sec) when the build-down capacity BC was set to 1.78 cc, and it is shown that when the build-down capacity BC is 1.78 cc, it becomes difficult to perform flow rate output once or more within 1 second if the flow rate is 50 sccm or less, and it becomes difficult to perform flow monitoring equivalent to real-time monitoring.
[0052] On the other hand, the pressure drop characteristic in the flow rate output enabling time (b) must have linearity in terms of measurement errors, and the range in which the flow rate calculation is possible is limited to the range in which the pressure drop rate is constant (that is, the portion with linearity).
[0053] FIG. 6 to FIG. 8 show the results of investigation on patterns of the pressure drop characteristic when the measured flow rate was 100, 50, and 10 sccm, and in each case, the pressure drop characteristic lost linearity immediately after build-down. In this case, the build-down capacity BC is 1.78 cc, and the fluid is a N 2 gas.
[0054] It is estimated that the deviations from the linearity immediately after build-down shown in FIG. 6 to FIG. 8 are caused by a gas internal temperature change due to adiabatic expansion of the gas according to a pressure change. It is found that as the measured flow rate becomes smaller, the deviation from the linearity tends to become larger, and this narrows the time width in which flow rate calculation is possible.
[0055] Next, a flow rate measurement error caused by deviation from linearity of the pressure drop characteristic curve was measured by measuring 5 points every 0.25 seconds in the case where the flow rate measurement enabling time (b) is within 1 second.
[0056] That is, in a state where the build-down capacity BC was set to 1.78 cc and 9.91 cc, the pressure drop range ΔP was set to 20 kPa abs , and the time from closing of the upstream side valve AV to flow rate stabilization was set to 1 second, the flow rate was calculated every 0.25 seconds, and the error in the calculated flow rate with respect to the controlled flow rate was examined.
[0057] FIG. 9 and FIG. 10 show the results of the examination, and in each case, it was found that when 0.25 seconds or more elapsed from closing of the upstream side valve AV, the error significantly decreased. That is, it was confirmed that as the pressure drop characteristic curve becomes closer to the straight line, the error decreased.
[0058] Table 2 shows the relationship among the build-down capacity BC, the measured flow rate, and the pressure drop time (b), and in the case where the build-down capacity BC=1.78 cc, flow rate output can be performed at intervals of approximately 1 second or less when the flow rate is 20 to 50 sccm.
[0059] In the case where the build-down capacity BC=9.91 cc, flow rate output can be performed at intervals of approximately 1 second or less when the flow rate is 100 to 200 sccm.
[0000]
TABLE 2
Pressure drop range: ΔP = 20 kPa abs.
Build-down capacity
Build-down capacity
BC: 1.78 cc
BC: 9.91 cc
Flow rate
Flow rate
(sccm)
Drop time (s)
(sccm)
Drop time (s)
5
4.22
50
2.35
10
2.11
100
1.17
20
1.05
200
0.59
50
0.42
[0060] Further, for confirmation of reproducibility, flow rate accuracies when measurements corresponding to FIG. 9 were repeatedly performed were investigated.
[0061] That is, flow rate calculation (3 points) was performed in the period from 0.5 to 1 second after the upstream side valve AV was closed. The flow rate computation was performed by using data until 0.5 seconds from the final point when the drop time is less than 1 second, or with respect to 50 sccm (BC=1.78) and 200 sccm (BC=9.91 cc), using the data (2 points) in 0.25 seconds.
[0062] FIG. 11 shows flow rate accuracy measured data when measurement was repeatedly performed (10 times), and shows that when the pressure drop time (b) is 0.5 seconds or less, as shown in FIG. 7 , flow rate computation is performed within the nonlinear region of the pressure drop characteristic curve, therefore, the flow rate error tends to appear in the positive direction as shown in FIG. 11 .
[0063] The flow rate Q by the build-down system has the relationship of Q=K×(pipe capacity×pressure drop rate×1/temperature) as is clear from the equation (1) given above. As a result, it is supposed that the pressure drop rate increases and the computed flow rate Q becomes constant even when a temperature drop is caused by adiabatic expansion according to a pressure change, however, in actuality, the computed flow rate increases. The supposed reason for this is that the gas temperature is measured on the body outer surface of the pressure type flow control system FCS, so that the temperature measured value is easily influenced by the room temperature, and in addition, the heat capacity of the temperature detection sensor is large although the heat capacity of the gas itself is small, and therefore, the gas temperature is not accurately measured.
[0064] The present invention was made based on the results of the respective tests described above, and the invention according to the first aspect is characterized in that a flow control system with build-down system flow monitoring includes an upstream side valve AV that opens/closes distribution of a gas from a gas supply source having a desired gas supply pressure, a flow control system with supply pressure fluctuation resistance connected to the downstream side of the upstream side valve AV, a build-down capacity BC being an internal volume of a passage communicatively connecting the outlet side of the upstream side valve AV and the flow control system inlet side, a temperature detection sensor T that detects the temperature of a gas distributed inside the passage forming the build-down capacity BC, a pressure sensor P that detects the pressure of the gas distributed inside the passage forming the build-down capacity BC, and a monitoring flow rate arithmetic and control unit CPb that controls opening/closing of the upstream side valve AV, and computes and outputs a monitoring flow rate Q by a build-down system by dropping the gas pressure to a set lower limit pressure value by closing the upstream side valve AV after a predetermined time of t seconds after setting the gas pressure inside the build-down capacity BC to a set upper limit pressure value by opening the upstream side valve AV, wherein the monitoring flow rate Q is computed by the following equation:
[0000]
Q
=
1000
760
×
60
×
273
(
273
+
T
)
×
V
×
Δ
P
Δ
t
[
Numerical
Equation
2
]
[0065] (Here, T is a gas temperature (° C.), V is a build-down capacity BC (I), ΔP is a pressure drop range (set upper limit pressure value−set lower limit pressure value) (Torr), Δt is a time (sec) from closing to opening of the upstream side valve AV).
[0066] The invention according to the second aspect is the invention according to the first aspect which is characterized in that the flow control system with supply pressure fluctuation resistance is a pressure type flow control system FCS including a control valve CV, an orifice OL or a critical nozzle, a pressure sensor P 1 and/or a pressure sensor P 2 , and a flow rate arithmetic and control unit CPa, and the build-down capacity BC is the internal volume of a passage communicatively connecting the outlet side of the upstream side valve AV and the inlet side of the control valve CV of the pressure type flow control system.
[0067] The invention according to the third aspect is the invention according to the first or second aspect which is characterized in that the build-down capacity BC is set to 1.8 to 18 cc, the set upper limit pressure value is set to 400 to 200 kPa abs, the set lower limit pressure value is set to 350 kPa abs to 150 kPa abs, and the predetermined time t is set to be within 1 second.
[0068] The invention according to the fourth aspect is the invention according to the first or second aspect which is characterized in that the build-down capacity BC is set to 1.78 cc, the set upper limit pressure value is set to 370 kPa abs, the set lower limit pressure value is set to 350 kPa abs, the pressure difference ΔP is set to 20 kPa abs, and the predetermined time t is set to be within 1 second.
[0069] The invention according to the fifth aspect is the invention according to the first or second aspect which is characterized in that the upstream side valve AV is a fluid pressure-operated solenoid direct-mounting type motor-operated valve or solenoid direct-operated type motor-operated valve, and a recovery time of the gas pressure from the set lower limit pressure value to the set upper limit pressure value by opening of the upstream side valve AV by valve high-speed opening/closing is set to be much shorter than the gas pressure drop time from the set upper limit pressure value to the set lower limit pressure value by closing of the upstream side valve AV.
[0070] The invention according to the sixth aspect is the invention according to the first or second aspect which is characterized in that by inserting a bar piece to the inside of a gas flow passage between the outlet side of the upstream side valve AV and the flow control system, the passage sectional area of the gas flow passage is changed to adjust the build-down capacity BC and linearize the gas pressure drop characteristic.
[0071] The invention according to the seventh aspect is the invention according to the first or second aspect which is characterized in that a chamber with an appropriate internal capacity is interposed in a gas passage between the outlet side of the upstream side valve AV and the control valve of the flow control system FCS, and by changing the internal volume of the chamber, the value of the build-down capacity BC is adjusted.
[0072] The invention according to the eighth aspect is the invention according to the first or second aspect which is characterized in that the flow rate arithmetic and control unit CPa of the flow control system and the build-down monitoring flow rate arithmetic and control unit CPb are integrally formed.
[0073] The invention according to the ninth aspect is the invention according to the seventh aspect which is characterized in that the chamber is structured by concentrically disposing and fixing an inner cylinder and an outer cylinder, and the gap between the inner cylinder and the outer cylinder forming the chamber is used as a gas flow passage, and a pressure sensor P 3 is provided in the chamber.
[0074] The invention according to the tenth aspect is the invention according to the second aspect which is characterized in that a bar piece is inserted to the inside of the gas passage between the outlet side of the upstream side valve AV and the control valve of the pressure type flow control system FCS to change the passage sectional area of the gas flow passage.
[0075] The invention according to the eleventh aspect is the invention according to the second aspect which is characterized in that a chamber with an appropriate internal volume is interposed in the gas passage between the outlet side of the upstream side valve AV and the control valve of the pressure type flow control system FCS.
[0076] The invention according to the twelfth aspect is the invention according to the second aspect which is characterized in that the flow rate arithmetic and control unit CPa of the pressure type flow control system and the build-down monitoring flow rate arithmetic and control unit CPb are integrally formed.
[0077] The invention according to the thirteenth aspect is the invention according to the ninth aspect which is characterized in that a gas passage in which the gas is distributed upward from the lower side is provided inside the inner cylinder, and the gas is made to flow into the gap between the inner cylinder and the outer cylinder from the upper end surface of the inner cylinder.
[0078] The invention according to the fourteenth aspect is the invention according to the thirteenth aspect which is characterized in that the gas passage provided inside the inner cylinder is a gap G 1 formed between a longitudinal slot provided at the center portion of the inner cylinder and a columnar pin inserted inside the longitudinal slot.
[0079] The invention according to the fifteenth aspect is the invention according to the ninth aspect which is characterized in that the inner cylinder is an inner cylinder the outer peripheral surface of which is threaded.
[0080] The invention according to the sixteenth aspect is the invention according to the ninth aspect which is characterized in that the inner cylinder is an inner cylinder with slits inside of which the gas is distributed.
[0081] The invention according to the seventeenth aspect is the invention according to the ninth aspect which is characterized in that the inner cylinder is an inner cylinder provided with a filter medium inside of which the gas is distributed.
[0082] The invention according to the eighteenth aspect is the invention according to the ninth aspect which is characterized in that the inner cylinder is made of a filter medium or a porous ceramic material.
Effects of the Invention
[0083] In the invention according to the first aspect of the present application, an upstream side valve AV is provided on the upstream side of the flow control system, the flow passage between the upstream side valve AV and the flow control system is formed as a build-down capacity BC, and by utilizing high responsiveness of the flow control system to input side pressure fluctuation, a pressure drop ΔP corresponding to a gas pressure difference in a range in which the input side pressure fluctuation of the flow control system is allowed is caused once or more per second in the build-down capacity BC, and the pressure drop value (pressure difference ΔP), the pressure drop time (Δt), and the build-down capacity BC are set from the pressure drop rate ΔP/Δt, the build-down capacity BC, and the gas temperature K so that the monitoring flow rate can be computed and output at least once or more per second.
[0084] As a result, by setting the pressure drop value (pressure difference) ΔP to approximately 20 to 30 kPa abs, the pressure drop time Δt to 0.5 to 0.8 seconds, and the build-down capacity BC to 1.8 to 18 cc, the monitoring flow rate can be computed with high accuracy at least once or more per second and output, so that highly accurate flow monitoring closely approximating real-time monitoring is realized in spite of the use of the build-down system.
[0085] As compared with the conventional system including a combination with a thermal type flow sensor, the flow control system with monitoring can be significantly simplified in structure, downsized, and reduced in manufacturing cost, and the added value of the flow control system with monitoring is greatly improved.
BRIEF DESCRIPTION OF THE DRAWINGS
[0086] FIG. 1 is a schematic structural diagram of test equipment for measuring flow monitoring characteristics of a flow control system with build-down system flow monitoring according to an embodiment of the present invention.
[0087] FIG. 2 is an explanatory view of a pressure drop state of build-down system flow monitoring.
[0088] FIG. 3 is a diagram showing an example of a pressure recovery characteristic curve at the time of build-down system flow rate measurement.
[0089] FIG. 4 is a partial enlarged view of FIG. 4 .
[0090] FIG. 5 is a diagram showing a pressure recovery characteristic curve in Test 1.
[0091] FIG. 6 is a diagram showing a pattern of the pressure drop characteristic (controlled flow rate=100 sccm).
[0092] FIG. 7 is a diagram showing a pattern of the pressure drop characteristic (controlled flow rate=50 sccm).
[0093] FIG. 8 is a diagram showing a pattern of the pressure drop characteristic (controlled flow rate=10 sccm).
[0094] FIG. 9 is a diagrammatic drawing showing a relationship between an elapsed time from closing of the upstream side valve AV and flow rate stability (build-down capacity BC=1.78 cc).
[0095] FIG. 10 is a diagrammatic drawing showing a relationship between an elapsed time from closing of the upstream side valve AV and flow rate stability (build-down capacity BC=9.91 cc).
[0096] FIG. 11 is a diagram showing flow rate accuracy at 10-times repeated measurement.
[0097] FIG. 12 is a schematic front view of a flow control system with build-down system flow monitoring according to a first illustrative example of the present invention.
[0098] FIG. 13 is a schematic front view of a flow control system with build-down system flow monitoring according to a second illustrative example of the present invention.
[0099] FIG. 14 is a cross sectional view showing a state where a bar piece Cu is inserted into a flow passage.
[0100] FIG. 15 is a pressure drop characteristic curve (N 2 : 10 sccm) when no bar piece Cu is inserted.
[0101] FIG. 16 is a pressure drop characteristic curve (N 2 : 10 sccm) when a bar piece Cu with a diameter of 2 mm is inserted.
[0102] FIG. 17 is a pressure drop characteristic curve (N 2 : 10 sccm) when a bar piece Cu with a diameter of 3 mm is inserted.
[0103] FIG. 18 is a pressure drop characteristic curve (N 2 : 50 sccm) when no bar piece Cu is inserted.
[0104] FIG. 19 is a pressure drop characteristic curve (N 2 : 50 sccm) when a bar piece Cu with a diameter of 2 mm is inserted.
[0105] FIG. 20 is a pressure drop characteristic curve (N 2 : 50 sccm) when a bar piece Cu with a diameter of 3 mm is inserted.
[0106] FIG. 21 is a pressure drop characteristic curve (N 2 : 100 sccm) when no bar piece Cu is inserted.
[0107] FIG. 22 is a pressure drop characteristic curve (N 2 : 100 sccm) when a bar piece Cu with a diameter of 2 mm is inserted.
[0108] FIG. 23 is a pressure drop characteristic curve (N 2 : 100 sccm) when a bar piece Cu with a diameter of 3 mm is inserted.
[0109] FIG. 24 is a diagrammatic drawing showing a changed state of the flow rate stabilization time when a bar piece Cu is used (build-down capacity BC=1.78 cc).
[0110] FIG. 25 is a diagrammatic drawing showing a changed state of the flow rate stabilization time when a bar piece Cu is used (build-down capacity BC=9.91 cc).
[0111] FIG. 26 is a structural diagram of a flow control system with build-down system flow monitoring according to a third illustrative example of the present invention.
[0112] FIG. 27 is a diagrammatic drawing showing a relationship between the gas flow rate (sccm) and the pressure drop gradient (kPa/sec) in a case where the measurement enabling time is set to 1 second or less in each of the chambers A to E used in the third illustrative example.
[0113] FIG. 28 is a diagram showing a pattern of the pressure drop characteristic when the pressure drop gradient is 20 kPa/sec in each of the chambers A to E used in the third example.
[0114] FIG. 29 is a diagrammatic drawing showing a relationship between an elapsed time from closing of the upstream side valve AV and the flow rate stability of each of the chambers A to E used in the third illustrative example.
[0115] FIG. 30 is a diagrammatic drawing showing a relationship between flow rate accuracy (% S.P.) and the flow rate (sccm) in repeated measurements in the chamber A and the chamber B used in the third illustrative example.
[0116] FIG. 31 is a diagrammatic drawing showing a relationship between flow rate accuracy (% S.P.) and the pressure drop gradient (kPa/sec) in repeated measurements in the chamber A and the chamber B used in the third example.
[0117] FIG. 32 is a longitudinal sectional view showing a second instance of the chamber used in the third illustrative example.
[0118] FIG. 33 is a basic structural diagram of a conventional pressure type flow control system.
[0119] FIG. 34 is a basic structural diagram of a conventional flow control system with flow monitoring.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0120] Hereinafter, an illustrative embodiment of the present invention is described based on each example with reference to the drawings.
First Example
[0121] FIG. 12 is a schematic front view of a flow control system with build-down system flow monitoring according to a first example of the present invention, and in FIG. 12 , the reference symbol P 1 denotes a pressure sensor, OL denotes an orifice, CV denotes a control valve, V 1 and V 2 denote inlet side valve blocks, V 3 , V 4 , and V 5 denote FCS main body blocks, V 6 denotes an outlet side block, V 7 denotes a gas outlet joint, CP denotes an arithmetic and control unit, AV denotes an upstream side valve, L 1 denotes a gas inlet side flow passage of the upstream side valve, L 2 denotes a gas outlet side flow passage of the upstream side valve, L 3 denotes an inlet side passage of the control valve CV, L 4 denotes an outlet side passage of the control valve CV, P 0 denotes a pressure sensor on the upstream side of the control valve CV, T denotes a temperature detection sensor, and F denotes a filter.
[0122] The pressure type flow control system itself is known, therefore, detailed description thereof is omitted here. As a matter of course, the filter F can be omitted.
[0123] The arithmetic and control unit CP is formed by integrally combining a flow rate arithmetic and control unit CPa that controls opening/closing of the control valve CV of the pressure type flow control system FCS and computes a flow rate distributed through the orifice and a monitoring flow rate arithmetic and control unit CPb that computes the build-down system monitoring flow rate and controls opening/closing of the upstream side valve AV.
[0124] That is, the build-down system monitoring flow rate arithmetic and control unit CPb forming the essential portion of the present invention controls opening/closing of the upstream side valve AV, and computes and outputs a build-down system flow rate Q from the pressure sensor P 0 , the temperature detection sensor T, and the builddown capacity BC consisting of the inlet side passage L 2 and the inlet side passage L 3 .
[0125] As described above, in the arithmetic and control unit CP, the arithmetic and control unit CPa that performs flow rate computation and flow control of the pressure type flow control system FCS portion, and the arithmetic and control unit CPb that performs computation of the flow rate measured value Q of the build-down system flow monitoring unit, measurement of the pressure drop rate ΔP/Δt, and opening/closing control of the upstream side valve AV, etc., are integrally provided, and by inputs of a command signal and/or a setting signal into the arithmetic and control unit CP, the flow control system with build-down system flow monitoring outputs a gas fluid the flow of which is controlled to a predetermined flow rate value, and this flow rate value is monitored and displayed at least once per second.
[0126] The structures and control methods of the pressure type flow control system FCS and the build-down system flow rate measuring unit are known, therefore, detailed descriptions thereof are omitted here.
[0127] When a difference equal to or more than a set value occurs between the monitoring flow rate output (flow rate output from the monitoring flow rate arithmetic and control unit CPb) and the flow rate output of the pressure type flow control system FCS (flow rate output from the pressure type flow rate arithmetic and control unit CPa), a flow rate abnormality warning can be issued, or if necessary, so-called flow rate self-diagnosis of the pressure type flow control system FCS can be performed to identify the cause and the location of the flow rate abnormality.
[0128] Further, when a flow rate difference equal to or more than the set value occurs, zero-point adjustment, etc., of the pressure type flow control system FCS can be automatically performed as well.
[0129] In the present first example, a direct-operated type solenoid driving valve is used as the upstream side valve AV, and the build-down capacity BC is selected in the range of 1.78 to 9.91 cc. Further, the pressure drop range ΔP is selected to be 20 kPa abs (350 to 320 kPa abs), and the monitoring flow rate is output at least once or more per second.
[0130] As the temperature detection sensor T, an outer surface-attaching type resistance temperature sensor is used, and it is also possible to use a thermostat type thermometer to be inserted into the body block V 3 .
[0131] The flow passages L 2 ′, L 2 , and L 3 forming the build-down capacity BC are formed to have inner diameters of 1.8 mm to 4.4 mm, and by appropriately selecting their inner diameters and flow passage lengths, a desired build-down capacity BC is obtained.
[0132] The build-down capacity BC may be adjusted by using a chamber with a pressure sensor as in the case of the third example described later.
Second Example
[0133] FIG. 13 shows a second example of the present invention in which the flow passages L 2 ′, L 2 , and L 3 forming the build-down capacity BC are formed to have inner diameters of 2.5 mm, 3.3 mm, and 4.4 mm, respectively, and a short bar piece, for example, a bar piece made of stainless steel is inserted into each flow passage L 2 ′, L 2 , L 3 to simulatively narrow a part of the pipe inner diameter and adjust the total internal capacity BC to 1.78 to 9.91, and accordingly, the pressure drop characteristic is improved.
[0134] In FIG. 13 , components except for the respective flow passages L 2 ′, L 2 , and L 3 are the same as in FIG. 12 according to the first example described above.
[0135] In this second example, a short bar piece (length: approximately 1 to 3 mm) Cu shown in FIG. 14 is inserted to an appropriate position inside each of the respective flow passages L 2 ′, L 2 , and L 3 , specifically, a bar piece with an outer diameter of 3 mm (or a bar piece with an outer diameter of 2 mm) is provided at a part of the flow passage L 3 with the inner diameter of 4.4 mm, or a bar piece Cu with an outer diameter of 2 mm is provided at the portion of the flow passage L 2 .
[0136] FIG. 15 to FIG. 17 show changed states of the pressure drop characteristic in the case where the bar piece Cu is inserted (the flow passage inner diameter is changed) when the gas is N 2 , the flow rate is 10 sccm, the build-down capacity BC=1.78 cc, and the pressure drop ΔP is 20 kPa abs, and FIG. 15 shows the case where no bar piece Cu is provided (that is, under the same condition as in FIG. 8 ), FIG. 16 shows the case where a bar piece Cu with a diameter of 2 mm is inserted to one position, and FIG. 17 shows the case where a bar piece with a diameter of 3 mm is inserted to one position.
[0137] FIG. 18 to FIG. 20 show the pressure drop characteristic under the same state as in FIG. 15 to FIG. 17 when the flow rate of the N 2 gas is set to 50 sccm, and further, FIG. 21 to FIG. 23 show the pressure drop characteristic when the N 2 gas flow rate is set to 100 sccm.
[0138] As is clear from comparison among FIG. 15 , FIG. 16 and FIG. 17 , among FIG. 18 , FIG. 19 and FIG. 20 , and among FIG. 21 , FIG. 22 and FIG. 23 , in the second example, linearity of the pressure drop characteristic is significantly improved by using the bar piece Cu, and as a result, the flow rate stabilization time from closing of the upstream side valve AV shown in FIG. 9 and FIG. 10 is shortened, and the flow rate accuracy shown in FIG. 11 is also significantly improved.
[0139] FIG. 24 and FIG. 25 show changes in flow rate errors relating to the flow rate stabilization time shown in FIG. 9 and FIG. 10 when the bar piece Cu is used, and in both of the cases where the build-down capacity BC is 1.79 cc and 9.91 cc, errors can be significantly reduced, that is, the flow rate stabilization time can be shortened and the flow rate detection time can be increased.
Third Example
[0140] FIG. 26 is a basic constitution diagram of a flow control system with build-down system flow monitoring according to a third example of the present invention. Major differences between this third example and the flow control systems with build-down system flow monitoring according to the first and second examples described above are that a chamber CH with a pressure sensor is used for forming the build-down capacity BC, the inner diameters of the respective gas passages L 2 , L 3 , and L 5 are set to small diameters of 1.8 mm, a pressure sensor P 2 is separately provided on the downstream side of the orifice, and the chamber CH is provided with a pressure sensor P 3 , etc., and the constitutions of the other members are substantially the same as in the first and second examples.
[0141] That is, in this third example, a small-sized pressure chamber CH is provided between the upstream side valve AV and the control valve CV of the pressure type flow control system FCS, and by adjusting the internal volume of the pressure chamber CH, the build-down capacity BC is adjusted.
[0142] This pressure chamber CH is formed into a double cylinder consisting of an outer cylinder CHa and an inner cylinder CHb, and a gap G between the inner and outer cylinders CHa and CHb is selected to be 1.8 mm in the present embodiment.
[0143] The internal volume of the pressure chamber CH is selected to be approximately 1.3 to 12 cc, and the pressure sensor P 3 is attached to this pressure chamber CH.
[0144] In FIG. 26 , the reference symbol V 6 denotes a chamber outlet side block, and P 1 , P 2 , and P 3 denote pressure sensors.
[0145] In this third example, the volume of the pressure chamber CH can freely be selected, and the gas flow passages L 5 and L 3 , etc., can be formed to have the same small diameter (for example, a diameter of 1.8 mm), so that the build-down capacity BC can be accurately and easily set to a predetermined capacity value.
[0146] In detail, as a chamber CH for testing, five kinds of chambers having the gaps G set to 1.8 mm and 3.6 mm and sized as shown in Table 3 were prepared, and the system shown in FIG. 26 using these chambers was applied to the test equipment shown in FIG. 1 and the relationship, etc., among the gas flow rate (sccm), the pressure drop gradient (kPa/sec), and the pressure drop time (sec), etc., was investigated.
[0147] In the investigation using the test equipment shown in FIG. 1 , the temperature detection sensor T was attached and fixed to the outer surface of the chamber CH. The volume of the gas flow passages L 3 and L 5 other than the chamber CH is 0.226 cc.
[0000]
TABLE 3
Chamber A
Chamber B
Chamber C
Gap
1.8
mm
Gap
1.8
mm
Gap
2.4
mm
Height
14.0
mm
Height
92.0
mm
Height
92.0
mm
Diameter
18.0
mm
Diameter
18.0
mm
Diameter
18.0
mm
Chamber
1.58
cc
Chamber
8.72
cc
Chamber
11.15
cc
Other
0.226
cc
Other
0.226
cc
Other
0.226
cc
flow
flow
flow
passage
passage
passage
volume
volume
volume
Actual
2.31
cc
Actual
9.70
cc
Actual
11.55
cc
total
total
total
volume
volume
volume
Chamber D
Chamber E
Gap
3.0
mm
Gap
3.6
mm
Height
92.0
mm
Height
92.0
mm
Diameter
18.0
mm
Diameter
18.0
mm
Chamber
13.35
cc
Chamber
15.31
cc
Other
0.226
cc
Other
0.226
cc
flow
flow
passage
passage
volume
volume
Actual
13.91
cc
Actual
15.45
cc
total
total
volume
volume
[0148] FIG. 27 shows the results of measurement of the relationship between the gas flow rate (sccm) and the pressure drop gradient (kPa/sec) in each case of using the chambers A to E when the pressure drop time (b) in FIG. 2 was set to be within 1 second, and although the volume of the flow passages L 5 and L 3 of the pressure type flow control system FCS, etc., shown in FIG. 26 was selected to be 0.226 cc as described above, each of the actual build-down capacities in FIG. 26 in the state where the system was assembled to the test equipment were 2.31 cc to 15.45 cc.
[0149] As is also clear from FIG. 27 , when the pressure drop range ΔP is set to 20 kPa/sec, in the case of the chamber A, the flow rate of 25.2 sccm can be measured, in the case of the chamber B, 106.6 sccm can be measured, and in the case of the chamber E, 169.0 sccm can be measured.
[0150] FIG. 28 is a diagrammatic drawing similar to FIG. 6 to FIG. 8 , showing linearity of the pressure drop when the gas flow rate was adjusted so that the pressure drop gradient reached 20 kPa/sec in the test equipment shown in FIG. 1 . The measured data were acquired by the data logger NR shown in FIG. 1 .
[0151] As is clear from FIG. 28 , the smaller the build-down capacity BC of the chamber CH (that is, the chamber A, B, etc.) is, the more excellent the linearity of the pressure drop characteristic.
[0152] FIG. 29 shows the results of obtaining flow rate measurement errors caused by deviations from the linearity of the pressure drop characteristic curve by measuring 5 points every 0.25 seconds within the flow rate measurement enabling time (b) within 1 second as in the case of FIG. 9 and FIG. 10 , and proves that the smaller the build-up capacity BC of the chamber A, B, the earlier the flow rate error decreases from the start of the pressure drop (that is, the more excellent in linearity of the pressure drop characteristic).
[0153] FIG. 30 shows the results of investigation on the reproducibility of the flow rate measurement accuracy by using the chamber A and the chamber B, and the investigation was performed for the same purpose as in the case of FIG. 11 .
[0154] In this flow rate measurement accuracy reproducibility test, to stabilize the pressure drop gradient, the measurement was performed after a predetermined waiting time from closing of the upstream side valve AV, and the measurement was performed for a long period of time to obtain the reproducibility, however, the flow rate output time was set to be within 1 second in each case.
[0155] As is also clear from FIG. 30 , in view of reproducibility, the flow rate of 3 to 50 sccm is the applicable range in the case of the chamber A, and 30 to 300 sccm is the applicable range in the case of the chamber B.
[0156] Table 4 shows basic data used for preparing the diagrammatic drawing showing reproducibility of the flow rate measurement accuracy shown in FIG. 30 , and the chamber A (build-down capacity BC=2.31 cc) and the chamber B (build-down capacity BC=9.47 cc) are set as test objects.
[0000]
TABLE 4
Chamber A (BC = 2.31 cc)
Flow rate
sccm
1
2
3
5
10
20
30
50
Temperature
° C.
22.7
23.0
23.1
22.8
22.6
22.6
22.6
22.7
Gradient
kPa/sec
0.8
1.6
2.4
4.0
7.9
16.1
23.4
39.2
Measurement
kPa abs.
370
370
370
370
370
370
370
370
start pressure
Measurement
kPa abs.
368
365
365
363
355
350
350
350
end pressure
Measurement
kPa
2
5
5
7
15
20
20
20
pressure
range: P
Measurement
sec
2.73
3.42
2.28
1.91
2.05
1.37
0.91
0.55
time: t
Chamber B (BC = 9.47 cc)
Flow rate
sccm
5
10
20
30
50
100
200
300
400
Temperature
° C.
22.7
23.0
22.4
22.4
22.5
22.5
22.5
22.6
22.59
Gradient
kPa/sec
0.9
1.9
3.8
5.7
9.4
18.9
37.7
57.3
77.204
Measurement
kPa abs.
370
370
370
370
370
370
370
370
370
start pressure
Measurement
kPa abs.
368
367
365
360
350
350
350
350
350
end pressure
Measurement
kPa
2
3
5
10
20
20
20
20
20
pressure
range: P
Measurement
sec
2.24
1.68
1.40
1.87
2.24
1.12
0.56
0.37
0.28
time: t
* Measured by changing the time and pressure range so as not to exceed 10,000 data.
[0157] FIG. 31 shows the results of investigation on the relationship between the pressure drop gradient (kPa/sec) and the error (% S.P.) of the chamber A and the chamber B from the data shown in Table 4 above, and proves that the flow rate measurement error (% S.P.) is within the range of ±1% as long as the pressure drop gradient is in the range of 2 to 60 kPa/sec.
[0158] FIG. 32 shows a second instance of the chamber CH forming the build-down capacity BC used in a third example of the present invention. The chamber CH according to this second instance is formed of an outer cylinder CHa and an inner cylinder CHb, and further, at the center of the inner cylinder CHb, a longitudinal slot 1 circular in section is provided downward from the upper end, and the lower side of the longitudinal slot is connected to the gas outlet passage L 2 of the upstream side valve AV through a gas passage 1 a.
[0159] A longitudinal and columnar pin 2 having a flange portion 2 a on the upper end is inserted and fixed into the longitudinal slot 1 at the center of the inner cylinder CHb from the upper side, and the longitudinal slot is communicatively connected to the inside of the gap G forming the gas passage through a plurality of small holes 2 b provided in the flange portion 2 a , and the end portion of the gap G is communicatively connected to the gas outlet passage L 5 of the chamber outlet side block.
[0160] That is, in the pressure chamber CH of this second instance, the gas flowed from the lower side toward the upper side of the inner cylinder CHb flows into the gap G between the outer cylinder CHa and the inner cylinder CHb from the upper end of the inner cylinder CHb.
[0161] The gap G between the outer cylinder CHa and the inner cylinder CHb of this chamber CH is selected to be 1 to 2 mm, the gap G 1 between the longitudinal slot 1 and the columnar pin or screw body 2 is selected to be 0.4 to 0.8 mm, and the height of the inner cylinder CHb is selected to be 30 to 35 mm, and these are used mainly for the pressure chamber CH with an internal volume V=2 to 5 cc.
[0162] The form of the chamber CH used in the third example of the present invention can be changed as appropriate, and can be structured so that, for example, the outer peripheral surface of the inner cylinder CHb of the chamber CH shown in FIG. 32 is threaded, and by changing the height and pitch of the thread, the volume of the portion of the gap G is adjusted, or the longitudinal slot 1 of the inner cylinder CHb of the chamber CH shown in FIG. 32 is formed into a screw hole, and by screwing a columnar pin 2 formed of a screw rod into the screw hole, the volume of the portion of the gap G 1 is adjusted.
[0163] Further, instead of the longitudinal slot 1 of the inner cylinder CHb and the columnar pin 2 shown in FIG. 32 , a plurality of longitudinal slits with small diameters communicatively connected to the gas passage 1 a may be formed at the center portion of the inner cylinder CHb, or the portion of the longitudinal slot 1 may be made of a filter medium.
[0164] It is also possible that the whole or the portion to project upward of the inner cylinder CHb shown in FIG. 32 is made of a filter medium to flow the gas flowed-in from the gas outlet passage L 2 of the upstream side valve AV into the gap G through the filter medium, or the whole or the portion to project upward of the inner cylinder CHb is made of a porous ceramic material to distribute the gas from the gas outlet passage L 2 of the upstream side valve AV into the gap G through the porous ceramic material.
INDUSTRIAL APPLICABILITY
[0165] The present invention is widely applicable not only to gas supply equipment for semiconductor manufacturing equipment but also to gas supply equipment for chemical goods production equipment as long as it is a pressure type flow control system using an orifice or a critical nozzle.
DESCRIPTION OF REFERENCE SYMBOLS
[0000]
FCS: pressure type flow control system
AV: upstream side valve
BC: build-down capacity
RG: pressure regulator
N 2 : N 2 supply source
T: temperature detection sensor (resistance temperature detector)
P 1 , P 2 , P 3 : pressure sensor
CV: control valve
OL: orifice
V 1 , V 2 : inlet side valve block
V 3 , V 4 : FCS main body block
V 5 , V 6 , V 8 : outlet side block
V 7 : gas outlet joint
V 9 : chamber outlet side block
CP: arithmetic and control unit
CPa: flow rate arithmetic and control unit
CPb: monitoring flow rate arithmetic and control unit
E 1 : power supply for pressure type flow control system
E 2 : power supply for arithmetic and control unit
E 3 : power supply for solenoid valve
ECV: electric drive unit
NR: data logger
S: signal generator
PC: arithmetic and display unit
L 1 : gas inlet side passage of upstream side valve AV
L 2 ′, L 2 : gas outlet side passage of upstream side valve AV
L 3 : inlet side passage of control valve CV
L 4 : outlet side passage of control valve CV
L 5 : gas passage of chamber outlet side block
Cu: bar piece
Q: build-down flow rate
CH: chamber
CHa: outer cylinder
CHb: inner cylinder
1 : longitudinal slot of inner cylinder
1 a : gas passage
2 : columnar pin or screw body
2 a : flange portion
2 b : small hole | To provide a flow control system with build-down system flow monitoring that realizes flow monitoring close to real-time monitoring by combining build-down system flow rate measurement with the upstream side of the flow control system without using a thermal type flow sensor by effectively utilizing high pressure fluctuation resistance characteristics of the flow control system, and can be significantly downsized and reduced in cost. | 8 |
This application is a continuation of application(s) application Ser. No. 09/403,001 filed on 15 Oct. 1999 now U.S. Pat. No. 6,577,489, which is a 371 of International Application PCT/DE98/01063 filed on Apr. 16, 1998 and which designated the U.S.
FIELD OF THE INVENTION
The present invention relates to a device for electrostatically charging a multilayer ribbon or paper web train.
DESCRIPTION OF THE PRIOR ART
It is generally known and described in EP 0 230 305 A2 that in rotogravure printing the incoming material webs, or respectively paper web trains or ribbons, are made to adhere to each other electrostatically, which adherence is called ribbon adherence. The stability of the material webs or paper web trains is increased by means of this electrostatic interlocking, so that the danger of a formation of corners of the printed products in the folding apparatus is reduced. Electrodes, which are arranged at both sides of the material webs and at a distance from the material webs are provided for applying the electrostatic charge.
In connection with this electrostatic charge, its low effectiveness on the paper web train or ribbon is disadvantageous, so that it became necessary to arrange additional devices, for example electrostatically charged guide devices, as disclosed in EP 0 230 305 A2 in order to reduce the effects of the so-called whip action, which leads to the formation of corners.
DE 31 17 419 C2 describes a method for the electrostatic charging of a multilayer paper web train ribbon. Here, the ribbon is charged by means of contactless acting electrodes after the webs have been brought together to form a ribbon downstream of a pair of compression rollers.
DE 27 54 179 C2 discloses a method for the electrostatic charging of a multilayer ribbon, wherein the edge areas of each layer are individually charged by means of rollers.
EP 0 378 350 A2 discloses a transport device for paper sheets in a plotter. This transport device has transport rollers for electrostatically charging a paper sheet and a plastic sheet.
U.S. Pat. No. 4,462,528 A describes a device for holding a web. This device has brushes, by means of which the web is held electrostatically.
SUMMARY OF THE INVENTION
The object of the present invention is based on providing a device for the electrostatic charging of a multilayer ribbon.
In accordance with the present invention, the object of the present invention is attained by the use of two rollers that are placed in opposition to each other and which are provided with opposing electrical charges. These rollers, which press the rubber or paper web train together, also act as charging electrodes. The multilayer paper ribbon is adhered together by the charge imparted to it from the roller pair. Alternatingly, the paper web train or ribbon can be electrostatically charged by oppositely polarized charge electrodes in the form of electrically conductive brushes which touch the printing paper web train or ribbon.
The advantages which can be achieved by means of the present invention lie, in particular, in that charging of the paper web train or ribbon takes place in a manner which is so lasting, that further devices for preventing, or reducing the formation of corners can be omitted. For example, an already provided pair of drawing rollers, which is required for the operation of the folding apparatus and has been modified in its design for the purpose of transmitting a voltage, is used as the device for charging the ribbon.
The strength of the voltage required for charging the ribbon is reduced in comparison with the voltage required by the prior art.
BRIEF DESCRIPTION OF THE DRAWINGS
Preferred embodiments of the present invention are represented in the drawings and will be described in greater detail in what follows.
Shown are in:
FIG. 1, a schematic representation of a longitudinal folding device, as well as the ribbon entry into a cylinder folding group;
FIG. 2, a longitudinal section through one roller of a pair of rollers of the present invention in accordance with FIG. 1;
FIG. 3, a representation analogous to FIG. 2, but with a second preferred embodiment; and in
FIG. 4, a representation analogous to FIG. 2, but with a third preferred embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A longitudinal folding device 3 with a pair of funnel folding rollers 4 , as well as first and second pairs of rollers, for example drawing roller pairs 6 , 7 , are arranged ahead of the entry for a multilayer ribbon 1 formed of, for example, a plurality of paper webs, into a cylinder folding group 2 , for example, of a folding apparatus of a rotary printing press. This structure is depicted most clearly in FIG. 1 .
The cylinder folding group 2 has a cutter cylinder 8 and a collection cylinder 9 , which operates against the cutter cylinder 8 and, in turn, works together with a folding jaw cylinder 11 . The printed products, which have been transversely folded in the cylinder folding group 2 , are supplied to a further processing station by means of a conveying device, for example a belt conveyor device which is not specifically shown in the drawings.
The second pair of drawing rollers 7 , arranged directly in front of the entry into the cylinder folding group 2 , consists of a first roller 13 , seated fixed in a lateral frame, and a second roller 16 , which is seated on a pivot arm or bearing element 14 as seen in FIG. 2 . This second roller 16 can be placed against the first roller 13 seated fixed in the lateral frame, with both rollers 13 and 16 of the second pair of drawing rollers 7 constituting the charging electrodes. The running paper web train or ribbon 1 is conducted between the two rollers 13 , 16 .
In accordance with a first preferred embodiment as seen in FIG. 2, both rollers 13 , 16 consist of a cylinder- or hollow cylinder-shaped roller body, a metal body 17 , which has a shell 18 of a resilient covering of reduced conductivity, for example rubber of a hardness of approximately 85° Shore. The metal body 17 is connected, fixed against relative rotation, at both ends by means of hubs 19 —only one end being represented in FIG. 2 —with the shaft journal 21 .
The hubs 19 are fastened, electrically insulated, by means of ball bearings 22 in the bearing element 14 . An insulation which consists, for example, of respective bushings 23 of insulating material, for example a resin-bonded fabric, arranged between the pivot arm, or respectively the bearing element 14 , and the ball bearing 22 , which has a radial bore 24 for receiving a cable feed 26 . The cable feed 26 receives a feed line, for example a cable 27 which, for the purpose of transferring energy via an intermediate ring 25 , is pressed by means of a spring-loaded contact element 28 against the ball bearing 22 .
At its end remote from the roller 16 the shaft journal 21 is connected, fixed against relative rotation, with an annular flange 29 , which, in turn, is in connection, fixed against relative rotation, via a piece 31 of insulating material with a driveshaft 32 .
Each one of the rollers 13 , 16 of the second drawings roller pair 13 can be separately driven. Moreover, the first roller 13 of the second pair 7 of drawing rollers is connected with a negative pole of a d.c. source, not represented, of approximately 5 kilovolts, for example a high tension d.c. generator, and the second roller 16 of the second pair 7 of drawing rollers is connected with a positive pole of the d.c. source. The polarity can also be reversed.
The paper web train or ribbon 1 preferably consists of paper webs, which are weakly mineralized and highly resistive.
It is also possible to drive only one roller 13 or 16 of the pair of rollers 13 , 16 , or neither of the rollers of the pair of rollers 13 , 16 .
In accordance with a second preferred embodiment, as shown in FIG. 3, both charge electrodes, which are designed as rollers 33 , 34 , also consist of a cylinder- or hollow cylinder-shaped metal body 36 , which has a multi-layer shell 37 comprised of a lower, electrically insulating layer 38 , a center layer 39 which conducts electricity well, and an outer layer 40 , which is of only limited electrical conductivity.
At an end of each of the respective rollers 33 , 34 a metallic contact ring 42 is arranged on a roller end face. An interior diameter of contact ring 42 is in connection with the shaft journal 43 , and a peripheral surface of contact ring 42 is in an electrically conducting connection with the electrically conducting center layer 39 of the roller shell 37 . This can be achieved, for example, in that the contact ring 42 has a shell-like contact surface 44 on its periphery, which extends concentrically in respect to the metal body 36 and which, in turn, supports contact tips 46 , which are arranged on the end face of contact ring 42 in a ring shape, are spaced apart from each other and are connected with the material of the center layer 39 of shell 37 which center layer 39 conducts electricity well.
The shaft journals 43 —only one of which is represented—are seated in the bearing element 14 in bearings 47 , which are also surrounded by an insulating material 48 .
A wiper element 49 , which is fixed on the bearing element 14 and which is insulated against it, is connected with the contact surface 44 of the contact ring 42 , and is pressed by means of a spring force against the contact surface 44 . As in the first preferred embodiment, the wiper element 49 is connected with a cable feed 26 and a cable 27 .
In accordance with a third preferred embodiment, as seen in FIG. 4, the rollers 51 , 52 which act as charge electrodes, respectively each consist of a stationary shaft journal 53 , fixed on the frame 14 in an insulating material 48 and having a roller body or metal body 36 . The metal body 36 is provided with an electrically high conductivity layer 39 , for example a steel shell, above which an outer layer 40 of limited electrical conductivity is arranged. One bearing 47 is arranged on both sides or ends of each of the rollers 51 , 52 between the shaft journal 53 and the steel shell 39 .
The supply of electrical energy to the rollers 51 , 52 takes place via a cable 27 , which is in electrically conducting contact with the shaft journal 53 , for example with an exterior surface 54 of the shaft journal 53 .
It would, of course, also be possible to arrange the shell 39 , 40 fixedly on the metal body 36 and to seat the journals 53 , electrically insulated and rotatably in the bearing element 14 fixed in place in the lateral frame. In this case the cable 27 would have to be connected by means of a collector ring with the exterior 54 of the shaft journal 53 .
In accordance with a fourth preferred embodiment, which is not specifically represented, the transfer of electrical energy to the ribbon 1 can also take place by means of conducting brushes, for example carbon brushes, arranged on both sides of the material webs of the ribbon 1 .
It is furthermore possible to design the first and second rollers 13 , 16 ; 33 , 34 ; 51 , 52 of the second drawing roller pair 7 also in the form of so-called sandwich rollers.
Such sandwich rollers consist, for example, of a rotatably seated shaft, which receives a number of disks, which are arranged, fixed against relative rotation, on the shaft in the radial direction. Here, a disk made of metal, for example steel, alternates with an adjoining disk, which consists of a metal body having an electrically well conducting layer 39 , and above it an outer layer 40 of limited electrical conductivity, such as shown in FIGS. 3 and 4. Electrical energy is introduced via the shaft journal.
Such a sandwich roller can be placed against a ribbon 1 as an individual roller, or also in opposing pairs, for example as a pair of drawing rollers.
When used in pairs, both sandwich rollers should be arranged in such a way that a metal disk of the first roller is placed opposite a layered disk of the second roller, and vice versa. Each roller of the pair of rollers has a different polarity.
While preferred embodiments of a method and a device for electrostatically charging a multilayer train or paper web ribbon in accordance with the present invention have been set forth fully and completely hereinabove, it will be apparent to one of skill in the art that a number of changes in, for example, the source of drive power for the rollers, the specific type of printing press and folding group used 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. | A multiple layer web is provided with an electrostatic charge for the purpose of adhering the multiple webs to each other. A pair of oppositely charged rollers contact the surface of the multiple layer printing aper web and impart the charge to the web. The pair of oppositely charged rollers are positioned directly before a cylinder folding group of a web-fed rotary printing press. | 1 |
BACKGROUND OF THE INVENTION
This invention is directed to a process for the removal of chlorinated organic compounds from aqueous waste streams in dichlorobutene manufacturing plants. Chloroprene (2-chlorobutadiene-1,3), the principal monomer from which neoprene rubber is made, is usually produced commercially by dehydrochlorination of 3,4-dichlorobutene-1 (hereafter, sometimes referred to as 3,4-DCB). A mixture of dichlorobutenes, containing both 3,4-DCB and 1,4-dichlorobutene-2, (hereafter, sometimes referred to as 1,4-DCB), is obtained by the vapor-phase chlorination of 1,3-butadiene. The relative proportions of the 1,4-DCB and 3,4-DCB isomers can be changed according to various isomerization processes including those described in U.S. Pat. Nos. 3,515,760 to Wild and 3,819,730 to Nakata et al and British Pat. Nos. 1,058,768 to Imperial Chemical Industries, Ltd. and 800,787 to The Distillers Company, Ltd. The process of U.S. Pat. No. 3,819,730, as shown in Example 6 of this reference, can be operated continuously by refluxing the dichlorobutene mixture with the catalyst system at a reduced pressure. In the plant, reduced pressure is often obtained by means of steam jets. Unavoidably, some 1,4-DCB and 3,4-DCB vapors are entrained by steam and, when steam is later condensed, remain dispersed in the resulting waste water. Frequently, this waste water is combined with brine from the 3,4-DCB dehydrochlorination step and discharged into natural bodies of water, such as lakes, rivers, or river estuaries. However, because of the high toxicity of 1,4-DCB to fish, for example, to salmon, the concentration of 1,4-DCB in the aqueous waste stream must be kept at a sufficiently low level to avoid depleting the aquatic life. It has been experimentally determined that the maximum biologically safe concentration of 1,4-DCB in the plant waste effluent water should not exceed about 27 parts per billion (ppb). Assuming a dilution factor of about 1,700 when aqueous DCB wastes are combined with other aqueous plant wastes, the maximum tolerable level of 1,4-DCB in the industrial DCB process waste stream can thus be calculated to be about 46 parts per million (ppm). It is, therefore, important to provide a process capable of reducing the level of 1,4-DCB in aqueous DCB wastes to less than the above figure.
SUMMARY OF THE INVENTION
According to the present invention, there is now provided a process for reducing the level of 1,4-DCB in aqueous wastes from an integrated chloroprene-manufacturing process, said integrated process comprising at least a dichlorobutene isomerization step and a 3,4-dichlorobutene-1 dehydrochlorination step, said process for reducing the level of 1,4-DCB comprising the steps of combining waste water from the dichlorobutene isomerization step with sodium chloride brine from the 3,4-DCB dehydrochlorination step in such proportions that the concentration of sodium chloride in the combined solution is about 1-5 weight percent, and extracting the combined solution, maintained at a pH of less than about 6, with about 0.5-4.0 weight percent of a liquid hydrocarbon.
BRIEF DESCRIPTION OF THE DRAWING
The drawing is a schematic illustration of a continuous process of the present invention, as described in Example 7, below.
DETAILED DESCRIPTION OF THE INVENTION
In the practical operation of the process of the present invention, the aqueous waste, whether from the DCB isomerization step or from the 3,4-DCB dehydrochlorination step, will contain some organic materials as a separate, distinct, organic phase and some as a dispersed or even dissolved material. If a separate organic phase is present, it should first be removed by decantation. The two aqueous phases are then combined. Normally, the concentration of sodium chloride in the brine from the dehydrochlorination step is about 20 weight percent, so that the respective weight ratios of the brine to the waste water will vary from about 1:19 to 1:5.7. Considering that a relatively small volume of waste water from the DCB isomerization step is formed, compared with the volume of brine formed in the 3,4-DCB dehydrochlorination step, it will be necessary to use only a portion of the available plant brine to disposed of all the 1,4-DCB-containing waste water. The concentration of sodium chloride in the combined aqueous phases can be ascertained in any convenient manner, for example by specific gravity (density) determination. The presence of sodium chloride in the combined aqueous phase increases the efficiency of subsequent extraction. Above the maximum recommended level of sodium chloride the extraction efficiency is not adversely affected, but the resulting larger volume of the aqueous phase increases the capital cost of the equipment required or the operation of the present process to a point that it may no longer be commercially attractive.
The preferred sodium chloride concentration in the aqueous waste is about 2-3%, especially 2%. At this concentration, good phase separation is obtained in the subsequent extraction step, while the liquid volume is not unduly large.
Since brine from the 3,4-DCB dehydrochlorination step usually still contains a small amount of sodium hydroxide, it is necessary to acidify either the brine or the combined aqueous phases to retard hydrolysis or 3,4-DCB, which also is present among the chlorinated organic contaminants. The products of 3,4-DCB hydrolysis are to some extent soluble in the aqueous salt solution and cannot be satisfactorily extracted therefrom by hydrocarbons. The preferred acidifying agent is 98% sulfuric acid, although other concentrated mineral acids, especially hydrochloric acid, can be used.
The crucial step of the present process, extraction with a liquid hydrocarbon, is normally carried out with agitation, especially stirring. It has been found that mild agitation and long contact time are more effective than intense agitation and short contact time. Suitable liquid hydrocarbon solvents include virtually all aliphatic, aromatic, alicyclic, and araliphatic hydrocarbons, such, for example, as normal or branched pentanes, hexanes, heptanes, octanes, and nonanes; cyclopentane and cyclohexane; benzene, toluene, xylene; and mixtures of two or more hydrocarbons of the same or different groups. Preferred is No. 2 diesel oil, also known as flux oil, because of its low cost, availability, good extraction efficiency, and low solubility in aqueous salt solutions. At lower solvent concentrations, the extraction efficiency of liquid hydrocarbons decreases. At the lower end of the recommended range, the extraction efficiency is about 60%; at the high end, about 95%. Preferred is a hydrocarbon solvent concentration of about 2 weight percent, which for diesel oil gives an extraction efficiency of about 90%. Amounts of hydrocarbon above the maximum recommended level do not further increase the extraction efficiency to a measurable degree while they add to the cost of the process.
Following mixing of the organic liquid and the aqueous phase for the desired period, the organic phase is removed from the aqueous phase and incinerated. The aqueous phase is discharged, usually without further purification, into the natural body of water. Any additional steps, such as filtration or sedimentation or further pH adjustment, can be added without departing from the scope of the invention. It will be clear that the present process can be run either batchwise or continuously, and an average chemical engineer will be able to select both the correct equipment and the correct conditions such as, for example, the rates of agitation, rates of flow, and extraction or residence times.
This invention is now illustrated by the following examples of certain preferred embodiments thereof, where all proportions, parts and percentages are by weight, unless otherwise indicated.
EXAMPLE 1
Twenty mL of a plant dichlorobutene-waste mixture containing 29.1% of chloroprene, 20.1% of α-chloroprene (1-chlorobutadiene-1,3), 25.3% of 3,4-DCB, 4.0% of 1,4-DCB and 21.1% of other waste materials was added to 2000 g of 2% sodium chloride solution contained in a 4 liter sepatory funnel. The contents of the funnel were shaken vigorously for 30 seconds and the phases were allowed to separate for 4 hours. The aqueous salt phase was then decanted from the organic phase. For analysis, 500 grams of the aqueous phase was extracted with two 20 mL portions of methylene chloride. The extracts were combined and 0.05 mL of bromodecane was added as internal standard. The extract was analyzed by gas chromatography, and the relative weight proportions of the organic components present in the aqueous phase were determined as fractions of the total organic materials.
Two percent of flux oil (diesel No. 2 oil) was then added to the remainder of the aqueous phase. After vigorous shaking for 30 seconds, the phases were allowed to separate for 18 hours. The aqueous phase was then separated from the flux oil and a second methylene chloride extract was analyzed by gas chromatography as described above. The experimental data and results are summarized in Table I.
TABLE I______________________________________ Component chloro- α-chlo- 3,4- 1,4- prene roprene DCB DCB Others______________________________________Relative proportionof component ininitial organicmixture (known) 0.291 0.201 0.253 0.040 0.211Relative proportionof organic compo-nent in aqueous saltphase prior to oilextraction (by gaschromatography) 0.315 0.219 0.316 0.050 0.100ppm of component inaqueous phase afteroil extraction (bygas chromatography) 27 19 53 10 13ppb of component inaqueous phase afterdilution (calculated)for 1700x dilution) 15.8 11.2 31.2 5.9 7.6______________________________________
The amount of 1,4-DCB in the diluted stream was well below the maximum tolerable limit of 27 ppb.
EXAMPLE 2
A 2% aqueous sodium chloride-dichlorobutene waste mixture having the composition given in Table II was extracted with 2% of flux oil as described in Example 1. The amount of 1,4-DCB was reduced from 7.7% to 19 ppm, which corresponded to 11.2 ppb in the final diluted stream.
TABLE II______________________________________ Component chloro- α-chlo- 3,4- 1,4- prene roprene DCB DCB Others______________________________________Relative proportion of component in organic mixture (known) 0.311 0.202 0.203 0.077 0.206Relative proportion of organic compo- nent in aqueous salt phase prior to oil extraction (by gas chromatography) 0.371 0.220 0.231 0.089 0.085ppm of component in aqueous phase after oil extraction (by gas chromatography) 38 23 33 19 16ppb of component in aqueous phase after dilution (calculated for 1700x dilution) 22.3 13.5 19.4 11.2 9.4______________________________________
EXAMPLE 3
A 1% aqueous sodium chloride-dichlorobutene waste mixture containing 10.4% of chloroprene, 38.7% of α-chloroprene, 24.7% of 3,4-DCB, 2.2% of 1,4-DCB and 24.0% of other waste materials was extracted with 2% of flux oil as described in Example 1. The amount of 1,4-DCB in the aqueous phase was reduced to 4.5 ppm after extraction and to 2.6 ppb after dilution.
EXAMPLE 4
A 2% aqueous sodium chloride-dichlorobutene waste mixture having the composition given in Table III was extracted with 2% of n-hexane by the procedure described in Example 1. After extraction, the level of 1,4-DCB in the aqueous phase was reduced to 3 ppm which was further reduced to 1.8 ppb in the final diluted waste stream.
TABLE III______________________________________ Component chloro- α-chlo- 3,4- 1,4- prene roprene DCB DCB Others______________________________________Relative proportionof component inorganic mixture(known) 0.300 0.290 0.230 0.012 0.170Relative proportionof organic compo-nent in aqueous saltphase prior to hexaneextraction (by gaschromatography) 0.260 0.210 0.410 0.030 0.090ppm of component inaqueous phase afterhexane extraction (bygas chromatography) 24 20 38 3 8ppb of component inaqueous phase afterdilution (calculatedfor 1700x dilution) 14.1 11.8 22.3 1.8 4.7______________________________________
EXAMPLE 5
A 3% aqueous sodium chloride-dichlorobutene waste mixture containing 8.1% of chloroprene, 36.0% of α-chloroprene, 31.4% of 3,4-DCB, 1.6% of 1,4-DCB and 22.9% of other chlorinated waste materials was extracted with 2% of n-hexane by the procedure described in Example 1. The level of 1,4-DCB in the aqueous phase was reduced to 1 ppm after extraction and to 0.6 ppb after dilution.
EXAMPLE 6
A 1% aqueous sodium chloride-dichlorobutene waste mixture containing 4.3% of chloroprene, 38.5% of α-chloroprene, 15.8% of 3,4-DCB, 5.4% of 1,4-DCB and 36.0% of other waste materials was extracted with 0.71% of n-hexane by the procedure described in Example 1. The level of 1,4-DCB in the aqueous phase was reduced to 53 ppm after extraction and to 31.2 ppb after final dilution. It can be seen that the desired maximum 27 ppb concentration of 1,4-DCB after dilution was here slightly exceeded. Hexane is not quite as good an extractant as flux oil, which would have reduced the 1,4-DCB concentration to an acceptable level.
EXAMPLE 7
The Drawing represents a schematic flow diagram of the continuous extraction process described herein.
A 3% sodium chloride solution was adjusted to a pH of 5 with 98% H 2 SO 4 and placed in holding tank A. The sodium chloride solution was pumped to mixing tank H and thoroughly contacted with a plant dichlorobutene waste mixture from vessel D. The mixture of aqueous sodium chloride and DCB waste was transferred to decanter B, where a separate lower aqueous medium chloride phase and the upper organic phase formed. Each phase was continuously removed from decanter B. The aqueous sodium chloride phase was pumped to extraction tank F and agitated for 20 minutes at 0.039 kW/1000 L with flux oil supplied from vessel E. The flux oil-aqueous salt mixture was then pumped to decanter C where two separate phases formed. Each phase was continuously removed from decanter C. The lower aqueous salt phase was removed at a rate sufficient to maintain a downward bulk velocity in vessel C of 5.1×10 -5 m/sec. All other flows were adjusted to maintain a continuous flow through the system. Samples of the aqueous phase were taken both at point G, before entering extraction tank F, and at the exit from decanter C and were analyzed for 1,4-DCB content by gas chromatography. Results are given in Table IV for different levels of flux oil added from vessel E.
TABLE IV______________________________________Flux oil addi- ppm 1,4-DCB in aqueous phasetion level, % from sample point G from vessel C______________________________________1.0 96.3 25.02.5 182.0 20.82.0 122.7 17.02.0 88.0 22.02.0 76.0 12.33.8 171.0 12.52.0 133.0 18.5______________________________________ | Chlorinated organic compounds from the aqueous waste streams from a process for manufacturing and isomerizing dichlorobutenes and dehydrochorinating 3,4-dichlorobutene-1 to chloroprene, which is the principal monomer in the manufacture of neoprene rubber, are removed by means of a process, wherein the aqueous waste from the dichlorobutene-isomerization step and brine formed in the dehydrochlorination step are combined to produce an aqueous solution containing about 1-5% sodium chloride and the solution, while maintained at a pH of less than about 6, is extracted with a small amount of a liquid hydrocarbon. The liquid hydrocarbon extract is then incinerated, while the extracted aqueous solution is discharged into a natural body of water. In this way, the level of 1,4-dichlorobutene-2, which is toxic to fish, in the natural body of water can be maintained at a safe level. | 2 |
FIELD OF THE INVENTION
[0001] This invention relates to a protective material, a clothing item and methods of protection and therapy and especially, but not exclusively, to use of special materials for manufacturing clothes which can effectively convert incident radiation in the form of sunlight to light comprising substantially wavelengths having dermatological therapeutic effect and in which wavelengths having deleterious effect are reduced, compared to sunlight.
BACKGROUND OF THE INVENTION
[0002] Various light sources have been proposed for therapy of different dermatological problems. For example, blue light in the range of 400-420 nm has been found helpful for acne treatment. U.S. Pat. No. 6,835,202 describes a device for acne treatment having spectrum 405-440 nm. Red light at 590 nm and 632 nm is used for skin rejuvenation and U.S. Pat. No. 6,676,655 describes a method of skin treatment using devices emitting light in narrowband multichromatic spectrum having the wavelengths corresponding to tissue absorption peaks. U.S. Pat. No. 6,645,230 describes devices for photodynamic therapy using specific light spectrum ranges.
[0003] Although some wavelengths of the electromagnetic spectrum have strong therapeutic effect, the full broad spectrum of sunlight, (which includes ultraviolet, visible and infrared ranges) is known to have deleterious effects on the skin. For example, exposure to direct sunlight is a major reason for skin damage and premature aging, and (particularly the ultraviolet component) can cause skin cancer.
SUMMARY OF THE INVENTION
[0004] According to a first aspect of the present invention a material is provided having the following optical properties:
[0005] absorption of at least a substantial proportion of the electromagnetic radiation in sunlight that causes skin damage; and
[0006] transmission of a substantial amount of the electromagnetic radiation in sunlight that has therapeutic effect for the human skin.
[0007] According to a second aspect of the present invention there is provided a material having the following optical properties:
[0008] absorption of at least a substantial proportion of the electromagnetic radiation in sunlight that causes skin damage; and
[0009] converting at least part of the absorbed radiation to radiation having therapeutic effect on human skin.
[0010] According to a third aspect of the present invention there is provided a material having the following optical properties:
[0011] absorption of at least a substantial proportion of the electromagnetic radiation in sunlight that causes skin damage; transmission of at least a part of the electromagnetic radiation in sunlight that has a therapeutic effect on human skin; and
[0012] converting at least part of the absorbed radiation to radiation that has a therapeutic effect on human skin.
[0013] Preferably, said optical properties of the material are at least partially resultant from the material having been dyed with one or more pigments. Such a material could be in the form of a continuous non-porous sheet of material.
[0014] Preferably, said material is a fabric.
[0015] Preferably, said fabric is made from polymer fiber dyed with one or more pigments.
[0016] One or more pigments may be a fluorescent agent.
[0017] Said radiation that has a therapeutic effect on human skin can include wavelengths absorbed by porphyrin.
[0018] Said radiation that has a therapeutic effect on human skin preferably has wavelengths greater than about 400 nm.
[0019] Said radiation that has a therapeutic effect on human skin can include wavelengths in the range of 400-490 nm.
[0020] Said radiation that has a therapeutic effect on human skin can include wavelengths stimulating collagen growth.
[0021] Said radiation that has a therapeutic effect on human skin can include wavelengths from 590 nm to 670 nm.
[0022] Preferably at least some of said radiation that causes skin damage has a wavelength less than about 400 mm.
[0023] Preferably at least some of the electromagnetic radiation in sunlight that causes skin damage which is absorbed by the material is ultra-violet radiation.
[0024] Preferably, the material prevents transmission therethrough of at least 50% of said radiation that causes damage in human skin.
[0025] Preferably the material prevents transmission therethrough of at least 75% of said radiation that causes damage in human skin.
[0026] Preferably the material prevents transmission therethrough of at least 90% of said radiation that causes damage in human skin.
[0027] Preferably the material prevents transmission therethrough of at least 98% of said radiation that causes damage in human skin.
[0028] Preferably the material allows transmission therethrough of at least 50% of a specific wavelength or selection of wavelengths of radiation in sunlight that have a therapeutic effect on human skin.
[0029] Preferably the material allows transmission of at least 70% of said one or more selected therapeutic wavelengths.
[0030] Preferably the material allows transmission of at least 90% of said one or more selected therapeutic wavelengths.
[0031] It will be appreciated that the above percentages relate to percentages of incident radiation (of the type specified), under normal conditions, with the angle of incidence of the radiation to the material being approximately 90 degrees.
[0032] The material may comprise a first layer and a second layer with different optical properties.
[0033] The first layer may include a fluorescent agent for emitting therapeutic radiation.
[0034] The second layer may have a filtration function to filter out a substantial amount of radiation that causes skin damage.
[0035] According to a fourth aspect of the present invention there is provided a portable item which includes at least a portion made from a material in accordance with at least one of the first to third aspects, such that in use, when being carried or worn by a wearer, in sunlight, the item of clothing can protect at least an area of the wearer's skin from electromagnetic radiation in sunlight that causes skin damage, while allowing radiation that has a therapeutic effect on human skin to be transmitted from said material to said area of the wearer's skin.
[0036] The item can be an item of clothing.
[0037] The material is preferably in accordance with at least one of the first second and third aspects.
[0038] According to a fifth aspect of the present invention there is provided a method for protection of the skin from electromagnetic radiation in sunlight that causes skin damage, comprising:
[0039] delivering some of the electromagnetic radiation from sunlight to the skin, through a material having the following optical properties:
[0040] absorption of at least a substantial proportion of the electromagnetic radiation in sunlight that causes skin damage; and
[0041] transmission of a substantial amount of electromagnetic radiation in sunlight that has therapeutic effect for the human skin;
[0042] and thereby allowing exposure of the skin to electromagnetic radiation from sunlight that has therapeutic effect for human skin.
[0043] According to a sixth aspect of the present invention there is provided a method for protection of the skin from electromagnetic radiation in sunlight that causes skin damage, comprising:
[0044] preventing delivery of at least some of the electromagnetic radiation in sunlight to the skin, by providing a barrier to sunlight, said barrier being at least partially formed by a material having the following optical properties:
[0045] absorption of at least a substantial proportion of the electromagnetic radiation in sunlight that causes skin damage;
[0046] converting at least part of the absorbed radiation to radiation having therapeutic effect on human skin;
[0047] and thereby allowing exposure of the skin to electromagnetic radiation that has therapeutic effect for human skin.
[0048] According to a seventh aspect of the present invention there is provided a method for protection of the skin from electromagnetic radiation in sunlight that causes skin damage, comprising:
[0049] delivering some of the electromagnetic radiation from sunlight to the skin, through a material having the following optical properties:
[0050] absorption of at least a substantial proportion of the electromagnetic radiation in sunlight that causes skin damage; and
[0051] transmission of a substantial amount of electromagnetic radiation in sunlight that has therapeutic effect for the human skin;
[0052] converting at least part of the absorbed radiation to radiation having therapeutic effect on human skin;
[0053] and thereby allowing exposure of the skin to electromagnetic radiation that has a therapeutic effect for human skin.
[0054] The method may be used for skin therapy.
[0055] A topical agent can be applied to the skin surface prior the light delivery.
[0056] The topical agent may be a precursor of photosensitizer.
[0057] According to one embodiment of the invention the fabric includes natural fibres, such as cotton, (and) or a mix of natural fibres with manmade fibres.
[0058] It will be appreciated that the optional or preferable features recited above will be applicable to various aspects of the invention.
[0059] It will be appreciated that the phrase “therapeutic effect for human skin” is to be construed broadly: for example radiation that destroys bacteria, but which has no significant other therapeutic or harmful effect on human skin should be considered to fall within the meaning of this phrase.
BRIEF DESCRIPTION OF THE DRAWINGS
[0060] Embodiments of the invention will hereafter be described, by way of example only, with reference to the accompanying drawings, in which:
[0061] FIG. 1 is a schematic cross sectional view of a piece of material in accordance with an embodiment of the present invention, with incident and transmitted electromagnetic radiation illustrated schematically thereon;
[0062] FIG. 2 is a schematic cross sectional view of a piece of material in accordance with an alternative embodiment of the present invention, with incident, emitted and transmitted electromagnetic radiation illustrated schematically thereon;
[0063] FIG. 3 is a schematic illustration of an item of clothing, in the form of a baseball cap in accordance with an embodiment of the present invention, in use; and
[0064] FIG. 4 is a schematic cross sectional exploded view of a piece of material in accordance with an alternative embodiment of the present invention, with incident, emitted and transmitted electromagnetic radiation illustrated schematically thereon.
DETAILED DESCRIPTION OF EMBODIMENTS
[0065] With reference to FIG. 1 , in one embodiment a material, designated 100 , is shown schematically, with a larger arrow 105 illustrating full spectrum sunlight incident upon the material 100 , and a smaller arrow 110 illustrating a lesser amount of radiation which has been transmitted through the material, the remainder having been effectively filtered by the material.
[0066] Importantly, certain wavelengths which exist in sunlight are known to be harmful to the skin, and the optical properties of the material 100 are such that a substantial amount of the harmful radiation is filtered out. Certain wavelengths which exist in sunlight are known to have therapeutic effect for certain skin conditions, and the optical properties of the material 100 are such that a substantial amount of the therapeutic radiation is transmitted.
[0067] In one embodiment the material 100 is a fabric which transmits only a relatively small proportion of the incident sunlight 105 , and transmits substantially only parts of the spectrum which have a therapeutic effect. Such a fabric can be used for shirts, hats and other clothes. The material may transmit radiation in one or more spectral bands.
[0068] With reference to FIG. 2 , in a second embodiment a material, designated 200 , is shown schematically. In this embodiment some of the radiation of the incident sunlight is transmitted, some is absorbed by the material 200 , and some of the absorbed radiation is re-emitted at one or more wavelengths which have a therapeutic effect. As illustrated in FIG. 2 , a larger arrow 205 illustrates full spectrum sunlight incident upon the material 200 , a first smaller arrow 210 illustrates a smaller amount of radiation which has been transmitted through the material 200 and a second smaller arrow 220 illustrates an amount of radiation which has been re-emitted by the material 200 .
[0069] As with the first embodiment 100 , the material 200 can be a fabric can be used for shirts, hats and other clothes. The material 200 may transmit and/or emit radiation in one or more spectral bands.
[0070] It will be appreciated that a further (third) embodiment comprises a material in which substantially no sunlight is simply transmitted through the material, but in which some therapeutic radiation is emitted from the side of the material opposite to the side upon which the sunlight is incident. A schematic illustration of such an embodiment would effectively be the same as the illustration of FIG. 2 , but with the first smaller arrow, 210 , omitted. Such an embodiment will not, therefore, be explicitly illustrated in a separate drawing.
[0071] With reference to FIG. 3 , an embodiment of an item of clothing in the form of a baseball cap 300 , has a brim 301 formed from a material in accordance with the embodiment of FIG. 2 (that is, by the second embodiment, although it will be appreciated that variations could be provided by use of the first or third of the three embodiments described above). Sunlight, illustrated by arrow 305 , incident upon the brim 301 , has a substantial amount of the harmful radiation filtered from it, and by a combination of transmission and re-emission results in radiation 310 , which includes a substantial therapeutic component (and a reduced harmful component compared to sunlight) being incident upon the face of a wearer 320 of the baseball cap 300 .
[0072] It will be appreciated that use of a material, such as is described in relation to the above general descriptions of three embodiments, to shield a subject from at least some of the harmful radiation in sunlight (or other electromagnetic radiation having a harmful component) so that therapeutic radiation is transmitted and/or emitted, so that it can reach a subject, might correspond to a method of protecting a subject from the harmful radiation, and a method of therapy. A particularly convenient form of such a method is to use clothing made from such a material, and to use sunlight as the light source. Of course, alternatives are possible: for example, a parasol or umbrella made from the material could provide a similar effect.
[0073] In one embodiment the optical properties of the material allow transmission and/or emission of wavelengths in the range 400-420 nm. Exposure of the skin of a subject to these wavelengths may provide a useful acne treatment. Radiation in this range of wavelengths interacts with porphyrin generated by bacteria, and this photodynamic reaction destroys the bacteria, reducing the acne. Of course, such an embodiment does not preclude transmission and/or emission of a broader range of wavelengths, such as 400-440 nm, or 400-490 nm and some embodiments target these wavelengths. In some embodiments, other wavelengths which may be suitable for treatment of acne can additionally or alternatively be targeted, such as wavelengths in the range 630-670 nm. Light can interact with porphyrins produced by human cells. The effect can be amplified by applying topical cream with photosensitizing properties. Such a cream may include some precursors of porphyrins or other photosensitizing agents. Application of an appropriate substance, which in one embodiment can be a topical cream, may improve the efficacy of a method of skin treatment such as those described above. The method can include the use of one or more photosensitizing agents. In a variation, photosensitizing agents may be utilized in ways other than being applied to the skin: for example orally or intravenously administered photosensitizing agents could be used.
[0074] Of course, wavelengths with therapeutic effect on conditions other than acne could be utilized. Wavelengths in the orange and red part of the visible spectrum are known to stimulate collagen growth and to have skin rejuvenation effect. Interaction of light in this spectral range with fibroblast stimulates its growth.
[0075] In preferred embodiments the material is a fabric, facilitating manufacture of comfortable clothing items from (or incorporating) such a material. In manufacture of a fabric having the desired optical properties, the following synthetics are examples of polymer materials which can conveniently be used: acetate; acrylic; nylon; latex; polyester; rayon. Of course, other materials could be used and, in particular, materials made from natural fibres, such as cotton, or a mix of natural fibres with manmade fibres, can be used.
[0076] Fluorescent or filtering dye can be impregnated into the polymer. There is a large number of laser and fluorescent dyes which provide light emission in the visible and near infrared spectrum, and from which dyes suitable for emitting desired therapeutic wavelengths can be selected for use in a material.
[0077] In one embodiment, in order to deliver therapeutic radiation to the skin of a subject while protecting the skin of the subject from harmful radiation the fabric should:
[0078] be substantially transparent (and/or translucent) to the desired therapeutic radiation;
[0079] absorb a substantial proportion of the harmful radiation part of sunlight; and
[0080] convert at least some non-desired parts of the sunlight into the desired therapeutic radiation.
[0081] In some embodiments, concentration of the dye in the fabric should be high enough to absorb most of the harmful radiation (but see also the description below, of the embodiment of FIG. 4 ).
[0082] By way of example, the following dyes can be used for transforming ultraviolet (UV) radiation into blue light: DAPI; Hoechst 334. These dyes are known per se and sometimes used in fluorescent spectroscopy.
[0083] Thus, for example, polyester fabric impregnated with DAPI dye can be used to protect the skin from UV radiation and enhance delivery of blue light in the range 400 nm-450 nm and should therefore provide therapeutic effect for acne.
[0084] The fluorescent dye known as Cy3 dye, has an excitation spectrum in the range of 470-570 nm and a fluorescence (emission) spectrum in the red spectrum 550-650 nm. Broadly speaking this dye may be considered to ‘shift’ the wavelength of incident radiation from a shorter wavelength to a longer wavelength. This dye can be imbedded into a polymer for manufacture of a fabric that can be used to stimulate fibroblast.
[0085] For example, a synthetic fabric, such as that sold under the trademark CoolDry, could be manufactured in a form dyed with Cy3 dye to deliver to the skin the red radiation. It will be appreciated that in this example conversion of at least part of the absorbed radiation to radiation that has a therapeutic effect on human skin is certainly occurring even though the absorbed radiation utilized for ‘conversion’ to therapeutic radiation is not considered particularly harmful.
[0086] In one embodiment a combination of a several dyes can be used to provide better protection from harmful radiation, and/or to provide exposure of the skin of the subject to more, or a greater range of, therapeutic radiation.
[0087] Additionally, or alternatively, a material in accordance with the present invention, may comprise more than one layer, with different layers having different optical properties, but so that the material as a whole has the desired optical properties. For example, as illustrated in FIG. 4 in schematic, exploded form, a material generally designated 400 , has a first, florescent, layer 402 and a second, filtration, layer 404 . The first, fluorescent, layer 402 , includes a dye which absorbs harmful radiation and emits therapeutic radiation. The second, filtration, layer 404 is substantially transparent to the therapeutic radiation but substantially opaque to harmful radiation. FIG. 4 illustrates schematically a situation where a considerable amount of incident harmful radiation 406 and a relatively small amount of incident therapeutic radiation 408 are incident upon the first layer 402 . The first, fluorescent, layer 402 absorbs a certain amount of harmful radiation and both transmits and emits therapeutic radiation, so that a reduced amount of harmful radiation 416 and an enhanced amount of therapeutic radiation 418 reach the second, filtration, layer 404 . The second, filtration, layer 404 filters out the remaining harmful radiation, so that substantially no harmful radiation passes through the material 400 , but so that substantially all of the enhanced amount of therapeutic radiation 418 exits the material. It will be appreciated that FIG. 4 is an exploded view and that in practical embodiments the layers 402 , 404 would usually be in contact with each other. It should also be appreciated that the representation of the radiation is schematic, and that the incident harmful and therapeutic radiation would be likely to be components of the spectrum of sunlight. In one embodiment the second, filtration, layer 404 can be a coating applied to a first, fluorescent, layer 402 which is in the form of a fabric. The coating could comprise nano particles of inorganic substance such as a suitable metal oxide, such as zinc oxide, which have been found to be effective in filtering ultra-violet radiation while allowing transmission of visible light.
[0088] It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or in any other country.
[0089] In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
[0090] Variations and modifications can be made in respect of the invention described above and defined in the following statement of claim. | A material and method delivering to the skin therapeutic radiation and filtering a part of the sun spectrum causing skin damage. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. provisional application 61/222,075, filed Jun. 30, 2009, which is incorporated by reference herein in its entirety.
STATEMENT REGARDING GOVERNMENT FUNDING FOR RESEARCH AND DEVELOPMENT
This invention was made with government support under AI063326 awarded by the National Institutes of Health. The government has certain rights in the invention.
BACKGROUND OF THE INVENTION
Quorum sensing (QS) is a process by which bacteria assess their population density through a language of low molecular weight signalling molecules (autoinducers). Gram-negative bacteria commonly use N-acylated homoserine lactones (AHLs) as their primary autoinducers and their respective receptors (R proteins) for QS. Assessing population density allows for the modulation of gene expression levels required for group behaviour. Genes regulated by QS in Pseudomonas aeruginosa include virulence factor production and biofilm production. [Geske, G. D.; O'Neill, J. C.; Miller, D. M.; Mattmann, M. E.; Blackwell, H. E., Modulation of Bacterial Quorum Sensing: Systematic Evaluation of N-Acylated Homoserine Lactones in Multiple Species and New Insights into Their Mechanism of Action. J. Am. Chem. Soc. 2007, 129, 13613-13625.]
At high cell densities, bacteria use this chemical signaling process to switch from a nomadic existence to that of multicellular community. This lifestyle switch is significant, as numerous pathogenic bacteria use quorum sensing to turn on virulence pathways and form drug-impervious communities called biofilms that are the basis of myriad chronic infections. Over 80% of bacterial infections in humans involve the formation of biofilms, as exemplified in lung infections by Pseudomonas aeruginosa , which is the primary cause of morbidity in cystic fibrosis patients. The treatment of infections by pathogens that form biofilms costs over $1 billion/year in the US alone. Biofilms are dense extracellular polymeric matrices in which the bacteria embed themselves. Biofilms allow bacteria to create a microenviroment that attaches the bacteria to the host surface and which contains excreted enzymes and other factors allowing the bacteria to evade host immune responses including antibodies and cellular immune responses. Such biofilms can also exclude antibiotics. Further, biofilms can be extremely resistant to removal and disinfection. For individuals suffering from cystic fibrosis, the formation of biofilms by P. aeruginosa is eventually fatal. Other bacteria also respond to quorum sensing signals by producing biofilms. Biofilms are inherent in dental plaques, and are found on surgical instruments, food processing and agriculture equipment and water treatment and power generating machinery and equipment.
Gram-negative bacteria represent numerous relevant pathogens using quorum-sensing pathways. Besides P. aeruginosa , other quorum sensing bacteria include: Aeromonas hydrophila, A. salmonicida, Agrobacterium tumefaciens, Burkholderia cepacia, Chromobacterium violaceum, Enterobacter agglomeran, Erwinia carotovora, E. chrysanthemi, Escherichia coli, Nitrosomas europaea, Obesumbacterium proteus, Pantoea stewartii, Pseudomonas aureofaciens, P. syringae, Ralstonia solanacearum, Rhisobium etli, R. leguminosarum, Rhodobacter sphaeroides, Serratia liguefaciens, S. marcescens, Vibrio anguillarum, V. fischeri, V. cholerae, Xenorhabdus nematophilus, Yersinia enterocolitica, Y. pestis, Y. pseudotuberculosis, Y. medievalis , and Y. ruckeri . Studies on the above listed bacteria indicate that, while the Al is generally an AHL compound, the genes affected as well as the phenotypes resulting from induction of the promoter differ according to the particular life cycle of each bacterium. Further, quorum sensing stimulation typically results in altered expression of multiple genes.
P. aeruginosa is an opportunistic pathogen that causes severe, often fatal, infections in burn victims and cystic fibrosis patients and is therefore of direct and profound biomedical importance. P. aeruginosa uses 3-oxo-dodecanoyal homoserine lactone (OdDHL) as its autoinducer (Compound A):
While successful modifications to the acyl tail region of autoinducers have been made, modifications to the AHL head group have met limited success. Modifications to the head group are important because the lactone ring is prone to hydrolysis at pH 7 and higher. [Glansdorp, F. G.; Thomas, G. L.; Lee, J. K.; Dutton, J. M.; Salmond, G. P. C.; Welch, M.; Spring, D. R., Synthesis and stability of small molecule probes for Pseudomonas aeruginosa quorum sensing modulation. Org. Biomol. Chem. 2004, 2, 3329-3336.] This work relates to non-homoserine lactone-based autoinducer analogs for QS modulation and provides a better understanding of the structural and electronic requirements of the autoinducer's head group. Certain of the compounds of this invention are designed as autoinducer analogs for QS modulation in P. aeruginosa.
Previous work in the field of P. aeruginosa QS modulators showed that many active non-lactone structures are highly conjugated and retain some form of the acyl chain, suggesting that a region of hydrophobicity in the acyl tail region is critical. [Muh, U.; Schuster, M.; Heim, R.; Singh, A.; Olson, E.; Greenberg, E. P., Novel Pseudomonas aeruginosa Quorum-Sensing Inhibitors Identified in an Ultra-High-Throughput Screen. Antimicrob. Agents Chemother. 2006, 50, 3674-3679; Muh, U.; Hare, B. L.; Duerkop, B. A.; Schuster, M.; Hanzelka, B. L.; Heim, R.; Olson, E. R.; Greenberg, E. P., A Structurally Unrelated Mimic of a Pseudomonas aeruginosa acyl-homoserine lactone quorum sensing signal. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 16948-16952; Lee, L. Y. W.; Hupfield, T.; Nicholson, R. L.; Hodgkinson, J. T.; Su, X.; Thomas, G. L.; Salmond, P. C.; Welch, M.; Spring, D. R., 2-Methoxycyclopentyl analogues of a Pseudomonas aeruginosa quorum sensing modulator. Molecular BioSystems 2008, 4, 505-507; Eberhard, A.; Widrig, C. A.; MaBath, P.; Schineller, J. B., Analogs of the autoinducer of bioluminescence in Vibrio fischeri . Arch. Microbiol. 1986, 146, 35-40; Rasmussen, T. B.; Givskov, M., Quorum sensing inhibitors: a bargain of effects. Microbiology 2006, 152, 895-904; Hjelmgaard, T.; Persson, T.; Rasmussen, T. B.; Givskov, M.; Nielsen, J., Synthesis of Furanone-based natural product analogues with quorum sensing antagonist activity. Bioorg. Med. Chem. 2003, 11, 3261-3271; Smith, K. M.; Bu, Y.; Suga, H., Induction and Inhibition of Pseudomonas aeruginosa quorum sensing by synthetic autoinducer analogs. Chem. Biol. 2003, 10, 81-89; Schaefer, A. L.; Hanzelka, B. L.; Eberhard, A.; Greenberg, E. P., Quorum sensing in Vibrio fischeri : Probing autoinducer-LuxR interactions with autoinducer analogs. J. Bacteriol. 1996, 178, 2897-2901; Passador, L.; Tucker, K. D.; Guertin, K. R.; Journet, M. P.; Kende, A. S.; Iglewski, B. H., Functional analysis of the Pseudomonas aeruginosa Autoinducer PAI. J. Bacteriol. 1996, 178, 5995-6000; Smith, K. M.; Bu, Y.; Suga, H., Library Screening for Synthetic Agonists and Antagonists of a Pseudomonas aeruginosa autoinducer. Chem. Biol. 2003, 10, 563-571; Ishida, T.; Ikeda, T.; Takiguchi, N.; Kuroda, A.; Ohtake, H.; Kato, J., Inhibition of quorum sensing in Pseudomonas aeruginosa by N-acyl cyclopentylamides. Appl. Environ. Microbiol. 2007, 73, 3183-3188; Fletcher, M. P.; Diggle, S. P.; Crusz, S. A.; Chhabra, S. R.; Camara, M.; Williams, P., A dual biosensor for 2-alkyl-4-quinolone quorum sensing signal molecules. Environ. Microbiol. 2007, 9, 2683-2693; Kim, C.; Kim, J.; Park, H. Y.; Park, H. J.; Lee, J. H.; Kim, C. K.; Yoon, J., Furanone derivatives as quorum sensing antagonists of Pseudomonas aeruginosa . Appl. Microbiol. Biotechnol. 2008, 80, 37-47; Estephane, J.; Dauvergne, J.; Soulere, L.; Reverchon, S.; Queneau, Y.; Doutheau, A., N-Acyl-3-amino-5H-furanone derivatives as new inhibitors of LuxR-dependent quorum sensing: Synthesis, biological evaluation and binding mode study. Bioorg. Med. Chem. Lett. 2008, 18, 4321-4324.]
Furthermore, a close examination of the crystal structure of the N-terminal domain of LasR reveals a hydrogen bond between the 3-oxo carbonyl in the acyl tail of OdDHL and a water molecule present in the LasR binding site [Bottomley, M. J.; Muraglia, E.; Bazzo, R.; Carfi, A., Molecular insights into quorum sensing in the human pathogen Pseudomonas aeruginosa from the structure of the virulence regulator LasR bound to its autoinducer. J. Biol. Chem. 2007, 282, 13592-13600.]
Published US application US2006/0178430, published Aug. 10, 2006 and International published application WO 2008/116029, published Sep. 25, 2008 relate to quorum sensing compounds and their uses. These documents are incorporated by reference in their entirety herein for their description of the state of the art and for additional methods of synthesis, methods of testing, and methods of application of quorum sensing compounds.
Janssens, J. C. A. et al. (2007) Applied Environ. Microbiol. 73 (2) 535-544 reports that certain N-acyl homoserine lactones including certain thiolactones are strong activators of SdiA, the Salmonella enterica Serovar Typhimurium LuxR homologues.
Published PCT application WO2002/052949 relates to the use of autoinducer compounds as additives to animal feeds for improving animal performance.
SUMMARY OF THE INVENTION
The invention provides a compound of formula I:
A-[Z] n -L1-[Y] q —W—[V] m -L2-HG
or a pharmaceutically acceptable salt or ester thereof
where:
W is —NH— or
Y is —CO—, —CO—CH 2 —CO—, —NH—CO—, —CO—CH 2 —C(Y1)-, —SO 2 —, where Y1 is —OH, —SH, —NH 2 or —F;
q is 1 or 0 to indicate the presence or absence, respectively of Y;
L1 and L2, independently, are —[CH 2 ] p1 — and —[CH 2 ] p2 —, where p1 and p2, independently, are 0 or integers ranging from 1-10 and one or more of the carbons of L1 or L2 can be substituted with one or two non-hydrogen substituents;
V is
where R N is an alkyl group having 1-3 carbon atoms;
m is 1 or 0 to indicate, respectively, the presence or absence of the V group;
Z is —CO—, —O—CO—, —CO—O—, —NH—CO—, —CO—NH—, —NH—CO—NH—, —O—, —S—, or —NH 2 —, n is 1 or 0 to indicate, respectively, the presence of absence of the Z group;
A is an aryl or heteroaryl group having one or two 5- or 6-member rings with 1-3 heteroatoms in a ring, a C 5 -C 8 cycloalkyl group, a C 5 -C 8 cycloalkenyl group, a heterocyclic group having one or two 5 to 8-member rings with 1-3 heteroatoms in a ring, a branched or unbranched C 1 -C 12 acyclic aliphatic group, all of which groups can have one or more non-hydrogen substituents selected from the group consisting of halogen, nitro, hydroxyl, nitrile, azide, —R, —OR, —COOR, —OCOR, —COR, —OCOOR, —CON(R) 2 , —OCON(R) 2 , —N(R) 2 , —SR, —SO 2 R, —SOR, and —SO 2 N(R) 2 , wherein each R is independently selected from the group consisting of hydrogen, an amine group, a substituted or unsubstituted unbranched C 1 -C 12 acyclic aliphatic group, a substituted or unsubstituted branched C 1 -C 12 acyclic aliphatic group, a substituted or unsubstituted C 3 -C 8 cycloalkyl group, a substituted or unsubstituted C 3 -C 8 cycloalkenyl group, a fluorinated C 1 -C 12 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a protecting group; additionally, two R groups in the same substituent, optionally form a 4-8 member ring; and
HG is a head group selected from an aryl or heteroaryl group having one or two 5- or 6-member rings with 1-3 heteroatoms in a ring; a C 5 -C 8 cycloalkyl group; a C 5 -C 8 cycloalkenyl group; a heterocyclic group having one or two 5 to 8-member rings with 1-3 heteroatoms in a ring; an alkyl group having 1-3 carbon atoms substituted with two aryl or heteroaryl groups; a cyclic lactone, lactam, thiolactone or ketone group having a 4-8 member ring, or an ester group R E —O—CO—, where R E is an optionally substituted alkyl group having 1-6 carbon atoms; all of which groups can have one or more non-hydrogen substituents selected from the group consisting of halogen, nitro, hydroxyl, nitrile, azide, —R, —OR, —COOR, —OCOR, —COR, —OCOOR, —CON(R) 2 , —OCON(R) 2 , —N(R) 2 , —SR, —SO 2 R, —SOR, and —SO 2 N(R) 2 , wherein each R is independently selected from the group consisting of hydrogen, an amine group, a substituted or unsubstituted unbranched C 1 -C 12 acyclic aliphatic group, a substituted or unsubstituted branched C 1 -C 12 acyclic aliphatic group, a substituted or unsubstituted C 3 -C 8 cycloalkyl group, a substituted or unsubstituted C 3 -C 8 cycloalkenyl group, a fluorinated C 1 -C 12 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a protecting group; additionally, two R groups on the same substituent optionally form a 4-8 member ring.
In specific embodiments, n is 0. In specific embodiments, m is 0. In specific embodiments, n is 0 and m is 0. In specific embodiments, n is 0 and q is 1. In specific embodiments, n is 0, m is 0 and q is 1. In specific embodiments, n is 0, m is 1 and q is 1. In specific embodiments, n is 1, m is 1 and q is 1.
In a specific embodiment, W is —NH—.
In an embodiment, HG is a group having formula:
where r is an integer ranging from 1-4, G is —O—, —S—, —NH— or —CH 2 —; R′ is hydrogen or a 1-6 carbon aliphatic group, particularly an alkyl group, and X represents optional substitution with one or more non-hydrogen substituents on one or more ring carbons. In specific embodiments, r is 1 or 2, the ring is unsubstituted and R′ is H.
In a specific embodiment, G is —S—. In a specific embodiment, G is —S— and r is 1. In a specific embodiment, G is —S—, r is 1 and R′ is an alkyl group. In a specific embodiment, G is —S—, r is 1 and R′ is an alkyl group. X represents 1, or 2 substituents on the ring.
In an embodiment, HG is a group other than a ketone, lactone, or lactam group, when W is —NH—.
In an embodiment, HG is selected from an optionally substituted phenyl, naphthyl, cyclohexyl, cyclohexenyl, cyclopentyl, pyridyl, piperidyl, furyl, thienyl, pyrroyl, or
where r is an integer ranging from 1-4, R′ is hydrogen or a 1-6 carbon aliphatic group, particularly an alkyl group, and X represents optional substitution with one or more non-hydrogen substituents on one or more ring carbons. In specific embodiments, r is 1, the ring is unsubstituted and R′ is H. In specific embodiments, r is 1, and R′ is an alkyl group, particularly a methyl group. In specific embodiments, r is 1, R′ is an alkyl group, particularly a methyl group and X represents 1, or 2 substituents on the ring.
In specific embodiments, when HG is an unsubstituted thiolactone ring (where G is S and all X and R′ are hydrogen) and W is —NH—, A is a group other than an unsubstituted alkyl group or a halogenated alkyl group. In specific embodiments, when HG is an unsubstituted thiolactone ring (where G is S and all X and R′ are hydrogen); W is —NH—, q is 1 and Y is —COCH 2 —CO—, A is a group other than an unsubstituted alkyl group or a halogenated alkyl group. In specific embodiments, when HG is an unsubstituted thiolactone ring (where G is S and all X and R′ are hydrogen); W is —NH—; m, n, p1 and p2 are all 0; q is 1 and Y is —CO—CH 2 —CO—, A is a group other than an unsubstituted alkyl group or a halogenated alkyl group.
In specific embodiments, HG is a group as illustrated in FIG. 1-1 , or 1 - 2 , where X, X1 and X2, represent optional substitution with one or more non-hydrogen substituents on one or more ring carbons. In these Figures X, X1 and X2 represents optional substitution with one or more non-hydrogen substituents on one or more ring carbons, RA is H or an alkyl group, particularly one having 1-3 carbon atoms. In more specific embodiments, HG is selected from groups HG1, HG4, HG7, HG8, HG10, HG11, or HG12. In other specific embodiments, HG is selected from groups HG2, HG3, HG14, HG15, HG17, HG18 or HG21. In specific embodiments, HG is a group of any of FIG. 2-1 , 2 - 2 , or 2 - 3 . In these Figures X, X1-X5 represents optional substitution with one or more non-hydrogen substituents on one or more ring carbons and R′ is an alkyl group having 1-6 or 1-3 carbon atoms.
In specific embodiments HG is an ester group R E —O—CO—, where R E is an unsubstituted alkyl group having 1-6 carbon atoms; an alkyl group substituted with one or more halogens, particularly fluorines; a phenyl group or optionally substituted phenyl group, particular a phenyl group substituted with one or more halogens, particularly fluorine, one or more nitro groups, one or more alkoxy groups (including 1C-3C alkoxy groups), or one or more trifluoromethyl groups. In specific embodiments, R E is methyl, ethyl, propyl or butyl groups. In more specific embodiments, R E is a methyl or ethyl group. In specific embodiments when HG is an ester group L2 is —CH(CH 3 )—.
In specific embodiments, HG is a group as illustrated in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 , and A is a branched or unbranched aliphatic group having 1-12 carbon atoms and more specifically is an alkyl or alkenyl group having 1-12 carbon atoms. In specific embodiments HG is a group as illustrated in FIG. 2-1 , 2 - 2 , or 2 - 3 .
In specific embodiments, A is a group as in FIG. 3 , where X represents optional substitution with one or more non-hydrogen substituents on one or more ring carbons or on a specific ring carbon, R′ is an alkyl group, particularly one having 1-6 or 1-3 carbon atoms. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3 . In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3 and
W is
In specific embodiments, A is one of A1-A13 ( FIG. 3-1 ). In specific embodiments, A is one of A1-A13 ( FIG. 3-1 ) and n is 0. In specific embodiments, A is one of A1-A13 ( FIG. 3-1 ), n is 0, q is 1 and Y is —CO— or —CO—CH 2 —CO—. In specific embodiments, A is one of A1-A13 ( FIG. 3-1 ), n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, and W is —NH—. In specific embodiments, A is one of A1-A13 ( FIG. 3-1 ), n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, and W is
In specific embodiments, A is one of A1-A13 ( FIG. 3 ), n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, W is —NH— and m is 0. In specific embodiments, A is one of A1-A13 ( FIG. 3 ), n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, W is —NH— and m is 1.
In specific embodiments, A is a branched or straight chain alkyl or alkenyl group. In specific embodiments, A is a branched or straight chain alkyl or alkenyl and n is 0. In specific embodiments, A is a branched or straight chain alkyl or alkenyl, n is 0, q is 1 and Y is —CO— or —CO—CH 2 —CO—. In specific embodiments, A is a branched or straight chain alkyl or alkenyl, n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO— and W is —NH—. In specific embodiments, A is a branched or straight chain alkyl or alkenyl, n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, and W is
In specific embodiments, A is a branched or straight chain alkyl or alkenyl, n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, W is —NH— and m is 0. In specific embodiments, A is a branched or straight chain alkyl or alkenyl n is 0, q is 1, Y is —CO— or —CO—CH 2 —CO—, W is —NH— and m is 1.
In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and W is NH and m is 1. In specific embodiments, HG is a group as in FIG. 1 - 1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 , L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 )0-1- and q is 1. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 , L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1 and Y is —CO— or —CO—CH 2 —CO—. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 , and L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1 and Y is —CO—.
In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a branched or straight chain alkyl or alkenyl and W is —NH— and m is 1. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a branched or straight chain alkyl or alkenyl, L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a branched or straight chain alkyl or alkenyl, L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1 and Y is —CO— or —CO—CH 2 —CO—. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a branched or straight chain alkyl or alkenyl, and L1 is —CH 2 — or —CH 2 —CH 2 -L2 is —(CH 2 ) 0-1 — and q is 1 and Y is —CO—.
In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3-1 and W is NH and m is 1. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3 , L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3 , L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1 and Y is —CO— or —CO—CH 2 —CO—. In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3 , with the exception that A is not the same group as HG and L1 is —CH 2 — or —CH 2 —CH 2 —, L2 is —(CH 2 ) 0-1 — and q is 1 and Y is —CO—.
In specific embodiments, HG is a group as in FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 , or 2 - 3 and A is a group in FIG. 3-1 with the exception that A is not the same group as HG.
In specific embodiments, HG is P1-P50. In specific embodiments, HG is P1-P50 and L2 is —(CH 2 ) 0-2 — and may be substituted on one carbon with an alkyl group having 1-3 carbon atoms. In specific embodiments, HG is P1-P50; L2 is —(CH 2 ) 0-2 — and is optionally substituted on one carbon with an alkyl group having 1-3 carbon atoms, and m is 0. In specific embodiments, HG is P1-P50; L2 is —(CH 2 ) 0-2 — and may be substituted on one carbon with an alkyl group having 1-3 carbon atoms, and m is 1. In specific embodiments, HG is P1-P50; L2 is —(CH 2 ) 0-2 — and may be substituted on one carbon with an alkyl group having 1-3 carbon atoms, and m is 1 and W is NH. In specific embodiments, HG is P1-P50; L2 is —(CH 2 ) 0-2 — and may be substituted on one carbon with an alkyl group having 1-3 carbon atoms, and m is 1, W is NH and q is 1. In specific embodiments, HG is P1-P50; L2 is —(CH 2 ) 0-2 — and may be substituted on one carbon with an alkyl group having 1-3 carbon atoms, and m is 1, W is —NH—, q is 1 and Y is —CO— or —CO—CH 2 —CO—. In specific embodiments HG is P1-P50 and L1 is —(CH2)0-2-. In specific embodiments HG is P1-P50 and n is 0.
HG groups may be unsubstituted. HG groups may be substituted. Optional substitution on HG groups includes substitution with one or more non-hydrogen substituents selected from the group consisting of halogen, nitro, hydroxyl, nitrile, azide, —R, —OR, —COOR, —OCOR, —COR, —OCOOR, —CON(R) 2 , —OCON(R) 2 , —N(R) 2 , —SR, —SO 2 R, —SOR, —SO 2 N(R) 2 , wherein each R is independently selected from the group consisting of hydrogen, an amine group, a substituted or unsubstituted unbranched C1-C12 acyclic aliphatic group, a substituted or unsubstituted branched C1-C12 acyclic aliphatic group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C3-C8 cycloalkenyl group, a fluorinated C1-C12 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and a protecting group, where two R groups on the same substituent optionally form a 4-8 member ring (carbon ring or a carbon ring with 1-3 heteroatom ring members); additionally, two X, X1 or X2 groups, particularly two such groups on adjacent ring positions can form a 4-8 member ring. Specific substituents include among others optionally substituted alkyl groups having 1-3 carbon atoms.
In specific embodiments, X, X1 or X2 represent one or more halogens, nitro, azide, nitrile, alkyl groups particularly those having 1-3 carbon atoms, —OR, —COOR, —SO 2 —R, —SR, or —N(R) 2 , particularly where R is hydrogen or an alkyl group having 1-3 carbon atoms.
In specific embodiments, one or more carbons of L1 can be substituted with an alkyl group having 1-3 carbon atoms, a hydroxyl or amine group or a halogen, particularly a fluorine. In a more specific embodiment one carbon of L1 can be substituted with one non-hydrogen substituent. In a specific embodiment L1 is —CH(R′)— where R′ is an alkyl group. In a specific embodiment L1 is —(CF 2 ) p1 —.
In specific embodiments, one or more carbons of L2 can be substituted with an alkyl group having 1-3 carbon atoms, a hydroxyl or amine group or a halogen, particularly a fluorine. In a more specific embodiment one carbon of L2 can be substituted with one non-hydrogen substituent. In a specific embodiment L2 is —CH(R′)— where R′ is an alkyl group. In a specific embodiment L2 is —(CF 2 ) p1 —.
The invention also provides a compound of formula II:
or a pharmaceutically acceptable salt or ester thereof
where variables are defined as for formula I. In an embodiment, q is 0. In an embodiment q is 1. In an embodiment, q is 1 and Y is —CO—, —CO—CH 2 —CO— or —CO—CH 2 —C(Y1)-.
In embodiments of formula II, A is a branched or unbranched C1-C12 acyclic aliphatic group. More specifically A is a branched or unbranched alkyl or alkenyl group having 1-15 carbon atoms. In more specific embodiments of formula II where A is a branched or unbranched C1-C12 acyclic aliphatic group, n is 0, q is 0 and L1 is —(CH 2 ) p1 —, where p1 is 0-6. In additional specific embodiments of formula II where A is a branched or unbranched C1-C12 acyclic aliphatic group, n is 0, q is 1, Y is —CO— or —CO—CH 2 —C(Y1)-, L1 is —(CH 2 ) p1 —, where p1 is 0-6. In more specific embodiments, A is a branched or unbranched alkyl group having 1-12 carbon atoms.
In embodiments of formula II, A is an optionally substituted aryl group. In more specific embodiments, q is 0, L1 is —(CH 2 ) p — where p is 0-6 and A is an optionally substituted aryl group, particularly an optionally substituted phenyl, biphenyl or naphthyl group. In additional specific embodiments, q is 0, L1 is —(CH 2 ) p —, where p is 1-3, and A is an optionally substituted aryl group, particularly an optionally substituted phenyl, biphenyl or naphthyl group. In additional embodiments, the phenyl, biphenyl or naphthyl group is unsubstituted or substituted with one or more halide, nitro, hydroxyl, nitrile, azide, —OR, —N(R) 2 , —SR, or —SO 2 R groups, where R is an alkyl group having 1-3 carbon atoms.
In embodiments of formula II, HG is an optionally substituted phenyl, naphthyl, cyclopentyl, cyclohexyl, cyclohexenyl, furyl, or group having formula:
where variables are as defined above and in specific embodiments, r is 1 or 2. In additional embodiments, the ring is unsubstituted and R′ is hydrogen. In additional embodiments, R′ is an alkyl group having 1-3 carbon atoms. In additional embodiments, the ring carries 1-3 substituents, particularly optionally substituted alkyl groups having 1-3 carbon atoms. Preferred optional substitution for phenyl, naphthyl, cyclopentyl, cyclohexyl, or cyclohexenyl HG groups is one or more halogen, nitro, or alkoxy (having 1-3 carbon atoms). In specific embodiments, HG is:
where r, X and R′ are as defined above. In specific embodiments, r is 1. IN specific embodiments, R′ is H. In specific embodiments, R′ is optionally substituted C1-C3 alkyl. In specific embodiments, X is 1-3 substituents on the ring. In specific embodiments, r is 1 and X is 1 or 2 substituents on the ring. In specific embodiments, X is 1 or 2 optionally substituted alkyl groups having 1-3 carbon atoms.
Compounds of this invention can be optically active, racemic, enantiomerically pure or mixtures of enantiomers. HG may have optically active carbons and may exist as enantiomeric pairs. For example, HG of formula:
can be in the enantiomeric forms:
Note that carbons in the HG ring other than that shown may be optically active dependent upon X substitution.
The invention also provides a compound of formula III:
A-[Z] n -L1-[Y] q —NH—[V] m -L2-HG
or a pharmaceutically acceptable salt or ester thereof,
where variables are defined as for formula I. In specific embodiments of formula III, m is 0. In other specific embodiments, n is 0. In other specific embodiments, m and n are both 0. In specific embodiments, m is 0 and q is 1. In more specific embodiments, m is 0, q is 1 and Y is —CO—, —CO—CH 2 —CO— or —CO—CH 2 —C(Y1)-. In more specific embodiments, m is 0, q is 1 and Y is —CO—, —CO—CH 2 —CO— or —CO—CH 2 —C(Y1)-, and A is an optionally substituted aryl group, particularly an optionally substituted phenyl group. In more specific embodiments, m is 0, q is 1 and Y is —CO—, —CO—CH 2 —CO— or —CO—CH 2 —C(Y1)-, and A is an optionally substituted branched or unbranched C 1 -C 12 acyclic aliphatic group. In specific embodiments HG is a group of any of FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 or 2 - 3 . In specific embodiments, HG is:
where r, X and R′ are as defined above. In specific embodiments, r is 1. In specific embodiments, R′ is H. In specific embodiments, R′ is optionally substituted C1-C3 alkyl. In specific embodiments, X is 1-3 substituents on the ring. In specific embodiments, r is 1 and X is 1 or 2 substituents on the ring. In specific embodiments, X is 1 or 2 optionally substituted alkyl groups having 1-3 carbon atoms.
The invention also provides a compound of formula IV:
or a pharmaceutically acceptable salt or ester thereof,
where variables are defined as for formula I. In specific embodiments, R N is hydrogen. In specific embodiments, q is 1 and Y is —CO—, —CO—CH 2 —CO— or —CO—CH 2 —C(Y1)-. In specific embodiments, HG is an optionally substituted aryl group, particularly an optionally substituted phenyl group. In specific embodiments, A is A is an optionally substituted aryl group, particularly an optionally substituted phenyl group. In specific embodiments, A is an optionally substituted branched or unbranched C 1 -C 12 acyclic aliphatic group, particularly an optionally substituted branched or unbranched alkyl or alkenyl group having 1 to 12 carbon atoms. In specific embodiments HG is a group of any of FIG. 1-1 , 1 - 2 , 2 - 1 , 2 - 2 or 2 - 3 . In specific embodiments, HG is:
where r, X and R′ are as defined above. In specific embodiments, r is 1. IN specific embodiments, R′ is H. In specific embodiments, R′ is optionally substituted C1-C3 alkyl. In specific embodiments, X is 1-3 substituents on the ring. In specific embodiments, r is 1 and X is 1 or 2 substituents on the ring. In specific embodiments, X is 1 or 2 optionally substituted alkyl groups having 1-3 carbon atoms.
The invention also provides a compound of formula V:
or a pharmaceutically acceptable salt or ester thereof, where variables are defined as for formula I. In specific embodiments, R E is an unsubstituted alkyl group having 1-6 carbon atoms. In specific embodiments, R E is methyl or ethyl. In specific embodiments, A is a branched or straight-chain aliphatic group having 1-12 carbon atoms. In specific embodiments, A is a branched or straight-chain alkyl group having 1-12 carbon atoms. In specific embodiments, A is an optionally substituted phenyl group. In specific embodiments, A is a phenyl group substituted with one or more halogens, nitro groups, alkoxy groups having 1-3 carbon atoms, or one or more trifluoroethyl groups. In specific embodiments W is —NH—. In specific embodiments L1 and L2 are independently either —CH 2 — or —CH 2 —CH 2 —. In a specific embodiment L2 is —CH(CH 3 )—. In specific embodiments, Y is —CO—, —CO—CH 2 —CO—, —NH—CO—, —CO—CH 2 —C(Y1)-. In specific embodiments, Y is —CO—, or —CO—CH 2 —CO. In specific embodiments, q is 1. In specific embodiments, n is 0. In specific embodiments, m is 0. In specific embodiments, n and m are 0 and q is 1. In specific embodiments Y is —CO— or —CO—CH 2 —CO—.
The invention also provides a compound of formula VI:
where R F is an optionally substituted a branched or unbranched C 1 -C 12 acyclic aliphatic group, L2, V and m are as defined above, f is 0 or 1 to show the absence of presence of the CO group, and HG is a head group as defined in formula I. In specific embodiments, m is 0. In specific embodiments m is 1. In specific embodiments L2 is —CH 2 — or —CH 2 —CH 2 —. In specific embodiments, HG can be any group as in FIG. 1-1 , 1 - 2 or 1 - 3 . In other specific embodiments, HG is an optionally substituted phenyl group. In specific embodiments, L2 is —CH 2 — and HG is an optionally substituted phenyl group. In specific embodiments, m is 1, L2 is —CH 2 — and HG is an optionally substituted phenyl group. In specific embodiments, m is 0, L2 is —CH 2 — and HG is an optionally substituted phenyl group. In specific embodiments R F is a branched or straight-chain alkyl group. In specific embodiments R E is a branched or straight-chain alkenyl group having one or two double bonds. In specific embodiments, f is 1 and m is 0. In specific embodiments, f is 0 and m is 0. In specific embodiments, f and m are both 1. In specific embodiments, f is 0 and m is 1. In specific embodiments, HG is a phenyl group substituted with 1 to 5 halogens, particularly bromine, chlorine or fluorine. In specific embodiments, HG is a phenyl group substituted with 1 to 5 fluorines. In specific embodiments, HG is a phenyl group substituted with 1 or 2 alkoxy groups having 1-3 carbon atoms. In specific embodiments, HG is a phenyl group substituted with 1-3 nitro groups. In specific embodiments, HG is a furyl group, particularly a 1-furyl group. In specific embodiments, m is 1, f is 1, L2 is —CH 2 — or —CH 2 —CH 2 — and HG is selected from HG groups of FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 , 2 - 3 or 2 - 4 . In specific embodiments, m is 1, f is 0, L2 is —CH 2 — or —CH 2 —CH 2 — and HG is selected from HG groups of 1-1, 1-2, 1-3, 2-1, 2-2, 2-3 or 2-4. In specific embodiments, m is 0, L2 is —CH 2 — or —CH 2 —CH 2 — and HG is selected from HG groups of FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 or 2 - 3 . In specific embodiments, m is 0, f is 1, L2 is —CH 2 — or —CH 2 —CH 2 — and HG is selected from HG groups of FIG. 11-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 , 2 - 3 or 2 - 4 . In specific embodiments, m is 0, f is 0, L2 is —CH 2 — or —CH 2 —CH 2 — and HG is selected from HG groups of FIG. 1-1 , 1 - 2 , 1 - 3 , 2 - 1 , 2 - 2 , 2 - 3 or 2 - 4 . In specific embodiments, HG is:
where r, X and R′ are as defined above. In specific embodiments, r is 1. In specific embodiments, R′ is H. In specific embodiments, R′ is optionally substituted C1-C3 alkyl. In specific embodiments, X is 1-3 substituents on the ring. In specific embodiments, r is 1 and X is 1 or 2 substituents on the ring. In specific embodiments, X is 1 or 2 optionally substituted alkyl groups having 1-3 carbon atoms.
The present invention provides compounds and methods for modulation of quorum sensing of bacteria. In an embodiment, the compounds of the present invention are able to act as replacements for naturally occurring bacterial quorum sensing ligands in a ligand-protein binding system; that is, they imitate the effect of natural ligands and produce an agonistic effect. In another embodiment, the compounds of the present invention are able to act in a manner which disturbs or inhibits the naturally occurring ligand-protein binding system in quorum sensing bacteria; that is, they produce an antagonistic effect. The present invention also provides methods of increasing or reducing the virulence of quorum sensing bacteria. In one aspect, the method comprises contacting a bacterium with an effective amount of a compound of the present invention. In another aspect, the method comprises contacting a bacterium with a therapeutically effective amount of a pharmaceutically acceptable salt or ester of the compounds of the present invention. In yet another aspect, the method comprises contacting a bacterium with a precursor which can form an effective amount of a compound of the present invention.
The present invention provides compositions for modulation of quorum sensing of bacteria which comprises one or more compounds of this invention, particularly one or more compounds of formulas I to VI herein. The compositions herein can further comprise an appropriate carrier, particularly a pharmaceutically acceptable carrier for therapeutic applications. In applications herein, one or more compounds of the invention can be compounds with one or more antibacterial compounds.
In an embodiment, the methods of the present invention can be used for disrupting a biofilm formed by a quorum sensing bacterium. A method of the present invention for disrupting a biofilm comprises contacting the biofilm with an effective amount of a compound of the present invention. In an embodiment, the methods of the present invention can be used to diminish or inhibit biofilm production. Alternatively, the methods of the present invention can be used for causing a quorum sensing bacterium to initiate or enhance biofilm production. Initiation or enhancement of biofilm formation of beneficial bacteria (those, for example, that provide a health benefit or are used in production of a valuable product) can facilitate or enhance such a health benefit or can be used to enhance or improve production of desirable valuable products. In a specific embodiment, compounds which activate quorum sensing of beneficial gut bacterial can provide a probiotic effect.
In an embodiment, the methods of the present invention can be used for inhibiting or diminishing the symbiotic behavior of a quorum sensing bacteria. In another embodiment, the methods of the present invention can be used for stimulating, initiating, or enhancing the symbiotic behavior of a quorum sensing bacteria.
In another embodiment of the methods, the compounds of the present invention can be administered to a subject to initiate modulation of quorum sensing of bacteria. In an embodiment, the administration of an effective amount of a compound of the present invention to a subject can initiate or enhance the symbiotic behavior of quorum sensing bacteria in the subject. In an embodiment, the administration of an effective amount of a compound of the present invention to a subject can disrupt a biofilm of quorum sensing bacteria in the subject. In an embodiment, the administration of an effective amount of a compound of the present invention to a subject can initiate or enhance the symbiotic behavior of a target species or a selected strain of a target species of quorum sensing bacteria in the subject. In an embodiment, the administration of an effective amount of a compound of the present invention to a subject can regulate the virulence of quorum sensing bacteria in the subject. In an embodiment, the administration of an effective amount of a compound of the present invention to a subject can regulate the virulence of a target species or a selected strain of a target species of quorum sensing bacteria in the subject.
The methods of the present invention also provide for regulation of the level of virulence of quorum sensing bacteria. In an embodiment, one or more compounds of the present invention is brought into contact with a quorum sensing bacteria to selectively regulate the virulence of the bacteria. In an embodiment, a mixture of the compounds of the present invention is brought into contact with a quorum sensing bacteria to selectively regulate the virulence of the bacteria. The amount of each compound in the mixture is that amount effective to achieve a desired effect on regulation of virulence. The methods of the present invention also provide for regulation of the production of a biofilm by quorum sensing bacteria. In an embodiment, one or more compounds of the present invention is brought into contact with a quorum sensing bacteria or bacterial biofilm to selectively regulate the biofilm production by the bacteria. In an embodiment, a mixture of the compounds of the present invention is brought into contact with a quorum sensing bacteria or bacterial biofilm to selectively regulate the biofilm production by the bacteria. The amount of each compound in the mixture is that amount effective for desired regulation of biofilm formation.
The methods of the present invention also provide for regulation of the virulence, biofilm production, or symbiotic behavior of a quorum sensing bacteria by contacting the bacteria with a photoactive compound and illuminating the bacteria and photoactive compound. In an embodiment, illuminating a photoactive compound of the present invention can change the agonistic or antagonistic behavior of the compound.
In an embodiment, the present invention provides a surface coating or polymer having incorporated therein a compound of the present invention. The amount of compound or polymer in the surface coating is that sufficient to provide antimicrobial or antifouling effect. In an embodiment, the compounds of the present invention are useful as an antimicrobial and/or antifouling agent. Compounds of the present invention are further useful in a medical, scientific, and/or biological application. In one aspect, the present invention provides a composition comprising one or more compounds of the present invention and a carrier or diluent. In a preferred embodiment, the carrier or diluent comprises a liquid. Such a liquid may comprises an aqueous solvent or a non-aqueous solvent. An exemplary solvent comprises one or more organic solvents. The carrier or diluent may also comprise an ionic liquid. In an embodiment of this aspect, the composition comprises an organic or inorganic polymeric substance. The polymeric substance may comprise one or more compounds of the present invention, admixed with a polymer, bound to a polymer, or adsorbed on to a polymer. In an exemplary embodiment of this aspect, the composition is in the form of a solution or suspension of said at least one compounds of the present invention, preferably in an aerosol or powder formulation.
In an embodiment of this aspect, the composition is formulated as a disinfectant or cleaning formulation. In another embodiment, the composition is in the form of a powder, a solution, a suspension, a dispersion, an emulsion, or a gel. In an exemplary embodiment, the composition is in the form of a pharmaceutical composition comprising a pharmaceutically acceptable carrier, diluent, and/or excipient and one or more compounds of the present invention. The composition may be in a form suitable for parenteral or non-parenteral administration. A preferred composition may be formulated for topical, intradermal, intramuscular, intraperitoneal, intravenous, subcutaneous, intranasal, epidural, ophthalmic, or oral administration. In an embodiment of this aspect the composition is formulated for administration by infusion or bolus injection, absorption through epithelial or mucocutanous linings and may be administered together with other biologically active agents. In an embodiment, the composition may further be formulated for use in an inhaler or nebulizer.
In another aspect, the present invention provides a method of treating an infection in a human or animal subject, the method comprising administration to the subject of an effective amount of one or more compounds of the present invention. In an embodiment, the treatment is therapeutic or prophylactic. In an embodiment, the method further comprises administering one or more pharmaceutically acceptable antibacterial compounds to the subject, prior to, at the same time as or after administration of the one or more compounds of this invention.
In a related embodiment, the present invention provides a method of treating an infection or condition in a subject that is characterized by biofilm formation, the method comprising administering one or more compounds of the present invention. In an embodiment, the method further comprises administering one or more pharmaceutically acceptable antibacterial compounds to the subject, prior to, at the same time as or after administration of the one or more compounds of this invention. In an embodiment, the condition is cystic fibrosis. In an embodiment, the condition is dental caries, periodonitis, otitis media, muscular skeletal infections, necrotizing fasciitis, biliary tract infection, osteomyelitis, bacterial prostatitis, native valve endocarditis, cystic fibrosis pneumonia, or meloidosis. In an embodiment, the condition is a nosocomial infection; preferably the infection is ICU pneumonia or an infection associated with sutures, exit sites, arteriovenous sites, scleral buckles, contact lenses, urinary catheter cystitis, peritoneal dialysis (CAPD) peritonitis, IUDs, endotracheal tubes, Hickman catheters, central venous catheters, mechanical heart valves, vascular grafts, biliary stent blockage, orthopedic devices, or penile prostheses. In an embodiment, the infection is a skin infection, a burn infection, or a wound infection. According to this aspect, the subject may preferably be an immunocompromised individual.
The present invention further provides a method for treating or preventing biofilm formation on a surface, the method comprising contacting said surface with one or more compounds in an amount effective for affecting biofilm formation of the present invention. In an embodiment, the method further comprises contacting the surface with one or more antibacterial compounds appropriate for the application, prior to, at the same time as or after contact with the one or more compounds of this invention. In an embodiment, the surface is a non-biological surface. In an embodiment, the surface is a natural surface. In an embodiment, the surface is a surface of a plant, seed, wood, fiber or hair. In an embodiment, the surface is a biological surface; preferably the surface is a surface of a tissue, membrane, or skin. In an embodiment, the surface is a hard surface; preferably the surface comprises a metal, an organic polymer, an inorganic polymer, a natural elastomer, a synthetic elastomer, glass, wood, paper, concrete, rock, marble, gypsum, or ceramic. In an embodiment, the said surface is coated or wherein the surface is a coating; in a preferred embodiment, the coating comprises enamel, varnish, or paint.
In an embodiment of this aspect, the surface is a soft surface, and may be the surface of a fiber comprising a yarn, a textile, a vegetable fiber, or rock wool. In another embodiment, the surface is a porous surface. In an embodiment, the surface is a surface of process equipment or components of cooling equipment. In a preferred embodiment, the process equipment is or is a component of a cooling tower, a water treatment plant, a dairy processing plant, a food processing plant, a chemical process plant, or a pharmaceutical process plant. In a preferred embodiment the surface is that of a filter or a membrane filter.
In an embodiment of this aspect, the surface is a surface of a toilet bowl, a bathtub, a drain, a high-chair, a counter top, a vegetable, a meat processing room, a butcher shop, food preparation areas, an air duct, an air-conditioner, a carpet, paper or woven product treatment, a diaper, personal hygiene products and a washing machine. In another embodiment, the surface is an industrial surface or a medical surface; preferably the surface is a surface in a hospital, a veterinary hospital, a mortuary, or a funeral parlor.
In another aspect, the compounds of the present invention are useful as a component of a dentifrice, a mouthwash, or a composition for the treatment of dental caries; for treatment of acne; or for cleaning and/or disinfecting contact lenses. The compounds of the present invention are further useful for incorporation into the surface of a medical device or an implant device. Preferably the implant device is an artificial heart valve, hip joint, an indwelling catheter, pacemaker, or surgical pin. The compounds of the present invention are further useful as an antifouling coating. The present invention further provides an optical lens, wherein at least a part of a surface of the lens is associated with one or more compounds of the present invention. Preferably, the optical lens is a contact lens.
In another aspect, the present invention provides a biofilm removing or inhibiting composition comprising one or more compounds of the present invention in an amount effective for removing or inhibiting biofilm formation and a vehicle or carrier, wherein the amount of the mixture is effective to remove or disrupt a bacterial biofilm or inhibit normal biofilm formation. An embodiment of this aspect may further comprise a surfactant selected from the group consisting of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a biological surfactant, and any combination of these; or a compound selected from the group consisting of an antibacterial which includes among others a biocide, a fungicide, an antibiotic, and any combination of these.
In another aspect, the present invention provides a method of removing a biofilm from a surface, the method comprising the step of administering a cleaning-effective amount of one or more compounds of the present invention to a biofilm-containing surface. A preferred method of this aspect comprises the step of administering an effective amount of one or more compounds of the present invention to the surface, wherein the amount is effective to prevent biofilm formation. Such a surface may be a hard or rigid surface or a surface selected from the group consisting of glazed ceramic, porcelain, glass, metal, wood, chrome, plastic, vinyl, composite materials (such as Formica® (Formica Corporation, Cincinnati, Ohio), and the surface of a drainpipe. In an embodiment, the surface is a soft or flexible surface, or the surface is selected from the group consisting of a shower curtain or liner, upholstery, laundry, clothing, and carpeting. In an embodiment, the surface is a biological surface and the effective amount is a therapeutically effective amount for application to the biological surface for inhibiting biofilm formation. The compounds of the present invention are useful in particular, for removing or disrupting a biofilm produced by a bacterium of the class Pseudomonas , a bacterium is of the species Pseudomonas aeruginosa , or an organism selected from the group consisting of bacteria, algae, fungi and protozoa. In a specific aspect, this method further comprises a step of applying or administering to a biofilm-containing surface an antibacterial compound before, at the same time as or after applying or administering the one or more compounds of this invention.
In another aspect, the invention provides a medicament for treating an infection or for disruption of a biofilm which comprises one or more of the compounds of this invention e.g., those of formulas I-VI, and a method for making a medicament which comprises one or more of the compounds of this invention. In particular, the method comprises the step of combining one or more compounds of this invention with a pharmaceutically acceptable carrier to form a pharmaceutical composition for treatment of infection and/or biofilm formation. In another particular embodiment, the method further comprises combining an antibacterial compound appropriate for the application to a medicament along with one or more compounds of this invention.
Without wishing to be bound by any particular theory, there can be discussion herein of beliefs or understandings of underlying principles relating to the invention. It is recognized that regardless of the ultimate correctness of any mechanistic explanation or hypothesis, an embodiment of the invention can nonetheless be operative and useful.
BRIEF DESCRIPTION OF THE FIGURES
FIG. 1 (2 pages) illustrates exemplary HG groups.
FIG. 2 (3 pages) illustrates exemplary HG groups.
FIG. 3 illustrates exemplary A groups.
FIG. 4 provides structures (and reference numbers) of exemplary non-homoserine lactone based autoinducer analogs synthesized by the method highlighted in Scheme 1.
FIG. 5A is a bar graph showing the results of agonism assay for initial heterocyclic and carbocyclic library (Scheme 1) shown as a percent of the positive control. The black bars are DH5α (pJN105L+pSC11) and the grey bars are PA01 MW1 (pUM15). Agonism positive control=activity of the reporter strain at full turn on for the strain. Full turn on for each strain: DH5α (pJN105L+pSC11)—100 nM OdDHL; PA01 MW1 (pUM15)—100 μM OdDHL. Negative control (Neg)=bacteria in the absence of natural and synthetic ligand. Error bars=standard deviation of the mean of triplicate samples.
FIG. 5B is a bar graph showing the results of agonism assay for initial heterocyclic and carbocyclic library (Scheme 1) shown as a percent of the positive control. Antagonism positive control (Pos)=activity of the reporter strain in the absence of synthetic ligand at the EC50 value for the strain. Strain EC50 values: DH5α (pJN105L+pSC11)—10 nM OdDHL; PA01 MW1 (pUM15)—1 μM OdDHL. Negative control (Neg)=bacteria in the absence of natural and synthetic ligand. Error bars=standard deviation of the mean of triplicate samples.
FIG. 6 provides structures (with reference numbers) of the racemic thiolactone library prepared as illustrated in Scheme 2.
FIGS. 7A and 7B are bar grafts presenting results of agonism ( 7 A) and antagonism ( 7 B) assays for the racemic thiolactone library ( FIG. 6 ). The biological testing conditions were the same as described in FIGS. 5A and 5B , respectively.
FIG. 8 provides structures (with reference numbers) of the enantiopure thiolactone library and EDC couplings.
FIGS. 9A-9H are bar grafts comparing agonism and antagonism of the racemic and enantiopure compounds of Libraries of FIG. 6 and FIG. 8 . All synthetic ligands were tested at 10 μM using standard methods described in FIGS. 5A and 5B .
FIGS. 10A and B are graphs comparing the functional half-lives of autoinducers as described in Example 4.
FIG. 11 provides structures (with reference numbers) of compounds having glycine ethyl ester structures.
FIGS. 12A and 12B are bar graphs with results of activity assays of the glycine ethyl ester library (for agonism 12 A and antagonism 12 B) according to the assay conditions described in FIGS. 5A and 5B .
FIG. 13 provides structures (with reference numbers) of an exemplary library having cyclopentyl amine head groups.
FIG. 14 provides structures (with reference numbers) of an exemplary library having aniline head groups.
FIGS. 15A and 15B are bar graphs with results of activity assays of the compounds of FIGS. 13 and 14 (for agonism 15 A and antagonism 15 B) according to the assay conditions described in FIGS. 5A and 5B .
DETAILED DESCRIPTION OF THE INVENTION
Unless defined otherwise, all technical and scientific terms used herein have the broadest meanings as commonly understood by one of ordinary skill in the art to which this invention pertains. In addition, hereinafter, the following definitions apply:
Quorum sensing assays conducted as described herein can be used to assess whether or no a given compound of the invention is a quorum sensing agonist or antagonist of a given bacterium, particularly a given Gram-Negative bacterium. It will be appreciated by one of ordinary skill in the art that assays other than those described herein can be employed to assess activation of or inhibition of biofilm formation as well as the effect of compounds of this invention on bacterial growth.
As defined herein, “contacting” means that a compound of the present invention is provided such that it is capable of making physical contact with another element, such as a microorganism, a microbial culture, a biofilm, or a substrate. In another embodiment, the term “contacting” means that a compound of the present invention is introduced into a subject receiving treatment, and the compound is allowed to come in contact in vivo.
Compounds of this invention that disrupt bacterial quorum sensing and biofilm formation can be used in combination with antimicrobial and antibacterial compounds (other than compounds which inhibit quorum sensing). The terms antimicrobial and antibacterial are employed broadly herein to refer to any compound that exhibits a growing inhibition activity on a microorganism or bacterium, respectively. A subset of such antimicrobial and antibacterial compounds are pharmaceutically acceptable for use in the treatment of humans and animals. A subset of antimicrobial and antibacterial compounds are biocides. A subset of antimicrobial and antibacterial compounds are antibiotics. In specific embodiments, compounds of the invention which are inhibitors or quorum sensing and biofilm formation are used to augment or facilitate the action of convention antibiotic treatment. The invention provides methods in which contact with or treatment with one or more quorum sensing compounds of the invention which inhibit quorum sensing is combined with contract with or treatment with one or more antimicrobial or antibacterial compounds. The invention provides methods in which contact with or treatment with one or more quorum sensing compounds of the invention which inhibit quorum sensing is combined with contract with or treatment with one or more antibiotics. Antibiotics include among others beta-lactam antibiotics, cephaosporins, clavulanic acid and derivatives thereof, aminoglycosides, tetracyclines, macrolide antibiotics.
Quorum sensing inhibitors of the invention can also generally be combined with antimicrobial agents, including antifungal agents, and antiviral agents.
In some cases, combination of one or more quorum sensing inhibitor of this invention with one or more antibacterial compound, antimicrobial compound or antiviral agent can enhance the activity of one or more antibacterial compound, antimicrobial compound or antiviral agent. In some case the combination of one or more quorum sensing inhibitor with one or more antibacterial compound, antimicrobial compound or antiviral agent synergizes the activity of the one or more antibacterial compound, antimicrobial compound or antiviral agent.
One or more quorum sensing inhibitor compounds of this invention can be combined with one or more antibacterial compounds, one or more antimicrobial compounds, one or more antiviral compounds and more specifically one or more antibiotics in pharmaceutically acceptable compositions useful for treatment of infections. Such pharmaceutical compositions typically further comprise a pharmaceutically acceptable carrier. Such combination compositions and medicaments can be employed for treatment of infection.
Contact with or treatment employing one or more quorum sensing inhibitor compounds of this invention can be combined with contact with or treatment with one or more antibacterial compounds, one or more antimicrobial compounds, one or more antiviral compounds and more specifically one or more antibiotics. In this case, contact or treatment is with one or more separate pharmaceutical composition which may be put in contact with the area to be treated (e.g., applied to a surface, including a biological surface) or administered to a subject at the same time or at different times. The quorum sensing inhibitor can be applied or administered before, after or at the same time as the antibacterial compound, antimicrobial compound or antiviral compound is applied or administered.
Aliphatic groups include straight chain, branched, and cyclic groups having a carbon backbone having from 1 to 30 carbon atoms. Aliphatic groups include alkyl groups, alkenyl groups, alkynyl groups, and aryl groups. Aliphatic groups are optionally substituted with one or more non-hydrogen substituents. Substituted aliphatic groups include among others those which are substituted with aryl groups, which in turn can be optionally substituted. Substituted aliphatic groups include fully halogenated or semihalogenated aliphatic groups, such as aliphatic groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. Substituted aliphatic groups include fully fluorinated or semifluorinated aliphatic groups, such as aliphatic groups having one or more hydrogens replaced with one or more fluorine atoms. Aliphatic groups are optionally substituted with one or more protecting groups.
Alkyl groups include straight-chain, branched and cyclic alkyl groups. Alkyl groups include those having from 1 to 30 carbon atoms. Alkyl groups include small alkyl groups having 1 to 3 carbon atoms. Alkyl groups include medium length alkyl groups having from 4-10 carbon atoms. Alkyl groups include long alkyl groups having more than 10 carbon atoms, particularly those having 10-30 carbon atoms. Cyclic alkyl groups include those having one or more rings. Cyclic alkyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring and particularly those having a 3-, 4-, 5-, 6-, 7-, or 8-member ring. The carbon rings in cyclic alkyl groups can also carry aliphatic groups. Cyclic alkyl groups can include bicyclic and tricyclic alkyl groups. Alkyl groups are optionally substituted with one or more non-hydrogen substituents. Substituted alkyl groups include among others those which are substituted with aliphatic groups, which in turn can be optionally substituted. Specific alkyl groups include methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, s-butyl, t-butyl, cyclobutyl, n-pentyl, branched-pentyl, cyclopentyl, n-hexyl, branched hexyl, and cyclohexyl groups, all of which are optionally substituted. Substituted alkyl groups include fully halogenated or semihalogenated alkyl groups, such as alkyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. Substituted alkyl groups include fully fluorinated or semifluorinated alkyl groups, such as alkyl groups having one or more hydrogens replaced with one or more fluorine atoms.
An alkoxy group is an alkyl group, as broadly discussed above, linked to oxygen and can be represented by the formula R—O—.
Alkenyl groups include straight-chain, branched and cyclic alkenyl groups. Alkenyl groups include those having 1, 2 or more double bonds and those in which two or more of the double bonds are conjugated double bonds. Alkenyl groups include those having from 2 to 20 carbon atoms. Alkenyl groups include small alkenyl groups having 2 to 3 carbon atoms. Alkenyl groups include medium length alkenyl groups having from 4-10 carbon atoms. Alkenyl groups include long alkenyl groups having more than 10 carbon atoms, particularly those having 10-20 carbon atoms. Cyclic alkenyl groups include those having one or more rings. Cyclic alkenyl groups include those in which a double bond is in the ring or in an alkenyl group attached to a ring. Cyclic alkenyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring and particularly those having a 3-, 4-, 5-, 6- or 7-member ring. The carbon rings in cyclic alkenyl groups can also carry aliphatic groups. Cyclic alkenyl groups can include bicyclic and tricyclic aliphatic groups. Alkenyl groups are optionally substituted with one or more non-hydrogen substituents. Substituted alkenyl groups include among others those which are substituted with aliphatic groups, which groups in turn can be optionally substituted. Specific alkenyl groups include ethenyl, prop-1-enyl, prop-2-enyl, cycloprop-1-enyl, but-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl, pent-1-enyl, pent-2-enyl, branched pentenyl, cyclopent-1-enyl, hex-1-enyl, branched hexenyl, cyclohexenyl, all of which are optionally substituted. Substituted alkenyl groups include fully halogenated or semihalogenated alkenyl groups, such as alkenyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. Substituted alkenyl groups include fully fluorinated or semifluorinated alkenyl groups, such as alkenyl groups having one or more hydrogens replaced with one or more fluorine atoms.
Alkynyl groups include straight-chain, branched and cyclic alkynyl groups. Alkynyl groups include those having 1, 2 or more triple bonds and those in which two or more of the triple bonds are conjugated triple bonds. Alkynyl groups include those having from 2 to 20 carbon atoms. Alkynyl groups include small alkynyl groups having 2 to 3 carbon atoms. Alkynyl groups include medium length alkynyl groups having from 4-10 carbon atoms. Alkynyl groups include long alkynyl groups having more than 10 carbon atoms, particularly those having 10-20 carbon atoms. Cyclic alkynyl groups include those having one or more rings. Cyclic alkynyl groups include those in which a triple bond is in the ring or in an alkynyl group attached to a ring. Cyclic alkynyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring and particularly those having a 3-, 4-, 5-, 6- or 7-member ring. The carbon rings in cyclic alkynyl groups can also carry aliphatic groups. Cyclic alkynyl groups can include bicyclic and tricyclic aliphatic groups. Alkynyl groups are optionally substituted with one or more non-hydrogen substituents. Substituted alkynyl groups include among others those which are substituted with alkyl or aryl groups, which groups in turn can be optionally substituted. Alkynyl groups include acetyl, methylacetyl, 1-pentynyl, and 2-pentynyl, all of which are optionally substituted. Substituted alkynyl groups include fully halogenated or semihalogenated alkynyl groups, such as alkynyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. Substituted alkynyl groups include fully fluorinated or semifluorinated alkynyl groups, such as alkynyl groups having one or more hydrogens replaced with one or more fluorine atoms.
Aryl groups include groups having one or more 5- or 6-member aromatic or heteroaromatic rings. Aryl groups can contain one or more fused aromatic rings. Heteroaromatic rings can include one or more N, O, or S atoms in the ring. Heteroaromatic rings can include those with one, two or three N, those with one or two O, and those with one or two S, or combinations of one or two or three N, O or S. Aryl groups are optionally substituted with one or more non-hydrogen substituents. Substituted aryl groups include among others those which are substituted with alkyl or alkenyl groups, which groups in turn can be optionally substituted. Specific aryl groups include phenyl groups, biphenyl groups, pyridinyl groups, and naphthyl groups, all of which are optionally substituted. Substituted aryl groups include fully halogenated or semihalogenated aryl groups, such as aryl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. Substituted aryl groups include fully fluorinated or semifluorinated aryl groups, such as aryl groups having one or more hydrogens replaced with one or more fluorine atoms. The term heteroaryl is used for aryl groups having one or more heteroaromatic rings. Aryl groups include those that are not heteroaryl groups.
Arylalkyl groups are alkyl groups substituted with one or more aryl groups wherein the alkyl groups optionally carry additional substituents and the aryl groups are optionally substituted. Specific alkylaryl groups are phenyl-substituted alkyl groups, e.g., phenylmethyl groups. Alkylaryl groups are alternatively described as aryl groups substituted with one or more alkyl groups wherein the alkyl groups optionally carry additional substituents and the aryl groups are optionally substituted. Specific alkylaryl groups are alkyl-substituted phenyl groups such as methylphenyl. Substituted arylalkyl groups include fully halogenated or semihalogenated arylalkyl groups, such as arylalkyl groups having one or more alkyl and/or aryl having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
The term “heterocyclic or heterocyclyl” generically refers to a monoradical that contains at least one ring of atoms, which may be a saturated, unsaturated wherein one or more carbons of the ring are replaced with a heteroatom (a non-carbon atom) To satisfy valence the heteroatom may be bonded to H or a substituent groups. Ring carbons may be replaced with —O—, —S—, —NR—, —N═ among others. More specifically heterocyclic groups can contain one or two 4-6 member rings wherein two rings may be fused. In specific embodiments, one or two rings of the heterocyclic group can contain one, two or three heteroatoms, particularly —O—, —S—, —NR— or —N═ and combinations of such heteroatoms.
Protecting groups are groups substituted onto an aliphatic hydrocarbon for protection of one or more substituents, for example protection of alcohols, amines, carbonyls, and/or carboxylic acids. Protecting groups include, but are not limited to, acetyl groups, MEM groups, MOM groups, PMB groups, Piv groups, THP groups, TMS groups, TBDMS groups, TIPS groups, methyl ethers, Cbz groups, BOC groups, FMOC groups, benzyl groups, PMP groups, acetal groups, ketal groups, acylal groups, dithiane groups, methyl esters, benzyl esters, t-butyl esters, and silyl esters. These and other protecting groups known in the art of organic synthesis may be optionally used as a substituent of an aliphatic group.
Optional substitution of aliphatic groups includes substitution with one or more aliphatic groups, wherein the aliphatic groups are optionally substituted.
Optional substituents for aliphatic groups include among others: —R, —COOR, —COR, —CON(R) 2 , —OCON(R) 2 , —N(R) 2 , —SR, —SO 2 R, —SOR, —OCOOR, —SO 2 N(R) 2 , and —OR; wherein R is selected from the group consisting of, a hydrogen, a halogen, an amine group, a substituted or unsubstituted unbranched C1-C12 acyclic aliphatic group, a substituted or unsubstituted branched C1-C12 acyclic aliphatic group, a substituted or unsubstituted C3-C8 cycloalkyl group, a substituted or unsubstituted C3-C8 cycloalkenyl group, a fluorinated C1-C12 alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocycle, a substituted or unsubstituted C1-C12 alkoxy group, a fluorinated C1-C12 alkoxy group, a hydroxyl group, a nitrile group, an azide group, a nitro group, an acyl group, a thiol group, a protecting group, —COOR, —COR, —CON(R) 2 , —OCON(R), —N(R) 2 , —SR, —SO 2 R, —SOR, —OCOOR, —SO 2 N(R) 2 , and —OR; additionally, R and R can form a ring.
Specific substituted alkyl groups include haloalkyl groups, particularly trihalomethyl groups and specifically trifluoromethyl groups. Specific substituted aryl groups include mono-, di-, tri, tetra- and pentahalo-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa-, and hepta-halo-substituted naphthalene groups; 3- or 4-halo-substituted phenyl groups, 3- or 4-alkyl-substituted phenyl groups, 3- or 4-alkoxy-substituted phenyl groups, 3- or 4-RCO-substituted phenyl, 5- or 6-halo-substituted naphthalene groups. More specifically, substituted aryl groups include acetylphenyl groups, particularly 4-acetylphenyl groups; fluorophenyl groups, particularly 3-fluorophenyl and 4-fluorophenyl groups; chlorophenyl groups, particularly 3-chlorophenyl and 4-chlorophenyl groups; methylphenyl groups, particularly 4-methylphenyl groups, and methoxyphenyl groups, particularly 4-methoxyphenyl groups.
As to any of the above groups which contain one or more substituents, it is understood, that such groups do not contain any substitution or substitution patterns which are sterically impractical and/or synthetically non-feasible. In addition, the compounds of this invention include all stereochemical isomers arising from the substitution of these compounds.
The term “effective amount” is used generically herein to refer to the amount of a given compound or in case of a mixture the combined amount of mixture components that provides a measureable effect for a listed function. For example, in certain aspects of the invention, a compound of the invention is contacted with an element in order to disrupt a biofilm and in this case, the effective amount or combined effective amount of the compound or compounds is that amount that shows a measurable disruption of a biofilm. The effective amount will vary dependent upon the stated function, the environment or element being contacted, the organism forming the biofilm or which is to be contacted, the state of development of the biofilm, among other conditions of the use of the compound. It will be understood by one of ordinary skill in the art, that for a given application, the effective amount can be determined by application of routine experimentation and without undue experimentation by methods that are described herein or that are known in the art.
The term “therapeutically effective amount” is used generically herein to refer to the amount of a given compound or in case of a mixture the combined amount of a mixture of components when administered to the individual (including a human, or non-human animal) that provides a measureable therapeutic effect for a listed disease, disorder or condition to at least partially ameliorate a symptom of such disease, disorder or condition. The present invention provides methods of treating disorders, diseases conditions and symptoms in a human or non-human animal and particularly in a human, by administering to an individual in need of treatment or prophylaxis, a therapeutically effective amount of one or more compounds of this invention to the individual in need thereof. The result of treatment can be partially or completely alleviating, inhibiting, preventing, ameliorating and/or relieving the disorder, condition or one or more symptoms thereof. As is understood in the art, the therapeutically effective amount of a given compound will depend at least in part upon, the mode of administration, any carrier or vehicle (e.g., solution, emulsion, etc.) employed, the extent of damage and the specific individual (human or non-human) to whom the compound is to be administered (age, weight, condition, sex, etc.). The dosage requirements needed to achieve the “therapeutically effective amount” vary with the particular compositions employed, the route of administration, the severity of the symptoms presented and the particular subject being treated. Based on the results obtained in standard pharmacological test procedures, projected daily dosages of active compound can be determined as is understood in the art.
Administration is intended to encompass administration of a compound, pharmaceutically acceptable salt, solvate or ester thereof alone or in a pharmaceutically acceptable carrier thereof or administration of a prodrug derivative or analog of a compound of this invention which will form an equivalent amount of the active compound or substance within the body. An individual in need of treatment or prophylaxis includes those who have been diagnosed to have a given disorder or condition and to those who are suspected, for example, as a consequence of the display of certain symptoms, of having such disorders or conditions.
Compounds of this invention can be employed in unit dosage form, e.g. as tablets or capsules. In such form, the active compound or more typically a pharmaceutical composition containing the active compound is sub-divided in unit dose containing appropriate quantities of the active compound; the unit dosage forms can be packaged compositions, for example, packaged powders, vials, ampules, pre-filled syringes or sachets containing liquids. The unit dosage form can be, for example, a capsule or tablet itself, or it can be the appropriate number of any such compositions in package form.
The dosage can vary within wide limits and as is understood in the art will have to be adjusted to the individual requirements in each particular case. By way of general guidance, the daily oral dosage can vary from about 0.01 mg to 1000 mg, 0.1 mg to 100 mg, or 10 mg to 500 mg per day of a compound of formulas herein or of the corresponding amount of a pharmaceutically acceptable salt thereof. The daily dose may be administered as single dose or in divided doses and, in addition, the upper limit can also be exceeded when this is found to be indicated.
Any suitable form of administration can be employed in the method herein. The compounds of this invention can, for example, be administered in oral dosage forms including tablets, capsules, pills, powders, granules, elixirs, tinctures, suspensions, syrups and emulsions. Oral dosage forms may include sustained release or timed release formulations. The compounds of this invention may also be administered topically, intravenously, intraperitoneally, subcutaneously, or intramuscularly, all using dosage forms well known to those of ordinary skill in the pharmaceutical arts.
Compounds of this invention can also be administered in intranasal form by topical use of suitable intranasal vehicles. For intranasal or intrabronchial inhalation or insulation, the compounds of this invention may be formulated into an aqueous or partially aqueous solution, which can then be utilized in the form of an aerosol. Administration includes any form of administration that is known in the art and is intended to encompass administration in any appropriate dosage form and further is intended to encompass administration of a compound, alone or in a pharmaceutically acceptable carrier. Pharmaceutical carriers are selected as is known in the art based on the chosen route of administration and standard pharmaceutical practice.
The compounds of this invention can also be administered to the eye, preferably as a topical ophthalmic formulation. The compounds of this invention can also be combined with a preservative and an appropriate vehicle such as mineral oil or liquid lanolin to provide an ophthalmic ointment. The compounds of this invention may be administered rectally or vaginally in the form of a conventional suppository. The compounds of this invention may also be administered transdermally through the use of a transdermal patch containing the active compound and a carrier that is inert to the active compound, is non toxic to the skin, and allows delivery of the agent for systemic absorption into the blood stream via the skin.
The compounds of the invention may be administered employing an occlusive device. A variety of occlusive devices can be used to release an ingredient into the blood stream such as a semipermeable membrane covering a reservoir containing the active ingredient with or without a carrier, or a matrix containing the active ingredient. Other occlusive devices are known in the literature.
Pharmaceutical compositions and medicaments of this invention comprise one or more compounds in combination with a pharmaceutically acceptable carrier, excipient, or diluent. Such compositions and medicaments are prepared in accordance with acceptable pharmaceutical procedures, such as, for example, those described in Remington's Pharmaceutical Sciences, 17th edition, ed. Alfonoso R. Gennaro, Mack Publishing Company, Easton, Pa. (1985), which is incorporated herein by reference in its entirety. The invention also encompasses method for making a medicament employing one or more compounds of this invention which exhibit a therapeutic effect.
Pharmaceutically acceptable carriers are those carriers that are compatible with the other ingredients in the formulation and are biologically acceptable. Carriers can be solid or liquid. Solid carriers can include one or more substances that can also act as flavoring agents, lubricants, solubilizers, suspending agents, fillers, glidants, compression aids, binders, tablet-disintegrating agents, or encapsulating materials. Liquid carriers can be used in preparing solutions, suspensions, emulsions, syrups and elixirs. The active ingredient can be dissolved or suspended in a pharmaceutically acceptable liquid carrier such as water (of appropriate purity, e.g., pyrogen-free, sterile, etc.), an organic solvent, a mixture of both, or a pharmaceutically acceptable oil or fat. The liquid carrier can contain other suitable pharmaceutical additives such as, for example, solubilizers, emulsifiers, buffers, preservatives, sweeteners, flavoring agents, suspending agents, thickening agents, colors, viscosity regulators, stabilizers or osmo-regulators. Compositions for oral administration can be in either liquid or solid form.
Suitable solid carriers include, for example, calcium phosphate, magnesium stearate, talc, sugars, lactose, dextrin, starch, gelatin, cellulose, methyl cellulose, sodium carboxymethyl cellulose, polyvinylpyrrolidine, low melting waxes and ion exchange resins. Suitable examples of liquid carriers for oral and parenteral administration include water of appropriate purity, aqueous solutions (particularly containing additives, e.g. cellulose derivatives, sodium carboxymethyl cellulose solution), alcohols (including monohydric alcohols and polyhydric alcohols e.g. glycols) and their derivatives, and oils. For parenteral administration, the carrier can also be an oily ester such as ethyl oleate and isopropyl myristate. Sterile liquid carriers are used in sterile liquid form compositions for parenteral administration. The liquid carrier for pressurized compositions can be halogenated hydrocarbon or other pharmaceutically acceptable propellant. Liquid pharmaceutical compositions that are sterile solutions or suspensions can be administered by, for example, intramuscular, intraperitoneal or subcutaneous injection. Sterile solutions can also be administered intravenously. Compositions for oral administration can be in either liquid or solid form. The carrier can also be in the form of creams and ointments, pastes, and gels. The creams and ointments can be viscous liquid or semisolid emulsions of either the oil-in-water or water-in-oil type. Pastes comprised of absorptive powders dispersed in petroleum or hydrophilic petroleum containing the active ingredient can also be suitable.
The term “pharmaceutically acceptable salts” refers to those salts which retain the biological effectiveness and properties of the free bases or free acids, which are not biologically or otherwise undesirable. The salts are formed with inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid and the like, preferably hydrochloric acid, and organic acids such as acetic acid, propionic acid, glycolic acid, pyruvic acid, oxylic acid, maleic acid, malonic acid, succinic acid, fumaric acid, tartaric acid, citric acid, benzoic acid, cinnamic acid, mandelic acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, salicylic acid, N-acetylcystein and the like.
In addition these salts may be prepared from addition of an inorganic base or an organic base to the free acid. Salts derived from an inorganic base include, but are not limited to, the sodium, potassium, lithium, ammonium, calcium, magnesium salts and the like. Salts derived from organic bases include, but are not limited to salts of primary, secondary, and tertiary amines, substituted amines including naturally occurring substituted amines, cyclic amines and basic ion exchange resins, such as isopropylamine, trimethylamine, diethylamine, triethylamine, tripropylamine, ethanolamine, lysine, arginine, N-ethylpiperidine, piperidine, polyimine resins and the like. Compounds of formula I can also be present in the form of zwitterions.
Pharmaceutically acceptable salts comprise pharmaceutically-acceptable anions and/or cations. Pharmaceutically-acceptable cations include among others, alkali metal cations (e.g., Li+, Na+, K+), alkaline earth metal cations (e.g., Ca2+, Mg2+), non-toxic heavy metal cations and ammonium (NH4+) and substituted ammonium (N(R′)4+, where R′ is hydrogen, alkyl, or substituted alkyl, i.e., including, methyl, ethyl, or hydroxyethyl, specifically, trimethyl ammonium, triethyl ammonium, and triethanol ammonium cations). Pharmaceutically-acceptable anions include among other halides (e.g., Cl−, Br−), sulfate, acetates (e.g., acetate, trifluoroacetate), ascorbates, aspartates, benzoates, citrates, and lactate.
Compounds of the invention can have prodrug forms. Prodrugs of the compounds of the invention are useful in the methods of this invention. Any compound that will be converted in vivo to provide a biologically, pharmaceutically or therapeutically active form of a compound of the invention is a prodrug. Various examples and forms of prodrugs are well known in the art. Examples of prodrugs are found, inter alia, in Design of Prodrugs, edited by H. Bundgaard, (Elsevier, 1985), Methods in Enzymology, Vol. 42, at pp. 309-396, edited by K. Widder, et. al. (Academic Press, 1985); A Textbook of Drug Design and Development, edited by Krosgaard-Larsen and H. Bundgaard, Chapter 5, “Design and Application of Prodrugs,” by H. Bundgaard, at pp. 113-191, 1991); H. Bundgaard, Advanced Drug Delivery Reviews, Vol. 8, p. 1-38 (1992); H. Bundgaard, et al., Journal of Pharmaceutical Sciences, Vol. 77, p. 285 (1988); and Nogrady (1985) Medicinal Chemistry A Biochemical Approach, Oxford University Press, New York, pages 388-392).
The invention expressly includes pharmaceutically usable solvates of compounds according to formulas herein. The compounds of formula I can be solvated, e.g. hydrated. The solvation can occur in the course of the manufacturing process or can take place, e.g. as a consequence of hygroscopic properties of an initially anhydrous compound of formulas herein (hydration).
In specific embodiments herein, compounds 2, 13, 18E, 20E, 23E, 25E 30E, 32, 33, 34, 35, 36, 37, 38, 39 are particularly useful for disruption of bacterial quorum sensing and biofilm disruption, particularly in E. coli, V. fischeri and/or A. tumefaciens.
In specific embodiments herein, compounds 3, and 19E are particularly useful for activation of bacterial quorum sensing and biofilm formation, particularly in E. coli, V. fischeri and/or P. aeruginosa.
In specific embodiments herein, compounds 2, 13, 18E, 30E, 32, 33, 34, 35, 36, 37 are particularly useful for disruption of bacterial quorum sensing and biofilm disruption in E. coli . In specific embodiments, compounds 1E, 18E, 20E, 22E, 23E, 25E, 26E, 27E, 28E, 30E, 33, 34, 36, 38 and 39 are particularly useful for disruption of bacterial quorum sensing and biofilm disruption in V. fischeri . In specific embodiments herein, compounds 1E, 26E, 27E, and 30E are particularly useful for disruption of bacterial quorum sensing and biofilm formation, particularly in A. tumefaciens.
In specific embodiments herein, compounds 3, 14, 16, 17, 1E, 19E, 22E, 26E, 27E, 28E, and 31 are particularly useful for activation of bacterial quorum sensing and biofilm formation in E. coli . In specific embodiments herein compound 24E is particularly useful for activation of bacterial quorum sensing and biofilm formation in A. tumefaciens . In specific embodiments herein compound 19E is particularly useful for activation of bacterial quorum sensing and biofilm formation in V. fischeri . In specific embodiments herein compounds 3 and 1E are particularly useful for activation of bacterial quorum sensing and biofilm formation in P. aeruginosa.
In specific embodiments herein compounds of the formulas herein which exhibit 20% or more inhibition in quorum sensing antagonism assays as described in the examples herein are particularly useful for disruption of bacterial quorum sensing and bacterial biofilm formation. In specific embodiments herein compounds of the formulas herein which exhibit 50% or more inhibition in quorum sensing antagonism assays as described in the examples herein are particularly useful for disruption of bacterial quorum sensing and bacterial biofilm formation. In specific embodiments herein compounds of the formulas herein which exhibit 75% or more inhibition in quorum sensing antagonism assays as described in the examples herein are particularly useful for disruption of bacterial quorum sensing and bacterial biofilm formation.
In specific embodiments herein compounds of the formulas herein which exhibit 20% or more activation in quorum sensing agonism assays as described in the examples herein are particularly useful for activation of bacterial quorum sensing and bacterial biofilm formation. In specific embodiments herein compounds of the formulas herein which exhibit 50% or more activation in quorum sensing agonism assays as described in the examples herein are particularly useful for activation of bacterial quorum sensing and bacterial biofilm formation. In specific embodiments herein compounds of the formulas herein which exhibit 75% or more activation in quorum sensing agonism assays as described in the examples herein are particularly useful for activation of bacterial quorum sensing and bacterial biofilm formation.
Compounds of this invention are additionally useful as tools for use in research in the study of quorum sensing in bacteria.
Well-known methods for assessment of drugability can be used to further assess active compounds of the invention for application to given therapeutic application. The term “drugability” relates to pharmaceutical properties of a prospective drug for administration, distribution, metabolism and excretion. Drugability is assessed in various ways in the art. For example, the “Lipinski Rule of 5” for determining drug-like characteristics in a molecule related to in vivo absorption and permeability can be applied (C. A. Lipinski, F. Lombardo, B. W. Dominy, P. J. Feeney, Experimental and computational approaches to estimate solubility and permeability in drug discovery and development settings, Adv. Drug Del. Rev., 2001, 46, 3-26 and Arup K. Ghose, Vellarkad N. Viswanadhan, and John J. Wendoloski, A Knowledge-Based Approach in Designing Combinatorial or Medicinal Chemistry Libraries for Drug Discovery, J. Combin. Chem., 1999, 1, 55-68.) In general a preferred drug for oral administration exhibits no more than one violation of the following rules:
(1) Not more than 5 hydrogen bond donors (e.g., nitrogen or oxygen atoms with one or more hydrogens);
(2) Not more than 10 hydrogen bond acceptors (e.g., nitrogen or oxygen atoms);
(3) Molecular weight under 500 g/mol and more preferably between 160 and 480; and
(4) log P less than 5 and more preferably between −0.4 to +5.6 and yet more preferably −1<log P<2.
Compounds of this invention preferred for therapeutic application include those that do not violate one or more of 1-4 above.
Compounds of this invention preferred for therapeutic application include those having log P less than 5 and more preferably between −0.4 to +5.6 and yet more preferably −1<log P<2.
The compounds of this invention may contain one or more chiral centers. Accordingly, this invention is intended to include racemic mixtures, diasteromers, enantiomers and mixture enriched in one or more steroisomer. The scope of the invention as described and claimed encompasses the racemic forms of the compounds as well as the individual enantiomers and non-racemic mixtures thereof.
It is understood that this invention is not limited to the particular methodology, protocols, cell lines, and reagents described, as these may vary. 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 limit the scope of the present invention which will be limited only by the appended claims.
It must be noted that as used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural reference unless the context clearly dictates otherwise. Thus, for example, reference to “a cell” includes a plurality of such cells and equivalents thereof known to those skilled in the art, and so forth. As well, the terms “a” (or “an”), “one or more” and “at least one” can be used interchangeably herein.
As used herein, the term “treating” includes preventative as well as disorder remittent treatment. As used herein, the terms “reducing”, “suppressing” and “inhibiting” have their commonly understood meaning of lessening or decreasing.
In certain embodiments, the present invention encompasses administering the compounds useful in the present invention to a patient or subject. A “patient” or “subject”, used equivalently herein, refers to an animal. In particular, an animal refers to a mammal, preferably a human. The subject either: (1) has a condition remediable or treatable by administration of a compound of the invention; or (2) is susceptible to a condition that is preventable by administering a compound of this invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are now described. All publications mentioned herein are incorporated herein by reference for the purpose of describing and disclosing the chemicals, cell lines, vectors, animals, instruments, statistical analysis and methodologies which are reported in the publications which might be used in connection with the invention. Nothing herein is to be construed as an admission that the invention is not entitled to antedate such disclosure by virtue of prior invention.
The invention includes compounds of formula I which exhibit activity as antagonist of quorum sensing in bacteria, particularly specific bacteria disclosed herein. The invention also includes compounds of formula I which exhibit activity as agonist of quorum sensing in bacteria, particularly specific bacteria disclosed herein.
In an embodiment, compounds of formula I have activity as an agonist or antagonist of native quorum sensing compounds. In an embodiment, compounds of formula I can be used to selectively adjust the virulence, biofilm production, or symbiotic behavior of a quorum sensing bacteria. In an embodiment, compounds of formula I can be administered to a subject to initiate an immune response towards a quorum sensing bacteria.
In an embodiment, certain compounds are preferred for selectively adjusting the virulence, biofilm production, or symbiotic behavior of a particular species or strain of a particular species of quorum sensing bacteria. In an embodiment, preselected mixtures of L- and D-isomers of compounds of the present invention can be used to selectively adjust the virulence, biofilm production, or symbiotic behavior of a particular species or strain of a particular species of quorum sensing bacteria.
In an embodiment, the compounds of the present invention are useful as a combinatorial library comprising a preselected mixture of two or more compounds of the present invention. In an embodiment, the two or more compounds can each be used to separately selectively adjust the virulence, biofilm production, or symbiotic behavior of a particular species or strain of a particular species of quorum sensing bacteria.
When a group of substituents is disclosed herein, it is understood that all individual members of those groups and all subgroups, including any isomers and enantiomers of the group members, and classes of compounds that can be formed using the substituents are disclosed separately. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure. When a compound is described herein such that a particular isomer or enantiomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomer and enantiomer of the compound described individually or in any combination. When an atom is described herein, including in a composition, any isotope of such atom is intended to be included. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently. Every formulation or combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure.
All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art. For example, when a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (particularly in referenced patent documents), are not intended to be included in the claim.
The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention. It will be apparent to one of ordinary skill in the art that methods, devices, device elements, materials, procedures and techniques other than those specifically described herein can be applied to the practice of the invention as broadly disclosed herein without resort to undue experimentation. All art-known functional equivalents of methods, devices, device elements, materials, procedures and techniques described herein are intended to be encompassed by this invention. Whenever a range is disclosed, all subranges and individual values are intended to be encompassed. This invention is not to be limited by the embodiments disclosed, including any shown in the drawings or exemplified in the specification, which are given by way of example or illustration and not of limitation.
The terms and expressions which have been employed herein are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments, exemplary embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. The specific embodiments provided herein are examples of useful embodiments of the present invention and it will be apparent to one skilled in the art that the present invention may be carried out using a large number of variations of the devices, device components, methods steps set forth in the present description. As will be obvious to one of skill in the art, methods and devices useful for the present methods can include a large number of optional composition and processing elements and steps.
Many of the molecules disclosed herein contain one or more ionizable groups [groups from which a proton can be removed (e.g., —COOH) or added (e.g., amines) or which can be quaternized (e.g., amines)]. All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein. With regard to salts of the compounds herein, one of ordinary skill in the art can select from among a wide variety of available counterions those that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt may result in increased or decreased solubility of that salt.
Every formulation or combination of components described or exemplified herein can be used to practice the invention, unless otherwise stated.
Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition or concentration range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. It will be understood that any subranges or individual values in a range or subrange that are included in the description herein can be excluded from the claims herein.
All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art as of their publication or filing date and it is intended that this information can be employed herein, if needed, to exclude specific embodiments that are in the prior art. For example, when composition of matter are claimed, it should be understood that compounds known and available in the art prior to Applicant's invention, including compounds for which an enabling disclosure is provided in the references cited herein, are not intended to be included in the composition of matter claims herein.
As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms “comprising”, “consisting essentially of” and “consisting of” may be replaced with either of the other terms. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
One of ordinary skill in the art will appreciate that starting materials, biological materials, reagents, synthetic methods, purification methods, analytical methods, assay methods, and biological methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such materials and methods are intended to be included in this invention. The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention that in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.
The invention is further illustrated by the following non-limiting examples.
THE EXAMPLES
Example 1
Heterocycles and carbocycles were chosen as head groups for a library ( FIG. 4 ) in order to probe the orientation and electronics necessary for a positive binding interaction with Trp60, shown to be an important residue in the N-terminal domain of the LasR crystal structure. Fluorine was chosen as a lactone carbonyl mimic due to its ability to accept hydrogen bonds. Multiple fluorine aromatic substitutions were examined to determine if Trp60 could hydrogen bond to multiple atoms given the correct spatial orientation. Non-hydrogen bonding oxygen-containing moieties were chosen to examine the effects of non-hydrogen bonding electrostatic interactions. The library also contained carbocycles to explore the necessity of the Trp60 binding interaction. A thiolactone analog shown to be active in previous experiments was chosen to serve as a control compound for our bacterial strains. [Passador, L.; Tucker, K. D.; Guertin, K. R.; Journet, M. P.; Kende, A. S.; Iglewski, B. H., Functional analysis of the Pseudomonas aeruginosa Autoinducer PAI. J. Bacteriol. 1996, 178, 5995-6000.] The glycine ethyl ester and the alanine methyl ester were chosen to explore the effects of variations on synthetic ring-opened forms of the lactone unavailable to nature.
Based upon this design strategy, a 17 member non-lactone based library ( FIG. 4 ) was synthesized using solution-phase chemistry. To facilitate the ease of synthesis, a Meldrum's Acid derivative was used as a common intermediate. Reacting Meldrum's Acid with decanoyl chloride afforded the Meldrum's Acid derivative, which was refluxed with the desired amines to form the initial library (Scheme 1).
Scheme 1 is a general synthetic method for producing 3-oxo-dodecanoyal derivatives of the natural autoinducer for P. aeruginosa . DMAP=dimethyl amino pyridine. TEA=triethyl amine. R can, for example, be a unsubstituted or substituted heterocycle or carbocycle:
This method can be employed for synthesis of various compounds herein by choice of starting materials and routine adaptation of methods disclosed herein or of methods that are well-known in the art. This method can be used for synthesis of compounds, where R is various substituted and unsubstituted heterocyclic rings, in particular, where R is a ring substituted thiolactone group. Appropriate starting materials for making ring-substituted compounds of this inventions are readily available either form commercial sources or by known synthetic methods. Additional references which provide details useful in the synthesis of thiolactones of this invention include among others U.S. Pat. Nos. 3,840,534 and 3,926,965 and Krasncv et al. (1999) Russian J. Org. Chem. 35(4):572-577.
The initial library was tested for LasR agonistic and antagonistic activity in two strains: Escherichia coli DH5α (pJN105L+pSC11) [Lee, J. H.; Lequette, Y.; Greenberg, E. P., Activity of purified QscR, a Pseudomonas aeruginosa orphan quorum-sensing transcription factor. Mol. Microbiol. 2006, 59 (2), 602-609] and P. aeruginosa PA01 MW1 (pUM15) [Muh, U.; Schuster, M.; Heim, R.; Singh, A.; Olson, E.; Greenberg, E. P., Novel Pseudomonas aeruginosa Quorum-Sensing Inhibitors Identified in an Ultra-High-Throughput Screen. Antimicrob. Agents Chemother. 2006, 50, 3674-3679] ( FIGS. 5A and 5B ). Both strains allow for synthetic autoinducer mimic evaluation and contain a reporter gene that allows for a quantitative readout of QS activity. DH5α (pJN105L+pSC11) is a heterologous β-galactosidase E. coli reporter strain containing a plasmid for the P. aeruginosa LasR gene. The PA01 MW1 (pUM15) strain uses the natural P. aeruginosa background containing a LasI deletion and the gene for yellow fluorescent protein (YFP) under the control of the LasI promoter to evaluate the LasI/R activity. Since the PA01 MW1 (pUM15) strain evaluates LasR in the natural P. aeruginosa background, in contrast to the heterologous E. coli strain, an improved idea of the interplay between the isolated LasI/R system and the combination of LasI/R with other QS subsystems such as QscR can be determined. Furthermore, additional nuances of the natural system such as compound permeability are incorporated in assays using the PA01 MW1 (pUM15) strain.
The initial library was also tested in Vibrio fischeri ESI 114 (Δ-LuxI) [Lupp, C.; Urbanowski, M.; Greenberg, E. P.; Ruby, E. G., The Vibrio fischeri quorum-sensing systems ain and lux sequentially induce luminescence gene expression and are important for persistence in the squid host. Mol. Microbiol. 2003, 50 (1), 319-331] and Agrobacterium tumefaciens WCF (pCF372). [Zhu, J.; Beaber, J. W.; More, M. I.; Fuqua, C.; Eberhard, A.; Winans, S. C., Analogs of the autoinducer 3-oxooctanoyl-homoserine lactone strongly inhibit activity of the TraR protein of Agrobacterium tumefaciens . J. Bacteriol. 1998, 180 (20), 5398-5405.] However, activities were low to modest in these species, except for compound 1, which is a good antagonist in both strains. The general lack of activity in the V. fischeri and A. tumefaciens strains is to be expected considering that the library was designed for the P. aeruginosa LasR protein and reinforces previous work demonstrating that the length of the acyl tail is highly species dependent. [Geske, G. D.; O'Neill, J. C.; Miller, D. M.; Mattmann, M. E.; Blackwell, H. E., Modulation of Bacterial Quorum Sensing: Systematic Evaluation of N-Acylated Homoserine Lactones in Multiple Species and New Insights into Their Mechanism of Action. J. Am. Chem. Soc. 2007, 129, 13613-13625.]
This set of screening data provides several noteworthy discoveries. First, the thiolactone derivative of the P. aeruginosa natural ligand (1) is highly active in all strains tested—either as an agonist in the strains examining LasR activity [94% agonist in DH5α (pJN105L+pSC11) and 88% agonist in PA01 MW1 (pUM15)] or as an antagonist in the V. fischeri (LuxR; 92% inhibition) and A. tumefaciens (TraR; 65% inhibition) strains. The high degree of activity across these four strains suggests that the sulfur substitution in the lactone ring does not sufficiently alter the binding of 1 from the natural ligand and suggests that the electronics at that position are not critical for binding. Second, the cyclopentyl amine derivative (3) is an agonist in both strains testing for LasR activity and a modest antagonist in the V. fischeri strain. This is remarkable because the cyclopentyl amine head group lacks functionality for hydrogen bond acceptance, which has been proposed as critical for neutral ligand binding based on the LasR crystal structure. This suggests that either the lactone carbonyl's hydrogen bonds are not as crucial as originally thought, or that 3 binds in an alternative manner. Third, compound 2 is of interest for its antagonism capabilities in both strains evaluating the LasI/R system, even though there are no hydrogen bond acceptor substitutions, further questioning the proposed critical nature of the lactone carbonyl. Fourth, compound 14 provides some insight into the differences between the isolated LasI/R system in E. coli and the LasI/R system in the natural P. aeruginosa background. LasR appears to be strongly agonized by 14 in the E. coli strain, while assays using the natural P. aeruginosa background show slight antagonism rather than an agonistic effect. Compound 14 represented an excellent candidate for further testing in additional heterologous strains containing isolated QS subsystems like QscR and RhII/R.
Additional comparative data for several compounds of FIG. 4 is provided in Table 1
TABLE 1
E. coli
DH5α
(pJN105L +
P. aeruginosa
V. fischeri
A. Tumefaciens
pSC11)
PA01 MW1
ESI 114 (Δ-Luxl)
WCF (pCF372)
Compd
Antagonist
Agonist
Antagonist
Agonist
Antagonist
Agonist
Antagonist
Agonist
2
53.7
—
28.7
—
—
—
—
—
3
—
83.5
—
54.2
89.4
—
—
—
7
38.8
—
—
—
—
3.1
—
—
10
—
—
25.5
—
—
3.3
—
—
12
—
—
−6.6
4.0
34.9
3.0
−22.0
—
13
41.0
—
16.8
—
43.8
1.7
—
—
14
−67.7
73.0
37.8
—
14.6
—
—
—
Agonist results are reported as a percent of activation compared to the positive control.
Antagonist results are reported as a percent inhibition compared to a positive control.
Negative values indicate agonist properties detected in an antagonist assay.
Example 2
Focused Libraries—Racemic Thiolactone Library
Based upon the results of the initial library screen, focused libraries around the most active leads (1, 2, 3, 16 from FIG. 4 ) were developed. In these libraries, the identified head group remained identical while the 3-oxo-C12 acyl tail was replaced with mimics previously shown to be active in AHL libraries. [Geske, G. D.; O'Neill, J. C.; Miller, D. M.; Mattmann, M. E.; Blackwell, H. E., Modulation of Bacterial Quorum Sensing: Systematic Evaluation of N-Acylated Homoserine Lactones in Multiple Species and New Insights into Their Mechanism of Action. J. Am. Chem. Soc. 2007, 129, 13613-13625.]
The first focused library ( FIG. 6 ) was a racemic homoserine thiolactone library, synthesized from 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) couplings between homoserine thiolactone and the appropriate carboxylic acid (Scheme 2).
Scheme 2 provides EDC coupling synthesis to make the racemic thiolactone library illustrated in FIG. 6 .
This method can be employed for synthesis of various compounds herein by choice of starting materials and routine adaptation of methods disclosed herein or of methods that are well-known in the art. This method can be used for synthesis of compounds, where R is various substituted and unsubstituted heterocyclic rings, in particular, where R is a ring substituted thiolactone group. Appropriate starting materials for making ring-substituted compounds of this inventions are readily available either form commercial sources or by known synthetic methods. Additional references which provide details useful in the synthesis of thiolactones of this invention include among others U.S. Pat. Nos. 3,840,534 and 3,926,965 and Krasncv et al. (1999) Russian J. Org. Chem. 35(4):572-577.
The racemic thiolactone library was tested in the same LasR reporter strains as the initial library ( FIGS. 7A and 7B ). Differences between the isolated LasR reporter system and LasR reporter system in the natural P. aeruginosa background have been uncovered in this second generation library. All of the library members were active in the heterologous LasI/R system while inactive in the intact P. aeruginosa QS system. One possibility is that library members are regulating multiple competing QS pathways, resulting in net inactivity in the natural background. For this reason it is crucial to examine the LasI/R system in the natural P. aeruginosa background where additional QS subsystems are also present and not simply as an isolated system in the E. coli background. Differences in cell permeability, especially since P. aeruginosa is known to be less permeable than E. coli , could also account for the discrepancy in activity between the two strains.
Example 3
Focused Libraries—Enantiopure Thiolactone Library
After finding several active compounds in the racemic thiolactone library in the heterologous E. coli LasI/R strain and the V. Fischeri strain, a third generation library was designed containing the enantiopure thiolactone along with additional acyl chain mimics to further explore the structure-activity relationship of the thiolactone head group ( FIG. 8 ). The L enantiomer of the thiolactone was chosen based on previous studies that found the L enantiomer of P. aeruginosa 's natural autoinducer to be active and the D enantiomer to be inactive. [Geske, G. D.; O'Neill, J. C.; Miller, D. M.; Mattmann, M. E.; Blackwell, H. E., Modulation of Bacterial Quorum Sensing: Systematic Evaluation of N-Acylated Homoserine Lactones in Multiple Species and New Insights into Their Mechanism of Action. J. Am. Chem. Soc. 2007, 129, 13613-13625; Glansdorp, F. G.; Thomas, G. L.; Lee, J. K.; Dutton, J. M.; Salmond, G. P. C.; Welch, M.; Spring, D. R., Synthesis and stability of small molecule probes for Pseudomonas aeruginosa quorum sensing modulation. Org. Biomol. Chem. 2004, 2, 3329-3336.]
FIG. 8 provides structures (with reference numbers) of compounds of the enantiopure thiolactone library synthesized from a combination of Meldrum's acid precursors and EDC couplings.
The third generation thiolactone compounds were similarly tested in bacterial assays beside the racemic version, if synthesized, to determine the effect of stereochemistry on activity ( FIGS. 9A-9H ). FIGS. 9A-9H provide a comparison between racemic and enantiopure thiolactone analogs. All synthetic ligands were tested at 10 μM using standard methods described in FIGS. 5A and 5B . Compounds 24-30 of the enantiopure library were not compared to a racemic counterpart. If stereochemistry played a large role in binding, the enantiopure compounds were expected to have approximately twice the activity of the racemic compounds when screened at 10 μM total synthetic ligand in each case. In both strains testing for LasR activity, it appeared, however, that stereochemistry was not important for activity of the non-native thiolactones in contrast to the lactones. Without wishing to be bound by any particular theory, we presently believe that binding is likely less specific for the thiolactones compared to the natural lactone ligand, where it is known that the L enantiomer is far more active than the D enantiomer.
Dose response analysis for the active enantiopure thiolactone compounds was conducted to quantify the activity of the synthetic ligands (Table 2). The activity of the thiolactone head group alone became evident through compound 21E in the heterologous LasR strain, whose AHL analogue was found to have little activity. [Geske, G. D.; O'Neill, J. C.; Miller, D. M.; Mattmann, M. E.; Blackwell, H. E., Modulation of Bacterial Quorum Sensing: Systematic Evaluation of N-Acylated Homoserine Lactones in Multiple Species and New Insights into Their Mechanism of Action. J. Am. Chem. Soc. 2007, 129, 13613-13625.] Based on the results of the enantiopure thiolactone dose response data, it appears that relatively long or electron withdrawing side chains are excellent antagonists of LasR isolated in the E. coli background. However, natural ligand mimics 1E and 25E are strong agonists for the heterologous LasR system. All of the active compounds in PA01 MW1 (PUM15) ( P. aeruginosa natural background) were also active in E. coli DH5α (pJN105L+pSC11). However, a significant number of the compounds active in the E. coli DH5α (pJN105L+pSC11) strain were not active in the P. aeruginosa PA01 MW1 (PUM15) strain. These findings corroborate our hypothesis that when LasR is evaluated in the natural P. aeruginosa background a muted effect is may be seen due to the effects of the other QS systems present in intact P. aeruginosa , such as QscR and the PQS system. A variety of other effects could be contributing to the differences seen between the two strains, including differences in cell permeability.
TABLE 2
Table 2. The IC 50 and EC 50 values for the most active enantiopure
thiolactone library members.
DH5α
(pJN105L +
PA01 MW1
ESI 114 (Δ-
pSC11)
(pUM15)
Luxl)
WCF (pCF372
E. Coli
P. aeruginosa
V. fischeri
A. tumefaciens
IC 50
EC 50
IC 50
EC 50
IC 50
EC 50
IC 50
EC 50
Comp. #
(μM)
(μM)
(μM)
(μM)
(μM)
(μM)
(μM)
(μM)
1E
0.092
3.2
0.45
1.8
18E
0.40
0.77
19E
4.1
11
20E
7.2
21E
2.5
22E
1.8
23E
2.9
0.35
24E
0.35
20
25E
1.9
21
26E
0.14
0.13
2.8
27E
0.79
0.31
10
28E
1.1
0.84
30E
0.13
13
3.2
Activity differences between the two strains evaluating LasR raise questions about the integrity and degradation of the ligands since the incubation time in the assay for the heterologous strain is shorter than for the native P. aeruginosa strain. It is well known that the homoserine lactone ring, used by all of the bacterial species of interest as their autoinducer head group, is prone to hydrolysis at pH 7 and above. [Eberhard, A.; Widrig, C. A.; MaBath, P.; Schineller, J. B., Analogs of the autoinducer of bioluminescence in Vibrio fischeri . Arch. Microbiol. 1986, 146, 35-40; Schaefer, A. L.; Hanzelka, B. L.; Eberhard, A.; Greenberg, E. P., Quorum sensing in Vibrio fischeri : Probing autoinducer-LuxR interactions with autoinducer analogs. J. Bacteriol. 1996, 178, 2897-2901; Byers, J. T.; C., L.; Salmond, G. P. C.; Welch, M., Nonenzymatic turnover of an Erwinia carotovora quorum sensing signaling molecule. J. Bacteriol. 2002, 184, 1163-1171.] Previous literature has indicated that the P. aeruginosa natural autoinducer has a half-life of approximately two days in growth media at 37° C., while shorter chain AHLs degrade in even shorter periods of time. [Glansdorp, F. G.; Thomas, G. L.; Lee, J. K.; Dutton, J. M.; Salmond, G. P. C.; Welch, M.; Spring, D. R., Synthesis and stability of small molecule probes for Pseudomonas aeruginosa quorum sensing modulation. Org. Biomol. Chem. 2004, 2, 3329-3336; Yates, E. A.; Philipp, B.; Buckley, C.; Atkinson, S.; Chhabra, S. R.; Sockett, R. E.; Goldner, M.; Dessaux, Y.; Camara, M.; Smith, H.; Williams, P., N-Acylhomoserine lactones undergo lactonolysis in a pH-, temperature-, and acyl chain length dependent manner during growth of Yersinia pseudotuberculosis and Pseudomonas aeruginosa. Infect. Immun. 2002, 70, 5635-5646]
Finding QS antagonists and agonists that are more hydrolytically stable are of considerable interest, since molecules that hydrolyze rapidly are not ideal therapeutic agents or biological probes. While many of the compounds synthesized in the initial library are non-hydrolyzable, the thiolactone derivative of the natural ligand (1E) is hydrolyzable. However, the differences in activities between the thiolactone derivatives and the natural lactone derivatives make the thiolactone derivatives both worthwhile to pursue as a target and for further half-life experiments.
Table 3 provides a summary of data for the antagonism assay for compounds tested having thiolactone head groups against selected bacteria. Compounds exhibiting 50% or higher inhibition in assays with Escherichia coli and Agrobacterium tumefaciens and those exhibiting 20% or higher inhibition with Vibrio fischeri are preferred for applications for disrupting bacterial quorum sensing, particularly in Escherichia coli, Agrobacterium tumefaciens and Vibrio fischeri strains, and for inhibiting and/or disrupting biofilm formation, particularly in Escherichia coli, Agrobacterium tumefaciens and Vibrio fischeri strains.
TABLE 3
Antagonism Assay Data Thiolactone Libraries
E. coli
V. fischeri
A. tumefaciens
Comp #
Inhib %
Comp #
Inhib %
Comp #
Inhib %
18
80
1
99
26E
99
27E
78
24E
99
30E
93
18E
68
23
98
1
92
21
65
18
97
27E
78
26E
64
28E
93
1E
51
21E
61
1E
91
19
33
28E
59
18E
91
19E
30
23
56
23E
85
23E
26
22E
54
26E
80
18E
25
20
51
27E
78
21E
13
20E
48
22E
75
23
9
23E
45
20
70
25E
6
29E
17
22
68
21
−22
22
16
30E
62
20E
−24
19E
−3
20E
59
22E
−26
19
−13
25E
57
18
−60
24E
−30
29E
42
29E
−70
1
−40
21
34
28E
−78
1E
−61
19E
30
22
−80
25E
−93
21E
30
24E
−89
30E
−119
19
19
20
−107
Table 4 provides a summary of data for the agonism assay for compounds tested having thiolactone head groups with certain bacteria. Compounds exhibiting 50% or higher inhibition in assays with Escherichia coli and P. aeruginosa are preferred for applications for activating bacterial quorum sensing, particularly in Escherichia coli , and P. aeruginosa strains and for activating biofilm formation therein.
TABLE 4
Agonism Assay Data for Thiolactones
E. coli
P. aeruginosa
Comp #
Act %
Comp#
Act %
1E
102
1E
127
1
94
1
88
26E
85
30E
76
19
82
25E
42
19E
81
29E
22
22E
72
28E
20
23
9
21E
17
18E
8
22
10
27E
8
18
8
30E
6
20
7
22
4
18E
5
25E
4
19
5
29E
4
20E
4
21E
3
19E
3
18
2
22E
3
21
2
23
3
20
1
24E
3
28E
1
21
2
20E
0
23E
1
23E
0
26E
0
24E
0
27E
0
Example 4
Comparison of Functional Half-Lives of Autoinducers
A biologically based assay was developed to determine the functional half-life of the P. aeruginosa natural ligand, OdDHL, and the corresponding thiolactone analog (1E). This assay does not directly measure hydrolysis, but rather the ability of the degraded ligand to cause a QS response. However, previous experiments have shown that the hydrolysis half-life for the P. aeruginosa natural ligand, OdDHL, is approximately two days, while racemization of the chiral center was found to be less than 5% over the course of a week. [Glansdorp, F. G.; Thomas, G. L.; Lee, J. K.; Dutton, J. M.; Salmond, G. P. C.; Welch, M.; Spring, D. R., Synthesis and stability of small molecule probes for Pseudomonas aeruginosa quorum sensing modulation. Org. Biomol. Chem. 2004, 2, 3329-3336.] This data suggests that most ligand degradation is due to hydrolysis and not epimerization. In these cases the results were determined by NMR experiments conducted in deuterated buffers. Due to problems with the water solubility of OdDHL, a 50% solution of DMSO was used. Unfortunately, the use of high levels of DMSO reduces the biological relevance of the assay because large concentrations of DMSO cannot be tolerated by biological systems. Furthermore, the required concentrations of ligand are lower in a biologically based functional assay than in an NMR experiment because YFP production is much more sensitive than NMR, which requires relatively high concentrations.
In this assay, media, ligand, and antibiotics are prepared in Teflon-capped vials and allowed to incubate at 37° C. for predetermined times. P. aeruginosa cells from the strain PA01 MW1 (pUM15) were cultured overnight. These cells were then pelleted and washed with LB containing 50 mM MOPS. After washing, the cells were resuspended in a minimal amount of media containing antibiotics and were added to a 96 well plate containing the media, natural ligand, and antibiotic previously prepared and incubated for specific, predetermined times. At this point, the optical density at 600 nm of the cells was comparable to the optical density after subculturing the cells during a traditional assay. The 96 well plate was incubated for 8 hours and then analyzed for optical density and YFP fluorescence. Bacteria were cultured, pelleted, and washed before addition to the assay plate. A traditional PA01 MW1 assay is completed to analyze for ligand degradation. Fluorescence was normalized to cell density and time points were analyzed as a percentage of the ability of the freshly prepared natural ligand to agonize the P. aeruginosa system. Since we predict that the ligand degradation is a product of hydrolysis, we assumed a pseudo first order rate and plotted the natural log of the agonism as a percent of the fresh natural ligand versus time. The slope of the graph can be used to determine the half-life of the ligand according to the formula t½=ln(2)/slope ( FIGS. 10A and 10B ).
We found the half-life for the OdDHL natural ligand to be 48.2 hours. This value corresponds closely with the previously found hydrolysis half-life of approximately two days. [Glansdorp, F. G.; Thomas, G. L.; Lee, J. K.; Dutton, J. M.; Salmond, G. P. C.; Welch, M.; Spring, D. R., Synthesis and stability of small molecule probes for Pseudomonas aeruginosa quorum sensing modulation. Org. Biomol. Chem. 2004, 2, 3329-3336.]
A similar analysis found the half-life of the thiolactone analog of the OdDHL P. aeruginosa natural ligand (1E) to be 82.3 hours. In the case of both the natural ligand and the thiolactone analog, the half-life of the compounds are sufficiently long so that standard in vitro assays on the time scale of 8 hours or less are testing the ligand in its native form. This is important because previous work has shown that the ring open form of the natural ligand is inactive. [Yates, E. A.; Philipp, B.; Buckley, C.; Atkinson, S.; Chhabra, S. R.; Sockett, R. E.; Goldner, M.; Dessaux, Y.; Camara, M.; Smith, H.; Williams, P., N-Acylhomoserine lactones undergo lactonolysis in a pH-, temperature-, and acyl chain length dependent manner during growth of Yersinia pseudotuberculosis and Pseudomonas aeruginosa . Infect. Immun. 2002, 70, 5635-5646; Kapadnis, P. B.; Hall, E.; Ramstedt, M.; Galloway, W. R. J. D.; Welch, M.; Spring, D. R., Towards quorum-quenching catalytic antibodies. Chem. Commun. 2009, (5), 538-540.]
It is interesting to note that the half-life of 1E is slightly less than double the half-life of OdDHL, the natural ligand. This is particularly intriguing because one would expect the sulfur analog to have a faster hydrolysis rate from an electronics argument. Our current hypothesis is that although compound 1E is able to ring open faster than OdDHL, 1E is also able to recyclize at a faster rate than the natural ligand. Previous analysis of lactone hydrolysis has shown that once ring opened, the lactone does not reclose in appreciable quantities until under pH 2 due to differences in the mechanisms for ring opening and closing. [Yates, E. A.; Philipp, B.; Buckley, C.; Atkinson, S.; Chhabra, S. R.; Sockett, R. E.; Goldner, M.; Dessaux, Y.; Camara, M.; Smith, H.; Williams, P., N-Acylhomoserine lactones undergo lactonolysis in a pH-, temperature-, and acyl chain length dependent manner during growth of Yersinia pseudotuberculosis and Pseudomonas aeruginosa . Infect. Immun. 2002, 70, 5635-5646.} In order for the lactone ring to close, the pH must first approach the pKa of the carboxyl group so that significant amounts of the acid as opposed to the acid salt are present. The differences in ring opening and closing mechanisms may cause the natural ligand to take longer to ring open, but remain ring opened, while the sulfur analog would ring open faster and close back up again so that it would have a longer hydrolysis half-life than the natural ligand. Conversely, the sulfur's increased nucleophilicity may be able to hold the lactone ring together in aqueous solution better than the corresponding oxygen.
Example 5
Focused Libraries—Non-Hydrolyzable Head Groups
While many of the natural ligands for QS systems contain a lactone ring, it would be advantageous to find QS modulators that are not prone to hydrolysis or degradation. To this end focused libraries based on non-hydrolyzable head groups screened in the initial library were designed, synthesized, and screened. Head groups based upon glycine ethyl ester (16), cyclopentyl amine (3), and aniline (2) were chosen as particularly interesting non-hydrolyzable head groups based on activity in the initial library screens.
The glycine ethyl ester head group is particularly interesting because the stereochemistry has been removed from the head group. The glycine ethyl ester head group is derived from the lactone ring when a disconnection is made between the carbons 2 and 3 in the lactone ring. (Scheme 3).
While the compounds of this library ( FIG. 11 ) are non-natural analogs of the lactone ring, it is interesting that some activity can be observed. One characteristic of this library is that the compounds appear to be cooperative agonists because many of the library members show heightened activity in antagonistic assays and minimal activity in agonistic assays ( FIGS. 12A and 12B ). Compound 34 showed excellent antagonistic activity in V. fischeri . While most library members do not seem to fit as traditional agonists or antagonists, further analysis could yield important information about alternative binding sites or methods, or information about dimerization requirements.
Cyclopentyl amine and aniline were used to synthesize libraries to explore the activity of ligands with a lack of hydrogen bonding capabilities on the head group ( FIG. 13 (cyclopentyl amine library HG=cyclopentyl), FIG. 14 (analine library, HG=phenyl)). Agonism and antagonism assays, performed as described above, are illustrated in FIGS. 15A and 15B , respectively. While these carbocycles were active when appended with the 3-oxo dodecanoyal containing acyl chain, only moderate activities were observed when paired with acyl tail mimics. These studies show that viable agonists and antagonists can be found either by altering the head group of the natural ligand or by creating acyl tail mimics. However, when both the head group and the acyl tail are modified in the same molecule, the molecule doesn't always combine the activities of the two initial modifications. In fact, the dual modifications are frequently deleterious to the activity of the molecule.
Pursuing QS modulators that are either non-hydrolyzable or hydrolyze slowly allows for new biological probes or therapeutics. It is important for therapeutics to remain biologically active for extended periods of time yet be cleared from the body in a time dependent manner. Compounds like the thiolactone derivatives of this invention may serve as excellent therapeutics because they are active for longer periods of time than the natural lactone analogs, yet do lose activity in a time dependent fashion. | Compounds which modulate quorum sensing in quorum sensing bacteria. Compounds of the invention inhibit quorum sensing and/or activate quorum sensing in various bacteria. Compounds that inhibit quorum sensing are particularly useful for inhibition of detrimental bacterial biofilm formation. Compounds that activate quorum sensing are particularly useful for promoting growth and biofilm formation of beneficial bacterial. | 2 |
CROSS REFERENCE TO RELATED APPLICATION
The present application is based on and claims priority from Japanese Patent Application 2005-162648, filed Jun. 2, 2005, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a generator control device that controls a generator so as to effectively reduce hazardous components of engine exhaust gases.
2. Description of the Related Art
Usually, a vehicle-mounted generator is controlled by controlling its field current according to a battery condition so that the battery does not become over-discharged, as shown in JP-A 2000-4502 or U.S. Pat. No. 6,621,250. Because the generator is driven by an engine, the fuel consumption of the engine increases as the load of the engine becomes heavier. As the engine load increases due to increase in the output electric power of a generator, more hazardous gas components such as NOx component are emitted from the engine.
U.S. Pat. No. 5,336,932A discloses an engine control device to operate a generator only when the fuel consumption can be controlled within a low level. However, it is difficult to limit the hazardous components when a large amount of electric power is required generated.
SUMMARY OF THE INVENTION
Therefore, a main object of the invention is to provide an improved generator control device that can control hazardous components emitted from an engine when a generator is operated.
According to a feature of the invention, a generator control device for controlling a generator that is driven by an engine includes first means for calculating a required electric power, second means for calculating a difference relating to an amount of a hazardous gas component of engine exhaust gas between a first case in which the generator generates the required electric power and a second case in which the generator does not generate an electric power, and third means for controlling the generator to generate the required electric power if the difference is equal to or smaller than a first reference value.
Thus, a hazardous component can be controlled at a low level. The battery is mainly charged while the emission of hazardous components is within a low level.
Preferably the second means calculates a difference rate (CEM) in an amount of a hazardous component per an electric power to be generated. The difference rate makes the calculation easier. The third means may further detect current charged into and discharged from the battery, calculate a battery charge ratio, and control the generator to charge the battery if the battery charge ratio is not larger than a second reference value even if the difference rate is larger than the first reference value.
In addition, the second means may calculate a difference between a first amount of fuel consumption when the generator generates no electric power and a second amount of fuel consumption when the generator generates a required electric power so as to provide the difference rate, and the third means may control the generator according to an increase in fuel consumption. In this case, the third means may control the generator to operate in one of a fuel-economic generation range and an emission control generation range according to a predetermined condition. Further, the third means may control the generator to operate according to electric power consumption, or engine operating condition.
The second means may include correction means for correcting the difference relating to an amount of hazardous gas component according to engine coolant temperature, or EGR (Exhaust Gas Re-circulation) condition.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features and characteristics of the present invention as well as the functions of related parts of the present invention will become clear from a study of the following detailed description, the appended claims and the drawings. In the drawings:
FIG. 1 is a block diagram of a generator control system that includes a generator control device according to the first embodiment of the invention;
FIG. 2 is a graph showing a relationship between amounts of NOx component emitted from an engine and engine torques;
FIG. 3 is a flow diagram of a generation control routine of the generator control device according to the first embodiment;
FIG. 4 is a graph showing a relationship between fuel consumption rates and engine torques;
FIG. 5 is a flow diagram of a portion of a generation control routine of the generator control device according to the second embodiment of the invention;
FIG. 6 is a flow diagram of the rest of the generation control routine of the generator control device according to the second embodiment;
FIG. 7 is a flow diagram of a portion of a generation control routine of the generator control device according to the third embodiment of the invention;
FIG. 8 is a map defining a relationship between engine rotation speeds and engine torques;
FIG. 9 is a flow diagram of a generation control routine of the generator control device according to the fourth embodiment of the invention;
FIG. 10 is an electronic circuit formed on a circuit board according to the fifth embodiment of the invention; and
FIG. 11 is a flow diagram of a generation control routine of the generator control device according to the fifth embodiment.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
A generator control device according to the first embodiment of the invention will be described with reference to FIGS. 1-3 .
As shown in FIG. 1 , a generator control device 11 according to the first embodiment of the invention is connected to a battery 12 via a key switch 13 , an engine ignition system 14 , a fuel injection system 15 , an alternator (ac generator) 16 and a current sensor 17 . The generator control device 11 is powered by the battery 12 to control the ignition system 14 , the fuel injection system 16 as well as the generator 16 . The generator control device 11 calculates a charge ratio SOC of the battery 12 and controls the generator 16 according to the charge ratio SOC. In the calculation of the charge ratio SOC, each amount of current charged into or discharged from the battery 12 is accumulated. That is, the amount of the current charged into the battery 12 is added, and the amount of the current discharged from the battery 12 is subtracted.
As shown in FIG. 2 , the amount of the NOx component that is emitted from an engine varies as the engine torque changes. If the engine rotation speed is constant, the increase rate of the NOx component becomes higher when the engine rotation speed is low. On the other hand, the increase rate of the NOx component becomes lower than the increase rate of the engine torque when the engine rotation speed is high.
When the generator 16 generates a certain amount of electric power, a corresponding generation torque is added to the engine, resulting in change in the engine operating condition. This changes emission of the NOx component. Therefore, it is possible to control the emission of the NOx component by selecting the engine operating condition.
The generator control device 11 operates according to a generation control routine shown in FIG. 3 . The control routine is repeated at a certain cycle, such as 8 ms.
Firstly, at step S 101 , certain engine conditions, such as an engine rotation speed, an intake air ratio and a required electric power, are read. Incidentally, a required electric power is calculated based on a difference in the current charge ratio SOC between a current ratio and a target ratio.
Thereafter, a current engine torque is calculated from current engine conditions at S 102 . Subsequently, a required electric power is converted into the term of a required generation torque to generate the required electric power, which is stored into a RAM of the control device 11 at S 103 . At the next step S 104 , whether the alternator 16 is generating electric power or not is examined.
If the result of the examination at S 104 is Yes, the step goes to S 105 , where a current generation torque is calculated from the currently generated electric power and is stored into the RAM of the control device 11 . Subsequently at S 106 , the current generation torque is subtracted from the current engine torque to get an engine torque without electric generation, which is a torque necessary for the engine to operate when the alternator does not generate electric power.
If the result of the examination at S 104 is No on the other hand, the step goes to S 107 , where it is determined that the current engine torque is the engine torque without electric generation.
At the next step S 108 , the engine torque without electric generation calculated at S 106 and the required generation torque calculated at S 103 are added together to get an engine torque with electric generation, which is a torque necessary for the engine to operate when the alternator generates electric power.
At the next step S 109 , a no-generation emission rate of hazardous components (g/s) that corresponds to a current engine rotation speed and the engine torque without electric generation is calculated based on a map shown in FIG. 2 . The no-generation emission rate corresponds to an emission rate of hazardous components when the alternator 16 does not generate electric power. Incidentally, the map stores emission rates of hazardous components that are measured at normal engine operating conditions beforehand.
Thereafter, the step goes to S 110 , where a generation emission rate of hazardous components (g/s) that corresponds to a current engine rotation speed and the engine torque with electric generation is calculated based on the map. The generation emission rate corresponds to an emission rate of hazardous components when the alternator 16 generates an amount of electric power.
At the next step S 111 , a difference between the generation emission rate of hazardous components and no-generation emission rate of hazardous components is divided by a current electric power generated by the alternator 16 to obtain a difference rate CEM (g/s·kw). That is:
CEM g/s·kw=( RC 1- RC 2)/ P,
wherein RC 1 is a rate of hazardous components emitted while the alternator 16 is generating an electric power P, RC 2 is a rate of hazardous components emitted while the alternator 16 is not generating electric power.
Thus, an increase or decrease in the hazardous components per a unit of generated electric power can be calculated. Thereafter, the step goes to S 112 , where the difference rate CEM is compared with a preset reference value Ref 1 .
If the difference rate CEM is equal to or smaller than the reference value Ref 1 , Yes is issued, so that the step goes to S 113 , where a command electric power is set to the required electric power. In other words, it is determined that the increase in the hazardous components is within an allowable range.
If the difference rate CEM is larger than the reference value Re 1 , No is issued, so that the step goes to S 114 , where the charge ratio SOC of the battery 12 is compared with a reference value Ref 2 .
If the charge ratio SOC is equal to or smaller than the reference value Ref 2 , the step goes to S 113 , where the required electric power is set to the command electric power, as it is determined that the battery 12 is not normally charged. Therefore, the alternator 16 is controlled to generate an electric power sufficient to charge the battery 12 to increase the charge ratio SOC irrespective of increase in the difference rate CEM.
If, on the other hand, the charge ratio is larger than the reference value Ref 2 , the step goes to S 115 , where the command electric power is set to 0. Accordingly, the alternator is controlled to stop generation to decrease the hazardous components.
A generator control device according to the second embodiment of the invention will be described with reference to FIGS. 4-6 .
As shown in FIG. 4 , the fuel consumption rate varies with the engine rotation speed and the engine torque. In particular, the fuel consumption rate significantly increases as the torque increases. Therefore, it is useful to take a fuel consumption increase rate into account in addition to the difference rate CEM described above. The fuel consumption increase rate is a difference rate CFC (g/s·kw) in the fuel consumption rate between a condition in which the alternator generates an electric power and a condition in which the alternator generates an electric power that is divided by a current electric power generated by the alternator 16 .
The generator control device 11 operates according to a generation control routine shown in FIGS. 5 and 6 . The control routine is repeated at a certain cycle, such as 8 ms. The control routine includes the same steps S 101 -S 111 for providing the difference rate CEM as the control routine of the generator control device according to the first embodiment. At the next step S 212 , a no-generation fuel consumption rate (g/s) that corresponds to a current engine rotation speed and the engine torque without electric generation is calculated based on a map shown in FIG. 4 . The no-generation fuel consumption rate corresponds to a fuel consumption rate when the alternator 16 does not generate electric power. The no-generation fuel consumption rates are measured at normal engine operating conditions and stored into the map beforehand.
Thereafter, the step goes to S 213 , where a generation fuel consumption rate (g/s) that corresponds to a current engine rotation speed and the engine torque with electric generation is calculated based on the map. The generation fuel consumption rate corresponds to a fuel consumption rate when the alternator 16 generates an amount of electric power.
At the next step S 214 , the fuel consumption increase rate is calculated as follows:
CFC (g/s·kw)=( FC 1- FC 2)/ P,
wherein FC 1 is a rate of the fuel consumption while the alternator 16 is generating an electric power P, FC 2 is a rate of the fuel consumption while the alternator 16 is not generating electric power.
Thereafter the step goes to S 215 , where a mean value of electric power consumption is calculated by means of annealing process or the like. At the next step S 216 , whether the mean value of the electric power consumption is equal to or larger than a predetermined value Pr 1 or not is examined.
If the result of the examination at S 216 is Yes, a fuel-economic generation is selected and the step goes to S 217 , where if the fuel consumption increase rate CFC is equal to or smaller than a predetermined value Pr 2 is examined to go to S 218 , if the examination result is Yes, to set the command electric power to the required electric power. In other words, it is determined that the increase in the fuel consumption increase rate is within an allowable range. If the fuel consumption increase rate CFC is not smaller than a predetermined value Pr 2 (No), the step goes to S 219 , where the charge ratio of the battery SOC is compared with a predetermined value Ref 2 to go to S 218 to set the command electric power to the required electric power if the charge ratio SOC is equal to or smaller than Ref 2 (i.e. Yes, battery is considered to be discharged). On the other hand, if the charge ratio SOC is not equal or smaller than Ref 2 (No), the step goes to S 220 to set the command electric power to 0. In other words, it is determined that the charge ratio is within an allowable range.
If the result of the examination at S 216 is No, a emission control generation is selected and the step goes to S 221 , where if the difference rate CEM is equal to or smaller than the predetermined value Ref 1 is examined to go to S 222 , if the examination result is Yes, to set the command electric power to the required electric power. In other words, it is determined that the increase in the emission increase rate is within an allowable range. If the difference rate CEM is not smaller than the predetermined value Ref 1 (No at S 221 ), the step goes to S 223 , where the battery charge ratio SOC is compared with the predetermined value Ref 2 to go to S 224 to set the command electric power to 0, if the result is No. In other words, it is determined that the charge ratio is within an allowable range. Otherwise, the step goes to S 222 to set the command electric power to the required electric power.
A generator control device according to the third embodiment of the invention will be described with reference to FIGS. 7 and 8 .
In order to select fuel-economic electric generation or emission control generation, the control routine of this embodiment includes steps S 215 a and S 216 a instead of the steps S 215 and 216 of the second embodiment. The other steps are the same as those of the second embodiment.
As shown in FIG. 8 , the fuel-economic generation range and the emission control generation range are selected by a reference torque curve along which the torque decreases as the engine rotation speed increases.
At S 215 a , the fuel-economic generation range and the emission control generation range are provided to be selected by the reference torque curve. At the next step S 216 a , the current engine torque is compared with a torque level on the reference torque curve at the same engine rotation speed as the current engine rotation speed.
If the current engine torque is smaller than the torque level (No), the step goes to S 217 to compare the fuel consumption increase rate CFC with the predetermined value Pr 2 , which is described above. If, on the other hand, the current torque is not smaller than the torque level (Yes) the step goes to S 221 to compare the difference rate CEM with the predetermined value Ref 1 as described above. Thus, as the engine rotation speed increases, the emission control range expands.
A generator control device according to the fourth embodiment of the invention will be described with reference to FIGS. 9-11 .
The emission increase rate varies with the engine coolant temperature, the air intake air temperature, the air-fuel ratio, the EGR ratio, EGR system condition, etc. The generator control device according to the fourth embodiment of the invention controls the generator taking some of the above information into account in addition to the difference rate CEM described above.
The generator control device 11 operates according to a generation control routine shown in FIGS. 9-11 . The control routine is repeated at a certain cycle, such as 8 ms. The control routine includes the same steps S 101 -S 108 for calculating torques necessary for the engine to operate when the alternator does and does not generate electric power.
Thereafter, the step goes to S 309 , where a coolant temperature detected by a temperature sensor is read. At the next step S 310 , a coefficient CCT for correcting coolant temperature is calculated based on data of a map. The coefficient CCT is a function of the coolant temperature, an engine operating condition such as the engine rotation speed and the torque without electric generation. Generally, the rate of NOx component becomes lower and the HC component becomes higher as the coolant temperature decreases. Therefore, the rates of the hazardous components emitted from an engine to be stored in the map are detected after the engine has been warmed up. The coefficient CCT is to correct the rates of the hazardous components according to a current coolant temperature.
Thereafter, the step goes to S 311 , where the intake air temperature detected by a temperature sensor is read. Subsequently, at S 312 , a coefficient CAT for correcting intake air temperature is calculated based on data of the map. The coefficient CAT is a function of the coolant temperature, an engine operating condition such as the engine rotation speed and the torque without electric generation. Generally, the rate of the NOx component becomes higher as the intake air temperature rises. Therefore, the rates of the hazardous components emitted from the engine to be stored in the map are detected when the intake air temperature is 25° C. The coefficient CAT is to correct the rates of the hazardous components according to a current intake air temperature.
Thereafter, the step goes to S 313 , where if an EGR valve erroneously opens or not is examined by an EGR diagnosis function that is included in the control device 11 . If the result is Yes, the step goes to S 314 , where an EGR ratio that corresponds to the present engine condition is provided by means of a map or the like. If, on the other hand, the result of S 313 is No, the step goes to S 315 , where if an EGR valve erroneously closes or not is examined by the EGR diagnosis function to go to S 316 if the result is Yes, where the EGR ratio is set to 0 or to go S 317 if the result is No, where the EGR ratio detected by an EGR ratio sensor is read.
Thereafter, the step goes to S 318 , where a coefficient CEGR for correcting EGR ratio is calculated based on data of the map. The coefficient CEGR is a function of the EGR ratio, an engine operating condition such as the engine rotation speed and the torque without electric generation. Generally, the rate of NOx component decreases and the HC component increases as the EGR ratio increases. Therefore, the rates of the hazardous components emitted from the engine to be stored in the map are detected after the engine has been warmed up. The coefficient CEGR is to correct the rates of hazardous components that are stored in the map according to a current EGR ratio.
Thereafter, the step goes to S 319 , where an air-fuel ratio detected by a air-fuel ratio sensor is read. At the next step S 320 , a coefficient CAF for correcting the air-fuel ratio is calculated based on data of the map. The coefficient CAF is a function of the air fuel ratio, an engine operating condition such as the engine rotation speed and the torque without electric generation. Generally, the rate of NOx component increases as the air-fuel mixture becomes leaner, but decrease as the air-fuel mixture becomes more leaner. Therefore, the rates of the hazardous components emitted from the engine to be stored in the map are detected at a predetermined air-fuel ratio (e.g. theoretical air-fuel ratio). The coefficient CAF is to correct the rates of hazardous components that are stored in the map according to a current air-fuel ratio.
Subsequently, the step goes to S 321 shown in FIG. 11 , where a basic no-generation emission rate of hazardous components (g/s) that corresponds to a current engine rotation speed and the engine torque without electric generation is read from a map as shown in FIG. 2 . An actual no-generation emission rate of hazardous components (g/s) is obtained by multiplying the basic no generation emission rate by the correction coefficients CCT, CAT, CEGR and CAF. That is:
actual no-generation emission rate of hazardous components (g/s) =basic no-generation emission rate of hazardous components (g/s)×CCT ×CAT×CEGR×CAF
Then the step goes to S 322 , where a basic generation emission rate of hazardous components (g/s) that corresponds to a current engine rotation speed and the engine torque with electric generation is calculated based on the map. The basic generation emission rate corresponds to an emission rate of hazardous components when the alternator 16 generates an amount of electric power. An actual generation emission rate of hazardous components (g/s) is obtained by multiplying the basic generation emission rate by the correction coefficients CCT, CAT, CEGR and CAF. That is:
actual generation emission rate of hazardous components (g/s)=basic generation emission rate of hazardous components (g/s)×CCT ×CAT×CEGR×CAF
At the next step S 111 , a difference rate CEM (g/s·kw) between the actual generation emission rate of hazardous components and actual no-generation emission rate of hazardous components is divided by a current electric power generated by the alternator 16 as described above.
The following steps are the same as the steps described in the first embodiment.
As a modification, the step S 111 shown in FIG. 3 or S 211 shown in FIG. 5 , the difference rate CEM (g/s·kw) may be corrected by one, some or all of the engine coolant temperature, the intake air temperature, the air-fuel ratio, the EGR ratio, or conditions (errors) of an EGR system. It is also useful to correct the difference rate CEM by a variable valve timing.
In the foregoing description of the present invention, the invention has been disclosed with reference to specific embodiments thereof. It will, however, be evident that various modifications and changes may be made to the specific embodiments of the present invention without departing from the scope of the invention as set forth in the appended claims. Accordingly, the description of the present invention is to be regarded in an illustrative, rather than a restrictive, sense. | A generator control device controls a generator that is driven by an engine to charge a battery and supply electric power to electric loads. In the generator control device the following steps are carried out: calculating a required electric power; calculating a difference rate that is a difference in an amount of a hazardous gas component of engine exhaust gas between a first case in which the generator generates the required electric power and a second case in which the generator does not generate an electric power divided by the electric power and controlling the generator to generate the required electric power if the difference is equal to or smaller than a first reference value. | 7 |
[0001] This application is a continuation of application Ser. No. 09/961,504 filed Sep. 24, 2001 entitled MULTIPLE POSITION CONTROL PANEL.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention generally relates to control panels and, more particularly, to control panels end caps that are designed to facilitate mounting the control panel in one of a plurality of orientations relative to a host machine.
[0004] 2. Description of the Related Art
[0005] In order to provide product differentiation while maintaining or reducing costs, it has been proposed to build a commercial appliance control panel that is positionable in one of a pair of orientations. A first orientation has the face of the control panel at a relatively steep slope or orientation relative to the surface of the machine. A second orientation, in which the face is rotated 180°, disposes the face at a relatively less steep angular orientation. Such a structure is illustrated in U.S. Pat. No. 4,798,424.
[0006] However, the assemblies known in the art do not include means to temporarily secure the control panel to the main body of the appliance. Accordingly, it has proven difficult for one person to handle the control panel during the assembly process.
[0007] Therefore, there exists a need in the art for a method and device for preliminarily securing the control panel to the appliance main body during assembly. Moreover, there exists a need in the art for a preliminary securement device that is operable regardless of the orientation of the multi-position control panel.
SUMMARY OF THE INVENTION
[0008] The present invention is directed toward a method and device for preliminarily securing the control panel to the appliance main body during assembly. The present invention is further directed toward a preliminary securement device that is operable regardless of the orientation of the control panel.
[0009] In accordance with the present invention, an end cap for preliminary attachment of a control panel to a main body of an appliance includes a generally planar body having a front side and first and second supporting sides. The supporting sides are disposed at a rear and bottom of the body and are adapted for securement to said appliance main body.
[0010] In further accordance with the present invention, each of said supporting sides has a plurality of securing tabs extending therefrom. The securing tabs are adapted to extend through an opening in the appliance main body and to engage the main body to preliminarily secure the control panel to the main body.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] These and further features of the invention will be apparent with reference to the following description and drawings, wherein:
[0012] [0012]FIG. 1 is an exploded perspective view of an appliance incorporating the present invention with the control panel in a first orientation;
[0013] [0013]FIG. 2 is a perspective view of the appliance of FIG. 1 with the control panel in a second orientation; and,
[0014] FIGS. 3 - 7 are perspective views of different embodiments of the end cap according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0015] It should be noted that in the detailed description which follows, identical components have the same reference numerals, regardless of whether they are shown in different embodiments of the present invention. It should also be noted that in order to clearly and concisely disclose the present invention, the drawings may not necessarily be to scale and certain features of the invention may be shown in somewhat schematic form. It is also noted that although the invention is shown and described herein as it relates to a washing machine, it is contemplated that the preliminary attachment technique taught herein can be used on other appliances.
[0016] With reference to FIG. 1, a control panel 10 is shown spaced from a top surface 12 of a washing machine 14 . The washing machine top surface 12 includes mounting openings 17 through which tabs from an end cap 16 , to be discussed hereinafter, extend. The control panel 10 is shown in a first orientation wherein it is at a relatively steep angle. The same control panel 10 is in a second orientation in FIG. 2, the second orientation being at a relatively shallow angle.
[0017] The control panel 10 includes a body 18 that extends between end caps 16 and is covered by a faceplate 20 . The faceplate 20 includes graphics or writing to assist the user in operating the conventional controls (not shown) mounted thereto. The control panel body 18 and faceplate 20 , as well as the general structure and operation of the washing machine 14 are unaffected by the present invention and will not be discussed further hereinafter.
[0018] With reference to FIGS. 3 - 7 , the end caps 16 include a front surface 22 and first and second support surfaces 24 , 26 . The front surface 22 is preferably curved, and includes first and second edges 28 , 30 . The first edge 28 is located at the intersection of the front surface 22 and the first support surface 24 . The second edge 30 is located at the intersection of the front surface 22 and the second support surface 26 .
[0019] When the control panel 10 is in the first orientation (FIG. 1), the end cap 16 is generally as shown in FIGS. 3 - 5 . In other words, the first support surface 24 is in abutting contact with the top surface 12 of the washing machine 14 , and the second support surface 26 is facing rearwardly relative to the washing machine 14 (and may have a rear cover plate secured thereto). The first edge 28 is adjacent the top surface 12 of the washing machine 14 , and the second edge 30 is remote from the top surface 12 of the washing machine 14 .
[0020] Alternatively, when the control panel 10 is rotated such that it is in the second orientation (FIG. 2), the second support surface 26 is in abutting contact with the top surface 12 of the washing machine 14 , and the first support surface 24 is facing rearwardly relative to the washing machine 14 (and may have a rear cover plate secured thereto). The second edge 30 is adjacent the top surface 12 of the washing machine 14 , and the first edge 28 is remote from the top surface 12 of the washing machine 14 .
[0021] With reference to the end cap 16 first embodiment shown in FIG. 3, the first support surface 24 and the second support surface 26 each have a pair of L-shaped tabs 32 extending therefrom. The tabs 32 have a first leg 34 that extends generally perpendicular to the associated support surface 24 , 26 and a second wedge-shaped leg 36 that extends from the first leg 34 . The face 38 of the second leg 36 facing the support surface 24 , 26 is angled, and the second leg 36 becomes gradually narrower as it extends away from the first leg 34 . Accordingly, the spacing between the second leg 36 and the support surface 24 , 26 gradually decreases as one moves from the distal end of the second leg toward the proximal end of the second leg (i.e., toward the first leg).
[0022] The end caps 16 , and hence the control panel 10 , may be preliminarily or temporarily mounted to the washing machine 14 by inserting the second legs 36 of the end cap 16 through the holes 17 in the top surface 12 of the washing machine 14 and then pushing the control panel 10 forwardly to trap the washing machine top surface 12 between the support surface 24 , 26 and the second leg face 38 . Accordingly, the control panel 10 is secured at each end to the washing machine. Moreover, the control panel 10 is positively positioned and in place for more permanent affixation and assembly.
[0023] With reference to FIG. 4, a second preferred embodiment of the end cap 16 is illustrated. The end cap 16 differs from the end cap 16 of FIG. 3 discussed hereinbefore in the structure and arrangement of the tabs 132 . The tabs 132 according to the second embodiment include a resilient retainer 134 , a locator pin 136 , and an L-shaped leg 138 . The resilient retainer 134 includes a web 140 that secures the retainer 134 to the associated support surface 24 , 26 , and a half-moon-shaped member 142 that extends from the web 140 . Naturally, in this case the top surface 12 of the washing machine 14 will have three holes 17 to receive the tabs 132 extending from the end caps 16 . The end caps 16 are secured by inserting the tabs 134 , 136 , 138 into the holes 17 in the washing machine top surface 12 , and then sliding the end caps 16 rearwardly such that the member 142 and the leg 138 are received under the washing machine top surface 12 .
[0024] With reference to FIG. 5, a third preferred embodiment of the end cap 16 is shown to include a pair of L-shaped tabs 232 . The tabs 232 include a first leg 234 that extends away from the associated support surface 24 , 26 and a second leg 236 that extends rearwardly from the first leg 234 and generally parallel to the support surface 24 , 26 . The end cap 16 is secured by inserting the tabs 232 through the holes 17 provided in the top surface 12 of the washing machine 14 and then pushing the control panel 10 and end caps 16 rearwardly so that a portion of the top surface 12 is received between the support surface 24 , 26 and the second leg 235 of the L-shaped tabs.
[0025] With reference to FIG. 6, a fourth preferred embodiment of the end cap 16 is shown to include an L-shaped tab 332 and a J-shaped tab 334 . The L-shaped tab 332 includes a first leg 336 extending away from the associated support surface 24 , 26 and a second leg 338 extending forwardly from the first leg 336 . A side 340 of the second leg 338 facing the support surface 24 , 26 is angled such that the second leg 338 adjacent the first leg 336 is closer to the support surface 24 , 26 than the end of the second leg 338 remote or distal from the first leg 336 . The J-shaped leg 334 has a proximal end 342 attached to the associated support surface 24 , 26 and a distal end 344 spaced from the support surface 24 , 26 to define a gap therebetween. The distal end 344 includes a surface facing the support surface 24 , 26 . The end cap 16 is attached to the washing machine 14 by inserting the tabs 332 , 334 through the holes 17 and then moving the control panel 10 and end caps 16 forwardly so that portions of the washing machine top surface 12 are trapped between the support surface 24 , 26 and the first tab 332 (i.e., the side 340 of the second leg 338 ) and between the support surface 24 , 26 and the second tab 334 (i.e., the surface of the distal end 344 ).
[0026] With reference to FIG. 7, a fifth preferred embodiment of the end cap 16 includes a first tab 432 and a second tab 434 . The first tab 432 is L-shaped and defines a short ledge-like surface 436 facing the associated support surface 24 , 26 . The second tab 434 includes a ramping or camming surface 438 facing toward the support surface 24 , 26 . The end cap 16 of the fifth embodiment is attached to the washing machine 14 by inserting the tabs 432 , 434 through the holes 17 in the washing machine top surface 12 and then sliding the control panel 10 and end caps 16 forwardly until the top surface 12 is trapped between the support surface 24 , 26 and the ledge-like surface 436 of the first tab.
[0027] In each of the preferred embodiments described hereinbefore, for purposes of clarity and completeness, the end cap 16 is shown with tabs permitting it to be secured in either of the two desired orientations. However, only one set of tabs are necessary to hold the control panel 10 to the appliance. Therefore, the end caps will preferably be manufactured with only the tabs that are to be used to hold the control panel 10 to the washing machine. The die used to mold or manufacture the end caps preferably accommodates inserts to selectively block the formation of the non-necessary tabs, as is well known in the plastic injection art. As such, end caps having tabs adapted for either of the desired orientations can be easily manufactured from a single mold, reducing manufacturing costs.
[0028] The present invention has been described herein with particularity, but it is noted that the scope of the invention is not limited thereto. Rather, the present invention is considered to be possible of numerous modifications, alterations, and combinations of parts and, therefore, is only defined by the claims appended hereto. | An end cap for preliminary attachment of a control panel to a main body of an appliance includes a generally planar body having a front side and first and second supporting sides. The supporting sides are disposed at a rear and bottom of the planar body and are adapted for securement to the appliance main body. Each of the supporting sides has a plurality of securing tabs extending therefrom. The securing tabs are adapted to extend through an opening in the appliance main body and to engage the main body to preliminarily secure the control panel to the main body. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to a process for preparing 5-mercapto-1,2,3-thiadiazole salts.
A 5-mercapto-1,2,3-thiadiazole salt is a chemical material having a wide application as an intermediate for pharmaceuticals, agricultural chemicals and so on, particularly as an important compound for a modifier of antibiotics.
Heretofore, as a process for preparing 5-mercapto-1,2,3-thiadiazole salt, there have been known, for example, (1) a method in which chloroacetaldehyde ethoxycarbonylhydrazone is subjected to reaction with thionyl chloride followed by the mercaptization reaction of the resulting product [Japanese Provisional Patent Publication No. 23974/1978]: ##STR1## or a method which uses a diazo compound [Tetrahedron Letters, Vol. 26, p. 2389 (1973)]: ##STR2## (2) a method in which a trihaloacetaldehyde and a hydrazine are subjected to a condensation reaction in a solvent, followed by the reaction of the resulting reaction product with a salt of a sulfide or a salt of a hydrosulfide compound [Japanese Provisional Patent Publication No. 95282/1984] or a method in which a hydrazone compound is subjected to the reaction with a sulfide compound represented by the formula: MM'S (wherein M is an alkali metal atom and M' is a hydrogen atom or an alkali metal) such as a reaction product of trichloroacetaldehyde-p-toluenesulfonylhydrazone and sodium sulfide [Japanese Provisional Patent Publication No. 51271/1984 which corresponds to European Patent application No. 103840]: ##STR3## and the like.
However, in the method of (1), there exist problems that the starting materials are unstable and hence accompanied by difficulties in handling thereof, and in the method of (2), a yield of the 5-mercapto-1,2,3-thiadiazole salt which is the intended compound is low and they were not the industrially advantageous processes.
SUMMARY OF THE INVENTION
The present inventors have carried out earnest studies to establish a process for producing a 5-mercapto-1,2,3-thiadiazole which is industrially advantageous. As a result, the present inventors have found that the purpose of the present invention can be attained by replacing the sulfide in the aforesaid process (2) with a polysulfide compound as a reactive reagent for a cyclization reaction of a hydrazone compound, and have found that yield of the intended compound has increased with great extent and thus have accomplished the present invention.
The reaction of the present invention can be shown by the following formula: ##STR4## wherein X represents a halogen atom, Ar represents an aryl group, M represents an alkali metal atom or an NH 4 group and x is an integer of 2 to 6.
That is, a process for preparing a 5-mercapto-1,2,3-thiadiazole salt of the present invention comprises reacting a hydrazone compound represented by the formula:
X.sub.3 C--CH═N--NH--SO.sub.2 Ar (II)
wherein X and Ar have the same meanings as defined in the above formula (I), with a polysulfide compound represented by the formula:
M.sub.2 S.sub.x (III)
wherein M and x have the same meanings as defined in the above formula (I).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The hydrazone compound represented by the formula (II) to be used in the present invention can be easily obtained by conventionally well-known methods such as, for example, a method as described in the literature (K. Bott, Chem. Ber., 1975, Vol. 108, p. 402), a method as disclosed in Japanese Provisional Patent Publication No. 95282/1984 and the like. Representative examples of the hydrazone compounds represented by the formula (II) may include trichloroacetaldehyde-p-toluenesulfonylhydrazone, tribromoacetaldehyde-p-toluenesulfonylhydrazone, triiodoacetaldehyde-p-toluenesulfonylhydrazone, trichloroacetaldehyde-benzenesulfonylhydrazone and the like. These hydrazone compounds represented by the formula (II) may be used for cyclization reaction after isolation from the reaction mixture in which there has been formed a hydrazone compound. However, as disclosed in the above Japanese Provisional Patent Publication No. 95282/1984, a method in which a trihaloacetaldehyde is subjected to the condensation reaction with an arylsulfonylhydrazine in a solvent, followed by the cyclization reaction of the reaction mixture which contains a hydrazone compound represented by the formula (II) can be utilized without isolation therefrom with the polysulfide compound to obtain an intended compound, is preferred since the procedures can be simplified, there is no loss of the reaction product which loss accompanies the isolation operation and the solvent used in the condensation reaction can effectively be utilized as the solvent for the cyclization reaction as it is.
As the polysulfide compound represented by the formula (III) to be used for formation of a 5-mercapto-1,2,3-thiadiazole salt by cyclization reaction of the hydrazone compound represented by the formula (II), there may be mentioned, for example, sodium disulfide, sodium trisulfide, sodium tetrasulfide, sodium pentasulfide, sodium hexasulfide, potassium disulfide, potassium trisulfide, potassium tetrasulfide, potassium pentasulfide, potassium hexasulfide, ammonium disulfide, ammonium trisulfide, ammonium tetrasulfide, ammonium pentasulfide, ammonium hexasulfide and the like. These polysulfides can be prepared by, for example, (1) a method as described in New Experimental Chemistry Lecture, Vol. 8, p. 382, published by Maruzen Co. (1976); Acta. Cryst. B29, p. 1463 (1963); or Acta. Chem. Scand., Vol. 25, p. 3329 (1971), (2) a method in which sodium sulfide, potassium sulfide and the like are subjected to the reaction with simple sulfur (sulfur simple substance) in a hydrous alcohol until the simple sulfur has been dissolved as described in Org. Syn., Coll. Vol. 1, p. 221 (1956), (3) a method in which sodium sulfide, potassium sulfide, ammonium sulfide or the like is subjected to the reaction with simple sulfur in water or a lower alcohol such as methanol and ethanol until the simple sulfur has been dissolved, or the like.
When the cyclization reaction of the hydrazone compound represented by the formula (II) has been carried out by using the polysulfide compound represented by the formula (III), a method in which the cyclization reaction is carried out by adding a polysulfide-containing solution in which is formed a polysulfide compound by the aforesaid method (2) or (3) to the solution containing a hydrazone compound, for example, a reaction mixture obtained by said cyclization reaction or a solution formed by disolving hydrazone compound in a solvent; a method in which the cyclization reaction is carried out by adding the hydrazone compound to a polysulfide compound-containing solution; a method in which the cyclization reaction is carried out by adding simple sulfur to a solution containing a hydrazone compound, followed by addition of a sulfide compound such as sodium sulfide, potassium sulfide, ammonium sulfide or the like to form a polysulfide in the reaction system; or the like can be employed. The polysulfide represented by the formula (III) may preferably be used, in general, in an amount of 2 to 8 moles based on a mole of the hydrazone compound, more preferably 3 to 5 moles.
In order to carry out the present invention, the cyclization reaction may preferably be carried out in a solvent, and as the solvent, there may be used water; a lower alcohol such as methyl alcohol, ethyl alcohol, isopropyl alcohol, t-butyl alcohol and the like; an aromatic hydrocarbon such as benzene, xylene, toluene and the like; a halogenated hydrocarbon such as methylene chloride, chloroform and the like; and mixtures of the above, among them, water, the lower alcohol and the like are particularly preferred.
Further, for carrying out the present invention, it is preferred that the pH of the reaction system is maintained in the range of 10 to 11 for carrying out the cyclization reaction. By adjusting and maintaining the pH of the reaction system within 10 to 11, side reactions such as a hydrolysis reaction of the hydrazone compound can be restrained whereby a yield of the 5-mercapto-1,2,3-thiadiazole salt to be obtained can be further increased. As the pH adjusting agent, an acid or a base may optionally be used. As the acid, there may be mentioned a mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid and the like; and an organic acid such as acetic acid, p-toluenesulfonic acid and the like, and as the base, there may be mentioned sodium hydroxide, potassium hydroxide, ammonia and the like.
In the present invention, the cyclization reaction may be carried out by any of methods such as a batch system, a continuous system and the like. The reaction temperature at which the cyclization reaction is carried out is -10° to 60° C., preferably 10° to 40° C., and the reaction time is not particularly limited, but generally the reaction is completed after 1 to 5 hours and a 5-mercapto-1,2,3-thiadiazole salt is formed.
Isolation of the 5-mercapto-1,2,3-thiadiazole salt from the reaction mixture can be easily carried out by removing a precipitate of an inorganic salt by-produced by the reaction and then condensing the reaction mixture to distill out the solvent and by separating crystals from the condensate, and according to the conventional manner, if desired, a 5-mercapto-1,2,3-thiadiazole salt having high purity can be obtained by recrystallizing the obtained crystals.
EXAMPLES
EXAMPLE 1
In 20 ml of methanol were dissolved 3.98 g (24 mmole) of chloral hydrate and 3.72 g (20 mmole) of p-toluenesulfonylhydrazine, and the mixture was stirred at room temperature for 40 minutes to form trichloroacetaldehyde-p-toluenesulfonylhydrazone.
On the other hand, 11.1 g (66 mmole) of sodium sulfide pentahydrate, 2.11 g (66 mmole) of sulfur simple substance and 4.8 g of water were heated to 50° to 60° C. and the heating was ceased when the mixture was a homogeneous solution to form sodium disulfide. The thus prepared solution of sodium disulfide was added to the previously prepared reaction solution of trichloroacetaldehyde-p-toluenesulfonylhydrazone for about 10 minutes while maintaining the pH of the reaction mixture within 10 to 11, and furhter stirring was continued for 4 hours while maintaining the pH of the reaction system within 10 to 11 by using a 30% by weight aqueous sodium hydroxide solution. After completion of the reaction, precipitated inorganic compounds such as sodium chloride were removed by filtration. A part of the filtrate was sampled and analyzed with the internal standard method by using liquid chromatography. A yield of the obtained product to the starting p-toluenesulfonylhydrazine was as follows.
Yield of sodium salt of 5-mercapto-1,2,3-thiadiazole was 73%.
EXAMPLE 2
In 20 ml of methanol were dissolved 0.99 g (6 mmole) of chloral hydrate and 0.93 g (5 mmole) of p-toluenesulfonylhydrazine, and the mixture was stirred at room temperature for 30 minutes to form trichloroacetaldehyde-p-toluenesulfonylhydrazone.
On the other hand, 3.96 g (16.5 mmole) of sodium sulfide nonahydrate, 2.11 g (66 mmole) of sulfur simple substance and 20 g of water were dissolved under room temperature and stirring was continued until the mixture became a homogeneous solution to form sodium pentasulfide. The thus prepared solution of sodium pentasulfide was added to the previously prepared reaction solution of tri-chloroacetaldehyde-p-toluenesulfonylhydrazone for 1 minute, and stirring was continued for 2 hours while maintaining the pH of the reaction system within 10 to 11 by using a 30 % by weight aqueous sodium hydroxide solution. The analysis after completion of the reaction was carried out in the same manner as in Example 1. A yield of the obtained product to the starting p-toluenesulfonylhydrazine was as follows.
Yield of sodium salt of 5-mercapto-1,2,3-thiadiazole was 78%.
COMPARATIVE EXAMPLE 1
In 40 ml of a 50% hydrous methanol were dissolved 3.96 g (16.5 mmole) of sodium sulfide nonahydrate, and to the mixture was added 1.58 g (5 mmole) of a powder of trichloroacetaldehyde-p-toluenesulfonylhydrazone at once while stirring under room temperature, and reaction was carried out for 1 hour at room temperature. The pH of the reaction mixture was 14 before addition of the hydrazone and 13.8 after addition thereof. Analysis was carried out in the same manner as in Example 1. The yield of sodium salt of 5-mercapto-1,2,3-thiadiazole was 10% to the starting p-toluenesulfonylhydrazone.
COMPRATIVE EXAMPLE 2
In 20 ml of methanol were dissolved 0.91 g (5.5 mmole) of chloral hydrate and 0.93 g (5 mmole) of p-toluenesulfonylhydrazine, and the mixture was stirred at room temperature for 30 minutes to form trichloroacetaldehyde-p-toluenesulfonylhydrazone. Then, a solution of 3.96 g (16.5 mmole) of sodium sulfide nonahydrate dissolved in 20 ml of water was added little by little to the aforesaid solution of the hydrazone under room temperature while maintaining the pH within 10 to 11. After about 60 minutes, about 2/3 amount of the sodium sulfide solution was added thereto and the pH of the reaction mixture remained at 11.2 or less. At this time, the reaction mixture was analyzed by sampling a part thereof, a yield of sodium salt of 5-mercapto-1,2,3-thiadiazole of 40% was obtained referred to the starting p-toluenesulfonylhydrazine. Thereafter, the remainder of the sodium sulfide solution was added thereto for about 30 minutes, the ultimate pH of the solution was 12.3 and the yield of sodium salt of 5-mercapto-1,2,3-thiadiazole was 46%.
EXAMPLE 3
In 20 ml of methanol were dissolved 0.91 g (5.5 mmole) of chloral hydrate and 0.93 g (5 mmole) of p-toluenesulfonylhydrazine, and the mixture was stirred at room temperature for 60 minutes to form trichloroacetaldehyde-p-toluenesulfonylhydrazone. The reaction mixture was added to the solution of 2.35 g (16.5 mmole) of potassium disulfide dissolved in 20 ml of water for 20 minutes while maintaining the pH within 10 to 11 under room temperature, and the reaction was further continued while maintaining the pH of the reaction system within 10 to 11 by using an aqueous potassium hydroxide solution. The analysis after completion of the reaction was carried out in the same manner as in Example 1. A yield of the obtained product to the starting p-toluenesulfonylhydrazine was as follows.
Yield of potassium salt of 5-mercapto-1,2,3-thiadiazole was 71%.
EXAMPLE 4
In 20 ml of methanol were dissolved 0.99 g (6 mmole) of chloral hydrate and 0.93 g (5 mmole) of p-toluenesulfonylhydrazine, and the mixture was stirred at room temperature for 30 minutes to form trichloroacetaldehyde-p-toluenesulfonylhydrazone. Then, to the reaction mixture was added under room temperature 30 ml of a 5% aqueous ammonia containing 3.44 g (17.5 mmole) of ammonium pentasulfide for 15 minutes. Thereafter, the reaction was continued for further 2 hours while maintaining the pH of the reaction system at 10.4 by using a 30% by weight aqueous potassium hydroxide solution. The analysis after completion of the reaction was carried out in the same manner as in Example 1. A yield of the obtained product to the starting p-toluenesulfonylhydrazine was as follows.
Yield of potassium salt of 5-mercapto-1,2,3-thiadiazole was 68%.
COMPARATIVE EXAMPLE 3
In 20 ml of methanol were dissolved 0.99 g (6 mmole) of chloral hydrate and 0.93 g (5 mmole) of p-toluenesulfonylhydrazine, and the mixture was stirred at room temperature for 30 minutes to form trichloroacetaldehyde-p-toluenesulfonylhydrazone. Then, to the reaction mixture was added under room temperature 15 ml of a 30% hydrated methanol solution containing 1.7 g (25 mmole) of ammonium sulfide for 10 minutes. Thereafter, the reaction was continued for further 2 hours while maintaining the pH of the reaction system at 10.4 by using 28% aqueous ammonia, a 30% aqueous potassium hydroxide solution, etc. The analysis after completion of the reaction was carried out in the same manner as in Example 1. The yield of the 5-mercapto-1,2,3-thiadiazole salt referred to the starting p-toluenesulfonylhydrazine was 22%.
As seen from the above Examples and Comparative examples, by using a polysulfide compound in the cyclization reaction of the hydrazone compound, in the process of the present invention, the yield of the 5-mercapto-1,2,3-thiadiazole salt has remarkably increased with great extent as compared with,the conventional method which uses a sulfide such as sodium sulfide. | There is disclosed a process for preparing 5-mercapto-1,2,3-thiadiazole salts comprising reacting a hydrazone compound represented by the formula:
X.sub.3 C--CH═N--NH--SO.sub.2 Ar
wherein X represents a halogen atom and Ar represents an aryl group, with a polysulfide compound represented by the formula:
M.sub.2 S.sub.x
wherein M represents an alkali metal atom or an NH 4 group and x is an integer of 2 to 6.
The present invention provides the 5-mercapto-1,2,3-thiadiazole salt with remarkably increased yield as compared with the conventional method. | 2 |
FIELD OF THE INVENTION
The present invention relates to a solid state imaging element which can be easily tested.
BACKGROUND OF THE INVENTION
Recently, accompanying the advance of silicon LSI technology, solid state imaging elements in which a plurality of photodetectors are arranged in a two-dimensional array on a semiconductor substrate and connected with a charge sweep device (hereinafter referred to as CSD) or a charge coupled device (hereinafter referred to as CCD) have been developed and put into practical use. Schottky-barrier diodes or photodiodes utilizing p-n junctions are usually employed for the photodetectors. Such solid state imaging elements are called "infrared imaging elements" or "visible light imaging elements" depending on the wavelength to be detected.
FIG. 12 is a block diagram of an infrared CSD imaging device in which a plurality of infrared detectors are arranged on a silicon substrate and scanning is carried out using CSD, disclosed in pages 42 to 48 of Defense Technology Journal, Vol.8, No.8, August 1987, published by Defense Technology Foundation. This device is constituted by a camera head 30, a signal processing part 31 and a monitor TV 33. In addition, this device employs a 512×512-element two-dimensional array type IRCSD (Infrared CSD) 32 as the imaging element. Since this IRCSD 32 scans electrically, a mechanical scanner is dispensed with, resulting in a small sized and light-weight camera head 30. In addition, since the camera head 30 includes a Stirling cycle refrigerator 302 utilizing a closed cycle for cooling the infrared detectors down to 77K, it is not necessary to provide a cooler.
An interline transfer CCD (hereinafter referred to as IL-CCD) is generally used for the charge transfer part of the two-dimensional element. In this IL-CCD, as shown in FIG. 13, one potential well for vertical transfer is provided for one detector and signal charges are transferred in the vertical and horizontal directions by a so-called bucket brigading system. Although this IL-CCD has very low noise, there is a limitation in its charge transfer ability. More specifically, when the signal charge amount increases and signal charges from one pixel exceed the storage capacity of one bucket, the signal charges are mixed with those from another pixel. In order to avoid this, it is necessary to increase the dimension of the vertical CCD. However, when the dimension of vertical CCD is increased, the fill factor (the ratio of the photodetector area to the pixel size) decreases, resulting in a reduction in sensitivity.
As another charge transfer system, there is a MOS system utilizing a MOS switch for reading out signals. The MOS system has an advantage over other systems in having a larger saturation charge amount. However, it has a disadvantage in that a large noise arises due to a large signal line capacitance and fixed pattern noise arises due to variations in the characteristics of the MOS switch. Although a reduction in pixel size is required for miniaturization and high resolution, a reduction in the pixel size induces a reduction in the signal charge amount obtained from one pixel. Thus, noise is a serious problem in the MOS system.
On the other hand, a CSD (Charge Sweep Device) used in the device of FIG. 12 is a new vertical charge transfer element, which has a large saturation charge amount and a noise level as high as that of the IL-CCD.
A description is given of the operation of the CSD with reference to FIGS. 13 and 14, which are shown in pages 41 to 45 of a journal "Television Technology" of September 1985.
As shown in FIG. 13, the transfer gates a CSD are controlled separately from each other. Only a transfer gate is selected in a vertical row during a horizontal period. In FIG. 13, only the second transfer gate from the left is turned on and signal charges in the photodiode connected to the transfer gate are transferred to the CSD. Other photodiodes are accumulating signal charges at this time.
The above operation will be described in detail with reference to FIG. 14. In the CSD, the signal charges are transferred by the charge sweep-out operation, in which the potential wall pushes the signal charges to the horizontal CCD as shown in FIGS. 14(b) to 14(d). A storage gate is provided between the horizontal CCD and the CSD, and the swept signal charges are stored in the storage gate as shown in FIG. 14(e). The sweep-out operation is completed in a horizontal period and the signal charges stored in the storage gate are transferred to the horizontal CCD during a horizontal blanking period as shown in FIG. 14(f) and then they are successively read out.
As described above, in the CSD, one vertical transfer element forms one potential well and the signal charges from one photodiode are output to the potential well. Therefore, sufficient signal charges can be obtained even when the channel width is reduced.
FIG. 9 shows a structure of a conventional infrared solid-state imaging element including Schottky barrier diodes serving as photodetectors, CSDs serving as vertical charge transfer circuits and a CCD serving as a horizontal charge transfer circuit. In FIG. 9, reference numeral 1 designates infrared detectors such as PtSi/Si Schottky barrier diodes. Reference numeral 2 designates vertical CSDs for transferring signal charges and reference numeral 3 designates a CSD scanner for driving the vertical CSD 2. Reference numeral 4 designates transfer gates (TG) for controlling the charge transfer from the infrared detector 1 to the vertical CSD 2 and reference numeral 5 designates a TG scanner for driving the transfer gates 4. Reference numeral 6 designates bus lines connecting the transfer gates 4 with the TG scanner 5. Reference numeral 7 designates a horizontal CCD for transferring signal charges and reference numeral 8 designates a CCD scanner for driving the CCD 7. Reference numeral 9 designates an output amplifier.
Operation thereof will be described. Infared rays radiated from the subject are incident on the photodetectors 1 arranged in a two-dimensional array and then converted into electricity in the photodetector 1. The signal charges thus generated are transferred to the vertical CSD 2 by opening the transfer gate 4. The switching of the transfer gate 4 is controlled by the TG scanner 5 connected to the transfer gate 4 by the bus line 6. When, the CSD scanner circuit 3 is driven, the signal charges in the vertical CSD 2 are transferred downward in the CSD 2 to reach the horizontal CCD 7. When the CCD scanner 8 is operated, the signal charges in the horizontal CCD 7 are transferred in the right direction in the CCD 7 to be output through the output amplifier 9. Then, signals from the photodetectors 1 arranged in a two-dimensional array are successively read out, whereby the intensity distribution of the infrared rays incident on the element is displayed on the monitor as an infrared image.
FIG. 10 shows a structure of a conventional infrared solid state imaging element having Schottky barrier diodes as photodetectors in which the signal charges are read out by an MOS system. In FIG. 10, reference numeral 1 designates infrared detectors such as PtSi/Si Schottky barrier diodes. Reference numeral 10 designates vertical MOS transistors for reading out signal charges and reference numeral 11 designates a vertical scanner for controlling the switching of the vertical MOS transistors 10. Reference numeral 12 designates bus lines connecting the vertical MOS transistors 10 with the vertical scanner 11. Reference numeral 13 designates a horizontal MOS transistor for reading out signal charges and reference numeral 14 designates a horizontal scanner for controlling the switching of the horizontal MOS transistors 13. Reference numeral 15 designates bus lines connecting the horizontal MOS transistors 13 with the horizontal scanner 14. Reference numeral 9 designates an output amplifier.
Operation thereof will be described. Infared rays irradiated from the subject are incident on the photodetectors 1 arranged in a two-dimensional array and then converted into electricity in the photodetectors 1 similarly as in FIG. 9. The signal charges thus generated are read out by the MOS system. More specifically, the signal charges from the photodetector 1 provided where a bus line 12 in a transverse direction selected by the vertical scanner 11 intersects a bus line 15 in a longitudinal direction selected by the horizontal scanner 14 are output through the output amplifier 9. The signal charges from the photodetectors 1 arranged in a two-dimensional array are successively read out and then the intensity distribution of the infrared rays incident to the element are displayed on the monitor as an infrared image.
FIG. 11 shows a structure of a conventional infrared solid-state imaging element having Schottky barrier diodes as photodetectors and CCDs as vertical and horizontal charge transfer circuits. In FIG. 11, reference numeral 1 designates infrared detectors such as PtSi/Si Schottky barrier diodes. Reference numeral 13 designates vertical CCDs for transferring signal charges and reference numeral 14 designates a CCD scanner for driving the CCDs. Reference numeral 4 designates transfer gates (TG) for controlling the charge transfer from the infrared detectors 1 to the vertical CCD 13. Reference numeral 15 designates an input pin for inputting a clock signal for driving the transfer gates 4. Reference numeral 6 designates bus lines connecting the input pin 15 with the transfer gates 4. Reference numeral 7 designates a horizontal CCD for transferring signal charges and reference numeral 8 designates a CCD scanner for driving the horizontal CCD 7. Reference numeral 9 designates an output amplifier.
In this infrared imaging element, unlike the infrared imaging element shown in FIG. 9, a CCD is used for the charge transfer in vertical direction. The operation thereof is fundamentally the same as that of the element shown in FIG. 9 except that the switching of the transfer gate 4 is controlled by the clock signal applied to the input pin 15 and the vertical CCDs 13 are controlled by the CCD scanner 14.
The infrared solid-state imaging elements shown in FIGS. 9, 10 and 11 are formed by a silicon LSI process. During the process, breakage of Al wirings for the bus lines 6, 12 and 15 may occur.
When the bus line 6 is broken in the infrared solid state elements shown in FIGS. 9 and 11, the transfer gate 4 on the right of the broken bus line in the figure cannot be opened and the signal charges from the photodetectors 1 cannot be read out. As a result, in the solid-state imaging element including such a broken bus line, an image defect A having continuous insensitive portions in the transverse direction as shown in FIG. 15 appears on the output image.
When the bus lines 12 and 15 are broken in the infrared solid-state imaging element shown in FIG. 10, an image defect A or B having continuous insensitive portions in the transverse direction or the longitudinal direction appears on the output image. In addition, when a diode is faulty or a contact part of the transfer gate is open, a black spot defect C as shown in FIG. 15 appears.
As a method for detecting such defects, the output image of an assembled is detected. This causes elements including defects to pass through a wafer test process or an assembly process, so that much time and a high cost are unfavorably incurred.
As another method for detecting these defects, the element may be driven in a wafer test. In a case of an infrared imaging element using Schottky barrier diodes, it is necessary to cool the element down to approximately 77K to operate the detector. However, it is technically difficult to perform a wafer test at such a low temperature.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a solid-state infrared imaging element which can detect a transverse black line defect or a longitudinal black line defect, i.e., a breakage of a bus line in a wafer test without actually operating the element.
Other objects and advantages of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific embodiment are given by way of illustration only, since various changes and modifications within the spirit and the scope of the invention will become apparent to those skilled in the art from this detailed description.
In accordance with the present invention, a solid state imaging element includes a checking means for detecting a breakage of a bus line.
Therefore, the breakage of a bus line can be detected at room temperature without actually operating the element.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of an infrared imaging element which reads out signal charges using a CSD system in accordance with a first embodiment of the present invention;
FIG. 2 is a schematic diagram showing a fundamental structure of a bus line breakage checking circuit in accordance with the first embodiment of the present invention;
FIG. 3 is a schematic diagram of an infrared imaging element which reads out signal charges using an MOS system in accordance with a second embodiment of the present invention;
FIG. 4 is a schematic diagram of an infrared imaging element which reads out signal charges using a CSD system in accordance with a third embodiment of the present invention;
FIGS. 5 and 6 are schematic diagrams showing fundamental structures of bus line breakage checking circuits in accordance with the third embodiment of the present invention;
FIG. 7 is a schematic diagram of an infrared imaging element which reads out signal charges using a CCD system in accordance with a fourth embodiment of the present invention;
FIG. 8 is a schematic diagram of an infrared imaging element which reads out signal charges using an MOS system in accordance with a fifth embodiment of the present invention;
FIG. 9 is a schematic diagram of an infrared imaging element using a CSD system in accordance with the prior art;
FIG. 10 is a schematic diagram of an infrared imaging system using an MOS system in accordance with the prior art;
FIG. 11 is a schematic diagram of an infrared imaging element using a CCD system in accordance with the prior art;
FIG. 12 is a block diagram of an infrared imaging device;
FIGS. 13 and 14 are diagrams showing a structure and a charge sweep-out operation of a basic CSD system; and
FIG. 15 is a diagram showing image defects appearing on an output image.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a schematic diagram showing a structure of an infrared imaging element which reads out signal charges using a CSD system in accordance with a first embodiment of the present invention. FIG. 2 is a schematic diagram showing a fundamental structure of a bus line breakage checking circuit in accordance with the present invention.
In FIG. 1, reference numerals 1 to 9 designate the same elements as those shown in FIG. 9. Reference numeral 16 designates a pad for detecting breakage of a wire in transverse direction from the outside. Each bus line 6 is connected with the pad 16 by the transistors 17. Reference numeral 18 designates a gate voltage applying pad for controlling the switching of the transistors 17. The transistors 17 and the pads 16 and 18 are part of a circuit for detecting breakage of a bus line.
When this infrared imaging element is operated, the pad 18 is short-circuited with the substrate to turn off the transistors 17. At this time, the breakage checking circuit is electrically isolated from the bus line 6 and then an infrared image is obtained by the same operation as in the conventional example of FIG. 9.
When the breakage of a bus line is to be detected, a wafer test is carried out in accordance with the following process. First, a gate voltage is applied to the pad 18 to turn on the transistors 17, thereby to connect the pad 16 with the bus lines 6. In this state, the TG scanner 5 is operated and a pulse voltage applied to each bus line 6 by the scanner circuit 5 is monitored from the pad 16. The TG scanner 5 applies a high level to a selected bus line and a low level to other non-selected bus lines while the element operates. When the breakage checking circuit is connected, however, a current flows from the selected bus line to the non-selected bus lines via this breakage checking circuit, so that normal scanning is not carried out. Therefore, in this wafer test, the non-selected bus lines are open, and a low level signal is not applied to these bus lines. The pulses monitored from the pad 16 are pulses sent from the scanner 5 when there is no breakage of the bus line, while a lack of pulses of the same number as the number of broken bus lines occurs when there is breakage of the bus line. Thus, breakage of the bus line is detected.
FIG. 3 is a schematic diagram showing a structure of an infrared imaging element which reads out signal charges using an MOS system in accordance with a second embodiment of the present invention. In FIG. 3, reference numerals 1 and 9 to 15 designate the sam elements as those shown in FIG. 10. Reference numeral 19 designates a pad for detecting breakage of bus lines 12 in a transverse direction. Each bus line in the transverse direction is connected with the pad 19 by the transistors 20. Reference numeral 21 designates a gate voltage applying pad for controlling the switching of the transistors 20. Reference numeral 22 designates a pad for detecting breakage of bus lines 15 in a longitudinal direction. Each bus line in the longitudinal direction is connected with the pad 22 by the transistors 23. Reference numeral 24 designates a gate voltage applying pad for controlling the switching of the transistors 23. The transistors 20 and the pads 19 and 21 are part of a bus line breakage checking circuit in the transverse direction and the transistors 23 and the pads 22 and 24 are included in a bus line breakage checking circuit in the longitudinal direction.
In this second embodiment, the two breakage checking circuits 19 to 21 and 22 to 24 have the same structure as that of the breakage checking circuit shown in FIG. 2. Accordingly, a wafer test can be carried out in accordance with the same process as described in the first embodiment of the present invention. More specifically, when the element is operated, the pads 21 and 24 are short-circuited with the substrate to turn off the transistors 20 and 23. At this time, the two breakage checking circuits are electrically isolated from the bus lines 12 and 15 and an infrared image can be obtained by the same operation as in the conventional example of FIG. 10.
When, the breakage of the bus line in the transverse direction is detected, the pulse from the vertical scanner 11 is monitored by the pad 19 in the same way as in the first embodiment. When the breakage of the bus line in the longitudinal direction is detected, the pulse from the horizontal scanner 14 is monitored by the pad 22.
While the breakage checking circuits of above-described first and second embodiments are appropriate for detecting which bus line is broken, third to fifth embodiments which will be described, hereinafter provide breakage checking circuits for detecting only the existence of a broken bus line.
FIG. 4 is a schematic diagram showing a structure of an infrared imaging element which reads out signal charges with a CSD system in accordance with a third embodiment of the present invention. FIGS. 5 and 6 are schematic diagrams showing fundamental structures of the breakage checking circuits.
In FIG. 4, reference numerals 1 to 9 designate the same elements as those shown in FIG. 9. Reference numeral 10 designates two pads for detecting breakage of a bus line. All bus lines are connected in series with the two pads 10 by the transistors 25. Reference numeral 12 designates a gate voltage applying pad for controlling the switching of the transistors 25. The transistors 25 and the pads 10 and 12 constitute are part of a breakage checking circuit.
FIG. 5 shows the breakage checking circuit of the infrared imaging element of FIG. 4. In these figures, reference numerals 10 to 12 designate the same elements as those shown in FIG. 4 and reference numeral 6 designates n bus lines.
In the infrared imaging element of FIG. 4, when the element is operated, the pad 12 is short circuited with the substrate to turn off the transistor 25. At this time, the breakage checking circuit is electrically isolated from the bus line 6 and then an infrared image is obtained by the same operation as in the conventional example of FIG. 9.
When breakage of the bus line is detected, a wafer test is carried out in accordance with the following process. First, the CSD scanner 3 is electrically isolated from the TG scanner 5. In this state, the circuit shown in FIG. 4 is electrically equivalent to the circuit shown in FIG. 5. In FIG. 5, a gate voltage is applied to the pad 12 to turn on the transistors 25, thereby to connect the two pads 10 in series with the n bus lines. In this state, whether current flows between the two pads 10 or not is checked, whereby the breakage of bus line can be detected.
In FIG. 5, the breakage checking circuit includes n bus lines 6 and (n+1) transistors 25. This breakage checking circuit can bus lines 6 and (n-1) transistors 25 as shown in FIG. 6.
FIG. 7 is a schematic diagram showing a structure of an infrared imaging element which reads out signal charges using a CCD system in accordance with a fourth embodiment of the present invention. In FIG. 7, reference numerals 1, 4, 6 to 9, and 13 to 15 designate the same elements as those shown in FIG. 11. Reference numerals 10 to 12 designate the breakage checking circuit shown in FIG. 5. Reference numeral 16 designates transistors connecting each bus line 6 in the transverse direction with the input pin 15, and reference numeral 17 designates a gate voltage applying pad for controlling the switching of the transistors 16.
When this infrared imaging element operates, the pad 12 is short circuited with the substrate to turn off the transistors 25, whereby the breakage checking circuit is electrically isolated from the bus lines 6. Then, a gate voltage is applied to the pad 17 to turn on the transistors 16, whereby the clock input pin 15 is connected in parallel with each bus line 6. In this state, the circuit shown in FIG. 7 is electrically equivalent to the circuit shown in FIG. 11 and an infrared image can be obtained by the same operation as in the conventional example of FIG. 11.
When breakage of the bus line is detected, the pad 17 is short circuited with the substrate to turn off the transistors 16, whereby the bus lines connected in parallel are electrically isolated from each other. Then, the CCD scanner 14 is electrically isolated from the vertical CCD. In this state, the circuit shown in FIG. 7 is electrically equivalent to the circuit shown in FIG. 5 and the breakage of bus line can be detected in the same way as in the third embodiment.
FIG. 8 is a schematic diagram showing a structure of an infrared imaging element which reads out signal charges using a MOS system in accordance with a fifth embodiment of the present invention. In FIG. 8, reference numerals 1, 6a, 6b, 9, 18 to 21 designate the same elements as those shown in FIG. 10. Reference numerals 10a to 12a and 10b to 12b designate the breakage checking circuit shown in FIG. 5, respectively.
The infrared imaging element of using an MOS system shown in FIG. 8 has the bus lines 6a in the longitudinal direction and the bus lines 6b in the transverse direction. Therefore, this infrared imaging element has a structure in which the breakage checking circuit shown in FIG. 5 is provided in the transverse direction and the longitudinal direction of the infrared imaging element shown in FIG. 10. When the element is operated, the breakage checking circuit 10a to 12a and the breakage checking circuit 10b to 12b are electrically isolated from each other, and then an infared image can be obtained by the same operation as in the conventional example of FIG. 10. In addition, when the vertical scanner 19 and the horizontal scanner 21 are electrically isolated from each other, the circuit shown in FIG. 8 is equivalent to the two breakage checking circuits shown in FIG. 5, so that the breakage of the bus line can be detected in the both directions in the same way as in the above third embodiment.
In the above-described first to fifth embodiments, infrared imaging elements using Schottky barrier diodes for the photodetectors are described. However, the present invention can be applied to infrared imaging elements or visible imaging elements using other photodetectors.
In addition, as the signal reading out systems, a CSD system, a CCD system, and an MOS system are used in the above embodiments. However, the breakage of the bus line can be detected using the breakage checking circuit of FIG. 5 or 6 also in a solid state imaging element having another reading out system, as far as it has bus lines in the transverse direction or longitudinal direction.
In the above described first to fifth embodiments, since a breakage checking circuit for detecting breakage of a bus line is provided in an infrared imaging element, it is possible to detect which bus line is broken in the first and second embodiments, and it is possible to detect the existence of a broken bus line in the third and fourth embodiments. Therefore, the time required for and cast of the wafer test process and the assembly process are reduced. In addition, since an identification of the broken bus line can be performed in the wafer test, the breakage checking circuit of the present invention is also effective for failure analysis. | A solid state imaging element includes a plurality of photodetectors arranged in a two-dimensional array on a semiconductor substrate, first and second charge transfer circuits for transferring signal charges in a vertical direction and a horizontal direction, respectively, a plurality of transfer gates for controlling charge transfer from the photodetectors to the first charge transfer circuit, a scanner for controlling switching of the transfer gates, a plurality of bus lines connecting the transfer gates with the scanner, and a bus line breakage checking circuit. The bus line breakage checking circuit includes a plurality of transistors connected in series with respective bus lines, a test pad connected with the bus lines through the transistors, and a voltage applying pad for applying a voltage to control switching of the transistors. Therefore, the breakage of a bus line can be detected in a wafer test without actually operating the element, whereby time and money are saved. | 7 |
CROSS-REFERENCED TO RELATED APPLICATIONS
[0001] The present invention is a Continuation of and claims priority from U.S. patent application Ser. No. 11/160,147, filed on Jun. 10, 2005, and entitled “Lacrosse Handle,” which claims priority from U.S. Provisional Application Ser. No. 60/578,488, filed Jun. 10, 2004, and entitled “Flower Shaped Handle.”
TECHNICAL FIELD
[0002] The present invention generally relates to the handle portion of a lacrosse stick for use by participants in the sport or game of lacrosse. The present invention, more particularly, relates to a lacrosse handle that has increased impact strength, allows for increased shooting accuracy and allows for a better grip than conventional lacrosse handles.
BACKGROUND OF THE INVENTION
[0003] Original lacrosse handles were constructed of wood. These wooden handles were shaped such that the lacrosse handle and lacrosse head were a single one-piece wood structure. These one-piece wooden lacrosse handles suffered from a variety of disadvantages. Initially, they were susceptible to damage from excess exposure to water. Further, these prior wooden handles were heavy and somewhat cumbersome. Additionally, the wooden handles were also susceptible to breakage. Moreover, because the wood had to be bent to form the single sidewall and the scoop, a significant amount of time was involved in forming or making each of these wooden lacrosse sticks. Accordingly, if any portion of the head or the handle broke or was damaged, the entire wooden stick needed to be replaced, which was a costly endeavor.
[0004] Subsequently, plastic lacrosse heads were developed. Thus, the lacrosse heads and the lacrosse handles were separate components that could be manufactured individually. Moreover, if either the lacrosse handle or the lacrosse head was damaged or broken, each of these components could be individually replaced.
[0005] Thereafter, metal lacrosse handles were developed for engagement with the plastic lacrosse heads. The initial metal handles were relatively heavy, which provided disadvantages from both a playability standpoint as well as from a safety standpoint. These lacrosse handles were constructed of a durable metal, such as aluminum. While these aluminum handles were acceptable from a strength standpoint and are still commonly used today, they are susceptible to damage from external forces. It is known that lacrosse is a fast-paced, high-contact sport and that the lacrosse handles can be subjected to large forces during play, such as when contacted by another stick. Lacrosse handles are most commonly subjected to external forces when a player is checked by an opponent's stick in an attempt to dislodge the lacrosse ball from the head. Further, if the external force is great enough, the stick can even break. Players, therefore, desire stronger and more durable handles with increased impact strength.
[0006] Therefore, a need exists for a lacrosse handle that has increased strength and durability and provides increased resistance to damage from external forces. It would also be desirable to provide a handle or stick with these characteristics that does not significantly add to the weight of the stick.
[0007] Accordingly, titanium handles were introduced that provided increased strength and resistance to damage from external forces. However, both the titanium and aluminum handles are still susceptible to damage. The damage can be in the form of dents or dings which will typically cause the stick to look worn or used. This is an undesirable feature for many players and can require a player to prematurely replace the handle or render a handle unplayable. Additionally, players seek a lacrosse stick that has an obvious head to handle orientation so that they can very quickly determine the proper grip on their handle. Finally, accuracy is another key element during the play of a lacrosse game. Therefore, players seek a very precise handle having a particular flex characteristic that increases accuracy when shooting the ball.
SUMMARY OF THE INVENTION
[0008] It is therefore an advantage of the present invention to provide a lacrosse handle that is stronger and more durable than existing lacrosse handles.
[0009] It is another advantage of the present invention to provide a lacrosse handle that has increased impact strength as compared to prior lacrosse handles.
[0010] It is still another advantage of the present invention to provide a lacrosse handle that gives a player feedback as to the orientation of a lacrosse head attached to the lacrosse handle based solely on how the player grips the handle.
[0011] It is yet another advantage of the present invention to provide a lacrosse handle that provides increased accuracy when shooting or passing a lacrosse ball.
[0012] It is a related advantage of the present invention to provide a lacrosse handle with flex characteristics that allow for increased shooting accuracy.
[0013] It is a further advantage of the present invention to provide a lacrosse handle with a unique cross-section that allows for better grip, which also results in more accurate control of the ball.
[0014] It is yet a further advantage of the present invention to provide a handle with a unique cross-section that provides tactile feedback as to the orientation of an attached lacrosse head during play.
[0015] In accordance with the above and the other advantages of the present invention, the present invention discloses an elongated handle for attachment to a lacrosse head. The handle includes a first side having a first channel, a second side having a second channel, a first end wall and a second end wall. The first side also includes a first edge and a second edge. Similarly, the second side includes a first edge and a second edge. The first end wall extends between the first edge of the first side and the first edge of the second side. The second end wall extends between the second edge of the first side and the second edge of the second side. The resultant handle has improved strength and resistance to impact.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The present invention will be described by way of example with reference to the following drawings.
[0017] FIG. 1 illustrates a front view of a lacrosse handle with an attached lacrosse head in accordance with a preferred embodiment of the present invention;
[0018] FIG. 2 illustrates a perspective view of a lacrosse handle in accordance with the preferred embodiment of the present invention; and
[0019] FIG. 3 illustrates a cross-sectional view of the lacrosse handle of FIG. 2 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] Referring to FIGS. 1-3 , the lacrosse stick of the present invention is generally referred to as reference number 10 and includes an elongated handle 12 that attaches to a lacrosse head 40 . In one embodiment, the handle 12 is generally hollow and is constructed of a metallic material, such as aluminum or titanium. It will be understood that the handle 12 can take on a variety of other configurations, i.e. solid or partially solid. Further, the handle 12 can be formed of a variety of other suitable materials, such as graphite, other composite materials, or plastic. The handle 12 has a first side or sidewall 14 and a second side or sidewall 16 .
[0021] Each of the sidewalls 14 , 16 includes a respective channel 18 , 20 . Further, each sidewall 14 , 16 has a first edge 22 , 24 located at an upper edge of the respective channel 18 , 20 , and a second edge 26 , 28 located at a lower edge of the respective channel 18 , 20 . A first end wall 30 extends between and connects the first edge 22 of the first sidewall 14 and the first edge 24 of the second sidewall 16 . Similarly, there is a second end wall 32 that extends between the second edge 26 of the first sidewall 14 and the second edge 28 of the second sidewall 16 . The end wall walls 30 , 32 are preferably oriented such that they are arched and bow out or curve away from each other and the sidewalls to which they connect. It will be understood by one of ordinary skill in the art that the walls 30 , 32 can take on a variety of different configurations as desired.
[0022] Each of the channels 18 , 20 preferably is set back with respect to the respective sidewall 14 , 16 in which it is formed. The channels 18 , 20 preferably extend along the length of the handle. However, the channels 18 , 20 may extend along less than all of the entire length as desired. Each channel 18 , 20 includes a bottom channel wall 42 , 44 . The bottom channel wall 42 extends between and connects the first edge 22 and the second edge 26 of the first sidewall 14 . The bottom channel wall 44 extends between and connects the first edge 24 and the second edge 28 of the second sidewall 16 . The bottom channel walls 42 , 44 are preferably curved, but may alternatively take on a variety of different configurations. Because the bottom channel walls 42 , 44 are disposed inwardly or set back with respect to the sidewalls 14 , 16 they provide increase strength and impact resistance to the handle 12 , particularly from contact to either end wall 30 , 32 of the handle 12 . Further, this channel configuration allows the handle to flex due to their set back configuration which provides a handle with more whip.
[0023] Each of the end walls 30 , 32 has an exterior surface. In one embodiment, the exterior surface of the end wall 30 is textured, as generally represented by reference number 33 while the exterior surface of the end wall 32 has a smooth surface as generally represented by reference numeral 37 . The end wall 30 , as shown in FIG. 1 , is illustrated as the upper wall, while the end wall 32 is illustrated as the lower wall. However, it will be understood that this is for purposes of illustration only and that the end walls 30 , 32 may be oriented such that either may be disposed as the top surface or the bottom surface of the handle 12 .
[0024] Further, the textured surface extends between a portion of the first sidewall 14 and a portion of the second sidewall 16 . Specifically, referring to the first sidewall 14 , the area 39 between the first sidewall 14 and first edge 22 to the first channel 18 is also preferably textured. Similarly, the area 49 on the second sidewall 16 between the first edge 24 and the second channel 20 is also textured. It will also be understood that the texture may extend along the end wall 30 along the entire length of the handle. Alternatively, the texture may instead be disposed over only a substantial part of the end wall 30 . Further, the texture may be located on the end wall 30 at only select locations along the length of the handle 12 , such as in locations where a player's hands typically contact a lacrosse handle during play. One of ordinary skill in the art will understand these locations. Similarly, the texture may extend over the entire length or only a portion of the first sidewall 14 and/or the second sidewall 16 .
[0025] The smooth surface also extends between and connects a portion of the first sidewall 14 and a portion of the second sidewall 16 . The area 59 between the second edge 26 of the first sidewall 14 and the first channel 18 is preferably smooth and the area 69 between the second edge 28 and the second sidewall 16 to the second channel 20 is smooth. In other words, half of the first sidewall 14 is smooth and half of the first sidewall 14 is textured. Similarly, half of the second sidewall 16 is smooth and half of the second sidewall 16 is textured. It will be understood that instead of a texture, a surface structure can be located on one side of the handle. Other textured surface to smooth surface configurations may be utilized.
[0026] Since half of the handle 12 is textured and the other half is smooth, the user or player has a much better handle to head orientation during play. Moreover, a texture on one side or half of the handle provides a player with a better grip on the stick for improved ball handling as well and improved shooting and passing accuracy. In other words, depending upon where or how the texture contacts the player's hands, it provides the player with tactile feedback as to the orientation of the attached head. One method of adding texture to the textured area is through sand blasting. However, a variety of other methods for forming the textured surface may be utilized.
[0027] The player can decide how to position the textured surface relative to the lacrosse head. For instance, in FIG. 1 , the smooth surface 37 is shown positioned adjacent to the front face of the lacrosse head 40 . It should be understood that the textured surface 33 could be positioned adjacent to the front face of the lacrosse head 40 .
[0028] Both channels 18 , 20 along each of the sidewalls 14 , 16 serve multiple purposes. One purpose is to provide an additional gripping surface on the handle 12 . Another purpose is to receive an insert 34 , 36 . The inserts 34 , 36 might be long, thin strips of plastic. Further, the inserts 34 , 36 may extend the whole length of the channel. However, it will be understood that the inserts 34 , 36 may instead extend along only a portion of the channels 18 , 20 . In one embodiment, the inserts 34 , 36 can have writing or include color and are for purposes of aesthetics. Some examples include, but are not limited to, the name of the handle manufacturer, the name of the player's team, or a team's colors. The inserts are preferably releaseably engageable with each channel 18 , 20 . Still another purpose is to provide a handle with increased flex.
[0029] Referring to FIG. 2 , first insert 34 is shown located within the first channel 18 and the second insert 36 is shown located within the second channel 20 . Although a total of two inserts are shown with, one in each channel, it is to be understood that there could be only one insert used in one of the channels while the other channel is left empty. Further, multiple inserts can be disposed in each channel at a given time.
[0030] The handle 12 has a first distal end 54 and a second distal end 56 . The lacrosse head 40 is attached to the handle 12 at its first distal end 54 and an end cap 52 is attached to the handle 12 at the second distal end 56 .
[0031] While the present invention has been described in what is presently considered to be its most practical and preferred embodiment or implementation, it is to be understood that the invention is not to be limited to the disclosed embodiment. On the contrary, the present invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as is permitted under the law. | A lacrosse handle having two sidewalls each with a channel and two arched walls extending between the sidewalls is disclosed herein. The channels contribute to increased gripping ability by the user and overall increased strength of the handle. Each channel is capable of receiving an insert that includes individualized information, for example, a school name or colors. Further, one of the arched walls may have a textured surface and the other arched wall may have a smooth surface to provide the user with a more accurate handle to head orientation than conventional lacrosse handles. | 0 |
FIELD OF THE INVENTION
[0001] The present invention relates to the field of synchronization and more particularly, to synchronization in an n-tier architecture.
BACKGROUND OF THE INVENTION
[0002] The Internet is changing many aspects of our lives, but no area is undergoing as rapid and significant a change as the way businesses operate. For businesses today, Internet technology is no longer an afterthought in forming a business strategy but has become a driving force. e-business is defined by many organizations as the transformation of key business processes through the use of Internet technologies. An e-business connects critical business systems directly to customers, employees, suppliers, and distributors via the Internet to improve time to market, access a broader base of customers and suppliers, improve efficiency, and reduce costs.
[0003] Examples of companies implementing an e-business model include retailers offering online purchasing integrated with online supply chain management or electronic financial service organizations that reduce the high cost of transactions while providing improved access to customer accounts. e-business has progressed from being a means of automating certain business functions to become an essential element of competitive business.
[0004] A framework is a reusable design expressed as a set of abstract patterns and the way their interfaces collaborate. It is a reusable design for all or part of a software system; a user interface framework only provides a design for the user interface of a system while an application framework provides a design for the entire application.
[0005] Application frameworks are becoming increasingly important for developing complex applications. An application framework describes a set of interacting components and services available to an application, the responsibilities of and the interactions between the components and services. A developer creates an application by composing and extending the components and services available in the application framework. Application frameworks typically address specific business domains, such as manufacturing or finance.
[0006] Early frameworks revolved around programming languages, such as an object-oriented (OO) design framework. Application frameworks do not have to be implemented in an object-oriented language, but they do have characteristics similar to 00 design in that each component of the framework has defined interfaces and behaviour. An application framework provides a context for the software, servers, and services necessary to create, deploy, and manage complex e-business applications.
[0007] The application framework used by International Business Machines Corporation for e-business provides a model for designing e-business solutions. This model has evolved from the traditional client/server computing model and is based on an “n-tier” distributed environment where tiers of application logic and business services are constructed from components that communicate with each other across a network.
[0008] In its most basic form, the framework can be depicted as a logical three-tier computing model meaning that there is a logical, but not necessarily physical, separation of processes. With reference to FIG. 1 , there is shown an example of a three-tier model ( 100 ) comprising a client tier ( 105 ), a middle tier ( 110 ) and a third tier ( 115 ).
[0009] The client tier ( 105 ) comprises clients (e.g. smartcards, digital wireless telephones, personal digital assistants (PDAs)) having logic related to sending requests to applications (e.g. through a browser or Java applet) and to presenting information and results produced by an application to the user (via a graphical user interface). The clients are sometimes referred to as “thin” clients, meaning that little or no application logic is executed on the client and therefore relatively little software is required to be installed on the client. Typically, only user interaction and input validation functions run on the client. Clients are implemented with industry-standard technologies and protocols (e.g. TCP/IP, HTTP, HTML/DHTML/XML, and Java (Java and all Java-based trademarks are trademarks of Sun Microsystems, Inc. in the United States, other countries, or both)) that enable them to interact with the user, communicate with a middle tier and send and receive standard data formats.
[0010] The use of thin clients improves manageability, flexibility, and time to market. Advantageously, a broader range of client devices can be supported since the dependency on device capabilities are reduced.
[0011] Furthermore, user's application environments can be centrally managed and distributed to client devices of different types and in different locations to provide support for mobile users.
[0012] The middle tier ( 110 ) comprises application servers, which are single application or multi-application servers. In an e-business environment, the servers are web application servers that are optimized for Internet applications. The application servers are the platforms that provide the run-time environment for an application's business logic. The business logic is executed independently of the client type and user interface style. The separation of presentation logic from the application logic enables the creation of reusable application components that can be used from a number of different styles of user interface.
[0013] The middle tier servers incorporate several application integration technologies for communicating with applications, data, and services in other tiers. Web application transaction servers are essential in the e-business infrastructure because the number of online transactions is increasing tremendously. Customers need high-speed transaction processing, robust system reliability, backup and quick recovery of mission-critical applications. Web application servers must also provide a comprehensive integration capability with other systems. They must also connect with each other as well as the back-end third tier to enable these new business processes.
[0014] The web application servers are implemented using various Internet and Java technologies, including the HTTP server and the platform independent Enterprise Java programming environment. The latter eliminates the dependence of the business logic on the underlying hardware, operating system and networking infrastructure, thus increasing portability and decreasing development and maintenance costs. The middle tier incorporates the network infrastructure and foundation services that enable rapid development and deployment of applications in a distributed network environment. Applications ( 120 ) run as a combination of servlets, server-side scripts, and Enterprise JavaBeans (EJBs) in the web application server and its Java Virtual Machine. EJBs provide much of the business logic of an application, particularly access to database and transaction services. EJBs isolate the developer from the unique characteristics of the underlying database and transaction services, simplifying the development of platform independent business logic.
[0015] The third tier ( 115 ) comprises legacy systems that have been used for many years (hence the term “legacy”) that support new and existing internal applications, services and data; and also external applications, services and data from new and existing business partners. Connections to these services leverage value for customers, business partners and employees. External services and legacy systems are fundamental to the emergence of the web application model because they are the result of years of corporate investment in information technology. These are the mission-critical applications and data that everyone depends on daily, and they are the business assets that need to be made available to the Web in a secure, controlled way to enable companies to leverage their value for customers, employees, and suppliers in intranets and extranets. The servers in this tier provide the data storage and transactional applications used by the web application server processes.
[0016] Application elements residing in these three logical tiers are connected through a set of industry-standard protocols, services, and software connectors. The connectors ( 125 , 126 , 127 ) connect the new, value-add business logic in the middle tier to the vast accumulated assets in a company's existing applications and data systems in the back-end tier. The business logic running on the middle tier accepts a request (e.g. HTTP request) from the client and invokes a connector to securely communicate with the back-end tier services on the client's behalf.
[0017] An alternative model is the “data synchronization” model. With reference to the distributed system ( 200 ) of FIG. 2 , an application resides on a server ( 215 ) (e.g. in storage ( 220 )) and a replica of the same application resides on a “fat client” (e.g. a personal computer) ( 205 ) (e.g. in storage ( 210 )). The fat client executes most or all of the processing of applications itself. When a user is offline, they can work locally on the replica data and at intervals, the user connects to the server ( 215 ), via a network ( 225 ) and the replica data is synchronized with the master data residing on the server ( 215 ). This model is often used for Personal Information Management (PIM) applications e.g. calendar, email etc and is particularly useful for mobile clients, which are only intermittently connected to the network.
[0018] Currently, many organizations would like to include data synchronization as a method to deliver e-business applications. For example, banks would like to provide customers with the ability to view and manipulate their accounts from a PDA application, with regular synchronization of the local data on the PDA with the master data on the back-end tier. However, the data synchronization model does not fit well with the e-business three-tier model. Specifically, organizations are unwilling or unable to synchronize their complex, highly protected back-end databases directly with the clients. Another complexity is that the business logic of applications running on a web application server, is driven by HTTP requests and produces HTTP responses. Synchronization protocols that are required between a client and the back-end tier are not understood by the business logic.
[0019] One possible solution is to extract a copy of the data from the back-end tier to the middle tier. The clients can then connect to the middle tier and update the data. The updated data can then be synchronized with the data stored on the back-end tier via the middle tier.
[0020] However, this solution has disadvantages. Firstly, the data that the client works on will always be out of date, especially if the data is extracted in an overnight batch. Furthermore, new application function must be developed to synchronize the updated data with the data on the back-end tier in order to maintain coherent data on the back-end tier. This in turn results in the need for distributed transaction processing, which has well-known drawbacks. For example, if a transaction coordinator “commits” a transaction (e.g. Bank A debits money from Account A and Bank B credits the money to Account B), to all resource managers that are participating in that transaction but then the network were to go down, the coherence of the state of the transaction can not be relied upon. Some of the resource managers would register the transaction as being completed, but some may not. Typically, the resource managers that require clarification on the outcome of the transaction need to contact the transaction coordinator. However, this is not possible until the network is live again and in the meantime, Accounts A and B could be locked for some time. Another disadvantage is that to scale the solution to several thin clients, the middle tier must typically comprise several web application servers. The problem of maintaining coherency therefore dramatically increases.
[0021] U.S. Pat. No. 6,023,684 discloses a three tier model, whereby at the initiation of a logical session with a client program, an application service refreshes data for a customer associated with the client program, by using data obtained from a back-end processing system through the host interface. The data is stored in local data memory associated with the application service and this data is then used by the application service for processing client requests during the logical session. The local data memory permits the processing of the client request to be decoupled from the updating of the back-end processing system.
[0022] Thus there is a need for a model that provides the benefits of the data synchronization model and the “n-tier” model, without the need for extensive change of the “n-tier” model.
DISCLOSURE OF THE INVENTION
[0023] According to a first aspect, there is provided a method of synchronization for use in a distributed data processing system comprising: at least one legacy computer having means for storing a master version of data, a first non-legacy computer having means for supporting synchronization, and a second non-legacy computer having means for storing a copy of said master version of data and means for executing at least one operation on said copy, said method comprising the steps of: executing, by said second non-legacy computer, said at least one operation on said copy, sending, by said second non-legacy computer, said at least one operation to said first non-legacy computer, executing, by said first non-legacy computer, said at least one operation on said master version at said at least one legacy computer, determining if said executing step is successful, and in response to a successful executing step, synchronizing said master version by applying said at least one operation.
[0024] As an example, the legacy computer is a mainframe computer, the fist non-legacy computer is a web application server and the second non-legacy computer is a PDA. Preferably, the method further comprises the step of: sending, by the second non-legacy computer, a synchronization protocol to the first non-legacy computer. The protocol will typically be particular to the type of second non-legacy computer. In a preferred embodiment, if there are two or more operations to be executed on the legacy computer, the operations are executed in sequence.
[0025] Aptly, once the at least one operation has been executed on the legacy computer, the first non-legacy computer sends the results (i.e. success/failure notification as well as the resulting data itself) and a new copy of the master version of data to the second non-legacy computer. Preferably, if the at least one operation cannot be executed on the master version (e.g. because of conflicting concurrent operations), master version is not synchronized.
[0026] According to a second aspect, there is provided a distributed data processing system for synchronization comprising: at least one legacy computer having means for storing a master version of data, a first non-legacy computer having means for supporting synchronization, and a second non-legacy computer having means for storing a copy of said master version of data and means for executing at least one operation on said copy, said system further comprising: means for executing, by said second non-legacy computer, said at least one operation on said copy, means for sending, by said second non-legacy computer, said at least one operation to said first non-legacy computer, means for executing, by said first non-legacy computer, said at least one operation on said master version at said at least one legacy computer, means for determining if said executing step is successful, and means, responsive to successful determination, for synchronizing said master version by applying said at least one operation.
[0027] According to a third aspect, there is provided a computer program comprising computer program code means adapted to perform all the steps of the above method when said program is run on a computer.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] The present invention will now be described, by way of example only, with reference to preferred embodiments thereof, as illustrated in the following drawings:
[0029] FIG. 1 is a schematic representation of a prior art “n-tier” model;
[0030] FIG. 2 is a schematic representation of a prior art data synchronization model;
[0031] FIG. 3 is a schematic representation of an “n-tier” model, in accordance with the present invention;
[0032] FIG. 4 is a flow chart showing the operational steps involved in a data synchronization process, implemented in the model as shown in FIG. 3 ;
[0033] FIG. 5 is a sequence diagram of the flows involved in the data synchronization process between the components in the model as shown in FIG. 3 ; and
[0034] FIG. 6 is a representation of the results of data synchronization.
DETAILED DESCRIPTION OF THE INVENTION
[0035] FIG. 3 shows a pictorial representation of a three-tier model ( 300 ) in which the present invention may be implemented. There is shown a client tier ( 305 ), a middle tier ( 315 ) and a back-end tier ( 325 ) having associated storage means ( 310 , 320 and 330 respectively). The client tier ( 305 ) and middle tier ( 315 ) are connected by a software connector ( 331 ) and the middle tier ( 315 ) and back-end tier ( 325 ) are connected by software connectors ( 332 and 333 ). The applications and services on the back-end tier ( 325 ) are protected by a firewall ( 335 ).
[0036] One embodiment of the present invention will now be described with reference to FIGS. 3, 4 and 5 . An example of a banking application is described, whereby the thin client ( 305 ) is a PDA, the middle tier ( 315 ) is a web application server and the back-end tier ( 325 ) is a data repository for storing master versions of bank account data.
[0037] Preferably, the thin client ( 305 ) comprises a function, which when executed, obtains a copy of a user's bank account data from the storage means ( 330 ) of the back-end tier ( 325 ). Preferably, the copy is stored locally in the storage means ( 310 ) associated with the thin client ( 305 ). In this example, bank account data with a balance of £300 is stored locally. The user executes (step 400 , 500 ) operations (e.g. changes/updates) against the local data. In this embodiment, the operations are:
A monetary transfer of £50 into the account Setting up a standing order of £100 out of the account Making a one-off payment of £75 out of the account
[0041] However, the local data is more than likely to be outdated with respect to the master version residing on the back-end tier ( 325 ). This is because some of the user-initiated operations may clash with concurrent operations being applied to the master version of the user's bank account at the back-end tier ( 325 ). For example, standing orders being paid, monetary transfers to savings accounts, mortgage payments, etc. In this embodiment, a concurrent operation has been applied to the master version of the user's bank account. In this example a one-off payment of £200 has been taken out of the user's bank account and therefore, the actual balance stands at £100 (i.e. £300−£200=£100).
[0042] Since the operations initiated by the user have not yet been reconciled with any concurrent operations that have been applied to the master version, preferably, the user's operations are retained in a list. The thin client ( 305 ) therefore stores two types of data, namely, a copy of the “current” (possibly slightly divergent from the master version) data (i.e. the user's bank account data) and a list of pending operations (i.e. a list of operations 1, 2 and 3 above).
[0043] Next, the user at the thin client ( 305 ) sends (step 405 , 505 ) a request (Request A) to synchronize the updated local data with the master version via an HTTP request to the middle tier ( 315 ). The middle tier ( 315 ) acknowledges receipt of “Request A” by sending (step 410 , 510 ) back an HTTP response (Response A′) instructing the thin client ( 305 ) to proceed with synchronization. It should be understood that this request/response exchange is an optional stage. Next, the user at the thin client ( 305 ) sends (step 415 , 515 ) an HTTP request (Request B) to the middle tier ( 315 ) in order to start synchronization. The thin client's standard synchronization protocol is also sent to the middle tier ( 315 ). Advantageously, in addition to exploiting the business application logic on the middle tier by using the HTTP request/response model, the functions of the middle tier, which can run native thin-client synchronization protocol(s), are also exploited.
[0044] The synchronization process now starts (step 420 ). Specifically, the data to be synchronized is the list of operations (1, 2 and 3 above) that the user at the thin client ( 305 ) would like to perform. In the synchronization step, the list of operations is loaded from the thin client ( 305 ) to the middle tier ( 315 ). The middle tier ( 315 ) then replays ( 520 ) the operations in the list on the back-end tier ( 325 ); that is, a monetary transfer of £50 is made into the account, a standing order of £100 out of the account is set up and a one-off payment of £75 is made out of the account. It should be understood that preferably, the replaying step occurs promptly, so that the chances of conflicts are decreased. Also, preferably, the list of operations is replayed sequentially.
[0045] It should be understood that some of the user-initiated operations may succeed and some of them may fail, depending on whether any conflicting concurrent operations have been applied to the master version residing on the back-end tier ( 325 ). If concurrent operations have been applied to the master version, these would have been applied after the thin client ( 305 ) had received a “current” copy of the data. At step 425 , for each operation, a determination is made as to whether it is successful or not. In response to a positive result, the master version of the data is synchronized (step 430 ) to reflect the successful user-initiated operations and in response to a negative result, the master version of the data is not synchronized (step 435 ). In this example, the actual bank account balance stands at £100. Therefore, operation 1 succeeds (after which, the actual bank account balance=£150), operation 2 succeeds (after which, the actual bank account balance=£50) and operation 3 fails (because the actual bank account balance would=£−25).
[0046] Next, the back-end tier ( 325 ) sends ( 525 ) the results of the user-initiated operations to the middle tier ( 315 ) as well as a copy of the new (updated) master version of the bank account (in this example, the actual bank account balance=£50).
[0047] The middle tier ( 315 ) monitors (step 440 ) the results of these operations and sends (step 445 , 530 ) the results and also the copy of the new master version of the bank account to the thin client ( 305 ). The new master version of the bank account replaces the local copy that was used by the user in step 400 .
[0048] The synchronization process has now ended and this is indicated to the user by sending (step 450 , 535 ) an HTTP response (Response B′) from the middle tier ( 315 ) to the thin client ( 305 ). Preferably, the user can then be presented with an updated view of the state of the bank account, a list of the successful operations and a list of failed operations. An example of the view ( 600 ) is shown in FIG. 6 . At step 455 , if no further operations are to be carried out, the process ends. However, in response to a positive result, processing returns to step 400 where, for example, a user can act upon the failed operations by canceling them, modifying them, deferring them etc.
[0049] Advantageously the middle tier only needs to access the master version of the data after synchronization has occurred, in order to send the thin client an up-to-date copy of the new master version of the data. Furthermore, the preferred embodiment accommodates the possibility that concurrent operations might have been applied to the master version of the data. This scenario is handled without the need for consistent copies of the data at the thin client and the back-end tier.
[0050] Another advantage is that the benefits of a data synchronization model are provided without the need to extensively change the three-tier model. Therefore, the present invention can be utilized in systems that are already supported by many organizations today. For example, the existing relationship between the thin client and middle tier can be used, namely, the currently available HTTP and PDA-synchronization protocols. However, it should be understood that the present invention could be implemented with other protocols. Furthermore, although a three-tier model has been described, the present invention could be implemented in a model with “n” tiers. Also, although a PDA, web application server and back-end host have been described, it should be understood that the tiers could comprise any other computer machine. | A method of synchronization for use in a distributed data processing system comprising a legacy computer having means for storing a master version of data, an application server, and a thin client computer which stores a copy of the master version of data. Firstly, the thin client executes operations locally on the copy. The operations are sent in a list to the application server. The application server executes the operations on the master data, on behalf of the thin client. If the operations can be executed successfully on the master version, synchronization occurs in that the successful operations are applied to the master version. | 6 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a Continuation of U.S. application Ser. No. 11/196,250, filed Aug. 4, 2005 now U.S. Pat. No. 7,268,443, which claims priority from Japanese patent application JP 2004-230058, filed on Aug. 6, 2004, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates to a wind turbine generator system, and in particular to a wind turbine generator system capable of continuous operation of a wind turbine by maintaining the rotational velocity of the wind turbine.
Explanation will be given on the conventional wind turbine generator system. The wind turbine is connected to a generator. The wind turbine is rotated by wind power and the wind turbine drives the generator, so that the generator generates electricity. When using a synchronous generator as the generator, the stator of the generator is connected to a converter and AC power outputted from the generator is converted into DC power by the converter. Furthermore, the power is converted into AC power of a commercial frequency by an inverter and supplied to a power system. The converter regulates the output of the generator according to a power instruction given from outside. An example of the wind turbine generator system having such a configuration is disclosed in JP-A-2002-233193 (Paragraphs [0029] to [0031]).
The wind turbine generator system is greatly affected by fluctuation of the wind velocity, which makes the rotational velocity of the wind turbine fluctuate. When the rotational velocity of the wind turbine is out of the operation range, the operation is normally stopped so as to protect the wind turbine. Here, conventionally, when the wind velocity fluctuates, the pitch angle of the wind turbine blade is controlled according to the wind velocity or the power instruction given to the converter is adjusted according to the wind velocity, thereby suppressing the wind turbine rotational velocity fluctuation.
However, control of the pitch angle by driving the wind turbine blade according to the wind velocity includes mechanical operation and cannot have a high response. When the power instruction given to the converter is adjusted according to the wind velocity, decision is normally made by the power curve based on the average wind velocity and it is difficult to follow the transient wind velocity change. Accordingly, when the wind velocity changes suddenly and the rotational velocity of the wind turbine deviates from the operation range, the wind turbine may stop. In this case, the wind turbine should be started again.
However, in order to increase the wind turbine generating electrical quantity, it is preferable that the wind turbine continuously operate even when the wind velocity suddenly changes. When the wind turbine generating electrical quantity increases, it is possible to reduce the wind turbine generation cost. Accordingly, it is important to operate the wind turbine continuously and improve the wind turbine use ratio. Moreover, when the wind turbine can be continuously operated, the number of operation times of a contactor or the like for linking the wind turbine with a system is decreased, and hence the service life of these devices can be increased.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a wind turbine generator system capable of controlling the wind turbine rotational velocity within an operation range even when the wind velocity suddenly changes so that the wind turbine can be continuously operated, thereby improving the wind turbine use ratio.
The present invention provides a wind turbine generator system including a generator connected to a shaft of a wind turbine and a converter connected to the generator. When the rotational velocity of the wind turbine is within a predetermined range, the power outputted from the generator is regulated so as to follow an instruction concerning the generator output given from the wind turbine to the converter. When the rotational velocity of the wind turbine is out of the predetermined range, the power outputted from the generator is regulated without following the instruction concerning the generator output.
According to another aspect of the present invention, the wind turbine generator system is characterized in that when the rotational velocity of the wind turbine is within a predetermined range, the power outputted from the generator is regulated so as to follow a value obtained by multiplying the instruction concerning the generator torque given from the wind turbine to the converter, by the rotational velocity of the wind turbine, and when the rotational velocity of the wind turbine is out of the predetermined range, the power outputted from the generator is regulated without following the value obtained by multiplying the instruction concerning the generator torque given from the wind turbine to the converter, by the rotational velocity of the wind turbine.
According to the present invention, it is possible to regulate the output of the wind turbine according to an instruction given from outside when the rotational velocity of the wind turbine is within a set range and when the rotational velocity of the wind turbine is out of the set range, the velocity is regulated so as to suppress the rotational velocity in the set range. Accordingly, when the wind velocity fluctuates, it is possible to prevent stop of the wind turbine.
Other objects, features and advantages of the invention will become apparent from the following description of the embodiments of the invention taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is block diagram showing configuration of a wind turbine generator system using a synchronous generator according to a first embodiment of the present invention.
FIG. 2 is a block diagram showing configuration of a velocity regulator according to the present invention.
FIG. 3 shows a waveform indicating operation characteristics of the velocity regulator according to the present invention.
FIG. 4 is a block diagram showing configuration of a wind turbine generator system using a doubly-fed generator according to a second embodiment of the present invention.
FIG. 5 is block diagram showing configuration of a wind turbine generator system using a synchronous generator according to a third embodiment of the present invention.
FIG. 6 is a block diagram showing configuration of a wind turbine generator system using a doubly-fed generator according to a fourth embodiment of the present invention.
FIG. 7 is a block diagram showing configuration of a wind turbine generator system using a doubly-fed generator according to a fifth embodiment of the present invention.
FIG. 8 is a block diagram showing configuration of a wind turbine generator system using a doubly-fed generator according to a sixth embodiment of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Description sill now be directed to embodiments of the present invention with reference to the attached drawings.
Embodiment 1
FIG. 1 shows the entire configuration of the present embodiment. As shown in FIG. 1 , the synchronous generator 2 has a rotor connected to the shaft of the wind turbine 1 . When the wind turbine 1 rotates according to the wind power based on the wind velocity, the synchronous generator 2 generates AC power of the variable frequency according to the rotational velocity of the wind turbine 1 . The synchronous generator 2 has a stator connected to a converter 3 . The AC power of variable frequency generated by the synchronous generator 2 is converted into DC power by the converter 3 . The converter 3 is DC-connected to the converter 5 via a DC capacitor 4 . The converter 5 converts the DC power fed from the converter 3 into AC power of fixed frequency. The converter 5 is connected to a power system via a system linkage transformer 6 and supplies AC power of a fixed frequency to the power system.
Between the synchronous generator 2 and the converter 3 , there are arranged a voltage detection sensor 7 and a current detection sensor 8 . The voltage detection sensor 7 detects terminal voltage of the stator of the synchronous generator 2 while the current detection sensor 8 detects current flowing through the stator of the synchronous generator. The voltage value detected is converted into the d-axis component V_d and q-axis component V_q by the 3-phase/2-phase converter 9 while the current value detected is converted into the d-axis component I_d and q-axis component I_q by the 3-phase/2-phase converter 10 . It should be noted that in this embodiment, the d-axis component represents an reactive component and the q-axis component represents an active component.
The velocity detector 11 detects the rotational velocity ω of the wind turbine 1 and the rotor phase θ of the synchronous generator 2 according to the signals V_d, V_q, I_d, I_q outputted from the 3-phase/2-phase converters 9 , 10 .
The power detector 12 detects active power P and reactive power Q outputted from the synchronous generator 2 , according to the signals V_d, V_q, I_d, I_q outputted from the 3-phase/2-phase converters 9 , 10 .
The velocity regulator 13 corrects the active power instruction P_c given to the synchronous generator 2 from outside according to the output obtained from a predetermined power curve and the wind velocity measured by the wind turbine, in accordance with the rotational velocity detection value ω detected by the velocity detector 11 and outputs the corrected active power instruction P_ref to the synchronous generator 2 .
The reactive power instruction operator 14 outputs a reactive power instruction Q_ref to the synchronous generator 2 from the active power instruction P_ref to the synchronous generator 2 outputted from the velocity regulator 13 . The reactive power instruction Q_ref is set so as to adjust the power factor of the synchronous generator 2 .
The active power regulator 15 inputs the active power instruction P_ref outputted by the velocity regulator 13 and the active power detection value P outputted by the power detector 12 and outputs the q-axis component I_q_ref of the current instruction to the converter 3 . The active power regulator 15 is formed, for example, by a proportional-integral regulator and decides the current instruction I_q_ref to the converter 3 in such a manner that difference between the active power instruction P_ref and the active power detection value P becomes zero.
The reactive power regulator 16 inputs the reactive power instruction Q_ref outputted from the reactive power instruction operator 14 and the reactive power detection value Q detected by the power detector 12 and outputs the d-axis component I_d_ref of the current instruction to the converter 3 . The reactive power regulator 16 is formed, for example, by a proportional-integral regulator and decides the current instruction I_d_ref to the converter 3 in such a manner that difference between the reactive power instruction Q_ref and the reactive power detection value Q becomes zero.
The q-axis current regulator 17 inputs the q-axis component I_q of the current detection value outputted from the 3-phase/2-phase converter 10 and the q-axis component I_q_ref of the current instruction to the converter 3 and outputs the q-axis component V_q_ref of the output voltage to the converter 3 . The q-axis current regulator 17 is formed, for example, by a proportional-integral regulator and decides the output voltage instruction V_q_ref to the converter 3 in such a manner that the difference between the current detection value I_q and the current instruction I_q_ref becomes zero.
The d-axis current regulator 18 inputs the d-axis component I_d of the current detection value outputted from the 3-phase/2-phase converter 10 and the d-axis component I_d_ref of the current instruction to the converter 3 and outputs the d-axis component V_d_ref of the output voltage to the converter 3 . The d-axis current regulator 18 is formed, for example, by a proportional-integral regulator and decides the output voltage instruction V_d_ref to the converter 3 in such a manner that the difference between the current detection value I_d and the current instruction I_d_ref becomes zero.
The q-axis component V_q_ref and the d-axis component V_d_ref of the output voltage instruction outputted from the q-axis current regulator 17 and the d-axis current regulator 18 are converted into a 3-phase output voltage instruction V_uvw_ref by a 2-phase/3-phase converter 19 .
The pulse generator 20 outputs gate pulse signals to the converter 3 by PWM (Pulse Width Modulation) according to the output voltage instruction V_uvw_ref. The converter 3 receives the gate pulse signals. The power semiconductor switching element such as IGBT and power MOSFET performs high-speed switching and the converter 3 outputs a voltage in accordance with the instruction.
FIG. 2 shows detailed configuration of the velocity regulator 13 . The velocity regulator 13 includes a limiter 21 , a subtractor 22 , an active power correction instruction operator 23 , a change ratio limiter 24 , and an adder 25 . The limiter 21 inputs the rotational velocity detection value ω detected by the velocity detector 11 . The upper limit value and the lower limit value of the limiter 21 are the upper limit value ω_max and the lower limit value ω_min of the rotational velocity of the wind turbine 1 . The subtractor 22 calculates the difference between the rotational velocity detection value ω and the output of the limiter 21 . According to the output of the subtractor, the active power correction instruction operator 23 calculates the active power correction instruction ΔP 1 . The active power correction instruction operator 23 is formed, for example, by a proportional-integral regulator. Furthermore, when its input becomes zero, the integral value is reset and the output is set to zero. The change ratio liter 24 ordinarily outputs directly the active power correction instruction ΔP 1 which is outputted from the active power correction instruction operator 23 but has a function to suppress the change ratio of the output within a certain range. The output is ΔP 2 . The adder 25 adds the output ΔP 2 of the change ratio limiter to the active power instruction P_c given from outside and outputs the active power instruction P_ref to the synchronous generator 2 .
Next, explanation will be given on the operation of the velocity regulator 13 . FIG. 3 shows an example of operation waveform of the velocity regulator 13 . When the rotational velocity detection value ω detected by the velocity detector 11 is between the upper limit value ω_max and the lower limit value ω_min of the limiter 21 , the output of the subtractor 22 is zero. Accordingly, the active power correction instruction ΔP 1 outputted from the active power correction instruction operator 23 is reset to zero and the output ΔP 2 of the change ratio limiter 24 is ordinarily zero. Consequently, the output P_ref of the adder 25 coincides with the active power instruction P_c given from outside. That is, when the rotational velocity detection value ω is between the upper limit value ω_max and the lower limit value ω_min of the rotational velocity of the wind turbine 1 , the velocity regulator 13 outputs the active power instruction P_c given from outside directly as the active power instruction P_ref to the synchronous generator 2 .
On the other hand, when the rotational velocity detection value ω detected by the velocity detector 11 is greater than the upper limit value ω_max of the limiter 21 , the output of the subtractor 22 is positive. Accordingly, the active power correction instruction ΔP 1 outputted from the active power correction instruction operator 23 increases and the output ΔP 2 of the change ratio limiter 24 also increases. Consequently, the output P_ref of the adder 25 is a value greater than the active power instruction P_c given from outside. That is, when the rotational velocity detection value ω is greater than the upper limit value ω_max of the rotational velocity of the wind turbine 1 , the velocity regulator 13 makes correction in the direction to increase the active power instruction P_ref to the synchronous generator 2 and this correction continues until the rotational velocity detection value ω detected by the velocity detector 11 becomes below the upper limit value ω_max of the limiter 21 . When the active power outputted from the synchronous generator 2 becomes greater than the power given from the wind to the blades of the wind turbine 1 , the rotational velocity of the wind turbine 1 decreases. Accordingly, when the rotational velocity detection value ω is greater than the upper limit value ω_max, correction is made in the direction to decrease the rotational velocity of the wind turbine 1 .
On the contrary, when the rotational velocity detection value ω detected by the velocity detector 11 is smaller than the lower limit value ω_min of the limiter 21 , the output of the subtractor 22 is negative. Accordingly, the active power correction instruction ΔP 1 outputted from the active power correction instruction operator 23 decreases and the output ΔP 2 of the change ratio limiter 24 also decreases. Consequently, the output P_ref of the adder 25 is a value smaller than the active power instruction P_c given from outside. That is, when the rotational velocity detection value ω is smaller than the lower limit value ω_min of the rotational velocity of the wind turbine 1 , the velocity regulator 13 makes correction in the direction to decrease the active power instruction P_ref to the synchronous generator 2 and this correction continues until the rotational velocity detection value ω detected by the velocity detector 11 becomes above the lower limit value ω_min of the limiter 21 . When the active power outputted from the synchronous generator 2 becomes smaller than the power given from the wind to the blades of the wind turbine 1 , the rotational velocity of the wind turbine 1 increases. Accordingly, when the rotational velocity detection value ω is smaller than the lower limit value ω_min, correction is made in the direction to increase the rotational velocity of the wind turbine 1 .
With the aforementioned operation of the velocity regulator 13 , when the rotational velocity of the wind turbine 1 is out of a predetermined range, the velocity is regulated so as to suppress the rotational speed of the wind turbine 1 within a predetermined range, and when the rotational velocity of the wind turbine 1 is within the predetermined range, the active power control is performed according to the active power instruction given from outside. As shown in this embodiment, even when the wind velocity suddenly changes, the wind turbine can continuously operate, which improves the use ratio of the wind turbine, increases the electrical quantity generated by the wind turbine, and reduces the cost of generation by the wind turbine. Furthermore, since the wind turbine can be continuously operated, the number of operation times of a device linking the wind turbine with a system such as a contactor can be reduced, which in turn increases the service life of these devices.
Embodiment 2
FIG. 4 shows the entire configuration of the second embodiment using a doubly-fed generator. In FIG. 4 , the rotor of the doubly-fed generator 26 is connected to the shaft of the wind turbine 1 . When the wind turbine 1 rotates by the wind power in accordance with the wind velocity, the doubly-fed generator 26 connected to a power system by the stator supplies AC power matched with the system frequency to a power system. The rotor of the doubly-fed generator 26 is connected to a converter 27 . The converter 27 AC-excites the rotor of the doubly-fed generator 26 . The converter 27 is DC-connected to a converter 29 via a DC capacitor 28 . The converter 29 supplies exciting power to the converter 27 . The converter 29 is connected to the power system via a system linkage transformer 6 .
Between the doubly-fed generator 26 and the converter 27 , there are arranged a voltage detection sensor 30 and a current detection sensor 31 . The voltage detection sensors detects a terminal voltage of the rotor of the doubly-fed generator 26 while the current detection sensor 31 detects current flowing to in the rotor of the double-fed generator 26 . The voltage value detected is converted into a d-axis component Vr_d and a q-axis component Vr_q by a 3-phase/2-phase converter 32 while the current value detected is converted into a d-axis component Ir_d and a q-axis component Ir_q by a 3-phase/2-phase converter 33 .
Between the doubly-fed generator 26 and the system linkage transformer 6 , there are arranged a voltage detection sensor 35 and a current detection sensor 36 . The voltage detection sensor 35 detects a system voltage while the current detection sensor 36 detects current flowing to the power system. The voltage value detected is converted into a d-axis component Vs_d and a q-axis component Vs_q by a 3-phase/2-phase converter 37 while the current value detected is converted into a d-axis component Is_d and a q-axis component Is_q by a 3-phase/2-phase converter 38 .
According to the signals Vr_d, Vr_q, Ir_d, Ir_q, Vs_d, Vs_q, Is_d, Is_q outputted from the 3-phase/2-phase converters 32 , 33 , 37 , 38 , the velocity detector 34 detects the rotational velocity ω of the wind turbine 1 , the rotor phase θr of the doubly-fed generator 26 , and the system voltage phase θs.
According to the signals Vs_d, Vs_q, Is_d, Is_q outputted from the 3-phase/2-phase converters 37 , 38 , the voltage detector 12 detects the active power P and reactive power Q outputted from the doubly-fed generator 26 .
The velocity regulator 13 uses a predetermined power curve and a wind velocity measured by the wind turbine to correct the active power instruction P_c given to the doubly-fed generator 26 from outside according to the rotational velocity detection value ω detected by the velocity detector 34 and outputs the corrected active power instruction P_ref to the doubly-fed generator 26 . Here, the velocity regulator 13 has the same configuration as in the first embodiment.
The reactive power instruction operator 14 outputs the reactive power instruction Q_ref to the doubly-fed generator 26 from the active power instruction P_ref to the doubly-fed generator 26 outputted from the velocity regulator 13 . The reactive power instruction Q_ref is set so as to adjust the power factor of the linkage point with the system.
The active power regulator 15 inputs the active power instruction P_ref outputted from the velocity regulator 13 and the active power detection value P detected by the power detector 12 . The output of the active power regulator 15 becomes the q-axis component Ir_q_ref of the current instruction to the converter 27 . The active power regulator 15 is formed, for example, by a proportional-integral regulator and decides the current instruction Ir_q_ref to the converter 27 in such a manner that the difference between the active power instruction P_ref and the active power detection value P becomes zero.
The reactive power regulator 16 inputs the reactive power instruction Q_ref outputted from the reactive power instruction operator 14 and the reactive power detection value Q detected by the power detector 12 . The output of the reactive power regulator 16 becomes the d-axis component Ir_d_ref of the current instruction to the converter 27 . The reactive power regulator 16 is formed, for example, by a proportional-integral regulator and decides the current instruction Ir_d_ref to the converter 27 in such a manner that the difference between the reactive power instruction Q_ref and the reactive power detection value Q becomes zero.
The q-axis current regulator 17 inputs the q-axis component Ir_q outputted from the 3-phase/2-phase converter 33 and the q-axis component Ir_q_ref of the current instruction to the converter 27 . The output of the q-axis current regulator 17 becomes the q-axis component Vr_q_ref of the output voltage instruction to the converter 27 . The q-axis current regulator 17 is formed, for example, by a proportional-integral regulator and decides the output voltage instruction Vr_q_ref in such a manner that the difference between the current detection value Ir_q and the current instruction Ir_q_ref becomes zero.
The d-axis current regulator 18 inputs the d-axis component Ir_d outputted from the 3-phase/2-phase converter 33 and the d-axis component Ir_d_ref of the current instruction to the converter 27 . The output of the d-axis current regulator 18 becomes the d-axis component Vr_d_ref of the output voltage instruction to the converter 27 . The d-axis current regulator 18 is formed, for example, by a proportional-integral regulator and decides the output voltage instruction Vr_d_ref in such a manner that the difference between the current detection value Ir_d and the current instruction Ir_d_ref becomes zero.
The q-axis component Vr_q_ref and the d-axis component Vr_d_ref of the output instructions outputted from the q-axis current regulator 17 and the d-axis current regulator 18 are converted to a 3-phase output voltage instruction Vr_uvw_ref by a 2-phase/3-phase converter 19 .
According to the 3-phase output voltage instruction Vr_uvw_ref outputted from the 2-phase/3-phase converter 19 , the pulse generator 20 outputs gate pulse signals to the converter 27 by PWM (Pulse Width Modulation). The converter 27 receives the gate pulse signals and outputs voltage in accordance with the instruction by the high-speed switching of the power semiconductor switching element such as the IGBT.
In this embodiment also, the velocity regulator 13 operates in the same way as the first embodiment. Accordingly, even when the doubly-fed generator is used, velocity is regulated so that the rotational velocity of the wind turbine 1 is suppressed within the set range if the rotational velocity of the wind turbine 1 exceeds the set range. When the rotational velocity of the wind turbine 1 is within the set range, the active power control is performed according to the active power instruction given from outside.
Embodiment 3
FIG. 5 shows the entire configuration of the wind turbine generator system according to the present embodiment. The present embodiment uses a synchronous generator and the instruction given from outside serves as a torque instruction to the generator. The torque detector 39 shown in FIG. 5 detects torque T outputted from the synchronous generator 2 according to the signals V_d, V_q, I_d, I_q outputted from the 3-phase/2-phase converters 9 , 10 and the rotational velocity detection value ω detected by the velocity detector 11 .
The velocity regulator 40 corrects the torque instruction T_c given to the synchronous generator 2 from outside according to the rotational velocity detection value ω detected by the velocity detector 11 and outputs the corrected torque instruction T_ref to the synchronous generator 2 . The velocity regulator 40 has the same configuration as the velocity regulator 13 explained in the first and second embodiments.
The torque regulator 41 inputs the torque instruction T_ref outputted from the velocity regulator 40 and the torque detection value T detected by the torque detector 39 . The output of the torque regulator 41 is formed, for example, by a proportional-integral regulator and decides the current instruction I_q_ref to the converter 3 in such a manner that the difference between the torque instruction T_ref and the torque detection value T becomes zero.
The d-axis current instruction operator 42 inputs the q-axis component I_q_ref of the current instruction outputted from the torque regulator 41 and the d-axis current instruction operator 42 outputs the d-axis component I_d_ref of the current instruction to the converter 3 . The d-axis component I_d_ref of the current instruction is set so as to adjust the power factor of the synchronous generator 2 .
The other configuration of the wind turbine generator system according to the present embodiment shown in FIG. 5 is similar to the configuration of FIG. 1 . Even when the instruction given from outside is the torque instruction to the generator, velocity is regulated so as to suppress the rotational velocity of the wind turbine 1 within the set range if the rotational velocity of the wind turbine 1 exceeds the set range. When the rotation speed of the wind turbine 1 is within the set range, torque regulation is performed according to the torque instruction given from outside.
Embodiment 4
FIG. 6 shows the entire configuration of the wind turbine generator system according to the present embodiment. The present embodiment uses a doubly-fed generator and the instruction given from outside serves as a torque instruction to the generator. The torque detector 39 shown in FIG. 6 detects torque T outputted from the doubly-fed generator 26 according to the signals Vs_d, Vs_q, Is_d, Is_q outputted from the 3-phase/2-phase converters 37 , 38 and the rotational velocity detection value ω detected by the velocity detector 34 .
The velocity regulator 40 corrects the torque instruction T_c given to the doubly-fed generator 26 from outside, according to the rotational velocity detection value ω detected by the velocity detector 34 and outputs the corrected torque instruction T_ref to the doubly-fed generator 26 . The velocity regulator 40 may be configured in a similar way to the velocity regulator 13 explained in the first and second embodiments.
The torque regulator 41 inputs the torque instruction T_ref outputted from the velocity regulator 40 and the torque detection value T detected by the torque detector 39 . The output of the torque regulator 41 is the q-axis component Ir_q_ref of the current instruction to the converter 27 . The torque regulator 41 is formed, for example, by a proportional-integral regulator and decides the current instruction Ir_q_ref to the convert 27 in such a manner that the difference between the torque instruction T_ref and the torque detection value T becomes zero.
The d-axis current instruction operator 42 inputs the q-axis component Ir_q_ref of the current instruction outputted from the torque regulator 41 and the output of the d-axis current instruction operator 42 is the d-axis component Ir_d_ref of the current instruction to the converter 27 . The d-axis component Ir_d ref of the current instruction is set so as to adjust the power factor of the linkage point with the system.
The other configuration of the wind turbine generator system according to the present embodiment shown in FIG. 6 is similar to the configuration shown in FIG. 4 . Even when the instruction given from outside is the torque instruction to the generator, velocity is regulated so as to suppress the rotation speed of the wind turbine 1 within a set range if the rotational velocity of the wind turbine 1 exceeds the set range. When the rotational velocity of the wind turbine 1 is within the set range, torque regulation is performed according to the torque instruction given from outside.
Embodiment 5
FIG. 7 shows the entire configuration of the wind turbine generator system according to the present embodiment. The present embodiment employs a doubly-fed generator and the instruction given from outside is the active power instruction to the generator. As shown in FIG. 7 , the arrangement of the voltage detection sensor 43 and the current detection sensor 44 is different from the second embodiment shown in FIG. 2 . The other configuration is similar to that of the second embodiment. In the embodiment shown in FIG. 7 also, when the rotational velocity of the wind turbine 1 exceeds the set range, velocity regulation is performed so as to suppress the rotational velocity of the wind turbine 1 to a set range. When the rotational velocity of the wind turbine 1 is within the set range, the active power regulation is performed according to the active power instruction given from outside.
Embodiment 6
FIG. 8 shows the entire configuration of the wind turbine generator system according to the present embodiment. The present embodiment employs a doubly-fed generator and the instruction given from outside is the torque instruction. This embodiment shown in FIG. 8 is similar to the fourth embodiment except for that the arrangement of the voltage detection sensor 43 and the current detection sensor 44 is different from the fourth embodiment shown in FIG. 6 . In the embodiment shown in FIG. 8 also, when the rotational velocity of the wind turbine 1 exceeds a set range, velocity regulation is performed so as to suppress the rotational velocity of the wind turbine 1 to the set range. When the rotational velocity of the wind turbine 1 is in the set range, the torque regulation is performed according to the torque instruction given from outside.
It should be further understood by those skilled in the art that although the foregoing description has been made on embodiments of the invention, the invention is not limited thereto and various changes and modifications may be made without departing from the spirit of the invention and the scope of the appended claims. | A wind turbine generator system can regulate the rotational velocity of the wind turbine within an operation range even when the wind velocity suddenly changes and can perform continuous operation of the wind turbine. The wind turbine generator system includes a generator connected to the shaft of the wind turbine and a converter connected to the generator. When the rotational velocity of the wind turbine is within a predetermined range, power outputted from the generator is controlled so as to follow the instruction concerning the generator output given from the wind turbine to the converter. When the rotational velocity of the wind turbine is out of the predetermined range, the power outputted from the generator is controlled without following the instruction concerning generator output given from the wind turbine to the converter. | 5 |
TECHNICAL FIELD
An adjustment mechanism for a vehicle brake utilizes an electric motor and controller to optimize brake clearance based on brake temperature and wheel speed.
BACKGROUND OF THE INVENTION
Vehicle brakes include adjustment mechanisms that adjust brake clearance, which comprises a distance between a brake pad and a rotating brake rotor when the vehicle brake is not applied. A minimum brake clearance is required such that brake pads do not drag against the brake rotor. As brake pads wear, the brake clearance increases, which can adversely affect the capability of the vehicle brake to achieve maximum brake torque. To compensate for this an adjustment mechanism is used to move the brake pads toward the brake rotor as the pad wears.
One type of known adjustment mechanism utilizes a mechanical adjustment system that operates in a manner similar to that of a clutch with a known amount of backlash. One disadvantage with this type of system is that if over-adjustment occurs, then the brakes drag. This decreases the overall life of the brake pads.
Another type of adjustment mechanism utilizes electric adjusters to adjust brake clearance. Typically these systems mimic the existing mechanical adjustment mechanism. These types of systems are often complex, expensive, and time consuming to install. Thus, there is a need for a simplified and cost-effective adjustment system that optimizes brake clearance, and which can adjust for brake wear as well as brake drag.
SUMMARY OF THE INVENTION
An adjustment mechanism for a vehicle brake uses an electric motor to optimize brake clearance. A controller controls the electric motor to adjust brake clearance based on brake temperature and wheel speed. An increase in brake temperature during non-braking events signifies brake drag, and once brake drag is identified, the controller actuates the electric motor to increase brake clearance. The controller also adjusts brake clearance to accommodate for brake wear. During a specified adjustment cycle, when wheel speed is above a predetermined speed value, the controller actuates the electric motor to optimize brake clearance.
In one example, the vehicle brake assembly includes a set of pads that are engaged against a rotating brake rotor during a braking event. If drag is identified, the controller actuates the electric motor to move the set of pads away from the rotating brake rotor. To accommodate for pad wear, if wheel speed is greater than the predetermined speed value, the controller actuates the electric motor to move the set of brake pads toward the rotating brake rotor until a predetermined temperature increase is sensed. Once the predetermined temperature increase is identified, the electric motor moves the non-rotating brake component away from the rotating brake component by a certain amount to provide an optimized brake clearance.
The subject invention provides a simple, effective, and reduced cost method and apparatus for optimizing brake clearance. These and other features of the present invention can be best understood from the following specification and drawings, the following of which is a brief description.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a vehicle brake assembly and associated adjustment mechanism incorporating the subject invention.
FIG. 2 is a flow chart describing a method of brake adjustment incorporating the subject invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
As shown in FIG. 1 , a vehicle brake 10 includes a rotor 12 that rotates about an axis 14 . Brake pads 16 are mounted to a non-rotating vehicle structure (not shown), and are spaced by a clearance shown generally at 18 from the rotor 12 when the vehicle brake 10 is not applied.
An adjustment mechanism 20 that operates according to the subject invention is used to optimize the clearance 18 to accommodate both pad wear and brake drag. While the vehicle brake 10 shown in FIG. 1 comprises a disc brake, it should be understood that the adjustment mechanism 20 and method of operating the adjustment mechanism 20 could also be used with other types of vehicle brakes.
The adjustment mechanism 20 includes an electric motor 22 that is operated by a control unit or controller 24 . The controller 24 includes a power/ground connection interface and a vehicle data link, as indicated in FIG. 1 . The electric motor includes a position sensor 26 that monitors motor position as known. Motor position data is communicated to the controller 24 via a motor signal 28 . The controller 24 compiles and tracks motor rotation data from the motor signal 28 to estimate the amount of clearance and to provide pad wear information to an operator.
A temperature sensor 30 measures and monitors the temperature of at least one brake component. Preferably, the temperature sensor 30 measures the temperature of the rotor 12 and/or brake pad 16 . The temperature sensor 30 generates a temperature signal 32 that communicates brake temperature data to the controller 24 . A single brake temperature sensor can be used to measure the temperature of either the rotor 12 or brake pad 16 , or separate temperature sensors could be used for each of the brake pad 16 and rotor 12 . The sensor is shown schematically and would be positioned in an appropriate location to sense the temperature.
A wheel speed sensor 34 measures and monitors wheel speed. The wheel speed sensor 34 generates a wheel speed signal 36 that communicates wheel speed data to the controller 24 .
The electric motor 22 includes a motor output shaft 40 that drives a gear reduction 42 . The gear reduction 42 drives a set of tappets 44 that are associated with the brake pads 16 . Under predetermined/specified conditions, the controller 24 generates a control signal 46 to actuate the electric motor 22 to adjust clearance 18 by driving the gear reduction 42 and tappets 44 . The electric motor 22 can be used to increase or decrease the clearance 18 between the rotor 12 and pads 16 . A connection between pads 16 and tappets 44 may be as known, and is not shown here for purposes of clarity. Further, any type of known gear reduction can be used to drive the tappets 44 . The controller 24 determines which type of adjustment is needed based on various factors, such as brake temperature and/or wheel speed, for example. This will be discussed in greater detail below.
FIG. 2 depicts a flowchart that sets forth the steps for adjusting clearance with the adjustment mechanism 20 . A closed-loop process is initiated at a start 100 . The controller 24 then determines if a measured brake temperature is excessive at step 110 . An excessive temperature level is typically a temperature at which a significant brake problem potentially exists. If an excessive brake temperature does exist, the controller 24 issues a warning and records the event at step 120 .
After such a warning is issued, the controller 24 then determines if a deceleration that would be indicative of a recent braking event has occurred at step 130 . This can be accomplished by looking at the derivative of the wheel speed. If a recent deceleration event is identified, the controller 24 waits for the brakes to cool as indicated at 140 and finishes a loop cycle as indicated at 200 . Thus, if an excessive temperature is identified in combination with a recent deceleration, the adjustment mechanism 20 is not used to adjust clearance. The controller 24 waits until the brakes have cooled before determining whether adjustment of clearance is needed in a subsequent loop cycle.
If during step 110 , the controller 24 determines that there is not an excessive brake temperature, the controller then compares a measured brake temperature to a predetermined temperature level as indicated at 115 . In one example, the predetermined temperature level is ambient temperature, however, other temperature levels could also be used.
A separate sensor could be used to measure ambient temperature. Or, ambient temperature could be defined as a temperature point where it is known that the brakes have not been applied, e.g. vehicle start-up, and/or after a long period of time has passed without a deceleration. It is also known that ambient temperature lies within a relatively narrow range, which is well below typical brake operating temperatures. Thus, it would be possible to consider any temperature above thirty-five degrees Celsius, for example, to be above ambient. Finally, it is also possible to look at the absolute temperature and the derivative of the temperature, i.e. is the temperature increasing or decreasing, to make a determination as to whether the brake temperature is above ambient. For diagnostic purposes it is also useful to compare temperatures from one side of a vehicle to an opposite side of the vehicle. However, a data link is required for this type of information comparison.
If, during step 115 , it is determined that the measured brake temperature is greater than the predetermined temperature level, the controller determines whether a recent deceleration has occurred as described above with regard to step 130 . If a recent deceleration is identified, the controller 24 performs steps 140 and 200 as described above.
If the measured brake temperature is greater than the predetermined temperature level and there has not been a recent deceleration, the controller then determines whether or not it is time to perform an adjustment as indicated at 135 . Adjustment times can be determined/defined in many different ways. For example, the time to adjust could be once per a certain predetermined number of vehicle stops. Or, the time to adjust could be once per a predetermined time interval, such as once per day, for example. Or, the time to adjust could be made dependent on deceleration level, i.e. time of deceleration and temperature reached during deceleration. It should be understood that these are just examples and that other methods could be used to determine whether or not it is time to perform a brake adjustment.
If the controller 24 determines that it is not time to perform an adjustment, then the loop cycle is completed as indicated at 200 . If the controller 24 determines that it is time to perform an adjustment, then the controller determines whether measured wheel speed is greater than a predetermined speed value as indicated at 145 . Preferably, the predetermined speed level is approximately thirty miles per hour, however, other speeds could also be used. A higher speed will result in more rapid and higher brake temperature increase making determination of brake pad contact easier. However the speed chosen must not be so high that the vehicle operates below the chosen speed for long periods of time. If the measured wheel speed is not greater than the predetermined speed value, then the loop cycle is completed as indicated at 200 .
If the measured wheel speed is greater than the predetermined speed value and the measured brake temperature is less than the predetermined temperature level, then the controller 24 activates the electric motor 22 to move the brake pad 16 toward the rotor 12 , i.e. clearance 18 is tightened. Preferably, clearance is tightened by one increment as indicated at 150 . One increment comprises a discrete, predetermined distance value. After clearance 18 has been tightened by one increment, the controller 24 waits to see if there is an increase in brake temperature as indicated at 155 .
After a predetermined time interval, the controller 24 compares the current measured brake temperature to the predetermined temperature level, which in the example discussed, is ambient temperature. This step is indicated at 160 . If the measured brake temperature is not greater than the predetermined temperature level, then the controller 24 returns to step 145 to determine whether wheel speed is above the predetermined speed value. If it is, the controller activates the motor to tighten clearance 18 by one more increment. The controller repeats steps 145 through 160 until the current measured brake temperature is greater than the predetermined temperature level.
Once the current measured brake temperature is greater than the predetermined temperature level, then the controller 24 sets an adjustment flag—adjustment complete, as indicated at 165 . Then the controller 24 opens clearance 18 , i.e. increases clearance 18 by one increment as indicated at 170 . This provides an optimized, minimum clearance between the brake pads 16 and rotor 12 , which keeps braking response fast and provides optimum, high brake torque.
Once the clearance 18 has been opened, the controller 24 waits for measured brake temperature to stabilize as indicated at 175 . Then the loop cycle is completed as indicated at 200 . The subject method is a closed loop system, thus, once a loop cycle is completed 200 , the controller returns to the start 100 and performs a subsequent loop cycle.
The adjustment mechanism 20 also avoids the problem of over adjustment. Over adjustment causes brake drag. When the brakes are subjected to brake drag, the brakes run hot and have increased wear rates, which results in reduced fuel economy. To identify and eliminate brake drag, the controller performs steps 100 - 130 as described above. If during step 130 , the controller 24 determines that there has not been a recent deceleration, but the current measured brake temperature is above the predetermined temperature level, the controller proceeds to step 170 . As described above, during step 170 clearance 18 is opened by one increment. The controller 24 then proceeds with steps 175 - 200 as described above.
The subject invention provides a method and apparatus for optimizing brake clearance in response to brake drag and brake wear. The subject invention is simpler than existing mechanical and electrical systems with better performance. The subject invention provides a simple closed loop approach that assures minimum clearance without risking the possibility of dragging brakes. Further, if brake temperature is being monitored for diagnostic purposes, only one additional component is needed, i.e. an electronic actuator. Either current feedback from the motor, or alternatively, a position/speed sensor on the motor output shaft 40 may be desirable to optimize control and enhance diagnostics.
Although a preferred embodiment of this invention has been disclosed, a worker of ordinary skill in this art would recognize that certain modifications would come within the scope of this invention. For that reason, the following claims should be studied to determine the true scope and content of this invention. | An adjustment mechanism for a vehicle brake uses an electric motor to adjust brake clearance based on brake temperature and wheel speed. A temperature sensor transmits brake temperature data to a controller. If a brake is dragging during non-braking events, the controller identifies an increase in brake temperature and actuates the electric motor to increase brake clearance. The controller also adjusts brake clearance to accommodate for brake wear. When wheel speed is above a predetermined speed value, the controller actuates the electric motor to move a non-rotating brake component toward a rotating brake component until a predetermined temperature increase is sensed. Once the predetermined temperature increase is identified, the electric motor moves the non-rotating brake component away from the rotating brake component to provide an optimized brake clearance. | 1 |
RELATED APPLICATIONS
This application is a 35 U.S.C. §371 filing from International Application No. PCT/US2013/072964, filed Dec. 4, 2013, which claims the benefit of U.S. Provisional Application No. 61/733,504, filed Dec. 5, 2012. Each of the aforementioned applications is herein incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
The retrovirus designated human immunodeficiency virus (HIV), particularly the strains known as HIV type-1 (HIV-1) and type-2 (HIV-2), have been etiologically linked to the immunosuppressive disease known as acquired immunodeficiency syndrome (AIDS). HIV seropositive individuals are initially asymptomatic but typically develop AIDS related complex (ARC) followed by AIDS. Affected individuals exhibit severe immunosuppression which makes them highly susceptible to debilitating and ultimately fatal opportunistic infections. Replication of HIV by a host cell requires integration of the viral genome into the host cell's DNA. Since HIV is a retrovirus, the HIV replication cycle requires transcription of the viral RNA genome into DNA via an enzyme known as reverse transcriptase (RT).
Reverse transcriptase has three known enzymatic functions: The enzyme acts as an RNA-dependent DNA polymerase, as a ribonuclease, and as a DNA-dependent DNA polymerase. In its role as an RNA-dependent DNA polymerase, RT transcribes a single-stranded DNA copy of the viral RNA. As a ribonuclease, RT destroys the original viral RNA and frees the DNA just produced from the original RNA. And as a DNA-dependent DNA polymerase, RT makes a second, complementary DNA strand using the first DNA strand as a template. The two strands form double-stranded DNA, which is integrated into the host cell's genome by the integrase enzyme.
It is known that compounds that inhibit enzymatic functions of HIV RT will inhibit HIV replication in infected cells. These compounds are useful in the prophylaxis or treatment of HIV infection in humans. Among the compounds approved for use in treating HIV infection and AIDS are the RT inhibitors 3′-azido-3′-deoxythymidine (AZT), 2′,3′-dideoxyinosine (ddI), 2′,3′-dideoxycytidine (ddC), d4T, 3TC, nevirapine, delavirdine, efavirenz, abacavir, emtricitabine, and tenofovir.
The RT inhibitor 3-chloro-5-({1-[(4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl]-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl}oxy)benzonitrile, related compounds and methods for making the same are illustrated in WO 2011/120133 A1, published on Oct. 6, 2011, and US 2011/0245296 A1, published on Oct. 6, 2011, both of which are hereby incorporated by reference in their entirety. The present invention is directed to a novel process for synthesizing 3-(substituted phenoxy)-1-[(5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl])pyridin-2(1H)-one derivatives and intermediates useful in the synthesis thereof. The compounds synthesized by the processes of the invention are HIV reverse transcriptase inhibitors useful for inhibiting reverse transcriptase, HIV replication and the treatment of human immunodeficiency virus infection in humans.
SUMMARY OF THE INVENTION
The present invention is directed to a novel process for synthesizing 3-(substituted phenoxy)-1-[(5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl])-pyridin-2(1H)-one derivatives. The compounds synthesized by the processes of the invention are HIV reverse transcriptase inhibitors useful for inhibiting reverse transcriptase, HIV replication and the treatment of human immunodeficiency virus infection in humans.
DETAILED DESCRIPTION OF THE INVENTION
The invention is directed to a method for synthesizing compounds of Formula I
wherein R 1 is C 1-6 alkyl, K 1 and K 2 are independently CH 3 , CF 3 , CHF 2 , CH 2 CF 3 , OCH 3 , Cl, Br, F, CN or SCH 3 , and R 2 is CF 3 , Cl or Br,
comprising
introducing a nitrogen protecting group PG into a compound of Formula A
wherein X 1 is a leaving group, to make a compound of Formula B
reacting a compound of Formula B with a compound of Formula C
in the presence of a first base selected from an inorganic base or a tertiary amine base in a first polar aprotic solvent to make a compound of Formula D
coupling the compound of Formula D with a compound of Formula E
to make a compound of Formula F
by way of step (1) or step (2) wherein:
step (1) comprise adding the compound of Formula E to the reaction mixture comprising the compound of Formula D from the previous step without further isolation to make a compound of Formula F, and
step (2) comprises isolating the compound of Formula D from the previous step and reacting the compound of Formula D with the compound of Formula E in the presence of a second base selected from an inorganic base or a tertiary amine base in a second polar aprotic solvent to yield the compound of Formula F,
and deprotecting the nitrogen protecting group PG in the compound of Formula F to yield a compound of Formula I.
The term “nitrogen protecting group” means a substituent that protects a nitrogen atom in a reaction from a reagent or chemical environment. Nitrogen protecting groups are well known in the art and include for example, t-butyl, vinyl, phenyl, benzyl, p-methoxybenzyl, 3,4-dimethoxybenzyl, p-nitrobenzyl, benzhydryl, trityl, trialkylsilyl, methoxymethyl ether, (2,2,2-trichloroethoxy)methyl and 2-(trimethylsilyl)ethoxy)methyl. Methods for deprotecting a nitrogen are also well within the skill of one having ordinary skill in the art. In an embodiment, the invention encompasses the process described herein wherein PG is selected from the group consisting of: C 1-6 alkyl, vinyl, C(O)—O-L, C(O)-L, aryl, hetroaryl, benzyl, benzhydryl, trityl, anthranyl and C 1-6 alkoxymethyl, wherein aryl, heteroaryl, benzyl, benzyhydryl and trityl optionally are substituted with 1 to 3 substituents independently selected from methoxy and nitro, C 1-6 alkoxymethyl is optionally substituted with trimethylsilyl and L is C 1-6 alkyl, aryl or benzyl. In another embodiment, the invention encompasses the process described herein wherein PG is 2-methoxypropan-2-yl.
The term “leaving group” means an atom or atom group that leaves from a substrate in a substitution or elimination reaction and includes for example halogen and sulfonate. In an embodiment, the invention encompasses the process described herein wherein X 1 is selected from the group consisting of: halogen, OMs (mesylate), OTs (tosylate), OBs (besylate), OP(O)(OR i ) 4 , OC(O)R i , OC(O)OR i and OC(O)NR i R ii , wherein R i and R ii are independently selected from H and C 1-6 alkyl. In another embodiment, the invention encompasses the process described herein wherein X 1 is chloro.
The first base is selected from an inorganic base or a tertiary amine base. Inorganic bases include, for example, sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium carbonate, lithium carbonate, potassium carbonate, cesium hydroxide, cesium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium phosphate and potassium phosphate. Tertiary amine bases include for example trimethylamine, dimethylethylamine, triethylamine, 1,4-diazobicyclo-[2,2,2]-octane, diisopropylethylamine, dicyclohexylethylamine. Suitable polar aprotic solvents include for example tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethyl sulfoxide, dimethylacetomide, N-methylpyrrolidinone. The first base and second base are selected independently from each other. Likewise, the first polar aprotic solvent and second polar aprotic solvent are also selected independently from each other.
In an embodiment, the invention encompasses the process described herein wherein the first base is potassium carbonate and the first polar aprotic solvent is dimethylformamide.
In an embodiment, the invention encompasses the process described herein wherein the compound of Formula F is made by step (1). In a further embodiment, the reaction of step (1) is heated to an elevated temperature. The term elevated temperature means above room temperature. In a further embodiment, the elevated temperature is about 95° C. to about 100° C.
In an embodiment, the invention encompasses the process described herein wherein the nitrogen protecting group PG in the compound of Formula F is deprotected by reacting the compound of Formula F with an acid.
Another embodiment of the invention encompasses the method for synthesizing a compound of Formula I as described herein further comprising synthesizing the compound of Formula A by condensing glycolic acid with a compound of Formula G
to yield a compound of Formula H
cyclizising the compound of Formula H under first basic conditions to make a compound of Formula J
and replacing the alcohol with the leaving group X 1 by reacting the compound of Formula J with an activating agent to yield a compound of Formula A.
“Basic conditions” can be achieved by use of an appropriate base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, potassium carbonate, sodium carbonate, and lithium carbonate.
The replacement of the alcohol with the appropriate leaving group X 1 can be accomplished by techniques well known to those skilled in the art. For example, the alcohol can be replaced with chloride by reaction with thionyl chloride. The term “activating agent” means an agent capable of replacing the alcohol with a desired leaving group X 1 for example mesyl chloride, tosyl chloride, (PhO) 2 POCl, oxalyl chloride, SOCl 2 and phosgene.
In an embodiment, the invention encompasses the process described herein wherein X 1 is chloro and the activating agent is SOCl 2 .
In an embodiment, the invention encompasses the process described herein wherein first basic conditions means in the presence of sodium hydroxide.
Another embodiment encompasses the method for synthesizing a compound of Formula I as described herein further comprising synthesizing the compound of Formula G by reacting a compound of Formula K
wherein R 2a is selected from aryl or heteroaryl, wherein said aryl or heteroaryl are optionally substituted with one or more substituents up to the maximum number allowed by valence selected from the group consisting of: halogen, C 1-6 alkyl, C 1-6 haloalkyl, OH, O—C 1-6 alkyl, O—C 1-6 haloalkyl, N(R A )R B , C(O)N(R A )R B , C(O)R A , CO 2 R A , SO 2 R A , N(R A )C(O)N(R A )R B , or N(R A )CO 2 R B ;
R A and R B are independently selected from H, C 1-6 alkyl and C 3-6 cycloalkyl, wherein said C 1-6 alkyl and C 3-6 cycloalkyl are optionally substituted with one or more substituents up to the maximum number allowed by valence selected from the group consisting of: halogen, OH, CN, C 1-4 alkoxy, C 3-6 cycloalkyl and phenyl;
with a compound of Formula L
R 1 —NH 3 L
under second basic conditions to yield a compound of Formula M
reacting the compound of Formula M with hydrazine to yield a compound of Formula G.
Second basic condition means “basic conditions” as described above, but is independent of first basic conditions.
The term “aryl” refers to phenyl, naphthyl, and anthranyl.
The term heteroaryl is independently (i) a 5- or 6-membered heteroaromatic ring containing from 1 to 4 heteroatoms independently selected from N, O and S, wherein each N is optionally in the form of an oxide, or (ii) a 9- or 10-membered heterobicyclic, fused ring system containing from 1 to 4 heteroatoms independently selected from N, O and S, wherein either one or both of the rings contain one or more of the heteroatoms, at least one ring is aromatic, each N is optionally in the form of an oxide, and each S in a ring which is not aromatic is optionally S(O) or S(O) 2 . Examples of heteroaryl include, for example, pyridyl (also referred to as pyridinyl), pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, thienyl, furanyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, isooxazolyl, oxadiazolyl, oxatriazolyl, thiazolyl, isothiazolyl, thiadiazolyl, indolyl, quinolinyl, isoquinolinyl, and quinoxalinyl
In an embodiment, the invention encompasses the process described herein wherein second basic conditions means in the presence of sodium hydroxide.
The invention also encompasses any of the embodiments described above wherein in the compound of Formula I K 1 is Cl, K 2 is CN, R 1 is CH 3 and R 2 is CF 3 .
Another embodiment of the invention encompasses a method for synthesizing a compound of Formula D
wherein R 1 is C 1-6 alkyl and R 2 is CF 3 , Cl or Br, comprising reacting a compound of Formula B
wherein PG is a nitrogen protecting group with a compound of Formula C
in the presence of a first base selected from an inorganic base or a tertiary amine base in a first polar aprotic solvent to make the compound of Formula D.
Another embodiment of the invention encompasses a method for synthesizing a compound of Formula A
wherein R 1 is C 1-6 alkyl and X 1 is a leaving group, comprising condensing glycolic acid with a compound of Formula G
to yield a compound of Formula H
cyclizising the compound of Formula H under first basic conditions to make a compound of Formula J
and replacing the alcohol with the leaving group X 1 by reacting the compound of Formula J with an activating agent to yield a compound of Formula A.
Another embodiment of the invention encompasses method for synthesizing a compound of Formula I
wherein R 1 is C 1-6 alkyl, K 1 and K 2 are independently CH 3 , CF 3 , CHF 2 , CH 2 CF 3 , OCH 3 , Cl, Br, F, CN or SCH 3 , and R 2 is CF 3 , Cl or Br,
comprising
reacting a compound of Formula A
wherein X 1 is a leaving group, with a compound of Formula C
in the presence of a first base selected from an inorganic base or a tertiary amine base in a first polar aprotic solvent to make a compound of Formula D1
coupling the compound of Formula D1 with a compound of Formula E
to make a compound of Formula I by way of step (1) or step (2) wherein:
step (1) comprise adding the compound of Formula E to the reaction mixture comprising the compound of Formula D1 from the previous step without further isolation to make a compound of Formula I, and
step (2) comprises isolating the compound of Formula D1 from the previous step and reacting the compound of Formula D1 with the compound of Formula E in the presence of a second base selected from an inorganic base or a tertiary amine base in a second polar aprotic solvent to yield the compound of Formula I.
Another embodiment of the invention encompasses a method for synthesizing a compound of Formula I
wherein R 1 is C 1-6 alkyl, K 1 and K 2 are independently CH 3 , CF 3 , CHF 2 , CH 2 CF 3 , OCH 3 , Cl, Br, F, CN or SCH 3 , and R 2 is CF 3 , Cl or Br,
comprising
coupling a compound of Formula A
wherein X 1 is a leaving group, with a compound of Formula N
in the presence of a first base selected from an inorganic base or a tertiary amine base in a first polar aprotic solvent to yield a compound of Formula I. Within this embodiment the invention encompasses the foregoing process wherein the compound of Formula A is not isolated after its synthesis and in situ reacted directly with the compound of Formula N. Also within this embodiment the invention encompasses the foregoing process wherein X 1 is selected from the group consisting of: halogen, OMs, OTs, OBs, OP(O)(OR i ) 4 , OC(O)R i , OC(O)OR i and OC(O)NR i R ii , wherein R i and R ii are independently selected from H and C 1-6 alkyl. In a further embodiment the invention encompasses the foregoing process for synthesizing the compound of Formula I wherein X 1 is chloro. In a further embodiment, the invention encompasses the foregoing process for synthesizing the compound of Formula I wherein the first base is N,N-Diisopropylethylamine and the first polar aprotic solvent is N-methylpyrrolidinone.
Another embodiment of the invention encompasses the foregoing method for synthesizing a compound of Formula I further comprising synthesizing the compound of Formula A by condensing glycolic acid with a compound of Formula G
to yield a compound of Formula H
cyclizing the compound of Formula H under first basic conditions to make a compound of Formula J
and replacing the alcohol with the leaving group X 1 by reacting the compound of Formula J with an activating agent to yield a compound of Formula A. Within this embodiment, the invention encompasses the foregoing method for synthesizing a compound of Formula I wherein X 1 is chloro and the activating agent is SOCl 2 . Also within this embodiment, the invention encompasses the foregoing method for synthesizing a compound of Formula I wherein basic conditions means in the presence of sodium hydroxide.
Another embodiment of the invention encompasses the foregoing method for synthesizing a compound of Formula I further comprising synthesizing the compound of Formula G by reacting a compound of Formula K
wherein R 2a is selected from aryl or heteroaryl, wherein said aryl or heteroaryl are optionally substituted with one or more substituents up to the maximum number allowed by valence selected from the group consisting of: halogen, C 1-6 alkyl, C 1-6 haloalkyl, OH, O—C 1-6 alkyl, O—C 1-6 haloalkyl, N(R A )R B , C(O)N(R A )R B , C(O)R A , CO 2 R A , SO 2 R A , N(R A )C(O)N(R A )R B , or N(R A )CO 2 R B ;
R A and R B are independently selected from H, C 1-6 alkyl and C 3-6 cycloalkyl, wherein said C 1-6 alkyl and C 3-6 cycloalkyl are optionally substituted with one or more substituents up to the maximum number allowed by valence selected from the group consisting of: halogen, OH, CN, C 1-4 alkoxy, C 3-6 cycloalkyl and phenyl;
with a compound of Formula L
R 1 —NH 3 L
under second basic conditions to yield a compound of Formula M
reacting the compound of Formula M with hydrazine to yield a compound of Formula G. Within this embodiment, the invention encompasses the foregoing method for synthesizing a compound of Formula I wherein second basic conditions means in the presence of sodium hydroxide.
The invention also encompasses any of the aforementioned methods for synthesizing the compound of Formula I wherein K 1 is Cl, K 2 is CN, R 1 is CH 3 and R 2 is CF 3 .
The compound 3-chloro-5-({1-[(4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl]-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl}oxy)benzonitrile has the following chemical structure.
Anhydrous 3-chloro-5-({1-[(4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl]-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl}oxy)benzonitrile is known to exist in three crystalline forms—Form I, Form II and Form III. The differential scanning calorimetry (DSC) curve for crystalline anhydrous Form II shows an endotherm with an onset at 230.8° C., a peak maximum at 245.2° C., and an enthalpy change of 3.7 J/g, which is due to polymorphic conversion of anhydrous Form II to anhydrous Form I, and a second melting endotherm with an onset at 283.1° C., a peak maximum at 284.8° C., and an enthalpy change of 135.9 J/g, due to melting of Anhydrous Form I. Alternative production and the ability of this compound to inhibit HIV reverse transcriptase is illustrated in WO 2011/120133 A1, published on Oct. 6, 2011, and US 2011/0245296 A1, published on Oct. 6, 2011, both of which are hereby incorporated by reference in their entirety.
The process of the present invention offers greater efficiency, reduced waste, and lower cost of goods relative to the methods for making the subject compounds existing at the time of the invention. Particularly, the late stage cyanation and methylation steps are not required.
The following examples illustrate the invention. Unless specifically indicated otherwise, all reactants were either commercially available or can be made following procedures known in the art. The following abbreviations are used:
ABBREVIATIONS
DMF=dimethylformamide
NMP=N-methylpyrrolidinone
IPA=isopropyl alcohol
NPA=n-propyl alcohol
LC=liquid chromatography
LCAP=Liquid chromatography area percent
Me=methyl
Example 1
Step 1
3-(Chloromethyl)-1-(2-methoxypropan-2-yl)-4-methyl-1H-1,2,4-triazol-5(4H)-one (2)
A 100 ml round bottom flask equipped with stir bar and a nitrogen inlet was charged with 1 (5 g, 33.9 mmol) and (1S)-(+)-10-camphorsulfonic acid (0.39 g, 1.694 mmol) at ambient temperature. After 2,2-dimethoxy propane (36.0 g, 339 mmol) was charged at ambient temperature, the resulting mixture was heated to 45° C. The resulting mixture was stirred under nitrogen at 45° C. for 18 hours and monitored by HPLC for conversion of the starting material (<5% by HPLC). After the reaction was completed, the batch was taken on to the next step without further work-up or isolation. 1 H NMR (CDCl 3 , 500 MHz): 4.45 (s, 2H), 3.35 (s, 3H), 3.21 (s, 3H), 1.83 (s, 6H).
Step 2
3-Fluoro-1-((1-(2-methoxypropan-2-yl)-4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl)-4-(trifluoromethy)pyridin-2(1H)-one (3)
A mixture of 2 (100 mg, 93.1% purity, 0.49 mmol), pyridone (117 mg, 97.6% purity, 0.49 mmol) and K 2 CO 3 (82 mg, 0.59 mmol) in DMF (0.5 ml) was aged with stirring at ambient temperature for 3 h. After the reaction was completed, the batch was taken on to the next step without further work up or isolation.
Step 3
3-Chloro-5-((1-((1-(2-methoxypropan-2-yl)-4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl)-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl)oxy)benzonitrile (4)
To a mixture of compound 3 in DMF (reaction mixture from the previous step) was added 3-chloro-5-hydroxybenzonitrile (1.77 g, 11.5 mmol) at ambient temperature. The resulting mixture was then heated to 95-100° C. and held for 20 hours.
Upon completion (typically 18-20 hours), the reaction was cooled to room temperature, diluted with ethyl acetate and washed with water. The aqueous cut was back extracted with ethyl acetate. The organic layers were combined and then concentrated to an oil. MeOH (80 ml) was added and the resulting slurry was taken on to the next step. 1 H NMR (CDCl 3 , 500 MHz): 7.60 (d, 1H), 7.42 (s, 1H), 7.23 (s, 1H), 7.12 (s, 1H), 6.56 (d, 1H), 5.14 (s, 2H), 3.30 (s, 3H), 3.22 (s, 3H), 1.82 (s, 6H).
Step 4
3-Chloro-5-((1-((4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl)-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl)oxy)benzonitrile (5)
To a solution of 4 (5.74 g, 11.53 mmol) in MeOH (from previous step) was added concentrated hydrochloric acid (1 ml, 12.18 mmol) at ambient temperature. The resulting mixture was agitated for 1 hour at room temperature.
The resulting solids were collected by filtration and dried under a nitrogen sweep, providing 5 as a white solid (2.63 g, 46% yield): 1 H NMR (DMSO, 400 MHz): 11.74 (S, 1H), 7.92 (d, 1H), 7.76 (s, 1H), 7.61 (s, 1H), 7.54 (s, 1H), 6.69 (d, 1H), 5.15 (s, 2H), 3.10 (s, 3H)
Example 2
Step 1
Phenyl Methylcarbamate:
40% Aqueous methylamine (500 g, 6.44 mol) was charged to a 2 L vessel equipped with heat/cool jacket, overhead stirrer, temperature probe and nitrogen inlet. The solution was cooled to −5° C. Phenyl chloroformate (500.0 g, 3.16 mol) was added over 2.5 h maintaining the reaction temperature between −5 and 0° C. On complete addition the white slurry was stirred for 1 h at ˜0° C.
The slurry was filtered, washed with water (500 mL) and dried under N 2 sweep overnight to afford 465 g (96% yield) of the desired product as a white crystalline solid; 1H NMR (CDCl 3 , 500 MHz): δ 7.35 (t, J=8.0 Hz, 2H), 7.19 (t, J=8.0 Hz, 1H), 7.12 (d, J=8.0 Hz, 2H), 4.95 (br s, 1H), 2.90 (d, J=5 Hz, 3H).
Step 2
2-(2-Hydroxyacetyl)-N-methylhydrazinecarboxamide
Part A: Phenyl methylcarbamate (300 g, 1.95 mol) was charged to a 2 L vessel with cooling jacket, overhead stirrer, temperature probe, reflux condenser and nitrogen inlet. IPA (390 mL) was added at 23° C. Hydrazine hydrate (119 g, 2.33 mol) was added and the slurry heated to 75° C. for 6 h.
Part B: On complete reaction (>99% conversion by HPLC), IPA (810 mL) and glycolic acid (222 g, 2.92 mol) were added and the mixture stirred at 83-85° C. for 10-12 h. The reaction mixture is initially a clear colorless solution. The mixture is seeded with product (0.5 g) after 4 h at 83-85° C. The slurry was slowly cooled to 20° C. over 2 h and aged for 1 h.
The slurry was filtered and washed with IPA (600 mL). The cake was dried under N 2 sweep to afford 241.8 g (81% yield) of the desired product as a white crystalline solid: 1 H NMR (D 2 O, 500 MHz): δ 4.11 (s, 2H), 2.60 (s, 3H).
Step 3
3-(Hydroxymethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one
2-(2-Hydroxyacetyl)-N-methylhydrazinecarboxamide (130 g @˜95 wt %, 0.84 mol), n-propanol (130 mL) and water (130 mL) were charged to a 1 L vessel with jacket, overhead stirrer, temperature probe, reflux condenser and nitrogen inlet. Sodium hydroxide (pellets, 16.8 g, 0.42 mol) was added and the slurry warmed to reflux for 3 h. The reaction mixture was cooled to 20° C. and the pH adjusted to 6.5 (+/−0.5) using conc hydrochloric acid (28.3 mL, 0.34 mol). Water was azeotropically removed under vacuum at 40-50° C. by reducing the volume to ˜400 mL and maintaining that volume by the slow addition of n-propanol (780 mL). The final water content should be <3000 ug/mL. The resultant slurry (˜400 mL) was cooled to 23° C. and heptane (390 ml) was added. The slurry was aged 1 h at 23° C., cooled to 0° C. and aged 2 h. The slurry was filtered, the cake washed with 1:2 n-PrOH/heptane (100 mL) and dried to provide 125 g (85% yield) of an off-white crystalline solid. The solid is ˜73 wt % due to residual inorganics (NaCl): 1 H NMR (CD 3 OD, 500 MHz): δ 3.30 (s, 3H), 4.46 (s, 2H).
Step 4
3-(Chloromethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one (1)
A mixture of 3-(Hydroxymethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one (54 g, at 73 wt %, 307 mmol) in ethyl acetate (540 mL) was stirred at 45° C. SOCl 2 (26.9 mL, 369 mmol) was added over 30-45 min and aged at 50° C. for 2 h. Monitor reaction progress by HPLC. On complete reaction (>99.5% by area at 210 nm), the warm suspension was filtered and the filter cake (mainly NaCl) was washed with ethyl acetate (108 mL). The combined filtrate and wash were concentrated at 50-60° C. under reduced pressure to approximately 150 mL. The resulting slurry was cooled to −10° C. and aged 1 h. The slurry was filtered and the filter cake washed with ethyl acetate (50 mL). The cake was dried under N 2 sweep to afford 40.1 g (86% yield) of the desired product as a bright yellow solid: 1 H NMR (CD 3 OD, 500 MHz): δ 3.30 (s, 3H), 4.58 (s, 2H).
Example 3
3-fluoro-4-(trifluoromethyl)pyridin-2(1H)-one (2)
To a 250 ml round bottom flask equipped with overhead stirring and a nitrogen inlet was added a mixture of sulfuric acid (24.31 ml, 437 mmol) and water (20.00 ml). To this was added 2,3-difluoro-4-(trifluoromethyl)pyridine (6.83 ml, 54.6 mmol) and the mixture was heated to 65° C. and stirred for 4 h. By this time the reaction was complete, and the mixture was cooled to room temperature. To the flask was slowly added 5M sodium hydroxide (43.7 ml, 218 mmol), maintaining room temperature with an ice bath. The title compound precipitates as a white solid during addition. Stirring was maintained for an additional 1 h after addition. At this time, the mixture was filtered, the filter cake washed with 20 mL water, and the resulting white solids dried under nitrogen. 3-fluoro-4-(trifluoromethyl)pyridin-2(1H)-one (2) was obtained as a white crystalline solid (9.4 g, 51.9 mmol, 95% yield): 1 H NMR (CDCl 3 , 400 MHz): 12.97 (br s, 1H), 7.36 (d, 1H), 6.44 (m, 1H).
Example 4
Step 1—Ethyl Ester Synthesis
Experimental Procedure
Ethyl 2-(3-chloro-5-cyanophenoxy)acetate (A)
A 1 L round bottom flask equipped with overhead stirring was charged with 3-chloro-5-hydroxybenzonitrile (50.0 g, 98 wt % purity, 319 mmol) and 15% aqueous DMF (200 mL DMF+35.5 mL H 2 O). To the resulting solution was added diisopropylethylamine (61.3 mL, 99.0% purity, 1.1 equiv) and ethyl 2-bromoacetate (35.7 g, 98% purity, 1.15 equiv) at ambient temperature. The resulting solution was warmed to 50° C. under nitrogen and aged for 12 h. Upon completion of the reaction the batch was cooled to 0-5° C. To the clear to slightly cloudy solution was added 5% seed (3.8 g, 16.0 mmol). H 2 O (64.5 mL) was added to the thin suspension via syringe pump over 3 h while maintaining the temp at 0-5° C. Additional H 2 O (200 mL) was added over 1 h while maintaining the temp at 0-5° C. The final DMF/H 2 O ratio is 1:1.5 (10 vol). The resulting slurry was typically aged 1 h at 0-5° C. The batch was filtered and the cake slurry washed with 2:1 DMF/water (150 mL, 3 vol), followed by water (200 mL, 4 vol). The wet cake was dried on the frit with suction under a nitrogen stream at 20-25° C.; note: heat must not be applied during drying as product mp is 42° C. The cake is considered dry when H 2 O is <0.2%. Obtained 73.4 g ethyl ester as a light tan solid, 96% yield (corrected), 99.5 LCAP: 1 H NMR (CDCl 3 , 400 MHz) δ=7.29 (s, 1H), 7.15 (s, 1H), 7.06 (s, 1H), 4.67 (s, 2H), 4.32 (q, 2H), 1.35 (t, 3H) ppm.
Step 2—Pyridone Synthesis
Experimental Procedures
Aldol Condensation, Ester A to Diene C
(2E/Z,4E)-Ethyl 2-(3-chloro-5-cyanophenoxy)-5-ethoxy-3-(trifluoromethyl)penta-2,4-dienoate (C)
Ester A (25.01 g, 104.4 mmol, 1.00 equiv) was charged to toluene (113.43 g, 131 mL, 5.24 vol) and 4-ethoxy-1,1,1-trifluoro-3-buten-2-one (26.43 g, 157.2 mmol, 1.51 equiv) was added.
The flow reactor consisted of two feed solution inlets and an outlet to a receiving vessel. The flow reactor schematic is shown in Figure 1.
The ester solution was pumped to one flow reactor inlet. Potassium tert-pentoxide solution was pumped to the second reactor inlet. Trifluoroacetic anhydride was added continuously to the receiver vessel. Triethylamine was added continuously to the receiver vessel.
The flow rates were: 13 mL/min ester solution, 7.8 mL/min potassium tert-pentoxide solution, 3.3 mL/min trifluoroacetic anhydride and 4.35 mL/min triethylamine.
Charged toluene (50 mL, 2 vol) and potassium trifluoroacetate (0.64 g, 4.21 mmol, 0.04 equiv) to the receiver vessel. The flow reactor was submerged in a −10° C. bath and the pumps were turned on. The batch temperature in the receiver vessel was maintained at 5 to 10° C. throughout the run using a dry ice/acetone bath. After 13.5 min the ester solution was consumed, the reactor was flushed with toluene (10 mL) and the pumps were turned off.
The resulting yellow slurry was warmed to room temperature and aged for 4.5 h. Charged methanol (160 mL) to afford a homogeneous solution which contained 81.20 area percent diene C by HPLC analysis.
The solution of diene C (573 mL) was used without purification in the subsequent reaction.
Cyclization, Diene C to E
3-Chloro-5-((2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl)oxy)benzonitrile (E)
To a solution of diene C in PhMe/MeOH (573 mL; 40.69 g, 104.4 mmol theoretical C) was charged methanol (25 mL, 0.61 vol). Ammonia (32 g, 1.88 mol, 18 equiv based on theoretical C) was added and the solution was warmed to 60° C. The reaction was aged at 60° C. for 18 h. The temperature was adjusted to 35-45° C. and the pressure was decreased maintain a productive distillation rate. The batch volume was reduced to ˜300 mL and methanol (325 mL, 8 vol) was charged in portions to maintain a batch volume between 250 and 350 mL. The heating was stopped and the system vented. The resulting slurry was cooled to room temperature and aged overnight.
The batch was filtered and the cake washed with methanol (3×, 45 mL). The wet cake was dried on the frit with suction under a nitrogen stream to afford 18.54 g of a white solid: 1 H NMR (DMSO-d 6 , 500 MHz): δ 12.7 (br s, 1H), 7.73 (t, 1H, J=1.5 Hz), 7.61-7.59 (m, 2H), 7.53 (t, 1H, J=2.0 Hz), 6.48 (d, 1H, J=7.0 Hz) ppm.
Step 3—Chlorination, Alkylation and Isolation of 3-Chloro-5-({1-[(4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl]-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl}oxy)benzonitrile
3-(Chloromethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one
3-(Hydroxymethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one (1.638 kg of 68 wt %, 8.625 mol) and N-methylpyrrolidinone (8.9 L) was charged into a 30 L vessel. The suspension was aged for 10 h at ambient temperature. The slurry was filtered through a 4 L sintered glass funnel under N 2 and the filter cake (mainly NaCl) was washed with NMP (2.23 L). The combined filtrate and wash had a water content of 5750 μg/mL. The solution was charged to a 75 L flask equipped with a 2N NaOH scrubber to capture off-gasing vapors. Thionyl chloride (0.795 L, 10.89 mol) was added over 1 h and the temperature rose to 35° C. HPLC analysis indicated that the reaction required an additional thionyl chloride charge (0.064 L, 0.878 mol) to bring to full conversion. The solution was warmed to 50° C., placed under vacuum at 60 Torr (vented to a 2N NaOH scrubber), and gently sparged with subsurface N 2 (4 L/min) The degassing continued for 10 h until the sulfur dioxide content in the solution was <5 mg/mL as determined by quantitative GC/MS. The tan solution of 3-(chloromethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one in NMP weighed 13.0 kg and was assayed at 9.63 wt % providing 1.256 kg (97% yield).
3-chloro-5-((1-((4-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl)-2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl)oxy)benzonitrile
To a 75 L flask was charged a 9.63 wt % solution of 3-(chloromethyl)-4-methyl-1H-1,2,4-triazol-5(4H)-one in NMP (11.6 kg, 7.55 mol), 3-chloro-5-((2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl)oxy)benzonitrile (2.00 kg, 6.29 mol), NMP (3.8 L) and 2-methyl-2-butanol (6.0 L). To the resulting suspension was slowly added N,N-diisopropylethylamine (4.38 L, 25.2 mol) over 4 h. The reaction was aged 18 h at ambient temperature. The reaction is considered complete when HPLC indicates <1% 3-chloro-5-((2-oxo-4-(trifluoromethyl)-1,2-dihydropyridin-3-yl)oxy)benzonitrile remaining. The tan solution was quenched with acetic acid (1.26 L, 22.0 mol) and aged at ambient temperature overnight. The tan solution was warmed to 70° C. Water (2.52 L) was added and the batch was seed with anhydrate Form II (134 g). The thin suspension was aged 1 h at 70° C. Additional water (14.3 L) was added evenly over 7 h. The slurry was aged 2 h at 70° C. and then slowly cooled to 20° C. over 5 h. The slurry was filtered and washed with 2:1 NMP/water (6 L), followed by water washes (6 L×2). The filter cake was dried over a N 2 sweep to give 2.53 kg (85% yield—corrected) of a white solid that was confirmed to be crystalline Form II by X-ray powder defraction analysis. | The present invention is directed to a novel process for synthesizing 3-(substituted phenoxy)-1-[(5-oxo-4,5-dihydro-1H-1,2,4-triazol-3-yl)methyl])-pyridin-2(1H)-one derivatives. The compounds synthesized by the processes of the invention are HIV reverse transcriptase inhibitors useful for inhibiting reverse transcriptase, HIV replication and the treatment of human immunodeficiency virus infection in humans. | 2 |
BACKGROUND OF THE INVENTION
[0001] The possibility of igniting energy-generating fusion by impact, essentially by firing a bullet into a target at extreme speed 1000 km/sec, was studied in the 1960s and 1970s. However, firing a bullet massing ˜10 mg to that speed is extremely demanding. The most plausible method, then and now, is accelerating a charged bullet in a modified particle accelerator. Unfortunately the charge that can be placed on a macroscopic body is limited by self-repulsion, tending to cause both burst-apart and field effect evaporation of atoms from the surface. The acceleration and vibration a macroscopic body can withstand is also a limiting factor. Even the most optimistic estimates, using an ideal diamond as a ‘bullet’, put the necessary accelerator length at >100 km. An alternative is to use a cluster of microparticles (herein also referred to as particles or pellets) or heavy ions in place of a single bullet, which would reduce the accelerator length. Unfortunately multiple problems exist with this strategy, including the very high accelerator power that would be needed.
[0002] However, a fusion reactor for use in space can have design parameters that would be impracticable on Earth. If an extremely long vacuum gap is available, there is time for a stream of microparticles fired from a linear accelerator of relatively modest power to catch up into a cluster if given a small speed differential, with the first particles launched travelling the slowest and the last the most rapidly: the accelerator power needed scales inversely as the size of vacuum gap.
BRIEF SUMMARY OF THE INVENTION
[0003] As a specific example, as shown in FIG. 1 , consider an accelerator at one of the Earth-Moon system's Lagrange points ( 1 ) about 62,000 km from the surface of the Moon ( 3 ), which fires a microparticle beam along a trajectory ( 4 ) aimed to graze the lunar surface at a point ( 2 ) on a great circle intersecting the Moon's poles. Transit time for the particles is about one minute. If they are fired over a 5-second period, with the firing speed varied from ˜960 km/sec for the first particles to ˜1040 km/sec for the last, all reach the target simultaneously. The accelerator requires only a few MW input power.
[0004] The particles must be steered by applying small course corrections en route. A first correction as they leave the accelerator is relatively straightforward. However much more accurate corrections must be made on arrival at the lunar surface. This is why a grazing angle is chosen: taking advantage of lunar topography, and siting both the first incoming course correction station and the reactor on 2 km high lunar mountaintops, a distance between the first incoming course correction station and the reaction site of about 100 miles is achievable.
[0005] The accelerator design is very similar to that of a linear accelerator for fundamental particles, but operating at a lower frequency as the particle speed is ˜ 1/300 that of light. The inter-electrode gaps therefore do not act as RF resonant cavities, and a dielectric (non-conducting) wall design can be chosen. Breakdown is more prone to occur over the surface of an insulator than within the interior. An internal accelerator cross section like that in FIG. 2 may therefore be optimal, in which each conducting electrode 5 is mounted within an insulating tube 6 of substantially larger internal diameter. Thus the surface path length between the wires 7 and 8 to which alternate electrodes are connected (in a 2-phase design) can be several times larger than the inter-electrode gap. An appropriate material for the insulator is Teflon or Rexolite, and for the electrodes copper, molybdenum or tungsten polished to maximize their surface field breakdown strength. Accelerator length will be of the order of a few kilometres.
[0006] Typically, particles will transit the accelerator spaced 2 n electrode intervals behind one another if it is a 2-phase accelerator, 3 n electrode intervals behind one another if it is a 3-phase acclerator, etc., where n is an integer, typically 1. (However the accelerator might operate with a group of particles, rather than a single one, at each such position.) Typically, particles will emerge with relative speeds proportional to the longitudinal interval between them, so that all particles ultimately meet at the same instant.
[0007] Appropriate material for the particles will have high tensile strength and low density for maximum charge/mass ratio. It should be stiff so that it does not overheat due to flexure, as the electric field and therefore acceleration experienced cycles at the drive frequency of the accelerator, and either an insulator of high breakdown strength or a reasonably good conductor, so that the charge flow induced on its surface does not damage it. Plausible candidates include diamond, boron-α, aluminium-lithium alloy, or even microspheres of an engineering plastic such as celazole with a thin surface coating of metal such as aluminium. The latter requires a longer accelerator, but has the advantage that if (in place of a conventional target of DT ice) a target of solid methane in which the hydrogen has been replace by deuterium and tritium is used, the average atomic weight of pellets and target can be made very similar, suppressing Rayleigh-Taylor instabilities.
[0008] The particles should preferably be given a positive rather than negative charge, as field effect electron emission becomes significant at a much lower voltage gradient than field effect evaporation. Whatever material is chosen, the smaller the particles, the higher charge/mass ratio they can tolerate: however obviously more particles are then required for a given total kinetic energy. Suitable particle size is likely to be on the general order of ˜10 microns radius, with between 10000 and 1 million particles used.
[0009] Accelerator optimal frequency will be much lower than that of a fundamental particle accelerator, ˜MHz rather than GHz. Commercially available options to provide this power supply include diacrodes, tetrodes, or MOSFET-based units in conjunction with air-core transformers to boost their output voltage.
[0010] As they approach impact with the target, the particles should be guided as precisely as possible into a close-packed array, for example resembling a crystal lattice. Ideal precision required is a small fraction of the particle size, preferably ˜1 micron or better. While this is demanding, it can be attained with consecutively finer corrections analogous to a spacecraft's mid-course corrections. The limiting factor is precision of position measurement. This can be done by CCD camera pairs with microscope-style lenses sited by the beamline. Exposure is controlled by laser pulse: laboratory desktop lasers with pulse <1 picosecond, corresponding to particle movement 1 micron, are available. CCD chips can do useful onboard processing, but readout rates are limited to a few tens of megabytes/sec, so many cameras will typically be needed at each measurement station. The number of lasers needed is far smaller: a laser feeding a leaky optical fibre running parallel to the beamline can serve many cameras.
[0011] Particle steering is done by the particles passing close to or between rapidly switched electrodes, which can steer them laterally in any direction and/or slightly alter their speed. Solid state power switches operating at tens of GHz are now available, so a relatively small number of electrodes can perform course corrections on thousands or even millions of particles as they pass. (An alternative to electric fields provided by electrodes is electromagnetic fields generated by rapidly switching current through short antenna-like wires.)
[0012] The particles require to be maximally charged for acceleration. Subsequently, mutual repulsion as they draw closer to one another is preferably minimised. The particles require only modest charge to be steered by successively smaller course corrections, so they can be progressively discharged, e.g. by passing through an electron beam or close to a hot or cold cathode after each course correction point, ultimately to zero.
[0013] The most easily achievable fusion reaction is deuterium-tritium. Because tritium does not occur naturally, it is desirable that as far as possible, all neutrons produced should be captured by lithium nuclei to bred more tritium. It is also desirable to minimize wear on the reaction chamber walls. A suitable arrangement is shown in FIG. 3 (necessarily not drawn not to scale: actual pellet number will typically be thousands, each ˜20 μm diameter). A sacrificial projectile ( 9 ) is fired into a reaction chamber ( 10 ) whose walls are protected by a ‘waterfall’ ( 11 ) of lithium or a lithium compound. The target ( 12 ) is, at the moment of impact, within the sacrificial projectile which has entered the reaction chamber in a direction substantially parallel to the particles ( 13 ). The projectile has a hole ( 14 ) which permits passage of the pellets to strike the target. The projectile can itself be wholly or partly made of lithium. Also shown are the vacuum pipe ( 16 ) from which the pellets emerge and a projectile loading barrel ( 17 ) containing the next projectile ( 18 ). For continuous power generation, several projectiles are fired in per second.
[0014] The melt from the reaction chamber is circulated through a heat exchanger (e.g. by electromagnetic pump) to extract its thermal energy: the projectile material is extracted for recycling, as new projectiles must continuously be made. Tritium is also extracted.
[0015] It is important to preserve a good vacuum behind the projectile. As the projectile proceeds into the chamber ( 10 ) any tendency of gas or plasma from within to escape via any gap between the sides of projectile and its enclosing tube to contaminate the vacuum behind the projectile is reduced or eliminated by the outer walls of the projectile being indented with one or more circumferential cavities ( 19 ) which act as traps for such escaping material. The projectile can easily be made sufficiently cold that the cavities ( 19 ) additionally act as cold traps for such escaping material.
[0016] As 100% capture efficiency is impossible, there can never be quite enough neutrons produced from DT reactions to replenish the tritium. To close the cycle, some DD reactions are therefore desirable, which produce both tritium directly and extra neutrons. This can be arranged by raising the impact speed, hence effective collision temperature, and/or as shown in FIG. 4 by packing material ( 20 ) richer in deuterium round the central DT target ( 21 ), optionally enclosed in a shell of denser material ( 22 ) to increase the confinement time: the outer shell has a hole ( 23 ) to permit entry of the particles.
[0017] While the above design is described as for space conditions, it is of course possible to implement it on Earth provided that a vacuum tube is provided through which the pellets pass as they travel from accelerator to target. It is possible to provide a perfectly straight line up to several hundred kilometres long on Earth by choice of suitable terrain, tunnelling, stringing a pipe between a coastline and an island with a deep-water trench in between, etc. It is also possible to deflect the course of the particles with electric or magnetic fields, so the vacuum tube can be bent to match local topography and the Earth's curvature. It is also possible to shorten the distance between the accelerator and the target to a more convenient value at the cost of increasing the power of the accelerator.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 shows an accelerator at one of the Earth-Moon system's Lagrange points firing a pellet beam along a trajectory aimed to graze the lunar surface.
[0019] FIG. 2 shows an accelerator cross section with conducting electrode mounted within an insulating tube of substantially larger internal diameter.
[0020] FIG. 3 shows a reaction chamber whose walls are protected by a ‘waterfall’ of lithium (hatched) into which a sacrificial projectile is fired: pellets proceed in the direction indicated by the arrow to strike a target within said projectile.
[0021] FIG. 4 shows a central DT target surrounded by material richer in deuterium, enclosed in a shell of denser material which has a hole to allow passage of pellets.
[0022] FIG. 5 shows pellets (solid circles) en route to striking a target (hatched): parts (a), (b), (c), (d) show consecutive timesteps.
[0023] FIG. 6 shows pellets (solid circles) en route to striking a target (hatched): parts (a), (b), (c), (d) show consecutive timesteps.
[0024] FIG. 7 shows pellets (solid circles) en route to striking a target of slower moving pellets: the four columns from left to right show consecutive timesteps.
[0025] FIG. 8 shows pellets (solid circles) en route to striking a target (hatched): parts (a), (b), (c), (d) show consecutive timesteps.
[0026] FIG. 9 shows pellets (solid circles) en route to striking a target (hatched): parts (a), (b), (c), (d) show consecutive timesteps.
DETAILED DESCRIPTION OF THE INVENTION
[0027] It might be thought that the ‘virtual bullet’ formed by the coalescing particles will be less dense than a normal solid of the same material, e.g. if the particles are perfect uniform spheres then at least by the ratio of the spherical packing fraction ˜0.74, and less than that if allowance is made for inevitable inaccuracies in their shape, position and size. However as the back layers of the bullet are travelling faster than the forward layers, the bullet will compress to many times the normal density of the raw material as (or just before or after) it strikes the target.
[0028] In each of FIGS. 5-9 , parts (a), (b), (c) and (d) show particle positions (black circles) at consecutive timesteps en route to striking the target (hatched). For clarity the drawings are necessarily not to scale, with particle size vastly exaggerated, and particle number vastly reduced, compared to a likely implementation. FIG. 5 shows a basic configuration: particles come together to form a precompressed bullet before striking the target. FIG. 6 shows a variant in which additional particles, fired first at lower speed, pre-compress the target before the bullet strikes it. FIG. 7 shows a variant in which there is no pre-positioned target: rather additional particles, fired earlier at lower speeds, actually constitute the target. FIG. 8 shows a variant in which the prepositioned target is not flat but conical, so that it is precompressed sideways as well as vertically before the bullet strikes it. FIG. 9 shows a bullet whose central part travels fastest, so first ignition occurs at the centre.
[0029] It will be appreciated that almost infinite variations on the theme are possible. For instance the particles may be of differing sizes, shapes and made of different materials, likewise the target (if a prepositioned target is provided) may consist of layers of different materials. For example, the ensemble may provide back and front portions of dense material constituting a ‘hammer’ and ‘anvil’, between which the material to be fused is sandwiched.
[0030] Diamond dust; chopped graphite whiskers; chopped carbon fibres; ceramic microspheres; frozen deuterium; frozen deuterium-tritium compound; frozen methane in which the hydrogen atoms have been replaced by deuterium and/or tritium; an engineering plastic in which the hydrogen atoms have been replaced by deuterium and/or tritium; tungsten; uranium: are all examples of constituents which could be used in the particles and/or target. The particles can comprise outer shells of one material containing a second material within, e.g. the second material might be helium-3.
[0031] During their transit, the particles may have their charge neutralised (e.g. by spraying electrons on to them) so that they do not repel one another as they come together. Electron sprays might combine the functions of charge neutralisation, electron microscopy for precise position measurement, and adjustment of particle trajectory by momentum exchange. In a terrestrial system, particles may equally conveniently be measured and adjusted at any point in flight, not just near the accelerator or target ends of the system.
[0032] Note that relative (rather than absolute) accuracy of the particle positions is required. This is easy to obtain, as all particles can pass through the same sensors. If a prepositioned target is provided, the target may be adjusted to precisely the correct position for impact as the particle cluster approaches, or vice versa.
[0033] Note that the guidance system avoids any disruptive premature collisions between particles occurring.
[0034] Obvious applications include power generation, spaceship propulsion, asteroid propulsion.
[0035] The Tetris method may be suitable for separating compression and ignition, which is difficult to do by either laser or with a single physical bullet, for two reasons: A Tetris accelerator can, at no extra cost, fire many slower pellets immediately preceding the higher energy ignition pulse, with all arriving near-simultaneously. The extra pellets can supply energy and/or momentum for target precompression. As the ignition bullet is made by a train of pellets of differing speed coming together, it can easily be both precompressed to high density, and given a very high mass per frontal area, like an armour-piercing bullet. Thus it can punch through and deposit most of its energy at the heart of even a dense target plasma.
[0036] Allowance must be made for inefficiencies. In laser compression hydrodynamic inefficiency—evaporating material from the outside of the pellet to compress the central fuel by rocket-like reactive force—reduces the useful kinetic energy to 10% of radiative energy supplied. Pellet impact is potentially more efficient. However for ignition the available energy must be calculated in the centre-of-mass frame of the bullet and an equal mass of target, reducing the available energy by half. Also, if the bullet has mean atomic mass equal to that of the target, half the energy will be wasted as internal heating of the bullet itself; if on the other hand its atomic mass is higher than the target's, energy is lost to Rayleigh-Taylor instabilities. Further energy is wasted as the bullet punches through low-density plasma en route: not all its kinetic energy is donated at the ideal point. For compression the impact method could in principle be extremely efficient. However pellets provided at near-ignition speed are moving much too fast to impart momentum directly to the target, and can probably not be spread sufficiently uniformly. A solution is to make them collide with a strip of foil which acts as a hohlraum. Radiation from the hohlraum evaporates a backing material to accelerate DT fuel, perhaps into a conical pit within a surround of dense metal, in much the same way that a spherical pellet is compressed by laser. As long as the gap between hohlraum and DT backing material is at least a few times greater than any inhomogeneities in the pellet wavefront or the foil itself, very uniform compression will be achieved.
[0037] The accelerator operates on the same principle as a fundamental particle accelerator. However because the pellets travel at less than 1% of light speed, the drive frequency can be much lower. Tiny cheap MOSFET transistors thus can be used in place of klystrons for power conditioning, with small air-core (or vacuum-core) transformers to boost their output voltage. The electrodes do not form RF resonant cavities, and can be simple disks of metal mounted within a Teflon tube. Three-phase electrodes can be used (or even more phases) so that individual pellets ride a ‘wave’ of near-constant electric field. This minimizes vibration and induced surface current, so the pellets can be made from any reasonably strong material, e.g. plastic microspheres.
[0038] At the start of the accelerator, pellets could be injected from a ‘waterfall’ which falls between a pair of electrode plates. Individual pellets are ‘zapped’ with electrons from a steerable cathode ray tube beam (or positive ions from an ion gun) to adjust their time and speed of entry into the accelerator.
[0039] As the pellets approach the target shuffling may be necessary because while the direction of every pellet can be adjusted, its longitudinal position cannot. It will therefore be necessary to reallocate pellet positions dynamically in order to form a close-packed array as required. Any surplus pellets may be discarded by turning them away to the side. It is this dynamic allocation which makes ‘Tetris’ an appropriate system name.
[0040] The ideal fusion reactor requires no rare or radioactive isotopes as input, and produces no radioactive isotopes as output. Basic DT fusion as above does not achieve this goal. Although the blast chamber could in principle be surrounded with pure elements which do not produce unwanted isotopes under neutron bombardment, for continued operation it is necessary to breed tritium from lithium. The DT reaction itself does not yield sufficient neutrons for this, so it is normally assumed that fissionable isotopes must be included in the blast chamber surround, which intentionally multiply up the number of neutrons available to react with the lithium. However a Tetris reactor can easily be scaled up to much higher energies. At a temperature 10× higher than that for DT burn, the reaction cross-section becomes large enough to support DD direct burn, with the reactions DD→Helium-3+n and DD→tritium+p taking place at approximately equal rates. So by raising the reaction temperature and including a higher proportion of D to T, the Tetris reactor can manufacture sufficient tritium for its own use. (Helium-3 is not radioactive.) More ambitiously, the reaction Boron-11+p→Helium-4 might be achievable. This is the ideal aneutronic reaction, but very challenging first because it would require enormous densities, and second because energy output ratio is relatively modest: indeed unless an initial degenerate compressed plasma can be produced, the electrons take up too much energy to make self-propagating fusion burn possible. For a Tetris system the outlook is much better. The temperature of 550 keV at which the reaction cross-section is maximized is achievable, vastly lowering the density requirement. The efficiency with which Tetris turns electrical into kinetic energy allows net energy generation with a very modest output ratio. And because a Tetris machine can produce pellets with any speed distribution required, varied over the pulse, gentle piston-like precompression with minimum heating (as required to produce a degenerate plasma) is possible. (If very much slower pellets are required for compression than ignition, for example to perform without a hohlraum-type membrane, either by direct momentum transfer by impact with the target or by colliding pellets with one another to heat them and so produce radiant energy to power compression, separate accelerators can be used for the purpose. Since these secondary accelerators can piggyback on the buildings, vacuum tubes and trajectory adjustment systems of the primaries, cost will be modest.) A pair of opposed Tetris accelerators firing boron pellets into a central hydrogen target may well be optimal. Boron-a pellets are strong and can be given a high charge-mass ratio. All mass used is actually involved in the fusion, and the centre of mass is stationary with respect to the frame of the accelerators, so hydrodynamic efficiency is close to 100%. The accelerators used do not necessarily have to face one another exactly, so problems with curvature of the Earth's surface are minimized.
[0041] It may be possible to fit multiple parallel accelerator tubes within the same building. Tubes need only be separated by only a few times their electrode spacing to minimize mutual interference. Spare tubes can be provided. A worst-case pellet disintegration damages only one tube; the system can continue functioning while it is replaced. The accelerators can be aimed so that the beams gradually converge, initially entering small individual vacuum tubes which converge to become a single tube nearer the target.
[0042] An angled mirror can be used so that a single camera can capture a stereo image. The unit can measure particle position in all dimensions to ˜0.1 micron. In practice a cheaper laser giving longer pulses can probably be used, with streak analysis to determine along-axis position.
[0043] The cameras can also assess the size of each particle (shape, spin, mass and mass/charge ratio can also be measured independently if desired, e.g. by measuring the charge and also the magnitude of deflection by a known magnetic field). The relative positions and timings of the particles can be adjusted, and their intended destinations within the final bullet interchanged if necessary, to ensure that the density of the final bullet is almost perfectly uniform despite variations in individual particle size etc. This is analogous to the computer game Tetris.
[0044] A possible advanced fusion target is hydrogen-boron, which produces no neutrons, hence no radionucleides. This reaction has resonance peaks. Given the fine-tuning possible for the virtual bullet, which can be precompressed, shape-tailored, and given any desired internal velocity distribution, the peaks may be usable. The pellets are assumed to be boron, an ideal material which is strong and very hard even as a pure element: compounds such as boron carbide are even tougher.
[0045] The target may be boranes, boron-hydrogen compounds which are stable at low temperature. An effective fusion burn wave can be generated in a proton-boron plasma providing the plasma is degenerate, i.e. not too hot in relation to its density. The intrinsic ability of a Tetris accelerator to provide a first wave of slower pellets carrying high momentum relative to their energy, which arrive at the target simultaneously with the faster ignition pellets, is perfectly suited to providing such piston-like compression. Note that energy several times greater than the ignition pulse is automatically available for target precompression, by firing lower-speed pellets before the high-speed ignition burst.
[0046] Target compression may optimally be performed by pellets travelling very much slower (orders of magnitude slower) than the ignition pellets. The ignition pellet accelerator would be capable of providing particles at the very slow speed appropriate, perhaps a few tens of kilometres per second, by leaving all except the first few electrodes switched off, but the impulse would be modest. A much larger impulse can be provided cheaply using a small ancillary accelerator which shares its expensive components—building, vacuum tube, insulation and course correction systems—with the main accelerator. Up to say 100 millisecond's worth of this machine's output can arrive at the target as a pulse: an output of just 20 MW can provide a 2 MJ compression pulse. To keep within the limits of the tweaking system, the pellet arrival rate should be no greater than that of the main pulse. The compression particles may therefore be of order one million times as massive as the ignition particles: e.g. 100× the diameter, 50 μm.
[0047] The ancillary accelerator will be around one-tenth the length of the main one, but a negligible fraction of its switch cost. Although the compression pellets each carry several thousand times the momentum of the ignition pellets, they also carry 100× the charge and remain within the effective vicinity of correcting fields for several hundred times as long, so the existing course tweakers can easily handle them. The speed ratio is so high that all compression pellets have cleared the final tweaker before the first ignition pellets arrive. A magnetic field is provided at a few points along the vacuum tube connecting accelerator and target to bend the compression pellet trajectories slightly upward, to prevent them falling too far under gravity.
[0048] As an alternative method of target compression, fast pellets may hit a front layer of material on the target which heats up and evaporates, pressing and compressing deeper layers. This ‘rocket-like thrust’ method whereby energy in the form of very fast particles heats material to cause propulsion at much lower speeds is analogous to laser-driven inertial confinement fusion, wherein the fast particles are however photons.
[0049] Compression may be performed by pellets, and heating at a point to cause ignition provided by other means, such as laser(s) or beam(s) of fundamental particles, atoms, etc. Or vice versa.
[0050] Fast and/or slow pellets may approach the target zone from opposite directions, or indeed from many directions. They may be fired from separate accelerators and/or have trajectories bent by passage through electric or magnetic fields. In this case there may or may not be a separate target: the pellets themselves may comprise all of the material to be fused.
[0051] Successive fusion reactions may take place at various points within a pipe, which may be long with a narrow internal diameter.
[0052] If fusion is ignited in pellets which continue to travel rapidly (for example by colliding pellets of markedly differing speeds) the rapid motion of the fusion source may help dispense the energy release (whether in the form of photons, neutrons, or other particles) along the length of the pipe so that no one portion of the pipe walls or equipment beyond is subject to damaging levels of heat, radiation, etc.
[0053] Development is greatly facilitated because optimisation of compression and ignition can be explored using software changes only to tailor the ‘bullet’, for example using a genetic algorithm to home in on effective patterns.
[0054] The diacrode's major limitation is that it a fixed frequency device. In the present application, about 20% launch speed variation is required. Using MOSFETs, this could be applied simply by steadily increasing the frequency during the period between the first and last pellet leaving the accelerator. With diacrodes, the solution is to switch in units at the fast end successively, resulting in sub-trains of pellets each a few metres long travelling at a uniform speed. After exiting the main accelerator, these sub-trains pass through a short run of MOSFET-controlled electrodes which are operated to speed up (or retard) pellets by differential amounts: e.g. from zero increment for the first pellet in each sub-train to a few metres per second for the last, so that each individual pellet now has a slightly different speed for perfect convergence as required.
[0055] At the low-speed end of the accelerator tube there will be a minimum acceptable pellet separation due to inter-pellet repulsion. In place of what would be the first few metres of the accelerator, a longer low-power leader section is therefore provided with fixed electrode separation and highly variable drive frequency. This leader section is continuously fed with pellets which are precharged to a moderate voltage and fired in at (say) 5 few km/sec. When the leader contains a line of all pellets required, the variable frequency electrodes then accelerate this line en bloc to (say) 50 km/sec, at which point it enters the main accelerator. During this process the pellet voltage is raised by offsetting the local electrode voltages to the required level: note that electrons can flow easily from a pellet to the electrode it passes through, though not vice versa, as the pellet acts as a discharge point source while the electrode surface is smooth. To feed the leader at 5 km/sec, pellets are released from a Pelletron-type Van de Graaff generator. This is a well known technology, except that normally pellets emerge from a source container at a chosen average rate rather than at precise intervals. Here this must be modified: a container with several orifices is used, but any pellet can be rejected just after its emergence is detected, e.g. by zapping it with an electron gun to remove its charge, or diverting it using a switched electrode. Most pellets are thus recycled, leaving just one per cycle to drop into the accelerator tube. (Note that the required rate is lower than the rate at which a modem bubblejet printer ejects ink droplets of comparable diameter.) The precise timing of those pellets which are allowed to fall into the accelerator can be adjusted with a smaller kick from the same electrodes used for rejection. A pair or larger group of pellets which happen to emerge from the same orifice simultaneously are always rejected. There will be occasional cycles when no pellet is available, because any Poisson distribution occasionally yields a value of zero, but these gaps can be closed up by in-flight shuffling as described elsewhere. Focussing to keep the pellets centered during acceleration can be provided by electric field, e.g. shaping the electrodes as cones to produce an inward radial field for part of each cycle. Magnetic lenses, e.g. quadrupole magnets as used in a fundamental particle accelerator, and/or active steering as described elsewhere in this document, can also be used e.g. to damp down lateral oscillations. Pellets can be strength-tested by charging them to slightly above operational voltage before firing. In-tube pellet failure is therefore unlikely. Any failure which does occur has the potential to become contagious. However worst-case energy release is 2 MJ, and the debris cloud kinetic energy reduces exponentially at each consecutive electrode it impacts: each electrode masses more than the entire pellet cloud, and its central hole constitutes <1% of its area. So damage will be very localised. The tube can be wrapped in a Kevlar blanket so that external equipment is not affected. Chicane traps can be incorporated at multiple points in the system: slight bends with lateral fields which divert pellets of exactly the correct charge/mass ratio into the next section, but allow other material to fly on into open ended ‘dump tubes’ in which the plasma from their impact is safely contained. The precise deflection of each pellet which passes successfully allows its exact charge to be monitored, and tweaked with an electron gun if necessary.
[0056] The tube connecting accelerator and target can contain a relatively soft vacuum by particle accelerator standards: it does not need to be housed in a building, and can comprise a simple pipe mounted on pylons or stilts. It can be given a much larger internal radius, say ˜10 cm, than the maximum pellet deviation from the beamline, so that it can tolerate lateral displacements due to wind etc. of several centimetres, and so that its vacuum can be maintained by pumping from a limited number of points along its length.
[0057] Pellet position measurement near the target end is demanding because of the high rate of pellet flow past a given point, increasing to theoretical infinity at the collision point. Measurement stations comprise lines of paired cameras, with a pulsed laser providing light via a leaky optical fibre. Exposure is controlled by the laser, not by shuttering: inexpensive CCDs with a shutter rate ˜50 Hz have a similar readout rate, ˜10 Mpixel/sec, as expensive high capture rate cameras, and are capable of binary processing involving bit shifts, adds and reads (normally used e.g. for pixel binning) To avoid confusion from overlaps, pellet trajectories are spread, and timings chosen, so that each pellet imaged appears in a different part of a camera's field of view: for example a 1000×1000 field may be subdivided into 100 squares each of 100×100 pixels. The position of each pellet is reduced to an X,Y value for readout. Given that a readout delay of up to 20 μs is acceptable (corresponding to a downstream flight distance ˜20 m) each camera pair can track ˜100 pellets per pulse. The laser can be a standard laboratory desktop model providing ˜10 μJ output pulses of duration <1 picosecond at repeat rate up to 2 MHz. A pellet moves only ˜1 μm in 1 picosecond.
[0058] At the final correction the pellets can be given slight radial velocities, with dynamic allocation of placement to make the end product, the cylindrical virtual bullet, as neatly packed as possible, allowing for any ‘missing pellet’ gaps and also taking detected variations in pellet size into account if an imperfect monodisperse such as diamond dust is used: hence the Tetris system name. After the final correction station, a further electron gun reduces the pellet charge to zero.
[0059] The basic design assumes that all pellets follow the same beamline. By intentionally diverting the pellets into a number of parallel beamlines, the linear separation between pellets may be kept large enough that independent pellet tweaks even close to the impact point are possible.
[0060] The basic design uses small rapidly switched electrodes to tweak pellet trajectories. An alternative is to have the pellets pass through fixed strength fields, having reduced the charge on each pellet to a precisely controlled value to produce the course adjustment required, using an electron gun.
[0061] The severity of the flexure and heating encountered by the pellets during acceleration can be greatly reduced by the following strategy. The Tetris accelerator, with its large number of independently switchable MOSFETs, can easily provide multiple phases of drive voltage. In a strategy very similar to that used in coilguns, if consecutive electrodes cycle 120° out of phase, the accelerating force becomes approximately constant: the pellet rides a wave of constant gradient. If the pellet is small compared to the inter-electrode distance, it experiences a field which is to a good approximation both spatially and temporally uniform, and suffers virtually no vibration or induced current.
[0062] To feed pellets into the accelerator at a controlled rate, they could be mechanically preplaced in (e.g.) a 500×500 array on a plate. Pellets are charged via pins on which they sit above an electrode. To launch each pellet at the chosen instant, the charge on the electrode is switched from negative to positive. Plates can be removed and reloaded in alternation so the pellet supply is continuous.
[0063] If the pellets are monodisperse microspheres, they can come together into a close-packed array (e.g. as found in various crystal lattices). Even at maximum packing density there will be voids, however these will rapidly be filled as the spheres crush together at (or just before) target impact. To minimise seeding of Rayleigh-Taylor instabilities, these voids can be filled with smaller microspheres, or even with a quasi-fractal pattern of microspheres of different sizes.
[0064] If a non-monodisperse such as sieved diamond dust is used, dynamic reallocation of pellet terminal position by in-flight trajectory tweaking can aim for a goal similar to dry-stone walling, to bring objects of arbitrary size and shape together into a mass with minimal internal voids. If the orientation and spin rate of each pellet has been measured, even orientation at the moment of collision can be taken into account.
[0065] Discharging of the pellets can be done by firing electrons at them from an electron gun, or emitting electrons from a hot or cold cathode close to the flightpath. The electron gun can fire electrons substantially parallel to and at the same speed as the pellets, so that a high capture rate results. Likewise positive ions could be fired or emitted in place of electrons to make the pellet charge more positive. Pellet charge reduction could be done as a continuous or multi-step process. Actual pellet charge (charge/mass ratio) can be measured at any point by passing the pellet stream through a known electric or magnetic field and measuring the angle of deflection of each pellet.
[0066] The basic design assumes a single accelerator tube. A vertical stack of parallel tubes, broadly comparable in size to a very long set of bookshelves, could be used. Once technical confidence has increased, it would be possible to suspend a set of 10 or more such stacks in parallel beneath the ceiling of the building, occupying most of its width, but with ˜2 m headroom below. Any stack can be lowered into this space along all or part of its length for easy maintenance access. When the stack is rehoisted, small positioning motors attached to each tube fine-tune the alignment.
[0067] The sacrificial projectile could be made from supercooled ice (whose vapour pressure at cryogenic temperatures becomes utterly negligible) thus generating steam directly within the reaction chamber. | In space, a linear accelerator firing charged pellets can be situated at a large distance from a target at which the pellets are aimed. The accelerator can fire a graduated-speed train of pellets over a period of seconds or longer which arrive at the target simultaneously, and impart a large pulse of energy. An accelerator of modest power can thus provide a pulse in the megajoule range, sufficient to ignite fusion. It is necessary to provide course corrections to the pellets, to bring them together with very high precision as they approach the target. An ideal siting is to place the accelerator at the Earth-Moon L1 or L2 Lagrange point, and the fusion target at a point on the surface of the Moon where the pellets will strike at grazing incidence, i.e. on a great circle intersecting the lunar poles. Length of the particle trajectory is over 60000 km | 6 |
FIELD OF THE INVENTION
The present invention is related to the field of object recognition and more particularly to object recognition in real world tasks.
BACKGROUND OF THE INVENTION
The object recognition in real-world tasks has to decide about the identity of a presented object. The most general case of object recognition is unsolved. In order to constrain the task common approaches use several segmentation algorithms based on color, motion, edges. This is often not robust. Two major difficulties of object recognition are shift and scale invariance. In common approaches recognition uses the models of objects on multiple positions and tries to match the right one. Such procedure considerably slows down the recognition. The actively moving cameras can solve the problem of shift-invariance by focusing the object. This principle is used by several tracking systems. An object recognition system that can be used in the context of the present invention is described in U.S. Pat. No. 6,754,368 which is incorporated by reference herein in its entirety.
What is needed is a system and method for an object recognizing system using depth information e.g. for focusing at a pattern (object) and constraining the task (e.g., pattern recognition).
SUMMARY OF THE INVENTION
One embodiment of the present invention is a method for generating a saliency map for a robot device having sensor means. The saliency map indicates to the robot device patterns in the input space of the sensor means which are important for carrying out a task. The saliency map comprises a weighted contribution from a disparity saliency selection carried out on the basis of depth information gathered from the sensor means such that a weighted priority is allocated to patterns being within a defined peripersonal space in the environment of the sensor means.
The contribution from the disparity saliency selection is combined with a weighted visual saliency selection and weighted motion selection in order to generate the saliency map.
According to another aspect a method for calculating actuator command signals for a robot device having sensor means, comprises the steps of: (a) generating a saliency map according to the method as described above, the saliency map indicating to the robot device patterns in the input space of the sensor means which are important for carrying out a task of the actuator, and (b) transforming the saliency map into an actuator control command space.
Such a saliency map can be used for a gaze selection.
A further aspect of the invention, related to a pattern recognition method, comprising the steps of: (a) generating a saliency map by the method as described above, and (b) carrying out a pattern recognition limited to patterns within the peripersonal space.
The invention also related to a computer software program product, implementing such a method when running on a computing device.
The invention also relates to a robot device having sensor means designed to gather spatial information from a sensor input space, the device being programmed to carry out a such a method.
The features and advantages described in the specification are not all inclusive and, in particular, many additional features and advantages will be apparent to one of ordinary skill in the art in view of the drawings, specification, and claims. Moreover, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter.
BRIEF DESCRIPTION OF THE DRAWINGS
Further advantages, features and objects of the present invention will become evident from figures of the enclosed drawings and the following description of a preferred embodiment.
FIG. 1 shows a block diagram of an implementation of the present invention.
FIG. 2 is a schematic application scenario in accordance with one embodiment of the present invention.
FIG. 3 shows a pattern recognition model in accordance with one embodiment of the present invention.
FIG. 4 illustrates the training of an recognition model in accordance with one embodiment of the present invention.
FIG. 5 illustrates the performance of the use of the invention in the framework of object recognition in accordance with one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
A preferred embodiment of the present invention is now described with reference to the figures where like reference numbers indicate identical or functionally similar elements. Reference in the specification to “one embodiment” or to “an embodiment” means that a particular feature, structure, or characteristic described in connection with the embodiments is included in at least one embodiment of the invention. The appearances of the phrase “in one embodiment” in various places in the specification are not necessarily all referring to the same embodiment.
Some portions of the detailed description that follows are presented in terms of algorithms and symbolic representations of operations on data bits within a computer memory. These algorithmic descriptions and representations are the means used by those skilled in the data processing arts to most effectively convey the substance of their work to others skilled in the art. An algorithm is here, and generally, conceived to be a self-consistent sequence of steps (instructions) leading to a desired result. The steps are those requiring physical manipulations of physical quantities. Usually, though not necessarily, these quantities take the form of electrical, magnetic or optical signals capable of being stored, transferred, combined, compared and otherwise manipulated. It is convenient at times, principally for reasons of common usage, to refer to these signals as bits, values, elements, symbols, characters, terms, numbers, or the like. Furthermore, it is also convenient at times, to refer to certain arrangements of steps requiring physical manipulations of physical quantities as modules or code devices, without loss of generality.
However, all of these and similar terms are to be associated with the appropriate physical quantities and are merely convenient labels applied to these quantities. Unless specifically stated otherwise as apparent from the following discussion, it is appreciated that throughout the description, discussions utilizing terms such as “processing” or “computing” or “calculating” or “determining” or “displaying” or “determining” or the like, refer to the action and processes of a computer system, or similar electronic computing device, that manipulates and transforms data represented as physical (electronic) quantities within the computer system memories or registers or other such information storage, transmission or display devices.
Certain aspects of the present invention include process steps and instructions described herein in the form of an algorithm. It should be noted that the process steps and instructions of the present invention could be embodied in software, firmware or hardware, and when embodied in software, could be downloaded to reside on and be operated from different platforms used by a variety of operating systems.
The present invention also relates to an apparatus for performing the operations herein. This apparatus may be specially constructed for the required purposes, or it may comprise a general-purpose computer selectively activated or reconfigured by a computer program stored in the computer. Such a computer program may be stored in a computer readable storage medium, such as, but is not limited to, any type of disk including floppy disks, optical disks, CD-ROMs, magnetic-optical disks, read-only memories (ROMs), random access memories (RAMs), EPROMs, EEPROMs, magnetic or optical cards, application specific integrated circuits (ASICs), or any type of media suitable for storing electronic instructions, and each coupled to a computer system bus. Furthermore, the computers referred to in the specification may include a single processor or may be architectures employing multiple processor designs for increased computing capability.
The algorithms and displays presented herein are not inherently related to any particular computer or other apparatus. Various general-purpose systems may also be used with programs in accordance with the teachings herein, or it may prove convenient to construct more specialized apparatus to perform the required method steps. The required structure for a variety of these systems will appear from the description below. In addition, the present invention is not described with reference to any particular programming language. It will be appreciated that a variety of programming languages may be used to implement the teachings of the present invention as described herein, and any references below to specific languages are provided for disclosure of enablement and best mode of the present invention.
In addition, the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter. Accordingly, the disclosure of the present invention is intended to be illustrative, but not limiting, of the scope of the invention, which is set forth in the claims.
In the present invention the peripersonal space is a predefined depth interval of the input space of a sensor of e.g. a humanoid robot. As the sensor will have to detect whether a sensed object is within this space or not, it is capable of gathering depth information. The predefined depth interval can be selected e.g. to be adjacent to the sensor and furthermore be optionally confined by sensoring angles (or x- and y-ranges).
According to one example this peripersonal space can e.g. be defined as the space wherein the robot being provided with such sensor means can reach out to manipulate objects. The benefit of using this concept is that it leads to a robust interaction and recognition and allows to build up the higher level abilities on the base of stable complete closed-loop system.
The full concept of peripersonal space includes sensory perception as well as manipulation.
One example of a technical system used for experiments is depicted in FIG. 1 . It comprises an image acquisition module which supplies sensor information to a visual saliency computation module, a disparity saliency selection module and a motion saliency selection module. The output signals of these three modules are weighted and added and then supplied to a mapping module transferring the thus generated map from sensor coordinates into actuator (motor) coordinates. The saliency map can then be exploited by a gaze selection & memory unit to carry out a head control.
The weighted sum of the visual saliency computation module, the disparity saliency selection module and the motion saliency selection module can also be used to obtain a region of interest for a view-based pattern recognition. Eventually a speech output module can output the result from the pattern recognition.
The disparity of two points is their respective difference in their dislocation from a reference point (usually the center of the retinal plane). If all the parameters of the camera-setup are known, depth can be calculated from disparity.
As pointed out above, the invention uses the relation between peripersonal space and attention shifting and the consequences for object recognition.
The functional elements of the system can be described as follows: The visual saliency computation can be implemented e.g. as suggested in L. Itti, C. Koch, and E. Niebur, “A model of saliency-based visual attention for rapid scene analysis,” IEEE Transactions on Pattern Analysis and Machine Intelligence , vol. 20, no. 11, pp. pp. 1254-1259, which is incorporated by reference herein in its entirety. This method extracts early visual features (e.g., intensity, orientation) with the help of a set of linear center-surround operations on different scales of a Gaussian pyramid created from the input image. The features are normalized and combined to produce a retinotopic saliency map Sv. In this map positions corresponding to visually interesting locations are activated, e.g., have a value between zero and one according to their degree of interestingness.
The motion saliency selection produces a map Sm with an activation corresponding to the largest connected area of motion within a defined time-span.
The disparity saliency selection performs a disparity computation and selection of the closest region within a specific distance range (depth interval) and angle of view, see FIG. 2 . The position of this region (e.g., the closest object within the predefined space) in image coordinates is represented as an activation within the disparity saliency map Sd. If there is no stimulus within the predefined space (e.g., the specified range and angle of view), the activation of the map is all zero. This simple mechanism represents a first approximation to the concept of the peripersonal space set forth above.
It establishes a body-centered zone in front of the robot system that directly influences the behavior of the overall system as we will show at the end of this paragraph. The selection and propagation of the closest region only corresponds to a hard weighting of the presented stimuli with respect to the “closeness” to the system. The maps of the visual saliency, the motion saliency selection and the disparity saliency selection are weighted, summed up and transformed from image-coordinates to actuator-coordinates, yielding the integrated saliency map
S =visuomotor( wV SV+wDSD+wMSM ) (1)
This saliency map is the main input to the gaze selection. The gaze selection is a dynamic neural field (DNF), an integrodifferential equation modeling the dynamics of activations on the cortex. The dynamics can roughly be described as maximum selection with hysteresis and local interaction. For more details of the gaze selection see I. Mikhailova and C. Goerick, “Conditions of activity bubble uniqueness in dynamic neural fields,” Biological Cybernetics, vol. 92, pp. 82-91, 2005 that is incorporated by reference herein in its entirety.
The DNF is parameterized to yield a unique activation, which is interpreted as the target gaze direction qT. This target gaze direction is propagated to the head (sensor) control unit, which delivers the current gaze direction qC, the second input to the gaze selection.
As an example, the system can be parameterized with wV=1.0, wM=3.0 and wD=4.0. This corresponds to prioritizing the disparity information over the motion and visual saliency and the motion information over the visual saliency. With those weights the system shows the following behavior:
Without any interaction the gaze selection is autonomously driven by the visual saliency and the memory of the gaze selection. A natural way for humans is to raise the attention by stepping into the field of view and waving at the system. Due to the chosen weights the system will immediately gaze in the direction of the detected motion. The motion cue can continuously (including substantially continuously) be used in order to keep the gaze direction of the system oriented towards the hand. Continued waving while reducing the distance to the system finally leads to a hand position within the peripersonal space of the system defined by the disparity saliency selection.
Again, due to the chosen weights the signal from the peripersonal space will dominate the behavior of the system. Practically this means that the system will continuously fixate the hand and what is in the hand of the user. This kind of behavior can be used in order to perform various tasks.
Due to the gaze selection via DNF's a system as described implicitly exhibits some tracking behaviour, because selected portions of the visual field obey a hysteresis, meaning that regions near to the previously selected gaze directions are preferred over others in the next timestep. If the objects that cause the gaze selection are displaced slowly, the resulting new gaze directions tend to drift along with the objects. Alternatively, the system can be augmented with tracking behaviour, which would cause an even stronger preference to follow moving objects with the gaze. In interaction mode within the peripersonal space this can be used to maintain the fixation on selected inputs, e.g. for following and maintaining a stable sensor input of an object that should be recognized or learned. A description of tracking algorithms that are based on multicue low level sensory inputs without requiring a priori information of the objects/regions to be tracked can be found e.g. in M. Spengler and B. Schiele, “Towards Robust Multi-cue Integration for Visual Tracking”, ICVS 2001, LNCS 2095, pp. 93-106, 2001, which is incorporated by reference herein in its entirety.
For a schematic visualization of the space in front of the system see FIG. 2 . Defining the peripersonal space as a body centered volume in the space in front of the system corresponds to the biological findings. Inducing attention shifts by objects within the peripersonal space also corresponds to biological data. As discussed above, the full concept of peripersonal space includes action centered parts of the representation, but here we focus on the consequences for object recognition only.
The main problems for the recognition of rigid objects are translation, scale and three-dimensional (3D) rotation invariance as well as invariance with respect to illumination changes and occlusion. As according to the invention the classification is only performed within the peripersonal space, those invariance requirements are reduced to a large extent. Translation invariance is established by the gaze control fixating the 3D blob in the peripersonal space, while the depth information is used for improving scale invariance. Since the depth region is limited to a specific range, the occurring size variations are bound to a certain interval. The main invariances that have to be established by the classifier itself are 3D rotation, illumination changes, occlusion and the remaining position and size fluctuations that occur due to inherent fluctuations in the disparity signal.
The invention proposes a view-based approach to object recognition, where the classification is limited to objects within a predefined depth interval called peripersonal space. The underlying object hypothesis is an isolated 3D blob within the disparity map that is segmented and used to compute a region of interest (ROI) centered around the blob. The size of the ROI is dependent on the estimated distance, computed from the average disparity of the blob to obtain a coarse size normalization of objects. Using the disparity blob simplifies the invariance requirements for the recognition system as pointed out above. The current output of the classifier is the identity of the recognized object with a confidence level. The classification is entirely learned by presenting the set of objects to be recognized. It represents an example of tuning a general system to solving a specific task by learning.
The object recognition module can be based on, for example, the biologically motivated processing architecture proposed in H. Wersing and E. Körner, “Learning optimized features for hierarchical models of invariant recognition,” Neural Computation , vol. 15, no. 7, pp. 1559-1588, 2003 which is incorporated by reference herein in its entirety, using a strategy similar to the hierarchical processing in the ventral pathway of the human visual system. Within this model, unsupervised learning is used to determine general hierarchical features that are suitable for representing arbitrary objects robustly with regard to local invariance transformations like local shift and small rotations. Object-specific learning is only carried out at the highest level of the hierarchy. This allows a strong speedup of learning, compared to other general purpose statistical classifiers, that need large amounts of training data for achieving robustness. The input of the hierarchy is the region of interest (ROI) that is obtained from the left camera images using the disparity blob within the peripersonal space. This ROI is scaled to a defined size and provides the color input image for the following computation stages. The processing hierarchy is implemented as a feed-forward architecture with weight-sharing (see, for example, K. Fukushima, “Neocognitron: A hierarchical neural network capable of visual pattern recognition,” Neural Networks , vol. 1, pp. 119-130, 1988 which is incorporated by reference herein in its entirety) and a succession of feature-sensitive and pooling stages, see FIG. 3 and the H. Wersing and E. Körner reference.
The output of the feature maps of the complex feature layer (C2) provides a general high-dimensional object representation that achieves a stronger view-based abstraction with higher robustness than the original pixel image. Classification of an input image with a resulting C2 output is done in the final S3 layer by so-called view-tuned neurons that are obtained by supervised gradient-based training of a linear discriminator for each object, based on the C2 activation vectors of a training ensemble.
In the setting that we consider here, we perform no additional segmentation of the objects to be recognized. Training is done by showing 20 different objects with changing backgrounds and we expect the learning algorithm to automatically extract the relevant object structure and neglect the clutter in the surround. To demonstrate the generality of the recognition approach we use different types of visual object classes such as number cards, hand gestures, toys, and household objects. The results and details of the training are given below.
For our experiments a stereo camera head with anthropometric dimensions as shown in FIG. 2 has been used. It has a pan and a tilt degree of freedom and represents an eyes-on-shoulder construction.
The training of the recognition system has been carried out by showing 20 different objects within the interaction range and collect 600 training views for each object. The object ensemble includes of 11 sign cards, (only slight rotation deviation—max. 20 degrees), 2 hand gestures, and 7 freely rotated objects (see FIG. 4 ). To obtain more variations, training is done by two people. Due to inherent fluctuations of the disparity signal, the objects are only coarsely centered within the input image, and size varies about ±20% Additionally we collect 1000 views of other objects for the rejection training. For this training ensemble of 13000 views, the corresponding C2 activations are computed (with a dimensionality of 53×18×18=17172), and the S3 view-tuned neurons are trained as linear discriminators for each object within this C2 feature space (see FIG. 3 ).
This training takes about 30 minutes. To investigate the generalization performance of the recognition model, an independent set of test views with a third person has been recorded that did not participate in the training. For testing 100 images for each object plus additional 1000 clutter images for rejection have been collected. The results of the trained recognition system on the test ensemble are shown in the form of a an ROC plot that shows the trade-off between false positives (clutter classified as object) and false negatives (objects erroneously rejected as clutter). The plot is obtained for each object by tuning the recognition threshold from low to high values. One achieves less than 5% detection error at the point of equal false-positive and false-negative rate for almost all objects. The only exceptions are the can (20%), toy ASIMO robot (8%) and the metallic coffee can (7%). The overall classification error is 7.2%, when the class of the maximally activated view-tuned neuron is assigned as the classifier output.
Considering the object variety and the fact that no segmentation information was used for training of the architecture, the results are good. Note also that rather similar objects were contained in the rejection set, increasing the difficulty of the detection task. Also a baseline comparison has been performed, using the original RGB images with dimensionality 144×144×3 and utilize a nearest-neighbour classifier for classifying the test images with all labeled 12000 training images.
Using the plain original image data, the overall nearest-neighbour classification error is 77.5%. This underlines the advantages of the hierarchical C2 feature representation for representing object appearance in a general and robust way.
This invention integrates the object recognition into an active attentive system. This system focuses (e.g. by moving the cameras in pan and tilt direction) the salient blobs. The saliency is combined out of several channels. These are, for example, color, motion, contrast, and depth. The weighting of channels is done according to the task of the system and can change dynamically. The user can attract attention of the system by moving objects and introducing signals in the motion channel.
Another possibility of attention attraction is to put an object into a particular predefined volume in space. It extends over a certain angle of view of camera and ranges from very near range to end of a natural interaction range for human users in the depth. The system analyzes if any salient blobs are in peri-personal space. Out of these blobs the system focuses the closest one. The chosen region is proceeded to a pattern recognition system. Thus the recognition has to deal only with bounded shifts in scale and nearly no shifts in space. The choice of what objects have to be recognized can be affected dynamically by changing the weights of saliency channels.
While particular embodiments and applications of the present invention have been illustrated and described herein, it is to be understood that the invention is not limited to the precise construction and components disclosed herein and that various modifications, changes, and variations may be made in the arrangement, operation, and details of the methods and apparatuses of the present invention without departing from the spirit and scope of the invention as it is defined in the appended claims. | A method for generating a saliency map for a robot device having sensor means, the saliency map indicating to the robot device patterns in the input space of the sensor means which are important for carrying out a task; wherein the saliency map comprises a weighted contribution from a disparity saliency selection carried out on the basis of depth information gathered from the sensor means, such that a weighted priority is allocated to patterns being within a defined peripersonal space in the environment of the sensor means. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of PCT NO. PCT/CN2015/085719 filed Jul. 31, 2015, which claims priority to CN 201410455826.7 filed Sep. 9, 2014, both of which are incorporated by reference.
TECHNICAL FIELD
[0002] The present invention relates to the organic synthetic route design and the technical field for APIs and intermediates preparation, especially relating to the preparation method of Nintedaib for the treatment of idiopathic pulmonary fibrosis.
BACKGROUND
[0003] Nintedanib developed by Boehringer Ingelheim is a kind of oral triple angiokinase inhibitor which can simultaneously block three growth factor receptors: the endothelial growth factor receptor, the platelet-derived growth factor receptor and the fibroblast growth factor receptor. The blockade of these receptors may lead to inhibition of angiogenesis, which plays a key role in inhibiting tumor growth. The drug used for the treatment of idiopathic pulmonary fibrosis was granted the title of “breakthrough therapy drug” by U.S. FDA for the first time in July 2014, and the trade name of its ethane sulfonate preparation is Vargatef. The drug does not have a standard Chinese translation, so the applicant here translates it into “ ” based on the pronunciation.
[0004] The chemical name of Nintedanib: (Z)-{1-[4-(N-((4-methyl-piperazin-1-yl)-methylcarbonyl)-N-methyl-amino) phenylamino]-1-phenyl-methyl}-2-oxo-2,3-dihydro-1H-indole-6-carboxylate (I); the structural formula as follows:
[0000]
[0005] The preparation method of Nintedanib has been reported, and the synthesis method of Nintedanib and its analogue has been reported in PCT patents WO2001027081 and WO2009071523 from the original company. In this method, the drug is generated through condensation reaction of two key intermediates A and B under the alkaline condition.
[0000]
[0006] Additionally, the synthesis method of intermediates A and B are further reported in the literature J. Med. Chem, Pages 4466-4480, Vol. 52, 2009 and Chinese Journal of Pharmaceuticals, Pages 726-729, Vol. 43, Issue 9, 2012. And based on the optimized reaction condition, reaction sequence, rate of charge and catalyst selection, the synthetic route stated above becomes more simple and reasonable.
[0000]
[0007] By analyzing the structural characteristics of Nintedanib and combination of the current synthesis method of this compound and its intermediates, the applicant finds cis “methylene on indoline ring” structure and its formation method is the key to the whole synthesis process. It is also one of the difficulties. The process from the original company is that through the 3-position substitution and condensation reactions on 2-oxo-indoline ring and trimethyl orthobenzoate under the action of acetic anhydride, the trans “methylene” derivative, namely intermediate A is obtained. The methoxy in intermediate A is used as the leaving group to get a substitution reaction with the anilino in intermediate B, thus generating the target product. The intramolecular hydrogen bond in intermediate A can promote the transformation from “trans” to “cis”.
[0008] However, there exist some flaws or weaknesses in the existing process route. For example, the alkylation on the benzene ring easily produces positional isomer due to the impacts from nitryl. The especial case is that the 2-oxo-indoline ring after ring formation must be protected by acylation to achieve the smooth condensation reaction in which methylene is produced. The removal of acylation Pg will affect the functional groups of the other amide in the product, leading to the increased side reactions to reduce yield and quality.
[0000]
[0009] In view of the flaws in the existing process, the development of economical and environmentally friendly preparation technique with simple process can greatly promote the industrial production of the API and improve its economic and social benefits, and in this technique, the seeking for the synthetic route without protection and with deprotection is especially important.
SUMMARY OF THE INVENTION
[0010] The present invention aims to provide a preparation method of Nintedanib. The preparation method has an easily obtained raw material and a simple process, is economical and environmentally friendly, and is suitable for industrial production.
[0011] To achieve the above object of the present invention, the following technical scheme is mainly adopted in the present invention: a preparation method of Nintedanib (I),
[0000]
[0012] comprising the following steps: carrying out a condensation reaction on 4-(R acetate-2-yl)-3-nitrobenzoate (II) and trimethyl orthobenzoate to obtain (E)-4-[(2-methoxybenzylidene) R acetate-2-yl]-3-nitrobenzoate (III); carrying out a substitution reaction on the compound (EI) and N-(4-aminophenyl)-N-methyl-2-(4-methyl piperazine-1-yl) acetamide (IV) under the action of an acid-binding agent to generate (Z)-4-{[2-(N-methyl-2-(4-methyl piperazine-1-yl) acetamido-aniline) benzylidene] R acetate-2-yl}-3-nitrobenzoate (V); and sequentially carrying out reduction reactions and cyc-lization reactions on the compound (V) to prepare the Nintedanib (I). Wherein, R in said 4-(R acetate-2-yl)-3-nitrobenzoate (II) is methyl, ethyl, aliphatic group with 1 to 10 carbon atoms, phenyl or benzyl, but methyl or ethyl for the optimization case.
[0000]
[0013] In addition, the following attached technical scheme is included in the present invention:
[0014] The molar ratio of raw material 4-(R acetate-2-yl)-3-nitrobenzoate (II) and trimethyl orthobenzoate for said condensation reaction is 1:1˜10, but 1:2˜6 for the optimization case.
[0015] The solvent used in said condensation reaction is acetic anhydride.
[0016] The temperature for said condensation reaction is 110˜130° C.
[0017] The molar ratio of raw material (E)-4-[(2-methoxybenzylidene) R acetate-2-yl]-3-nitrobenzoate (III) and N-(4-aminophenyl)-N-methyl-2-(4-methyl piperazine-1-yl) acetamide (IV) for said substitution reaction is 1:0.5-1.5, but 1:1˜1.2 for the optimization case.
[0018] The solvents used in said substitution reaction are N,N-dimethylformamide, N,N-dimethylacetamide, dioxane, dimethylsulfoxide, methylbenzene or dimethylbenzen, but N,N-dimethylformamide or dioxane for the optimization case.
[0019] The acid-binding agents used in said substitution reaction are triethylamine, pyridine, 4-methylmorpholine, diisopropylethylamine, 4-dimethylaminopyridine, potassium carbonate, lithium carbonate or potassium tert-butoxide, but pyridine, lithium carbonate or diisopropylethylamine for the optimization case.
[0020] The temperature for said substitution reaction is 50˜100° C., but 80˜90° C. for the optimization case.
[0021] The reductive agents used in said reduction reaction are iron powder, tin powder, zinc powder, aluminite powder, rongalite, hydrazine hydrate, stannous chloride, sodium sulphide or hydrogen, but iron powder, zinc powder or hydrogen for the optimization case.
[0022] The acid catalysts added for said metal reduction are hydrochloric acid, phosphoric acid, acetic acid or acetic anhydride, but anhydride for the optimization case.
[0023] If the hydrogen is used as the reductive agent in said reduction reaction, the catalysts used are palladium carbon, platinum carbon, palladium hydroxide or raney nickel, but palladium carbon or platinum carbon for the optimization case.
[0024] The solvents used in said catalytic hydrogenation are methyl alcohol, ethyl alcohol, propyl alcohol or isopropyl alcohol, but ethyl alcohol or isopropyl alcohol for the optimization case.
[0025] The temperature for said cyclization reaction is 50˜150° C., but 110˜120° C. for the optimization case.
[0026] The solvents used in said cyclization reaction are benzene, methylbenzene, dimethylbenzene, acetic acid, acetic anhydride or dioxane, but methylbenzene, acetic acid or acetic anhydride for the optimization case.
[0027] The product from said reduction reaction needs no post-processing, and can be directly used for the cyclization reaction.
[0028] Compared with the existing technology, the preparation method of Nintedanib (I) in the present invention has an easily obtained raw material and a simple process and is economical and environmentally friendly, which is beneficial to the industrial production of the API consequently to promote the development of economy and technology.
DETAILED DESCRIPTION
[0029] The unrestricted detailed description for the technical scheme of the present invention is further given, based on the following several preferred embodiments. The preparation method of raw material 4-(R acetate-2-yl)-3-nitrobenzoate (II) and N-(4-aminophenyl)-N-methyl-2-(4-methyl piperazine-1-yl) acetamide (IV) can be referred to J. Med. Chem, Pages 4466-4480, Vol. 52, 2009 and Chinese Journal of Pharmaceuticals, Pages 726-729, Vol. 43, Issue 9, 2012 where the preparation method of the same compounds are introduced.
Embodiment 1
[0030] Add 4-(methyl acetate-2-yl)-3-nitrobenzoate (II) (2.53 g, 10 mmol), trimethyl orthobenzoate (9.10 g, 50 mmol) and 30 mL acetic anhydride into the reaction bottle, and get it heated to reflux status with the reaction of 6˜8 hours. After that, the end of the reaction is found by TLC detection.
[0031] When it cools down to the room temperature, there is separated solid. The crude generated product is recrystallized through normal hexane and ethyl acetate (1:1, V/V) and dried in the air to get 2.65 g off-white solid (E)-4-[(2-methoxybenzylidene) methyl acetate-2-yl]-3-nitrobenzoate (III) with 71.4% yield.
[0032] Melting point is 172-474° C. and mass spectrum (EI) is m/z 372(M+H).
Embodiment 2
[0033] Add 4-(benzyl acetate-2-yl)-3-nitrobenzoate (II) (3.29 g, 10 mmol), trimethyl orthobenzoate (5.46 g, 30 mmol) and 40 mL acetic anhydride into the reaction bottle, and get it heated to reflux status with the reaction of 8 hours. After that, the end of the reaction is found by TLC detection. When it cools down to the room temperature, there is separated solid. The crude generated product is recrystallized through normal hexane and ethyl acetate (1:2, V/V) and dried in the air to get 3.35 g off-white solid (E)-4-[(2-methoxybenzylidene) benzyl acetate-2-yl]-3-nitrobenzoate (Ill) with 74.9% yield. Melting point is 205-209° C. and mass spectrum (EI) is m/z 448 (M+H).
Embodiment 3
[0034] Add (E)-4-[(2-methoxybenzylidene) methyl acetate-2-yl]-3-nitrobenzoate (III) (3.71 g, 10 mmol), N-(4-aminophenyl)-N-methyl-2-(4-methyl piperazine-1-yl) acetamide (IV) (2.88 g, 11 mmol) and 50 mL N,N-dimethylformamide into the reaction bottle and get it heated to 80˜85° C., and then stir it with the reaction of 2 hours. When it cools down to the room temperature, the acid-binding agent pyridine (5 mL) is added with the stirring of 2 hours at the room temperature. Pour the reaction liquid into 150 mL water, and produce the separated solid. Said separated solid is filtered, and the crude product from filtration is recrystallized through ethyl alcohol to get 4.32 g yellow solid (Z)-4-{[2-(N-methyl-2-(4-methyl piperazine-1-yl) acetamido-aniline) benzylidene] methyl acetate-2-yl}-3-nitrobenzoate (V) with 71.9% yield. Melting point is 185˜188° C. and mass spectrum (EI) is m/z602 (M+H).
Embodiment 4
[0035] Add (E)-4-[(2-methoxybenzylidene) benzyl acetate-2-yl]-3-nitrobenzoate (III) (4.47 g, 10 mmol), N-(4-aminophenyl)-N-methyl-2-(4-methyl piperazine-1-yl) acetamide (IV) (2.88 g, 11 mmol) and 50 mL dioxane into the reaction bottle and get it heated to 80˜85° C., and then stir it with the reaction of 2.5 hours. When it cools down to the room temperature, the acid-binding agent lithium carbonate (1.1 g) is added with the stirring of 3 hours at the room temperature. Pour the reaction liquid into 150 mL water, and produce the separated solid. Said separated solid is filtered, and the crude product from filtration is recrystallized through methyl alcohol to get 4.93 g light yellow solid (Z)-4-{[2-(N-methyl-2-(4-methyl piperazine-1-yl) acetamido-aniline) benzylidene] benzyl acetate-2-yl}-3-nitrobenzoate (V) with 73.9% yield. Melting point is 222˜224° C. and mass spectrum (EI) is m/z 678 (M+H).
Embodiment 5
[0036] Add (Z)-4-{[2-(N-methyl-2-(4-methyl piperazine-1-yl) acetamido-aniline) benzylidene] methyl acetate-2-yl}-3-nitrobenzoate (V) (3.0 g, 5 mmol), 10% palladium carbon (0.3 g, 10% w/w) and 25 mL isopropyl alcohol into the hydrogenation reactor, and based on the hydrogenation operating procedures, the following actions are taken: add hydrogen at the room temperature and under the pressure of 5-8 Kg/cm 2 ; then stir it with the reaction of 4 hours until no hydrogen is consumed. After filtration, the catalyst palladium carbon is recovered, the filtrate undergoing a condensation process through reducing the pressure, and then the residue is dissolved through methylbenzene. Under the increased temperature of 115˜120° C., the reaction lasts 5 hours. After that, the end of the reaction is found by HPLC detection. Methylbenzene is recovered through reducing the pressure, and the residue is recrystallized through methyl alcohol to get 2.37 g yellow solid Nintedanib (I) with 87.9% yield. Melting point is 241-243° C. and mass spectrum (EI) is: m/z 540 (M+H), 1 H NMR (DMSO d 6 ): 2.27 (s, 3H), 2.43 (111, 8H), 2.78 (s, 2H), 3.15 (s, 3H), 3.82 (s, 3H), 5.97 (d, J=8.3 Hz, 1H), 6.77 (d, J=8.7 Hz, 1H), 6.96 (d, J=8.6 Hz, 2H), 7.32-7.62 (m, 8H), 8.15 (s, 1H), 12.15 (s, 1H).
Embodiment 6
[0037] Add (Z)-4-{[2-(N-methyl-2-(4-methyl piperazine-1-yl) acetamido-aniline) benzylidene] benzyl acetate-2-yl}-3-nitrobenzoate (V) (3.4 g, 5 mmol) and 50 mL acetic anhydride into the reaction bottle, and iron powder (0.85 g, 15 mmol) is added in batches. The reaction lasts 4 hours at the increased temperature of 55˜60° C. The following processes are cooling down and filtration, and then the filtrate is heated to 110˜115° C. with the reaction of 5-6 hours. After that, the end of the reaction is found by HPLC detection. After condensation through reducing the pressure, the residue is recrystallized through methylbenzene to get 2.30 g yellow solid Nintedanib (I) with 85.3% yield. Melting point is 241˜243° C. and mass spectrum (EI) is: m/z 540 (M+H), 1 H NMR (DMSO d 6 ): 2.27 (s, 3H), 2.43 (m, 8H), 2.78 (s, 2H), 3.15 (s, 3H), 3.82 (s, 3H), 5.97 (d, J=8.3 Hz, 1H), 6.77 (d, J==8,7 Hz, 1H), 6,96 (d, J=8.6 Hz, 2H), 7.32-7.62 (m, 8H), 8.15 (s, 1H), 12.15 (s, 1H).
[0038] It should be pointed out that the embodiments mentioned above are used to only describe the technical designs and features of the present invention rather than limit the scope of protection of the present invention, because the aim is to make the persons familiar with this technology learn the contents of the present invention and then conduct implementation according to these embodiments. Any equivalent changes or modifications made according to the spirit and principles of the present invention will be included in the protection scope of the present invention. | Disclosed is a preparation method of nintedanib (I), comprising the following steps: carrying out a condensation reaction on 4-(R acetate-2-yl)-3-nitrobenzoate (II) and trimethyl orthobenzoate to obtain (E)-4-[(2-methoxybenzylidene) R acetate-2-yl]-3-nitrobenzoate (III); carrying out a substitution reaction on the compound (EI) and N-(4-aminophenyl)-N-methyl-2-(4-methyl piperazine-1-yl) acetamide (IV) under the action of an acid-binding agent to generate (Z)-4-{[2-(N-methyl-2-(4-methyl piperazine-1-yl) acetamido-aniline) benzylidene] R acetate-2-yl}-3-nitrobenzoate (V); and sequentially carrying out reduction reactions and cyc-lization reactions on the compound (V) to prepare the nintedanib (I). The preparation method has an easily obtained raw material and a simple process, is economical and environmentally friendly, and is suitable for industrial production. | 2 |
CLAIM OF PRIORITY
[0001] This application is a continuation-in-part of application Ser. No. 10/773,506, filed Feb. 6, 2004, which is incorporated herein by reference.
TECHNICAL FIELD OF THE INVENTION
[0002] The present invention relates generally to carbon dioxide (CO 2 ) slab lasers. The invention relates in particular to a slab laser having a dielectric coupling-element between metal slab electrodes.
DISCUSSION OF BACKGROUND ART
[0003] CO 2 lasers are commonly used in commercial manufacturing for operations such as cutting or drilling, in particular, in nonmetallic materials. One form of CO 2 laser suited for such operations is known to practitioners of the art as a “slab” laser. Such a laser has an assembly including a pair of elongated, slab-like planar electrodes arranged face-to-face and spaced apart to define a gap between the electrodes. The electrodes are usually contained in a gas tight enclosure. The enclosure and the gap between the electrodes are filled with a lasing gas mixture including CO 2 . A radio frequency (RF) potential is applied across the electrodes to cause an electrical discharge in the CO 2 laser gas mixture. The discharge energizes the CO 2 lasing gas. A pair of mirrors is arranged, with one thereof at each end of the pair of electrodes, to form a laser resonator. A preferred type of resonator is an unstable resonator. The energized CO 2 lasing gas provides optical gain allowing laser radiation to be generated in the resonator. The electrodes form a waveguide or light guide for the laser radiation in an axis of the resonator perpendicular to the plane of the electrodes. This confines the lasing mode of the resonator in that axis. The mirrors define the lasing mode in an axis parallel to the plane of the electrodes. In an unstable resonator arrangement, laser radiation is delivered from (in effect, spilled out of) the resonator by bypassing one of the resonator mirrors.
[0004] In a slab laser used for drilling, cutting, and other machining operations a high output power, for example, greater than about 100 Watts (W), and maximum possible efficiency are important. In any given slab laser configuration, available output power generally increases with increasing gas pressure, provided that there is sufficient RF power to maintain a full discharge. Further, when operating in a pulsed-mode, faster rise and fall times for the pulses are possible at the higher pressure. A common problem limiting the output power of a slab laser is instability of the RF discharge. As RF power to the discharge (pump power) is increased to increase output power, the discharge eventually becomes unstable and is constricted into arcs. This adversely affects mode quality and efficiency of the lasers. This problem is exacerbated by higher gas pressures. Another problem in RF-energized slab lasers results from a substantial difference in RF impedance across the electrodes when there is no discharge (an “unlit” condition) from the RF impedance across the electrodes when there is a discharge (a “lit” condition). This impedance difference causes a change (a drop) in the resonant RF frequency when the discharge is ignited, i.e., the laser is changed from the unlit to the lit condition. Further, increasing gas pressure increases the difficulty of igniting the discharge, i.e., in turning on the laser. There is a need for an improvement of discharge stability in high peak power slab lasers.
SUMMARY OF THE INVENTION
[0005] In one aspect a laser in accordance with the present invention comprises first and second elongated electrodes arranged spaced apart and face-to-face. At least one solid dielectric insert extends longitudinally along the length of said electrodes. A first portion of the insert is located between the electrodes in contact therewith and a second portion of the insert extends laterally beyond corresponding edges of the electrodes. The first portion of the insert has a width less than the width of said electrodes, thereby leaving an elongated gap between said electrodes. The gap is filled with a lasing gas. A pair of mirrors is configured and arranged to define a laser resonant cavity extending through said elongated gap. Means are provided for exciting the lasing gas to create a gas discharge, thereby causing laser radiation to circulate in the resonant cavity. The height of the gap is selected such that the gap forms a waveguide for the laser radiation in the height direction. The width of said gap is selected such that the laser radiation is allowed to propagate in free space in the width direction of the gap in a manner controlled by the configuration and arrangement of the mirrors.
[0006] The dielectric insert increases the resistance-capacitance (RC) time constant of the electrode impedance by increasing the capacitive component of the time constant. This hinders the formation of arcs in the discharge, which, in turn enables the inventive laser to operate with higher excitation power or higher lasing-gas pressure than would be possible without the dielectric insert. The ceramic insert also decreases the difference in impedance of the electrodes with and without a discharge. This leads to a better-behaved discharge, and a discharge that is easier to light.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] The accompanying drawings, which are incorporated in and constitute a part of the specification, schematically illustrate a preferred embodiment of the present invention, and together with the general description given above and the detailed description of the preferred embodiment given below, serve to explain the principles of the present invention.
[0008] FIG. 1 schematically illustrates one preferred embodiment of a CO 2 slab laser in accordance with the present invention including first and second elongated metal slab electrodes arranged face-to-face and spaced apart by two ceramic inserts extending laterally partway between the electrodes and longitudinally along the length of the electrodes, and also including two mirror forming a one-axis unstable resonator extending between the electrodes.
[0009] FIG. 1A schematically illustrates the laser of FIG. 1 further including ceramic mirror-shields located between the ends of the electrodes and the mirrors.
[0010] FIG. 2 schematically illustrates another preferred embodiment of a CO 2 slab laser in accordance with the present invention, similar to the laser of FIG. 1 , but wherein there is only one ceramic insert extending laterally partway between the electrodes and extending along the length of the electrodes.
[0011] FIG. 3 is a cross-section view seen generally in the direction 3 - 3 of FIG. 4 schematically illustrating still another embodiment of a CO 2 slab laser in accordance with the present invention similar to the laser of FIG. 2 but wherein one of the slab electrodes is provided by a sealed enclosure surrounding the other electrode and the ceramic insert.
[0012] FIG. 4 is a three-dimensional view schematically illustrating details of the electrode and ceramic slab arrangement of FIG. 3 .
[0013] FIG. 5 is a graph schematically illustrating measured maximum RF peak power input to the electrodes as a function of lasing-gas pressure for an example of the laser of FIG. 1 , an example of the laser of FIG. 2 and similarly configured prior-art laser without any ceramic inserts.
[0014] FIG. 6 illustrates still yet another preferred embodiment of a CO 2 slab laser in accordance with the present invention including first and second elongated metal slab electrodes each having a single-stepped cross-section stepped and arranged face-to-face with a ceramic insert extending laterally partway between the electrodes, longitudinally along the length of the electrodes and having a height less than the step height of the electrodes.
[0015] FIG. 7 illustrates a further preferred embodiment of a CO 2 slab laser in accordance with the present invention including first and second elongated metal slab electrodes each having a double-stepped cross-section and arranged face-to-face with ceramic inserts laterally partway between the electrodes, longitudinally along the length of the electrodes an each having a height less than the step height of the electrodes.
DETAILED DESCRIPTION OF THE INVENTION
[0016] Turning now to the drawings, wherein like components are designated by like reference numerals, FIG. 1 schematically illustrates one preferred embodiment 10 of a CO 2 slab laser in accordance with the present invention. Laser 10 includes upper and lower elongated slab electrodes 12 and 14 , respectively, arranged spaced-apart and face-to-face. The electrodes have an overall width E. The electrodes are spaced apart by dielectric (ceramic) inserts or spacers 16 having a height H, and extending laterally, i.e., in the width direction of the electrodes, partway between the electrodes. Inserts 16 preferably also extend laterally beyond longitudinal edges respectively 12 E and 14 E of the electrodes by at least about 2.0 millimeters (mm). Most preferably, inserts 16 extend at least about 5.0 mm beyond the electrode edges. Inserts 16 , here, further extend along the entire length of the electrodes. This lateral extension of ceramic inserts 16 increases the surface path length from electrode 12 to electrode 14 across the ceramic insert, thereby increasing the surface resistance across the ceramic to minimize the possibility of arc or discharge formation between the electrode edges.
[0017] The assembly of electrodes and inserts is held together by ceramic clamps 18 attached to electrodes 12 and 14 by screws 20 . Preferred ceramic materials for inserts 16 include alumina (aluminum oxide—Al 2 O 3 ), beryllia (beryllium oxide—BeO), zirconia (zirconium dioxide ZrO 2 ) and zirconia and alumina mixtures. Alumina is also a preferred material for ceramic clamps 18 .
[0018] The cross-section configuration of electrodes 12 and 14 , and the thickness of inserts 16 is selected such that there is a gap 26 (the discharge gap), having a height G, between thick central portions respectively 13 and 15 of electrodes 12 and 14 . The electrode surfaces 12 B and 14 A bounding the gap are parallel to each other. Gap 26 has a width W, here, determined by the width of the thick portions of the electrodes. Width W of course, is less than the total width E of the electrodes. The stepped cross-section shape of the electrodes, with thinner portions of the electrodes on either side of gap 26 , provides that height H of inserts 16 can be greater than the height G of discharge gap 26 . This provides that the corresponding edges of the electrodes are further apart than electrode surfaces 12 B and 14 A of the electrodes forming the gap. This minimizes the possibility of a discharge forming between the electrode edges. The capacitance (Cx) added by the ceramic inserts can be approximated to a first order by an equation:
C X =ε( E−W ) L/H (1)
where ε is the dielectric constant of the ceramic and L is the length of the electrodes. The percentage of space between the electrodes occupied by the ceramic (P C ) is approximated by an equation:
P C =100( E−W )/ E (2)
and P C is preferably at least about 30%.
[0019] The assembly of electrodes 12 and 14 , ceramic inserts 16 , and ceramic clamps 18 and ceramic slab 20 is contained in an enclosure (not shown) filled with a lasing gas mixture including CO 2 . The lasing gas mixture fills gap 26 . Ceramic inserts 16 include apertures 19 extending therethrough to facilitate flow of the lasing gas into gap 26 . An RF potential is applied across electrodes 12 and 14 . Here, the RF potential (supplied by an RF generator designated symbolically in FIG. 1 ) is applied to electrode 12 (the “hot” electrode), and electrode 14 (the ground electrode) is connected to ground potential. Electrodes 12 and 14 are inductively coupled by inductors 32 . Applying the RF potential across the electrodes sustains an electrical discharge in the lasing gas in gap 26 , thereby exciting (energizing) the laser gas. Electrodes 12 and 14 include channels 34 that allow the passage of a cooling fluid through the electrodes to remove heat generated by the discharge.
[0020] The cooling water passages are typically constructed from materials that will not corrode when water is used as a coolant, for example, copper, nickel, or brass. Cooling channels should be arranged such that the flatness of electrodes 12 and 14 is not distorted by temperature gradients. An example of such an arrangement is described in U.S. Pat. No. 5,237,580, the complete disclosure of which is hereby incorporated by reference.
[0021] Energized CO 2 molecules in the discharge in gap 26 provide a gain medium for laser 10 . Laser 10 includes a hybrid resonator formed including a waveguide resonator and an unstable resonator 36 . Unstable resonator 36 is formed by a concave mirror 38 held in a mirror holder 40 , and a concave mirror 42 (indicated in phantom in FIG. 1 ) held in a mirror holder 44 . Both mirror 38 and mirror 42 preferably have a reflectivity of about 99.5% or greater at the laser wavelength. The width W of gap 26 is selected such that laser radiation propagates in free space in a direction parallel to the electrodes, i.e., in the width direction of the gap. The mode propagation is determined, inter alia, by the spacing and curvature of the mirrors and the location of straight edge 42 A of mirror 42 .
[0022] In this example, the mirrors of unstable resonator 36 are arranged and configured such that laser radiation circulates through gap 26 between electrodes 12 and 14 in a zigzag fashion, as indicated by dashed lines 46 . The laser radiation exits the resonator around edge 42 A of mirror 42 and then through an aperture 48 in mirror holder 44 . Concave curved walls 17 of ceramic inserts bound gap 26 on opposite sides thereof. It is advantageous to roughen the surface of curved walls 17 of ceramic inserts 16 to avoid the possibility of any waveguide action by these walls that could interfere with the function of mirrors 38 and 42 in determining laser modes in the width direction of the electrodes. The curvature of walls 17 also serves to increase the surface resistance of the ceramic inserts between the electrodes as discussed above.
[0023] The waveguide portion of laser resonator is defined by electrodes 12 and 14 and mirrors 38 and 42 and is perpendicular to the above described unstable resonator portion. Height G of gap 26 is selected such that plane parallel surfaces 12 B and 14 A of electrodes 12 and 14 , respectively, effectively form a waveguide for laser radiation in a direction perpendicular to the plane of electrodes 12 and 14 , i.e., in the height direction of the gap. The waveguide portion of the resonator is completed by mirrors 38 and 42 . Laser radiation propagation modes are restricted, in that direction only, by the waveguide effect. Height G of gap 26 is further selected to provide a desired far field beam profile in combination with maximum laser power.
[0024] It is preferable to space mirrors 38 and 42 at a distance from the ends of electrodes 12 and 14 sufficient that the mirrors are not degraded by the discharge in gap 26 . Preferably the spacing is about 20.0 mm or greater. Such a spacing, however, can lead to optical losses of laser radiation being redirected into gap 26 by the mirrors. One means of minimizing such optical losses is depicted in FIG. 1A . Here laser 10 includes a ceramic (dielectric) extension 21 at each end of electrode 12 . Extension 21 is attached to electrode 12 by countersunk screws 17 extending through the ceramic extension and into the electrode. The electrode 14 extends under the ceramic extensions. Ceramic extensions 21 preferably have the same cross-section shape as electrode 12 . Spacing between the ceramic extensions and electrode 14 is similar to the spacing between electrodes 12 and 14 . Extensions 21 (in cooperation with opposing electrode 14 ) provides a waveguiding effect similar to that provided by the electrodes. The extensions may extend to within about 5.0 mm of the mirror. Ceramic inserts 16 are correspondingly increased in length to extend at least partway along the length of the extensions.
[0025] Preferred dimensions G, E, W and H depend on desired operating parameters such as the lasing gas pressure, the frequency and power loading of the RF power applied to the electrodes and the output power of the laser. By way of example, for a gas pressure between about 80 and 200 Torr, an RF frequency of about 100 megahertz (MHz) and an output power between about 100.0 and 500.0 Watts (W), G is preferably between about 1.0 and 2.0 mm. Gap width W is preferably between about 20.0 and 80.0 mm for electrode length between 40.0 and 85.0 centimeters (cm). P C is preferably between about 30% and 70%. The ceramic insert height H is, determined, inter alia, by the dielectric constant of the dielectric material and the desired capacitive loading. Height H is preferably between about 2.0 mm and 6.0 mm for an alumina ceramic.
[0026] It should be noted here that only details of laser 10 sufficient for understanding principles of the present invention are described above. General aspects of CO 2 slab laser construction, such as lasing-gas enclosure, and RF power supplies and connection thereof, are well known in the art to which the present invention pertains and, accordingly, are not described in detail herein. A detailed description of examples of slab lasers is provided in U.S. Pat. No. 5,123,028 the complete disclosure of which is hereby incorporated by reference.
[0027] An object of locating ceramic inserts 16 between electrodes 12 and 14 is to increase the capacitive component of the impedance experienced by the applied RF potential in general, and to limit, in particular, the difference of this impedance in the lit and unlit conditions of the discharge in gap 26 . In an unlit condition, this gas is effectively a dielectric and the electrodes and the gas-filled gap behave as a capacitor. In the lit condition, the gas is electrically conductive, and the capacitive effect of the electrodes and the gap therebetween is minimized. Including inserts 16 in the gap between the electrodes according to principles of the present invention provides a strong capacitive component of the electrode impedance even when the discharge in gap 26 is lit, and also minimizes the capacity difference between the lit and unlit conditions. Preferably the ceramic inserts should have an electrode-covered area greater than or equal to about 30% of the total area of the electrodes and most preferably between about 30% and 70% of the total area of the electrodes as noted above.
[0028] The greater the ratio or percentage area of the ceramic inserts, of course, the more dominant will be the spacers in determining the capacitive component of the electrode impedance and the smaller the difference in impedance in the lit and unlit conditions. If the area of the ceramic inserts exceeds about 70% of the total area of the electrodes the current required to charge and discharge the capacitance during an RF cycle increase to a point where the efficiency of the laser is compromised.
[0029] FIG. 2 schematically illustrates another embodiment 60 of a slab CO 2 laser in accordance with the present invention. Laser 60 includes first and second elongated slab electrodes 62 and 64 . The electrodes are held spaced apart by ceramic clamps 18 as in laser 10 . Electrodes 62 and 64 in laser 60 have the same width. Located between electrodes 62 and 64 between thin edge-portions 62 E and 64 E, respectively, thereof is a ceramic insert 66 extending laterally partway between the electrodes. Ceramic spacer 66 is in contact with both electrodes and extends along the entire length of the electrodes. Spacer 66 also extends laterally beyond corresponding edges of electrodes 62 and 64 , preferably by at least 2.0 mm and most preferably by at least 5.0 mm for reasons discussed above with reference to inserts 16 of laser 10 . Edge portions 63 and 65 of electrodes are thickened to permit, inter alia, insertion of fluid cooling channels 34 . Surfaces 62 B and 64 A of electrodes 62 and 64 respectively, in thickened portions 63 and 65 , respectively, thereof define a discharge gap 26 . An RF discharge is created in gap 26 as described above with reference to laser 10 of FIG. 1 . Gap 26 here again has a width W less than the overall width E of the electrodes. An unstable resonator 36 is formed by a concave mirror 38 a concave mirror 42 as described above with reference to laser 10 of FIG. 1 .
[0030] The function of the single ceramic insert 66 is similar to that of the two ceramic inserts 16 of laser 10 . Using only a single insert asymmetrically arranged only one pair of electrode edges leaves discharge gap 26 open along the opposite electrode edges except for a relatively small proportion, preferably less than about 20%, covered by ceramic clamps 18 . This is very effective in facilitating flow of lasing gas into discharge gap 26 and for preventing acoustic resonances from occurring under pulsed discharge conditions.
[0031] In embodiments of the inventive slab laser described above, the assembly of slab electrodes, ceramic spacers and the ceramic insert between the electrodes is structurally independent of any enclosure containing the assembly and a lasing-gas mixture. It is possible, however, to integrate the electrode-ceramic assembly into such an enclosure. A description of one example of such an integrated structure is set forth below with reference to FIG. 3 and FIG. 4 .
[0032] FIG. 3 is a cross-section view schematically illustrating an embodiment 70 of a slab CO 2 laser in accordance with the present invention integrated into a metal enclosure 82 . FIG. 4 is three-dimensional view schematically illustrating laser 70 with enclosure 82 partially cut away. Those skilled in the art will recognize that laser 70 is similar to laser 10 of FIG. 1 integrated into a water-cooled enclosure. Accordingly, components with a common function in the two lasers are designated by the same reference numeral even though there may be some slight difference in shape therebetween.
[0033] Enclosure 82 is preferably formed from machined aluminum components and is electrically connected to ground potential. Interior 84 of enclosure 82 is filled with a lasing gas via a port 86 , the tip 88 of which can be sealed off to seal enclosure 82 once lasing-gas filling is complete. Cooling channels 34 are provided in the base, sidewalls, and top of enclosure 82 . Cooling fluid is directed into the channels via an inlet port 90 and exits the channels via an outlet port 92 .
[0034] A raised base-portion 94 of enclosure 82 forms a ground electrode for slab laser 70 . A separate top or “hot” electrode 12 is spaced apart from ground electrode 94 by a two ceramic inserts 16 . Electrode 12 has an overall width E. Raised portion 94 of housing 82 (the ground electrode) has a width W. Inserts 16 extend laterally partway between electrodes 12 and 94 and along the entire length of the electrodes. A discharge gap 26 is formed between upper surface 94 A of ground electrode 94 and lower surface 12 B of electrode 12 . The gap-spacing G is defined by ceramic inserts 16 . Gap 26 has a width W defined by the width of raised portion 94 of housing 82 . Apertures 19 extend through the ceramic inserts in fluid communication with discharge gap 26 .
[0035] A discharge is sustained in gap 26 by an RF potential applied across the gap. RF power is supplied by an RF generator designated only symbolically in FIG. 3 . The generator is attached to a connector 108 , which enters enclosure 82 via an insulated feedthrough 110 . An inductive path to ground is provided by a serpentine inductor 112 spaced apart from electrode 96 by ceramic insulating pads 114 . Inductor 112 is connected to grounded enclosure 82 via low inductance, compressive springs 116 . These springs also provide pressure for assisting clamps 18 hold the electrodes in contact with ceramic inserts 16 , thereby maintaining the spacing of gap 26 .
[0036] Referring in particular to FIG. 4 , resonator arrangements for laser 80 are similar to those of other above-described embodiments of the inventive laser. An unstable resonator 36 is formed by a concave mirror 38 held in a mirror holder 40 , and a concave mirror 42 (indicated in phantom in FIG. 4 ) held in a mirror holder 44 . The unstable resonator is arranged such that laser radiation circulates through gap 26 between ceramic slab 20 and electrode in a zigzag fashion as indicated by dashed lines 46 before exiting the resonator via an aperture 48 in mirror holder 44 .
[0037] FIG. 5 is a graph illustrating measured peak RF power as a function of a laser similar in configuration to laser 10 of FIG. 2 (solid curve) having only one ceramic insert, a laser similar to the laser of FIG. 1 (long-dashed curve) having two ceramic inserts, and similarly configured laser without any ceramic inserts (short-dashed curve). The electrode length is about 60.0 cm; the electrode total width (E) is about 44.0 mm; and the gap height (G) is about 1.4 millimeters (mm). Mirrors 38 and 42 are spaced apart by about 64.0 cm. Ceramic waveguide extensions about 15.0 mm in length are clamped to each end of the electrodes. In the case of the lasers having the inventive ceramic insert or insert, the insert or inserts occupy a total of about 47% of the electrode width. Lasing gas was a mixture of helium (He) nitrogen (N 2 ) and CO 2 in a ratio 3:1:1. The laser was operated in an RF super-pulsed mode at a 12% duty cycle and at pulse repetition frequencies between 700 Hz and 10 KHz.
[0038] The maximum RF peak power is that maximum RF power applied to the discharge at which it is possible to sustain a stable discharge. At a higher RF peak power, the discharge becomes unstable and arcs begin to form in the discharge. The data of FIG. 5 indicate that in the case of the prior-art laser without a ceramic insert, it was not possible to sustain a discharge at any pressure greater than about 140 Torr. In the case of the inventive laser having two ceramic inserts (the laser of FIG. 1 ), it was not possible to sustain a discharge at any pressure greater than about 160 Torr, however, a peak input power of 10.8 kilowatts (KW) was possible at the highest pressure compared with 8.7 KW at the highest pressure for the prior-art laser. In the case of the inventive laser having only one ceramic insert (the laser of FIG. 2 ), leaving the discharge gap open (unconstrained) along one side thereof, a discharge was still sustainable at a pressure of 180 Torr, at which pressure a peak RF input power of 12.6 KW was possible. Here, a limit was reached because of reaching an upper limit for the output power of the available RF power supply used to power the test laser. Generally the output laser power scales with gas pressure and the input RF power.
[0039] FIG. 6 schematically illustrates yet another embodiment 120 of a slab laser in accordance with the present invention. Laser 120 includes upper and lower slab electrodes 122 and 124 having a ceramic insert 126 therebetween. As in other above described embodiments of the inventive slab laser an unstable resonator 36 is formed by a concave mirror 38 and a concave mirror 42 with laser radiation circulating through a discharge gap 26 between the electrodes. In laser 120 the electrodes and the ceramic insert are arranged such that the discharge gap 26 is open along both sides thereof, so that there is no possibility of interference by the ceramic insert with laser modes determined by the resonator mirrors.
[0040] Each of the electrodes 122 and 124 has a single-stepped cross-section. Electrode 122 (the “hot” electrode) has a thin portion 123 and a thick portion 125 . Electrode 124 (the “ground” electrode) has a thin portion 127 and a thick portion 129 . The electrodes are arranged face-to-face, with the thin portion of one electrode facing the thick portion of the other electrode. Ceramic insert 126 is located between thick portion 125 of electrode 122 and thin portion 127 of electrode 124 in contact therewith. As in other above described embodiments, the ceramic insert extends laterally beyond the electrode edges (here edges 122 E and 124 E) to minimize the possibility of a surface arcing over the ceramic between the electrodes. For this same reason, ceramic insert 126 preferably also extends laterally beyond thick portion 125 of electrode 122 toward thick portion 129 of electrode 124 . Most preferably the width of the ceramic insert is sufficiently greater than the width of thin portion of electrode 124 than the ceramic insert contacts thick portion 129 of electrode 124 .
[0041] Discharge gap 26 is formed between thick portion 129 of electrode 124 and thin portion 123 of electrode 122 . Thick portion 125 of electrode 122 has a plurality of apertures 130 extending therethrough to facilitate flow of lasing gas into discharge gap 26 and to preventing acoustic resonances from occurring under pulsed discharge conditions, as discussed above. Gap 26 is open along the edges of the electrodes formed by thick portion 129 of electrode 124 and thin portion 123 of electrode 122 , although this is entirely visible in FIG. 6 . Spacing between the electrodes is maintained by ceramic clamps 18 , attached to edges 122 E and 124 E of the electrodes by screws 20 .
[0042] Electrodes 122 and 124 can be defined as having a step height S, being the difference in thickness between the thin and thick portions of the electrodes. Ceramic insert has a thickness C, which is less than the step height S. Preferably the height of ceramic insert S is between about 25% and 75% of the step height. Discharge gap 26 has a width W determined by the width of thick portion 129 of electrode 124 . There is a distance Y between the thin portions of the electrodes, which distance is equal to the step height S plus the height of discharge gap 26 . The total electrode width is E. Thin portion 123 of electrode 122 has a width (W+X). Values of X and Y are selected to minimize the possibility of a discharge occurring between the thin portions of the electrodes. In one example of a laser 120 having a capability of 400 W output power, the length of electrodes 122 and 124 is 82.5 cm, the width (W) of discharge gap 26 is 55.0 mm. The discharge gap height (Y−S) is 1.2 mm, S is 3.8 mm, E is 88.0 mm, Y is 5 mm, X is 5.0 mm. The thickness C of dielectric insert 126 C is 1.0 mm. The width of the dielectric insert 126 , is 29 mm and the length of the dielectric insert is equal to the length of ground electrode 124 . For a given pressure, the output power of the laser will scale directly with the discharge width (W) and the electrode length. The optimum discharge gap (Y−S) dimension will vary inversely with pressure. FIG. 7 schematically illustrates a further embodiment 140 of a slab laser in accordance with the present invention. Laser is similar in principle to a above-discussed laser 120 but includes slab electrodes 142 and 144 having a double-stepped cross-section.
[0043] Electrode 142 (the “hot” electrode) has a thin portion 143 and two thick portions 141 .
[0044] Electrode 144 (the “ground” electrode) has two thin portions 145 and a thick portion 147 . The electrodes are arranged face-to-face, with the thin portion of electrode 142 facing the thick portion of the electrode 144 . A ceramic insert 126 is located between each of thick portions 141 of electrode 142 and the thin portions 145 of electrode 144 . The ceramic inserts extends at least beyond the electrode edges to minimize the possibility of a surface arcing over the ceramic between the electrodes as discussed above with reference to laser 120 of FIG. 6 . Discharge gap 26 is formed between thick portion 147 of electrode 144 and thin portion 143 of electrode 142 .
[0045] Thick portions 141 of electrode 142 each a plurality of apertures 130 extending therethrough although the apertures are visible in only one thick portion in FIG. 7 . These apertures are, as discussed above, to facilitate flow of lasing gas into discharge gap 26 and to prevent acoustic resonances from occurring under pulsed discharge conditions. Spacing between the electrodes is maintained by ceramic clamps 18 , attached to edges 142 E and 144 E of the electrodes by screws 20 . Laser 140 potentially has a higher inter-electrode capacitance and a lesser difference in capacitance between lit and unlit conditions than laser 120 of FIG. 6 . This is achieved, however, at the expense of not having one side of discharge gap fully open for facilitating gas flow into the gap. For this purpose, reliance, here, is placed primarily on ports 30 in the thick portions of electrode 142 .
[0046] Those skilled in the art to which the present invention pertains will recognize without further illustration that while lasers 60 , 70 , 120 , and 140 are depicted without ceramic waveguide extensions between electrodes and mirrors, such extensions may be, and preferably are, incorporated in a configuration similar to that described above with reference to extensions 21 and 23 of laser 10 of FIG. 1A . Preferably, such extensions for lasers 60 and 70 have the same cross-section shape as the electrodes to which they correspond.
[0047] The present invention is described above in terms of a preferred and other embodiments. The invention is not limited, however, by the embodiments described and depicted. Rather, the invention is limited only by the claims appended hereto. | An slab CO2 laser includes spaced-apart elongated slab electrodes. A lasing gas fills a discharge gap between the electrodes. An RF power supply is connected across the electrodes and sustains an electrical discharge in the lasing gas in the discharge gap. Either one or two ceramic inserts occupy a portion of width of the electrodes and in contact with the electrodes. A discharge gap is formed between the portions of the width of the electrodes not occupied by the insert or inserts. Provision of the ceramic insert or inserts increases the resistance-capacitance (RC) time constant of the electrode impedance by increasing the capacitive component of the time constant. This hinders the formation of arcs in the discharge, which, in turn enables the inventive laser to operate with higher excitation power or higher lasing-gas pressure than would be possible without the dielectric insert. The ceramic insert also decreases the difference in impedance of the electrodes with and without a discharge. This leads to a better-behaved discharge, and a discharge that is easier to light. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to building construction, and particularly to a roof system for buildings, especially metal buildings with insulated roofs.
Expanded metal, metal screen, and other types of mesh have been proposed previously for use in constructing walls and ceilings of buildings. In some cases, as in U.S. Pat. No. 4,522,004, cementitious material or plaster is applied over the mesh. Mesh has also been used to support or retain insulating material, as in U.S. Pat. No. 2,148,281 and wire mesh reinforcement has been proposed, as in U.S. Pat. No. 4,047,346.
In U.S. Pat. No. 3,506,746, a net supported by poles serves as a support for receiving plaster, which hardens to form a structure in which doors and windows are subsequently cut. U.S. Pat. No. 545,301 describes a method of constructing an arched roof by applying concrete or cement to a corrugated wire mesh supported by structural beams.
U.S. Pat. No. 4,557,092 describes an insulating blanket having a strong scrim layer attached to its fiber barrier, to resist falling objects. It has been found difficult, however, to create joints of sufficient strength in such material to prevent heavy objects from falling through.
Finally, flexible materials have been used to support ceiling insulation in a dropped ceiling construction, as shown in U.S. Pat. No. 3,791,089.
None of the above patents adequately addresses the issue of worker safety, which is a particular object of this invention.
Butler Manufacturing's U.S. Pat. Nos. 5,251,415 and 5,406,764 describe roofing methods employing mesh laid over a roof prior to completion to catch dropped objects and to support insulation which is installed subsequently.
We are especially concerned with construction worker safety. Unfortunately, serious falling injuries occur from time to time during roof construction. It is therefore standard and required practice to provide safety netting or other material below roof installers to protect them and those below, and/or to require workers to be tied or tethered to the structure.
Tethers are only temporarily effective. When one neglects to apply a required tether, or while it is being moved, the workman and those below him are at risk. It would be better to have a restraint that could not be avoided, and did not require a positive act to be effective. Additionally, it would be preferable to use safety netting that would become part of the roof, to save the labor of removing the netting.
SUMMARY OF THE INVENTION
An object of the invention is to improve worker safety while constructing a roof.
The improvement comprises a nonmetallic mesh installed over and supported by the purlins, and which can be left in place while insulation, roof panels and the like are laid over it.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is an isometric view of an uncompleted building;
FIG. 2 is an enlarged view from above of one corner of the building, showing a portion of a mesh web and fasteners connecting the mesh to the substructure;
FIG. 3 is an isometric view of a connecting strap to which an edge of the mesh is attached;
FIG. 4 is an exploded isometric view showing a structural element, two connecting straps, and associated hardware at one eave of the roof;
FIG. 5 is a sectional view, on a vertical plane, of the mesh and connecting hardware shown along the eave of the roof in FIG. 2;
FIG. 6 illustrates one mesh connection point in detail;
FIG. 7 is a view like FIG. 4, showing the connecting hardware along one gable of the roof;
FIG. 8 is an view like FIG. 5, at the gable;
FIG. 9 is a plan view of the mesh installation along a gable;
FIGS. 10 a and 10 b show two varieties of mesh web, the one in FIG. 10 a having a heavier gauge along one edge;
FIGS. 11 a and 11 b are plan and side views of a splice between two parallel mesh webs;
FIGS. 12-15 show steps of installing mesh upon the substructure;
FIG. 16 shows the substructure covered with mesh, and roof panels laid over the mesh at one corner; and
FIG. 17 is an enlarged view showing insulation laid upon the mesh, then covered with roof panels.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The building shown in FIG. 1 has a frame composed of plural pairs of vertical structural members or columns 12 , the upper ends of each pair of columns being interconnected by a structural beam 14 extending in a direction transverse to the roof ridge line R—R. The transverse beams support an array of parallel purlins 16 , each orthogonal to the beams, that is, extending along the length of the building, parallel to the roof ridge line. The purlins are equally spaced, for example at five foot intervals. The purlins may be C- or Z-section members formed from sheet metal. Their exposed ends at either end of the building are capped by gable angles 18 . Eave struts 20 are installed at the edges of the roof, each extending parallel to the purlins; the eave struts are preferably C-section members whose open sides face toward the center of the roof.
As FIG. 2 shows, a mesh material 22 is stretched across the roof, directly over the purlins, and attached to the substructure along the edges of the roof.
The preferred mesh material is a knotted nylon mesh forming a nominal 2¾″×2¾″ grid. The mesh must have sufficient strength to break the fall of a typical worker and his tools working at the level of the purlins, midway between purlins. For added safety, we require the material to pass a dropping test with a 400 pound bag of sand dropped from a height of 42″ above the top of the purlins. A mesh material weighing 1.8 ounces per square yard, and meeting the strength requirements of the preceding sentence, is available from Diamond Nets, Inc., Everson, Wash.
FIG. 2 shows a corner of the building from above. Energy-absorbing steel straps 24 have been installed along the gable angles and eave struts, and the mesh is connected to these by ⅛″ diameter spring wire clips 26 passing through elongated openings 28 provided in the straps at 7¾″ intervals. A better view of one of the clips is in FIG. 6 . The clips are designed to allow the mesh to be quickly and easily hooked into the wire clip but not to allow the mesh to escape once the wire clip is hooked. Additionally, the clip is designed so that when the mesh pulls against the wire clip, the mesh can only pull on a double-wire section of the clip, not on the single wire section. This reduces any potential tendency of the single wire to cut the mesh.
FIG. 3 shows a preferred strap in detail. Made of 18-gauge galvanized steel, it is 40⅞″ long and has a negative dihedral angle of twenty degrees between two wings 30 , 32 of unequal width. One of the wings 30 has two holes 34 , one at either end; the other has the elongated openings 28 mentioned previously. Lengthwise 9½″ long slots 36 at either end of the strap promote yielding of the strap under heavy loads, causing it to act as an energy absorber when, for example, a workman falls on the mesh near the roof edge. In such a case, both wings yield plastically, so that the strap comes to resemble the letter “X” or “K”. Because the deformation is permanent, the straps affected must be replaced, once they have performed their energy-absorbing function. The event of deformation absorbs substantial energy right at the edge of the roof, thus protecting the selvedge from tearing at its attachment points to the substructure.
Loading tests were performed on sample straps to evaluate their strength. The strap was screwed to a fixture simulating a roof eave. Then force was applied to the free portions of the strap by pulling in a direction perpendicular to the length of the strap, in the plane of the strap. The strap was observed to deform elastically up to a its elastic limit; thereafter, at about 60 pounds per lineal foot, it deformed plastically with increasing resistance up to the point of failure. The failure mode was tensile failure of the strap at the screw holes. The ultimate strength of the strap exceeds that of the mesh so that, in actual use, the strap will not fail.
FIG. 4 shows the eave strut 20 to which two straps 24 are about to be attached by means of self-drilling screws 42 inserted through the holes 34 of the overlapped straps. Clips 26 have been pre-installed in the openings 28 to speed mesh installation. In FIG. 5, one sees the mesh now secured to the eave struts. It is apparent that the dihedral angle causes the inner wing 32 to angle downward, more or less at the angle of the mesh, when it is loaded.
The installation along a gable is very similar (see FIGS. 7 and 8 ).
FIG. 9 shows the reinforced selvedge 44 . Two versions of the mesh, one reinforced along one edge, are shown in FIGS. 10 a and 10 b. The reinforcement would be placed along a gable angle, at the edge of the roof, where the chance of failure is the greatest. Toward the middle of the roof, the mesh has more give and thus does not have to be as strong.
Standard building bays (the distance between beams) vary in width. The mesh is fabricated to order, to match the bay dimensions. One piece of mesh extends from eave to eave and may cover one or two bays. The maximum mesh width is sixty-five feet.
Adjacent widths of mesh are joined by means of clips 26 , as shown in FIGS. 11 a and 11 b, passed through the selvedge of width. Mesh-to-mesh splices are located above the primary frames.
FIG. 12 shows the building with heavy lines around the perimeter representing a series of straps 24 which has been attached to the entire perimeter as described above.
A packaged bundle of the mesh is placed at the edge of the roof framing. One end of the mesh is temporarily attached to the eave strut, and then the bundle is pulled across the roof purlins, allowing the mesh to string out behind the bundle (FIG. 13 ).
At the far eave, the bundle is left on top of the roof framing while the mesh at the starting end is stretched across the width of the bay. The mesh is attached first to the wire clips along the eave strut and then along the gable (FIG. 14 ).
The mesh at the far eave is then attached. The next bay of mesh is then strung out over the roof purlins in a similar manner. After it is attached along the eave, the second mesh is connected edgewise to the first mesh (FIG. 15 ). This process is continued the length of the building.
As a precaution, workers should be tethered to the structure while applying the mesh. Care must be taken not to tear the mesh during installation; an observer should look for and report any rips he discovers. The mesh is strong enough to withstand foot traffic, but such traffic should be limited to avoid damaging the mesh.
Once the entire roof has been covered with mesh and insulation, metal roof panels 50 are laid over both (and this should be done within sixty days of the mesh installation, since prolonged weathering can have a deleterious effect). During this phase, the strong mesh provides protection against falling, and from larger dropped objects. The mesh provides excellent support for the insulation and enhances the appearance of the insulation, as one can see in FIG. 17 .
The roof panels are secured to the purlins or joists by screws or specially designed panel clips.
With the present invention, added worker safety is obtained at minimal effort, since the mesh need not be removed; it remains in position for the life of the roof.
The foregoing description illustrates only one mode—the best now contemplated—of practicing the invention. Many changes can be made to details without departing from the gist of the invention claimed below. For example, the metal purlins described above could be any functional equivalent, including wooden joists, or truss-type members such as Butler Manufacturing's “Delta Joist”.
Inasmuch as the invention is subject to these and other modifications and variations, it is intended that the foregoing description and the accompanying drawings shall be interpreted as illustrative of only one form of the invention, whose scope is to be measured by the following claims. | A roofing system designed to protect roof construction workers from falls includes a strong nonmetallic mesh placed over an array of purlins, and secured to the periphery of the roof by a series of metal straps which plastically deform individually under large loads to absorb energy. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to an improved soda-lime-silica flat glass composition that yields economic advantages in melting and forming, better tempering characteristics, and improved surface durability. The composition is particularly suited to the manufacture of flat glass by the float process.
The composition of commercially produced flat glass has become rather narrowly standardized, with the compositions of flat glass products made by various manufacturers around the world seldom varying more than one or two percentage points of the major constituents from the following typical compositions:
______________________________________Constituent Weight Percent______________________________________SiO.sub.2 73.08Na.sub.2 O 13.68K.sub.2 O 0.02CaO 8.94MgO 3.88Al.sub.2 O.sub.3 0.11SO.sub.3 0.23Fe.sub.2 O.sub.3 0.12______________________________________
Compositions of this type have become standard because they yield a carefully balanced set of properties that are desired for manufacture and subsequent processing of flat glass products. Varying one constituent for the sake of improving one property usually has adverse effects on at least one or more other properties. Some of the properties for which the standard flat glass composition had heretofore been considered optimized include: minimized melting temperature, avoidance of devitrification during forming, surface abrasion resistance, surface weather durability, low refractory attack during melting, temperability, and batch cost. The melting temperature of the standard flat glass composition set forth above is 2630° F. It has long been known that reducing the amount of silica and/or increasing the amount of alkali in the glass can lower the melting temperature of the glass and lower the energy requirements for melting, but doing so undesirably reduces the surface durability of the glass product. Adjusting other constituents to compensate for the loss of durability can result in other drawbacks such as a reduction in the "working range," that is, a reduction in the temperature range in which the glass can be formed without substantial devitrification of the glass. As a result, it has heretofore been considered impractical for flat glass producers, particularly float glass producers, to lower the silica content of the glass significantly below 70 percent in order to obtain the melting advantages and energy savings.
U.S. Pat. No. 3,833,388 (Ohlberg et al.) discloses a flat glass composition having a higher alkali content than usual, but with the silica content no lower than 70 percent. Therefore, the full potential of reducing the melting temperature is not realized by that composition.
U.S. Pat. No. 3,779,733 (Janakirama-Rao) discloses broad compositional ranges for flat glass compositions that include silica concentrations considerably below 70 percent, but does not provide enablement for successfully producing flat glass having a silica concentration lower than 70 percent. The patent deals with producing a glass product having certain transmittance characteristics, not with improving melting properties.
U.S. Pat. No. 2,581,639 (Duncan et al.) discloses a television faceplate glass adapted to be sealed to a metal component and described as being suitable for manufacture by the sheet drawing process. The silica concentration is only slightly below 70 percent.
U.S. Pat. No. 2,669,808 (Duncan et. al.) discloses another glass composition adapted for sealing to metal components of a television tube. The glass is intended to be made by a sheet drawing process, but the silica concentration is extremely low for the glass to be considered suitable for general flat glass applications such as building or vehicle glazing. The low silica concentration would be expected to result in low surface durability.
Japanese Patent No. 61-197444 discloses soda-lime-silica glass compositions with silica concentration below 70 percent for the purpose of improving the tempering properties of the glass. The lower SiO2 concentrations together with higher than usual CaO concentrations would be expected to yield melting advantages. However, the reliance on increasing the CaO concentration and maintaining relatively moderate amounts of alkali result in undesirable flattening of the temperature/viscosity curve, so that temperatures at the viscosity range suitable for forming into a flat ribbon are increased and the danger of devitrification is increased (i.e. the working range is decreased). For some float forming operations, some of the examples disclosed in the Japanese patent could not be formed without devitrification or would require considerable cooling of the glass between the melting and forming stages. Although the patent discloses a fairly broad range of alumina, attainment of the desired results appears to require a relatively large amount of alumina (5%) in the examples or a combination of alumina and titania, both of which add substantially to the batch cost. A relatively high total of silica and alumina in the examples also indicates that reduction of the melting temperature was not optimized.
A general discussion of soda-lime-silica glasses, their constituents, and the relationship between the constituents and some of the properties of the glass products can be found in The Properties of Glass by G. W. Morey (Reinhold, 1954) pages 74-78. Of the several examples of glass compositions given there, none of the examples having less than 70 percent silica are mass-produced flat glass. Example 1 at 60 percent silica is described as lacking in durability.
SUMMARY OF THE INVENTION
The present invention is a specifically defined range of soda-lime-silica glass compositions that has been discovered to possess a unique combination of advantageous properties for flat glass manufacture: lower melting temperatures (lower than 2590° F., and in the best examples lower than 2560° F.); a suitably wide working range for flat forming into flat glass of at least 50° F.; improved surface durability; and improved tempering capabilities. This combination of properties has been found to be yielded by a composition characterized in general by silica concentrations reduced below 70%, relatively high alkali content, substantially more alumina than is common in flat glass, and carefully defined amounts of CaO and MgO. More specifically, the composition of the present invention is defined as follows:
______________________________________ Range Preferred RangeConstituent (Weight Percent) (Weight Percent)______________________________________SiO.sub.2 66.0-69.1 66.5-68.5Al.sub.2 O.sub.3 2.0-4.0 2.0-4.0(SiO.sub.2 + Al.sub.2 O.sub.3) Less than 71.6 Less than 71.1Na.sub.2 O 15-19 16.5-19K.sub.2 O 0-2 0-2(Na.sub.2 O + K.sub.2 O) 15-20 17.2-20CaO 7.5-9 7.5-8.5MgO 2-4 2-4(CaO + MgO) 10.2-12.0 10.2-12.0(CaO/MgO) 1.9-3.5 1.9-3.5______________________________________
Colorants such as iron oxide, selenium, cobalt oxide may also be present in the glass in minor amounts seldom exceeding one percent of the total composition in accordance with conventional practice for making colored glass. Traces of melting and refining aids conventionally employed in the art such as SO3 may also be present in minor amounts without affecting the properties of the glass.
DETAILED DESCRIPTION OF THE INVENTION
In a soda-lime-silica glass, silica is the major constituent because it primarily forms the glass network. Silica is also the most difficult constituent to melt. Reducing the silica content of the glass of the present invention below 70% results in lower melting temperatures. Alumina also tends to increase the melting temperature, but in the present invention it has been discovered that by substituting alumina for some of the silica permits the total content of silica plus alumina to be lowered, thereby lowering the melting temperature. At the same time, alumina improves the durability of the glass against surface corrosion, so the loss of durability caused by reducing the amount of silica in the glass has been found to be more than offset by substituting a lesser amount of alumina. Surprisingly, the surface durability has been found to be even greater than standard commercial flat glass. Accordingly, with a silica content of 66.0 to 69.1 percent by weight, preferably from 66.5 to 68.5 percent, and a total silica plus alumina content less than 71.6 percent by weight, melting temperatures less than 2590° F., and in the best cases less than 2560° F., are attained by the present invention without loss of durability. Melting temperature is defined as the temperature of the glass at which its viscosity is 100 poises. The alumina content is limited to the range of 2.0 to 4.0 percent by weight because alumina concentrations outside this range have been found to raise the liquidus temperature of this type of glass composition. The liquidus temperature is that at which the glass begins to devitrify, which causes undesirable haziness in the glass product. It is essential that the glass be cooled relatively quickly through the devitrification temperatures after it has been formed into a flat ribbon or other product shape so that devitrification is not occurring during forming. Therefore, it is desirable for the liquidus temperature to be substantially lower than the forming temperature. For the purposes of the present invention the forming temperature is defined as the temperature at which the viscosity of the glass is 10000 poises. The difference between the forming temperature and the liquidus temperature is known as the working range. It is desirable for the working range to be greater than 40 degrees F., preferably greater than 50 degrees F. This is achieved in part by the carefully delimited alumina concentration range of the present invention.
The chief alkali in soda-lime-silica glass is sodium oxide, with minor amounts of potassium oxide entering as an impurity from some of the raw materials, particularly the source material for the alumina. The alkalis act as fluxes, that is, they help dissolve the grains of silica, thereby permitting melting to take place substantially below the melting temperature of silica alone. The alkali content of the glass composition of the present invention is relatively high for the sake of lowering the melting temperature, but amounts in excess of the 20 percent maximum can result in reduction of surface durability and an increase in the corrosive effect of the molten glass on furnace refractories.
Calcium oxide and magnesium oxide also act as fluxes to aid the dissolution of the silica. Their presence is also desirable for the sake of improving durability, but calcium oxide can have a negative effect on the working range. By carefully controlling the amounts of calcium and magnesium oxides individually and in total, as well as the amount of calcium oxide relative to the amount of magnesium oxide, it has been found that the glass of the present invention can attain the combined advantages of reduced melting temperature, enhanced durability, and an adequate working range. More specifically, it has been found that the calcium oxide concentration should be 7.5 to 9 percent by weight, preferably 7.5 to 8.5 percent by weight. The best examples have less than 8.1 percent by weight for optimum working range. It has been found that the total calcium and magnesium oxide content should be from 10.2 to 12.0 weight percent of the total glass composition, and that the weight ratio of the calcium oxide concentration to the magnesium oxide concentration should be from 1.9 to 3.5 . The presence of magnesium oxide is useful in that it serves many of the same functions of calcium oxide but without as much of a harmful effect on the working range.
The examples set forth herein demonstrate the principles of the invention discussed above. Examples 1 through 15 (Table I) show soda-lime-silica glass compositions that are close to but outside the compositional ranges of the present invention, and the failure of those examples to attain the advantages of the present invention is shown in the physical properties set forth. Examples 16 to 28 (Table II), on the other hand, are embodiments of the present invention and, to a varying degree, exhibit the advantageous combination of improved physical properties that have been discussed. In the examples the melting temperature and forming temperature were determined by the rotating cylinder method. This method is described in the Journal of Research of the National Bureau of Standards, Vol. 68A, No. 5, September-October 1964. The forming temperature is defined as the temperature at which the logarithm of the viscosity of the glass in poises is 4.0. The working range is the forming temperature minus the liquidus temperature, the latter having been determined by means of ASTM procedure C-829 which employs a platinum boat of the glass in a gradient furnace.
Examples 1, 3, 7, 8, and 12 exhibit higher melting temperatures than desired, attributable at least in part to high SiO 2 concentrations or high totals of SiO 2 plus Al 2 O 3 . Example 7 is also low in its Na 2 O concentration, but comparing Examples 7 and 8 demonstrates that merely raising the amount of Na 2 O and lowering the amount of SiO 2 does not yield the degree of improvement desired. Example 9, with a low Al 2 O 3 content and a slightly high SiO 2 concentration, might be considered marginally acceptable, but the minor improvement in melting temperature does not justify changing composition. Many of the other examples in Table I show the unacceptable reduction in the working range (in some cases even producing a negative working range) that can be caused by attempting to lower the melting temperature by partially replacing SiO 2 with Na 2 O and CaO. The poor working range in Examples 5, 6, and 14 can be attributed to an excess of CaO. In Examples 10 and 11 too much MgO appears to be the cause of undesirably small working ranges. Example 11 also has a low concentration of Al 2 O 3 . High totals for CaO plus MgO lead to unacceptable working ranges in Examples 4, 6, 10, 11, 13, and 15. The poor working ranges in Examples 5 and 14 illustrate the importance of the ratio of the amount of CaO to the amount of MgO. This ratio appears to be a factor in the unacceptable working ranges of Examples 6, 10, and 11 as well. In Table II all of the examples have acceptable working ranges and melting temperatures, although the melting temperatures of Examples 17, 18, and 20 are slightly higher than the others and are therefore not among the preferred examples.
TABLE I______________________________________ 1 2 3 4 5______________________________________SiO.sub.2 69.52 68.59 67.66 67.43 67.29Al.sub.2 O.sub.3 3.17 3.13 4.83 2.67 2.66(SiO.sub.2 + Al.sub.2 O.sub.3) 72.69 71.72 72.49 70.10 69.95Na.sub.2 O 15.98 15.44 15.14 16.62 17.50K.sub.2 O 0.67 0.67 1.01 0.58 0.58(Na.sub.2 O + K.sub.2 O) 16.65 16.11 16.15 17.20 18.08CaO 7.62 8.70 8.23 8.96 9.10MgO 2.63 3.01 2.82 3.39 2.48(CaO + MgO) 9.25 11.71 11.05 12.35 11.58(CaO/MgO) 2.897 2.916 2.918 2.64 3.669SO.sub.3 0.30 0.27 0.31 0.29 0.30Fe.sub.2 O.sub.3 0.102 0.052 0.067 0.072 0.73Melting Temp. °F. 2603 2558 2637 2532 2497Forming Temp. °F. 1848 1835 1881 1817 1791Working Range °F. 146 5 63 16 13______________________________________ 6 7 8 9 10______________________________________SiO.sub.2 67.23 73.09 71.37 70.60 67.66Al.sub.2 O.sub.3 2.69 1.35 1.31 1.30 2.24(SiO.sub.2 + Al.sub.2 O.sub.3) 69.92 74.44 72.68 71.90 69.90Na.sub.2 O 16.49 13.30 15.62 15.63 15.69K.sub.2 O 0.59 0.29 0.29 0.30 0.49(Na.sub.2 O + K.sub.2 O) 17.08 13.59 15.91 15.93 16.18CaO 10.08 7.99 8.09 8.03 8.56MgO 2.54 3.54 2.88 3.72 4.96(CaO + MgO) 12.62 11.53 10.97 11.75 13.52(CaO/MgO) 3.968 2.257 2.809 2.159 1.726SO.sub.3 0.32 0.35 0.29 0.30 0.33Fe.sub.2 O.sub.3 0.073 0.87 0.88 0.089 0.075Melting Temp. °F. 2496 2697 2616 2591 2500Forming Temp. °F. 1801 1924 1860 1849 1801Working Range °F. -66 124 137 98 7______________________________________ 11 12 13 14 15______________________________________SiO.sub.2 67.72 69.34 67.66 67.46 66.76Al.sub.2 O.sub.3 1.64 3.22 2.06 3.24 3.13(SiO.sub.2 + Al.sub.2 O.sub.3) 69.36 72.56 69.72 70.70 69.89Na.sub.2 O 16.32 15.47 17.01 16.21 17.00K.sub.2 O 0.38 0.69 0.48 0.70 0.68(Na.sub.2 O + K.sub.2 O) 16.78 16.16 17.49 16.91 17.68CaO 8.61 7.69 8.98 9.30 8.76MgO 4.92 3.33 3.40 2.70 3.26(CaO + MgO) 13.53 11.02 12.38 12.00 12.02(CaO/MgO) 1.750 2.279 2.641 3.444 2.687SO.sub.3 0.33 0.31 0.34 0.31 0.27Fe.sub.2 O.sub.3 0.083 0.64 0.067 0.088 0.102Melting Temp. °F. 2529 2632 2499 2548 2518Forming Temp. °F. 1823 1869 1789 1818 1799Working Range °F. -37 107 47 0 -16______________________________________
TABLE II______________________________________ 16 17 18 19 20______________________________________SiO.sub.2 67.26 67.89 69.09 67.93 68.72Al.sub.2 O.sub.3 3.80 3.17 2.06 2.70 2.68(SiO.sub.2 + Al.sub.2 O.sub.3) 71.06 71.06 71.15 70.63 71.40Na.sub.2 O 17.33 16.46 16.63 17.00 15.90K.sub.2 O 0.82 0.69 0.47 0.58 0.58(Na.sub.2 O + K.sub.2 O) 18.15 17.15 17.10 17.58 16.48CaO 8.09 7.85 7.51 8.70 7.95MgO 2.38 3.56 3.82 2.69 3.81(CaO + MgO) 10.47 11.41 11.33 11.39 11.76(CaO/MgO) 3.399 2.205 1.966 3.234 2.087SO.sub.3 0.29 0.31 0.34 0.33 0.29Fe.sub.2 O.sub.3 0.058 0.065 0.080 0.065 0.067Melting Temp. °F. 2550 2566 2561 2533 2570Forming Temp. °F. 1806 1828 1827 1806 1836Working Range °F. 73 76 94 64 84______________________________________ 21 22 23 24 25______________________________________SiO.sub.2 68.33 67.06 68.33 68.00 67.26Al.sub.2 O.sub.3 2.02 3.65 2.01 2.62 3.11(SiO.sub.2 + Al.sub.2 O.sub.3) 70.35 70.71 70.34 70.62 70.37Na.sub.2 O 17.34 17.33 17.42 16.84 17.31K.sub.2 O 0.47 0.79 0.47 0.57 0.68(Na.sub.2 O + K.sub.2 O) 17.81 18.12 17.89 17.41 17.99CaO 8.42 8.04 7.95 7.87 7.91MgO 3.03 2.75 3.38 3.72 3.33(CaO + MgO) 11.45 10.79 11.33 11.59 11.24(CaO/MgO) 2.779 2.924 2.352 2.116 2.375SO.sub.3 0.30 0.31 0.35 0.30 0.31Fe.sub.2 O.sub.3 0.097 0.084 0.095 0.097 0.095Melting Temp. °F. 2516 2550 2531 2547 2547Forming Temp. °F. 1793 1814 1803 1814 1812Working Range °F. 60 81 95 71 103______________________________________ 26 27 28______________________________________SiO.sub.2 67.18 67.07 67.30Al.sub.2 O.sub.3 3.19 3.16 3.17(SiO.sub.2 + Al.sub.2 O.sub.3) 70.37 70.23 70.47Na.sub.2 O 17.67 17.50 18.05K.sub.2 O 0.69 0.69 0.65(Na.sub.2 O + K.sub.2 O) 18.36 18.19 18.70CaO 7.79 8.36 7.88MgO 3.09 2.84 3.15(CaO + MgO) 10.88 11.20 11.03(CaO/MgO) 2.521 2.943 2.502SO.sub.3 0.29 0.30 0.005Fe.sub.2 O.sub.3 0.101 0.100 0.084Melting Temp. °F. 2537 2532 2464Forming Temp. °F. 1805 1798 1774Working Range °F. 95 50 55______________________________________
The raw material formulations from which the glass compositions of the present invention may be melted can readily be calculated by those of skill in the art. By way of example, the batch mixture for Example 28 was:
______________________________________Ingredient Parts by Weight______________________________________Sand 3899Soda ash 1846Limestone 374Dolomite 1042Rouge 2Nepheline syenite 837______________________________________
Other raw materials are known to yield the same constituents and may be used in place of or in addition to the raw materials set forth in the example above. It should also be understood that various refining aids and coloring agents may be added in minor amounts without affecting the desired qualities of the glasses of the present invention. For commercial production some adjustments in the batch mixture may be necessary to accommodate losses of some of the materials due to volatilization or entrainment in accordance with the characteristics of the particular melting operation being used.
The following table shows the superior abrasion resistance of the glass of the present invention as compared to the standard commercial float glass composition set forth in the Background section above. The comparison is with Example 28 of the present invention, which was also formed into a flat sheet by the float process. The surface of the glass which was in contact with the molten tin during the float process is normally more abrasion resistant than the other ("air") side, therefore the results for both surfaces are reported separately. Abrasion was tested by the Taber abrasion test of ASTM C-501 in which the increase in the amount of haze is measured after a certain number of rotations of the glass sample in contact with an abrasive pad. It can be seen that the glass of the present invention shows less formation of haze due to abrasion on both surfaces compared to the standard glass composition.
______________________________________Abrasion TestHaze Difference (percent)Number Standard Example 28of Cycles Tin Air Tin Air______________________________________ 500 0.81 0.83 0.44 0.501000 1.16 1.09 0.82 0.711500 1.25 1.24 0.98 0.882000 1.39 1.36 1.17 1.04______________________________________
In another test of surface durability samples of the standard float glass and Example 28 were placed into a closed chamber and subjected to heating and cooling cycles to repeatedly vaporize and condense water vapor on their surfaces. The surfaces that had been contacted by tin during the float process of all of the samples showed resistance to corrosion, but corrosion of the non-tin side of the standard samples progressed to the point of substantially impairing transparency in 17 to 19 days, whereas no impairment of transparency occurred with the glass of Example 28 until after 90 days of exposure.
The improved thermal tempering capabilities of the invention can be attributed to a higher coefficient of thermal expansion. The expansion coefficient of the standard float glass composition set forth above is 8.62×10 -6 /°C. as compared to 10.44×10 -6 /°C. The expansion coefficients were determined by the dilatometer method using a one inch rod of glass in accordance with the procedure of ASTM E-228-71, and the coefficients reported are for the range 25° C. to 300° C. Sheets of the standard float glass and the glass of Example 28 were thermally tempered side-by-side in the same process under four different sets of process variables. In each case the amount of surface compression as measured by a differential surface refractometer, which is an indication of the degree of strengthening attained by the tempering, was 10 to 15 percent higher with the glass of the present invention. In another comparison, sheets of varying thickness were tempered on the same thermal tempering line to the maximum surface compression level attainable on that line. The maximum surface compression attainable by the standard glass composition was 26,000 pounds per square inch with a sheet 0.225 inches thick. The glass of example 28, however, was able to attain the same surface compression level with a sheet only 0.155 inches thick. This indicates that the glass of the present invention has the capability of providing a given level of strength with a thinner, and therefore lighter, product than standard float glass.
Some proposed glass compositions having reduced melting temperatures have the disadvantage of being more corrosive than usual to the refractory structure of melting furnaces. In tests of the corrosiveness of the glasses of the present invention in comparison with the standard float glass composition, the corrosiveness has been found to be substantially equivalent at the same temperatures. Furthermore, since the glasses of the present invention are intended to be melted at lower temperature, significantly less corrosion of the furnace refractories can be expected.
The range of viscosities encountered in manufacturing flat glass is exhibited by the glasses of the present invention over a smaller range of temperatures than standard float glass. This leads to several manufacturing advantages in addition to the obvious savings of energy due to lower melting temperatures. Because the melting and forming temperatures are closer together, a melting furnace can be operated at higher throughputs without inducing thermal instabilities because less cooling is needed at the downstream end of the melting furnace to prepare the glass for forming. The forming temperatures and annealing temperatures are also closer together, which has benefits in operating a float forming chamber at greater throughputs. Alternatively, a shorter, less costly float forming chamber could be utilized with the glasses of the present invention. Similarly, thermally tempering is easier because of a smaller difference between the softening point and the strain point of the glass of the present invention.
Although the advantages of the present invention could be applicable to the making of any glass product, the glass of the present invention is particularly suitable for making flat glass, most of which is made by the float process. Therefore, flat glass products made in accordance with the present invention will typically have a trace of tin oxide present near at least one surface due to the contact of the glass with molten tin during the forming process. Typically, a piece of float glass has a tin oxide concentration of at least 0.05 percent by weight (measured as SnO 2 ) within the first few microns below the surface that was in contact with the molten tin. Other deliberate modifications of the surface portion of glass during or after forming are known. These include migrating ions into the surface of the glass to modify the color of the glass or to strengthen the glass. It should be understood that the compositions given herein relate to the bulk glass composition, that is, the vast majority of the interior volume of a glass product, and do not preclude the possibility of compositional variations of this type at minor surface portions.
This description of the invention has been made with reference to specific examples, but it should be understood that variations and modifications as are known to those of skill in the art may be resorted to without departing from the scope of the invention as defined by the claims that follow. | A glass composition particularly suitable for flat glass manufacture having lower melting temperature, wide working range, improved surface durability, and enhanced tempering performance has the following composition:
______________________________________
SiO 2 66.0-69.1 weight percentAl 2 O 3 2.0-4.0(SiO 2 + Al 2 O 3 ) Less than 71.6Na 2 O 15-19K 2 O 0-2(Na 2 O + K 2 O) 15-20CaO 7.5-9MgO 2-4(CaO + MgO) 10.2-12.0(CaO/MgO) 1.9-3.5______________________________________ . | 2 |
This is a continuation-in-part of Ser. No. 10/304,774 filed Nov. 26, 2002, now U.S. Pat. No. 6,758,021 which is a continuation-in-part of Ser. No. 10/224,837 filed Aug. 21, 2002.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to clip on spacers for rebars or welded fabric used in structures to space the rebars or welded fabric a specified distance from concrete mold walls.
2. Description of the Related Art
In the past concrete rebars or welded fabric have been held in place by a variety of devices. Some of the devices are for holding the rebars or welded fabric a specified distance above the ground and so have a large ground contacting area to form a stable base for holding the rebars or welded fabric up without the spacer tipping over. Other spacers are used to hold mold walls away from a lattice of intersecting rebars or welded fabric. In this use a large contact area with the wall will leave a large area of the spacer exposed when the mold is removed. The concrete is thereby prevented from filling in the volume against the mold wall in the space occupied by the spacer. It is important to have as small a footprint of the spacers at the mold so that the edges of the poured concrete has more concrete on the outer surface for greater strength and for a better appearance.
Some spacers have clip on portions where two clips on each rebar are very close together such that the spacer can twist or turn on the rebar. These spacers are thus not held sufficiently straight, resulting in variations of spacing distance between the mold wall and the rebars or welded fabric. It is important to have spacers that will stay aligned to hold the mold wall a specified distance from the rebars or welded fabric.
Some spacers have clip on connections, which can come loose during impacts received during the construction process. It is desired to have clips that will stay connected once installed on the rebars or welded fabric.
Strike Tool 31785 64 th Ave., Cannon Falls, Minn. 55009, has a pyramid spacer with a C-shaped clip-on portion for engaging rebars.
SUMMARY OF THE INVENTION
The pyramid spacers have a pointed tip for contacting the mold walls thus leaving a small footprint on the outer portion of the poured concrete. The pyramid spacers also have a wide base with the clips spaced at the ends of the base for engaging rebars or welded fabric to provide stability against twisting forces such that the pyramid spacer remains oriented to space the rebars or welded fabric at a specified distance from the mold walls. Further the clips on the pyramid spacers have a rebar engaging portion for the rebar or welded fabric to fit into and two arms pressing on the rebar or welded fabric to lock the rebar or welded fabric snugly in place. The pyramid spacers also have a pair of pads at the corners of the base for engaging a perpendicularly crossing rebar or welded fabric to stably hold the pyramid spacers in a plane defined by the intersection of the rebars or welded fabric. Having only one pair of clips makes it easier to install the pyramid spacers.
In another embodiment the cage spacers have a trapezoid body portion and a double apex body portion with pads and clips for engaging the rebars or welded fabric. The double apex embodiment provides more stability of the cage spacer relative to the mold wall by having two contact points. In a further embodiment the cage spacer has two perpendicular double apex portions providing four apexes for engaging the mold wall and defining the plane of contact such that the cage spacer is stable on all axis against the mold wall.
OBJECTS OF THE INVENTION
It is an object of the invention to provide a spacer for spacing rebars or welded fabric a specified distance from molds.
It is an object of the invention to provide a spacer that will not come off of the rebars or welded fabric once installed.
It is an object of the invention to provide a spacer that will not twist or turn once installed which will change the distance of the rebars or welded fabric to the mold wall.
It is an object of the invention to provide a small footprint of the spacer at the mold wall.
It is an object of the invention to provide spacers with clips that are easy to install.
It is an object of the invention to provide an inexpensive, reliable and durable spacer.
Other objects, advantages and novel features of the present invention will become apparent from the following description of the preferred embodiments when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top angled perspective view of the cage spacer with a sideways facing clip.
FIG. 2 is a bottom angled perspective view of the cage spacer with a sideways facing clip.
FIG. 3 is a front view of the cage spacer with a sideways facing clip.
FIG. 4 is a side view of the cage spacer with a sideways facing clip.
FIG. 5 is a top angled perspective view of the cage spacer with a downward facing clip.
FIG. 6 is a bottom angled perspective view of the cage spacer with a downward facing clip.
FIG. 7 is a side front of the cage spacer with a downward facing clip.
FIG. 8 is a side view of the cage spacer with a downward facing clip.
FIG. 9 is a bottom angled perspective view of the cage spacer with a sideways facing clip having rebar engaging pins and feathers.
FIG. 10 is a top angled perspective view of the cage spacer having two apexes with a sideways facing clip.
FIG. 11 is a bottom angled perspective view of the cage spacer having two apexes with a sideways facing clip.
FIG. 12 is a front view of the cage spacer having two apexes with a sideways facing clip.
FIG. 13 is a side view of the cage spacer having two apexes with a sideways facing clip.
FIG. 14 is a top angled perspective view of the cage spacer having four apexes with a sideways facing clip.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
There are two cage spacer clip orientations shown in the figures. In FIGS. 1-4 the cage spacer 10 has a sideways facing clip portion 80 for engaging a reinforcing rod. In a second embodiment, shown in FIGS. 5-8 , the cage spacer 100 has a downward facing clip portion 180 for engaging a reinforcing rod. In all other respects the structure of cage spacers 10 and 100 are the same in the two embodiments.
The cage spacer 10 has a pyramid portion 20 comprising two triangle body portions 30 and 40 , intersecting right angles to each other and overlapping in their center portions along a common central apex axis. The triangles 30 and 40 are offset at their tips and bases such that the top of triangle portion 40 is the tip of apex 70 . The tip of triangle 30 is slightly lower than the tip of triangle 40 . The footprint of the apex 70 of the cage spacer 10 is thus reduced at the interface with the mold thus increasing the concrete available at the mold surface. The base 35 of triangle 30 is lower than the base 45 of triangle 40 to accommodate the difference in height of the intersecting rebars or welded fabric to which they are attached. Triangle portion 30 has the clip portions 80 attached at the corners of base 35 . Triangle 40 has pad portions 50 attached at the corners of base 45 for engaging a rebar. Aperture 60 is removed from the center of triangle portion 30 at its base 35 to accommodate a rebar passing therethrough. Thus the cage spacer is designed to attach at the intersection of two rebars or at the intersection of the fabric in the welded fabric such that the cage spacer apex 70 it perpendicular to the plane formed by the intersecting rebars or of the welded fabric.
Clip 80 has a rebar engaging portion 82 , two arm supporting segments 86 , and two angled arms 84 angling inward from the arm supporting segments 86 toward the open end of the rebar engaging portion 82 near the center of clip 80 . Clip 80 is placed on the rebar by forcing the angled arms 84 apart until the rebar rests in the rebar engaging portion 82 . Then the angled arms 84 are able to spring back into their unstressed position. When the rebar is enclosed in the rebar engaging portion 82 it can not escape since arms 84 have captured it in place. Clips 80 are spaced apart at the ends of base 35 on triangular body portion 30 such that the cage spacer 10 is stabilized.
The cage spacer 10 is held securely on the plane defined by the intersecting rebars or intersecting fibers in a welded fabric by pads 50 and clips 80 . The apex 70 of the pyramid is thereby held firmly so that it will always provide a specified distance from the plane of the rebars or welded fabric to the mold surface.
Clip portion 80 has arms 84 forming an entry to the rebar engaging portion 82 at a right angle to the apex axis may present a problem in that it may be difficult to force the cage spacer 10 on to the rebar or the fabric in a welded fabric from the side. It would be easier to place the cage spacer 10 on the rebars or fabric of the welded fabric at the intersection of the rebars or fabric of the welded fabric if the clip portion 80 was oriented to push straight down on the rebars or welded fabric.
In a second embodiment 100 , shown in FIGS. 5-8 , the cage spacer 100 has clip portion 180 rotated 90 degrees compared to the first embodiment cage spacer 10 . In this embodiment the cage spacer 100 can be attached by pushing the cage spacer 100 straight down into the plane of the intersecting rebars or the intersecting fabric of a welded fabric.
There are tradeoffs between the embodiments of cage spacer 10 and cage spacer 100 . In cage spacer 10 the clips 80 are at 90 degrees to the plane of the base of the pyramid and are more difficult to install over the rebars or the fabric of a welded fabric. The advantage is that the rebar engaging portion 82 has a wall engaging the rebar such that there will be very little play to move the spacer on the rebar such that the apex 70 will more reliably point perpendicular to the plane of the intersecting rebars or fabric of a welded fabric.
In the embodiment of cage spacer 100 the cage spacer is easier to install but the arms 84 may allow the cage spacer to pivot on the axis of the rebar or welded fabric due to the arms 84 not being as solid a barrier and as well positioned as the wall 88 of the clip portion 80 of cage spacer 10 .
The arms 84 are designed to have their ends engage the rebar or fabric of the welded fabric at angles such that the rebar or fabric of the welded fabric is held snugly in the recess of the rebar engaging portion 82 with the ends of arms 84 blocking the escape of the rebars or fabric of the welded fabric by engaging the rebars' or fabrics' circumference.
The triangular body portions 30 and 40 do not have to be of equal heights, or have equal length bases, or equal angles. The triangles 30 and 40 may be offset in height by differing amounts. Alternatively triangular body portions 30 and 40 need not be offset at all, such that the apex of both triangles are at the apex of the pyramid. Further, a pin 75 ( FIG. 8 ) may be extended from the apex of the higher of the pyramids to form the tip of the cage spacer and extent the height of the cage spacer while presenting a small footprint at the mold wall. Similarly, feathers 175 ( FIG. 9 ) on the base of pads 50 also provide a smaller footprint of the pads 50 on the rebars or welded fabric the cage spacers 100 are installed on. Further, when the rebars or welded fabric contact the feathers 175 the feathers are deformed or bent over by the pressure at the contact points. The contact points absorb shocks and vibrations and reduce the movement of the rebars or welded fabric on the pads.
As FIG. 9 shows, pins 90 can be used to position the top rebar or fabric on a welded fabric between the pins 90 to align the top rebar or fabric of the welded fabric within aperture 60 and to serve as a back stop for the bottom rebar in clip portion 80 . The pins 90 also align with the back portion of rebar engaging portion 82 to act as a guide for installing the cage spacer on the rebars or fabric of the welded fabric and to hold the rebars or fabric of the welded fabric in a straight line.
Although the triangular body portions 30 and 40 are shown as equilateral triangles any triangles may be used. Further, the apex and base of the first and second triangle segments can vary is as to which is has the higher apex and lower base. Alternatively, one triangle segment can have the higher apex and the lower base.
In a third embodiment 200 , shown in FIGS. 10-13 , the cage spacer 200 has two apexes 270 spaced apart from each other providing two points of contact with a wall for linearly aligning the cage spacer 200 with the wall on one axis. A single point of contact 70 can be tilted to the side relative the clip portions 80 whereas two points of contact form a line so that the cage spacer is not tilted on this axis. Pads 50 on cage spacer 200 are spaced apart and provide a line of contact with reinforcing rods on a perpendicular axis to the two apexes 270 in contact with the wall. In this manner the cage spacers 200 are made more stable and do not twist relative to the face of the wall due to a non exact fit of clip portion 80 on a rebar or fabric of a welded fabric.
Cage spacer 200 has a base portion the same as the base portions of cage spacers 10 and 100 . Cage spacer 200 has pads 50 , aperture 60 , and a clip portion 80 which can be either perpendicular (as in cage spacer 10 ) or parallel (as in cage spacer 100 ) to the top to bottom axis.
Cage spacer 200 has a trapezoid portion 230 and a double apex portion 240 which are perpendicular to each other and have a plateau portion 290 at their intersection. The apexes are on opposite sides of the cage spacer to provide for stability when in contact with a wall. In another embodiment the trapezoid portion 230 can be replaced with another double apex portion 240 to provide stability in four corners so that the plane of the cage spacer is defined with respect to the wall it engages.
Cage spacer 200 may have different styles of apex portion 240 portions. As shown the apex is at the top of a triangular extension from plateau 290 however any style of height extension may be employed. Further a pin 75 may be employed to extend the apex 270 so that the pin 75 engages the wall with a smaller cross section of cement being displaced at the interface of the wall and the cage spacer.
The cage spacers 10 , 100 and 200 can be made to fit various sized rebars or welded fabrics and have differing heights for spacing the mold walls at different distances from the rebars or welded fabric. Although the cage spacers are described as attaching to rebars or welded frabrics throughout the application wires or other means for making cages to support cage spacers and reinforce the concrete can be used with the cage spacers.
The cage spacers 10 , 100 and 200 can each optionally have features such as the pins 75 and 90 or feathers 175 .
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described. | A cage spacer for spacing reinforcing rods or welded fabric a specified distance from mold walls for poring concrete during construction projects. The cage spacer comprises two intersection bodies oriented perpendicular to each other and preferable with one body having a base higher than the other. A pair of pads on opposite ends of a first body base for stabilizing the body on the rebar. A pair of rebar engaging clips on opposite ends of the second body base for snapping onto and gripping a perpendicularly intersecting rebar such that the rebar is held securely in the clips. The cage spacer attaches over the intersection of a pair of rebars. At least one apex of the bodies engages a mold wall to keep the mold wall a specified distance from the rebars while concrete is being poured in the mold. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. application Ser. No. 09/990,282, filed Nov. 23, 2001, now allowed, which is a continuation of U.S. application Ser. No. 09/811,487, filed Mar. 20, 2001, now abandoned, which is a divisional of U.S. patent application Ser. No. 09/117,372, filed Oct. 28, 1998, now U.S. Pat. No. 6,235,942, issued May 22, 2001, which is the U.S. national stage of International Patent Application No. PCT/EP97/00370, filed Jan. 28, 1997 and designating the United States, and published by the International Bureau on Aug. 7, 1997 as WO 97/28122. The disclosures of U.S. application Ser. Nos. 09/990,282, 09/811,487 and 09/117,372 are herein incorporated by reference in their entireties and relied upon.
BACKGROUND OF THE INVENTION
[0002] This invention relates to a process for preparing ketone compounds and the products obtained by this process. More particularly, the invention relates to the preparation of intermediate compounds in the manufacture of pesticides.
[0003] Pesticidal 4-benzoylisoxazoles, particularly 5-cyclopropylisoxazole herbicides and intermediate compounds in their synthesis, are described in the literature, for example in European Patent Publication Nos. 0418175, 0487357, 0527036, 0560482, 0609798 and 0682659.
[0004] Various methods for preparing these compounds are known. It is an object of the present invention to provide improved methods for the preparation of these compounds and the intermediate compounds thereto.
SUMMARY OF THE INVENTION
[0005] According to a first aspect of the invention, there is provided a process for the preparation of a compound of formula (I) by the reaction of a compound of formula (II) with a compound of formula (III), according to the reaction scheme Sc1 indicated below:
[0006] wherein:
[0007] R 1 is lower alkyl;
[0008] R 2 is lower alkyl; or phenyl optionally substituted by from one to five groups which may be the same or different selected from lower alkyl, lower haloalkyl, halogen and —SR 4 ;
[0009] R 3 is halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, —S-alkyl, cycloalkyl having from 3 to 7 ring carbon atoms, alkenyl or alkynyl having from 3 to 7 carbon atoms, or —(CR 5 R 6 ) q —SR 2 wherein q is one or two;
[0010] n is zero or an integer from one to three;
[0011] R 4 is lower alkyl;
[0012] and R 5 and R 6 independently represent hydrogen, lower alkyl or lower haloalkyl.
[0013] According to a second aspect of the present invention, there is provided a process for the preparation of a compound of formula (II) by the reaction of a compound of formula (V) with a mercaptan of formula (IV), optionally present in the form of the thiolate, according to reaction scheme Sc2 indicated below:
[0014] wherein R 2 , R 3 and n in formulae (II) and (V) have the same meanings as given before in reaction scheme Sc1. The group —NO 2 is generally present in the 2- or 4-position, preferably the 2-position of the phenyl ring.
[0015] According to a third aspect of the invention there is provided a process for the preparation of a compound of formula (V) by the reaction of a compound of formula (VII) or (VI), as well as a process for the preparation of a compound of formula (VI) from a compound of formula (VII), according to the reaction scheme Sc3 indicated below:
[0016] wherein R 3 and n have the same meanings as in reaction schemes Sc2 and Sc1, and X represents halogen, preferably chlorine or fluorine. Preferably, the group —NO 2 in formula (VII) is in the 2- or 4-position, most preferably in the 2-position of the phenyl ring.
[0017] Certain intermediate compounds of formula (II) are novel and as such constitute a further feature of the present invention, in particular 2-methylthio-4-trifluoromethylacetophenone and 3,4-dichloro-2-(methylthio)acetophenone.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The compounds of formula (I) and a number of processes for their preparation have been described in the European Patent Applications cited above.
[0019] By the term “lower” is meant radicals comprising at least one hydrocarbon chain, it being understood that such radicals contain from one to six carbon atoms linked together in a straight- or branched-carbon chain.
[0020] Preferably, R 1 and R 2 are lower alkyl (most preferably, methyl).
[0021] Preferably, the group —SR 2 occupies the 2-, 3- or 4-position of the phenyl ring (most preferably, the 2-position).
[0022] Preferably, n is one or two.
[0023] The reaction generally proceeds in better yield when a group R 3 is not halogen in the 2-position of the phenyl ring.
[0024] Preferably, R 3 is halogen or trifluoromethyl. More preferably, (R 3 ) n is 4-CF 3 or 3,4-dichloro.
[0025] The compounds of formula (III) above used in Scheme Sc1 are known in the literature and their preparation has been expressly described in the prior art known to the skilled worker. Some references particularly pertinent to the preparation of this reagent may be found by the skilled worker in various sources of chemical literature, including Chemical Abstracts and information databases available to the public.
[0026] The preparation of compounds of formula (I) using compounds of formula (II) and (III) according to scheme Sc1 above may be preferably effected in a polar or apolar aprotic solvent. Examples of polar aproptic solvents include dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, a compound of formula (III); an ether compound, particularly dioxane and tetrahydrofuran; or an aromatic or aliphatic halogenated hydrocarbon, particularly chlorobenzenes. Examples of apolar aprotic solvents include aromatic or aliphatic hydrocarbons, particularly toluene and xylenes.
[0027] Generally, the reaction temperature used in Sc1 above is from 0° C. to the boiling point of the solvent, preferably, between 0° C. and 100° C. Generally the Sc1 reaction takes place in the presence of a strong base, which is most preferably selected from an alkoxide of an alkali or alkaline earth metal, notably sodium ethoxide, sodium methoxide, sodium or potassium t-butoxide; and a metal hydride (notably sodium hydride).
[0028] According to a preferred variant of the process of Sc1 of the present invention, the reaction is performed with continuous distillation of the alcohol R 1 —OH formed in the course of the reaction, at atmospheric pressure or under reduced pressure (preferably from 1 to 20% below atmospheric pressure). Optionally, the alcohol R 1 —OH formed may be removed by the use of a suitable molecular sieve, for example a 4 Angstrom molecular sieve.
[0029] Compounds of formula HSR 2 used in reaction scheme Sc2 are known in the literature and their preparations are expressly described in the prior art known to the skilled worker. The references particularly pertinent to the preparation of this reagent may be found by the skilled worker in various sources of classical chemistry including Chemical Abstracts and information databases available to the public. The salts or thiolates derived from the compound of formula (IV) may be prepared by means known to the skilled worker. These thiolates are preferably alkaline salts, particularly sodium or potassium thiolate.
[0030] The preparation of compounds of formula (II) according to scheme Sc2 from the acetophenone of formula (V) and a compound of formula (IV) is preferably performed in a solvent of the compound of formula (IV) which may be inert to the reaction conditions. Examples of other suitable solvents include sulfoxides such as dimethylsulfoxide; amides such as dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; ketones such as acetone and methyl isobutyl ketone; ether solvents, particularly dioxane and tetrahydrofuran; aromatic, aliphatic and cycloaliphatic hydrocarbons and halogenated or non-halogenated hydrocarbons, particularly chlorobenzene, dichloromethane and toluene. The presence of a small quantity of water is also acceptable in allowing the solubilization of the thiolate.
[0031] When the reaction according to scheme Sc2 takes place using a compound of formula (IV) in the form of the mercaptan and not in the form of a thiolate salt, the reaction is preferably effected in the presence of a base such as a hydroxide of an alkali metal or alkali earth metal (preferably, sodium or potassium), or a carbonate or hydride (such as sodium hydride). The reaction may also be performed using various forms of catalyst, particularly phase transfer catalysts such as a quaternary ammonium salt, for example, tetrabutylammonium bromide.
[0032] The two reactions which comprise together the reaction scheme Sc3 above are generally distinct but preferably they may occur in succession. That is, the compounds of formula (V) may be prepared from the compounds of formula (VII) via an intermediate of formula (VI) which may be isolated or used in situ in the course of the reaction.
[0033] The reaction conditions for the preparation of the compound of formula (V) from the compound of formula (VI) are known in the art and described in the literature, notably by J. G. Reid and J. M. Reny Runge in Tetrahedron Letters, Vol. 31(1990), pp. 1093-1096; G. A. Olah et al. Synthesis (1980), pp. 662-663; N. Kornblum et al, J. Org. Chem., Vol. 47 (1982), pp. 4534-38; S. Chandrasekaran et al, Synthetic Communications, Vol. 17 (1987), pp. 195-201.
[0034] The invention is thus also concerned with the preparation of compounds of formula (VI) from compounds of formula (VII) by the reaction of nitroethane in the presence of a base in a solvent which is selected from a compound of formula (VII), nitroethane, a solvent inert to the reaction conditions, and the base being selected from an hydroxide, a carbonate, a hydride, an alkoxide of an alkaline metal or an alkaline earth metal, and guanidine. An advantage of this aspect of the present invention is that relatively simple bases may be used in the reaction scheme Sc3.
[0035] Solvents suitable for use in preparing compounds (VI) from compounds (VII) include nitroethane itself (used in excess compared to the quantity normally used as a reactant); aromatic or aliphatic halogenated or non-halogenated hydrocarbons, particularly chlorobenzene; aromatic or aliphatic hydrocarbons, particularly toluene and xylenes; polar aproptic solvents such as dimethylsulfoxide, dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; acetonitrile; ether solvents, particularly dioxane and tetrahydrofuran. The presence of a small quantity of water is also acceptable in allowing the solubilization of the reaction mixture, while not reacting with the reactants themselves.
[0036] The reaction temperature for converting (VII) to (VI) is generally from 0° C. to 50° C. The reaction may also be carried out in an aqueous or non-aqueous medium. Among the bases suitable for the use in this process, one may cite hydroxides or carbonates of alkali metals or alkaline earth metals, preferably sodium or potassium, sodium carbonate, potassium carbonate or cesium carbonate; or tetramethylguanidine. These bases may be used alone or in mixture with others. The reaction may also be conveniently performed using various types of catalyst, particularly phase transfer catalysts such as a quaternary ammonium salt, for example, tetrabutylammonium bromide.
[0037] The following non-limiting examples illustrate the invention.
EXAMPLE 1
[0038] Preparation of 1-cyclopropyl-3-(2-methylthio-4-trifluoromethylphenyl)propane-1,3-dione (Reaction Scheme Sc1)
[0039] In a reaction vessel under an inert atmosphere, one adds 1.15 g of sodium methoxide and 22 ml of toluene. This is heated to 80° C. at a pressure of 400 mbars. A mixture of 3.3 ml of methyl cyclopropylcarboxylate and 3.8 g of 2-methylthio-4-trifluoromethylacetophenone in 6 ml of anhydrous toluene is added over 3 hours with constant distillation of methanol formed. The reaction is stirred for one hour at 80° C. The reaction is then cooled and the diketone precipitated in a mixture of 80 ml of ice water containing 0.75 ml of concentrated sulfuric acid. The organic phase is retained, washed with water and the toluene removed under reduced pressure to give 3.67 g of 1-cyclopropyl-3-(2-methylthio-4-trifluoromethylphenyl)propane-1,3dione in the form of an orange powder, m.p. 64° C. Yield=75%.
[0040] By proceeding in a similar manner, but heating at a temperature of 70° C. and a pressure of 230 mbars, 3-(4-chloro-2-methylthiophenyl)-1-cyclopropylpropan-1,3-dione cyclopropylpropan-1,3-dione was prepared in 98% yield (purity greater than 80%). This compound was also similarly prepared wherein the reaction took place at a temperature of 70° for 6.5 hours and in the presence of 4 Angstrom molecular sieves in place of constant distillation of the methanol formed.
EXAMPLE 2
[0041] Preparation of 1-cyclopropyl-3-[3,4-dichloro-2-(methylthio)phenyl]propane-1,3-dione (Reaction Scheme Sc1)
[0042] Sodium hydride (0.178 g, 60% oil dispersion, 0.0045 M) is suspended in tetrahydrofuran (1.8 ml), stirred and heated at reflux while a solution of a mixture of methyl cyclopropanecarboxylate (0.42 g, 0.0042M) and 3,4-dichloro-2-(methylthio)acetophenone (0.5 g, 0.0021M) in tetrahydrofuran (3 ml) is added. The mixture is stirred and heated at reflux for 3.5 hours, then cooled and poured onto saturated aqueous sodium bicarbonate. The mixture is then extracted with ether, washed with brine, dried over magnesium sulfate, filtered and evaporated to give a gum (which is purified by dry column flash chromatography eluted with ethyl acetate in cyclohexane to give 3-cyclopropyl-1-[3,4-dichloro-2-(methylthio)phenyl]propane-1,3-dione (0.35 g, 55%) as a yellow oil.
EXAMPLE 3
[0043] Preparation of 2-methylthio-4-trifluoromethylacetophenone (Reaction Scheme Sc2)
[0044] To 0.15 g of 2-nitro-4-trifluoromethylacetophenone diluted in 0.5 ml of acetone is added 0.256 g of an aqueous solution of 21% wt/wt sodium thiomethoxide and the mixture is stirred for five hours at 20° C. The aqueous phase is separated, then removed, then 2 ml of water are added and the acetone removed under reduced pressure. The mixture is then treated with dichloromethane and the aqueous phase removed. The organic phase is washed with fresh water, then the solvent is evaporated under reduced pressure to obtain 0.085 g of 2-methylthio-4-trifluoromethylacetophenone with a melting point of 71° C.
[0045] By proceeding in a similar manner, 3,4-dichloro-2-(methylthio)acetophenone may be prepared, 1 H NMR (CDCl 3 ) 2.4 (s,3H), 2.6 (s,3H), 7.15 (d,1H), 7.5 (d,1H).
EXAMPLE 4
[0046] Preparation of 1-(2-nitro-4-trifluoromethylphenyl)-1-nitroethane (Reaction Scheme Sc3)
[0047] 0.87 g of sodium carbonate in 5 ml of anhydrous toluene are placed in a 30 ml reaction vessel, and 0.11 g of benzyltriethylammonium chloride and 1.13 g of 4-chloro-3-nitrobenzotrifluoride and 0.38 g of nitroethane are added at the same time. The mixture is stirred for 16 hours at 20° C., 10 ml of water are added and the aqueous phase is separated, then acidified by a 4N solution of sulfuric acid. It is then extracted with 5 ml of methyl t-butyl ether. After removing the organic solvent, 0.18 g of a mixture is obtained which is separated by column chromatography using reverse phase silica eluting with a mixture of water and acetonitrile to obtain 0.12 g of the title compound, m.p. 48° C. | A process for preparing compounds of the formula:
wherein R 2 is lower alkyl; or phenyl optionally substituted by from one to five groups, the same or different, which are lower alkyl, lower haloalkyl, halogen or —SR 4 ; R 3 is halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, —S-alkyl, cycloalkyl having from 3 to 7 carbon atoms in the ring, alkenyl or alkynyl having from 3 to 7 carbon atoms, or —(CR 5 R 6 )—SR 2 wherein q is one or two; R 4 is lower alkyl; R 5 and R 6 independently represent hydrogen, lower alkyl or lower haloalkyl; and n is zero or an integer from one to three; intermediate compounds of the formula:
and processes for preparing them. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a substantially pure exopolysaccharide adhosin isolated from a particular strain of Staphylococcus epidermidis , to a general method capable of isolating this compound in substantially pure form, and to uses of said purified adhesin product as a vaccine for the production of antibodies effective against the binding of homologous bacterial cells to polymeric materials, and as a probe for the development of polymeric materials useful as catheters and medical prostheses.
[0003] 2. Description of the Background Art
[0004] Both Staphylococcus aureus (coagulase-positive) and Staphylococcus epidermidis (coagulase-negative) have a characteristic propensity for invading skin and adjacent tissues at the site of prosthetic medical devices, including intravascular catheters, cerebrospinal fluid shunts, hemodialysis shunts, vascular grafts, and extended-wear contact lenses. Within 48 to 72 hours, relatively large numbers of staphylococci are demonstrable at the site of insertion of these foreign bodies. Archer, G. L., “ Staphylococcus epidermidis : The Organism, Its. Diseases, and Treatment,” in Remington, J. S., et al., eds., Current Clinical Topics in Infectious Diseases , McGraw-Hill, New York, 1986, pp. 25-46; Youmans, G. P., et al., The Biologic and Clinical Basis of Infectious Diseases , Saunders, Philadelphia, 1985, pp. 618-625, 738-9. It has been demonstrated that S. epidermidis cells attach and proliferate on the inner or outer surfaces of catheters, irrespective of their composition (polyethylene, polyvinylchloride, polyvinylfluoride, or polyester based materials).
[0005] Although the virulence of coagulase-negative staphylococci clearly is enhanced in the presence of a foreign body, the microbial factor(s) that permit these normal skin commensals to become nosocomial pathogens have not been well characterized. As adherence is believed to be the critical first step in the pathogenesis of coagulase-negative staphylococcal foreign-body infections, attention has focused on surface properties of these organisms that might mediate adherence to, and colonization of, polymeric prosthetic materials.
[0006] The most promising candidate for the source of a specific staphylococcal adhesin is an extracellular material often referred to as “slime.” It has been hypothesized that the slime substance may protect the S. epidermidis cells against antibiotics, as well as against natural host defense mechanisms. Youmans et al., supra; Peters, G., et al., Journal of Infectious Diseases 146:479-82 (1982).
[0007] It has been known since 1972 that coagulase-negative bacteria isolated from cerebrospinal fluid shunt infections elaborate a mucoid material that stains with alcian blue and is presumably a polysaccharide. Bayston, R., et al., Developmental and Medical Child Neurology 14 ( Supp. 27):25-8 (1972). The extracellular polysaccharide substance of slime-producing bacteria is a loose amorphous material composed of a range of low and high molecular weight polymers composed, in gonoral, of neutral monosaccharides such as D-glucose, D-galactose, D-mannose, L-fucose, and L-rhamnose, and also contain amino sugars, uronic acid, and polyols such as ribitol and glycerol. Gristina, A. G., Science 237:1588-95 (1987). Glucose, galactose, phenylalanine, mannose, hexosamine, phosphorous, glycine and alanine have been found as components of the slime produced by S. epidermidis strains in clinical specimens unrelated to biomaterial infections. Ichiman, J., et al., J. Appl. Bact. 51:229 (1981). Isolates of such bacteria from sites of infections are more likely to produce slime than are random isolates from skin. Ishak, M. A., et al., Journal of Clinical Microbiology 22:1025-9 (1985). Moreover, slime-producing strains adhere well to a variety of polymeric materials. Christensen, G. D., et al., Infect. Immun. 37:318-26 (1982).
[0008] Coagulase-positive staphylococci ( S. aureus ) are reported to produce multiple cell surface proteins which can be released from such cells by thermal extraction and which can be shown to bind to influenza virus-infected canine kidney cells. It was considered that S. aureus produces multiple cell surface protein adhesins. Sanford, B. A., et al., Infect. Immun. 52:671-5 (1986); Proc. Soc. Exp. Biol. Med. 181:104-11 (1986).
[0009] Identification of other microbial adhesins has been reported. Pier (U.S. Pat. No. 4,285,936, Aug. 25, 1981; U.S. Pat. No. 4,528,458, Mar. 25, 1986) discloses a method for partial purification of a polysaccharide antigen from Pseudomonas aeruginosa slime. Escherichia coli fimbrial protein adhesins have been identified and partially purified by several investigators (Orskov, I., et al., Infect. Immun. 47:191-200 (1985); Chanter, H., J. Gen. Microbiol. 1:225-243 (1983); Ferreiros, C. M., et al., Rev. espanol, de fisiolog, 3:45-50 (1983); and Moch, T., et al., Proc. Natl. Acad. Sci. 84:3462-6 (1987)).
[0010] Lectin-like glycoprotein adhesins have been identified in the Bacteroides fragilis group, and a 70 kDa adhesin has been purified by affinity chromatography (Rogemond, V., et al., Infect. Immun. 53:99-102 (1986)). Monoclonal antibody affinity chromatography was used to purify a 165 kDa surface protein of Mycoplasma pneumoniae which mediates attachment of such bacteria to target cells (Leigt, D. K., et al., J. Bacteriol. 157:678-80 (1984)), and to isolate a 150 kDa adhesin protein from Streptococcus sanguis FW213 (Elder, B. L., et al., Infect. Immun. 54:421-7 (1986)). A uroepithelial cell adhesin protein of 17.5 kDa was partially purified from fimbrii of Proteus mirabilis , a frequent cause of urinary tract infection (Wray, S. K., et al., Infect. Immun. 54:43-9 (1986)).
[0011] Ludwicka (Ludwicka, A., et al., Zbl. Bakt. Hyg. A 258:256-67 (1984)) fractionated by ion-exchange chromatography a phenol-saline extract of slime from S. epidermidis and obtained four crude fractions. Both the phenol-saline extract and two of the four crude fractions inhibited the attachment of bacterial cells to polymeric material. On the basis of the presence of monosaccharides in the fractions, the reaction of the fractions with lectins, and the complete inhibition of the production of the four fractions by protreatment of the bacteria by tunicamycin (inhibitor of glycoprotein synthesis), the authors concluded that the extracellular slime substance is a complex of glycoconjugate (i.e., glycoprotein) character.
[0012] Hogt (Hogt, A. H., et al., Infect, Immun 51:294 (1986) have also observed that crude extracellular products from the slime of homologous strains of S. epidermidis inhibit the adherence of homologous bacterial cells to polymeric materials used as catheters and prostheses. No information was provided in this report as to the chemical nature of the extracellular products.
[0013] Bacterial cells and materials derived from the surface of such cells have been used as vaccines to produce antibodies directed against homologous bacteria. Frank (Frank, R., et al., French Patent Application 85-07315, published Nov. 21, 1986) discloses a covalent conjugate between a capsular protein adhesin (MW-74 kDa) from Streptococcus mutans and a polysaccharide from the same (serotypically) organism, and the use of said conjugate as an anti-caries vaccine. Pier (Pier, G. B., et al., U.S. patents, supra) disclose a vaccine comprising a high molecular weight mucoid exopolysaccharide from Pseudomonas aeruginosa strain 2192 slime which induces in recipient animals an immunity to said organism. Sadowski (Sadowski, P., U.S. Pat. No. 4,443,549, Apr. 17, 1984; U.S. Pat. No. 4,652,498, Mar. 24, 1984; and EP 82401506.1, published Apr. 27, 1983) discloses monoclonal antibodies specific for surface adhesions of Escherichia coli and Pseudomonas aeruginosa which may be used for the therapeutic treatment of diseases induced by adhesin-bearing homologous bacteria in humans and animals. Nagy (Nagy, L. K., et al., Dev. Biol. Stand. 53:189-97 (1983)) discloses multi-adhesin vaccines for the protection of the neonatal piglet against Escherichia coli infections.
SUMMARY OF THE INVENTION
[0014] The inventors considered-that, if a substantially pure capsular polysaccharide adhesin antigen could be isolated from the slime of strains of pathogenic S. epidermidis , a vaccine could be prepared from such an antigen that could be used to raise polyclonal antibodies in vivo in a human or animal, or monoclonal antibodies in hybridoma cells. Reasoning that adhesin-mediated colonization is required for the onset of pathogenesis, the inventors conceived that the polyclonal or monoclonal antibodies produced against the adhesin of the invention, by preventing the adherence of adhesin-bearing pathogenic bacteria to the recipient's tissue cells or polymeric medical prostheses or catheters, represent a new means for preventing or treating diseases and infections due to S. epidermidis.
[0015] Further, the substantially pure capsular polysaccharide adhesin of the invention is useful as a probe to test new polymeric materials for medical devices.
[0016] Therefore, in a preferred embodiment, the present invention provides a substantially pure polysaccharide from extracts of S. epidermidis RP-62 strain (an isolate from a patient with catheter-related bacteremia that produces copious quantities of slime) that mediates adherence to polymeric materials and also appears to be the capsule for this organism. In another preferred embodiment, the present invention provides a method for producing a substantially pure polysaccharide adhesin from extracts of S. epidermidis strain RP-62.
[0017] In another preferred embodiment, the substantially pure polysaccharide adhesin of the invention is used as a vaccine to raise in animals antibodies against said adhesin that inhibit the attachment of adhesin-bearing bacteria to polymeric materials.
[0018] The substantially pure polysaccharide of the invention may also be used as an antigen to produce monoclonal antibodies in hybridoma cells. Such monoclonal antibodies can be administered for prophylaxis or therapeutic purposes to humans or animals in order to prevent or reduce infections by coagulase-negative staphylococci.
[0019] In yet another preferred embodiment, the substantially pure polysaccharide adhosin of the invention is used to screen polymeric materials for resistance to attachment by bacteria.
DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1A demonstrates the immunodiffusion pattern of crude extract (A), purified teichoic acid (B) and purified adhesin (C) against antisera raised to whole cells of S. epidermidis strain RP-62A.
[0021] FIG. 1B demonstrates immunoelectrophoresis of S. epidermidis antigens. Troughs were filled with antisera to strain RP-62A whole cells. A, crude extract; B, teichoic acid, C, purified adhesin; D, mixture of teichoic acid and purified adhesin.
[0022] FIG. 2 demonstrates the electrophoresis pattern of restriction enzyme digests of bacterial DNA from strains RP-62A (left-hand pattern of each pair) and RP-62NA (right-hand pattern of each pair). Lanes 1 and 12, HindIII digest of phage lambda DNA; Lanes 2 and 3, undigested DNA from RP-62A and RP-62NA; Lanes 4 and 5, EcoRI digest; Lanes 6 and 7, SauIIIA digest; Lanes 8 and 9, RsaI digest; Lanes 10 and 11, ClaI digest.
[0023] FIG. 3 demonstrates the inhibition of binding of S. epidermidis strain RP-62 cells to silastic catheter tubing after incubation of the tubing in the indicated concentrations of the various bacterial antigens prior to dipping in bacterial suspension (10 6 cells per ml). Significant (p<0.05, t test) inhibition was seen only with crude extracts from strain RP-62A at concentrations of 0.12-0.50 mg/ml and with purified adhesin at concentrations of 0.06-0.50 mg/ml.
[0024] FIG. 4 demonstrates the inhibition of adherence of various strains of coagulase-negative staphylococci to silastic catheter tubing by different antigen preparations (0.1 mg/ml concentration) from S. epidermidis strain RP-62A. An asterisk indicates significant (p<0.05, t test) inhibition.
[0025] FIG. 5 shows transmission electron microscopy of various strains of coagulase-negative staphylococci following incubation with normal rabbit serum, rabbit serum raised to either whole RP-62A cells or rat antiserum raised to purified adhesin and ferritin-labeled goat antibody to rabbit or rat IgG. A) is strain RP-62 stained with normal rabbit serum (×75,000); B) strain RP-62 stained with rabbit antisera to whole cells (×62,000); C) strain RP-62A stained with rat antiserum to purified adhesin (×48,000); D) strain RP-14 stained with rabbit antiserum to strain RP-62A whole cells (×35,000); E) strain RP-14 stained with rat antiserum to purified adhesin (×65,000); and F) strain RP-62NA stained with rabbit antiserum to strain RP-62 whole cells (×50,000). Bar is each graph represents 200 nm.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0026] The invention comprises the isolation in substantially pure form of an exopolysaccharide adhesin antigen from coagulase-negative staphlococci bacteria, use of said adhosin as a vaccine to raise polyclonal and monoclonal antibodies against said adhesin, use of said adhesin to prevent adherence of said bacteria to polymeric materials, and use of said adhesin as a probe to test for polymeric materials to which said bacteria will not adhere.
Materials and Methods
[0027] Bacterial strains. The following strains were provided by Dr. Gordon Christensen, Memphis, Tenn., and have been described previously (Christensen, G. D., et al:, Ann. Intern. Med. 96:1-10 (1982); Infect. Immun. 37:318-26 (1982)): (a) Staphylococcus epidermidis strains RP-62A (slime-producing, highly adherent, from a patient with catheter-related sepsis), RP-62NA (a variant of RP-62A which is less adherent and produces no slime by macroscopic examination), and RP-12; (b) S. hominis strain RP-14; and (c) S. haemolyticus strain SP-2.
[0028] DNA analysis of S. epidermidis strains. Bacterial cells are lysed by the enzyme lysostaphin. The lysate is digested with RNase A (Sigma) and RNase T 1 (Sigma) to degrade bacterial RNA, dissolved in a detergent solution such as sodium dodecyl sulfate, and the proteins digested with proteolytic enzymes such as pronase and proteinase K (Boehringer-Mannheim). DNA is extracted from the digested cells by multiple extractions into phenol, and precipitated from the phenolic solution by the addition of ethanol at −20° C. at a final concentration of 60-70% alcohol. The precipitated DNA is collected by centrifugation, washed with 70% aqueous ethanol, dried in vacuo, then digested with restriction endonucleases (EcoRI, SauIIA, RsaI and ClaI (New England Biolabs, Beverly, Mass.)). The restriction digest is electrophoresed on a 1% agarose gel; restriction fragments are visualized by ethidium bromide staining.
[0029] Characterization of crude extracts, purified adhesin, and teichoic acid. Samples are hydrolyzed at 100° C. in 6 N HCl from 4 to 48 hours prior to analysis. Reducing carbohydrate content is detected and estimated by the phenol-sulfuric acid reaction (Dubois, M., et al., Anal. Chem. 28:350-6 (1956)), proteins by a positive reaction in the Bradford dye test (Bradford, M., Anal. Biochem. 72:248-54 (1976)), nucleic acids by absorbance at 254 nm against a DNA standard; phosphate by a positive reaction in the method of Chen (Chen, P. S., et al., Anal. Chem. 28:1256 (1956)); lipids by gas-liquid chromatography against fatty acid methyl esters as standards (Lee, J. C., et al., Infect, Immun ., in press (1987)); and amino acids and amino sugars by an amino acid analyzer (Model 121 MB, Beckman Instruments, Inc., Fullerton, Calif.) using a lithium citrate system. Monosaccharides are individually identified by gas liquid chromatography of the trimothylsilyl derivatized monosaccharide methyl esters (Chambers, R. C., et al., Biochem. J. 125:1009-18 (1971)) in a Hewlett-Packard 500 instrument using simultaneous injections of identical samples onto 25-foot capillary columns of RSL-310 (Alltech Associates, Deerfield, Ill.) and SP-2330 (Supelco, Delfont, Pa.). The injector and initial oven temperatures are 140° C., which is held for 3 minutes; a 5° C./min rise to 150° C. is then performed, followed by a 30° C./min rise to 210° C., which is then held for an additional 9 minutes. The flame ionization detector is maintained at 250° C. Samples are identified by retention times compared to standards. Serologic analyses can be performed by double diffusion and immunoelectrophoresis methods (Ouchterlony, O., et al., In Immunochemistry , Vol. I, Blackwell, Oxford, 1978, Chapter 39).
[0030] Adherence assays. The adherence of coagulase-negative staphylococcal strains to polymeric (i.e., silastic) catheter tubing (French 3, Jesco International Inc., San Antonio, Tex.) is determined as follows. An overnight culture of bacteria in tryptic soy broth is diluted to contain 10 6 colony-forming units (cfu)/ml. A 3 cm length of tubing fitted with a 21 gauge needle and sterilized with ethylene oxide gas is then dipped into the culture for 15 min at room temperature. The tubing is washed in saline by vigorously agitating the tubing, as-well as repeatedly drawing saline through the tubing with a 3 ml syringe fitted to the needle. Washing is continued until wash fluids contain less than 1 cfu/100 μl. This occurs in about 3 separate washes. After discarding a 1 cm section of the tubing, bacteria adhering to the remaining 2 cm is quantified by rolling the tubing over the surface of a tryptic soy agar plate in several directions, followed by overnight incubation at 37° C. The cfu/catheter are counted the next day. The efficiency of the transfer of bacteria from plastic tubing to the agar plate can be estimated by radio-labelling the organisms by including one μCi of [ 14 C]-sodium acetate in the preliminary overnight culture medium. The number of cfu adhering to the tubing before and after rolling on the agar plate is determined by liquid scintillation counting and correlated with bacterial counts obtained by plating identical samples.
[0031] Direct adherence of the purified adhesin to catheter tubing is determined by incubating a 0.5 cm length of tubing with a 0.5 mg/ml solution of adhesin in 40 mM phosphate buffer, pH 7.2, for two hours at 37° C., washing the tubing in phosphate-buffered saline 0.05% Tween 20, and performing a standard ELISA or RIA assay on the sensitized piece of tubing (Bryan, L. E. et al. J. Clin. Microbiol. 12:276-82 (1983)). By the term “ELISA” is intended an enzyme-linked immunoassay. By the term “RIA” is intended a radioimmunoassay.
[0032] Inhibition of adherence of bacteria to catheter tubing by crude extracts and purified adhesin is performed by incubating the catheter tubing in solutions of these materials for two hours at 37° C., washing the coated tubing in sterile saline, placing it in bacterial cultures (10 6 cfu/ml), and completing the adherence assay as described supra. When poorly adherents strains of S. epidermidis (e.g., strains CL and SP-2) are used in inhibition assays, the input inoculum should be increased to 10 7 cfu/ml, which increases the number of adhering bacteria as much as 5-fold. Inhibition of adherence is calculated as follows:
% inhibition = 100 - ( 100 ) ( no . of cfu adhering following adhesin treatment ) no . of cfu adhering without treatment
[0033] Inhibition of adherence by rabbit antibody to purified adhesin (see infra) is performed by incubating the bacteria with the indicated concentration of normal and immune serum for 2 hr at 4° C., washing the bacteria three times in tryptic soy broth, resuspending to 10 6 cfu/ml tryptic soy broth, and continuing the adherence assay as described supra. Inhibition of adherence is calculated as follows;
% inhibition = 100 - ( 100 ) ( no . of cfu adhering with immune serum ) no . of cfu adhering with normal serum
Inhibition data should be statistically analyzed for significance by Students t test.
[0035] Transmission electron microscopy. Transmission electron microscopy of S. epidermidis strains is performed as previously described (Pier, G B, J. Clin, Microbiol ., 24:189-96 (1986). For visualization of extracellular structures, bacterial cells are incubated with either a 1:2 dilution of rabbit antibody to whole cells or undiluted rat antibody raised to purified adhesin (see infra), or with normal serum controls. After three saline washes, bacteria are incubated with ferritin-conjugated antibody to either rabbit or rat IgG.
Preparation of Crude Bacterial Extracts
[0036] Crude extracts are prepared by incubation of cell suspensions with the enzymes lysostaphin and lysozyme. Insoluble material is removed by sequential centrifugation and filtration through a micropore filter (0.45 μm), the filtrate is dialyzed against water, and then lyophilized (freeze-dried in vacuo at low temperature).
Isolation of Adhesin
[0037] Eighteen-hour cultures of S. epidermidis strains are subjected to thermal shock (95-100° C.) at about pH 5.0. The mixture is brought to neutral pH (preferably 6.8) and room temperature, then clarified by sequential centrifugation and passage through a micropore filter. The clear extract is concentrated, neutralized, and the conductivity reduced (preferably to below 10 millisiemans) by repeated ultrafiltration through a 10,000 dalton cut-off membrane and washing with water. The retained concentrate; which contains macromolecules of mass greater than 10,000 daltons, is then fractionated by ion-exchange chromatography at neutral pH (preferably about 7.0); a preferred system is DEAE Zota-Prop 250 cartridge (LKB Instruments, Rockville, Md.). Adhesin is eluted by 0.2 M NaCl at neutral pH (preferably about 7.0), as determined by an adherence assay (infra). Adhosin-containing fractions are then subjected to affinity chromatography on a Concanavalin A-Sepharose column (LKB Instruments) to remove a mannan containment that is contributed by the original bacterial tryptic soy broth growth medium and that co-purifies with the bacterial polysaccharide adhesin. The unbound fraction is repeatedly dialyzed against water to remove salts and small molecules, then lyophilized. After reconstitution of the adhesin-containing powder in calcium-containing buffer at an acidic pH (preferably 5.0), the solution is incubated-sequentially with DNase (to remove contaminating DNA), RNase (to remove contaminating RNA), and pronase (to remove contaminating protein). The purified adhesin solution is then fractionated on a molecular sieve column in an ammonium carbonate buffer at neutral pH (preferably about 7.0). Elution is monitored by measuring A 206 nm; adhesin fractions eluting with a Kav of 0.0-0.2 are collected and pooled. This fraction contains substantially pure capsular polysaccharide adhesin.
Isolation of Teichoic Acid
[0038] Teichoic acid, another component of the slime of S. epidermidis , is recovered from the DEAE Zeta Prep 250 ion-exchange column used in fractionating adhesin, in the fraction eluting with a higher concentration (0.6 M) of NaCl than eluted adhesin (0.2 M). This material is then digested with nuclease enzymes as described above, protein is denatured by heating at 100° C. at an acid pH (preferably about 4.0), then chromatographed on a molecular sieve column (Sepharose CL-4B) in ammonium carbonate buffer at neutral pH. Serologically-active fractions that elute with a Kav of 0.33-0.57 are pooled, dialyzed, and lyophilized.
Adhesin Vaccine
[0039] Polyclonal antibodies. Polyclonal antibodies to epitopic regions of the purified adhesin may be raised by a plurality of injections of said adhesin antigen into a host animal. In a preferred embodiment, antibodies are produced in rabbits by subcutaneous administration of 0.5 mg of antigen in complete Freund's adjuvant, followed 7 days later by intravenous injections three times weekly with 0.5 mg of antigen in saline. The thrice weekly injections are performed for 3 consecutive weeks, and blood is then drawn 5 days after the last injection. Normal (pre-immune) serum is obtained in all cases.
[0040] Polyclonal antibodies to purified adhesin may also be raised in rats given three 50 μg injections five days apart, with blood drawn 5 days after the final injection.
[0041] Polyclonal antibodies to whole cells of S. epidermidis strains are raised in rabbits as previously described (Pier, G. B., et al., J. Infect. Dis. 147:494-503 (1983)).
[0042] Monoclonal antibodies. Monoclonal antibodies are immunoglobulins directed to specific epitopic regions on an antigen. Monoclonal antibodies against the substantially pure polysaccharide adhesin of the invention can be produced by the hybridoma technology of Köhler and Milstein (Köhler, G., Science 233:1281-6 (1986); Milstein, C., Science 231:1261-8 (1986)).
[0043] Briefly, the purified adhesin is used to once-prime or hyperimmunize animal donors of antibody-producing somatic B cells (e.g., lymphocytes). Lymph nodes and spleens of immunized animals are convenient sources. Although mouse and rat lymphocytes give a higher percentage of stable fusions with mouse myoloma lines, the use of rabbit, human and frog cells is also possible. In a preferred embodiment, hyperimmunized mouse spleen cells are used to make the fused cell hybrids.
[0044] Specialized myeloma cell lines are available for use in hybridoma-producing fusion procedures (Köhler, G., et al., Eur. J. Immunol. 6:511-9 (1976); Schulman, M., et al., Nature 276:269-70 (1978)). Methods for generating hybrids of anti-adhesin antibody producing spleen or lymph node cells and myeloma cells usually comprise mixing somatic cells with myeloma cells in a 10:1 proportion (though the proportion can vary from 20:1 to 1:1, respectively) in the presence of an agent(s) that promotes fusion. It is preferred that the same species of animal is the source of both the somatic and myeloma cells. Fusion methods have been described by Köhler and Milstein (Köhler, G., et al., Nature 256:495-7 (1975); Eur. J. Immunol. 6:511-19 (1976)), in which Sendai virus is the fusion agent, and by Gefter (Gefter, S., et al., Somatic Cell Genet. 2:231-6 (1977)), in which polyethylene glycol, is the fusion agent. In a preferred embodiment, the method of Gefter et al, is modified to include dimethylsulfoxide as an additional fusion agent.
[0045] Isolation of clones and antibody detection are carried out by standard techniques. Fusion cell hybrids are selected by culturing the cells on media that support growth of hybridomas but prevent the growth of unfused myeloma cells. (The unfused somatic cells do not maintain viability in in vitro cultures and hence do not pose a problem.) In a preferred embodiment, myeloma cells lacking hypoxanthine phosphoribosyltransferase (HPRT − ) are used. These cells are selected against in a hypoxanthine/aminopterin/thymidine (HAT) medium in which hybridoma cells survive due to the HPRT + genotype of the spleen cells, but unfused myeloma cells do not. Myeloma cells with different genetic deficiencies that can be selected against in media supporting the growth of genotypically competent hybrids are also possible.
[0046] The detection of anti-adhesin antibody-producing hybrids can be achieved by any one of several standard assays, including ELISA and RIA techniques that have been described in the literature (Kennet, R., et al., eds., Monoclonal Antibodies, Hybridomas: A New Dimension in Biological Analysis , Plenum, New York, 1980, pp. 376-84; Bryan, L. E., et al., J. Clin. Microbiol. 18:276-82 (1983)).
[0047] Once the desired fused cell hybrids have been selected and cloned into individual anti-adhesin antibody-producing cell lines, each cell line may be propagated in either of two standard ways: injection of the hybridoma into a histocompatible animal and recovery of the monoclonal antibodies in high concentration from the body fluids of the animal (e.g., serum or ascites fluid), or propagation in vitro in tissue culture, wherein the antibody in high concentration is recoverable from the culture medium.
Therapeutic Use of Anti-Adhesin Antibody
[0048] Monoclonal antibodies specific to epitopic regions on the colonization-mediating adhesin, as well as the non-specific polyclonal antibodies described above, can be used clinically for the prevention or treatment of diseases caused by pathogenic bacteria producing and bearing such adhesins. For example, polyclonal and monoclonal antibodies specific for the capsular polysaccharide adhesin of the present invention can be administered to any animal species for the prevention and/or treatment of infections due to pathogenic Staphylococcus epidermidis , e.g., those that colonize polymeric implanted medical devices and catheters. By the term “administer” ls intended, for the purpose of this invention, any method of treating an animal with a substance, such as orally, intranasally, or parenterally (intravenously, intramuscularly, or subcutaneously). By the term “animal” is intended any living creature that is subject to staphlococcal infection, including humans, farm animals, domestic animals, or zoological garden animals. The mode of administration of these antibodies is preferably parenteral. The antibodies may be suspended or dissolved in any of several suitable liquid vehicles and delivered to the patient by any one of several parenteral means. In some instances, and particularly where human treatment is involved, purification may be desired or required pursuant to government regulations. Provided the antibody is present in a pharmacologically effective dosage, other liquid-compositions are also pharmaceutically effective, including mixtures of antibodies and skim milk and/or antibodies in aqueous salt solutions of serum albumin. In humans, the antibody may be preferably administered in parenteral form, though any compatible carrier may be used. Of course, the dosage administered will be dependent upon the age, health, and weight of the recipient, kind of concurrent treatment, if any, frequency of treatment, and the nature of the effect desired. Preferably, the dosage should result in a concentration of at least about one μg of specific antibody per milliliter of blood.
Diagnostic Use of Anti-Adhesin Antibody
[0049] The adhesin-specific antibodies are also useful for medical and research purposes. For example, the antibodies can be used diagnostically to detect with great accuracy the presence of Staphylococcus epidermidis strains among a general population of bacteria. Other applications include the use of adhesin-specific monoclonal antibodies in affinity chromatography systems for the purification of Staphylococcus epidermidis polysaccharide adhesin or in assay systems for the quantitative estimation of such adhesin.
Use of Purified Adhesin as a Probe
[0050] The purified capsular polysaccharide adhesin of the invention can be used in conjunction with the adherence assays described supra as a probe in designing new polymeric materials to which coagulase-negative staphlococci bacteria will not adhere. Such new polymers would be extremely beneficial to patients in whom catheters and other medical prosthetic devices and shunts are employed and who now suffer from the nosocomial effects of such bacteria.
[0051] Having now described the invention in general term, the following specific examples will serve to illustrate more fully the nature of the present invention, without acting as a limitation upon its scope.
EXAMPLE I
Isolation of Strain PR-62A Adhesin
[0052] Staphylococcus epidermidis RP-62A was grown in 15 l of tryptic soy broth in an LSL Biolaffite fermentor with aeration (0.5 l/min), stirring (200 rpm), and maintenance of the pH at 7.2 by titration with 50% acetic acid and 0.5 NaOH. After 18 hr growth at 37° C., the pH was adjusted to 5.0 with 50% acetic acid and the temperature of the culture raised to 95-100° C. for 1 h. After cooling, the pH was adjusted to 6.8, the culture removed from the fermentor, and bacterial cells removed by centrifugation. The supernatant was passed through a 0.5μ filter and then concentrated to about 400: ml on a Pellicon ultrafiltration system (Millipore Corp., Bedford, Mass.) using membranes with a molecular weight cut-off of 10,000 dalton. The supernatant was then diluted with 2 l deionized water and reconcentrated to 400 ml. This step was repeated until the pH of the solution was 6.8 and the conductivity was around 4.8 millisiemens. A portion (¼) of the solution was then applied to a DEAE Zeta-prep 250 cartridge (LKB Instruments, Rockville, Md.) previously equilibrated in 0.05 M Tris buffer, pH 6.8. After loading, the cartridge was washed with 600 ml of 0.05 M Tris buffer and the eluate discarded. The adhesin was then recovered in the fraction eluting with 0.2 M NaCl in 0.05 M Tris buffer, after preliminary assays determined that this molarity of NaCl eluted material which inhibited the adherence of strain RP-62A to silastic catheter tubing (see infra). The 0.2 M NaCl eluate was pooled, dialyzed against numerous changes of deionized water, and lyophilized. The material was then resuspended in 0.1 M sodium acetate, pH 6.0, at 25 mg/ml. and chromatographed on an affinity column of Concanavalin A-Sepharose (LKB Instruments) to remove a mannan component from the tryptic soy broth medium which co-purified with the adhesin. The unbound adhesin-containing fraction was recovered, dialyzed against numerous changes of deionized water, and lyophilized. The material was then dissolved (25 mg/ml) in 0.1 M NaOH, 1.0 mM MgCl 2 , and 1.0 mM CaCl 2 , pH 5.0, and digested with DNase (1 mg/ml) and RNase (3 mg/ml) for 16 hr at 37° C., after which time pronase (1.0 mg/ml) was added and an additional 4 hr digestion at 37° C. carried out. This solution was then applied to a 2.6×90 cm column of Sepharose CL-4B (Pharmacia Fine Chemicals, Piscataway, N.J.) equilibrated in 0.2 M ammonium carbonate, pH 6.8. Fractions (8 ml) were collected, and pools were made from fractions absorbing UV light at 206 nm that eluted with a K av of 0.0-0.2 (peak=0.02).
EXAMPLE II
Isolation of Strain PR-62A Teichoic Acid
[0053] Teichoic acid was recovered from the Zeta-prep 250 cartridge in the fraction eluting with 0.6 M NaCl. This material was digested with nuclease enzymes as described above, heated at 100° C., pH 4.0, for 1 h, then chromatographed on a 2.6×90 cm column of Sepharose-CL-4B in 0.2 M ammonium carbonate. Serologically active fractions eluting with a Kav of 0.33-0.57 (peak-0.48) were pooled, dialyzed against deionized water, and lyophilized.
EXAMPLE III
Chemical Components of Crude Extract Teichoic Acid Fraction of Slime, and Purified Adhesin
[0054] Utilizing the methodology described above, a fraction isolated from the culture supernatant of S. epidermidis strain RP-62A that appeared to have the properties of an adhesin was analyzed. The chemical components of the crude extract, the isolated teichoic acid, and the purified adhesin are shown in Table 1.
TABLE 1 Chemical Components Identified in Crude Extract, Teichoic Acid, and Purified Adhesin of Staphylococcus epidermidis strain RP-62A Preparation Crude Teichoic Purified Component Extract Acid Adhesin Reducing sugar 12* 20 54 Amino sugars 5 25 20 Uronic acids 2 <1** 10 Phosphate 11 14 <0.02** Protein 3 2 1 Nucleic acids 7 1 1 Lipids <0.01** <0.01** <0.01** Unidentified 60 38 14 Monosaccharides (percent of total sugars) Glycerol 20 <0.1** Glucose 20 <0.1** Galactose <0.1** 22 Glucosamine 10 15 Galactosamine <0.1** 5 *Percent of total weight. **Lower limit of detection.
[0055] Crude extract contained numerous components, of which carbohydrate and phosphate were predominant. The teichoic acid fraction of slime was composed principally of phosphate, glycerol, glucose, and glucosamine. The purified adhesin was principally composed of carbohydrate with only low to non-detectable levels of protein, nucleic acids, and phosphate. No lipids were detected in the purified adhesin. The principal monosaccharides identified were galactose, glucosamine and galactosamine, glucose was absent. In addition, a complex chromatogram of monosaccharides indicated the presence of galacturonic and glucuronic acids, as well as smaller amounts of mannosamine, fucosamine, and neuraminic acid. Trace amounts of ribose and muramic acid were identified, likely due to low level contamination with RNA and peptidoglycan.
EXAMPLE IV
Serological Properties of Crude Extract, Teichoic Acid, and Purified Adhesin
[0056] Serologically, crude extract gave three precipitin lines in double diffusion when tested against a rabbit antisera raised against whole cells of strain RP-62A ( FIG. 1A ), while teichoic acid and the purified adhesin gave single precipitin lines. By immunoelectrophoresis ( FIG. 1B ), the crude extract had multiple precipitin lines against antisera to whole cells. In contrast, purified adhesin gave a single precipitin line which did not move in the electric field. Purified teichoic acid gave a strong precipitin line migrating towards the anodal end of the gel, as well as a weaker, more negatively charged line when high concentrations of antigen were used. A mixture of teichoic acid and purified adhesin resulted in two precipitin lines corresponding to the individual, purified components.
EXAMPLE V
Adherence of S. Epidermidis Strains to Polymeric Tubing
[0057] The adherence assay described supra was used to quantify the binding of strains of coagulase-negative staphylococci to silastic catheter tubing. When the inoculant size of strain RP-62A was varied from 10 2 -10 9 cfu/ml, linear binding was obtained between input inocula of 10 3 -10 6 cfu/ml. When 10 6 cfu/ml of radiolabeled bacteria were used in this adherence assay, and pieces of catheter tubing counted before and after being rolled over the tryptic soy agar plate, 67-75% of the counts were dislodged in three separate experiments, indicating that a majority of the adherent bacterial population was being measured by this technique.
[0058] Strains of coagulase-negative staphylococci were screened in the adherence assay at inocula of 10 6 cfu/ml. Three highly adherent strains of coagulase-negative staphylococci in addition to strain RP-62A (strains RP-12, RP-14, F-3284), and poorly adherent strains (Table 2).
TABLE 2 Expression of Slime and Adhesin, and Adherence of Coagulase-Negative Staphylococci to Silastic Catheter Tubing Production of: Mean No. CFU Strain Species Slime 1 Adhesin Adhering (±SD) RP-62A S. epidermidis +++ Pos 2 233 ± 20 RP-12 S. epidermidis +++ Neg 295 ± 40 RP-14 S. hominis + Pos 167 ± 24 F-3284 S. epidermidis ++ Pos 144 ± 3 RP-62NA S. epidermidis − Pos 3 68 ± 30 SP-2 S. haemolyticus − Neg 7 ± 7 CL S. haemolyticus − Neg 19 ± 5 1 Semi-quantitative measurement as described by Christensen, G.D., et al. Infect. Immun. 37: 318-26 (1982). 2 Presence (Pos) or absence (Neg) of adhesin determined by double immunodiffusion. 3 Strain RP-62NA is only weakly positive for adhesin production.
[0059] Of the three additional highly adherent strains, two expressed an antigen giving a precipitin line of identity in double diffusion with the purified adhesin of strain RP-62A, while two of the poorly adherent strains expressed no detectable antigen. The adherence properties of strain RP-62NA were also evaluated in the adherence assay (Table 2). Strain RP-62NA adhered only about ⅓ as well as its parent strain, and a weak precipitin line corresponding to purified adhesin could be detected by immunodiffusion only if culture supernatants of strain RP-62NA were concentrated 10-fold.
[0060] Restriction enzyme digestion of total cellular DNA of strains RP-62A and RP-62NA indicated that the parent strain and its variant were closely related, as the digestion patterns using four different restriction enzymes were identical ( FIG. 2 ).
EXAMPLE VI
Properties of Purified Adhesin
[0061] The adhesin purified from S. epidermidis strain RP-62A was tested for its ability to inhibit adherence of the homologous strain to silastic catheter tubing. A dose-related inhibition of adherence was seen with both crude extract and purified adhesin prepared from strain RP-62A ( FIG. 3 ). Teichoic acid did not inhibit adherence of strain RP-62A, nor did the extract from the poorly adherent strain SP-2, prepared in a manner identical to that of crude extract from strain RP-62A. When these same materials (0.1 mg/ml) were tested for their ability to inhibit adherence of other strains of coagulase-negative staphylococci to silastic catheter tubing, only the two strains expressing the adhesin antigen were significantly (P<0.05, t test) inhibited from adhering by purified adhesin ( FIG. 4 ). Some of the strains were inhibited from adhering to the catheter material by crude extract from strain RP-62A, and adherence of strain SP-2 was inhibited by teichoic acid from strain RP-62A.
[0062] In a similar fashion, rabbit antibodies raised to strain RP-62A-purified adhesin from strain RP-62A inhibited the adherence of this strain in a dose-related fashion at serum concentrations of ≧0.25%. Using a serum concentration of 1%, there was significant (P<0.05, t test) inhibition of adherence of strains of coagulase-negative staphylococci expressing the adhesin antigen, while antigen-negative strains were not inhibited from adhering to silastic catheter tubing at this serum concentration (Table 3).
TABLE 3 Inhibition of Adherence of Coagulase-Negative Staphylococci to Silastic Catheter Tubing by Rabbit Antibody to Adhesin Purified from Staphylococcus epidermidis Strain RP-62A Percent Inhibition of Strain Adherence (±1 SD) 1 Adhesin positive RP-62A 59 ± 17* RP-14 53 ± 1* F-3284 65 ± 14* RP-62NA 2 1 ± 13 RP-12 3 62 ± 8 Adhesin negative SP-2 17 ± 9 CL 0 1 Serum concentration 1%. 2 P < 0.05, t test. *Produces greatly reduced amount of adhesin. 3 Initial studies with RP-12 were negative. However, more recent studies have shown that RP-12 does in fact produce this adhesin. Apparently, the sera used initially failed to detect the production of adhesin from strain RP-12.
[0063] Silastic catheter tubing coated with the purified adhesin readily bound rabbit antibodies raised to whole cells and purified adhesin, while antibodies in pre-immunization sera had only a slight reaction with coated catheter tubing (Table 4).
TABLE 4 Reaction of Rabbit Antibody to Purified Adhesin from Strain Staphylococcus epidermidis RP-62A with Silastic Catheter Tubing Cather Coated with Purified Adhesin Reaction with: Serum Uncoated Adhesin-Coated (5% Concentration) Catheter Catheter Pre-immune 0.150* 0.202 Immune to Whole cell 0.191 1.212 Purified adhesin 0.076 1.443 *Mean A 405 of triplicate wells containing indicated catheter.
EXAMPLE VII
Transmission Electron Microscopy
[0064] Transmission electron microscopy was used to examine the appearance of bacterial cells of RP-62A, RP-62NA, RP-14, RP-12 and CL after treatment with normal rabbit or rat serum, rabbit-antiserum raised to whole RP-62A cells, and rat antiserum raised to purified adhesin. Both of these antisera revealed an extracellular structure surrounding strains RP-62A and RP-14 that appeared to be a capsule ( FIG. 5A -D) which was not seen with normal serum (shown in the figure only for normal rabbit serum and strain RP-62A; all other strains treated with any normal serum looked identical to FIG. 5A ). Strain RP-62NA appeared to have only a slight amount of capsular material when reacted with antibodies to whole cells ( FIG. 5F ) and purified adhesin (not shown), consistent with the serologic findings mentioned supra. Both strains RP-12 and CL lacked any detectable capsule using sera to RP-62A whole cells and purified adhesin (not shown).
[0065] The invention now being fully described, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein. | A substantially pure capsular exopolysaccharide adhesin of coagulase-negative staphylococcal strains, and a gonoral method to prepare such adhesins, are described. Vaccines composed of such adhesins, and uses of such adhesins to produce polyclonal and monoclonal antibodies against such adhesins, are also disclosed. The adhesins are useful in coating polymoric medical materials to prevent colonization by coagulase-negative staphylococcal strains, and as a probe in selecting desirable polymeric medical materials. Such adhesin antibodies are useful in vivo to prevent infection by nosocomial coagulase-negative staphylococcal strains, in assays for the detection of such bacteria, in assays for the estimation of such adhesins in complex mixtures, and as an affinity chromatography matrix. | 8 |
BACKGROUND OF INVENTION
[0001] 1. Field of the Invention
[0002] The inventive devices and method relate to optical waveguides and particularly to optical fibers. More specifically, the inventive devices and method relate to optical transmission cables with particular fiber orientations, bundle and ribbon cables, coherent bundles for imaging, and transitions between geometric shapes of waveguide cables and connectors.
[0003] 2. Background
[0004] The background of the inventive devices and method involves the manufacture and use of optical fiber cables.
[0005] Well known in the art is the direct melt method of creating optical fibers. For example, see U.S. Pat. No. 4,040,807 to Midwinter et al (“Drawing Dielectric Optical Waveguides,” Aug. 09, 1977). The technique described by Midwinter and improved in the intervening decades involves multi-component glass or other materials rods combined in a molten state to form a fiber core and cladding. The “double-crucible” method is the most common process and combines the rods into a single, solid “preform,” which is then pulled into optical fiber. The concentric crucibles used allow the core to be surrounded by the cladding directly. The preform is fed into a drawing furnace that softens the end to its melting point. The softened preform is pulled into a fiber that is then pulled onto a drum that rolls the fiber into a spool. The typical materials used in optical fiber cores include silica glass, chalcogenide, other glass materials, poly and single element crystals, assorted plastics, or various other transmissive materials.
[0006] To create optical fiber ribbon cables, the successive loops of fiber pulled onto the drum can be stopped or spaced once a desired number of loops have been reached. A layer of adhesive, possibly including RTV, epoxy, or a myriad of other substances, is applied to the loops of fiber coating the drum. The adhesive adds strength to the fibers and gives them a cohesive structure, so that when they are cut on the drum, they form ribbon cables made of as many strands as there were loops on the drum before the stop or terminal spacing. The ribbon cable is as long as the circumference of the drum.
[0007] Also well known in the art are the routing limitations of optical fibers. When routing optical fibers, the fibers can be bent and curved to some minimum bend radius. Beyond the minimum bend radius (i.e., with tighter bends) the optical fiber fractures, cracks, or otherwise reduces or loses its light transmission capability. Although naked (or single) optical fibers have limited minimum bend radii, the limiting factor is often related to the mechanics of creating optical fiber ribbons or bundles.
[0008] Typically, ribbon cables have minimum bend radii greater than half an inch when bending the cable out of its plane, and far greater minimum bend radii when bending the ribbon “sideways,” within its plane. In a sideways bend, the outside fibers must not only bend, but must also elongate significantly, to accommodate a bend in the cable. Similarly, the fibers on the inside of the sideways bend must compress to accommodate the bend. Brittle substances, such as glasses, crystals, and plastics cannot compress or elongate significantly without being damaged. Therefore, typically in the art, any significant sideways bend may snap the optical fibers, so cables must be routed in such a way that avoids tight bends. Such avoidance may be impossible when cables need to follow tight mechanical contours.
[0009] Additionally, the use of optical fibers in imaging systems is well known in the art. U.S. Pat. No. 6,175,678 to Sanghera, et al, describes using chalcogenide fibers in an infrared imaging system. In such an imaging system, a lens may focus an image onto a bundle of optical fibers (for example, a sixteen by sixteen square array of fibers). The fibers, maintaining such a sixteen by sixteen bundle, can carry the image to a remotely located sixteen by sixteen pixel imaging-sensor. The fibers must be organized so that the top left fiber at the image-receiving side remains in position to project the image to the top left corner of the sensor, and likewise for each of the other fibers in the cable.
[0010] Fiber optic reformattors are also well known in the art. U.S. Pat. No. 4,678,332 to Rock et al, describes the use of a fiber optic reformattor that is, a coherent bundle of fiber optics at one end, converted to a single row of fiber optics at the other end. Rock takes an image, focused onto a two dimensional array (square, rectangular, etc) of fibers, and converts the rows or columns of the two-dimensional array into at least one linear array. That is, for example, an m by n array of fibers is converted to a single linear array, m times n fibers wide. This allows the entire two-dimensional image to be passed to the entrance slit a spectrometer.
[0011] In order to reformat a bundle of optical fibers to a linear array, the fibers must be spread over a wide area. A square bundle of fibers sixteen fibers wide, for example, must be spread to two hundred fifty six fibers wide. Such an arrangement, made out of single fibers, is very difficult to implement. Manipulating two to one hundred micron fibers to arrange them in a bundle at one end and then a cohesive linear array at the other end, especially over a short length, is impracticable. However, attempting to create such a reformattor with optical fiber ribbon cables, where the fibers are already organized in a linear manner, is also quite difficult, as doing so requires a sideways bend of the cables that calls into consideration the minimum bend radius of the cables. Because of the limited bend radius in the plane of the cable, in order to make such a reformattor conversion, a relatively long length of transition cable is needed. Such a configuration may not be appropriate in some applications, including in compact spectrometers, where reformatting may need to be completed in a very small amount of space. If a geometric change were needed within a limited size apparatus, long optical fiber cables would require complex routing that may not be possible.
[0012] This problem is exacerbated in cases where less flexible optical fibers are used. For example, certain chalcogenide optical fibers are too brittle to use as single fibers and are too inflexible to use in ribbon cables, in terms of sideways bends. This is especially a limitation in the art in the case of infrared spectrometers, as flexible, durable visible light optical fibers cannot efficiently transmit infrared light, so the more physically restrictive chalcogenide fibers are often employed. These fibers are flexible to some small degree, when alone, but too brittle to be manipulated, and too sensitive to bending in cable form.
[0013] Therefore, there is a need in the art for a way to complete geometric changes to optical fiber cabling that allows dramatically reduced bend radii from those of typical bundle or ribbon cables. There is a need in the art for a method to convert a linear array of optical fibers into a square bundle of fibers, while providing a mapped organization. There is a further need in the art for a ribbon cable capable of being routed as necessary for such reformatting, as well as a device to complete such reformatting with such ribbon cables.
SUMMARY OF INVENTION
[0014] Accordingly, the first aspect of the invention comprises a method of manufacture for a fiber optic ribbon cable capable of being bent and curved through a very small bend radius. The method involves a modification to the direct-melt ribbon-cable manufacturing process. Once a desired number of wraps of the drum have been completed, the application of the adhesive is modified so that the adhesive is placed on less than the entire circumference of the drum, leaving a portion of the circumference un-adhered. The ribbon cable is then cut through the adhesive-covered portion (though not necessarily in the middle of the covered portion), creating the inventive ribbon with adhered ends, and un-adhered fiber centers. Such a ribbon cable solves the problem described above with ribbon cable sideways bend radius limitations. The cable can bend sideways and the un-adhered fiber centers can move to allow radii approaching the limit of the fiber, far smaller than the sideways bend limit of a typical ribbon cable.
[0015] The inventive ribbon cable created by the inventive method is a second aspect of the invention. It is an object of this aspect of the invention to provide a cable useful where tight bend radii are necessary, especially in cases where using the optical fibers completely un-adhered would be impractical or impossible, due to difficulty in manipulating small, short fibers, or due to their fragile nature.
[0016] A third object of the present invention is to provide a reformattor comprised of at least two of the inventive ribbon cables. By placing two or more of the inventive cables on top of one another to form a rectangular array of optical fibers and aligning the opposite ends of the cables in a linear manner, the inventive reformattor provides a compact optical fiber reformattor for use in space limited locations, including in infrared spectrometers.
BRIEF DESCRIPTION OF DRAWINGS
[0017] The accompanying views of the drawings are incorporated in, and constitute a part of, this specification and illustrate one or more exemplary non-limiting embodiments of the invention, which, together with the description, serves to explain the principles of the invention. In the drawings:
[0018] FIG. 1 is a schematic diagram of a typical direct melt optical fiber apparatus;
[0019] FIG. 2 shows a view of the inventive method;
[0020] FIG. 3 is a schematic view of the direct melt drum diagramming the inventive changes to the typical procedure;
[0021] FIG. 4 is a schematic view of an embodiment of the inventive ribbon cable; and
[0022] FIG. 5 is a schematic view of an embodiment of the inventive reformattor.
DETAILED DESCRIPTION
[0023] The following detailed description illustrates the invention by way of example, not by way of limitation of the principles of the invention. This description will clearly enable one skilled in the art to make and use the invention, and describes several embodiments, adaptations, variations, alternatives, and uses of the invention, including what are presently believed to be the best modes of carrying out the invention.
[0024] In this regard, the invention is illustrated in the several figures and is of sufficient complexity that the many parts, interrelationships, process steps, and sub-combinations thereof simply cannot be fully illustrated in a single patent-type drawing or table. For clarity and conciseness, several of the drawings show particular elements in schematic and omit other parts or steps that are not essential in that drawing to a description of a particular feature, aspect, or principle of the invention being disclosed.
[0025] FIG. 1 is a schematic diagram of a typical direct melt optical fiber apparatus. In the figure, the feed rod apparatus ( 110 ) is a double crucible for illustrative purposes only. Any direct melt feed system is contemplated. In the double crucible system ( 110 ), the center crucible ( 112 ) contains the core feed material, which is typically glass, crystal, or plastic, including silica for typical visible light optical fibers or chalcogenides for typical infrared applications. The outer crucible ( 114 ) contains the cladding material that provides the change in refraction index to the optical fiber as well as other properties (such as protection). The optical fiber ( 116 ) is pulled out of the feed rod apparatus ( 110 ) and passes through a several additional process steps, which can vary by specific direct melt technique. In FIG. 1 , the included components are a thickness monitor ( 118 ), a final coating applicator ( 120 ), and a coating-curing oven ( 122 ). The optical fiber ( 116 ) is then pulled onto the take-up drum ( 124 ) where it spools onto the drum ( 124 ). To make a ribbon cable consisting of ten optical fibers, the optical fiber ( 116 ) is pulled onto the drum and wrapped around the drum ( 124 ) ten times. The drum ( 124 ) is indexed or translated one fiber optic diameter between each wrap. After the tenth wrap, the drum ( 124 ) moves slightly further to leave a space between the tenth and eleventh wrap. The process then optionally starts again to make a second group of ten wraps. Eventually, when the drum is wrapped as desired, the drum is coated with adhesive. When the adhesive is sufficiently strong to hold the optical fibers together, the groups of fibers are cut from one another and sliced in such a way to open the fibers as ribbon cables whose length is the circumference of the drum ( 124 ).
[0026] The inventive method, shown in FIG. 2 , begins with a typical direct melt process as shown in FIG. 1 . The inventive method begins ( 140 ) with pulling the optical fiber onto the drum. The first inventive step ( 142 ) is to place the adhesive on the drum without coating the entire circumference of the drum; rather, only a limited portion of the circumference receives adhesive. The second inventive step ( 144 ) comprises the ribbon cables being cut at any location within the adhesive-coated portion of the fibers. When pulled off the drum ( 146 ), the new ribbon cables consist of adhered ends and un-adhered center portions, allowing the ribbon cables a greater degree of sideways bending freedom. The inventive method either ends here, with an inventive ribbon ( 147 ) or the optional last inventive step ( 148 ) then comprises placing appropriate lengths of at least two inventive optical fiber ribbon cables in a stack one on top of the next at one end and along side one another at the other end. The last step thus forms a rectangular array of optical fibers at one end and a linear array of optical fibers at the other end and provides a reformattor for a two dimensional image to be projected in a “one-dimensional” one fiber wide array. The linear array can then provide optical signal to the entrance slit of a spectrometer.
[0027] The inventive method of FIG. 2 is shown in schematic form in FIG. 3 . The drum ( 124 ) is shown with an exemplary adhesive inclusive angle ( 150 ) over which the adhesive is applied. In this example, the number of wraps of the drum before the “break” is ten (shown as 164 ). The dashed line ( 152 ) represents the location of the cut used to form the inventive ribbon cables (cables shown in FIG. 4 ) with ends ( 156 , 158 ). The drum's circumference ( 162 ) will determine the length of the inventive ribbon cable. FIG. 4 shows a schematic view of the inventive ribbon cable ( 154 ), which has two coated ends ( 156 , 158 ) and a non-coated center section ( 160 ) allowing tight bend radii for such cables. The length ( 162 ) of the inventive ribbon cable ( 154 ) is equal to the circumference of the drum shown in FIG. 3 . The number of optical fibers (ten, shown at 164 ) in the ribbon cable is determined by the number of wraps of the drum completed before a space was inserted in the wrapping of the drum.
[0028] Finally, FIG. 5 is a schematic view of an embodiment of the inventive reformattor. Several inventive ribbon cables ( 154 ) are piled one on top of the other to form a rectangular array ( 172 ) of optical fibers. In this example, the array is a five by four array. In other words, the ribbon cables contain five optical fibers each and there are four of them stacked together. For clarity, the optical fibers are numbered 11 to 15 for row one, 21 to 25 for row two, and so on to 41 to 45 for row five. At the other end of the cables, the ends are lined up in a linear array, with the fibers maintaining their same numbering structure. This organized arrangement allows the reformattor to put the source light into the entrance slit of a spectrometer, for example. The fibers are shown with inventive adhered ends ( 156 , 158 ) and unadhered flexible centers ( 160 ).
[0029] The method presented herewith represents the current best mode of economically producing the devices of the present invention in relatively low volumes. However, those familiar with the art will see other methods of created the inventive devices, and such methods are contemplated. For example, to reduce packaging size and transmission attenuation (at the possible cost of aperture distortion), the inventive reformattor could be formed with the rectangular array side of the reformattor being fused to form a more closely packed array. This method would involve either capturing loose fiber ends or using the method of the inventive patent and cutting the adhered ends off and fusing the rectangular array side of the reformattor. Also contemplated is using acid dissolving adhesive and/or cladding to allow the reformattor rectangular array to be fused even when using the inventive cables and reformattor.
[0030] Moreover, it is contemplated to test optical fiber devices made in accordance with the present inventive method to determine whether there is perfect fiber alignment at each end of the inventive cable or reformattor. Any incongruence with the expected alignment can be accounted for: for example, in an imaging system, by computer means, switching pixel information.
[0031] Industrial Applicability
[0032] It is clear that the flexible optical fiber ribbon cable, fiber optic reformattor, and manufacturing method of the present invention will have wide industrial applicability wherever fiber optic ribbon cables are used in small confines where flexible ribbon cables are necessary or desired. The reformattor of the present invention will have great applicability in many slit-spectroscopy applications. The inventive devices and method will further have great applicability in any circumstance where image reformatting for infrared applications are desired, or where space, weight, or cost are important factors. | The inventive method and apparatus relate to fiber optic ribbon cable capable of being bent and curved through a very small bend radius. The method involves an improvement to the direct-melt ribbon-cable manufacturing process, creating ribbon cables with adhered ends, and un-adhered fiber centers. Such ribbon cable overcomes typical sideways bend radius limitations. This ribbon cable is a second aspect of the invention. A reformatter is further contemplated by this invention, wherein at least two of the inventive ribbon cables are arranged to form a rectangular array of optical fibers at one end and a linear array at the other, provding a compact optical fiber reformattor for use in space limited locations. | 6 |
FIELD OF THE INVENTION
The present invention relates to an ion optics set for an ion beam source, particularly ion beam sources for space propulsion, such as ion thrusters.
BACKGROUND OF THE INVENTION
Space propulsion, surface cleaning, ion implantation, and high energy accelerators use ion beam sources. These beam sources typically use two or three closely spaced multiple-aperture electrodes to extract ions from a source and eject them in a collimated beam. These electrodes are called "grids" because they have a large number of small holes. Typically, tile grids are made from molybdenum. A series of grids constitute an electrostatic ion accelerator and focusing system commonly referred to as the "ion optics."
Ion beam sources designed for spacecraft propulsion, that is, ion thrusters, should have long lifetimes (10,000 hours or more), be efficient, and be lightweight. These factors can be important in other applications as well, but they are not as critical to successful use as they are for ion thrusters. Ion thrusters have been successfully tested in space, and show promise for significant savings in propellant because of their high specific impulse (an order of magnitude higher than that of chemical rocket engines). They have yet to achieve any significant space use, however, due in part to lifetime limitations imposed by grid erosion and to performance constraints imposed by thermal-mechanical design considerations resulting from the use of metallic grids.
A typical configuration of an ion thruster is known as an electron bombardment ion thruster. In an electron bombardment ion thruster, electrons produced by a cathode strike neutral gas atoms introduced through a propellant feed line. The electrons ionize the gas propellant and produce a diffuse plasma. In other types of ion thrusters, known as "radio frequency ion thrusters," the propellant is ionized electromagnetically by an external coil, and there is no cathode. In both cases, an anode associated with the plasma raises its positive potential. To maintain the positive potential of the anode, a power supply pumps some of the electrons that the anode collects from the plasma down to ground potential. These electrons are ejected into space by a neutralizer to neutralize the ion beam. Magnets act to inhibit electrons and ions from leaving the plasma Ions drift toward the ion optics, and enter the holes in a screen grid. A voltage difference between the screen grid and an accelerator grid accelerates the ions, thereby creating thrust. The screen grid is at the plasma potential, and the accelerator grid is held at a negative potential to prevent downstream electrons from entering the thruster. Optionally, the optics can include a decelerator grid located slightly downstream of the accelerator grid and held at ground potential or at a lesser negative potential than the accelerator grid to improve beam focusing and reduce ion impingement on the negative accelerator grid.
A primary life limiting mechanism in ion thrusters is erosion of the ion optics (i.e., the grids) from ions impacting the grid material and sputtering it away. In ion thrusters, slow moving ions are produced within and downstream of the ion optics by a charge exchange (i.e., electron hopping) from neutral propellant atoms to fast moving ions that pass close by. These "charge exchange" ions are attracted to the accelerator grid and strike it at high energy, gradually eroding it away. The screen grid also experiences some erosion, mostly on the upstream side. This erosion of both the screen grid and accelerator grid eventually produces additional holes in the grids, causing them to cease functioning properly. Grid erosion is the primary life-limiting mechanism for ion optics.
A principal factor affecting both the efficiency and the weight of ion thrusters is how closely and precisely the grids can be positioned while maintaining relative uniformity in the grid-to-grid spacing under conditions conducive to significant thermal distortion. In the past, this factor has limited the maximum practical diameter of ion thrusters, which severely constrains taking advantage of scale effects that theoretically would improve efficiency, thrust-to-weight ratio, and reliability.
Molybdenum ion thruster grids are precisely hydroformed into matching convex shapes. The apertures are chemically etched. The convex shapes provide a predictable direction for the deformation that occurs due to thermal expansion when a thruster heats in operation. Changes in the actual spacing and the uniformity of spacing over the grid surfaces between the molybdenum grids is unpredictable and uncontrollable. The thermal expansion distribution is complex.
The changes in spacing that occur adversely effect performance. Although techniques have been developed to compensate for such changes, the unpredictable and nonuniform nature of the changes prevents complete compensation.
In ion beam sources used for terrestrial applications, today's grids are sometimes made of graphite, which expands much less than molybdenum when heated. Graphite is, however, relatively flexible and fragile and is not suitable for beam sources larger than about 15-20 cm in diameter, or for ion thruster grids, which are subject to severe vibration during launch from Earth.
It is desirable to have a screen grid and accelerator grid that have lifetimes of 10,000 to 20,000 hours for use in a variety of space propulsion applications. Such grids should also have an increased efficiency and should be lightweight for space applications. Additionally, the screen grids should allow for the construction of an ion optics set wherein the magnitude and uniformity of the spacing between the grids can be precisely predicted and maintained over the temperature range and pattern of differential surface heating the grids experience in use.
SUMMARY OF THE INVENTION
The present invention relates to an ion thruster having improved performance arising from using screen grids and accelerator grids made of carbon-carbon composite material. Carbon-carbon grids are lightweight and resistant to erosion. Carbon-carbon composite material can be fabricated such that its coefficient of thermal expansion is essentially zero. Heat effects on the carbon-carbon grids, therefore, are negligible. The grids maintain their relative spacing across the range of operating temperatures. They maintain their shape against differential surface temperatures. The gradient across the grids has no significant affect. In another aspect, the present invention relates to a process for producing grids made of carbon-carbon composite material.
In one aspect, the present invention is a grid element in an ion optics set for use in an ion beam source. The grid element includes a body having a plurality of apertures. The body is a carbon-carbon composite comprising carbon fibers embedded in a carbon matrix. This grid element can either be a screen grid, accelerator grid, or a decelerator grid.
In another aspect, the present invention is a process for manufacturing a carbon-carbon composite grid element for an ion beam source. The process includes the steps of positioning a plurality of carbon fibers in a crossed or woven array. This array of carbon fibers is then embedded in a carbon matrix. Apertures can be provided in the array during the positioning of the fibers, or the apertures may be cut after the fibers are embedded in the matrix.
In yet another aspect, the present invention is an ion optics set that includes a screen grid and an accelerator grid that each include a plurality of apertures and a body comprised of a composite of carbon fibers and a carbon matrix. Due to the virtually nonexistent thermal expansion of the grids formed in accordance with the present invention, the ion optics set can include a narrow gap which will remain substantially constant during operation.
It is important that the apertures between grids be precisely aligned and that they remain aligned. Otherwise, accelerated ions are directed into the next grid or are ejected at an angle to the desired axial direction. Carbon-carbon grids maintain this precise alignment of holes from grid to grid.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will be better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings.
FIG. 1 is a schematic diagram of an ion thruster constructed in accordance with this invention;
FIG. 2 is an illustration of ion optics included in the thruster of FIG. 1 and having grids and mounting rings constructed in accordance with this invention;
FIG. 3 is a plan view from the top of a screen grid formed in accordance with the present invention;
FIG. 4 is a plan view of the top of a second embodiment of a screen grid formed in accordance with the present invention;
FIG. 5 is a plan view of the top of a third embodiment of a screen grid formed in accordance with the present invention;
FIG. 6 is a plan view of the top of one embodiment of an accelerator grid formed in accordance with the present invention;
FIG. 7 is an enlarged plan view of a portion of the top of the screen grid of FIG. 1;
FIG. 8 is an enlarged plan view of a portion of the top of a screen grid formed in accordance with the present invention;
FIG. 9 is an enlarged plan view of a portion of the top of the screen grid of FIG. 5;
FIG. 10 is an elevational view of a cross section of an aperture in the screen grid of FIG. 2;
FIG. 11 is an elevational view of a cross section of an aperture in the accelerator grid of FIG. 6;
FIG. 12 is a graph of accelerator grid impingement current (J a ) as a function of beam voltage (V b ) for an ion optics set formed in accordance with the present invention;
FIG. 13 is a graph of accelerator grid voltage (V a ) as a function of beam current (J b ) for an ion optics set formed in accordance with the present invention; and
FIG. 14 is a graph of the ratio of accelerator grid impingement current (J a ) to beam current (J b ) as a function of net-to-total voltage ratio (R=V b /V t ) for an ion optics set formed in accordance with the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is described in the context of an ion thruster 1, shown schematically in FIG. 1. This type of thruster is referred to as an electron-bombardment ion thruster, and includes a cathode 2, propellant feedline 3, anode 4, power supply 5, neutralizer 6, magnet 7, and ion optics 8. The general operation of an ion thruster is described in the Background of the Invention and is not repeated here.
Additional details regarding ion thrusters, and particularly ion optics 8, are set forth in Hedges and Meserole, Demonstration and Evaluation of Carbon-Carbon Ion Optics, to be published in JOURNAL OF PROPULSION AND POWER and Garner and Brophy, Fabrication and Testing of Carbon-Carbon Grills for Ion Optics, AMERICAN INSTITUTE OF AERONAUTICS AND ASTRONAUTICS, 92-3149 (1992), the disclosures of which are hereby incorporated by reference.
Referring now to FIG. 2, the ion optics set 8 is shown in greater detail, as including a screen grid 20 and an accelerator grid 50. An optional decelerator grid 10, shown in FIG. 1 but not FIG. 2, may also be employed. Screen grid 20 and accelerator grid 50 are secured to the frame of the ion thruster (not shown) by annular dish-shaped mounting rings 12 and 14, respectively, whose spacing is controlled by spacers 16. It should be understood that the benefits and advantages of the present invention will be applicable to ion beam sources that are used for applications other than ion thrusters.
In the embodiment shown in FIG. 2, screen grid 20 is a substantially planar element that is a carbon-carbon composite comprising a carbon fiber array embedded in a carbon matrix. Referring additionally to FIG. 10, screen grid 20 includes an entry plane 22 and an opposing exit plane 24. As described in more detail below, entry plane 22 and exit plane 24 are substantially parallel which provides a screen grid of substantially uniform thickness. In the illustrated embodiment, screen grid 20 has a thickness on the order of about 0.8 millimeters (mm) and includes an array of apertures 26. Each aperture is approximately 10 centimeters (cm) in diameter. It should be understood that the foregoing dimensions are illustrative only; different diameters and thicknesses could be employed. For ion thrusters, it would be preferred to have the grids thinner, e.g., on the order of 0.4 mm, and larger in diameter, e.g., up to 50 cm or more, if possible. Thinner grids are preferred from the standpoint of increasing the electric field strength. Thickness is important from handling, assembly, and lifetime viewpoints, but the goal is to make the grids as thin as possible while retaining stiffness, uniformity, and the other required assembly properties.
Adjacent the periphery of screen grid 20 are a plurality of equally spaced mounting holes 28, shown in FIG. 3, that extend through screen grid 20 from entry plane 22 to exit plane 24. As described above, the central portion of screen grid 20 includes a plurality of round apertures 26 that extend through screen grid 20 from entry plane 22 to exit plane 24. As shown in FIG. 10, apertures 26 have a diameter at entry plane 22 that is greater than the diameter at exit plane 24. In this manner, apertures 26 have a vertical profile that narrows from entry plane 22 to exit plane 24. In the illustrated embodiment, screen grid 20 includes approximately 1,600 apertures that have a hole diameter of approximately 1.83 mm. The open area fraction through screen grid 20, then, is about 0.59. The spacing between the center points of adjacent apertures 26 is approximately 2.29 min.
In the illustrated embodiment, apertures 26 in screen grid 20 are arranged in a hexagonal array. The hexagonal array provides an aperture at the center of a hexagon with other apertures centered on the intersection of the six sides of a hexagon. Such hexagonal array is more clearly illustrated in FIG. 7, which is a magnified view of a portion of entry plane 22 of screen grid 20.
Referring to FIG. 7 in more detail, screen grid 20 includes carbon fibers 30 arranged in an array between apertures 26 and carbon matrix 38 that is infiltrated into the array. In the illustrated embodiment, carbon fibers 30 are arranged parallel to three different axes. Sets of carbon fibers 30 are arranged parallel to a first axis 32. Other carbon fibers 30 are arranged parallel to a second axis 34. In the illustrated embodiment, first axis 32 is offset from second axis 34 by 60°. A third group of fibers 30 is arranged parallel to a third axis 36. Third axis 36 is offset from both the first axis 32 and second axis 34 by 60°. In the illustrated embodiment, spacing between the periphery of apertures 26 is large enough that carbon fibers 30 can extend in a straight line from edge to edge of screen grid 20. As described below in more detail, when apertures 26 are larger and the carbon fibers cannot be run in a straight run from edge to edge, the carbon fibers can be "snaked" around the apertures, as shown in FIG. 8, where screen grid 20 includes fibers 42, carbon matrix 43, and apertures 40 that are larger diameter than apertures 26 illustrated in FIGS. 2 and 6. As noted above, when apertures 40 attain a certain diameter, carbon fibers 42 cannot extend in a straight line from edge to edge of screen grid 20. To achieve this "snaking" of the carbon fibers, the array can be laid up on a pattern of pegs or inserts that serve to define apertures 40.
It is also possible that in specific applications the size of the apertures passing through the screen grid will make it possible to have some fibers run in a straight line between the edges of the screen grid and other fibers that "snake" around the apertures.
Referring to FIG. 4, another embodiment of screen grid 20 is illustrated having apertures 44 that are hexagonal in shape and arranged in a hexagonal array. Depending on the dimensions of hexagonal apertures 44, carbon fibers can extend from edge to edge of the screen grid in a straight line or they may be "snaked" around hexagonal apertures 44 as described above. Under certain operating conditions, hexagonal holes may provide slightly better thruster performance than round holes.
Referring to FIG. 5, another embodiment of screen grid 20 formed in accordance with the present invention is illustrated with apertures 46 that are rectangular in shape. When rectangular apertures 46 are employed, they can be arranged in orthogonal rows and columns or any other suitable arrangement. When apertures 46 are arranged in orthogonal rows and columns, carbon fibers 48 infiltrated with carbon matrix 49 extend in straight lines (FIG. 9) from edge to edge of the screen grid in an orthogonal array. This arrangement offers the advantage of providing orthogonal straight paths for the fibers across the entire grid, thereby maximizing the grid's stiffness.
As an alternative to arranging individual carbon fibers or tows of carbon fibers in the arrays described above, pre-woven sheets of carbon fibers can be arranged in layers to provide the needed carbon fiber array. When sheets of woven carbon fibers are used, the sheets can be arranged in layers that are offset, for example by 60°, from each other with respect to the direction of the weave or in any other suitable pattern. Pre-woven sheets of carbon fibers are preferred over the individual tows of fibers from an ease of handling perspective; however, the pre-woven sheets are generally thicker than the individual fibers or tows and therefore are not preferred from the standpoint of providing a thin grid.
Referring to FIG. 6, the accelerator grid 50 is substantially identical to screen grid 20 described above with the exception that the size of apertures 52 is much less so as to restrict the flow of neutral atoms out of the thruster. The electric field between the screen and accelerator grid is shaped so as to focus the ions passing through the large screen grid apertures into and through the smaller accelerator grid apertures. For example, for screen grid 20 described with reference to FIG. 2, a counterpart accelerator grid could include apertures 52 having a diameter of about 1.09 mm. Such an accelerator grid would have an open area fraction of about 0.29. Accelerator grid 50 has substantially the same number of apertures 52 as the screen grid and when the two are combined to form an ion optics pair, the axes of the apertures of the screen grid and the axes of the apertures of the accelerator grid are aligned.
The screen grid and the accelerator grid can both include hexagonal apertures or rectangular apertures arranged in the same manner as described above, or other arrays suitable for the application. Similarly, one could vary the size of apertures as a function of their position in the grids to match the distribution of plasma over the grids.
Referring to FIG. 11, as with the screen grids, accelerator grid 50 includes an entry plane 53 and an opposing exit plane 55. Entry plane 53 and exit plane 55 are substantially parallel so that the accelerator grid has a substantially uniform thickness. The diameter of aperture 52 at entry plane 53 is less than the diameter of aperture 52 at exit plane 55. In this manner, aperture 52 has a profile through accelerator grid 50 that is tapered from entry plane 53 to exit plane 55.
The carbon fibers that can be used in the context of the present invention include those that are commercially available from a number of sources, including the K-1100 high modulus fiber available from the Amoco Company or the E-55 fiber available from the DuPont Company. Such fibers are usually drawn and may be interwoven to provide tows or sheets of fibers. The fibers available exhibit a range of physical properties. For ion thrusters, fibers having an elastic modulus on the order of 4×10 5 MPa to 1×10 6 MPa and a diameter of about 10 microns are suitable. Carbon fibers having an elastic modulus on the upper end of the foregoing range will generally allow thinner grids of adequate overall stiffness to be made than will carbon fibers having an elastic modulus near the lower end of the range. Stiffer fibers are generally preferred; however, they should also have commensurate strength so as not to be brittle and fragile during handling. Grids made with carbon fibers near the lower end of the range will require appropriate thermal processing after forming to increase the fiber modulus to a higher value, preferably above 100 million psi.
A carbon matrix is built around the carbon fiber array by a repetitive process. Each repetition of the process involves the steps of infiltration with a carbonaceous material, as described below, and high-temperature pyrolysis. The carbonaceous materials can be pitch, resin, or organic gases. A combination of these materials also may be used, although only one material is used in any given infiltration and pyrolysis sequence. Pyrolysis is a thermal process which decomposes the carbonaceous precursor material to leave a residue of pure carbon as the carbon matrix around the carbon fiber array. The process of building the carbon matrix is referred to as densification because the density is increased as fibers become embedded in the carbon matrix.
Pitch and resin infiltration is accomplished by pouring or squeezing the pitch or resin into the carbon fiber array. This infiltration can also be effected by using carbon fibers or tows of carbon fibers that have been laid up on a tape and preimpregnated with pitch or a phenolic polymer. Two companies that perform pitch or resin infiltration are Fiber Materials, Inc., of Biddeford, Me. and Kaiser Aerotech of San Leandro, Calif.
Organic gas infiltration, otherwise known as chemical vapor infiltration, is generally carried out in a controlled atmosphere furnace where an organic gas infiltrates the carbon fiber array, decomposes at the surfaces, and leaves a carbon residue which binds the fibers together and forms a continuous matrix. One company that provides chemical vapor infiltration services is B. F. Goodrich of Sante Fe Springs, Calif.
Although the described screen and accelerator grids are planar, in certain applications, it may be desirable to curve the grid a small amount to add stiffness.
As noted previously, the screen grid 20 and accelerator grid 50 are coupled to the frame of the ion thruster by mounting rings 12 and 14. Rings 12 and 14 are also preferably formed using the same carbon-carbon composite employed in the grids, although alternative materials can be employed. A greater variety of fiber arrays can also be used in rings 12 and 14, given the absence of the grid apertures. Each ring includes a central opening 18 dimensioned to enclose the apertured region of the grid it is used with. Each ring includes a plurality of grid mounting holes 19 and frame mounting holes 21.
The mounting rings 12 and 14 are attached to grids 20 and 50 via the grid mounting holes 19 and mounting screws 23. The rings are also attached to the thruster frame by screws (not shown). Alignment pins would typically be employed to achieve the desired relative alignment of these various components.
The carbon-carbon grids and mounting rings do not expand upon heating. In fact, they might contract, but only slightly. Their coefficient of thermal expansion is essentially zero. Since expansion of the grids and mounting rings is negligible over the operational temperature gradients, which can be on the order of 350 degrees Celsius, alignment of the apertures and a constant spacing between the screen grid and the accelerator grids can be better maintained. When spacing between the grids can be reliably maintained constant during the operational temperature changes, the grids can be spaced closer together without the risk that expansion will cause the grids to touch each other and be electrically shorted together, or that the beam density will be excessive where the gap is smaller than intended. Shorting destroys the voltage gradient needed to accelerate the ions. Excessive beam densities increase the production of charge exchange ions that increase grid erosion. Also, when the spacing can be maintained constant, larger grid diameters can be designed without increasing the likelihood that thermal expansion will adversely affect performance. Large grid diameters can translate into efficiency, thrust-to-weight, and reliability advantages.
In addition to the foregoing advantages, carbon-carbon grids are more resistant to erosion by ions than the materials used today to make grids, such as molybdenum. Space applications require that such grids have a lifetime on the order of 10,000 hours. Carbon-carbon grids formed in accordance with the present invention show potential to exceed such lifetimes without restrictions imposed on the thruster operating conditions (specifically, without limiting the beam density for the purpose of reducing the erosion rate).
In accordance with the present invention, the screen and accelerator grids can be combined in a conventional manner to provide an ion optics set 8, as shown in FIG. 2, for use in the ion thruster 1 or other ion beam sources. When the carbon-carbon composite screen and accelerator grids are used in an ion optics set 8, grid spacings of approximately 0.2 mm to 0.5 mm can be used. Grid spacing outside the exemplary range given above can be employed in accordance with the present invention. The narrow grid spacing described above is achievable with the carbon-carbon grids because the thermal-mechanical stability of the carbon-carbon composite and the stiffness of the grids allows the screen and accelerator grids to be spaced closer together than conventional grids. The use of carbon-carbon composites for the mounting rings further contributes to the thermal-mechanical stability of the ion optics, hence, the ability of the grids to be closely spaced. Spacing the grids closer together increases the field strength between the grid, which increases the maximum achievable beam density. A carbon-carbon grid set is tested for voltage stand-off capability, maximum perveance condition, electron backstreaming limit and defocusing limit in the example that forms a part of this detailed description.
Generally, the fabrication of the grids described above includes selecting a high-modulus carbon fiber, an appropriate lay-up pattern, a suitable means of densification, and a method for making apertures of the desired shape and arrangement. Minimizing the thicknesses of the screen grid and accelerator grid, subject to structural and erosion constraints, is also an important design consideration.
The carbon fibers can be laid up on a solid substrate in any of the patterns described above. The substrate that is chosen should be compatible with the subsequent infiltrating step. For example, a flat carbon block may be suitable as a base for laying up the fibers. The carbon fibers should be laid up in as dense an arrangement as possible given the desired thickness of the particular grid. Thinner grids may be desirable; however, as the grids are made thinner, care must be taken that they do not become too flexible. With respect to the particular form of the fiber chosen, tapes of fibers or tows are preferred over woven fabrics since woven fabrics tend to introduce added thickness at the points of the overlapping weaves and the curing of the fibers in the weave reduces the effective grid stiffness. When fabric is used, the fibers may be used in an amount that they comprise approximately 50-65 volume percent of the overall grid and when a tape is used the fibers comprise approximately 75-90 volume percent of the grid. Generally, the higher the volume percent fibers, the stiffer the grid.
As described above, the lay-up of fibers can be densified using techniques such as pitch infiltration, resin infiltration, or chemical vapor infiltration. Pitch infiltration can be used to fill the larger internal voids and the smaller voids can be filled with chemical vapor infiltration. Since neither densification method provides a void-free body, to improve the erosion resistance, internal voids exposed when the apertures are cut, as described below in more detail, should be filled by chemical vapor infiltration. The densification steps preferably provide a carbon-carbon composite having a density greater than 1.9 g/cm 3 . Accordingly, when the grid comprises about 50 volume percent fibers, the carbon matrix will comprise approximately 50 volume percent of the grid. Similarly, when the grid comprises about 90 volume percent fibers, the carbon matrix will comprise approximately 10 volume percent of the grid.
The apertures in the grids can be cut by several different methods. For example, for round apertures, you can use mechanical drilling with diamond tip drills, or faster cutting methods, such as laser cutting, ultrasonic milling, water jet cutting, or electron discharge machining, can be employed.
For some applications, you may prefer to employ a technique providing uniformly tapered apertures of the type described above. Such apertures advantageously enable a wider range of operating conditions without the beam impinging upon the side walls of the apertures. As a result, thicker grids can be employed to achieve the desired grid stiffness, without incurring a performance penalty. You may also wish to remove the "sharp" perimeter of the openings of the aperture to reduce erosional effects at the openings.
Alternatively, you can form the apertures by providing a pattern of pegs or other inserts around which the carbon fibers are laid up and around which the carbon infiltration of the array is carried out. In this manner, the apertures will be preformed rather than requiring subsequent drilling after infiltration.
EXAMPLE
We made a 10-cm diameter, flat, circular screen grid and a 10-cm diameter, flat, circular accelerator grid from two 14-cm square carbon-carbon panels we obtained from B. F. Goodrich of Sante Fe Springs, Calif. The panels consisted of three plys of carbon fiber fabric densified by chemical vapor infiltration. The fibers making up the fabric had an elastic modulus of about 105 million psi. The infiltrated panels were 0.8 mm thick and were machined to include 1,615 apertures. The apertures in the accelerator grid had a diameter of 1.09 mm and the apertures in the screen grid were 1.83 mm in diameter. The screen grid had an open area fraction of 0.59 and the accelerator grid had an open area fraction of 0.21. Hole spacing between the apertures in both grids was 2.29 mm and the hole profile was a tapered 6° cut, which was a result of the particular laser cutting operation used to produce the apertures.
No special surface preparation, either cleaning or smoothing, was done prior to testing. The laser machining process left a soot-like discoloration on the laser entry side of each grid. The surface roughness due to the fiber weave was about 0.05 mm. When mounted, these grids were measured to be flat to within 0.025 mm.
Optics tests were conducted using a 15-cm ion source produced by Ion Tech, Inc. of Fort Collins, Colo. An adapter was used to mask down the 15-cm source to 10 cm and to accept a separate conventional molybdenum grid mount that was used to mount the carbon-carbon grids.
The ion source used tungsten filaments for both the cathode and the neutralizer. Variable alternating current sources (variacs) drove the cathode and neutralizer. We isolated the cathode from its variac using an isolation transformer. The beam supply was rated at 3,000 volts and 1 amp and was referenced to facility ground. The discharge supply floated at beam potential with its positive terminal connected to the positive terminal of the beam supply and its negative terminal connected to tile mid-point of the secondary winding on the cathode isolation transformer. The discharge supply was rated at 200 volts and 17 amps. The accelerator supply was rated at 600 volts and 1.5 amps. The tests were conducted using xenon as the propellant, although other inert gases (such as argon and krypton), or other elements or molecules (such as mercury, or carbon-60) can be employed.
We conducted the tests in a diffusion pumped vacuum chamber, 0.9 meters in diameter by 1.8 meters in height, that maintained approximately 5×10 -5 tort during testing. With a digital data acquisition system, beam voltage and current, accelerator grid voltage and current, discharge voltage and current, cathode filament current, neutralizer filament, and emission current, and propellant flow were measured. Vacuum chamber pressure was measured with an ion gauge.
Before operating the grids on the thruster, we conducted voltage standoff tests. The optics set was mounted to the molybdenum grid mount, gapped to 0.58 mm and then tested until voltage breakdown occurred in both air and vacuum using a high voltage, variable DC power supply. A 100K ohm power resistor was placed in series with the high voltage power supply to limit the current when arcing occurred.
With the carbon-carbon grids installed in the grid mount at a gap setting of 0.58 mm, and exposed to atmospheric conditions, we increased the voltage across the grids slowly. Arcing was observed initially as the voltage was increased above 1,000 volts, but by pausing the increase at each occurrence, the rate of arcing decreased, and eventually stopped. The voltage was increased to 2,500 volts. After some initial arcing, the voltage was held at 2,500 volts for several minutes until no further arcing was observed. The voltage gradient at that point was 4,300 volts per min. Inspection of the grids under a microscope following the tests showed that the arcing had no visible effect on the grids, other than to produce some slight, localized surface discoloration.
We repeated the procedure in a vacuum chamber pumped down to 1×10 -5 torr. No arcing was visible up to 3,500 volts. At 3,500 volts, a small, steady current of about 0.5 milliamps was observed on the power supply analog current meter. At 3,750 volts, arcing began, but it subsided with time. Eventually, 5,000 volts with only occasional arcing was reached, but a steady current of 1 milliamp was recorded. At 5,250 volts, arcing was observed. At 5250 volts, the voltage gradient was 9050 V/mm. Maximum voltage gradients of 6420 V/mm during operation at 0.2 mm spacing for the carbon-carbon grids was also observed.
Three grid-to-grid gaps of 0.2 mm, 0.3 mm, and 0.5 mm were chosen at which to operate the thruster. These gaps provided effective acceleration lengths of 1.35 mm, 1.42 mm, and 1.58 min.
Prior to starting the thruster for each run, the chamber background pressure was recorded while xenon flowed at the rate desired for that run. The thruster was then started and allowed to warm up for at least 30 minutes prior to data acquisition. For all runs, the initial run conditions were as follows:
(1) the propellant utilization efficiency (η p ) was set to approximately 75%, determined by the ratio of beam current to propellant flow rate, where flow rate was convened to an equivalent current flow using 1 amp equal to 13.95 standard cubic centimeters per minute for singly ionized atoms.
(2) the discharge voltage V d was set to 35 volts, which was less than or equal to 10% of the total accelerating voltage V t . The total accelerating voltage is given by V t =V b +|V a | where V b is the beam (and also the net accelerating) voltage and |V a | is the absolute value of the accelerator grid voltage.
(3) the net to total voltage ratio R was set to 0.8, where R=V b /V t ; and
(4) the total voltage was set high enough to preclude direct ion impingement (by choosing a V t such that further increases in V t at a fixed R did not reduce accelerator grid impingement current).
Perveance expresses total current in terms of applied voltage. For a fixed beam current, the maximum perveance condition of an ion optics set occurs at the minimum total voltage (V t ) prior to the onset of direct ion impingement. For the carbon-carbon grids, we measured accelerator grid impingement current as a function of decreasing beam voltage to identity the minimum total voltage prior to direct ion impingement. We made measurements for each of five beam current (J b ) levels from 80 milliamps to 160 milliamps, and for an acceleration length of 1.35 mm. We held beam current constant by adjusting the discharge current as necessary in response to changes in the beam voltage. Accelerator grid voltage was fixed for each run. FIG. 12 shows a representative plot of accelerator grid impingement current (J a ) as a function of beam voltage (V b ) for the carbon-carbon optics.
Electron backstreaming occurs when the accelerator grid voltage is no longer sufficient to shield external electrons from the positive potential of the discharge chamber. Electrons are then free to flow from the external environment into the discharge chamber.
After completing each data run for determining the maximum perveance condition, the initial conditions were reestablished and then beam current (J b ) was measured as a function of decreasing accelerator grid voltage (V a ) for each of the effective acceleration lengths. The accelerator grid voltage was slowly reduced as the analog current meter on the beam supply was monitored. As the accelerator grid voltage fell below the electron backstreaming limit, a rapid increase in beam current was observed. The accelerator grid voltage at which this beam current occurred was recorded as the electron backstreaming limit. FIG. 13 represents plots of the electron backstreaming limit for each run.
After completing each data run for determining the electron backstreaming limit, the initial run conditions were reestablished. For an effective acceleration length of 1.42 mm, accelerator grid impingement current as a function of net-to-total voltage ratio (R) was measured while holding total voltage (V t ) constant. This determined the minimum R prior to the onset of direct ion impingement. For the selected total voltage, R was adjusted down from an initial value of 0.8 by decreasing the beam voltage, then increasing the accelerator grid voltage by the same amount, thereby lowering the beam (net) voltage while maintaining a fixed total voltage. At each step, accelerator grid impingement current was recorded. As the defocusing limit was approached, the accelerator grid impingement current increased from the background level. The value of R at which the accelerator grid current first increased above the background level was identified as the defocusing limit for each run condition. FIG. 14 shows the ratio of accelerator grid impingement current (J a ) to beam current (J b ) plotted as a function of R. For the carbon-carbon optics at an effective acceleration length of 1.42 millimeters, the defocusing limit occurred for R values between 0.4 and 0.5.
During these tests, we did not observe buckling or breaking of the ion optics. Accordingly, this test also demonstrates how fiat carbon-carbon ion optics made have sufficient thermomechanical stability to operate with grid spacings on the order of 0.2 mm.
While the preferred embodiment of the invention has been illustrated and described, it will be appreciated that various changes can be made therein without departing from the spirit and scope of the invention. | Carbon-carbon elements for ion optics sets are thermomechanically stable under the extreme temperature changes that are experienced in ion thrusters. The elements described include screen and accelerator grids and methods of producing such grids. The described elements are thermomechanically stable, lightweight, and resistant to sputtering. | 5 |
BACKGROUND
[0001] Many people use dedicated weather applications to obtain weather data about their area. Such applications provide the user with basic weather information such as current and expected temperature. Users interpret the provided weather data based on their past weather-related experiences. However, a user may experience new and different weather conditions while traveling. It is important that a dedicated weather application convey weather data to the user in an efficient and natural way such that the user may get the most out of the weather data.
SUMMARY
[0002] In general, in one aspect, the invention relates to a method for presenting weather data. The method includes displaying a first weather video panel comprising a first video element and a second weather video panel comprising a second video element, where the first video element and the second video element are synchronized, and receiving an instruction to add a third weather video panel. The method further includes, in response to receiving the instruction to add a third weather video panel, displaying the third weather video panel comprising a third video element, and restarting the first weather video panel and the second weather video panel, where after the restarting, the first video element, the second video element, and the third video element are synchronized.
[0003] In general, in one aspect, the invention relates to a non-transitory computer-readable medium comprising instructions that, when executed by a processor, perform a method for presenting weather data. The method includes displaying a first weather video panel comprising a first video element and a second weather video panel comprising a second video element, where the first video element and the second video element are synchronized, and receiving an instruction to add a third weather video panel. The method further includes, in response to receiving the instruction to add a third weather video panel, displaying the third weather video panel comprising a third video element, and restarting the first weather video panel and the second weather video panel, where after the restarting, the first video element, the second video element, and the third video element are synchronized.
[0004] In general, in one aspect, the invention relates to a method for presenting an image. The method includes receive an instruction to display the image, generating a first virtual tile and a second virtual tile from the image, where the first virtual tile and the second virtual tile are associated with a contiguous portion of the image, and where the first virtual tile and the second virtual tile share an edge. The method further includes initiating a first image bleeding from a first non-edge location on the first virtual tile, determining a future time target at which the first image bleeding will reach an edge location on the first virtual tile, and initiating a second image bleeding from a second non-edge location on the second virtual tile, where the second image bleeding is initiated to reach a corresponding edge location on the second virtual tile at the future time target.
[0005] In general, in one aspect, the invention relates to a non-transitory computer-readable medium comprising instructions that, when executed by a processor, perform a method for presenting weather data. The method includes receive an instruction to display the image, generating a first virtual tile and a second virtual tile from the image, where the first virtual tile and the second virtual tile are associated with a contiguous portion of the image, and where the first virtual tile and the second virtual tile share an edge. The method further includes initiating a first image bleeding from a first non-edge location on the first virtual tile, determining a future time target at which the first image bleeding will reach an edge location on the first virtual tile, and initiating a second image bleeding from a second non-edge location on the second virtual tile, where the second image bleeding is initiated to reach a corresponding edge location on the second virtual tile at the future time target.
[0006] Other aspects of the invention will be apparent from the following description and the appended claims
BRIEF DESCRIPTION OF DRAWINGS
[0007] FIG. 1 shows a system in accordance with one or more embodiments of the invention.
[0008] FIGS. 2A-2E show a system in accordance with one or more embodiments of the invention.
[0009] FIG. 3 shows a flow diagram in accordance with one or more embodiments of the invention.
[0010] FIGS. 4A-4C show an example in accordance with one or more embodiments of the invention.
[0011] FIGS. 5A-5E show a system in accordance with one or more embodiments of the invention.
[0012] FIG. 6 shows a flow diagram in accordance with one or more embodiments of the invention.
[0013] FIGS. 7A-7E show an example in accordance with one or more embodiments of the invention.
[0014] FIG. 8 shows a flow diagram in accordance with one or more embodiments of the invention.
[0015] FIG. 9 shows a flow diagram in accordance with one or more embodiments of the invention.
[0016] FIG. 10 shows a computer system in accordance with one or more embodiments of the invention.
DETAILED DESCRIPTION
[0017] Specific embodiments of the invention will now be described in detail with reference to the accompanying figures. Like elements in the various figures are denoted by like reference numerals for consistency.
[0018] In the following detailed description of embodiments of the invention, numerous specific details are set forth in order to provide a more thorough understanding of the invention. However, it will be apparent to one of ordinary skill in the art that the invention may be practiced without these specific details. In other instances, well-known features have not been described in detail to avoid unnecessarily complicating the description.
[0019] In general, embodiments of the invention provide a method and system for conveying weather data to a user. Specifically, embodiments of the invention may be implemented in a dedicated weather application used to obtain and interpret weather data received from weather data servers.
[0020] FIG. 1 shows a diagram of a system in accordance with one or more embodiments of the invention. As shown in FIG. 1 , the system includes multiple weather data servers (weather data server A ( 100 A), weather data server N ( 100 N)), a weather application server system ( 102 ), and a weather application client system ( 104 ) communicatively coupled to one another via a network ( 106 ). Weather application server system ( 102 ) includes a weather application server ( 108 ). Weather application client system ( 104 ) includes a weather application client ( 110 ), a device location module ( 112 ), and a display ( 114 ).
[0021] In one or more embodiments of the invention, the weather data servers (weather data server A ( 100 A), weather data server N ( 100 N)), are computer systems or groups of computer systems under the control of a weather data service provider (e.g., National Weather Service, etc.). In one embodiment of the invention, the weather data servers (weather data server A ( 100 A), weather data server N ( 100 N)) provide weather data to the weather application server ( 102 ).
[0022] In one or more embodiments of the invention, weather data includes future weather data (e.g. weather forecasts), past weather data, and current weather data. Weather data may further include future (i.e., predicted) or past environmental metrics (e.g., temperature, barometer, humidity, etc.), conditions (e.g., rain, snow, cloudy, fog, etc.), diagrams describing weather patterns (e.g., past or predicted hurricane paths), and/or images describing weather forecasts (e.g., radar maps, satellite maps, etc.).
[0023] In one or more embodiments of the invention the weather application server system ( 102 ) is a computer system or group of computer systems configured to execute a weather application server ( 108 ). In one embodiment of the invention, the weather application server ( 108 ) is a process or group of processors configured to obtain weather data from weather data servers (weather data server A ( 100 A), weather data server N ( 100 N)). In one embodiment of the invention, the weather application server ( 108 ) provides processed weather data to the weather application client ( 110 ) executing on the weather application client system ( 112 ).
[0024] In one or more embodiments of the invention, the weather application client system ( 104 ) is a computer system or group of computer systems configured to execute weather application client ( 110 ). The weather application client system ( 104 ) may also include a device location module ( 112 ) used by the weather application client ( 110 ) to obtain location data describing the current location of the weather application client system ( 104 ). In one embodiment of the invention, the weather application client ( 110 ) generates a weather data query using the location data obtained from the device location module ( 112 ). The weather data query may then be submitted to the weather application server ( 108 ) executing on the weather application server system ( 102 ). Examples of weather application client systems ( 104 ) include, but are not limited to, desktop computers, laptop computers, tablet computers, smart phones, and smart television sets.
[0025] In one or more monuments of the invention, weather data obtained from the weather application server ( 108 ) may be processed by the weather application client ( 110 ) for presentation on the display ( 114 ). Such presentations may include video windows, tile bleeding, context-based weather reports, and weather report discrepancies, as described below.
[0026] Video Windows
[0027] In one or more embodiments of the invention, the weather application client ( 110 in FIG. 1 ) is configured to present weather data in a set of video panels. Each video panel may display an animated video element related to the weather data. The set of video panels may be used to create the illusion of a single animated video element divided by a set of video panels, where one or more of the video panels present a variation of the animated video element. In one embodiment of the invention, the video element may be pre-recorded or rendered in real-time.
[0028] FIGS. 2A-2E show a presentation mechanism in accordance with one or more embodiments of the invention. Specifically, FIGS. 2A-2E show a sequence of presentations on a display ( 200 ) that includes two video panels (video panel A ( 202 A), video panel B ( 202 B)). Video panel A ( 202 A) includes video element A ( 204 A), and video panel B ( 202 B) includes video element B ( 204 B). Each video element (video element A ( 204 A), video element B ( 204 B)) is represented by an animated clock.
[0029] In one or more embodiments of the invention, each video panel (video panel A ( 202 A), video panel B ( 202 B)) may be set to represent a weather condition in a different geographic location. For example, video panel A ( 202 A) may be set to represent a weather condition in Houston, Tex., and video panel B ( 202 B) may be said to represent a different weather condition in New York City.
[0030] In one or more embodiments of the invention, one or more of the video elements (video element A ( 204 A), video element B ( 204 B)) varies from one or more of the other video elements (video element A ( 204 A), video element B ( 204 B)). For example, each video panel (video panel A ( 202 A), video panel B ( 202 B)) may display a sky image as a video element (video element A ( 204 A), video element B ( 204 B)). The sky image in video panel A ( 202 A) may be clear and sunny, while the sky image in video panel B ( 202 B)) may be dark and stormy.
[0031] FIG. 2A shows video panel A ( 202 A) and video panel B ( 202 B) at the sync frame. In one embodiment of the invention, the sync frame is a frame of the presented animation used to reset the animation, such as the beginning of a looped animation. The sync frame in FIGS. 2A-2E is represented by the clocks displaying 12:00. As shown in FIG. 2A , both video elements (video element A ( 204 A), video element B ( 204 B)) are at the sync frame.
[0032] FIG. 2B shows the video panels (video panel A ( 202 A), video panel B ( 202 B)) after the animation has been initialized from the sync frame (i.e., a successive frame of the presented animation). As shown in FIG. 2B , the video panels (video panel A ( 202 A), video panel B ( 202 B)) are synchronized and both show the video element (video element A ( 204 A), video element B ( 204 B)) displaying 12:15.
[0033] FIG. 2C shows the video panels (video panel A ( 202 A), video panel B ( 202 B)) after an instruction to add an additional video panel have been received. As shown in FIG. 2C , the video panels (video panel A ( 202 A), video panel B ( 202 B)) are reset to the sync frame and both show the video element (video element A ( 204 A), video element B ( 204 B)) displaying 12:00.
[0034] FIG. 2D shows the video panels (video panel A ( 202 A), video panel B ( 202 B)) after an additional video panel has been added. As shown in FIG. 2D , three video panels (video panel A ( 202 A), video panel B ( 202 B), video panel C ( 202 C)) are displayed. Each video panel shows the sync frame and each video element (video element A ( 204 A), video element B ( 204 B), video element C ( 204 C)) is displaying 12:00.
[0035] In one or more embodiments of the invention, the process described with reference to FIGS. 2C and 2D may vary. Specifically, the sync frame may be dynamic in nature, and designated as the frame displayed at the time when the additional video panel is added. Instead of resetting the first set of video panels (video panel A ( 202 A), video panel B ( 202 B)), the current frame of the video panels (video panel A ( 202 A), video panel B ( 202 B)) may be designated as the sync frame, and the additional video panel (video panel C ( 202 C)) may be set to the newly designated sync frame when it is added.
[0036] FIG. 2E shows the video panels (video panel A ( 202 A), video panel B ( 202 B), video panel C ( 202 C)) after the animation has been initialized from the sync frame. As shown in FIG. 2E , each of the three video panels (video panel A ( 202 A), video panel B ( 202 B), video panel C ( 202 C)) shows a successive frame of the presented animation and each video element (video element A ( 204 A), video element B ( 204 B), video element C ( 204 C)) is displaying 12:15.
[0037] FIG. 3 shows a flowchart for adding a synchronized video panel in accordance with one or more embodiments of the invention. While the various steps in these flowcharts are presented and described sequentially, one of ordinary skill will appreciate that some or all of the steps may be executed in different orders, may be combined or omitted, and some or all of the steps may be executed in parallel.
[0038] In Step 310 , the weather application client displays a set of weather video panels. In Step 312 , the weather application client initiates animation from the sync frame on the set of weather video panels. In Step 314 , weather application client listens for an instruction to add an additional weather video panel. In Step 316 , a determination is made as to whether an instruction has been received. If in Step 316 no instruction is received, then in Step 318 , a determination is made as to whether next frame in the animation exists.
[0039] If the next frame in the animation exists in Step 318 , then the weather application client displays the next frame on the set of weather video panels (Step 320 ). Process then returns to Step 314 . If there is no next frame in the animation in Step 318 , then the animation is restarted from the sync frame on each of the set of video panels (Step 322 ).
[0040] If an instruction to add an additional video panel is received (Step 316 ), then the animation is restarted from the sync frame on the current set of video panels (Step 324 ). In Step 326 , the additional video panel is displayed. In Step 328 , the animation is initiated from the sync frame on the additional weather video panel. In one embodiment of the invention, animation on each of the video panels, including the additional video panel, is synchronized.
[0041] FIGS. 4A-4C show an example in accordance with one or more embodiments of the invention. As shown in FIG. 4A , four video panels are shown. The first weather video panel ( 402 ) represents the weather conditions in Houston, Tex. The second weather video panel ( 404 ) represents the weather conditions in Harlingen, Tex. The third weather video panel ( 406 ) represents the weather conditions in San Francisco, Calif. The fourth weather video panel ( 408 ) represents the weather conditions in New York City, N.Y.
[0042] As shown in FIG. 4A , each weather video panel displays a portion of a landscape. The landscape is animated to show a video element (grass) moved by blowing wind. The landscape, as shown in the first weather video panel ( 402 ) and second weather video panel ( 404 ), is clear. The landscape, as shown in the third weather video panel ( 406 ), is rainy. The landscape, as shown in the fourth weather video panel ( 408 ), is cloudy.
[0043] FIG. 4B shows the addition of a fifth weather video panel ( 410 ) representing the weather conditions in Tokyo, Japan. Each of the weather video panels is displaying sync frame (more specifically, a portion of the sync frame). The video elements (such as the grass) are synchronized. FIG. 4C shows a successive frame of the animation.
[0044] Tile Bleeding
[0045] In one or more embodiments of the invention, the weather application client ( 110 in FIG. 1 ) is configured to present weather data in an animation using a tile bleeding effect. The effect may be used to create the illusion of a spreading weather condition over a geographic region.
[0046] FIGS. 5A-5E show a presentation mechanism in accordance with one or more embodiments of the invention. Specifically, FIGS. 5A-5E show a sequence of presentations on a display ( 500 ) that includes two virtual tiles (virtual tile A ( 502 A), virtual tile B ( 502 B)). FIG. 5A shows virtual tile A ( 502 A) presenting image bleeding A ( 504 A). A point along the contiguous region between virtual tile A ( 502 A) and virtual tile B ( 502 B) has been designated the edge location ( 506 ).
[0047] In one or more embodiments of the invention, a virtual tile (virtual tile A ( 502 A), virtual tile B ( 502 B)) is a portion of the display that initially shows no image. The images to be displayed in each virtual tile (virtual tile A ( 502 A), virtual tile B ( 502 B)) are “bled” in. Said another way, only a portion of the image is initially displayed, and that portion becomes larger until it fills the virtual tile (virtual tile A ( 502 A), virtual tile B ( 502 B)). In one embodiment of the invention, the portion of the image grows larger in a manner resembling liquid spreading to cover a surface.
[0048] In one or more embodiments of the invention, the point at which image bleeding A ( 504 A) is initiated is selected at random between a set numbers of non-edge points within virtual tile A ( 502 A). In one embodiment of the invention, edge location ( 506 ) is selected at random between a set number of points along the shared edge between virtual tile A ( 502 A) and virtual tile B ( 502 B). Alternatively, in one embodiment of the invention, edge location ( 506 ) is selected based on the closest point on the edge of virtual tile A ( 504 A) to the point at which image bleeding A ( 504 A) is initiated.
[0049] FIG. 5B shows the display ( 500 ) after some pre-determined period of time. As shown in FIG. 5B , image bleeding A ( 504 A) has grown larger. The growth of image bleeding A ( 504 A) is at a rate such that the image bleeding A ( 504 A) will reach the edge location ( 506 ) at some future time target. FIG. 5B also shows that image bleeding B ( 504 B) has been initiated.
[0050] FIG. 5C shows the display ( 500 ) after an additional period of time. As shown in FIG. 5C , image bleeding A ( 504 A) has continued to grow larger at the same rate. Image bleeding B ( 504 B) has been initiated to grow larger at a different rate. Specifically, image bleeding B ( 504 B) has been initiated to grow at a rate such that image bleeding B ( 504 B) will reach edge location ( 506 ) at or near the future time target (the time at which image bleeding A ( 504 A) will reach edge location ( 506 )). As shown in FIG. 5C , image bleeding B ( 504 B) is growing at a faster rate then image bleeding A ( 504 A), and therefore has grown larger than image bleeding A ( 504 A).
[0051] FIG. 5D shows the display ( 500 ) after an additional period of time. As shown in FIG. 5C , both image bleeding A ( 504 A) and image bleeding B ( 504 B) have grown larger, but at different rates. FIG. 5E shows the display ( 500 ) at the future time target. As shown in FIG. 5E , both image bleeding A ( 504 A) and image bleeding B ( 504 B) have reached edge location ( 506 ). The image to be displayed on virtual title A ( 502 A) occupies approximately 25% of virtual tile A ( 502 A), and the image to be displayed on virtual title B ( 502 B) occupies approximately 60% of virtual tile B ( 502 B). Both image bleeding A ( 504 A) and image bleeding B ( 504 B) may continue to grow at their individual rates until the image fills each respective tile.
[0052] FIG. 6 shows a flowchart for bleeding an image onto a virtual tile in accordance with one or more embodiments of the invention. While the various steps in these flowcharts are presented and described sequentially, one of ordinary skill will appreciate that some or all of the steps may be executed in different orders, may be combined or omitted, and some or all of the steps may be executed in parallel.
[0053] In Step 610 , instruction is received to present an image on a display. In Step 612 , the weather application client generates virtual tiles using the image. In one embodiment of the invention, the virtual tiles are rectangular. However, one skilled in the art will appreciate that the virtual tiles may be generated as a shape with any number of sides or a combination of different shapes. In one embodiment of the invention, the division between virtual tiles on the display is not visible.
[0054] In Step 614 , the weather application client initiates a first image bleeding from a non-edge location on one of the virtual tiles. In Step 616 , the weather application client determines a future time target at which the first image bleeding will reach an edge location. In Step 618 , the weather application client initiates a second image bleeding from a non-edge location on another virtual tile using the future time target. Specifically, the second image bleeding is initiated such that the second image bleeding will reach the edge location at or near the future time target.
[0055] FIGS. 7A-7E show an example in accordance with one or more embodiments of the invention. Specifically, FIGS. 7A-7E show a temperature map image (image bleeding) being bled on top of a map of the southern United States. FIG. 7A shows the image bleedings (the lighter irregular shapes) (e.g., ( 702 ), ( 704 ), ( 706 )) at a point in time just after initialization. FIG. 7B shows the same display at some later point in time. As shown in FIG. 7B , the image bleedings (e.g., ( 702 ), ( 704 ), ( 706 )) have grown larger.
[0056] FIG. 7C shows the same display at some later point in time. As shown in FIG. 7C , the individual image bleedings (e.g., ( 702 ), ( 704 ), ( 706 )) on each tile have grown to cover the majority of each tile. FIG. 7D shows the same display at some later point in time. As shown in FIG. 7D , the individual image bleedings (e.g., ( 702 ), ( 704 ), ( 706 )) have begun to reach the edge locations between the tiles. Finally, as shown in FIG. 7E , the image bleedings (e.g., ( 702 ), ( 704 ), ( 706 )) have completely encompassed each tile.
[0057] Context-based Weather Reports
[0058] In one or more embodiments of the invention, the weather application client ( 110 in FIG. 1 ) is configured to present weather data based on a context. A context may include the location of a weather application client system and/or recent historical weather data. In one embodiment of the invention, a context-based weather report is a presentation of weather data that focuses on unusual or unexpected weather events (such as rain during a dry season, or a sunny day during a rainy season).
[0059] FIG. 8 shows a flowchart for generating a context-based weather report in accordance with one or more embodiments of the invention. While the various steps in these flowcharts are presented and described sequentially, one of ordinary skill will appreciate that some or all of the steps may be executed in different orders, may be combined or omitted, and some or all of the steps may be executed in parallel.
[0060] In Step 810 , the weather application client determines the current location for the device using the device location module. In one embodiment of the invention, the weather application client also obtains the current date and current time from the weather application client system. In one embodiment of the invention, the current location may be obtained by alternative means (e.g., based on user search, directly inputted by a user, etc.). In Step 812 , the weather application client obtains an unfiltered weather report for the current time using the current device location. In one embodiment of the invention, an unfiltered weather report includes weather data for the current location of the device. In one embodiment of the invention, the current location of the device is obtained from a device location module on the weather application client system.
[0061] In Step 814 , the weather application client obtains the historical weather data for the device's historical location and time. In one embodiment of the invention, the historical weather data is obtained from one or more weather data server systems via the weather application server system. In one embodiment of the invention, the device location module maintains historical location data about where the device has been over a period of time. For example, if the weather application client system has remained in the same geographic location during the recent past, then the current location of the device will be similar to the historical location data. However, if the user is traveling, then the current location of the device may differ from the historical location data.
[0062] In Step 816 , the weather application client determines the expected weather condition from historical weather data. In one embodiment of the invention, the weather application client uses the historical weather data to determine the weather condition commonly associated with a time period and location. The expected weather condition may be determined using annual condition and temperature averages for the current day, week, or month. For example, the expected weather condition for December 10 th in Houston, Tex. may be foggy and 60 degrees.
[0063] In Step 818 , the weather application client generates a context-based weather report for the time period by filtering out the expected weather condition from the unfiltered weather report. In one embodiment of the invention, the weather application client filters out the expected weather condition from the unfiltered weather report to determine if the current weather data varies from the historical expectation. For example, if the current weather forecast for December 10 th for Houston, Tex. is clear and 60 degrees, the context-based weather report would indicate that December 10 th will be clear (because 60 degrees is an expected weather condition and that data (60 degrees) was therefore filtered out and not shown).
[0064] Weather Report Discrepancies
[0065] In one or more embodiments of the invention, the weather application client ( 110 in FIG. 1 ) is configured to present weather data based on discrepancies between weather reports.
[0066] FIG. 9 shows a flowchart for determining weather report discrepancies in accordance with one or more embodiments of the invention. While the various steps in these flowcharts are presented and described sequentially, one of ordinary skill will appreciate that some or all of the steps may be executed in different orders, may be combined or omitted, and some or all of the steps may be executed in parallel.
[0067] In Step 910 , the weather application client obtains first weather data from a first weather data server. In Step 912 , the weather application client obtains second weather data from a second weather data server. In Step 914 , the weather application client compares the first weather data and the second weather data to obtain a weather data discrepancy. In Step 916 , a determination is made as to whether the weather data discrepancy is within a (pre-defined) tolerance level. In one embodiment of the invention, the tolerance level is a number of units between two weather metrics (e.g., 3 degrees between two temperature measurements, 5 percentage points between two humidity measurements or the chance of precipitation, etc.). In one embodiment of the invention, the tolerance level is a comparison of weather conditions. For example, a reported weather condition of “cloudy” and another reported weather condition of “partly cloudy” may be considered to be within tolerance levels. Whereas a reported weather condition of “cloudy” and another reported weather condition of “sunny” may be considered outside tolerance levels.
[0068] If in Step 916 , the weather application client determines that the weather data discrepancy is outside the tolerance level, then in Step 918 , an alert is sent to the user (be it the weather service or the user of mobile device) that contains the weather data discrepancy. If in Step 916 the weather application client determines that no weather data discrepancy exists or that the weather data discrepancy is within the tolerance level, then in Step 920 , the weather application client sleeps.
[0069] Embodiments of the invention may be implemented on virtually any type of computer regardless of the platform being used. For example, as shown in FIG. 10 , a computer system ( 1000 ) includes one or more computer processors ( 1002 ) such as a central processing unit (CPU) or other hardware processor(s), associated memory ( 1004 ) (e.g., random access memory (RAM), cache memory, flash memory, etc.), a storage device ( 1006 ) (e.g., a hard disk, an optical drive such as a compact disk drive or digital video disk (DVD) drive, a flash memory stick, etc.), and numerous other elements and functionalities typical of today's computers (not shown). In one or more embodiments of the invention, the processor ( 1002 ) is hardware. For example, the processor may be an integrated circuit. The computer system ( 1000 ) may also include input means, such as a keyboard ( 1008 ), a mouse ( 1010 ), or a microphone (not shown). Further, the computer system ( 1000 ) may include output means, such as a monitor ( 1012 ) (e.g., a liquid crystal display (LCD), a plasma display, or cathode ray tube (CRT) monitor). The computer system ( 1000 ) may be connected to a network ( 1014 ) (e.g., a local area network (LAN), a wide area network (WAN) such as the Internet, or any other type of network) via a network interface connection (not shown). Those skilled in the art will appreciate that many different types of computer systems exist, and the aforementioned input and output means may take other forms. Generally speaking, the computer system ( 1000 ) includes at least the minimal processing, input, and/or output means necessary to practice embodiments of the invention.
[0070] Further, those skilled in the art will appreciate that one or more elements of the aforementioned computer system ( 1000 ) may be located at a remote location and connected to the other elements over a network. Further, embodiments of the invention may be implemented on a distributed system having a plurality of nodes, where each portion of the invention may be located on a different node within the distributed system. In one embodiment of the invention, the node corresponds to a computer system. Alternatively, the node may correspond to a processor with associated physical memory. The node may alternatively correspond to a processor or micro-core of a processor with shared memory and/or resources. Further, software instructions in the form of computer readable program code to perform embodiments of the invention may be stored, temporarily or permanently, on a non-transitory computer readable storage medium, such as a compact disc (CD), a diskette, a tape, memory, or any other computer readable storage device.
[0071] While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims. | In general, in one aspect, the invention relates to a method for presenting weather data. The method includes displaying a first weather video panel comprising a first video element and a second weather video panel comprising a second video element, where the first video element and the second video element are synchronized, and receiving an instruction to add a third weather video panel. The method further includes, in response to receiving the instruction to add a third weather video panel, displaying the third weather video panel comprising a third video element, and restarting the first weather video panel and the second weather video panel, where after the restarting, the first video element, the second video element, and the third video element are synchronized. | 7 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of The Invention
[0002] The present invention relates to a method of using an optical apparatus for drug development and evaluation. More specifically, the present invention provides a convenient and cost effective method to evaluate the action of a drug at the cellular level, including its uptake, distribution, binding characteristics, etc.
[0003] 2. Background Information
[0004] The determination of drug action at the cellular level is a problem of great importance to drug evaluation and development. Recently, the implementation of rational drug design, combinatorial chemistry techniques, and high throughput screening have led to large numbers of new potential drugs. However, currently there is no cost effective way to understand the details of how these potential drugs work at the cellular level. This lack of methodology requires pharmaceutical companies to spend millions of dollars in animal and clinical studies to evaluate a candidate drug.
[0005] The most direct way of evaluating a drug, however, is its actions at the cellular level. For example, the efficacy of a drug is generally determined by the following drug-cell interactions: (1) cellular distribution of the drug, (2) cellular uptake of the drug, (3) binding characteristics of the drug, and (4) biochemical pathways of the drug.
[0006] Another major obstacle of drug efficacy is the resistance of some cells to a drug. The underlying molecular and cellular mechanisms of this resistance are not totally understood. However, a number of mechanisms appear to contribute to the resistance: (1) increased efficiency of DNA repair mechanism after the DNA has been damaged by the drug, (2) decreased cellular uptake or increased efflux of drugs, (3) increased levels of “target” enzymes or alterations in “target” enzymes, (4) decreased drug efficacy because of increased drug breakdown, and (5) alternative biochemical pathways.
[0007] In addition to the efficacy of the drug, the safety of a drug must also be evaluated at the cellular level. For example, to identify if a drug has a low toxicity to normal cells but high toxicity to tumor cells generally requires an understanding of the unique biochemical differences between normal and abnormal cells.
[0008] Using methods in molecular biology to study drug actions at the cellular level is difficult if only conventional optical microscopes are used. This is because biomolecules are generally transparent in visible light and are therefore indistinguishable under optical microscopes. A molecularly selective imaging microscope (sometimes called a chemical imaging microscope) is needed to differentiate between molecular targets.
[0009] Laser scanning fluorescent microscopy, as a chemical imaging technique, has been routinely used for in vitro sample analysis for many years. Molecular imaging is acquired by choosing a stain or fluorescing agent that selectively, chemically or physically, bonds to specific regions of the sample. Quantitative measurements of intensity in fluorescence can provide images that illustrate the distribution of fluorescent markers in cells. The distribution of these markers determines the distribution of specific antibodies, ligand affinities, or covalent bonds that are tagged by the markers. However, the fluorescent approach has several disadvantages and limitations: (1) the sample preparation procedure is complicated and time consuming, (2) the fluorescent markers used in the specimen may cause undesireable pharmacological or toxicological effects, (3) suitable markers are not available for all biomolecules, (4) the fundamental problems of fluorophore photon bleaching during measurement severely limit the use of fluorescence microscopy, and (5) the relatively short wavelength used in fluorescence microscopy can easily cause photo-damage to the specimen.
[0010] Infrared microscopy is another chemical imaging technique that can provide molecular-specific images. An image of a sample is obtained by imaging the transmitted infrared radiation. Molecular selectivity is obtained by tuning the wavelength to a vibrational energy level of a selected molecular type in the sample. Since infrared imaging is derived from a material's intrinsic vibrational energy level, no external markers, dyes, or labels are required to contract the infrared image. However the spatial resolution of the image is usually several times the wavelength of infrared radiation. This is usually 10-20 μm, which is too large to resolve structures at the cellular level. In addition, many samples of biological interest are opaque in the infrared due to the presence of water since vibrational modes with a high change of dipole moment have a large infrared sensitivity. Consequently, it is often difficult, and sometimes impossible to obtain images of many molecular groups of interest by infrared microscopy.
[0011] Raman spectroscopy, in contrast to infrared techniques, is a technique for determining the vibrational modes of a molecule that is based on the scattering of a photon from the molecule. The Raman spectrum, formed by a plurality of scattered frequencies shifted from the illumination wavelength, has a long history of being used to distinguish different molecules. The Raman spectrum of a particular substance depends on the structure (vibrational states and chemical bonds) of the molecules. Therefore, a Raman spectrum can uniquely identify a particular type of molecule by its unique combination of scattered frequencies (also referred to as Raman peaks or Raman modes).
[0012] Raman images, acquired at selected Raman modes using a tunable filter, can provide an overview of the spacial arrangement of a particular type of molecule within a heterogenous specimen. Like infrared imaging, Raman imaging requires no external markers, dyes, or labels as required in fluorescent imaging. However, Raman scattering is superior to infrared absorption or transmission measurements of biological systems in that water has little effect on the Raman spectrum and, therefore, interference by water in Raman are negligible compared to infrared imaging. This is expected since the sensitivity of the vibrational mode in the Raman spectrum is related to the change in polarizability of the vibration, rather than a high change in dipole moment which is characteristic of infrared.
[0013] In addition, near-infrared excitation of biological systems has a number of advantages in Raman imaging. With this excitation source, Raman imaging produces less laser-induced fluorescence and photo-thermal degradation, and allows better perspective depth into a living cell.
[0014] Unfortunately, the signal for a Raman spectrum is inherently weak compared to the strength of the fluorescent signals, and therefore, can be difficult to detect. Consequently, Raman spectroscopy, especially Raman imaging, was not practical until the recent development of a number of new signal generation, processing and detection tools. Some examples are robust laser sources, holographic filters, and low-noise CCD (charge-coupled device) cameras. In addition, various Raman imaging techniques are being developed to enhance the Raman signal, for example, surface enhanced Raman imaging and coherent anti-stroke Raman imaging. The first commercial Raman imaging microscope became available in the early 1990s. Recently the Raman microscope has achieved resolution of 0.5 μm, and it is now feasible to obtain chemical imaging at the cellular level.
[0015] The present invention demonstrates that Raman imaging microscopy can be applied to the study of drug actions in a single cell. Specifically, the invention describes the methods of using Raman imaging microscopy to detect drug uptake, distribution, binding and metabolism in a single cell, and to study drug pharmacokinetics at the cellular level. Even though this application speaks to more conventional Raman imaging techniques, various enhanced Raman imaging techniques can be applied as well, including but not limited to, surface enhanced Raman imaging and anti- Stroke Raman imaging.
SUMMARY OF THE INVENTION
[0016] It is a primary object of the present invention to provide a method of using Raman imaging to estimate the cellular distribution of a drug.
[0017] Another objective of the present invention is to provide a method of using Raman imaging to detect the drug uptake within a cell.
[0018] Still another objective of the present invention is to provide a method of using Raman imaging to study the local binding and biochemical pathway of a drug.
[0019] Yet another objective of the present invention is to provide a method of using Raman imaging to study the cell resistance to a drug.
[0020] Another objective of the present invention is to provide a method of using Raman imaging to study drug pharmokinetics.
[0021] It is still another objective of the present invention to provide a method of using Raman imaging to study drug metabolism.
[0022] It is yet another objective of the present invention to provide a method which utilizes a petri dish coated with gold or other Raman inactive materials for Raman imaging of cells.
[0023] Still another objective of the present invention is to provide a numerical model for a Raman image that describes the physics of the imaging process and the degradation caused by a microscopic system.
[0024] Another objective of the present invention is to provide a method of Raman image restoration.
[0025] It is yet another objective of the present invention to provide a method of using ratio Raman imaging to indicate the drug action in a cell.
[0026] Still another objective of the present invention is to provide a method of using ratio Raman imaging to quantify local drug concentration.
[0027] Another objective of the present invention is to provide a convenient and cost effective method to evaluate the efficacy of drugs at the cellular level.
BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 is a Raman spectrum of the anti-cancer drug taxol.
[0029] FIG. 2 is a Raman spectrum of cytoplasm in a MDA435 breast tumor cell.
[0030] FIG. 3 is a Raman spectrum of the nucleus in a MDA435 breast tumor cell.
[0031] FIG. 4 is a drug delivery system for Raman imaging.
[0032] FIG. 5 is a Ratio Raman image (b) that illustrates the drug distribution (bright areas) within a breast tumor cell after treatment with 0.3 mg/ml taxol.
[0033] FIG. 6 is a Ratio Raman image (b) that illustrates there is no drug distribution within a breast tumor cell after treatment with 0.3 mg/ml diluent-only solution.
[0034] FIG. 7 illustrates Ratio Raman images (b-g) that show drug distribution at different depths of a breast tumor cell after treatment with 0.3 mg/ml taxol.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0035] FIGS. 1-7 represent the results obtained using Raman imaging microscopy in the study of interactions between the anticancer drug taxol and MDA435 breast cancer cells. While the present description speaks to this preferred embodiment, this technique could be used in the study of the interactions of any type of drug in any type of cell.
[0036] Raman imaging of the cell-drug interactions consists of several steps. First, the Raman spectrum of the drug is measured. From the Raman spectrum, the locations and relative intensities of the Raman peaks (or Raman modes) is determined. The combination of the multiple Raman peaks and their relative intensities provides a unique fingerprint of the drug. In the preferred embodiment, the Raman spectrum of the anticancer drug taxol was measured as illustrated in FIG. 1 . From the spectrum the most significant Raman mode is 1002 cm −1 .
[0037] Next, a Raman spectrum is obtained for the cells to determine their fingerprint and in order to ultimately distinguish the drug location from the cellular background. From the Raman spectrum of the cells, the locations and relative intensities of the Raman peaks is determined. These Raman peaks, however, may indicate Raman modes of different constituents of the cells.
[0038] In the preferred embodiment the Raman signal of a breast tumor cell was studied and the Raman spectrum was measured. The tumor cell was cultured in a gold-coated (gold is a Raman inactive material) petri dish in order to prevent Raman signals coming from the petri dish during the measurement. The laser beam was focused in the cell cytoplasm and nucleus areas to determine if there was any difference in their spectra. Each measurement was 120 seconds long. FIGS. 2 and 3 illustrate the Raman spectra of the cytoplasm and nucleus of the breast tumor cell, respectively. The spectra are actually the combination of Raman signals from different cell constituents.
[0039] Subsequently, the cells are cultured in a petri dish coated with gold or other Raman inactive materials and allowed to adhere to the bottom of the petri dish. Raman images are acquired from a cell in phosphate buffered salt (PBS) at the Raman modes of the drug or at the cell constituent. The Raman modes are again determined. These obtained Raman images act as control images of the cell.
[0040] In the preferred embodiment approximately 500,000 breast cancer cells (MDA435) were plated on a gold-coated petri dish and allowed to stabilize for 24 hours prior to imaging. At Raman mode of 1002 cm −1 , direct Raman images (control images) were obtained from a cell in PBS solution.
[0041] Next, using the drug delivery system of FIG. 4 , the PBS is replaced with the drug solution. The imaging position is maintained during this procedure. The cells are then exposed for a specific period of time. The drug solution is then withdrawn and the cells are reintroduced into the PBS solution. Raman images are again acquired at the same locations of the cell and at the Raman modes of the drug or the cell constituent. The obtained Raman images serve as post-treatment images of the cell.
[0042] In the preferred embodiment, using the drug delivery system illustrated in FIG. 4 , 0.3 mg/ml taxol solution was carefully introduced into the petri dish to replace the PBS solution. After exposure to the taxol solution for one hour, the cells were reintroduced into the PBS solution. During the procedure of solution exchange, the imaging locations were kept unchanged. Raman images (post-treatment images) were taken again at the same locations and same Raman modes of the drug.
[0043] The acquired Raman images are then processed by smoothing noises, de-blurring, and removing the intensity contributed from the fluorescence. The processed post-treatment images were divided by the corresponding processed control images to create a ratio of images. The ratio of images indicate the changes of the cell after the drug treatment. With this procedure it is possible to obtain a stack of Raman images at various times and hence different depths of a cell separately. A three dimensional Raman image can be obtained by constructing the stack of two dimensional images.
[0044] If Raman images are taken at Raman modes of the drug, the ratio images indicate the drug accumulation and distribution within the cell. The relative drug uptake can be estimated from the intensity of the bright areas in the ratio images. Raman images taken at several Raman modes of a drug can be used to confirm the drug distribution. If Raman images are recorded for different cells, the ratio images indicate the drug distributions and uptakes for these cells, respectively. These images show the sensitivity of different cells to the drug. In general, the ratio images of drug sensitive cells have relatively high intensity or large bright areas compared to drug resistant cells.
[0045] If Raman images are obtained in the following cases: (1) a series of Raman images are taken at certain time intervals after cell exposure to a drug, (2) a series of Raman images are taken for the same type of cells treated with the same drug but with different exposure time, or (3) a series of Raman images are taken for the same type of cells treated with the same drug but with different concentration, the ratio images, indicating the changes of drug uptake and distribution along time and concentration, can be used to study the pharmokinetics of the drug.
[0046] If Raman images are taken at Raman modes of a specific cell constituent, the ratio images indicate the change in abundance of the constituent. This change will suggest the drug binding characteristics. The biochemical or metabolic pathway of the drug can also be derived from the information cell constituent changes.
Raman Image Processing
[0047] A difficulty with Raman imaging processing is that the recorded Raman images (both control and post-treatment images) suffer the following problems which make it difficult to identify the drug locations: (1) severe noise, (2) blurring by the microscope system, (3) non-uniform illumination effects caused by the laser system, and (4) mixed with fluorescent contribution.
[0048] In order to restore the degraded Raman images, a Raman image model was established based on the physics of Raman scattering as well as the Raman imaging system. The model is described in the following paragraphs.
[0049] Let us assume a laser beam illuminates a point at location (x,y) with an intensity of i(x,y) photons per second. The Raman scattering coefficient for the heterogeneous area is K(x,y). The fluorescent background is K 0 (x,y). Then the Raman signal s(x,y) can be modeled as:
S ( x,y )=( K ( x,y )+ K 0 ( x,y ))· i ( x,y )· t,
where t is the exposure time. Usually the intensity of the illumination i(x,y) is dependent on the location of x and y. This hetereogeneity of the illumination causes the non-uniform illumination effect on the recorded images.
[0050] If we assume the images formation system is a linear and time invariant system with a point spread function (PSF) h(x,y), then the recorded image g(x,y) can be represented as:
g ( x,y )= h ( x,y )* s ( x,y )+ n ( x,y )
where n(x,y) is the additive noise during image recording and * is the linear convolution operator. The Raman signal s(x,y) was blurred by the PSF of the microscopic system because of the limited resolution and further degraded by the additive noise.
[0051] The purpose of the Raman image processing is to determine the Raman scattering coefficient K(x,y) of the imaging area from the recorded image g(x,y). In order to determine K(x,y), we (1) reduced the noise n(x,y) from the image g(x,y), (2) compensated for the point-spread function h(x,y), and (3) eliminated the non-uniform illumination i(x,y) and subtracted the fluorescent background K 0 (x,y) from the image.
[0052] Before developing Raman imaging processing algorithms, the following tasks were completed. First, the PSF of the Raman microscopic system was estimated by measuring the Raman image of an edge target. From the estimated PSF, the resolution of the microscopic system is about 0.7 μm. Second, the noise model was established by measuring Raman images of a uniform surface. The additive noise is signal-dependent, Gaussian, and white. And third, synthetic Raman images were generated based on the model.
[0053] Using the synthetic images, an anistropic diffusion filter was developed which effectively reduced the signal dependent Gaussian noise without blurring the edges of the Raman signals. After noise smoothing, a Wiener filter was developed using the estimated PSF. The Wiener filter de-blurred the Raman images and restored the Raman signal s(x,y) from the recorded image g(x,y).
[0054] The restored Raman signal still contained the non-uniform illumination effect and fluorescent contribution, illustrated as follows:
s ( x,y )= K ( x,y )· i ( x,y )· t+K 0 ( x,y )· i ( x,y )· t.
From the Raman spectra illustrated in FIGS. 1-3 , Raman peaks are riding on a broadband baseline that is contributed from the fluorescence. For Raman images, the equivalent fluorescent baseline is the background intensity K 0 (x,y)·i(x,y)·t. The fluorescent background in the post-treatment Raman image usually had lower intensity than the fluorescent background in the control Raman image due to the accumulation of fluorescent bleaching. This often caused the total intensity in post-treatment image to be lower than that of the control image, which makes comparison of the two images meaningless (since we assume the drug areas in the post-treatment image should have higher Raman energy or be brighter than that in the control image). If the minimum value of the Raman image is subtracted from every point on the image, most parts of the fluorescent background are eliminated (assume most of the fluorescent background is contributed by water, which is fully distributed in a cell and surrounding solution). After the subtraction, the control Raman image and post-treatment Raman image of the cell become:
s ( x,y )= K ( x,y )· i ( x,y )· t , and s ′( x,y )= K ′( x,y )· i ( x,y )· t,
respectively. Taking the ratio of the two images s(x,y) and s′(x,y) produces the ratio image
s ′ ( x , y ) s ( x , y )
which cancels out the non-uniform illumination.
s ′ ( x , y ) s ( x , y ) K ′ ( x , y ) K ( x , y )
The ratio image indicates the concentration change of the target molecules in the cell after drug treatment. In this case the target molecule is taxol. Taxol is believed to be located in the areas where s′(x,y)/s(x,y) is greater than 1.
Results And Discussion
[0055] The ratio image in FIG. 5 ( b ) illustrates that the taxol is located on the top (left corner and right corner) of the image. The closer to the membrane, the higher the taxol concentration. This indicates that taxol entered the tumor cell from the top membrane and gradually penetrated into the center of the cell. More drugs entered the top-left membrane than the top-right membrane. The breast tumor cell was exposed to 0.3 mg/ml taxol solution for one hour in this experiment.
[0056] FIG. 6 illustrates the Raman image of a cell treated with taxol-diluent-only solution. The solution was prepared the same as the taxol solution, but without taxol. The cell was exposed to the diluent for one hour, the same period of time as the experiment with the taxol solution. FIG. 6 ( b ) indicates there is no drug distribution in the cell (one bright spot on the image is most likely the noise).
[0057] FIG. 7 illustrates a stack of Raman images at different depths of a breast tumor cell. The tumor cell was also treated with 0.3 mg/ml taxol solution for one hour. The drugs entered the cell from various locations at different layers: some from the top, some from the left, and some from the bottom. More drug entered the cell from the middle layer (Z=6 μm) (The height of the cell is about 10 to 12 μm). From this set of 2-D images, a 3-D drug distribution image can be constructed for the cell. The volume, concentration, and the relative uptake of the drug can be estimated.
Instrumentation
[0058] For the study, a Renishaw Model 2000 Raman microscopic system (Gloucestershire, UK, 1993) was used. This system is capable of taking Raman spectra, scanning dot-by-dot Raman images, and performing fast direct Raman imaging with an expanded laser beam. A 30-mw diode laser at 780 nm was used as the excitation source. The system can achieve the spectral resolution of 1cm −1 for spectral measurement. For direct imaging, the tunable filter has a bandwidth of 10-20 cm −1 .
[0059] The Raman system was put in a dark room to eliminate ambient light during imaging and also to provide better isolation from noise and dust. In addition, the system was stabilized on a vibration-controlled table—the Vibraplane Air Suspension System (Kinetic System, Inc., Boston, U.S.A.). This setup provides an ideal imaging environment.
[0060] A 60x Olympus water immersion, high infrared (IR) transmission objective (1-UM571 LUMPLFL 60x W/IR, Olympus, Japan) was used to obtain living cells cultured in aqueous solution. This lens is specially designed for the use of near infrared wavelengths. The transmission coefficient of the lens at 780 nm excitation wavelength is 71%.
[0061] This lens has a numerical aperture (NA) of 0.90. The calculated diffraction-limited resolution of the lens is about 0.53 μm. By considering the magnification of the microscope and the pixel size of the CCD camera, the microscope system can achieve spatial resolution of 0.7 μm.
[0062] This lens has a depth of field (DOF) of 1.2 μm. DOF is the depth through which the objective can be focused without any appreciable change in the sharpness of the image. In other words, all the features within the DOF will be sharply in focus in the recorded image. From this parameter we also understand that the axial resolution of the microscope is about 1.5-2 μm.
[0063] Although the invention has been described with reference to specific embodiments, this description is not meant to be construed in a limited sense. Various modifications of the disclosed embodiments, as well as alternative embodiments of the inventions will become apparent to persons skilled in the art upon the reference to the description of the invention. It is, therefore, contemplated that the appended claims will cover such modifications that fall within the scope of the invention. | A method of using Raman imaging microscopy to evaluate drug actions in living cells is disclosed. Specifically the invention describes the methods of using Raman imaging microscopy to detect drug uptake, distribution, binding, and metabolism in a single cell, and to study drug pharmacokinetics at the cellular level. The method involves measuring the Raman image of both the drug and the cell. Control images and post-treatment images of the cell were studied. Ratio images were calculated and the requisite information was obtained from a study of the intensity of the bright areas in the ratio images. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims domestic priority from commonly owned, copending, U.S. Provisional Patent Application Ser. No. 61/419,322, filed Dec. 3, 2010, the disclosure of which is hereby incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention pertains to azeotropic and azeotrope-like compositions of (Z)-1-chloro-3,3,3-trifluoropropene (cis-1233zd or 1233zd(Z)) and hydrogen fluoride (HF).
BACKGROUND OF THE INVENTION
[0003] In recent years there has been some concern that some long lived fluorocarbons might be contributing, albeit in a small way, to global warming. Consequently, there is a worldwide effort to use fluorine-substituted hydrocarbons which have short atmospheric lifetime and therefore do not persist in the atmosphere. In this regard, (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) having low global warming potential, is being considered as a replacement for some fluorocarbons such as 141b in solvents and as a blowing agent.
[0004] The production of 1223zd(Z) has been the subject of interest to provide an environmentally desirable product for use in blowing agents, refrigerants, cleaning agents, aerosol propellants, heat transfer media, dielectrics, fire extinguishing compositions and power cycle working fluids. It is known in the art to produce fluorocarbons such a 1233zd(Z) by reacting hydrogen fluoride with various hydrochlorocarbon compounds.
[0005] Because many CFCs are known to be ozone-depleting compounds, the use of these compounds has been curtailed in favor of chemicals that are more commercially acceptable. In some cases, alternate CFC compounds have been found to be both effective and more environmentally friendly.
[0006] As one example, 1-chloro-3,3,3-trifluoropropene (1233zd) has been found to have a wide variety of uses, for example as a heat transfer agent, as a foaming agent, and as a solvent, among other uses. See for example, U.S. Pat. No. 7,833,433, entitled “Heat Transfer Methods Using Heat Transfer Compositions Containing Trifluoromonochloro-propene”, U.S. Patent Publication No. 2008-0207788, entitled “Foaming Agents, Foamable Compositions, Foams and Articles Containing Fluorine Substituted Halogens, and Methods of Making the Same”, and U.S. Pat. No. 6,362,383, entitled “Hydro-Fluorination of Chlorinated Hydrocarbons”, which disclose examples of such uses.
[0007] The compound 1233zd may be produced by a number of different methods. See, for example, U.S. Pat. No. 7,829,747, entitled “Process for Dehydrofluorination of 3-chloro-1,1,1,3-tetrafluoropropane to 1-chloro-3,3,3-trifluoropropene”; U.S. Pat. No. 5,710,352, entitled “Vapor Phase Process for Making 1,1,1,3,3-pentafluoropropane and 1-chloro-3,3,3-trifluoropropene,” U.S. Pat. No. 6,111,150, entitled “Method for Producing 1,1,1,3,3-pentafluoropropane,” and U.S. Pat. No. 6,844,475, entitled “Low Temperature Production of 1-chloro-3,3,3-trifluoropropene (HCFC-1233zd)”, which describe several methods for making 1233zd.
[0008] All of the documents cited above are hereby incorporated herein by reference in their entirety.
SUMMARY OF THE INVENTION
[0009] It has now been found that an important intermediate in the production of substantially pure 1233zd(Z), is an azeotrope or azeotrope-like mixture of 1233zd(Z) and hydrogen fluoride (HF). This binary intermediate, once formed, may thereafter be separated into its component parts by extraction or distillation techniques. The compound 1233zd(Z) has a boiling point of about 18° C. and HF has a boiling point of about 20° C. at standard atmospheric pressure. These azeotrope or azeotrope-like compositions find use not only as intermediates in the production of 1233zd(Z), but they are additionally useful as solvents and as compositions for removing surface oxidation from metals.
[0010] In addition, the formation of an azeotropic or azeotrope-like composition of 1233zd(Z) and HF is useful in separating a mixture of 1233zd(Z) and an impurity. When it is desired to separate a mixture of 1233zd(Z) and an impurity, HF is added to form an azeotropic mixture of 1233zd(Z) and HF, and then the impurity is removed from the azeotropic mixture, such as by distillation, scrubbing or other known means.
[0011] One embodiment of the invention provides an azeotropic composition consisting essentially of (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) and hydrogen fluoride (HF).
[0012] Another embodiment of the invention provides an azeotropic or azeotrope-like composition which consists essentially of from about 1 to about 95 weight percent hydrogen fluoride and from about 5 to about 99 weight percent 1233zd(Z) , which composition has a boiling point of about 0° C. to about 60° C. at a pressure of about 3 psia to a pressure of about 73 psia. In certain embodiments the composition consists of hydrogen fluoride and (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)). In certain embodiments, the hydrogen fluoride is present in an amount of from about 5 to about 90 weight percent. In certain embodiments, the hydrogen fluoride in present in an amount of from about 20 to about 35 weight percent. Certain embodiments of the invention have a boiling point of from about 0° C. to about 61° C. at a pressure of from about 3 psia to about 73 psia.
[0013] Another embodiment of the invention provides a method of forming an azeotropic or azeotrope-like composition which consists essentially of blending from about 1 to about 95 weight percent hydrogen fluoride and from about 5 to about 99 weight percent (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)), which composition has a boiling point of from about 0° C. to about 60° C. at a pressure of about 3 psia to about 73 psia. In certain embodiments the composition consists of hydrogen fluoride and (Z)-1-chloro-3,3,3-trifluoro-propene (1233zd(Z)). In certain embodiments, the hydrogen fluoride is present in an amount of from about 5 to about 90 weight percent. In certain embodiments, the hydrogen fluoride in present in an amount of from about 20 to about 35 weight percent. In certain embodiments, the hydrogen fluoride is present in an amount of about 26±3 weight percent. In certain embodiments of the invention the composition has a boiling point of from about 0° C. to about 61° C. at a pressure of from about 3 psia to about 73 psia. In certain embodiments the composition has a boiling point of about 25° C. at a pressure of about 14.7 psia.
[0014] In certain embodiments, 1233zd(Z) can be isolated from the azeotropic like mixture of 1233zd(Z) and HF by extraction of HF. In certain embodiments, the extraction of HF is accomplished using water or other aqueous solution. In certain embodiments, the extraction of HF is accomplished using sulfuric acid. In certain embodiments, the extraction of HF is accomplished by distillation, for example by extractive distillation, or pressure swing distillation.
[0015] The azeotropic and azeotrope-like mixtures of (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) and hydrogen fluoride of the present invention are useful as an intermediate in the production of 1233zd(Z). This purified material is useful as a nontoxic, zero ozone depleting chlorofluorocarbon useful as a solvent, blowing agent, refrigerant, cleaning agent, aerosol propellant, heat transfer medium, dielectric, fire extinguishing composition and power cycle working fluid.
BRIEF DESCRIPTION OF THE DRAWING
[0016] FIG. 1 shows a plot of the vapor pressures of the mixtures formed in Example 1 as measured at 0° C., 25° C., and 60° C.
DETAILED DESCRIPTION OF THE INVENTION
[0017] The binary azeotrope of 1233zd(Z) and HF can be formed as described in the U.S. Pat. No. 7,829,747 where 244fa is dehydrofluorinated to yield 1233zd(Z), HF and other components such as (E)-1-chloro-3,3,3-trifluoropropene, hydrogen chloride, 1,3,3,3-tetrafluoropropene, 1,1,1,3,3-pentafluoropropane. Upon removal of the other compounds the binary azeotrope of 1233zd(Z) and HF remains.
[0018] 1233zd(Z) forms azeotropic and azeotrope-like mixtures with HF. The thermodynamic state of a fluid is defined by its pressure, temperature, liquid composition and vapor composition. For a true azeotropic composition, the liquid composition and vapor phase are essentially equal at a given temperature and pressure range. In practical terms this means that the components cannot be separated during a phase change. For the purpose of this invention, an azeotrope-like composition means that the composition behaves like a true azeotrope in terms of its constant boiling characteristics and tendency not to fractionate upon boiling or evaporation. During boiling or evaporation, the liquid composition changes only slightly, if at all. This is in contrast with non-azeotrope-like compositions in which the liquid and vapor compositions change substantially during evaporation or condensation.
[0019] One way to determine whether a candidate mixture is azeotrope-like within the meaning of this invention is to distill a sample of it under conditions which would be expected to separate the mixture into its separate components. If the mixture is a non-azeotrope or non-azeotrope-like, the mixture will fractionate, i.e., separate into its various components with the lowest boiling component distilling off first, and so on. If the mixture is azeotrope-like, some finite amount of the first distillation cut will be obtained which contains all of the mixture components and which is constant boiling or behaves like a single substance.
[0020] Another characteristic of azeotrope-like compositions is that there is a range of compositions containing the same components in varying proportions which are azeotrope-like. All such compositions are included by the term azeotrope-like as used herein. As an example, it is well known that at different pressures the composition of a given azeotrope will vary at least slightly as does the boiling point of the composition. Thus an azeotrope of two components represents a unique type of relationship but with a variable composition depending on the temperature and/or pressure. As is well known in the art, the boiling point of an azeotrope will vary with pressure.
[0021] As used herein, an azeotrope is a liquid mixture that exhibits a maximum or minimum boiling point relative to the boiling points of surrounding mixture compositions. An azeotrope or an azeotrope-like composition is an admixture of two or more different components which, when in liquid form under a given pressure, will boil at a substantially constant temperature, which temperature may be higher or lower than the boiling temperatures of the components and which will provide a vapor composition essentially identical to the liquid composition undergoing boiling.
[0022] For the purpose of this invention, azeotropic compositions are defined to include azeotrope-like compositions which means, a composition that behaves like an azeotrope, i.e., has constant-boiling characteristics or a tendency not to fractionate upon boiling or evaporation. Thus, the composition of the vapor formed during boiling or evaporation is the same as or substantially the same as the original liquid composition. Hence, during boiling or evaporation, the liquid composition, if it changes at all, changes only to a minimal or negligible extent. This is in contrast with non-azeotrope-like compositions in which during boiling or evaporation, the liquid composition changes to a substantial degree.
[0023] Accordingly, the essential features of an azeotrope or an azeotrope-like composition are that at a given pressure, the boiling point of the liquid composition is fixed and that the composition of the vapor above the boiling composition is essentially that of the boiling liquid composition, i.e., essentially no fractionation of the components of the liquid composition takes place. Both the boiling point and the weight percentages of each component of the azeotropic composition may change when the azeotrope or azeotrope-like liquid composition is subjected to boiling at different pressures. Thus, an azeotrope or an azeotrope-like composition may be defined in terms of the relationship that exists between its components or in terms of the compositional ranges of the components or in terms of exact weight percentages of each component of the composition characterized by a fixed boiling point at a specified pressure.
[0024] The present invention provides a composition which comprises effective amounts of HF and 1233zd(Z) to form an azeotrope or azeotrope-like composition. By effective amount is meant an amount of each component which, when combined with the other component, results in the formation of an azeotrope or azeotrope-like mixture. The inventive compositions preferably are binary azeotropes which consist essentially of combinations of only HF with 1233zd(Z).
[0025] In the preferred embodiment, the inventive composition contains from about 1 to about 95 weight percent HF, preferably from about 5 weight percent to about 90 weight percent HF and most preferably from about 20 weight percent to about 35 weight percent HF. In the preferred embodiment, the inventive composition contains from about 5 to about 99 weight percent 1233zd(Z), preferably from about 10 weight percent to about 95 weight percent and most preferably from about 65 weight percent to about 80 weight percent. The composition of the present invention has a boiling point of about from 0° C. to about 60° C. at a pressure of about from 3 psia to about 73 psia. An azeotropic or azeotrope-like composition having about 26±3 weight percent HF and about 74±3 weight percent 1233zd(Z) has been found to boil at about 25° C. and 14.7 psia. The following non-limiting examples serve to illustrate the invention.
Example 1
[0026] 60 g of 1233zd(Z) were dissolved in 40 g of HF to form a heterogeneous azeotrope mixture. This experiment was conducted at 25° C., and at 14.6 psia.
Example 2
[0027] Binary compositions containing solely 1233zd(Z) and HF are blended to form heterogeneous azeotrope mixtures at different compositions. The vapor pressures of the mixtures were measured at about 0°, 25° and 60° C. and the following results are noticed. Table 1 shows the vapor pressure measurement of 1233zd(Z) and HF as a function of composition of weight percent HF at constant temperatures of about 0°, 25°, and 61° C. The data show that 1233zd(Z) and HF formed a heterogeneous mixture.
[0000]
TABLE 1
Pressure versus composition measurements of 1233zd(Z)
and HF at 0°, 25° and 60° C.
HF
T = 0° C.
T = 25° C.
T = 60° C.
Wt %
Press, psia
Press, psia
Press, psia
0
3.2
8.9
28.5
7.3
9.3
24.6
72.8
13.4
9.7
25.2
72.4
20
9.9
25.5
72.7
26.7
10
25.5
73.4
33.4
10.1
25.5
73.4
56
9.7
24.6
73.2
75.5
9.3
23.8
69.2
92.4
8.2
20.5
58.8
100
6.9
17.8
52.4
[0028] These data also show that the mixture is an azeotrope since the vapor pressure of mixtures of 1233zd(Z) and HF is higher, at all indicated blend proportions, than 1233zd(Z) and HF alone, i.e., as indicated in the first and last rows when HF is 0 wt. % and 1233zd(Z) is at 100 wt. % as well as in the last row where 1233zd(Z) is at 0 wt. % and HF is at 100 wt. %. The data from Table 1 are also shown in graphic form in FIG. 1 .
Example 3
[0029] The azeotropic composition of the 1233zd(Z)/HF mixture is also verified by a Vapor-Liquid-Liquid equilibrium (VLLE) experiment. Here 66.6 g of 1233zd(Z) are dissolved in 33.4 g of HF to form a heterogeneous mixture (visual observation) at 26° C. The vapor composition, upper liquid (HF rich), and bottom liquid (organic) were sampled. The result shows that the azeotropic composition is about 26±3 wt % HF at 26° C.
[0030] As used herein, the singular forms “a”, “an” and “the” include plural unless the context clearly dictates otherwise. Moreover, when an amount, concentration, or other value or parameter is given as either a range, preferred range, or a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. Where a range of numerical values is recited herein, unless otherwise stated, the range is intended to include the endpoints thereof, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values recited when defining a range.
[0031] While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily appreciated by those of ordinary skill in the art that various changes and modifications may be made without departing from the scope of the invention. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives which have been discussed above and all equivalents thereto. | Disclosed are azeotropic and azeotrope-like mixtures of (Z)-1-chloro-3,3,3-trifluoropropene (1233zd(Z)) and hydrogen fluoride. Such compositions are useful as an intermediate in the production of 1233zd(Z). The latter compound is useful as a nontoxic, zero ozone depleting fluorocarbon useful as a solvent, blowing agent, refrigerant, cleaning agent, aerosol propellant, heat transfer medium, dielectric, fire extinguishing composition and power cycle working fluid. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of U.S. Provisional Application No. 60/192,666, filed Mar. 28, 2000.
BACKGROUND OF THE INVENTION
[0002] Cellulose-based films have an extensive history and technology. A common characteristic is that such films are produced by chemical, mechanical or combinations of chemical and mechanical processing of structural plant matter to provide a sheet-like matrix. This matrix contains dispersed or partially disintegrated cell walls and may contain numerous additives to improve processing or end-use function. The most prevalent commercial form is paper and paper related constructs such as cardboard or corrugated cardboard. Other specialized products are well known in the art such as tissue and glassine papers representing the extremes of mechanical processing. Tissues are low bulk density web like entanglements of dispersed plant fibers with low additive content, whereas glassine is a high density fragmented fiber product with substantial additive content. Many modifications of the above constituting commercial forms selected for specific function are known in the art of paper and paper related products.
[0003] Paper products and paper related constructs have been traditionally manufactured from rolled sheet stock. In the paper making process, a dispersed structural plant cell suspension is deposited on a mobile belt or static filtering interface such as a woven screen to provide a fiber entangled mat which is dewatered by mechanical or vacuum assisted expression and subsequent thermal assisted evaporation to provide a continuous or discrete sheet. These products are deliberately calendered or compressed to further enhance physical entanglement. This results in a higher tear modulus, better wet strength and hence less dispersibility, and smooth surfaces for high density roll production. While these properties are desirable for purposes such as packaging applications, they are diametrically opposed to those desired for the application intended in accordance with this invention. That is to say, conventional paper and paper related products are not considered as desired components of comestibles and have low organoleptic acceptance.
[0004] Fine paper products such as glassines and tobacco wrapper products, in contrast to packaging forms of cellulosic films, are produced by evaporative processing only. Typically a dispersed cellulosic phase is cast on a horizontal nonfiltering surface such as a belt and evaporative removal of the volatile continuous phase is effected as the belt moves into an elevated thermal environment. The resulting film is removed from the mobile support as a continuous sheet and collected in rolls for further processing and conversion into discrete forms for the intended use. As with conventional paper products the film/sheet is characterized by high wet strength, low dispersibility and desirably smooth surfaces on both sides. Again, these products have low organoleptic acceptance.
[0005] In contrast to paper related products, numerous film products based on natural polymers such as proteins, gums and starches are organoleptically well tolerated. Additionally, synthetic, water soluble polymers, such as those based on maleic anhydride, polyvinylpyrrolidone and cellulose ethers are also well accepted. However, films derived from water soluble polymers or hydrocolloids suffer from the very property that makes them organoleptically acceptable and easy to make, i.e. they readily disintegrate in the presence of water. With the exception of dried cereal products and powdered mixes, most food products contain substantial water.
[0006] Consequently, an edible film possessing the beneficial particulate structural characteristics of paper, yet displaying the organoleptic quality of water soluble polymer films would be useful in applications for improving processed food products. Such films could serve as lipophilic or hydrophilic barriers within a compartmentalized food construct, as edible wraps or packaging materials, as a texturizing and laminating agent or structural enhancement component. The application opportunities for such films are numerous and diverse. Yet in spite of need and opportunity, such films have not become commercially available. The physical constraints on the products produced by continuous cast film technology which are based on belt systems have limited the application of the resulting products in food systems.
[0007] Drum driers have been used as a means of continuous drying of high solids, viscous products. Water or the continuous solvent phase is removed by evaporative means through heat transferred to the external surface of the drum from steam delivered to the internal cavity of the drum. In contrast to dispersed droplet drying such as spray drying, very high viscosity materials can be processed efficiently. In usual practice the dried product is removed from the drum by a scraper assembly or doctor knife in the form of brittle flakes. Films are not desired as their release is generally a problem and uneven build up on the drum leads to poor control of heat transfer and ultimately unstable drying. Furthermore, all products dried on drum driers are destined to ultimately be recovered in powdered form and a substantially sheetlike released product is difficult to collect and grind. Hence drum driers have historically been used to produce products which are not discharged as flexible film sheets.
SUMMARY OF THE INVENTION
[0008] It has now been found that certain compositions based on cellulosic matter can be continuously cast, dried and released inact, as a continuous, coherent film sheet.
[0009] According to one aspect, the present invention provides a process for continuous casting of film sheets, comprising passing a film-forming fluid through the nip of a pair of side-by-side heated rollers, so as to convert the fluid to a film having opposite coherent surfaces respectively engaging opposite rollers of the pair. The film becomes divided between the opposite surfaces into two distinct, self-supporting, continuous film sheets after exiting the nip of the rollers. Each sheet has one side comprising one of the opposite coherent surfaces and adhering to a surface of one of the rollers, and a second side which is opposite the side adhering to the roller surface. The second side has microscopic protuberances extending from the surface thereof, in contrast to the side facing the roller surface which is relatively smooth. The rollers are heated sufficiently to dry the resulting continuous film sheets, which release intact from the surface of each roller.
[0010] The film sheets thus produced possess sufficient flexibility to form rolls, but have organoleptic quality distinct from existing paper products. The resulting rolled stock is suitable for subsequent processing on specialized converting equipment for production of discrete sheeted forms which can be used to advantage in various comestibles.
[0011] An unexpected feature of the process of this invention is that the film sheets produced thereby possess anisotropic morphologies on the opposite surfaces, as noted above. More specifically, the side of the film sheet contiguous with the drum surface is generally smooth, while the opposite side is highly irregular, with dendritic projections, the dimensions of which approach 25 to 50% of the apparent film thickness. This latter characteristic has important adherent properties in comestible applications.
DETAILED DESCRIPTION OF THE INVENTION
[0012] The prior art related to this invention is largely found in U.S. Pat. No. 5,487,419 which describes a process for preparing dried, rehydratable forms of a mechanically disintegrated cellulose. In this patent two thin film drying methods individually combined with encasement and/or stabilizer additives were described to produce rehydratible products in flake and powder form. Of special interest to the practice of the invention of U.S. Pat. No. 5,487,419 is the double drum drier. While continuous thin film drying, by the nature of the process, produces a contiguous film on the revolving surfaces, such films are difficult to remove as a contiguous sheet, unless they possess paper-like qualities such as a high tear modulus. Such properties are not compatible with the intended applications of the present invention.
[0013] In a typical drum drier application, mechanical intervention in the form of a stationary doctor blade applied to the rotating surface is required for release or removal of the dried product. The dried product preferably possesses brittle, inelastic character which readily flakes from the drying surface. Flexible and elastic films represent a class of dried products which are not indicated for drum driers as they generate delicate, adhering films requiring constant manual scraping to maintain a clean drying surface. This situation produces discontinuous sheet-like segments, as the product must be manually stripped from the drying surface producing a material form that is difficult to handle and grind.
[0014] The method of the present invention, by contrast, enables the production of edible cellulosic films which are released intact from the surface of the drum drier. As can be seen in the accompanying drawing, the process of the present invention is conveniently carried out using a system 10 comprising a pair of side-by-side heated rollers, 12 a , 12 b , as in a conventional double drum drier. An aqueous dispersion 16 of a suitable film-forming fluid, preferably comprising a food grade cellulosic material, is introduced into reservoir 18 , from which it is dispensed for introduction into the nip of rollers 12 a , 12 b . As the fluid traverses the nip of rollers 12 a , 12 b , heat applied at the roller surfaces causes evaporation of the aqueous phase, thus producing a hardenable film having opposite coherent surfaces respectively engaging the opposing roller surfaces. As the film thus produced proceeds through the zone of divergence defined by the rotating roller surfaces at the exit side of the nip, it is divided between the opposing roller surfaces into two distinct, self-supporting, continuous film sheets, each sheet having one side, which comprises one of the opposite coherent surfaces of the originally formed film, that adheres to the surface of one of the rollers, and a second side which is opposite the side adhering to the roller surface. The second side has microscopic protuberances extending from the surface thereof, as previously noted, whereas the one side is relatively smooth. The resulting sheets release intact from their respective roller surfaces and are easily wound onto winder assembly reels 14 a and 14 b as rolled stock.
[0015] The expression “releasing intact”, as used herein in reference to the film produced by the method of the invention, is intended to signify that the film is free of damage of the sort which would render it unfit for its intended use. Insofar as is known, continuous, coherent cast films producing a homogeneous roll by means of a drum drier do not exist in the art. Furthermore, a method of producing cast films with substantially anisotropic morphologies on opposite surfaces is not believed to be known in the art.
[0016] The film-forming fluid is preferably a dispersion of structurally expanded cellulose in a continuous liquid phase and may optionally include a variety of additives, such as are typically included in comestibles. These additives include, without limitation, plasticizers, release agents, tensile strength promoting agents and rehydration agents.
[0017] Among the plasticizers suitable for use in this invention are glycerol, propylene glycol, erythritol, maltitol, sorbitol and polyethylene oxides which are used in amounts sufficient to impart flexibility to the resulting film sheet.
[0018] Representative examples of useful release agents are alkali metal salts of medium and long chain saturated fatty acids.
[0019] Tensile strength promoting agents which may be used in practicing the invention include water soluble oligosaccharides and polysaccharides, water soluble proteins and water soluble cellulose ethers. The same classes of additives may be employed as rehydration agents, if desired.
[0020] The resulting film sheet can be formed into various shapes, e.g. by die-cutting or the like, depending on the intended use. The film sheets may also be perforated, if desired. See, for example U.S. Pat. No. 5,716,658 to Donnelly et al., the entire disclosure of which is incorporated by reference herein.
[0021] The film sheets of the invention can be beneficially incorporated into a variety of comestible substances, and in particular, frozen or parbaked dough pieces, to which the film sheets are readily laminated. For example, the film sheets of the invention are useful as an edible baking substrate for frozen pizza products, as they have sufficient structural stability to resist the deformation of the pizza dough over the rods of an oven rack, which can result in uneven baking.
[0022] The film sheets of the invention are also useful for providing a barrier between components of heterogeneous comestible substances, e.g. to prevent migration of water from one component to another. The film sheets described herein can also be interleaved with sliced cheese foods for ease of separating one slice from the next.
[0023] Composite film sheets can also be produced in accordance with this invention, in which another material, such as a lipid, may be uniformly dispersed throughout the sheet or provided as a distinct coating layer thereon. Suitable lipids for this purpose are monoglycerides, diglycerides and triglycerides of unsaturated and saturated fatty acids having at least five carbons; lecithin; and various waxes including those of insect, animal, vegetable of mineral origin, as well as synthetic waxes such as polyethylene wax.
[0024] The following example section is provided to describe the present invention in further detail. This example section is intended merely to illustrate a specific embodiment of the process of the invention and should in no way be construed as limiting the invention.
EXAMPLE 1
[0025] A cellulosic gel containing 4.9% w/w refined cellulose derived from wheat straw was produced according to the method described in U.S. Pat. No. 5,487,419, the entire disclosure of which is incorporated by reference herein. The formula for the gel is found in Table 1.
TABLE 1 Wheat Straw Cellulose 590 lb. Glycerin 90 lb. Propylene Glycol 60 lb. CMC High Viscosity 80 lb. CMC Low Viscosity 80 lb. Sorbic Acid 2 lb. Water 11190 lb.
[0026] The sodium carboxymethylcellulose (CMC) products employed were obtained from Diachi Chemical Company, Ltd., Japan and are identified as type HP 5HS (high viscosity) and type HP 8A (low viscosity). The company specifications and Code of Federal Regulations (CFR-21) regarding food grade CMC are incorporated by reference. Wheat straw cellulose is a proprietary product manufactured by Watson Foods Company, Incorporated, Connecticut and is a chemically delignified, bleached form of alpha cellulose. Glycerin, propylene glycol and sorbic acid are food grade ingredients complying with chemical and regulatory standards of identity for food use.
[0027] The cellulosic gel was refined over a period of 5 hours to a limiting viscosity of 2000 cps as measured on a 2% w/w aqueous homogenate prepared from the refiner paste with a Brookfield RTV viscometer at 20° C. using a #5 spindle at 50 RPM.
[0028] A reconditioned, chrome-plated double drum drier originally manufactured by the American Drum Drier Company, Michigan with drum dimensions of 11 foot length and 42 inch diameter was employed. The internal drum temperature was 280° F. supplied by 35 psi steam. The gap between the drums was maintained at 0.030 inch. The drum rotation speed was set at 1.2 rpm. The flow to the nip reservoir was maintained at approximately 2.5 gpm to achieve a steady state level. The resulting film spontaneously released and was collected by means of a winder assembly for each drum that was controlled by an electronic tension sensor which regulated the winder motor.
[0029] The film was collected onto a 4 inch diameter core in ten foot long rolls to a width of 24 inches. The apparent moisture content as measured by weight lost at 104° C. for 16 hours was 8.0%. Surprisingly the film while relatively fragile was robust enough to be consistently formed into rolls without tears or rips. To evaluate the degree of irregularity on the distal film surface from the drum, a method was devised to literally shave and calender the microscopic protuberances from the base film. A section of the film was laid flat on a hard, smooth surface. A fresh safety razor blade was positioned perpendicular to the surface and manually drawn across the irregular film surface in a lateral stroke transverse to the plane of the blade several times until it moved smoothly without resistance. The film thickness was then measured with a micrometer in the shaved area and contiguous unshaved areas. Several measurements were averaged. The technique required some practice but once mastered was highly reproducible. The thickness of the above film base was 0.00293 inches and the apparent thickness of the unshaven film was 0.00660 inches +\− 0.00099 inches yielding an approximate dendritic depth to the irregular film surface of 50%. It is believed that the irregular surface is important in providing adherence to semisoft food matrices and could serve as a bilayer containing lipid or lipid-like substances in structured comestibles with laminated features.
[0030] While certain embodiments of the present invention have been described and/or exemplified above, various other embodiments will be apparent to those skilled in the art from the foregoing disclosure. The present invention is, therefore, not limited to the particular embodiments described and exemplified, but is capable of considerable variation and modification without departing from the scope or the appended claims. | Disclosed is a process for continuous casting of edible cellulose-containing film sheets having unique physical characteristics. The cellulose film sheets have diverse applications in the processed food industry. | 2 |
BACKGROUND OF THE INVENTION
Food storage containers, conventionally of an appropriate plastic or synthetic resinous material such as polypropylene, are frequently also used as convenient containers for the heating or reheating of foodstuffs within a microwave oven. However, in order to accommodate the buildup of internal pressures during heating, the seal of the container must be removed or at least partially released. Complete removal of the seal is often not desirable because of potential spillage problems, an exposure of other goods within the oven to fumes emitted from the container stored goods, and the like.
Similarly, a partial opening of the seal, normally by an upward stripping of one section of the frictionally engaged edge flange, is inexact, particularly when dealing with round containers and seals, and could lead to an accidental release of the entire seal as a result of internal pressures.
SUMMARY OF THE INVENTION
The present invention comprises a seal for use with a storage and/or microwave heating container which incorporates a separate covered vent. The vent is selectively openable without disruption of the seal, that is without requiring partial release or removal of the seal.
The vent is integrally formed within the top panel of the seal and so oriented as to provide no projection or raised interruption in the planar upper face of the seal panel. This is of significance in that storage containers of the general type herein involved are conventionally stacked, one upon the other, thereby requiring substantially planar upper and lower stacking faces.
The vent cover, notwithstanding the flush positioning thereof when closed, is easily grasped and opened, even by the infirm or elderly. In addition, to facilitate cleaning, the cover, including the hinge assembly thereof, is removable from and remountable to the seal.
Structurally, the vent assembly is incorporated in the planar top panel of the seal, adjacent the peripheral flanged edge thereof. The vent assembly includes an annular depression in the seal panel inward relative to the outer or top face thereof and surrounding a central vent hole defined at the upper end of a truncated generally conical stem at a height slightly below the outer top face of the seal panel.
The vent cover is generally planar and includes an integral depending sealing plug selectively snap-locked within the vent opening for a sealing thereof. The cover, in the closed sealing position thereof, presents an upper surface substantially coplanar with the outer face of the seal panel, or sufficiently close thereto as to provide a flat stacking face.
The cover is integrally joined, by a living hinge, to an elongate mounting bar having a pair of depending headed lugs which snap-lock into sockets or hollow pedestals formed integral with a portion of the wall of the upwardly directed depression or recess. The cover, so mounted, will, upon manual manipulation, pivotally or hingedly move between open and close positions.
The cover projects beyond the sealing plug sufficient so as to extend slightly beyond the conical stem, the upper end of which defines the vent opening. This projecting portion slightly overlies the recess both forward and to the opposed sides of the cover, relative to the mounting bar. In this manner, and notwithstanding the planar relationship between the cover and the top panel of the seal, the cover can be easily grasped for manual manipulation. Basically, one need merely extend the fingers of one hand in the recess to underlie the projecting periphery of the cover and exert an upward pull thereon for a snap-disengagement. It is contemplated that the upwardly directed recess be such as to accommodate several fingers well below the cover, thus making manipulation of the cover easy for even the infirm. As an example, the finger accommodating portion of the annular recess, which will extend about a major portion of the cover other than for the hinged mounted portion thereof, can have an arcuate cross-section with a radius of approximately 1.085 cm drawn from a midpoint at or slightly below the lip portion of the vent opening. This in turn will result in a recess depth of approximately 1.085 cm, and a transverse recess width, at the upper portion thereof, of approximately 2.17 cm. These dimensions may vary, and are presented as representative to clearly illustrate that the recess is such as to accommodate a substantial tip portion of the manipulation fingers.
Other features and advantages of the invention will become apparent as the details of the invention are more fully hereinafter set forth.
BRIEF DESCRIPTIONS OF THE DRAWINGS
FIG. 1 is a perspective view of a storage container with the vented seal of the invention;
FIG. 2 is a partial top plan view illustrating the vent assembly portion of the seal;
FIG. 3 is an enlarged transverse cross-sectional view taken substantially on a plane passing along line 3--3 in FIG. 1 and illustrating the vent with the cover in its closed position;
FIG. 4 is a partial cross-sectional view similar to FIG. 3 and illustrating the vent open;
FIG. 5 is a bottom partial perspective view of the vent assembly seen from beneath the seal;
FIG. 6 is a top exploded perspective view of the components of the vent assembly; and
FIG. 7 is an enlarged longitudinal cross-sectional view through the vent cover and mount therefor.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring now more specifically to the drawings, FIG. 1 illustrates a storage container 10 with the vented seal 12 of the invention mounted thereon. Both of these units, including the various components of the seal 12 and vent, are of appropriate food-compatible and microwavable plastic or synthetic resinous material, for example high crystalline polypropylene.
The peripheral configuration of the seal 12 will be compatible to the shape of the mouth of the particular bowl 10 to which it is associate. For purposes of illustration, the seal 12 has been illustrated as circular, the bowl 10 being of a rather conventional rounded configuration.
The seal 12, as is generally conventional, includes a container-covering top panel 14 surrounded by an integral mounting flange 16. The panel 14 has an upper or outer face 18 which is preferably planar or substantially planar to allow for a stacking of multiple storage containers, and a similar planar or substantially planar under or inner face 20.
The peripheral mounting flange 16, preferably slightly upwardly offset from the upper face 18 of the panel 14, defines a downwardly directed groove 22 annularly about the seal 12 and adapted to releasably snap-lock to the upper rim of the bowl 10 in an obvious manner.
As the container is specifically intended for use in the heating or reheating of foodstuff in a microwave oven or the like, the seal 12, as a principal feature of the invention, is provided with a vent assembly 24. The vent assembly 24 comprises an upwardly opening annular depression or recess 26 formed in the panel 14 preferably adjacent the peripheral mounting flange 16. The recess is formed entirely below the planar upper or outer face 18 of the panel 14 and, in traverse cross-section, presents a substantially semicircular configuration. This in turn, as noted in FIG. 5, provides a generally toroidal appearance when viewed from the under face of the panel 14.
The annular recess 26 defines a central substantially conical upwardly directed hollow stem 28. The stem terminates in a truncated upper end defining a vent opening or hole 30 which provides for direct communication through the seal panel 14. The upper end of the stem 28, whereat the opening 30 is defined, is offset inwardly or below the plane of the upper face 18 of the panel 14 for reasons to be explained subsequently. Further, the inner surface of the upper end portion of the stem 28, about the defined opening, includes a slight peripheral undercut area or notch 32 therein.
In order to selectively close and seal the vent opening or hole 30, for example when a venting of the interior of the container is not necessary such as during use as a storage container, the vent assembly 24 is provided with a vent cover 34. The vent cover 34 comprises a generally circular panel 36 with an integrally formed depending or inwardly directed plug 38. The plug 38 is of a size for snug frictional reception within the vent opening 30 for an effective closing of the vent and a sealing of the vent assembly. In order to releasably secure the plug 38 within the opening 30, provision is made for a releasible snap-locking engagement by means of an annular integral bead 40 formed about the plug 38 in slightly spaced relation below the cover panel 36 for engagement within the notch 32 simultaneously with a seating of the cover panel 36 on the upper rim of the stem 28 about the opening 30, as best illustrated in the sectional detail of FIG. 3. With continued reference to FIG. 3, it will be appreciated that with the vent cover 34 closed, the upper surface of the cover panel 36 is substantially coplanar with the upper or outer face 18 of the seal panel 14, thus maintaining a planar stacking surface without any disruptive projection within the peripheral mounting flange 16. Basically, the thickness of the panel 36 of the cover 34 is equal or slightly less than the vertical spacing of the upper end of the vent stem 28 below the upper face 18 of the seal panel 14.
The cover panel 36 is, in the illustrated embodiment, substantially circular with the plug 38 positioned eccentric, that is in more closely spaced relation to one portion of the periphery or circumference. Diametrically opposed therefrom, and along a cord perpendicular to this diameter, the cover panel 36 is integrally joined to an elongate mounting bar 42 by a living hinge 44.
The mounting bar 42 includes a pair of spaced integral shoulder portions 46, each having an elongate projecting integral mounting lug 48 thereon. Each lug 48 is in turn formed with an enlarged tapered head or leading end 50.
In order to accommodate the mounting bar 42 and lugs 48, a pair of hollow upwardly opening pedestals 54 are integrally formed with and project radially inward from the peripheral wall of the recess 26 at a spacing corresponding to the spacing of the mounting bar lugs 48. These pedestals 54 define upwardly opening sockets with planar upper surfaces 56 surrounding the lug-receiving apertures 58.
Noting FIGS. 3 and 4 in particular, the lugs 48 engage through the corresponding pedestal openings 58 with the enlarged headed ends 50 thereof locking within the sockets as the mounting bar shoulders 46 seat on the respective upper surfaces of the respective pedestals 54. The inherent resiliency of the material of the pedestals and lugs, and the tapered configuration of the lug heads 50, allow for snap-mounting. Similarly, for cleaning or replacement purposes, the lugs, upon application of appropriate pressure, can be withdrawn. As illustrated, the pedestals 54 open downwardly or inwardly as a molding expedient. However, as desired, the pedestal sockets can be formed with closed inner ends.
The cover panel 36, forwardly from the opposed ends of the living hinge 44, projects sufficiently beyond the plug 38 as to partially overlay the recess 26 radially outward of the vent stem 28. The overlaying of the recess generally diametrically opposed from the living hinge 44 provides for a gripping lip, enhanced by a peripheral bead 60, sufficient as to allow for positive manual engagement by one or more fingers of a user for an upwardly opening of the cover 34. As will be appreciated from FIGS. 1 and 2 in particular, this peripheral extension of the cover panel 36 progressively increases rearwardly toward the living hinge. However, at least a major portion of the recess 26 forward of the living hinge 44 is readily accessible for at least one and possibly as much as four fingers, thus providing for positive engagement with the cover and substantial leverage to disengage the plug and upwardly pivot the cover to open the vent.
While the recess 26 has been defined as symmetrical about the central stem 28, interrupted only by the pedestals 54, obvious variations are also contemplated. For example, the centrally formed stem 28 can be offset closer toward the pedestals 54, thus in effect providing a relatively wider finger-accommodating recess area toward the forward side of the cover opposed from the hinge. Such a variation might also involve a more central positioning of the cover plug 38 on the cover panel 36.
Other possible variations of the preferred illustrated embodiment may include recesses of other than annular configuration. However, in each instance, the recess will extend peripherally along or about a substantial or major portion of the periphery of the cover and be of a width and depth sufficient to accommodate multiple fingers in underlying relation to the extending peripheral edge of the cover panel. In addition, in each variation the cover, in the closed position thereon, is to be substantially in or slightly below the plane of the top panel of the seal to maintain the planar stacking surface thereof.
The vent assembly of the invention provides a unique means for venting or providing a steam and pressure release for food containers when used in a microwave oven. In this manner, the versatility of a standard food container can be substantially enhanced, while at the same time retaining all of the desirable features of the conventional storage container, including a complete sealing thereof, an ability to stack the containers, and the retained ability to open and close the containers in the conventional manner.
The foregoing is illustrative of the features of the invention. As indicated, other embodiments incorporating such features may occur to those skilled in the art, and should be considered as within the scope of the invention more particularly defined in the claims following hereinafter. | A vent assembly for the seal of a food container including a vent opening in the seal panel at least partially surrounded by an upperwardly opening recess with the vent opening and recess being below the plane of the upper face of the panel. A vent cover pivotally mounts to the seal and, when selectively closed over the vent hole, partially overlies the recess to allow for engagement of fingers with the cover in the recess for upwardly opening of the cover. The closed cover does not project above the plane of the top panel of the seal as to interrupt the planar nature thereof. | 1 |
CROSS-REFERENCE TO RELATED APPLICATION
This patent application is a continuation-in-part of U.S. patent application Ser. No. 08/116,405, filed Sep. 3, 1993 now U.S. Pat. No. 5,366,560.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to the art of cleaning contamination such as old paint, grease, rust and the like from surfaces by blast cleaning. In particular, the invention is concerned with blast cleaning wherein relatively soft abrasive particles such as sodium bicarbonate particles are transported into impact engagement with the contaminated surface by a stream of pressurized air or water, and, more particularly, is concerned with novel means and methods of uniformly dispersing the soft abrasive particles into the pressurized air or water stream.
2. Summary of Prior Art
In recent years, there has been an increase in the use of cleaning systems utilizing a blast of abrasive sodium bicarbonate particles suspended in a stream of pressured air or water. Sodium bicarbonate as an abrasive blast media has distinct advantages over sand particles used for many years as the abrasive media for blast cleaning. Because of the toxic nature of sand particles (crystalline silica) when inhaled, government regulations require the use of sophisticated fresh air breathing masks to insure the health of the operator by preventing the ingestion of the silica product into the lungs. Sand blasting, moreover, cannot be economically utilized to clean softer substrates such as aluminum, plastic laminates and the like or used to blast clean machines in food processing plants because of the difficulty of removing the silica particles such as from bearing surfaces.
On the other hand, sodium bicarbonate or other like relatively soft abrasives having a Mohs hardness of less than 4.0 can effectively clean softer substrates such as aluminum or plastic components without harming the underlying surface. Importantly, sodium bicarbonate particles are reasonably soluble in water and can be readily removed by hosing down the machine and substrate after the blast cleaning. Sodium bicarbonate is not toxic and does not require elaborate fresh air breathing masks for the operator. Only standard protective clothing and ear and eye protection may be utilized. This is not necessarily a requirement but depends primarily on the substrate and the coating being removed. Sodium bicarbonate can be utilized to remove surface corrosion, lime, scale, paint, grease and machine oil from any surface, without damaging the surface and can be washed away from bearing surfaces of machinery.
Standard sand blasting equipment consists of a pressure vessel or blast pot to hold particles of sand, connected to a source of compressed air by means of a hose and having a means of metering the blasting medium from the blast pot, which operates at a pressure that is the same or slightly higher than the conveying hose pressure. The sand/compressed air mixture is transported to a nozzle where the sand particles are accelerated and directed toward a workpiece. Flow rates of the sand or other blast media are determined by the size of the equipment. Commercially available sand blasting apparatus typically employ media flow rates of 10-30 pounds per minute. About 1.2 pounds of sand are used typically with about 1.0 pound of air, thus yielding a ratio of 1.20.
As discussed above, when it is required to remove coatings such as paint or to clean surfaces such as aluminum, magnesium, plastic composites and the like, less aggressive abrasives, including inorganic salts such as sodium chloride and sodium bicarbonate can be used in conventional sand blasting equipment. The media flow rates required for the less aggressive abrasives is substantially less than that used for sand blasting, and has been determined to be from about 0.5 to about 10.0 pounds per minute, using similar equipment. This requires much lower medium to air ratio, in the range of about 0.05 to 0.40.
The employment of less aggressive abrasives such as sodium bicarbonate as a blast cleaning medium does encounter problems in effecting the transfer of the abrasive particles from a supply hopper to the nozzle from which pressured water or air issues and where the abrasive is mixed into the pressured fluid. For example difficulties have been encountered in maintaining continuous flow of sodium bicarbonate particles at the low flow-rates used for this abrasive when conventional sand blasting equipment relying on gravity feed were employed. The fine particles of a medium such as sodium bicarbonate are difficult to convey by pneumatic systems by their very nature. Further, they tend to agglomerate upon exposure to a moisture-containing atmosphere, as is typical of the compressed air used in sand blasting. In an attempt to overcome these particle delivery problems, a sodium bicarbonate crystal has been developed and marketed under the trademark "ARMEX" by Church & Dwight Co., Inc. of Princeton, N.J. A flow additive such as hydrophobic silica has been applied to the sodium bicarbonate particles to promote the flow of the resulting crystals from the hopper and into the pressured stream of air or water passing through the discharge nozzle. Even this improved particle form of sodium bicarbonate still suffers from sporadic clogging and/or inconsistent rates of delivery of the sodium bicarbonate particles to the pressurized fluid stream, which in turn leads to erratic performance.
The methods and apparatus employed for delivering sodium bicarbonate or other less aggressive abrasive media have been improved by Church & Dwight and are the subjects of U.S. Pat. Nos. 5,081,799; 5,083,402 and 5,230,185 herein incorporated by reference. Briefly, as disclosed therein a high air pressure is maintained on the top of the mass of sodium bicarbonate particles disposed in the supply hopper to maintain a differential pressure between the top of the hopper and the air conveying line which directs the abrasive particulate to the blast nozzle which accelerates the particles to the substrate surface. Further, fine control of the flow of abrasive from the hopper to the conveying line is achieved by causing the abrasive to pass through an orifice. By controlling the differential pressure and size of the orifice, fine and exact control of abrasive flow has been obtained. Under these conditions, the sodium bicarbonate particles have been found to feed uniformly and consistently into a stream of pressured air or air and injected water. However, the feeding equipment is somewhat specialized, can be relatively expensive for certain common blast cleaning applications and has not specifically addressed adding the particles to a pressurized water stream used as the primary fluid carrier to the substrate.
There is therefore still a need for an improved method and apparatus for effecting blast cleaning through the utilization of less aggressive abrasives such as sodium bicarbonate particles, whether treated with a flow promotion agent or not, which will effect a more reliable and consistent delivery of such particles to the blast nozzle and which can be conveniently adjusted to accommodate a substantial range of particle sizes of abrasives.
SUMMARY OF THE INVENTION
In accordance with this invention, improvements are provided to the method and apparatus for blast cleaning with less aggressive abrasive media such as sodium bicarbonate and, in particular, to the media delivery system which directs the abrasive particles to the pressurized air or water stream which in turn carries the abrasive particles to the surface to be treated. The apparatus of this invention comprises a hopper for containing a supply of sodium bicarbonate particles and which has a conical bottom surface terminating in a vertical flow passage. An orifice ring is removably mounted in the vertical flow passage. A plurality of such orifice rings, having different orifice sizes, are provided to insure the optimum performance of the delivery system for different sizes of sodium bicarbonate particles placed in the hopper. The invention includes alternative embodiments as to the placement of the orifice ring along the vertical flow passage. The top of the hopper is exposed to atmospheric pressure.
A pair of pipes are sealingly secured in transverse relationship to the bottom end of the vertical flow passage by a T-fitting which provides communication with such passage. Thus particles may flow by gravity into the pipes but such flow will be limited to a pile of particles filling the portion of the bores of the pipes immediately beneath the discharge passage. One of the transverse pipes is open to the atmosphere.
A blast nozzle is connected to the end of a first hose, and water under pressure, approximately 750 to 15,000 pounds per square inch, or air under a pressure of 30 to 250 psi is supplied through such hose. A venturi passage is disposed between the end of the hose and the discharge end of the blast nozzle. A transverse flow passage is provided in communication with the venturi passage adjacent to the minimum diameter portion thereof. The transverse flow passage further communicates with a second hose which is disposed with the end of one of the transverse pipes mounted on the bottom of the hopper. In operation, as the water or air under pressure is passed through the venturi passage a suction force or vacuum is generated in the transverse flow passage, the pair of pipes at the bottom of the hopper and the vertical flow passage.
The end of the transverse pipe open to the atmosphere has an air flow regulating valve connected thereto so as to permit reduction of the flow of atmospheric air through the pipe, due to the modest suction force on the order of 0.5 to 14.3 psi (1 to 29 in. Hg) produced by the connection of the second hose and transverse flow passage to the venturi passage. By proper selection of the diameter of the bore of the orifice ring and the amount of restriction of air flow into the end of the pipe below the hopper, a stream of particles will be transported to the blast nozzle which occupies not more than 25 percent of the cross-sectional area of the pipe. In effect, the moving particles constitute a fluidized bed of such particles, commonly referred to as dilute phase pneumatic conveying, within the second hose hence there is no tendency for the particles to clog or for the volume of particles to significantly vary per unit of time during delivery to the discharge nozzle.
The method and apparatus of this invention function well with the aforesaid "ARMEX" sodium bicarbonate blast media, untreated sodium bicarbonate particles, as well as other less aggressive abrasive media such as other inorganic salts or plastic media.
The size of the abrasive particles determines the size of the bore of the orifice ring. Larger particles require a larger bore diameter than do smaller particles.
Further advantages of this invention will be readily apparent to those skilled in the art from the following detailed description, taken in conjunction with the annexed sheets of drawings, on which is shown a preferred embodiment of the invention.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a schematic view of the apparatus embodying this invention.
FIG. 2 is a perspective view of a hopper for containing abrasive media and the mechanism for metering the flow rate of the abrasive particles out of the hopper.
FIG. 3 is a partial sectional view taken on the Plane 3--3 of FIG. 2.
FIG. 4 is a sectional view of a conventional venturi utilized in the blasting nozzle.
FIG. 5 is an enlarged-vertical sectional view of the discharge portion of the apparatus of this invention including the hopper, the orifice ring and vertical flow passage.
FIG. 6 is an enlarged vertical sectional view of an alternative embodiment of the discharge portion of the apparatus of this invention.
DESCRIPTION OF PREFERRED EMBODIMENT
Referring to FIGS. 1, 2, 3 and 5, the apparatus 1 embodying this invention comprises a container 10 for sodium bicarbonate abrasive particles P and the like. Container 10 is mounted on an annular base portion 10a, and has a conically shaped, inwardly sloping bottom wall, 10b, terminating in a central aperture 10c.
While a preferred blast media is sodium bicarbonate, other blast media such as potassium bicarbonate, ammonium bicarbonate, sodium chloride, sodium sulfate and other water-soluble salts or mixtures thereof, are meant to be included herein. Non-water soluble materials such as calcium carbonate are also useful. Also included are mixtures of such less aggressive media with more aggressive materials, such as, aluminum oxide, which is water insoluble, especially where precise flow control is necessary.
The abrasive blast media particles useful in this invention will generally range from about 50 to 2,000 microns depending on the abrasive used. Particle sizes of 50 to 1,000 microns are more common. Preferred sizes for sodium bicarbonate particles range from 50-500 microns. The selection of the size of the abrasive media is based on the particular application.
A hollow bolt 12 having a shank portion 12a, projects through the aperture 10c and threadably engages the shank portion 13a of an ordinary T-shaped pipe fitting 13. The size of the vertical discharge passage for the particles P is determined by selecting one of a plurality of tubular orifices 11, which are threadably secured to internal threads 12c, provided in the bolt 12. A sealing washer 14 is provided between the bottom wall 10b of the hopper and the end of the shank portion 13a of the pipe fitting 13. Each tubular orifice element 11 has a different size discharge passage 11a formed therein, thus regulating the flow rate of the particles of sodium bicarbonate or other abrasive into the T-shaped pipe fitting 13.
For larger abrasive particles, the selected orifice 11 would have a larger passage 11a than for smaller particles of abrasive. A cover 10d is provided for the top of the hopper 10, but this cover is merely for the purpose of preventing dirt from falling into the supply of sodium bicarbonate particles and is not airtight, thus exposing the particles within the hopper 10 to atmospheric pressure.
The lateral ends of the T-shaped pipe coupling 13 are respectively threadably connected to an air inlet pipe 15 and a suction pipe 16, both of which are disposed within the hollow interior of the base 10a. In effect, the head portion 13b of the T-shaped coupling 12 and the pipes 15 and 16 may be considered to be a continuous pipe which is transversely connected to the orifice 11a, through which particles P may flow into the continuous pipe.
As best shown in FIG. 1, the air suction pipe 16 is connected by a hose 17 to a discharge nozzle element 20 connected to the end of a supply hose 19 for supplying pressured air or water to the nozzle 20. As best shown in FIGS. 1 and 4, the hose 17 and suction pipe 16 communicate with a transverse fluid passage 20b in the nozzle 20. Transverse fluid passage 20b communicates with venturi passage 20a, defined within nozzle 20. The suction pipe 16 is subjected to a suction pressure or vacuum produced by the discharge of pressured fluid supplied by hose 19 through venturi 20a.
The air inlet pipe 15 is provided with a conventional adjustable flow valve 22, by which the amount of air sucked into the pipe 15 by the suction produced by the venturi passage 20a in blast nozzle 20 may be adjusted. An unexpected feature of the apparatus embodying this invention is the fact that if the valve 22 is shifted by its operating handle 22a to a fully closed position, the entire suction pressure generated by the venturi passage 20a is applied to the bottom of the hopper full of particles P. Under this condition, the particles P will not flow continuously through the selected aperture 11a of the orifice 11, but will tend to move in clumps, which often results in the plugging of the air suction pipe 16 and/or hose 17.
For the successful operation of the apparatus, the amount of inlet air permitted for passage through pipe 15 by the valve 22 is correlated with the size of orifice passage 11a, so as to produce a volume flow of particles P which at all times occupies up to 25 percent of the cross-sectional area of the pipe 16 and hose 17. When the hose 16 is fabricated from a transparent plastic material, the particles P can be observed as a distinct stream, similar to a fluidized bed, generally moving along the bottom surface of the hose 16 and, as stated above, occupying a minor portion of the cross-sectional area of such hose. Under these conditions, no clogging of the abrasive particles occurs.
The suction pressure applied to the abrasive particles P varies, of course, with the pressure of the air or water supplied to the nozzle 20. For most applications, a suction pressure on the order of 0.5 to 14.3 pounds per square inch (1 to 29 inch Hg) will produce a satisfactory feeding of the abrasive particles P from the hopper 10 into the pipe 13. Preferably a suction pressure or vacuum 1 to 7.5 psi of (2 to 15 inch Hg) is applied to deliver the abrasive. This amount of suction pressure is readily obtained when the pressurized fluid applied to the nozzle 20 by hose 19 is maintained at a conventional level of 750 to 15,000 pounds per square inch for water and 30 to 100 psi for air. In no case, should suction pressure be applied to the abrasive particles P to produce a filling of the cross-section area of the pipe 16 and/or the hose 17. The size of discharge opening 11a in tubular orifice 11 will typically range from about 0.09 to 0.250 inch, preferably from about 0.110 to 0.219 inch. As previously stated, the size of the discharge opening 11a selected will depend upon the size of the abrasive media particles to be used.
All of the factors which determine the media flow rate through the blast nozzle including particle size, the size of the discharge opening in the orifice ring, the pressure of the fluid carrier stream through the nozzle, the vacuum applied under the hopper and the amount of atmospheric air allowed into the vacuum lines to control the vacuum are interdependent so as to maintain the conveying velocity of the air and the fluidization of the abrasive particles through pipe 16 and hose 17 to the nozzle. During the blast cleaning process, it would be worthwhile to be able to manipulate only one of the operational variables and still accurately control the delivery of the abrasive to the nozzle and maintain the optimum blast cleaning performance. It has been found that it is best as well as easiest to control the amount of atmospheric air allowed into pipe 15 by controlling valve 22 during blast cleaning to control abrasive particle delivery to the blast nozzle. However, precise control of the media flow rate cannot be readily obtained even by experience if there is no way to correlate the amount of vacuum needed to deliver a particular abrasive media at a given carrier fluid pressure at the blast nozzle. Thus, if there is no means for the operator to determine the operational vacuum, there is no means to accurately and very finely control the amount of atmospheric air allowed into and passing through pipe 15 to precisely control particle flow rate. Thus, inefficiencies in the delivery system are observed only when the blast cleaning performance is adversely affected.
Additionally, the media delivery system such as shown in FIG. 5 while fully achieving the advantages described for the invention cannot be readily changed during a particular blast cleaning operation. Thus, to change the orifice ring 11, the hopper must be substantially devoid of the abrasive particles. An alternative embodiment of the abrasive particle discharge portion of the invention is shown in FIG. 6 and alleviates some of the inconveniences described immediately above.
Referring to FIG. 6, it can be seen that the alternative media delivery system includes a hopper 30 having a conically shaped, inwardly sloping bottom wall 32 and a central aperture 34 equivalent to the hopper 10 of the embodiment shown in FIGS. 1-5. Threaded into boss 35 welded to the bottom of hopper 30 and contiguous with central aperture 34 is an on/off valve 36 such as a ball valve or the like. Valve 36 includes a pipe nipple 38 containing external threads 40 which can be threaded onto the internal threads 41 of boss 35. Any other conventional means can be used to attach valve 36 to hopper 30, e.g. welding, as long as aperture 34 is not excessively restricted. A handle 42 can be moved to place the typical ball valve in the on or off position whereby in the "on" position the media flows from hopper 30 through pipe nipple 38 and through a passage in the movable ball in valve 36 whereas in the "off" position, the passage in the movable ball is not in alignment with aperture 34 and accordingly the media particles cannot flow through the valve.
Downstream of valve 36 is orifice ring 44 which includes discharge opening 46 to precisely control the volume of media flowing from hopper 30 to the blast nozzle. Orifice ring 44 rests upon a seal 48. In turn, seal 48 rests on the outer circumferential edge of flange 51 of a pipe fitting 50 which is threaded at the end opposite flange 51 into T-shaped pipe fitting 52. To secure orifice ring 44 and seal 48 in place, a slidable nut 54 which has a bottom edge 56 slidable around pipe fitting 50 and capable of engagement with flange 51 of pipe fitting 50 and includes upper internal threads 60 is threaded onto external threads 62 placed at the bottom of valve 36. As nut 54 is threaded onto valve 36, nut 54 brings into a tight sealing engagement the bottom of valve 36, orifice ring 44, seal 48 and flange 51 of pipe fitting 50. To change the size of discharge opening 46, nut 54 is simply unthreaded from valve 36 and slid down on pipe fitting 50 to reveal orifice ring 44. Orifice ring 44 can then be replaced with a different orifice ring and nut 54 again threaded into tight engagement with valve 36. By incorporating an on/off valve 36 between the hopper 30 and the orifice ring 44, the orifice ring can be changed without the need to empty the hopper of the abrasive particles.
The lateral flow areas on each side of the T-fitting 52 are substantially equivalent to that shown in FIGS. 3 and 5. Thus, connected to one end of T-fitting 52 is a conventional air flow valve 64 such as a ball valve or the like and including a handle 66 which can be manipulated to control the amount of atmospheric air allowed into and flowing through the T-fitting 52 and through lateral pipe connection, shown as hose coupling 68, which forms the abrasive delivery line to the blast nozzle in the equivalent manner as provided by pipe 16, hose 17 and blast nozzle 20 shown in FIG. 1.
To allow the operator to precisely control the delivery of the media to the blast nozzle and, importantly, to provide consistent control over time, it would be preferred that the operator know the precise vacuum being applied to the system during the operation of the nozzle so that with a particular media, the amount of atmospheric air being allowed to flow through the system such as through valve 64 can be controlled to yield the optimum performance. Thus, in the media delivery system shown in FIG. 6, a vacuum gauge 70 is placed and tapped into T-fitting 52 upstream of the point where the media is discharged into T-fitting 52. During blast cleaning the precise vacuum in the system can be read by the operator and the valve 64 can be controlled continuously to provide and maintain the desired vacuum. Over time, experience will allow the operator to know which vacuum level operates best with a particular media allowing the operator to simply control the volume flow of atmospheric air by controlling valve 64 to maintain the desired vacuum which can be read from gauge 70. Disruption of the vacuum can now be corrected to maintain the desired flow of abrasive before such disruption results in uneven blast cleaning performance. With a particular blast media, a known size of the orifice ring opening 46, and the vacuum level measured via gauge 70, the flow rate of media can be readily determined.
EXAMPLE
The media flow rate of abrasive media through a blast nozzle utilizing the media discharge system as shown in FIG. 6 was tested utilizing different orifice ring sizes and varying the vacuum applied to the system. In each case, water at a pressure of around 1500 psig was passed through the blast nozzle. In Table 1, the particle size of the sodium bicarbonate particles was about 300 microns and in Table 2, the sodium bicarbonate media had an average size of about 170 microns. Media flow rates ranging from 0.4 to 4 lbs per minute are preferred.
TABLE 1______________________________________ Sodium bicarbonate (300 microns)Media Type Media Orifice Size, InchVacuum, 0.219 0.187 0.157 0.125 0.110in. Hg Media Flow lbs/min______________________________________2 1.2 0.9 0.6 0.5 0.34 1.6 1.2 0.8 0.6 0.46 1.9 1.4 1.0 0.8 0.58 2.2 1.6 1.2 0.9 0.610 2.7 2.0 1.4 1.1 0.812 3.0 2.2 1.6 1.2 0.914 3.3 2.4 1.8 1.3 1.016 3.6 2.6 2.0 1.418 3.8 2.8 2.220 4.1 3.0______________________________________
TABLE 2______________________________________ Sodium bicarbonate (170 microns)Media Type Media Orifice Size, InchVacuum, 0.219 0.187 0.157 0.125 0.110in. Hg Media Flow lbs/min______________________________________2 1.6 1.2 0.9 0.7 0.54 2.2 1.6 1.1 0.9 0.66 2.5 1.8 1.3 1.1 0.78 2.7 2.0 1.6 1.2 0.810 3.3 2.4 1.8 1.4 1.012 3.6 2.7 2.0 1.6 1.114 3.9 3.0 2.2 1.8 1.216 4.2 3.3 2.4 2.018 4.5 3.6 2.620 4.9______________________________________ | A method and apparatus for effecting the continuous reliable supply of sodium bicarbonate particles to a blasting nozzle employing pressured air or water for conveying such particles into contact with a surface to be cleaned. The apparatus includes a hopper at atmospheric pressure and a removable orifice through which the abrasive particles are directed from the hopper to an open ended pipe. One end of the pipe is connected to a media conveying line and a venturi passage provided in a blast nozzle whereby a pressurized fluid passing through the venturi passage creates a suction force in the conveying line and the pipe such that atmospheric air and abrasive particles are drawn from the air pipe to the blast nozzle. The amount of air flow permitted through the pipe can be adjusted by a valve to control the vacuum within the conveying line and along with the particle feeding orifice controls the concentration of abrasive particles in the air stream directed to the nozzle. | 1 |
[0001] This application claims priority to U.S. provisional application Ser. No. 61/840,482, filed Jun. 28, 2013, the entire disclosure of which is hereby incorporated by reference herein.
FIELD OF THE INVENTION
[0002] New types of nanoparticle-based dual-modality positron emission tomography/magnetic resonance imaging (PET/MRI) and positron emission tomography/computed tomography (PET/CT) tumorspecific contrast agents have been developed. The base of the new type contrast agents is biopolymer-based nanoparticle with PET, MRI and CT active ligands. The nanoparticle contains at least one polyanion and polycation, which form nanoparticles via ion-ion interaction. The self-assembled polyelectrolytes can transport gold nanoparticles as CT contrast agents, or SPION or Gd(III) ions as MRI active ligands, and are labeled using a complexing agent with gallium as PET radiopharmacon. Furthermore, these dual modality PET/MRI and PET/CT contrast agents are labeled with targeting moieties to realize the tumorspecificity.
BACKGROUND OF THE INVENTION
[0003] Molecular imaging plays a very important role in molecular or personalized medicine. Molecular imaging enables visualization of the biological targets and understanding its complexities for diagnosis and treatment of the disease. An accurate and realtime imaging of biological targets provides a thorough understanding of the fundamental biological processes and helps to diagnose various diseases successfully. It is difficult to obtain all the necessary information about the biological structure and function of an organ by any single imaging modality among all the existing imaging techniques. Therefore attempts are being made to fuse the advantages of different imaging techniques by combining two or more imaging modalities while reducing their disadvantages.
[0004] In the past decade, a wide variety of nanoparticles has been used for diagnostic applications. Use of nanotechnology in diagnostic is very useful because only a small volume of sample is enough to achieve the appropriate low limit of detection. Often the use of nanoparticles in diagnosis is more sensitive than use biomolecules.
[0005] Some publications attest to the variety of nanoparticles used in diagnostic. Nanocarriers including magnetic resonance imaging (MRI), computed tomography (CT), single photon emission computed tomography, positron emission tomography, or multifunctional nanoparticles such as PET/MR and SPECT/CT have been disclosed.
[0006] The fusion of PET and MRI or PET and CT in a single contrast agent has proved to be beneficial as it gives images of high sensitivity and high resolution and nanoparticles are the ideal devices that allow the integration of several different imaging modalities onto a single platform.
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THE STATE OF THE ART
[0020] U.S. Pat. No. 7,976,825 relates to macromolecular contrast agents for magnetic resonance imaging. Biomolecules and their modified derivatives form stable complexes with paramagnetic ions thus increasing the molecular relaxivity of carriers. The synthesis of biomolecular based nanodevices for targeted delivery of MRI contrast agents is described. Nanoparticles have been constructed by self-assembling of chitosan as polycation and poly-gamma glutamic acids (PGA) as polyanion. The nanoparticles are capable of Gd-ion uptake forming a particle with suitable molecular relaxivity. Folic acid is linked to the nanoparticles to produce bioconjugates that can be used for targeted in vitro delivery to a human cancer cell line.
[0021] WO06042146 relates to conjugates comprising a nanocarrier, a therapeutic agent or imaging agent and a targeting agent. Disclosed are conjugated comprising a nanocarrier, a therapeutic agent or imaging agent, and a targeting agent, wherein the nanocarrier comprises a nanoparticle, an organic polymer, or both. Compositions comprising such conjugates and methods for using the conjugates to deliver therapeutic and/or imaging agents to cells are also disclosed. The conjugate is a compound having the following formula: A-X-Y wherein A represents the chemotherapeutic agent or imaging agent; X represents the nanoparticle, organic polymer or both, wherein the organic polymer has an average molecular weight of at least about 1,000 daltons; and Y represents the targeting agent.
[0022] WO0016811 relates to an MRI contrast agent wherein imaging capability is expressed only within the target abnormal cells, such as tumor, and imaging is not conducted at the site where imaging is not necessary, thereby the detection sensitivity of the abnormal cells such as tumor is improved. Disclosed is an MRI contrast agent, which comprises a complex of a polyanionic gadolinium (Gd) type contrast agent and a cationic polymer, or a complex of a polycationic Gd type contrast agent and an anionic polymer, both complexes being capable of forming a polyion complex, and which expresses an MRI capability at a neutral pH in the presence of a polymer electrolyte.
[0023] The state of the art so far failed to provide for the improved compositions according to the present invention.
SUMMARY OF THE INVENTION
[0024] The present invention is directed to novel, targeting dual-modality PET/MRI or PET/CT tumorspecific contrast agents.
[0025] In some embodiments, the fusion nanoparticulate composition comprises (i) at least two polyelectrolyte biopolymers, (ii) targeting molecules conjugated to a polyanion biopolymer, (iii) a complexing agent conjugated to a polycation biopolymer, (iv) an MR or CT active ligand complexed to the nanoparticles, and (v) a radionuclide complexed to the nanoparticles.
[0026] The MR active ligands can be gadolinium ions as T1 MR active ions, superparamagnetic iron oxide nanoparticles (SPION) as T2 MR active ligands, or gold nanoparticles as CT contrast ligand.
[0027] Gadolinium ions are complexed to the nanoparticles via complexing agents conjugated to a polycation biopolymer. SPION and gold nanoparticles are formed in presence of a polyelectrolyte biopolymer to produce complexed ligands.
[0028] In a preferred embodiment, the polycation biopolymer is preferably chitosan; and the polyanion biopolymer is preferably poly-gamma-glutamic acid.
[0029] In a further embodiment, the chitosan of the nanoparticles ranges in molecular weight from about 20 kDa to 600 kDa, and the poly-gamma-glutamic acid of the nanoparticles ranges in molecular weight from about 50 kDa to 2500, preferably 1500 kDa. In a preferred embodiment, the degree of deacetylation of chitosan ranges between 40% and 99%.
[0030] Targeting moieties are conjugated to polyanion to realize a targeted delivery of imaging agents.
[0031] The targeting agent is preferably folic acid, LHRH, RGD.
[0032] The self-assembled nanosystems contain complexing agents. The polycation modified by the complexing agent allows the chelation of gallium for PET imaging and allows the chelation of gadolinium for MR imaging. Preferable complexing agents include, but are not limited to: diethylenetriaminepentaacetic acid (DTPA), 1,4,7,10-tetracyclododecane-N,-N′,N″,N′″-tetraacetic acid (DOTA), ethylene-diaminetetraacetic acid (EDTA), 1,4,7,10-tetraazacyclododecane-N,N′,N″-triacetic acid (DO3A), 1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (CHTA), ethylene glycol-bis(beta-aminoethyl ether)N,N,N′,N′,-tetraacetic acid (EGTA), 1,4,8,11-tetraazacyclotradecane-N,N′,N″,N′″-tetraacetic acid (TETA), 1,4,7-triazacyclononane-N,N′,N″-triacetic acid (NOTA).
[0033] In a further embodiment, the nanoparticles have a mean particle size between about 30 and 500 nm, preferably between about 50 and 400 nm, and most preferably between 70 and 250 nm.
[0034] Accordingly, the invention concerns a targeting PET/MRI or PET/CT tumorspecific nanoparticulate contrast composition comprising (i) at least two, preferably water-soluble, biocompatible and biodegradable nanoparticle polyelectrolyte biopolymers; (ii) a targeting molecule conjugated a polyanion biopolymer; (iii) a complexing agent conjugated to a polycation biopolymer, (iv) an MR or CT active ligand complexed to the nanoparticles, and (v) a radionuclide, preferably gallium complexed to the nanoparticles.
[0035] Furthermore, the invention relates to a process for the preparation of a targeting contrast composition according to the invention, comprising the steps of
[0036] a) contacting of a solution comprising the polyanion, the targeting agent and the MR or CT active ligand; with the conjugate of the polycation and the complexing agent; and
[0037] b) labeling of the conjugate of the polycation and the complexing agent or the self-assembled nanoparticles.
[0038] Still further, the invention relates to the use of the contrast composition according to the invention as fusion PET/MR or PET/CT imaging agents in diagniosis, preferably cancer diagnosis.
[0039] The present invention provides fusion PET/MR or PET/CT imaging agents that are compositions comprising radioactively labeled MR or CT active nanoparticles. The compositions of the invention target tumor cells, selectively internalize and accumulate in them in consequence of the presence of targeting ligands, therefore are suitable for early tumor diagnosis.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0040] FIG. 1 shows the size and size distribution of self-assembled nanoparticles.
[0041] FIGS. 2A and 2B show the T 1 -weighted MRI images of non Gd conjugated self-assembled nanoparticles SI=301 ( FIG. 2A ) and Gd conjugated self-assembled nanoparticles SI=1486 ( FIG. 2B ). The Gd-NPs show a significant contrast enhancement, which is exhibited in the high signal intensity.
[0042] FIGS. 3A and 3B show the chromatogram of normal generator-eluted 68 Ga solution ( FIG. 3A ) and 68 Ga-NPs ( FIG. 3B ). Free, unbound Ga-68 was migrated with the solvent to the front line (Rf=1), while the labeled nanoparticle compound was located at the origin (Rf=0). Integrating measured peaks showed the proper ratios of labeled and non-labeled components.
[0043] FIG. 4 shows uptake percent of total activity of self-assembled nanoparticles radiolabeled with 68 Ga radionuclide on KB cells.
DETAILED DESCRIPTION OF THE INVENTION
[0044] The present invention provides novel, targeting, dual-modality PET/MRI or PET/CT tumorspecific contrast agent and method for forming them for targeted delivery. Self-assembled particles are provided as nanocarriers, labeled with targeting moieties, containing complexone ligands conjugated to a polycation biopolymer, MR or CT active ligand complexed to the nanoparticles, and radionuclide complexed to the nanoparticles. Methods for making these targeting dual-modality contrast agents are also provided.
[0045] Nanoparticles, as Contrast Agent Compositions
[0046] The present invention is directed to biocompatible, biodegradable, polymeric nanoparticles, as dual-modality tumorspecific contrast agent, formed by self-assembly via the ion-ion interaction of oppositely charged functional groups of polyelectrolyte biopolymers, as nanocarriers for PET and MRI or CT active ligands.
[0047] In a preferred embodiment, the biopolymers are water-soluble, biocompatible, biodegradable polyelectrolyte biopolymers. One of the polyelectrolyte biopolymers is a polycation, a positively charged polymer, which is preferably chitosan or any of its derivatives. The other of the polyelectrolyte biopolymers is a polyanion, a negatively charged biopolymer. The polyanion is preferably selected from a group consisting of polyacrylic acid (PAA), poly-gamma-glutamic acid (PGA), hyaluronic acid (HA), and alginic acid (ALG).
[0048] In a preferred embodiment, the polycation of the nanoparticles ranges in molecular weight from about 20 kDa to 600 kDa, and the polyanion of the nanoparticles ranges in molecular weight from about 50 kDa to 2500, preferably 1500 kDa.
[0049] In a preferred embodiment, the degree of deacetylation of chitosan ranges between 40% and 99%.
[0050] The nanoparticles contain targeting moieties necessary for targeted delivery of nanosystems.
[0051] The targeting agent is coupled covalently to one of the biopolymers using a carbodiimide technique in aqueous media. The water soluble carbodiimide, as coupling agent forms amide bonds between the carboxyl and amino functional groups, therefore the targeting ligand could be covalently bound to one of the polyelectrolyte biopolymers.
[0052] In the present invention, the preferred targeting agent is selected from folic acid, lutenizing hormone-releasing hormone (LHRH), and an Arg-Gly-Asp (RGD)-containing homodetic cyclic pentapeptide such as cyclo(-RGDf(NMe)V) and the like.
[0053] In a preferred embodiment, the most preferred targeting agent is folic acid, which facilitates the folate mediated uptake of nanoparticles, as tumor specific contrast agents. The nanoparticles of the present invention are preferably targeted to tumor and cancer cells, which overexpress folate receptors on their surface. Due to the binding activity of folic acid ligands, the nanoparticles selectively link to the folate receptors held on the surface of targeted tumor cells, internalize and accumulate in the tumor cells.
[0054] Folic acid is coupled covalently to the polyanion biopolymer using a carbodiimide technique. The folic acid due to its carboxyl and amino groups can be coupled to the polyanion biopolymer directly or via a PEG-amine spacer.
[0055] In a preferred embodiment, the self-assembled nanoparticles are comprised of a polyanion biopolymer, a polycation biopolymer, a targeting agent covalently attached to one of the biopolymers and at least one complexing agent covalently coupled to the polycation.
[0056] The complexing agent is coupled covalently to the polycation biopolymer. Water-soluble carbodiimide, as coupling agent is used to make stable amide bonds between the carboxyl and amino functional groups in aqueous media. Using reactive derivatives of complexing agents (e.g. succinimide, thiocyanete), the polycation-complexone conjugate can be directly formed in one-step process without any coupling agents. The nanoparticles can make stable complex with the radionuclide metal ions and for PET/MRI T1 modality, paramagnetic ions through these complexone ligans.
[0057] In a preferred embodiment, the complexing agents are preferably diethylenetriaminepentaacetic acid (DTPA), 1,4,7,10-tetracyclododecane-N,-N′,N″,N′″-tetraacetic acid (DOTA), ethylene-diaminetetraacetic acid (EDTA), 1,4,7,10-tetraazacyclododecane-N,N′,N″-triacetic acid (DO3A), 1,2-diaminocyclohexane-N,N,N′,N′-tetraacetic acid (CHTA), ethylene glycol-bis(beta-aminoethyl ether)N,N,N′,N′,-tetraacetic acid (EGTA), 1,4,8,11-tetraazacyclotradecane-N,N′,N″,N′″-tetraacetic acid (TETA), 1,4,7-triazacyclononane-N,N′,N″-triacetic acid (NOTA) or their reactive derivatives. More preferably, the complexing agents are DOTA, DTPA, EDTA and NOTA, most preferably DTPA for paramagnetic ligand and NOTA for radionuclide metal ions.
[0058] The targeted, dual-modality self-assembled nanoparticles described herein are radiolabeled with radionuclide metal ion, which is preferably 68 Ga to realize the PET modality.
[0059] In a preferred embodiment, the radionuclide metal ions are homogeneously distributed throughout the self-assembled nanoparticle. The radionuclide metal ions can make stable complex with the free complexing agents attached to the polycation biopolymer, therefore they could be performed homogeneously dispersed.
[0060] To achieve the dual-modality PET/MR tumorspecific contrast agents, T1 or T2 ligands are conjugated to the nanocarriers, and thereafter radiolabelling with radionuclide gallium is carried out.
[0061] For T1 MRI modality, paramagnetic ions are complexed to the nanocarriers. The paramagnetic ions are preferably lanthanide or transition metal ions, more preferably gadolinium-, manganese-, chromium-ions, most preferably gadolinium ions, useful as MRI contrast agent.
[0062] The paramagnetic ions are homogeneously distributed throughout the self-assembled nanoparticle.
[0063] The paramagnetic ions can make stable complex with the complexone ligands attached to the polycation biopolymer; therefore they could be performed homogeneously dispersed.
[0064] For T2 modality, superparamagnetic ligand, preferably superparamagnetic iron oxide nanoparticles are conjugated to a polyelectrolyte biopolymer, and they are preferably homogenously dispersed. The superparamagnetic iron oxide nanoparticles (SPION) are synthesized in situ in the presence of the polyanion, and then the self-assembling with the polycation is performed.
[0065] The size of the dried SPIONs ranges between 1 and 15 nm, preferably 3 and 5 nm.
[0066] To achieve the dual-modality PET/CT tumorspecific contrast agents, gold nanoparticles are conjugated to the nanocarriers, and thereafter radiolabelling with radionuclide gallium is carried out.
[0067] The gold nanoparticles are synthesized in situ in the presence of the polyanion, and then the self-assembling with the polycation is performed.
[0068] In a preferred embodiment, the nanoparticles described herein have a hydrodynamic diameter between about 30 and 500 nm, preferably between about 50 and 400 nm, and the most preferred range of the hydrodynamic size of nanoparticles is between 70 and 250 nm.
[0069] Methods of Making Nanoparticles, as Dual-Modality Contrast Agent Compositions
[0070] The present invention is directed to novel, biocompatible, biodegradable, targeting nanoparticles as dual-modality PET/MRI or PET/CT contrast agents. The nanoparticle compositions described herein are prepared by the self-assembly of oppositely charged polyelectrolytes via ion-ion interaction between their functional groups. The targeting ligands are conjugated covalently to one of the polyelectrolyte biopolymers and complexing agents covalently coupled to the polycation biopolymer.
[0071] These nanoparticles can contain paramagnetic ligand as MRI T1, superparamagnetic ligands as MRI T2 agents or gold nanoparticles as CT active ligands. These targeted nanoparticles are radioactively labeled with 68 Ga radionuclide to produce dual-modality fusion contrast agents.
[0072] In a preferred embodiment, the targeting ligand is attached to one of the biopolymers covalently. The targeting agent is preferably folic acid, LHRH, RGD, the most preferably folic acid.
[0073] The folic acid is coupled covalently to the polyanion biopolymer using a carbodiimide technique. The folic acid due to its carboxyl and amino groups can be coupled to the polyanion biopolymer directly or via a PEG-amine spacer.
[0074] The polyanions via their reactive carboxyl functional groups can form stable amide bond with the amino functional groups of folic acid or the folic acid-PEG amino spacer using carbodiimide technique. Folated biopolymer meaning folated polyanion can be used for the formation of nanoparticles, as targeted dual-modality contrast agent.
[0075] In a preferred embodiment, the polycation-complexone polyelectrolyte derivatives are used for the formation of self-assembled nanoparticles. These derivatives of the polycation are produced by coupling complexing agent to it covalently. Water soluble carbodiimide is used as coupling agent to form stable amide linkage between the amino groups of polycation and carboxyl groups of complexing agent. Using reactive derivatives of complexing agents (e.g. succinimide, thiocyanete), the polycation-complexone conjugate can be directly formed in one-step process without any coupling agents. In the present invention several complexing agent having reactive carboxyl groups are used to make stable complex with metal ions and therefore afford possibility to use these systems as imaging agent.
[0076] For the formation of conjugation, the concentration of the biopolymer ranges between about 0.05 mg/ml and 5 mg/ml, preferably 0.1 mg/ml and 2 mg/ml, and the most preferably 0.3 mg/ml and 1 mg/ml.
[0077] The overall degree of substitution of the compexing agent in polycation-complexone conjugate is generally in the range of about 1-50%, preferably in the range of about 5-30%, and most preferably in the range of about 10-20%.
[0078] Two types of polycation-complexone conjugate can be used for the formation of nanoparticles: (i) a polycation-complexone conjugate, when the complexing agent specific to the radionuclide is covalently attached to the polycation; and (ii) a polycation-complexone conjugate, when two different complexing agents are covalently coupled to the polycation biopolymer, one of them is specific to the paramagnetic ligand and the other is to the radionuclide.
[0079] In a preferred embodiment, nanoparticulate compositions, as targeted, dual-modality PET/MRI T1 contrast agents are provided. The T1 MR active agent is a paramagnetic ligand, which is preferably a lanthanide or transition metal ion, more preferably a gadolinium-, a manganese-, a chromium-ion, most preferably a gadolinium ion, useful for MRI. The preferred paramagnetic ions can make stable complex with the targeting, self-assembled nanoparticles due to the complexing agents covalently conjugated to polycation.
[0080] The gadolinium-chloride solution was used as simple aqueous solution without any pH adjusting. In a preferred embodiment, concentration of gadolinium ion ranges between about 0.2 mg/ml and 1 mg/ml, most preferably between 0.4 mg/ml and 0.5 mg/ml. The molar ratio of said gadolinium ions and complexone conjugated to the polycation ranges preferably between 1:10 and 1:1, more preferably 1:5 and 1:1, and most preferably 1:1.
[0081] In a preferred embodiment, nanoparticulate compositions, as targeted, dual-modality PET/MRI T2 contrast agents are provided. The T2 MR active agent is a superparamagnetic ligand, preferably iron-oxide ligand, which is preferably nanoparticulate iron-oxide (SPION), which is complexed to a polyelectrolyte biopolymer, and preferably homogenously dispersed.
[0082] The superparamagnetic iron oxide nanoparticles are produced in situ in presence of polyanion or targeted polyanion biopolymers, therefore superparamagnetic iron oxide particles are coated by a polyelectrolyte biopolymer.
[0083] The SPION synthesis can be performed using several types of Fe(III) and Fe(II) ions, such as pl. FeCl 3 xnH 2 O (hydrate), Fe 2 (SO 4 ) 3 , Fe(NO 3 ) 3 , Fe(III)-phosphate, FeCl 2 xnH 2 O, FeSO 4 xnH 2 O (hydrate), Fe(II)-fumarate, or Fe(II)-oxalate.
[0084] Preferably, the concentration of polyanion is between 0.01-2.0 mg/ml, the ratio of Fe(III) and Fe(II) ions ranges between 5:1 and 1:5. The reaction takes place at elevated temperature ranging between 45 and 90° C. under N 2 atmosphere.
[0085] In a preferred embodiment, nanoparticulate compositions, as targeted, dual-modality PET/CT contrast agents are provided. The CT active ligands are gold nanoparticles with size range of 2-15 nm, preferably 5-12 nm. The gold nanoparticles are produced in situ in the presence of a polyanion or a targeted polyanion biopolymer, therefore the gold nanoparticles are homogenously dispersed and coated by the polyelectrolyte biopolymer.
[0086] Preferably, the concentration of polyanion is between 0.01-3.0 mg/ml, the molar ratio of AuCl 3 and polyanion monomers ranges between 2:1 and 5:1. Synthesis of gold nanoparticles in situ in presence of polyanion may be performed using sodium borohydride as reducing agent and optionally sodium citrate dehydrate as stabilizing agent. The molar ratio of gold chloride, sodium borohydride and optionally sodium citrate dehydrate is 1:1:1.
[0087] For production of dual modality contrast agents, the T1 MR, T2 MR or CT active ligand bearing nanoparticles are radioactively labeled with a PET active radionuclide ligand, which is preferably 68 Ga ion. The preferred radioactive metal ions can make stable complex with the targeting, self-assembled nanoparticles due to the complexing agents, which are covalently conjugated to polycation.
[0088] In the last step, targeted, self-assembled nanoparticles are radiolabeled with 68 Ga to produce dual modality radiodiagnostic imaging agents. The radiolabeling takes place in HEPES solution. For labeling, a 68 Ge/ 68 Ga generator is eluted with 1 M ultra pure HCl. The second fraction is buffered with 800 μl HEPES buffer solution and 25% ultra pure NaOH to ensure a pH of 6.4-6.6. Thereafter an aqueous solution of nanoparticle is added to the solvent. The incubation temperature for radiolabeling is room temperature, the incubation time for radiolabeling ranges preferably between 2 min and 60 min, more preferably 5 min and 30 min, and the most preferably 15 min. The raw product is purified using mPES MicroKros Filter Module (10 kD, Spectrumlabs) and osmolarity is adjusted to 280+−10 mOsm/L with 5% glucose solution.
[0089] The nanocarrier formation of the present invention can be obtained in several steps. For production of PET/MR T1 dual-modality contrast agent, solution targeted polyanion and polycation-complexone are mixed to form stable, self-assembled nanoparticles, and after that aqueous solution of paramagnetic ions is added to these nanoparticles to make stable paramagnetic nanoparticulate contrast agent. Thereafter these paramagnetic nanoparticles are radioactively labeled with 68 Ga PET active radionuclide metal ions to produce the fusion contrast agent.
[0090] For the production of PET/MR T2 dual-modality contrast agent, solution of targeted, a SPON-loaded polyanion and a polycation-complexone are mixed to form stable, superparamagnetic self-assembled nanoparticles. Then these superparamagnetic nanoparticles are radioactively labeled with 68 Ga PET active radionuclide metal ions to produce the fusion contrast agent.
[0091] For the production of a PET/CT dual-modality contrast agent, a solution of the targeted, gold nanoparticles-loaded polyanion and the polycation-complexone are mixed to form stable, superparamagnetic self-assembled nanoparticles. Then these CT active nanoparticles are radioactively labeled with 68 Ga PET active radionuclide metal ions to produce the fusion contrast agent.
[0092] The nanoparticle compositions of present invention are prepared by mixing of the aqueous solution of biopolymers at given ratios and order of addition. The polyelectrolytes have statistical distribution inside the nanoparticles to produce globular shape of the nanosystems.
[0093] The size of nanoparticles can be controlled by several reaction conditions, such as the concentration of biopolymers, the ratio of biopolymers, and the order of addition. The charge ratio of biopolymers depends on the pH of the environment. In preferred embodiment, the pH of the polycation or its derivatives varies between 3.5 and 6.0, and the pH of the aqueous solution of polyanion or its derivatives ranges between 7.5 and 9.5.
[0094] Biopolymers with high charge density form stable nanoparticles due to these given pH values. The surface charge of nanoparticles could be influenced by several reaction parameters, such as ratio of biopolymers, ratio of residual functional groups of biopolymers, pH of the biopolymers and the environment, etc. The electrophoretic mobility values of nanoparticles, showing their surface charge, could be positive or negative, preferably negative, depending on the reaction conditions described above.
[0095] In a preferred embodiment, the concentration of biopolymers ranges between about 0.005 mg/ml and 2 mg/ml, preferably between 0.2 mg/ml and 1 mg/ml, most preferably 0.3 mg/ml and 0.5 mg/ml. The concentration ratio of biopolymers mixed is about 2:1 to 1:2, most preferably about 1:1. The biopolymers are mixed in a weight ratio of 6:1 to 1:6, most preferably 3:1 to 1:3.
[0096] Methods of Using Nanocarrier Compositions
[0097] The radiolabeled, targeting dual-modality nanoparticle compositions are useful for targeted delivery of radionuclide metal ions MR or CT active ligands coupled or complexed to the nanoparticles. The present invention is directed to methods of using the above-described nanoparticles, as targeted, dual-modality PET/MR or PET/CT contrast agents.
[0098] In a preferred embodiment, the nanoparticles as nanocarriers deliver the imaging agents to the targeted tumor cells in vitro, therefore can be used as targeted, dual-modality PET/MR or PET/CT contrast agents. The radiolabeled nanoparticles internalize and accumulate in the targeted tumor cells, which overexpress folate receptors, to facilitate the early tumor diagnosis. The side effect of these contrast agents is minimal, because of the receptor mediated uptake of nanoparticles.
[0099] In a preferred embodiment, the radioactively labeled, targeted dual-modality imaging agents are stable at pH 7.4, they may be injected intravenously. Based on the blood circulation, the nanoparticles could be transported to the area of interest.
[0100] The osmolarity of nanosystems was adjusted using formulating agents. The formulating agent was selected from the group of glucose, physiological salt solution, phosphate buffered saline (PBS), sodium hydrogen carbonate and other infusion base solutions.
[0101] The ability of the radiopharmaceutical, dual-modaity nanoparticles to be internalized was studied in cultured cancer cells, which overexpresses folate receptors using confocal microscopy and flow cytometry.
[0102] Specific localization, accumulation and biodistribution of these radioactively labeled targeted nanoparticles were investigated in vivo using tumor induced animal. Targeted, radiolabeled nanoparticles specifically internalize into the tumor cells overexpressing folate receptors on their surface. The specific localization was examined by PET/MR and PET/CT methods, and the biodistribution was estimated by quantitative ROI analysis.
EXAMPLES
Example 1
Preparation of Folated Poly-Gamma-Glutamic Acid (γ-PGA)
[0103] Folic acid was conjugated via the amino groups to γ-PGA using carbodiimide technique: γ-PGA (m=300 mg) was dissolved in water (V=300 ml) to produce aqueous solution at a concentration of 1 mg/ml. The pH of the polymer solution was adjusted to 6.0. After addition of 1-hydroxybenzotriazole hydrate (m=94 mg), the reaction mixture was sonicated for 5 min. The reaction mixture was cooled to 4° C. and cold water-soluble 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDC) (m=445 mg in V=15 ml water) was added dropwise to the γ-PGA aqueous solution. The reaction mixture was stirred at 4° C. for 10 min, then folic acid (FA) solution (m=69 mg in V=15 ml water) and triethylamine (V=324 μl) were added dropwise to the reaction mixture. The reaction mixture was stirred for 24 h. The folated poly-γ-glutamic acid (γ-PGA-FA) was purified using mPES MicroKros Filter Module (10 kD).
Example 2
Preparation of Folated Poly-Gamma-Glutamic Acid
[0104] Synthesis of folated PGA was performed in a two steps process. First PEG amine was coupled to FA based on a well-known reaction described in the literature. [ JACS, 130 (2008) 11467] After that FA-PEG amine was conjugated via the amino groups to PGA using the carbodiimide technique: γ-PGA (m=300 mg) was dissolved in water (V=300 ml) to produce aqueous solution at a concentration of 1 mg/ml. The pH of the polymer solution was adjusted to 6.0. After addition of 1-hydroxybenzotriazole hydrate (m=94 mg), the reaction mixture was sonicated for 5 min The reaction mixture was cooled to 4° C. and cold water-soluble 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (EDC) (m=445 mg in V=15 ml water) was added dropwise to the γ-PGA aqueous solution. The reaction mixture was stirred at 4° C. for 10 min, then folic acid-PEG-amine solution (m=100 mg in V=15 ml water) and triethylamine (V=324 μl) were added dropwise to the reaction mixture. The reaction mixture was stirred for 24 h. The folated poly-y-glutamic acid (γ-PGA-PEG-FA) was purified using mPES MicroKros Filter Module (10 kD).
Example 3
Preparation of Folated Poly-Gamma-Glutamic acid coated iron oxide (PFS)
[0105] The pH of the folated PGA solution (c=0.3 mg/ml, V=30 ml) was adjusted to 2.8. After the dropwise addition of FeCl 3 x6H 2 O solution (c=0.5 mg/ml, V=13.9 ml), the pH of the reaction mixture was raised to 8.5 and after that it was reduced to 6.0. The reaction mixture was stirred for 30 min under N 2 atmosphere, and FeCl 2 x4H 2 O (m32 8.9 mg) was added to the reaction mixture. Reaction temperature was raised to 80° C. and the pH was raised by addition of ammonium solution (V=3 ml, c=12.5 m/m%). Reaction time is 15 min.
Example 4
Preparation of Folated Poly-Gamma-Glutamic Acid Coated Gold Nanoparticles
[0106] Folated PGA was dissolved in distilled water (V=10 ml) to produce a solution with a concentration of c=0.5 mg/ml. After the dropwise addition of solution of gold (III) chloride hydrate (V=500 μl, c=1.7 mg/ml), solution of sodium citrate tribasic dihydrate (V=75 μl, c=10 mg/ml) was added dropwise to the reaction mixture. Then solution of sodium borohydride (V=40 μl, c=1 mg/ml) was added to the reaction. The reaction mixture was stirred at room temperature for 4 h, after that it was purified by dialysis.
Example 5
Preparation of Chitosan-EDTA Conjugate
[0107] Chitosan (m=15 mg) was solubilized in water (V=15 ml); its dissolution was facilitated by dropwise addition of 0.1 M HCl solution. After the dissolution, the pH of chitosan solution was adjusted to 5.0. After the dropwise addition of EDTA aqueous solution (m=11 mg, V=2 ml), the reaction mixture was stirred at room temperature for 30 min, and at 4° C. for 15 min after that, CDI (m=8 mg, V=2 ml distilled water) was added droppwise to the reaction mixture and stirred 4° C. for 4 h, then at room temperature for 20 h. The chitosan-EDTA conjugate (CH-EDTA) was purified by dialysis.
Example 6
Preparation of Chitosan-EDTA-NOTA Conjugate
[0108] The pH of the chitosan-EDTA solution (c=0.5 mg/ml, V=10 ml) was adjusted to 6.1. NODA-GA-NHS ester 10 mg was dissolved in 1 ml DMSO. The NODA-GA-NHS solution (c=10 mg/ml, V=230 μl) was added dropwise to chitosan-EDTA solution and the reaction mixture was stirred at room temperature for 24 h. The chitosan-EDTA-NOTA conjugate (CH-EDTA-NOTA) was purified by dialysis.
Example 7
Preparation of Self-Assembled MRI (T1) Nanoparticles
[0109] Stable self-assembled nanoparticles were developed via an ionotropic gelation process between the folated poly-γ-glutamic acid (γ-PGA-FA) and chitosan-EDTA-NOTA conjugate. Briefly, CH-EDTA-NOTA solution (c=0.3 mg/ml, V=1 ml, pH=4.0) was added into γ-PGA-FA solution (c=0.3 mg/ml, V=1 ml, pH=9.0) under continuous stirring. An opaque aqueous colloidal system was gained, which remained stable at room temperature for several weeks at physiological pH. ( FIG. 1 ) After radioactive labeling, Gd-ions were added to the nanosystem to produce fusion PET/MR T1 contrast agent. ( FIG. 2 )
Example 8
Preparation of Self-Assembled MRI (T2) Active Nanoparticles
[0110] CH-EDTA-NOTA solution (c=0.3 mg/ml, V=1 ml, pH=4.0) was added into folated poly-gamma-glutamic acid coated iron oxide (PFS) solution (c=0.3 mg/ml, V=2 ml, pH=9.0) under continuous stirring.
Example 9
Preparation of Self-Assembled CT Active Nanoparticles
[0111] CH-EDTA-NOTA solution (c=0.2 mg/ml, V=1 ml, pH=4.0) was added into folated poly-gamma-glutamic acid coated gold nanoparticle solution (c=0.2 mg/ml, V=3 ml, pH=9.0) under continuous stirring.
Example 10
Labeling Method of Self-Assembled Nanoparticles
[0112] A 68 Ge/ 68 Ga generator was eluted with 1.5 ml fractions of 1 M ultra pure HCl. The second 1250 μl fraction (280+−20 MBq) was buffered with 800 μl HEPES buffer solution (7.2 g HEPES was dissolved in 6 ml ultra-pure water) and 155 μl 25% ultra pure NaOH to ensure a pH of 6.4-6.6. Thereafter an aqueous solution of NOTA-Nanoparticle compound (V=245 μl c=0.3 mg/ml) was added to the solvent. The mixture was incubated at room temperature for 15 min The raw product was purified using mPES MicroKros Filter Module (10 kD, Spectrumlabs) and Osmolarity was adjusted to 280+−10 mOsm/L with 5% glucose solution.
Example 11
Characterization of 68 Ga Labeled Self-Assembled Nanoparticles
[0113] Radiochemical purity was examined by means of thin layer chromatography, using silica gel as the coating substance on a 100 mm glass-fibre sheet (ITLC-SG). Plates were developed in 0.1M Na-citrate. We applied Raytest MiniGita device (Mini Gamma Isotope Thin Layer Analyzer) to determine the distribution of radioactivity in developed ITLC-SG plates. Normal generator-eluted 68Ga solution was used as control. We examined labelling efficiency 30 min after labeling. Radiochemical samples were stored at RT in dark place. The radiolabeled products showed high degree and durable labelling efficiency (above 99%). ( FIG. 3 ) | New types of nanoparticle-based dual-modality positron emission tomography/magnetic resonance imaging (PET/MRI) and positron emission tomography/computed tomography (PET/CT) tumorspecific contrast agents have been developed. The base of the new type contrast agents is biopolymer-based nanoparticle with PET, MRI and CT active ligands. The nanoparticle contains at least one polyanion and polycation, which form nanoparticles via ion-ion interaction. The self-assembled polyelectrolytes can transport gold nanoparticles as CT contrast agents, or SPION or Gd(III) ions as MRI active ligands, and are labeled using a complexing agent with gallium as PET radiopharmacon. Furthermore, these dual modality PET/MRI and PET/CT contrast agents are labeled with targeting moieties to realize the tumorspecificity. | 0 |
This application is a continuation application of application Ser. No. 07/545,668, filed Jun. 20, 1990, now abandoned, which is a continuation application of application Ser. No. 07/249,903, filed Sep. 27, 1988, also now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to semiconductor integrated circuit devices and particularly to a semiconductor integrated circuit device, used in a manner in which output terminals of at least two such devices are connected together. The invention has particular applicability to semiconductor memories such as dynamic random access memories.
2. Description of the Prior Art
In recent years, semiconductor memories have been frequently utilized for image processing. Particularly, in the technical fields of image processing, a plurality of semiconductor memories are used for image processing and data stored in the memories are required to be output at high speed.
FIG. 1 is a conceptional diagram showing a conventional image processing system including a plurality of semiconductor memories. Referring to FIG. 1, this image processing system comprises a plurality of memory devices 20a to 20c for image processing, a digital-to-analogue (D/A) converting portion 42 for converting data signals from the memory devices 20a to 20c to analogue signals, a display portion 43 for displaying an image based on the analogue signals, and a control portion 41. The memory devices 20a to 20c are connected to receive output control signals OEa to OEc, respectively, from the control portion 41 and respective outputs thereof are connected together to an input of the D/A converting portion 42.
In operation, the memory devices 20a to 20c successively output successively signals stored therein in response to the signals OEa to OEc, respectively, supplied from the control portion 41. The output signals are converted to analogue signals by the D/A converting portion 42 and supplied to the display portion 43.
FIG. 2 is a block diagram showing an example of a conventional dynamic random access memory (referred to hereinafter as DRAM). This DRAM is applicable to a memory device shown in FIG. 1.
The DRAM such as shown in FIG. 2 is disclosed in "A Reliable 1-M Bit DRAM with a Multi-Bit-Test Mode" by M. Kumanoya et al., 1985 (IEEE Journal Solid-State Circuits, vol. SC-20, pp. 909-913) and also in "A Fast 256K×4 CMOS DRAM with a Distributed Sense and Unique Restore Circuits" by Ho Miyamoto et al., 1987 (IEEE Journal Solid-State Circuits, vol. SC-22, pp. 861-867).
Referring to FIG. 2, this DRAM comprises: a memory cell array 25 for storing data signals, a row and column address buffer 21 for receiving externally applied address signals A0 to A9 for selecting a memory cell, a row decoder 22 and a column decoder 23 for designating a memory cell by decoding the address signals A0 to A9, a sense refresh amplifier 24 for amplifying the signal stored in the designated memory cell, a data-in buffer 26 and a data-out buffer 27 for input and output of data, and a clock generator 10 for generating clock signals Φ1 and Φ2. The clock generator 10 is connected to receive a row address strobe signal RAS and a column address strobe signal CAS, applied externally. A preamplifier 29 is provided between the sense refresh amplifier 24 and the data-out buffer 27. The data-out buffer 27 is connected to receive an output enable signal OEa applied externally through a terminal 10a receiving the output enable signal.
In operation, the data signal stored in the memory cell designated by the address signals is read out by the sense refresh amplifier 24 and then supplied to the data-out buffer 27 through the preamplifier 29. The data-out buffer 27 outputs the data signal in response to the signal OEa and the clock signal from the clock generator 10.
FIG. 3 is a circuit diagram showing data-out buffers in the respective DRAMs as shown in FIG. 2. A circuit similar to the data-out buffer circuit shown in FIG. 3 is indicated, for example in an analysis report of 1986 on 1M DRAM published by MOSAID-INC. Referring to FIG. 3, DRAMs 20a to 20c have output terminals connected together as shown in FIG. 1. The DRAMs 20a to 20c comprise data-out buffers 27a to 27c, respectively, which are identical tri-state buffers. For example, the data-out buffer 27a comprises NOR gates 3a and 4a each having two inputs, N channel enhancement type MOS transistors 1a and 2a connected in series between a power supply Vcc (+5 volts) and the ground Vss (0 volt), and an inverter 5a. The NOR gates 3a and 4a are connected to receive the output enable signal OEa through respective inputs on one side thereof. The NOR gate 4a is connected to receive, at the other input thereof, a signal Sai from the preamplifier 29, while the NOR gate 3a is connected to receive, at the other input thereof, the signal Sai from the preamplifier 29 through the inverter 5a. Outputs of the NOR gates 3a and 4a are connected to respective gates of the transistors 1a and 2a. The other data-out buffers 27b to 27c also have the same circuit configuration.
In operation, for example, if the signal OEa of low level is applied to the data-out buffer 27a of the DRAM 20a, the NOR gates 3a and 4a invert the signals applied to the respective other inputs thereof and output the inverted signals. More specifically, the NOR gate 3a supplies the data signal Sai from the preamplifier 29 to the gate of the transistor 1a through the inverter 5a because the above-mentioned other input of the NOR gate 3a is connected to the inverter 5a, while the NOR gate 4a supplies the inverted data signal Sai to the gate of the transistor 2a. Consequently, when the signal Sai is at high level, the transistor 1a is turned on and the transistor 2a is turned off, whereby a signal Sao of high level is output. When the signal Sai is at low level, the transistor 1a is turned off and the transistor 2a is turned on, whereby the signal Sao of low level is output.
On the other hand, if the signal OEa of high level is applied to the data-out buffer 27a, both the NOR gates 3a and 4a output signals of low level irrespective of the level of the signal Sai. Consequently, the transistors 1a and 2a are both turned off and the output terminal 9a is brought into a high-impedance state, that is, a floating state.
FIGS. 4A and 4B are timing charts for explaining operation of the DRAMs 20a and 20b, the output terminals of which are connected together. As described previously, when the DRAMs are applied to an image processing system, the output terminals of the DRAM 20a to 20c are connected together. The DRAM 20a to 20c successively output data signals stored therein, in response to the output enable signals OEa to OEc applied thereto, respectively. However, if timing of application of the signals OEa to OEc is not suitably controlled, the following disadvantages are brought about.
FIG. 4A shows a case in which data signals Sao and Sbo from two DRAMs 20a and 20b are output simultaneously in a certain period. This phenomenon occurs when the output enable signals OEa and OEb are simultaneously at a low level. More specifically, the DRAM 20a outputs data D1 in response to the signal OEa of low level. On the other hand, the DRAM 20B outputs data D2 in response to the signal OEb. The data D1 is first provided (in a period t1) and then the data D2 is provided as a common output signal SO (in a period t3) from a node where the respective output terminals of the two DRAMs are connected together. However, as can be seen from the figure, there exists a period (t2) in which the data D1 and D2 are output simultaneously. In this period t2, an accurate common output signal So cannot be obtained. In addition, if the data D1 and D2 as provided by turn-on of the transistors 1a and 2b in FIG. 3, for example, are output in the period t2, a large penetration current flows from the power supply Vcc of the DRAM 20a to the ground Vss of the DRAM 20b through the terminals 9a and 9b. As a result, consumption of electric power is increased.
FIG. 4B shows a case in which the data signals Sao and Sbo from the two DRAMs 20a and 20b are output with a long time interval. This means that the output enable signals OEa and OEb of low level are supplied with a long time interval therebetween. Consequently, as can be seen from the figure, there exists a long period (t2')in which neither the data D1 nor the data D2 is output. In this period, the output terminals 9a and 9b of the two DRAMs 20a and 20b are both in the floating state as described above and, accordingly, the common output signal So is likely to be affected by external noise. Therefore, an accurate common output signal So cannot be obtained in this period t4.
As described above, although it is necessary to apply the output enable signals with optimally controlled timing to the DRAMs having the output terminals connected together, the timing control is difficult and an accurate common output signal So cannot be obtained.
SUMMARY OF THE INVENTION
An object of the present invention is to obtain an accurate output signal from at least two semiconductor integrated circuit devices having respective outputs connected together.
Another object of the present invention is to obtain an accurate output signal from at least two semiconductor memories having respective outputs connected together.
Still another object of the present invention is to prevent a common output signal from at least two semiconductor memories having respective outputs connected together from being affected by external noise.
A further object of the present invention is to prevent at least two semiconductor memories having their outputs connected together from simultaneously providing output signals.
A further object of the present invention is to prevent flow of a large electric current between a power supply and the ground through the respective outputs of at least two semiconductor memories having their outputs connected together.
A further object of the present invention is to obtain an accurate output signal from at least two DRAMs having their outputs connected together.
A further object of the present invention is to prevent a common output signal from at least two DRAMs having their outputs connected together from being affected by external noise.
A further object of the present invention is to prevent at least two semiconductor memories having their outputs connected together from simultaneously providing output signals.
A further object of the present invention is to provide flow of a large electric current between a power supply and the ground through the respective outputs of at least two DRAMs having their outputs connected together.
Briefly stated, a semiconductor integrated circuit device according to the present invention comprises: a circuit for applying a data signal, a buffer circuit for applying the data signal from the above-mentioned circuit to an output terminal of the device in response to an externally applied output control signal, and a latch circuit connected to the output terminal and responsive to the signal applied from the buffer circuit to hold the signal and to apply it to the output terminal. Plural semiconductor integrated circuit devices according to the present invention are used. At least two semiconductor integrated circuit devices according to the present invention are used, having their output terminals connected together. The latch circuit of each of the two devices is also responsive to the signal from the buffer circuit of the other device and holds the signal and supplies it to the output terminal connected thereto. Accordingly, the signal from the buffer circuit of one device is held by the two latch circuits and supplied to the common output terminal. Subsequently, the signal provided from the buffer circuit of the other device is also held by the two latch circuits. Since the signal from either buffer circuit is held by those two latch circuits in a period from output of the signal from one buffer circuit until output of the signal from the other buffer circuit, the signal can be prevented from being affected by external noise. In addition, a time duration of the output control signal applied externally is shortened because the latch circuits are provided. Accordingly, simultaneous output of the signals from the two buffer circuits can be prevented. In the above described manner, an accurate common output signal is obtained.
In a preferred embodiment, the present invention is applied to semiconductor memories. Consequently, when at least two semiconductor memories having their output terminals connected together are used, an accurate common output signal is obtained.
In a variation of the preferred embodiment, the present invention is applied to DRAMs. Consequently, when at least two DRAMs having their output terminals connected together are used, an accurate common output signal is obtained.
These objects and other objects, features, aspects and advantages of the present invention will become more apparent from the following detailed description of the present invention when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a conceptional diagram showing a conventional image processing system including a plurality of semiconductor memories;
FIG. 2 is a block diagram showing an example of a conventional DRAM;
FIG. 3 is a circuit diagram showing data-out buffers of conventional DRAMs, the output terminals of which are connected together;
FIGS. 4A and 4B are timing charts for explaining the operation of the two data-out buffers shown in FIG. 3;
FIG. 5 is a circuit diagram showing data-out buffers of DRAMs according to an embodiment of the present invention, the output terminals of which are connected together;
FIG. 6 is a timing chart for explaining operation of the two data-out buffers shown in FIG. 5; and
FIG. 7 is a circuit diagram showing an example of a latch circuit used in the data-out buffer shown in FIG. 5.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 5 is a circuit diagram of data-out buffers in an embodiment of the present invention. Referring to FIG. 5, compared with the conventional case shown in FIG. 3, the data-out buffers further include latch circuits 8a to 8c connected to output terminals 9a to 9c, respectively. For example, the latch circuit 8a in the DRAM 20a includes two inverters 11a and 12a. An output of the inverter 11a, an input of the inverter 12a and the output terminal 9a are connected together, and an input of the inverter 11a and an output of the inverter 12a are connected together. The latch circuits 8b and 8c also have the same circuit configuration. Other circuit construction in this embodiment is the same as that of the conventional case shown in FIG. 3 and therefore a description thereof is omitted.
FIG. 6 is a timing chart for explaining operation of the data-out buffers shown in FIG. 5. Referring to FIGS. 5 and 6, the operation will be described as follows.
First, an output enable signal OEa of low level is applied to the DRAM 20a. A data signal Sao representing data D1 for example is output from a connection point of transistors 1a and 2a (at time T1). The latch circuit 8a responds to the data signal Sao, so that a state of the latch circuit 8a is determined and the data D1 is held. Thus, a data signal sla indicating the data D1 is output. On the other hand, the latch circuit 8b in the DRAM 20b also responds to the data signal Sao applied through the output terminals 9a and 9b, so that a state of the latch circuit 8b is determined and a data signal slb indicating the data D1 is output. Accordingly, after the output enable signal OEa of low level is applied, a common output signal So indicating the data D1 is obtained. Since the data D1 is maintained by the latch circuits 8a and 8b, the common output signal So indicating the data D1 is output (at time T2 to T3) even after the signal OEa has been raised to high level.
Then, the output enable signal OEb of low level is applied to the DRAM 20b. A data signal Sbo indicating data D2 is output from a connection point of transistors 1b and 2b (at time T3). The latch circuits 8b and 8a both hold the data D2 in response to the data signal Sbo as described above. Thus, a data signal Slb indicating the data D2 is output from both the DRAMs 20a and 20b. Accordingly, after the output enable signal OEb is applied to the DRAM 20b, the common output signal So indicating the data D2 is obtained. Since the data D2 is held by the latch circuits 8a and 8b, the common output signal So indicating the data D2 is output (at time T4 and thereafter) even after the signal OEb has been raised to high level.
Thus, the data signals are output successively from the DRAMs 20a and 20b having their output terminals connected together as described above. In the same manner, data signals are output successively from other DRAMs and the latch circuits 8a to 8c perform holding operation in response to the respective data signals. Consequently, even if the data signals Sao to Sco are output from the DRAMs 20a to 20c with long time intervals therebetween, the common output signal So can be prevented from being affected by external noise since the data signals Sao to Sco are held by the latch circuits 8a to 8c. Accordingly, an accurate common output signal So is obtained.
In addition, since the latch circuits 8a to 8c are provided, a pulse duration tw of the respective output enable signals OEa to OEc can be shortened compared with the conventional case. In other words, it is not needed to continuously output the data signals for a long period by increasing the pulse duration tw of the signals OEa to OEc. The pulse duration tw may only have a duration necessary for changing the states of the latch circuits 8a to 8c. Thus, the short pulse duration tw of the signals OEa to OEc serves to prevent simultaneous output of plural data signals as shown in FIG. 4A. Consequently, an accurate common output signal So is obtained and flow of a large penetration current can be prevented.
FIG. 7 is a circuit diagram showing an example of the latch circuit used in the data-out buffer shown in FIG. 5. Although only the latch circuit 8a is shown as an example in FIG. 7, the other latch circuits 8b and 8c have the same construction. Referring to FIG. 7, the inverter 11a comprises a CMOS inverter formed by a PMOS transistor 111 and an NMOS transistor 112, and a CMOS inverter formed by a PMOS transistor 121 and an NMOS transistor 122.
In order to perform, in the latch circuits 8a to 8c, the operation described in connection with FIG. 6, the below indicated circuit conditions are required. More specifically, as for the latch circuit 8a, assuming that mutual conductances of the transistors 1a, 2a, 111 and 112 are g m1 , g m2 , g m3 and g m4 , the following conditions are required.
g.sub.m1 >g.sub.m4 (1)
g.sub.m2 >g.sub.m3 (2)
As is generally known, a mutual conductance is defined by a ratio of a voltage change between a gate and a source of an FET to a current change in its drain. Therefore, if the sizes of the transistors 1a, 2a, 111 and 112 are set to satisfy the inequalities (1) and (2), the operation in FIG. 6 can be performed.
Furthermore, the inverter 11a needs to satisfy conditions for supplying a predetermined output voltage. More specifically, Mitsubishi Data Book (on Memories) of 1988, for example prescribes current values and voltage values as below to be satisfied by output data signals of the DRAM.
TABLE 1______________________________________ current value voltage value______________________________________output data signal "H" -2 mA(I.sub.OH) Min. 2.4 V(V.sub.OH)output data signal "L" 4.2 mA(I.sub.OL) Max. 0.4 V(V.sub.OL)______________________________________
In order to output the data signal "H" (high level), the on resistance r3 (=1/g m3 ) of the transistor 111 is as follows.
r3=(Vcc-V.sub.OH)/(-I.sub.OH) (3)
Accordingly, assuming that the power supply voltage Vcc is 4.5V, the value of r3 should be set to about 1 KΩ.
In addition, in order to output the data signal "L" (low level), the on resistance r4 (=1/g m4 ) of the transistor 112 is as follows.
r4=V.sub.OL /I.sub.OL (4)
Accordingly, the value of r4 should be set to about 100Ω.
On the other hand, the on resistance r1 (=1/g m1 ) of the transistor 1a and the on resistance r2 (=1/g m2 ) of the transistor 2a are set to about several hundreds of Ω or less and several tens of Ω or less, respectively.
As described in the foregoing, when at least two semiconductor integrated circuit devices according to the present invention are used with their output terminals being connected together, a data signal is always held in the latch circuits 8a to 8c and, accordingly, the common output signal So can be prevented from being affected by external noise. Furthermore, since the pulse duration of the output enable signals OEa to OEc can be shortened, and therefore simultaneous output of plural data signals can be prevented. As a result, the common output signal So can be prevented from being unstable and, in addition, flow of a large penetration current between the power supply Vcc and the ground Vss through the output terminals 9a to 9c can be prevented. Thus, an accurate common output signal is obtained without requiring complicated control procedures.
Although the present invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, the spirit and scope of the present invention being limited only by the terms of the appended claims. | A plurality of devices or memories, preferably dynamic random access memories (DRAMs), are used with their output terminals connected together, and the devices or DRAMs output data signals successively in response to externally applied output enable signals. A latch circuit is provided at the output terminal of each device or DRAM. The latch circuits hold not only the output signal of the DRAM to which it belongs but also the commonly connected output signal of another DRAM in response thereto. Consequently, the output signal from any one DRAM is held by the latch circuits until an output signal is provided from another DRAM. Thus, an accurate common output signal can be obtained without being affected by external noise or the requirement for extremely accurate timing signals. | 6 |
[0001] The present application claims the priority of German patent application no. 10 2007 016 953.3 “Guide Rail Assembly and Driving Element for Motor Vehicle Window Lifters and Method for the Production Thereof” filed on 5 Apr. 2007, the content of which is expressly included herewith by way of reference for the purposes of disclosure.
FIELD OF THE INVENTION
[0002] The present invention relates in general to guide rail assemblies made of plastic material for motor vehicle window lifters and relates in particular to a guide rail assembly according to the preamble of claim 1 , a driving element (follower) for motor vehicle window lifters and a method for the production thereof.
BACKGROUND OF THE INVENTION
[0003] From the prior art are known plastic carrier plates, also referred to as assembly carriers, which after being connected to a module carrier enable a moisture-proof separation of the wet space and the dry space, a pre-assembly of door module components and door module functions, for example of door operating elements, electric window lifters, side airbag module, speakers or similar, and allow for high mechanical strength requirements with easy installation. The advantage of using plastic as a material emerges particularly in that it is possible as a result to produce the carrier plate in a simple manner by means of injection moulding.
[0004] Examples of such carrier plates are disclosed for example in DE 199 44 965 A1 by the applicant or DE 197 32 225 A1 (corresponding to U.S. Pat. No. 5,906,072), the content of which is expressly included in the present application by way of reference.
[0005] DE 10 2005 033 115 A1 (corresponding to WO 2007/006296 A1) discloses a unit carrier made of plastic material for a motor vehicle door with a guide rail moulded integrally thereon in one piece. The guide rail should be characterised by high stability and rigidity in order to resist the considerable forces arising during operation of the guide rail. The guide rail comprises two guide webs spaced apart from each other formed on each of which are guide protrusions that protrude inwards away from the respective guide web. Additional stiffening beads and concavities are provided in the region of the guide rail to increase the rigidity. Thus the guide webs are not bendable in the sense of the present application.
[0006] FIG. 7 of this application illustrates an injection moulding tool for the production of such a guide rail. The injection moulding tool comprises one central slider and two lateral sliders in the region of the guide rail, which have lateral protrusions to form the guide protrusions on the guide webs. Thus the total number of the injection moulding tool's sliders is comparatively high which increases the costs for the injection mould and also for the injection moulding process. As there are no recesses provided on the central slider for moulding of the guide protrusions, the principle of demoulding the guide rail assembly from (out of) the injection moulding tool also deviates distinctly from that according to the present invention.
[0007] DE 10 2004 063 514 A1 (corresponding to WO 2006/069 559 A1) relates to a window pane made of synthetic material for motor vehicles. Disclosed is a carrier plate made from a plastic material on which a guide rail is formed integrally. To safeguard against transverse forces, the guide rail is stepped in design as illustrated in FIGS. 2A to 2C . The guide rail does not have two guide webs spaced apart from each other with guide protrusions formed thereon protruding inwards or outwards. The principle of production, particularly demoulding from (out of) an injection moulding tool, also deviates distinctly from the procedure according to the present invention.
[0008] DE 36 00 413 C2 (corresponding to U.S. Pat. No. 4,700,508) discloses a central guide rail, formed from a sheet metal profile and fixed to the motor vehicle bodywork, for a motor vehicle window lifter, wherein slide elements are disposed on the guide rail spaced apart from each other and are slidable on flanges of the guide rail which are orientated perpendicularly and parallel to the window pane.
[0009] A cost benefit emerges particularly if the guide rail, which serves to guide a driving element serving to connect the window pane to the window lifter, is also made of plastic material, is in particular integrally with the carrier plate, namely by means of injection moulding of a plastic material. In order to guide the window pane and the driving element securely in a direction at right angles to the vehicle's longitudinal direction, the driving element must engage behind the guide rail's guiding profile. Only in this way does the driving element remain securely guided on the guide rail even at comparatively high accelerations in the motor vehicle's transverse direction such as occur particularly when the door is slammed shut. As explained previously particularly on the basis of DE 10 2005 033 115 A1, comparatively large sliders are necessary in the moulding tool in order to implement such a rear grip when injection moulding the carrier plate from a plastic material. This increases the cycle time when injection moulding the carrier plate and thus also the costs and risks.
SUMMARY OF THE INVENTION
[0010] Thus it is an object of the present invention to provide a guide rail assembly made of a plastic material for motor vehicle window lifters, said assembly being inexpensive and easy to produce and install and which reliably guides a driving element. According to a further aspect of the present invention, there is also to be provides a driving element for a motor vehicle window lifter made of a plastic material, said driving element being inexpensive and easy to produce and install and being reliably guided on a guide rail, in particular on a guide rail which will be explained subsequently in greater detail. According to further aspects of the present invention, there is also to be provided a method for the production of a guide rail assembly and a driving element, as explained subsequently.
[0011] These and further objects are achieved according to the present invention by means of a guide rail assembly having the features according to claim 1 , by a driving element or follower according to claim 20 and by a method for the production or assembly thereof according to claims 17 , 27 and 28 , respectively. Further advantageous embodiments are the subject-matter of the related dependent claims.
[0012] Thus the present invention proceeds according to a first aspect from a guide rail assembly for motor vehicle window lifters, which is formed from a plastic material and comprises a flat carrier and at least one guide rail for guiding a window lifter driving element, wherein the guide rail has two guide webs spaced apart from each other, which protrude from the carrier, and wherein guide protrusions are formed on the guide webs, each of which extends over the entire guidance length of the guide webs, and which protrude by a predetermined distance inwards or outwards from the respective guide web such that the driving element cooperating therewith is securely guided against detachment perpendicular to the carrier.
[0013] According to the invention, the guide webs are designed such that in the region of the guide protrusions they are each elastically bendable inwards or outwards by at least the predetermined distance. Thus according to the invention, the guide rail may be demoulded from an injection moulding tool by means of elastic deformation of its guide webs. Consequently, according to the invention, it is possible to reduce the number of sliders necessary for the moulding tool. In particular, no cross sliders or transversal sliders are necessary for forming the guide webs as all the moulding tool parts can be withdrawn in the same direction in order to demould the guide rail from (out of) the moulding tool.
[0014] In this case the guide protrusions protrude preferably perpendicularly or, according to further embodiments, virtually perpendicularly away from the carrier and are formed integrally therewith. The carrier may, according to a further embodiment, be extended into a carrier plate basically known from the prior art, also referred to as a door module carrier, which can also carry at least one further guide rail. At the same time, the guide rail is formed according to the invention from two guide webs spaced apart from each other, which together form a guide rail having a substantially U-shaped cross-section, wherein a guide protrusion protrudes inwards and/or outwards from the inside or outside of the guide webs, said guide protrusion cooperating positively with correspondingly formed sections of the driving element in order to guide it securely in the guide rail's longitudinal direction and to safeguard against detachment of the driving element perpendicular to the longitudinal direction, i.e. in the intended transverse direction of the vehicle. For this purpose the driving element preferably engages behind one or a plurality of the guide rail's guiding protrusions as explained below.
[0015] To implement such a rear grip, the protrusions each have, according to a further embodiment, a guide surface facing towards the carrier, which preferably represents a plane, wherein the notional extension of the guide surface includes a first acute angle with a line perpendicular to the carrier. The protrusion of the inclined guide surface onto the plane defined by the carrier in the region of the guide rail thereby defines the predetermined distance referred to previously by which the guide webs are bent elastically inwards or outwards on demoulding from the moulding tool. Sections of a moulding tool also engage, in a similar manner to the driving element, behind the guide protrusions after injection moulding of the guide rail assembly. According to the invention, demoulding of the guide rail assembly from the moulding tool is made easier in that the guide surface previously mentioned extends at an angle and not in parallel with the carrier. According to a further embodiment, however, such a rear grip can also be still be implemented in principle if the guide surface previously mentioned extends in parallel with or substantially in parallel with the carrier.
[0016] According to a further embodiment, the protrusions each also have a bevel facing away from the carrier, the notional extension o which includes a second acute angle with a line perpendicular to the carrier. In this case the first acute angle is smaller than the second acute angle. The bevel facing away from the carrier is thus formed preferably steeply in the installation (assembly) direction to enable effortless clipping or pushing of the driving element onto the guide rail. As a result, it is possible to advantageously reduce installation forces in particular. On the other hand, the guide surface facing the carrier is formed flatter in this case to enable high detachment forces of the driving element perpendicular to the carrier and thus to ensure a high holding force of the driving element on the guide webs. However, the angle must be chosen such that demoulding of the guide rail assembly from the injection mould or from the tool can be carried out without problems, particularly without damage to the guiding regions of the guide rail assembly.
[0017] The angles of inclination of the guide surface or bevel referred to previously are appropriately chosen in this case such that the limits of elastic deformability of the material regions concerned are taken into account when designing the tool and when specifying the dimensions of the portions of the guide rail. The demoulding forces arising in this case are not essential for the invention.
[0018] According to a further embodiment, the guide protrusions each have a spherical, i.e. essentially ball-shaped or outwardly convex guide surface on the side facing towards the carrier, which merges into the associated guide web at an obtuse angle. It is also possible to implement forcible demoulding of the guide rail assembly from the moulding tool with elastic deformation of the guide webs due to a spherical guide surface.
[0019] According to a further embodiment, the guide webs in the region of the guide protrusions are each bendable elastically inwards or outwards by the predetermined distance on operation of a minimum force, whereby the minimum force corresponds to a force required for demoulding of the guide rail or guide rail assembly made of plastic from the moulding tool. Expediently, the required minimum force is greater in this case than a maximum force which corresponds to a maximum holding force of the driving element on the guide rail during intended use. Such a maximum holding force may be specified here, for example, by the driving element's mass multiplied by a maximum intended transverse acceleration, i.e. acceleration in the vehicle's transverse direction. Consequently, sufficient resistance to detachment of the driving element on the guide rail is implemented even without additional securing elements which secure the driving element on the guide rail.
[0020] According to a further embodiment, the guide rail assembly referred to above comprises a window lifter driving element having contact sections, which are formed in correspondence with the guide protrusions of the guide webs and cooperate therewith in order to guide the driving element securely perpendicular to the carrier to prevent detachment. Preferably, the window lifter driving element is guided in the process substantially without play in the vehicle's longitudinal direction and secured against tilting about the guide rail's longitudinal axis.
[0021] According to a further embodiment, formed in each case on the driving element are securing means which counteract or prevent or inhibit bending of the guide webs. Here the securing means may be permanently in contact on the inner or outer sides of the guide webs or may only come into contact with them when the guide webs are bent inwards or outwards and namely by a distance that is smaller than the predetermined distance previously referred to which would lead to cancellation of the positive fit previously referred to between the driving element and the guide protrusions. At the same time the securing means have sufficient rigidity, particularly in the vehicle's longitudinal direction, to suppress or inhibit bending or further bending of the guide webs.
[0022] Expediently, the driving element has a central protrusion which protrudes into an inner side of the essentially U-shaped guiding profile of the guide rail.
[0023] The central protrusion may at the same time be thickened in a mushroom-shape in order to implement the rear grip referred to previously, in particular in order to implement a positive fit between the mushroom-shaped thickened section of the driving element and the guide protrusions of the guide webs protruding into the inner volume of the guide rails. In such an embodiment, the securing means are disposed on an outer side of the guide webs, i.e. on a side of the guide webs opposing the guide protrusions.
[0024] According to a further embodiment, the securing means are designed as resilient webs, which are bent up at an acute angle and, directed towards a base of the driving element, are inclined towards the outsides of the guide webs. In this way it is possible to implement an advantageously high intrinsic stiffness of the securing webs against outward bending of the guide rail's guide webs. Preferably, in this case the mushroom-shaped thickening on the driving element's central section protrudes further into the inside of the guide rail than the elastic securing webs stand out from the driving element's base. In this way it is possible to virtually exclude detachment of the driving element from the guide rail in the vehicle's transverse direction.
[0025] According to a further embodiment, the guide protrusions are provided on the outside of the guide web, whereby resilient securing webs protrude in the manner of wings from the outer sides of the driving element, the front free ends of said securing webs being designed to correspond with the guide protrusions and being in contact therewith. At the same time the driving element is disposed practically jammed against the guide webs of the guide rail which reliably prevents detachment of the driving element from the guide rail in the vehicle's transverse direction. Expediently, the contact surfaces are formed as concave dished webs.
[0026] For reliable introduction of the driving element into the guide rail profile referred to previously, introductory bevels are provided at the same time on the sides of the guide protrusions facing away from the carrier, said bevels coming into contact with a central protrusion of the driving element and/or with the securing means on introduction of the driving element into the guide rail and so bringing about elastic bending of the guide webs of the guide rail or of the securing means on introduction of the driving element into the guide rail profile.
[0027] According to a further aspect of the present invention, a method is provided for the production of a guide rail assembly, as described previously, by means of injection moulding from a plastic material. To form the guide rail, the moulding tool in this case comprises three movable moulding tool parts, which together form cavities for forming the flat carrier and for forming the guide webs with the guide protrusions formed integrally therewith. According to the invention, in the process the part of the moulding tool defining the guide rail's interior is designed in a wedge shape, thus its marginal surfaces run towards or away from each other at an acute angle. In this case, for forming the guide rail profile, the wedge-shaped moulding tool part is disposed between two adjacent moulding tool parts, which are expediently formed in one piece. According to the invention, these three movable moulding tool parts are withdrawn in the same direction when demoulding the guide rail assembly from the moulding tool. The moulding tool according to the invention thus manages without a cross slider (transverse slider) which conventionally leads to an increased cycle time and thus to higher costs and risks. When the wedge-shaped part of the moulding tool is withdrawn, there is elastic bending of the guide webs forming the guide rail at the same time, as described previously.
[0028] According to a further aspect of the present invention, which may also in principle be claimed separately by means of an independent claim, but which is particularly designed or suitable for a guide rail assembly, as described previously, according to the invention a driving element for motor vehicle window lifters is further provided, which has at least one U-shaped longitudinal recess and is comprised of a first material, expediently of plastic and produced in a plastic injection moulding process. According to the invention, the driving element has at least one sliding insert, which is formed from a second material that is different from the first material and which is held securely in the relevant longitudinal recess of the body. At the same time the sliding insert has a guide groove, which is formed to correspond at least in sections to a guide web of the associated guide rail such that the driving element (follower) is movably guided in the guide web's longitudinal direction by positive-fit engagement of the guide web in the guide groove and is secured against detachment perpendicular to the longitudinal direction.
[0029] The sliding insert is thus formed as a separate component from a different material such that, according to the invention, it is possible to provide a particularly appropriate tribological pairing for the counterpart, i.e. for the associated guide web.
[0030] According to a further preferred embodiment, according to the invention, a guide rail assembly is provided, which comprises a driving element (follower), wherein a longitudinal recess is formed in the driving element, which extends parallel to the carrier's guide webs, and whereby a locking web furthermore protrudes from the carrier, said locking web engaging in the longitudinal recess so as to counteract bending of the web's surfaces forming the longitudinal recess and/or to prevent the at least one sliding insert from popping out of the associated U-shaped longitudinal recess on detachment of the driving element perpendicular to a plane defined by the carrier. In this manner the locking web locks each sliding insert inserted into the driving element.
[0031] At the same time, according to the invention, it is possible to simplify the assembly of a guide rail assembly which comprises a guide rail and a driving element engaging therein. The driving elements are conventionally threaded (inserted) into the guide rail profile at the top and bottom end of the guide rail and then slid into a position determining the window lifter's assembly position. As also with the previously mentioned first aspect of the present invention, relating to the guide rail assembly in which the driving element may be pressed onto or clipped into the guide rail under elastic deformation of the guide webs in the vehicle's transverse direction, the driving element may also, according to the second aspect of the present invention, be assembled by pressing on or clipping in under the application of force in the vehicle's transverse direction. In this case, first of all the appropriate sliding insert is placed onto or slid onto the associated guide web, if necessary under elastic deformation of side walls of the U-shaped sliding insert. The driving element is subsequently pushed onto the sliding insert or sliding inserts such that each sliding insert is accommodated in the driving element's associated longitudinal recess and thus a driving element is formed which is securely guided on the guide web in its longitudinal direction but is secured on the guide web against detachment perpendicular to the longitudinal direction, i.e. in the vehicle's transverse direction.
[0032] According to a preferred alternative embodiment, the sliding inserts are, however, first inserted in the driving element, in particular clipped in, in order to thus form a pre-assembled driving element unit. This is then placed on the associated guide webs in such a manner that the driving element is movably guided on each guide web in the longitudinal direction thereof and is secured in a direction perpendicular thereto. Subsequently, the driving element is pushed into a region in which the carrier's locking webs engage in the driving element's longitudinal recess in such a manner that bending of the driving element's surfaces forming the longitudinal recess and/or popping of the at least one sliding insert out of the associated U-shaped longitudinal recess on detachment of the driving element perpendicular to a plane defined by the carrier is counteracted such that the sliding inserts are locked or secured in the driving element.
[0033] At the same time, the driving element may comprise securing means in order to hold the sliding insert securely in each longitudinal recess. Basically, such securing means may be implemented by means of a friction fit, force fit or positive fit. Especially preferred, the securing means according to the invention are implemented by means of a positive fit. This may be implemented by the engagement of securing protrusions and securing recesses formed on the driving element and the sliding insert respectively into securing recesses and securing protrusions corresponding to the sliding insert or the driving element.
[0034] According to a preferred embodiment, the securing means in this case are implemented as protruding longitudinal edges of the driving element's relevant longitudinal recess. Thus the sliding insert may be introduced therein by clipping on of the driving element.
[0035] In a further embodiment, having two sliding inserts spaced apart from each other, a central web may be formed between the sliding inserts, said web having a central longitudinal recess, which enables elastic bending of the side walls limiting the driving element's longitudinal recesses when the sliding inserts are clipped in. At the same time, securing hooks, which hold the sliding inserts securely in the longitudinal recess by means of positive fit, may be formed on the central web.
OVERVIEW OF FIGURES
[0036] The invention will be described in the following in an exemplary manner and with reference to the associated drawings, from which will ensue further features, advantages and objects to be achieved. The figures show:
[0037] FIG. 1 in a schematic cross-sectional view the engagement of a driving element in a guide rail according to a first embodiment of the present invention;
[0038] FIG. 2 in a schematic sectional view three moulding tool parts for injection moulding of the guide rail assembly according to FIG. 1 ;
[0039] FIG. 3 the guide rail assembly according to FIG. 1 in a first phase of demoulding from the moulding tool according to FIG. 2 ;
[0040] FIG. 4 the guide rail assembly according to FIG. 1 in a second phase of demoulding from the moulding tool according to FIG. 2 ;
[0041] FIG. 5 in a schematic cross-sectional view the engagement of a driving element in a guide rail of a guide rail assembly according to a second embodiment of the present invention;
[0042] FIG. 6 in a schematic sectional view the production of a guide rail according to a third embodiment of the present invention in a moulding tool with three movable moulding tool parts;
[0043] FIG. 7 the cooperation of a driving element with the guide rail according to FIG. 6 according to a third embodiment of the present invention;
[0044] FIG. 8 a driving element with two sliding inserts of a different material according to a further embodiment of the present invention;
[0045] FIG. 9 a a driving element according to a further embodiment of a guide rail assembly of the present invention, which is held securely on the carrier against detachment perpendicular to the carrier using a locking web provided on the carrier;
[0046] FIG. 9 b in a schematic partial view from above the guide web of the guide rail assembly according to FIG. 9 a;
[0047] FIG. 10 a in a partial section and in a view from above the cooperation of the driving element and the locking web of the guide rail assembly according to FIG. 9 a on attaching the driving element to the guide webs close to their end region; and
[0048] FIG. 10 b in a partial section and in a view from above the cooperation of the driving element and the locking web of the guide rail assembly according to FIG. 9 a in a defined working range of the driving element.
[0049] Identical reference numerals in the Figures indicate identical elements or element groups or those with substantially the same effect.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0050] According to FIG. 1 , two guide webs 4 , which together form a substantially U-shaped rail profile, protrude essentially perpendicularly from carrier plate 1 on which the guide rail is formed, said carrier plate being substantially flat and only a protruding section of which is illustrated for reasons of simplification. According to FIG. 1 , protruding into inner space 3 of the rail profile from the insides of guide webs 4 are triangular guide protrusions 5 . Guide protrusions 5 each have a bevel 7 facing towards base 2 of the rail profile and an introductory bevel 6 facing away from base 2 . Engaging in the rail profile thus formed is a central thickened section 11 of driving element 10 . More precisely, the acute angle at which a notional extension line of bevel 7 intersects the plane defined by carrier plate 1 in the region of the guide rail corresponds to the angle at which rear bevels 15 intersect side walls 12 of central section 11 . According to FIG. 1 , the front ends of guide webs 4 are in contact with the base of driving element 10 in such a manner that driving element 10 , due to the positive fit, is guided movably overall on the guide rail thus formed in its longitudinal direction and is secured against detachment from the rail profile in a direction perpendicular thereto, i.e. in the vehicle's transverse direction y.
[0051] As will be described subsequently with reference to FIGS. 2-4 , guide webs 4 may be bent elastically outwards, namely in the region of guide protrusions 5 , by at least a distance which corresponds to the distance by which guide protrusions 5 protrude from the inside of guide webs 4 , i.e. substantially by at least the height of the point of triangle-shaped guide protrusion 5 relative to the inside of guide web 4 . Consequently, driving element 10 may be pressed into or clipped onto the rail profile formed by guide webs 4 . For this purpose, formed on the upper front face of central thickened section 11 are two bevels 14 , which on being pressed onto driving element 10 ultimately come into contact with introductory bevels 6 and subsequently, on further pressing of driving element 10 onto the rail profile, bring about an expansion of guide webs 4 until finally central thickened section 11 slides at its widest point past pointed, triangle-shaped guide protrusions 5 and slides into inner space 3 of the rail profile. On further pushing on of driving element 10 , guide webs 4 ultimately return to the initial position shown in FIG. 1 in which they are pre-tensioned.
[0052] According to FIG. 1 , driving element 10 also has two wing-like marginal webs 16 , 17 , which in cross-section almost form a closed equilateral triangle with the base of driving element 10 , wherein front free ends 17 are inclined at an acute angle to the base of driving element 10 and are disposed a short distance from the outside of guide webs 4 or, according to a further embodiment (not illustrated) are permanently in contact on the outside of guide webs 4 . Webs 16 , 17 serve as securing elements in order to additionally secure the driving element against detachment from the guide rail in the vehicle's transverse direction y. According to FIG. 1 , inclined marginal web 17 is spaced further from base 2 of the guide rail than the widest part of central thickened section 11 . On detaching driving element 10 from the guide rail, guide webs 4 are pressed outwards due to the cooperation of rear bevels 15 with bevels 7 . This evasive movement of guide webs 4 is, however, at least obstructed or even prevented by securing webs 16 , 17 which depends on the elastic properties of securing webs 16 , 17 and their geometric design. It should be emphasized that additional securing webs 16 , 17 are not absolutely necessary.
[0053] In the embodiment according to FIG. 1 , rear bevels 15 of driving element 10 engage behind guide protrusions 5 of guide webs 4 . In the embodiment illustrated, the angle at which bevels 7 are inclined towards base 2 is approximately 45 degrees. This acute angle may be varied within broad limits and may even be relatively small but should not be negligibly small so as to enable demoulding of the rail profile from the moulding tool.
[0054] A method for injection moulding of the carrier plate with the guide rail according to FIG. 1 is described below with reference to FIGS. 2 to 4 . FIG. 2 illustrates three adjacent moulding tool parts 30 - 32 , which together define the carrier plate in the region of the guide rail. In this case moulding tool part 32 is wedge-shaped, i.e. the marginal areas of moulding tool part 32 taper towards one another at a comparatively small acute angle. According to FIG. 2 , formed in the marginal areas of wedge-shaped moulding tool part 32 are recesses 34 , 35 , which define the guide protrusions and guide webs of the subsequent rail profile. Together moulding tool parts 30 - 32 form a central cavity 33 , which is limited by a male mould not illustrated, in order to thus define the shape of the carrier plate. Moulding tool parts 30 - 32 are slidable in the direction of the arrow for demoulding of the work piece, whereby regions 30 , 31 are expediently integrally formed such that sliders 32 forms the second tool part. The third tool part is formed at the same time by the male mould not illustrated, which together with the other tool parts forms the cavity to be filled.
[0055] The following procedure is followed to produce the carrier plate with the guide rail: first of all the moulding tool is formed according to FIG. 2 and the male mould not illustrated is inserted. Injection moulding of the carrier plate with the guide rail formed integrally therein is carried out subsequently. Then both lateral moulding tool parts 30 and 31 are first withdrawn in the direction of the arrow for demoulding. This procedure is illustrated schematically in FIG. 3 , which is a hugely inflated representation from a perspective point of view. In this state, wedge-shaped moulding tool part 32 continues to be engaged with the guide rail.
[0056] In a subsequent step, as shown in FIG. 4 , wedge-shaped moulding tool part 32 is then also lifted off in the same direction. In FIG. 4 one can identify triangle-shaped notches 38 formed in marginal areas 37 , said notches defining guide protrusions 5 on the insides of guide webs 4 . On withdrawal of wedge-shaped moulding tool part 32 , guide webs 4 are bent elastically outwards such that the tips of guide protrusions 5 slide on marginal areas 37 until guide webs 4 finally return into the initial position illustrated in FIG. 4 due to their elastic properties.
[0057] FIG. 5 shows a second embodiment in which driving element 10 can no longer be detached from the guide rail without destroying it. To this end, driving element 10 is formed substantially in a C-shape having two marginal webs 19 , which extend perpendicularly to the base of driving element 10 . According to FIG. 5 , protruding from the insides of marginal webs 19 are two protrusions acting as securing elements, which may be permanently in contact on the outsides of guide webs 4 but which may also be disposed at a short distance from them, said distance being smaller than the predefined distance referred to previously. According to FIG. 5 , guide protrusions 5 have on their inside a bevel 7 , which cooperates with centrally thickened section 11 of driving element 10 . According to FIG. 5 , securing protrusions 20 and the widest sections of centrally thickened section 11 are disposed at the same distance from base 2 of the rail profile. In order to detach driving element 10 from the rail profile in the vehicle's transverse direction y, it is necessary not only to bend guide webs 4 outwards but also marginal webs 19 at the same time. Thus it is possible to achieve a high resistance to detachment of driving element 10 . Expediently, such a driving element is assembled by threading onto one of the ends of a guide rail.
[0058] As can be seen from FIG. 5 , rear sides 18 of centrally thickened section 11 extend at a right angle to lateral surfaces 12 . Basically, however, an inclined surface may also be provided at this point as in the embodiment according to FIG. 1 .
[0059] A third embodiment is described below with reference to FIGS. 6 and 7 . According to FIG. 7 , triangle-shaped guide protrusions 5 protrude from the outsides of guide webs 4 . Three moulding tool parts 30 - 32 , as illustrated by way of example in FIG. 6 , are used to produce such a rail profile. According to FIG. 6 , the spaces, which are defined by guide webs 4 and guide protrusions 5 , are formed in the marginal areas of moulding tool part 30 , 31 . Central moulding tool part 32 is wedge-shaped, i.e. its lateral surfaces taper towards each other at a relatively small acute angle, as described previously on the basis of FIG. 2 .
[0060] The following procedure is followed to demould such a guide rail: first of all wedge-shaped moulding tool part 32 is withdrawn in the wedge direction illustrated such that the insides of guide webs 4 are exposed. Subsequently, adjacent moulding tool parts 30 , 31 are withdrawn in the same direction as indicated by the arrows. In the process, introductory bevels 7 of guide protrusions 5 slide off on the narrowed sections of moulding tool parts 30 , 31 which leads to elastic bending of guide webs 4 in the inward direction. Finally, guide webs 4 return to their unstressed initial position 4 according to FIG. 7 .
[0061] To further secure driving element 10 on the rail profile, provided laterally on driving element 10 are marginal webs 19 , 17 , whereby lateral webs 19 extend substantially perpendicular to the base of driving element 10 and securing webs 17 face towards guide protrusions 5 at an acute angle. According to FIG. 7 , centrally thickened section 11 slides directly on the insides of guide webs 4 . To secure driving element 10 on the rail profile, a securing section 21 formed on each of the front free ends of securing webs 17 is in direct contact on the opposing surface of guide protrusion 5 facing towards base 2 of the rail profile. The surfaces may be bevelled as described previously on the basis of FIG. 1 . In the embodiment according to FIG. 7 , these lateral surfaces 9 are convex in shape and securing sections 21 formed correspondingly to them are concave in shape. According to FIG. 7 , convex securing section 9 merges into the outer surface of securing web 4 at an obtuse angle, i.e. an angle greater than 90 degrees. Overall, driving element 10 is secured against detachment in the vehicle's transverse direction y by clamping on the rail profile.
[0062] FIG. 8 shows a driving element for motor vehicle window lifters according to a further aspect of the following invention, which is suitable for a guide rail assembly, as described previously, but which is also basically suitable for any other rail profiles, also for those that are not made of a plastic material. The guide rail has, in the embodiment according to FIG. 8 , two guide webs 4 spaced apart from each other, which are formed according to the first embodiment of FIG. 1 . Basically, however, a single guide web 4 , from which, for example, two guide protrusions 5 protrude in opposing directions, is also sufficient to guide the driving element. According to FIG. 8 , driving element 10 is comprised of two different materials, namely a body 10 , which is preferably formed out of a plastic material, particularly is injection moulded out of plastic, in which U-shaped longitudinal recesses are formed, in which U-shaped slider inserts 27 are securely accommodated, said slider inserts being comprised of a different material. This other material is particularly suitable for a particularly appropriate tribological pairing with the material of guide webs 4 , may in particular be a metal or a metal insert, also in the form of a sintered body, but may also in principle be comprised of another plastic material. According to FIG. 8 , slider inserts 27 engage with a positive fit in the U-shaped longitudinal recesses of driving element 10 . Edges 24 , 25 on the inside of driving element 10 engage behind edges on the top end of slider inserts 27 to secure slider inserts 27 in the longitudinal recesses.
[0063] The following procedure is followed for assembly of such a guide rail assembly: first of all a guide rail is provided, for example with two guide webs 4 spaced apart from one another, as illustrated in FIG. 8 . Then slider inserts 27 are pushed onto the front free ends of guide webs 4 . At the same time the lateral webs of U-shaped slider inserts 27 must be elastically expanded, which is possible due to the design of the inner sides of the lateral flanks and of guide protrusion 5 . Subsequently, driving element 10 in FIG. 8 is pushed onto the guide rail from above with slider inserts 27 attached to it until the bottom ends of slider inserts 27 are in contact on edges 24 , 25 or on the introductory bevels formed on these edges, which leads to an elastic expanding of the webs of driving element 10 which form the longitudinal recess. According to FIG. 8 , the central section of driving element 10 has a U-shaped longitudinal cut-recess 26 , such that the inner side walls of driving element 10 can be bent elastically inwards. On further pushing on of driving element 10 , slider inserts 27 finally slide completely into the longitudinal recess of the driving element until then edges 24 , 25 finally snap back and engage behind the front ends of slider inserts 27 in order to thus secure driving element 10 against detachment in the vehicle's transverse direction, i.e. in the vertical direction in FIG. 8 .
[0064] FIG. 9 a shows a variation of the guide rail assembly according to FIG. 8 . Unlike FIG. 8 , standing up from base 2 of the module carrier is a locking web 260 , which in the working range of the driving element engages in the U-shaped longitudinal recess or cut-out 26 of driving element 10 . Sliding inserts 27 are at the same time clipped into driving element 10 , with elastic deformation or bending of securing hooks 25 limiting longitudinal recess 26 . In the working range of the driving element, locking web 260 engages in longitudinal recess 26 in such a manner that bending of securing hooks 25 towards one another on detaching driving element 10 perpendicularly from base 2 of the module carrier is prevented. This effectively prevents sliding inserts 27 from popping out of the longitudinal recesses of driving element 10 and secures driving element 10 on guide webs 4 .
[0065] To be able to assemble the driving element illustrated on guide webs 4 of a carrier 1 provided with locking web 260 , said locking web 260 according to FIG. 9 b has a narrowed section or cut-out 261 on at least one end region. To assemble the driving element, the positive fit between driving element 10 and protrusions 5 of guide webs 4 may be created first of all by simply clipping on driving element 10 with slider inserts 27 inserted therein in the region of narrowed section 261 . On moving driving element 10 within its working range, locking web 260 then engages in recess 26 of the driving element, as described previously, such that large detachment forces acting perpendicular to the module carrier can be transferred. In addition, the width of locking web 260 corresponds in the working range or adjustment range of driving element 10 substantially to the width of longitudinal recess 26 of driving element 10 .
[0066] It is possible to dispense with the narrowed section or cut-out 261 previously referred to if the geometry of the module carrier allows the driving element to be pushed on in the adjustment direction of driving element 10 . The advantage of locking web 260 is therefore, that unintentional bending upwards of securing hooks 25 and thus unbuttoning of protrusions 5 from slider insert 27 can be securely prevented. Of course, for this it is necessary for the outer regions of the driving element or the body of the driving element as such to be designed with sufficient rigidity.
[0067] As will clearly be self-explanatory to the person skilled in the art on studying the preceding description, the features of the embodiments described previously may also be combined with each other in any other way than previously described.
LIST OF REFERENCE NUMBERS
[0068] 1 Carrier plate
[0069] 2 Base of guide rail
[0070] 3 Inside of guide rail
[0071] 4 Guide web
[0072] 5 Guide protrusion
[0073] 6 Introductory bevel
[0074] 7 Bevel
[0075] 8 Front face of guide web 4
[0076] 9 Rounded contact section/guiding section
[0077] 10 Driving element
[0078] 11 Central thickened section
[0079] 12 Narrowing
[0080] 13 Front face of the central thickened section 11
[0081] 14 Front bevel
[0082] 15 Rear bevel
[0083] 16 Inclined marginal web
[0084] 17 Securing web
[0085] 18 Edge
[0086] 19 Marginal web
[0087] 20 Securing element
[0088] 21 Rounded securing section
[0089] 22 Stiffening rib
[0090] 23 Bevel
[0091] 24 Front end
[0092] 25 Securing hook
[0093] 26 Recess
[0094] 260 Locking web
[0095] 261 Cut-out/narrowed end of locking web 260
[0096] 27 Sliding insert
[0097] 28 Inner leg
[0098] 29 Outer leg
[0099] 30 First half of moulding tool
[0100] 31 Second half of moulding tool
[0101] 32 Wedge insert of moulding tool
[0102] 33 Central cavity
[0103] 34 Cavity
[0104] 35 Narrowing
[0105] 36 Lateral surface of first half of moulding tool
[0106] 37 Lateral surface of wedge insert 32
[0107] 38 Notch | A guide rail assembly for motor vehicle window lifters and a method for the production thereof. Two guide webs having protrusions formed thereon form a guide rail on a carrier plate made from a plastic material. The guide webs may be bent elastically inwards or outwards, enabling the driving element to be clipped on by pushing it on in the vehicle's transverse direction y and considerably simplifies production in an injection moulding process because the guide rail may be removed by elastically bending the guide rails such that a smaller number of sliders is required in the moulding tool. In one embodiment, there is also provided a driving element comprising a body of a first material and, securely held therein, sliding inserts comprised of a second material which material ensures a particularly good tribological pairing with the material of the associated guide web. | 4 |
BACKGROUND OF THE INVENTION
The present invention relates to a novel amino-trifluoromethylpyridine compound as an intermediate from which a compound effective in controlling various harmful organisms or an effective component compound of medicines can be easily derived, and a process for preparing the same.
A number of pyridine derivatives have hitherto been known to be useful intermediates for the production of organic compounds. For example, 2-amino-5-trifluoromethylpyridine as a starting material for the production of imidazopyridines and a process for the production thereof from 5-carboxy-2-hydroxypyridine are described in U.S. Pat. No. 3,681,369. And 2-amino-trifluoromethylhalogenopyridine is described in U.S. Pat. No. 4,349,681.
The pyridine compound of this invention is different in chemical structure from such known pyridine derivatives and has a novel utility.
Also amino-trifluoromethylpyridines are described generally in U.S. Pat. No. 3,787,420, however the pyridine compounds of this invention are not described concretely therein.
SUMMARY OF THE INVENTION
An object of the present invention is to provide at least one amino-trifluoromethylpyridine compound selected from the group consisting of 3-amino-5-trifluoromethylpyridine, 2-amino-4-trifluoromethylpyridine, and 2-amino-4,6-bis(trifluoromethyl)pyridine.
Another object of the present invention is to provide a process for preparing the amino-trifluoromethylpyridine compound by reacting at least one halogeno-trifluoromethylpyridine compound selected from the group consisting of 3-halogeno-5-trifluoromethylpyridine, 2-halogeno-4-trifluoromethylpyridine, and 2-halogeno-4,6-bis(trifluoromethyl)pyridine, with ammonia at a temperature of 50° to 200° C. Although a halogen atom constituting the halogeno-trifluoromethylpyridine compound includes a fluorine atom, a chlorine atom, and a bromine atom, etc., the chlorine atom is preferable.
When the process of the present invention is carried out, generally a halogeno-trifluoromethylpyridine compound and aqueous ammonia which is prepared by dissolving ammonia in water are charged in a closed vessel, e.g., an autoclave, or liquid ammonia is introduced into the halogeno-trifluoromethylpyridine compound, followed by the reaction at a temperature of 50° to 200° C., preferably, 100° to 180° C. In this reaction, a catalyst, e.g., cuprous chloride, can be added, and the amount of the catalyst added is 1 to 30 parts by weight with respect to 100 parts by weight of the halogeno-trifluoromethylpyridine compound. When the reaction temperature exceeds the above specified upper limit, the desired product tends to decompose, whereas when it is below the lower limit, the reaction does not take place sufficiently. When the aqueous ammonia is used as the ammonia, one having a concentration of 20% or more, preferably 28 to 40% is usually used. The reaction pressure reaches about 2 to 120 atm due to an increase in temperature inside the closed vessel. The amount of ammonia used is 1 mol or more, preferably 3 to 30 mols, per mol of the halogenotrifluoromethylpyridine compound. The reaction time is 5 hours or longer, preferably 5 to 100 hours.
The reaction product thus obtained is allowed to cool and usually extracted with a solvent, such as methylene chloride, benzene, diethyl ether, or the like. The solvent is then evaporated off, and if necessary, usual distillation is carried out to obtain the desired product. The desired product in the reaction product is obtained as an oily substance or crystals, and thus, impurities can be removed by the above extraction. When aqueous ammonia is used as the ammonia, the desired product may be contained in the aqueous phase of the reaction product, but the desired product can sufficiently be recovered by the above extraction.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Detailed preparation examples of an amino-trifluoromethylpyridine compound of the present invention will be described hereinafter, which however do not limit the invention in any way.
EXAMPLE 1
Preparation of 3-amino-5-trifluoromethylpyridine
40.8 g of 3-chloro-5-trifluoromethylpyridine, 12.2 g of cuprous chloride, and 76.5 g of liquid ammonia were charged in a 300-ml autoclave, and the mixture was reacted at 150° C. for 63 hours (internal pressure: about 120 atm).
After the completion of the reaction, the mixture was allowed to cool and pourred into water to obtain the reaction product consisting of the aqueous and oily phases. The aqueous phase was separated from the reaction product, and the desired product was extracted by methylene chloride. The methylene chloride was evaporated off, and normal distillation was carried out to obtain 25.3 g of 3-amino-5-trifluoromethylpyridine (boiling point: 105.5° to 106° C./ll mmHg).
EXAMPLE 2
Preparation of 2-amino-4-trifluoromethylpyridine
14.5 g of 2-chloro-4-trifluoromethylpyridine and 108 ml of 28% aqueous ammonia were charged in a 200-ml autoclave, and the mixture was reacted at 180° C. for 10 hours (internal pressure: about 20 atm).
After the completion of the reaction, the reaction system was allowed to cool. The resultant crystals were washed with water and dried, thus obtaining 10.2 g of 2-amino-4-trifluoromethylpyridine (melting point: 69° to 70° C.).
EXAMPLE 3
Preparation of 2-amino-4,6-bis(trifluoromethyl)pyridine
25 g of 2-chloro-4,6-bis(trifluoromethyl)pyridine and 85 g of 40% aqueous ammonia were charged into a 200-ml autoclave, and the mixture was reacted at 150° C. for 5 hours (internal pressure: about 26 atm).
After the completion of the reaction, the reaction system was allowed to cool. The resultant crystals were washed with water and dried, thus obtaining 16.5 g of 2-amino-4,6-bis(trifluoromethyl)pyridine (melting point: 70.8° to 71.2° C.).
The amino-trifluoromethylpyridine compound of the present invention is useful as an intermediate for the synthesis of agricultural chemicals and medicines, and examples thereof will be described below. For example, compounds Nos. 1 to 4 can be derived from the compound of the present invention by the processes described in the following reference examples.
REFERENCE EXAMPLE 1
Preparation of N-(2,6-difluorobenzoyl)-N'-(5-trifluoromethyl-3-pyridyl)urea (compound No. 1)
1.0 g of 3-amino-5-trifluoromethylpyridine was dissolved in 5 ml of dioxane, and a solution of 1.35 g of 2,6-difluorobenzoylisocyanate in 2 ml of dioxane was dropwise added to the former solution. The reaction was carried out at room temperature for 1 hour, while stirring.
After the completion of the reaction, the reaction product was pourred into about 100 ml of water to precipitate crystals. The precipitate was filtered and washed with methanol, followed by drying, thus obtaining 1.73 g of N-(2,6-difluorobenzoyl)-N'-(5-trifluoromethyl-3-pyridyl)urea (melting point: 233° to 235° C.).
REFERENCE EXAMPLE 2
Preparation of N-(2,6-difluorobenzoyl)-N'-(4-trifluoromethyl-2-pyridyl)urea (compound No. 2)
0.50 g of 2-amino-4-trifluoromethylpyridine was dissolved in 7 ml of dioxane, and the solution was dropwise added to a solution of 0.56 g of 2,6-difluorobenzoylisocyanate in 7 ml of dioxane. The reaction was carried out at room temperature for about 15 hours, while stirring.
After the completion of the reaction, the reaction product was pourred into about 100 ml of water to precipitate crystals. The precipitate was filtered and washed with water, followed by drying, thus obtaining 1.0 g of N-(2,6-difluorobenzoyl)-N'-(4-trifluoromethyl-2-pyridyl)urea (melting point: 167° to 169° C.).
REFERENCE EXAMPLE 3
Preparation of N-(2,6-difluorobenzoyl)-N'-[2,4-bis(trifluoromethyl)-6-pyridyl]urea (compound No. 3)
2.2 g of 2-amino-4,6-bis(trifluoromethyl)pyridine was dissolved in 10 ml of dioxane, and the solution was dropwise added to a solution of 1.9 g of 2,6-difluorobenzoylisocyanate in 20 ml of dioxane. The reaction was then carried out at room temperature for about 1 hour.
After the completion of the reaction, the reaction product was pourred into about 200 ml of warm water at 40° to 50° C. to precipitate crystals. The precipitate was filtered and dried, thus obtaining 3.2 g of N-(2,6-difluorobenzoyl)-N'-[2,4-bis(trifluoromethyl)-6-pyridyl]urea (melting point: 151.5° to 152.5° C.).
REFERENCE EXAMPLE 4
Preparation of N-[2,4-bis(trifluoromethyl)-6-pyridyl]-2,6-dinitro-3-chloro-4-trifluoromethylaniline (compound No. 4)
1.5 g of 2-amino-4,6-bis(trifluoromethyl)pyridine was dissolved in 30 ml of dioxane, and 1.5 g of potassium hydroxide powder was added thereto while stirring. Thereafter, 2.3 g of 2,4-dichloro-3,5-dinitrobenzotrifluoride was added to the former mixture, and the resultant mixture was reacted for about 15 hours.
After the completion of the reaction, the reaction product was pourred into a dilute sulfuric acid solution and extracted with methylene chloride. The extracted phase was washed with water and dried to evaporate the solvent, followed by crystallization. The resultant crystals were washed with hexane, followed by drying, thus obtaining 2.0 g of the desired product (melting point: 169° to 170° C.).
Compounds Nos. 1 to 4 derived from the aminotrifluoromethylpyridine compounds are useful as pesticides. Reference test examples of compounds Nos. 1 to 4 will be described below.
REFERENCE TEST EXAMPLE 1
Pieces of cabbage leaves were immersed in an aqueous solution which had been prepared by dispersing an effective component compound in water and adjusting its effective component concentration to 100 ppm, and the leaf pieces were then air-dried. Wet filter paper was placed in a petri dish (diameter: 9 cm), and the leaf pieces were put therein. The second and third instar larvae of a diamondback moth (Plutella xylostella) were released onto the cabbage leaves. The petri dish was capped and left in an air-conditioned vessel with illumination at 28° C. The numbers of alive and dead insects were counted 8 days later, and a mortality rate was calculated by the following formula to obtain the results shown in Table 1 below:
TABLE 1______________________________________Mortality rate = 100 × (the number of dead insects)/the number of released insects)Compound No. Mortality Rate (%)______________________________________1 1002 1003 100______________________________________
REFERENCE TEST EXAMPLE 2
Following the same procedures as in Reference Test Example 1, the test was carried out, except that the effective component concentration of the aqueous solution was altered from 100 ppm to 10 ppm and the 2nd to 3rd instar larvae of the diamondback moth were replaced with 2nd to 3rd instar larvae of a common cutworm (Spodoptera litura), and the results shown in Table 2 below were obtained.
TABLE 2______________________________________Compound No. Mortality Rate (%)______________________________________1 1002 1003 100______________________________________
REFERENCE TEST EXAMPLE 3
When a cucumber seedling (Suyo type) which had been grown in a clay pot having a diameter of 9 cm, reached the 1-leaf stage, 10 ml of an aqueous solution, in which a concentration of an effective component compound was adjusted to 100 ppm, was sprayed thereto using a spray gun. After the plant was left in a greenhouse at 24 to 25° C. for 24 hours, disks of Batrytis cinerea (agar punching) which had been preliminarily cultured on a potato-dextrose-agar medium (PDA medium) were placed on the leaves of the cucumber plant to inoculate it. Three days later, the spot length was evaluated, and the pest control ratio was calculated by the following formula, thus obtaining the following result.
______________________________________Pest Control Ratio (%) = {1 - (spot length in treated plot)/(spot length in untreated plot)} × 100Compound No. Pest Control Ratio (%)______________________________________4 100______________________________________
REFERENCE TEST EXAMPLE 4
When a cucumber seedling (Suyo type), which had been grown in a clay pot having a diameter of 9 cm, reached the 2-leaf stage, 20 ml of an aqueous solution in which a concentration of an effective component compound was adjusted to 100 ppm was sprayed thereto using a spray gun. After the plant was left in a greenhouse at 24° to 25° C. for 24 hours, a Pseudoperonespora cubensis spore suspension was sprayed and inoculated. Six days after the inoculation, the number of spots on the first leaf was counted, and the pest control ratio was calculated by the following formula, thus obtaining the following result.
______________________________________Pest Control Ratio (%) = {1 - (the number of spots in treated plot)/(the number of spots in un- treated plot)} × 100Compound No. Pest Control Ratio (%)______________________________________4 100______________________________________
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. | A novel amino-trifluoromethylpyridine compound selected from the group consisting of 3-amino-5-trifluoromethylpyridine, 2-amino-4-trifluoromethylpyridine, and 2-amino-4,6-bis(trifluoromethyl)pyridine, and, a process for preparing the same by reacting a halogeno-trifluoromethylpyridine compound with ammonia at a temperature of 50° to 200° C. The compound is useful as an intermediate from which a compound effective in controlling various harmful organisms or an effective component compound of medicines can be easily derived. | 0 |
FIELD OF THE INVENTION
[0001] The present invention pertains generally to needle protection devices. More particularly, the present invention pertains to needle protection devices that use a cylindrical guard to extend beyond the needle's tip to prevent contact with the tip. The present invention is particularly, but not exclusively useful as a needle protection device that uses cooperation between a “V” shaped slot and a radially-extending boss to limit relative movement between the guard and the needle.
BACKGROUND OF THE INVENTION
[0002] Needles are very common in medical practices, and are frequently used to deliver medications or to draw blood for diagnosis. As a result of their intensive use, it is estimated that some 600,000 to 800,000 accidental needle stick injuries occur every year. Further, there are roughly 8,000,000 healthcare workers in the United States who are at risk of being stuck with a contaminated needle. As the risks involved in providing medical treatment have risen and individual safety and sanitation are taken into consideration, disposable or single-use type of injection devices have become prevalent. While safer than reusable injection devices, these needles must still be handled carefully and the needle tips must be covered before and after use.
[0003] Although currently there exist various needle protection devices, most require the user to take an affirmative step to cover the needle tip after its use, thereby causing potential risk of contact with the needle. Other devices require specially designed needles, plungers, or medicament chambers.
[0004] In light of the above, it is an object of the present invention to provide a protective device that can be installed on a needle to ensure there is only a single use of the needle. It is another object of the present invention to provide a protective device having a guard that passively covers and protects the needle after an injection. It is another object of the present invention to provide a protective device that controls movement of the guard relative to the needle. Still another object of the present invention is to provide a protective device that requires an affirmative step to uncover the needle, but automatically covers the needle after an injection. Yet another object of the present invention is to provide a protective device for a needle that is relatively easy to manufacture, reliable and easy to use, and is comparatively cost effective.
SUMMARY OF THE INVENTION
[0005] In accordance with the present invention, a needle protection device includes an adapter for holding a needle. The device also includes a guard having a cylindrical wall that is dimensioned to engage the adapter for relative axial movement therebetween. Such movement is biased by a spring that urges the guard away from the adapter. Further, the guard includes an orifice for selectively passing the needle therethrough. In order to guide relative movement between the adapter and the guard, the guard is provided with a “V” shaped slot having a first leg and a second leg with an apex therebetween. Correspondingly, the adapter is provided with a radially-extending boss. The boss is received within the slot to limit relative movement between the guard and the adapter.
[0006] As a result of cooperation between the slot and the boss mentioned above, the device is only moveable from a first position to a second position, and from the second position to a third position. In the first position, the boss is in the first leg of the slot and the needle partially extends through the orifice of the guard. In the second position, the needle fully extends through the orifice of the guard and the boss is held at the apex of the slot in response to a force opposing the biasing means. In the third position, the boss is in the second leg of the slot and the needle is retracted into the guard to protect the needle.
[0007] For the purposes of the present invention, the boss is provided with an engagement face that is designed to interact with the slot to ensure that the boss moves to the end of the second leg from the apex during movement of the guard from the second position to the third position. Specifically, the face is inclined toward the second leg, so that contact between the face on the boss and the edge of the slot causes the boss to move toward the end of the second leg.
[0008] In order to protect the needle before use, the device may further include a removable shield. Structurally, the shield includes a hollow portion for receiving the needle. Further, the shield includes a radially extending rib that can be selectively positioned in the orifice of the guard to prevent axial movement of the guard from the first position to the second position.
[0009] For the present invention, the device may further include a locking mechanism that locks the device in the third position, to thereby prevent further relative movement between the guard and the adapter. Specifically, the adapter is provided with a shoulder that extends radially outward, and the guard is provided with an abutment that extends radially inward. When the device moves into the third position, the shoulder and the abutment engage one another to prevent further relative movement between the guard and the adapter.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The novel features of this invention, as well as the invention itself, both as to its structure and its operation, will be best understood from the accompanying drawings, taken in conjunction with the accompanying description, in which similar reference characters refer to similar parts, and in which:
[0011] FIG. 1A is a perspective view of a needle protection device of the present invention;
[0012] FIG. 1B is a perspective view of the guard shown in FIG. 1A , illustrating the movement of the boss in the “V” shaped slot;
[0013] FIG. 2A is a cross section view of the needle protection device of FIG. 1A , as seen along line 2 - 2 in FIG. 1B ;
[0014] FIG. 2B is a cross section view of the needle protection device of FIG. 2A with the removable shield rotated for removal in accordance with the present invention;
[0015] FIG. 3 is a cross section view of the needle protection device of FIG. 2B , as seen along line 3 - 3 in FIG. 1B , with the shield removed and the needle inserted into a subject in accordance with the present invention;
[0016] FIG. 4A is a cross section view of the needle protection device of FIG. 3 , as seen along line 4 - 4 in FIG. 1B , with the needle withdrawn from the subject and the guard advanced to cover the needle tip in accordance with the present invention;
[0017] FIG. 4B is a cross section view of the needle protection device of FIG. 4A , as seen from a view taken ninety degrees from the view in FIG. 4A ; and
[0018] FIG. 5 is a side view of the slot and boss arrangement showing the configuration of the slot and the boss in the first, second and third positions.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Referring initially to FIG. 1A , a needle protection device in accordance with the present invention is shown and generally designated 10 . As shown, the device 10 covers a needle 12 (shown in phantom) to prevent inadvertent contact with the needle tip 14 . For discussion of the present invention, the needle 12 defines an axis 16 , a proximal direction 15 and a distal direction 17 . Structurally, the device 10 includes a guard 18 having a cylindrical wall 20 that slidingly engages an adapter 22 . Further, the wall 20 includes a radially extending “V” shaped slot 24 that corresponds with and receives a boss 26 that extends radially outward from the adapter 22 . The slot 24 includes a first leg 28 which meets a longer second leg 30 at an apex 32 . As shown, the boss 26 is positioned in the first leg 28 of the slot 24 . For the purposes of the present invention, the slot 24 and boss 26 cooperate to guide axial movement of the guard 18 relative to the adapter 22 .
[0020] Still referring to FIG. 1A , the guard 18 is shown as including an axially extending orifice 34 that is formed with a long axis 36 and a short axis 38 . In addition to the guard 18 and the adapter 22 , the device 10 includes a removable shield 40 . In FIG. 1A , the shield 40 is shown passing through the orifice 34 and including radially extending grips 42 to facilitate rotation of the shield 40 about the axis 16 as discussed below. As shown, the device 10 further includes a spring 44 that biases the guard 18 away from the adapter 22 .
[0021] Referring to FIG. 1B , the boss 26 ′ is positioned in the first leg 28 of the slot 24 (i.e., the first position of the device 10 ), the boss 26 ″ is positioned at the apex 32 of the slot 24 (i.e., the second position of the device 10 ), and the boss 26 ′″ is positioned in the second leg 30 of the slot 24 (i.e., the third position of the device 10 ). As can be understood from cross-referencing FIG. 1A with FIG. 1B , movement of the boss 26 between these positions results in rotational movement of the guard 18 about the axis 16 relative to the adapter 22 , particularly during movement from boss 26 ′ to boss 26 ″.
[0022] Referring now to FIGS. 2A and 2B , internal components and features of the device 10 can be seen. As shown, the adapter 22 includes an axially-extending and substantially cylindrical base member 46 centered about the axis 16 . Further, the adapter 22 includes a radially-extending cap member 48 . As shown, the adapter 22 has an external surface 50 and an internal surface 52 , with the internal surface 52 defining an internal cavity 54 . As further shown, the needle 12 passes through an aperture 56 formed in the cap member 48 .
[0023] Turning to the guard 18 , it can be seen from FIGS. 2A and 2B , that the cylindrical wall 20 includes an outer side 58 and an inner side 60 . As shown, the inner side 60 defines a chamber 62 in which the adapter 22 is partially received. The chamber 62 is further bounded by an end member 64 mounted to the cylindrical wall 20 and forming the orifice 34 . For the purposes of the invention, the spring 44 is positioned in the chamber 62 between the cap member 48 of the adapter 22 and the end member 64 of the guard 18 to bias the guard 18 axially away from the adapter 22 .
[0024] As further shown in FIGS. 2A and 2B , the device 10 includes a removable shield 40 having a hollow portion 66 for receiving the needle 12 . As shown in FIG. 2A , the shield 40 includes radially extending ribs 68 that are engaged with the guard 18 and the adapter 22 . In the orientation of FIG. 2A , the ribs 68 prevent axial movement of the guard 18 toward the adapter 22 . Cross-referencing FIG. 2A with FIG. 2B , it can be seen that the ribs 68 may be removed from contact with the guard 18 . Specifically, FIG. 2B depicts the shield 40 of FIG. 2A after the shield 40 has been rotated ninety degrees about the axis 16 . As a result, the ribs 68 are aligned with the long axis 36 of the orifice 34 (see FIG. 1A ) and the shield 40 may be removed from the device 10 .
[0025] Typically, the device 10 is stored and transported in the orientation shown in FIG. 2A . Before the needle 12 is used for an injection, the shield 40 is rotated as in FIG. 2B and is removed. Regardless of the position of the shield 40 , each of FIGS. 1A, 2A and 2 B depict the device in a first position 70 in which the boss 26 is received within the first leg 28 of the slot 24 . After the shield 40 is removed, the guard 18 may be moved in the proximal direction 15 toward the adapter 22 if a sufficient force is applied thereto. Specifically, if a force greater than the biasing force of the spring 44 is applied.
[0026] In FIG. 3 , the result of an application of such a force is shown. As shown, the needle 12 has been injected into a subject 72 . As a result, the force of the subject 72 on the guard 18 has caused the guard 18 to move toward the adapter 22 . Specifically, the device 10 has moved to the second position 74 in which the boss 26 is positioned at the apex 32 of the slot 24 . When the boss 26 reaches the apex 32 , further movement of the guard 18 toward the adapter 22 is prevented by the interaction between the slot 24 and the boss 26 .
[0027] After the needle 12 has injected a fluid 76 into the subject 72 , the needle 12 is withdrawn from the subject 72 . During withdrawal, the spring 44 pushes the guard 18 away from the adapter 22 . At the same time, the boss 26 moves from the apex 32 to the second leg 30 (as shown in FIG. 4A ).
[0028] To ensure that the boss 26 moves to the end of the second leg 30 rather than back to the first leg 28 , the boss 26 is provided with an engagement face 78 . The face 78 is inclined toward the second leg 30 so that when the boss 26 moves out of the apex 32 it slides to the end of the second leg 30 .
[0029] Referring now to FIG. 4A , the device 10 is shown in its third position 80 with the boss 26 in the second leg 30 . As shown, the guard 18 is extended and fully covers the needle tip 14 . In order to prevent any further use of the needle 12 , the device 10 is provided with the locking mechanism 82 seen in FIG. 4B . FIG. 4B is a cross section view of the device 10 taken from a view ninety degrees from the view in FIG. 4A . Approximately ninety degrees from the bosses 26 shown in FIG. 4A are two shoulders 84 shown in FIG. 4B that extend radially outward from the adapter 22 . As further seen in FIG. 4B , the device 10 includes two corresponding abutments 86 that extend radially inward from the guard 18 . As shown, the shoulders 84 and abutments 86 are tapered. This construction allows the shoulders 84 to slide in the proximal direction 15 along the inner side 60 of the guard 18 until they pass the abutments 86 . Once the shoulders 84 pass the abutments 86 , the guard 18 can no longer be moved toward the adapter 22 . As a result, the device 10 is locked with the needle 12 protected by the guard 18 .
[0030] Referring now to FIG. 5 , the interaction between the slot 24 and the boss 26 can be clearly shown. In FIG. 5 , the boss 26 is shown in the various stations (indicated by 26 ′, 26 ″, and 26 ′″) it passes through during operation of the device 10 . Specifically, the boss 26 ′ is shown in the first leg 28 adjacent the first stop 88 when the device 10 is in the first position 70 . The first stop 88 may serve to prevent axial movement of the guard 18 away from the adapter 22 . As noted above, the shield 40 prevents axial movement of the guard 18 toward the adapter 22 when the ribs 68 are positioned between the guard 18 and adapter 22 . When the ribs 68 are disengaged from the guard 18 and the shield 40 has been removed, the spring 44 retains the boss 26 ′ in the first leg 28 .
[0031] When a force is applied to the guard 18 in the proximal direction 15 to move the guard 18 toward the adapter 22 , i.e., during an injection, the boss 26 ′ moves from the first stop 88 to its position as boss 26 ″ at the apex 32 . Movement of the guard 18 toward the adapter 22 may be stopped by contact between the boss 26 ″ and the apex 32 , or by contact between other components in the device 10 .
[0032] When the force in the proximal direction 15 is removed, i.e., during withdrawal of the needle 12 from the subject 72 , the spring 44 forces the guard 18 away from the adapter 22 in the distal direction 17 . As a result, the boss 26 ″ moves axially away from the apex 32 to its position at boss 26 ′″ in the second leg 30 of the slot 24 . As indicated by FIG. 5 , during movement from boss 26 ″ to boss 26 ′″, the engagement face 78 may contact the edge 90 of the slot 24 . Due to the inclination of the engagement face 78 toward the second leg 30 and the slope of the edge 90 of the slot 24 , contact between the boss 26 and the edge 90 of the slot 24 causes the boss 26 to move to the second stop 92 of the second leg 30 . Alternatively, the boss 26 ″ may move substantially in the proximal direction 15 directly to the second stop 92 of the second leg 30 . In either case, the spring 44 forces the guard 18 away from the adapter 22 until the boss 26 ′″ contacts the second stop 92 or until further axial movement of the guard 18 away from the adapter 22 is otherwise prevented. As shown in FIG. 4B , the locking mechanism 82 then prevents any further relative movement between the guard 18 and the adapter 22 .
[0033] While the particular Automatic Needle Guard for Medication Pen as herein shown and disclosed in detail is fully capable of obtaining the objects and providing the advantages herein before stated, it is to be understood that it is 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 other than as described in the appended claims. Further, it is contemplated that the boss and slot cooperating structures may be reversed such that the boss be formed on the guard and the slot be formed in the adapter. Such an embodiment is considered to be an equivalent combination of structure to the specific embodiment disclosed and claimed herein. | A device for selectively protecting a needle includes an adapter holding the needle and a guard engaging the adapter for relative movement therebetween. Further, the device includes a means for guiding movement between the adapter and the guard. Structurally, the guiding means includes a “V” shaped slot in the guard and a radially-extending boss on the adapter. The boss is received in the slot to limit relative movement between the guard and the adapter. Specifically, in a first position of the device, the boss is in a first leg of the slot and the needle partially extends beyond the guard. In a second position, the boss is held at the apex of the slot and the needle fully extends beyond the guard. In a third position, the boss is in the second leg of the slot and the needle is retracted into the guard to protect the needle. | 0 |
TECHNICAL FIELD
[0001] The present invention concerns a ventilation system and a method for continuously regulating the temperature of gas flowing through a ventilation system.
BACKGROUND OF THE INVENTION
[0002] Ventilation systems usually comprise resistive heating elements to heat gas passing through the ventilation system. A heater usually contains one or more resistive heating elements, such as electrically conductive wires or foils, which are connected to an electrical supply (usually a mains voltage of 230-480 V, 50-60 Hz). As electricity passes through said resistive heat elements, some energy is lost as heat due to the resistance of said elements. The more current that flows through the resistive heat elements, the more heat is generated.
[0003] If a resistive heater comprises a plurality of resistive heating elements, fuses and relays are used to connect different numbers of resistive heating elements in order to increase or decrease the heating capacity of the resistive heater (i.e. the amount of usable heat produced by the resistive heater). Such a solution means that the heating capacity of a resistive heater may only be adjusted in steps. Step-wise adjustment means that the heating capacity of the resistive heater can not be continuously controlled or optimised nor accurately matched to both specific and fluctuating demands, which limits the possibility of fine tuning processes while reducing energy costs. The more temperature adjustment options/steps a user has, the more electric components are required, which increases the size, cost and complexity of a ventilation system's temperature control unit.
SUMMARY OF THE INVENTION
[0004] An object of the present invention is to provide a ventilation system with simple and cost-effective means to regulate the temperature of gas, such as air, flowing therethrough.
[0005] This object is achieved by a ventilation system comprising resistive heating means for heating gas flowing through (i.e. into, out of, or through at least part of) the ventilation system and means that are arranged to provide a controlled, continuously variable AC voltage/current to at least part of the resistive heating means of the ventilation system to modulate the power being supplied thereto and to enable continuous regulation of the temperature of gas flowing through the ventilation system.
[0006] According to an embodiment of the invention a variable frequency drive (VFD) or a matrix drive is arranged to modulate the power being supplied to at least part of the resistive heating means to enable continuous regulation of the temperature of gas flowing through the ventilation system.
[0007] The expression “resistive heating means” is intended to include heating elements that are arranged to primarily conduct heat and does not include inductive heating elements that are primarily arranged to induce heat electromagnetically. The resistive heating means may be arranged to heat said gas directly or indirectly, i.e. the resistive heating means may be in direct contact with said gas or they may be arranged to conduct heat to at least one another component, such as a metal tube surrounding said resistive heating means which is in direct contact with the said gas.
[0008] A VFD (which is also known as an adjustable speed drive, adjustable frequency drive (AFD), variable speed drive (VSD), AC drive, frequency drive and inverter drive) is an electronic controller that firstly converts an AC input power to a DC intermediate power, using a rectifier bridge for example. The DC intermediate power is then converted to a variable AC voltage output using pulse width modulation for example, whereby the inverter switches are used to divide the quasi-sinusoidal output waveform into a series of narrow voltage pulses and modulate the width of the pulses.
[0009] A matrix drive directly converts AC power at one frequency to AC power at another without an intermediate DC link. A matrix drive utilizes bi-directional high power semiconductor switches, which can be implemented utilizing back to back insulated gate bipolar transistors (IGBTs) and diodes.
[0010] The present invention utilizes the variable AC voltage/current output from the VFD or a matrix drive to supply power to one, some, or all of the resistive elements of resistive heating means and consequently utilizes a VFD or a matrix drive to vary the heating capacity of said resistive heating element(s).
[0011] A VFD or a matrix drive is able to vary the voltage (and not only the frequency) of its output signal and may therefore be arranged to provide continuous (i.e. step-less) temperature regulation in a more simple and cost effective way than conventional solutions. Step-less adjustment means that the heating capacity of resistive heating means can be continuously controlled and optimised and accurately matched to both specific and fluctuating demands, thereby allowing operators to fine tune processes while reducing energy costs. Step-less adjustment also means that a ventilation system's temperature control unit can be arranged to have a simpler and thus less expensive construction since only one, relatively simple electrical circuit is needed to regulate the temperature of gas flowing through a ventilation system.
[0012] It should be noted that conventional ventilation systems often comprise a VFD that is used to vary the rotational speed of an asynchronous motor that drives a component such as a fan or pump. Asynchronous motors are designed to run at a fixed rotational speed that is proportional to the number of poles and the power frequency (usually 50 Hz in Europe and 60 Hz in the USA). This means that the motor cannot produce such a large shaft horsepower at lower rotational speeds as compared to higher rotational speeds, since current surges through the motor's windings could quickly occur and result in overheating if the power output is disproportionally large in relation to the rotational speed. A VFD therefore has to be constructed to vary the output voltage in time with the output frequency varying. Small departures from a purely linear relationship between the supply voltage and frequency to a motor can be accomplished by most VFDs, for example, in order to compensate for non-linearities between the necessary power requirement on downward regulation of a pump motor for example so that the voltage is then decreased more than the frequency on downward regulation from nominal rotational speed.
[0013] The fact that a VFD regulates the voltage between 0 and 100% can be utilized to regulate the power from a resistive heater comprising heat resistant resistance wire that is heated by a voltage forcing a current through said wire that then becomes warm and emits its heat to passing air via an electrically insulated metal covering surrounding the wire. Since the electrical resistance in the wire is completely independent of the supply voltage (Ohm's law) for normally occurring frequencies less than 1000 Hz, a resistance wire connected to such a VFD will emit heat in proportion to the supply voltage independently of the supply frequency. Even though the VFD has a function that limits the voltage at low frequencies (due to the explanation given in the paragraph above) it does not affect the heat regulation of a space because the heat control itself merely makes a comparison between the actual and target value. If a room does not become warm enough the VFD just has to be set to a higher modulated frequency, which results in an increased output voltage and consequently a higher power supply to the air heater.
[0014] It is of course possible to provide voltage variation without variation of frequency with other devices in the form of different semiconductor components for example which can in different ways can supply a hearing wire with power and cause it to emit a variable heating capacity. Such devices are however substantially more expensive than VFDs since VFDs are more widely used than these devices that are consequently manufactured in much smaller quantities. Such devices must furthermore be used in conjunction with advanced electric filters to avoid EMC-interference to the surroundings and to the supply network. Such electric filters are standard components in VFDs. VFDs also standardly contain different types of current limiting protection, thus eliminating the need of a separate such component.
[0015] The present invention therefore makes use of existing technology in a completely new, advantageous and cost effective way.
[0016] According to an embodiment of the invention the ventilation system comprises a VFD that not only is arranged to modulate the power being supplied to at least part of the resistive heating means of the ventilation system, but that is also arranged to regulate the rotational speed of at least one electric motor, such as a motor that drives at least one component, such as fan or a pump, contained in the ventilation system or in its vicinity. A single component of a ventilation system may therefore be used in two different applications; namely to regulate the rotational speed of at least one motor and to regulate the heating capacity of at least part of at least one resistive heating means. In this way very economic heat regulation is achieved. It is even possible to have a system comprising a supply air fan, followed by an air heater and then an exit air fan to maintain pressure balance in the system whereby both fans and the air heater are driven by the same VFD.
[0017] According to an embodiment of the invention the ventilation system comprises a controller, such as a VFD- or matrix drive-controller, and means to provide said controller with a manually or automatically inputted target value, such as a desired cabin or room temperature, whereby the power being supplied to at least part of the resistive heating means is modulated in accordance with said manually or automatically inputted target value.
[0018] According to another embodiment of the invention the ventilation system comprises a sensor that is arranged to detect or monitor a parameter indicative of the heating capacity of the resistive heating means. Such a parameter may be the temperature of gas passing through the ventilation system, the temperature of part of the ventilation system or its surroundings, or the temperature or resistance of the resistive heating means for example. The sensor reading provides a controller with an actual value indicative of the heating capacity of the heating means. The power being supplied to at least part of the resistive heating means is then modulated so as to achieve or maintain a heating capacity that is in accordance with said manually or automatically inputted target value, i.e. the power being supplied is modulated so that the actual heating capacity corresponds to the target heating capacity.
[0019] According to a further embodiment of the invention the VFD or a matrix drive is arranged to supply the resistive heating means with a nominal voltage between 200-700 V AC , 50-60 Hz.
[0020] The present invention also concerns a method for continuously regulating the temperature of gas flowing through a ventilation system comprising resistive heating means. The method comprises the step of providing a controlled, continuously variable AC voltage/current to at least part of the resistive heating means of the ventilation system to modulate the power being supplied thereto and to enable continuous regulation of the temperature of gas flowing through the ventilation system.
[0021] According to an embodiment of the invention the method also comprises the step of modulating the power being supplied to at least part of the resistive heating means using a VFD or a matrix drive.
[0022] According to an embodiment of the invention the method also comprises the step of providing a controller with a manually or automatically inputted target value and modulating the power being supplied to at least part of the resistive heating means in accordance with said target value.
[0023] According to another embodiment of the invention the method comprises the step of detecting or monitoring a parameter that is indicative of the heating capacity of the resistive heating means and modulating the power being supplied to at least part of the resistive heating means so as to achieve or maintain a heating capacity that is in accordance with said manually or automatically inputted target value.
[0024] The present invention further concerns a computer program product that comprises a computer program containing computer program code means arranged to cause a computer or a processor to execute at least one of the steps of a method according to any of the embodiments of the invention, stored on a computer-readable medium or a carrier wave and an electronic control unit (ECU) comprising such a computer program product. The ECU may contain a database containing pre-programmed heating/cooling schedules and/or may keep a log of information concerning a VFD or matrix drive power input and output and/or the performance of the resistive heating means to assist trouble-shooting and maintenance work.
[0025] The inventive ventilation system, method, computer program product and ECU are intended for use particularly but not exclusively on a sea-going vessel, such as a passenger ship, another movable or fixed offshore installation that is divided into a plurality of isolated cells, such as cabins, public spaces and/or non-public spaces such as, for example, engine rooms, storage spaces and/or lift shafts.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] The present invention will hereinafter be further explained by means of non-limiting examples with reference to the appended figures where;
[0027] FIG. 1 shows schematically a ventilation system according to an embodiment of the invention,
[0028] FIG. 2 shows schematically a ventilation system according to another embodiment of the invention, and
[0029] FIG. 3 shows an electric circuit of a variable frequency drive according to an embodiment of the invention,
[0030] FIG. 4 shows an ideal switch equivalent circuit of a three-phase AC to three-phase AC frequency changer with matrix converter topology,
[0031] FIG. 5 shows a solid state switch realization of each pole of the switch of the matrix drive of FIG. 4 , and
[0032] FIG. 6 is a flow diagram showing the steps carried of a method according to an embodiment of the invention.
[0033] It should be noted that the drawings have not been drawn to scale and that the dimensions of certain features have been exaggerated for the sake of clarity.
DETAILED DESCRIPTION OF EMBODIMENTS
[0034] FIG. 1 shows a ventilation system 10 comprising a purely resistive heating element 12 consisting of one or more electrically conductive wires or foils located inside a stainless steel tube that heats up the supply air delivered to a cabin of a passenger ship. A VFD 14 supplies at least part of the resistive heating element 12 with electrical power and thereby controls the total heating capacity of the resistive heating element 12 . A control panel on a VFD controller 16 presents various features that allow for automatic or manual control of the VFD 14 and includes display means, such as an LCD, to provide information concerning the operation of the VFD 14 and/or the resistive heating element 12 .
[0035] In this example the VFD controller is provided with a target value only and not an actual value indicative of the heating capacity of the resistive heating element 12 . The ventilation system 10 is calibrated so that the VFD controller supplies a pre-determined amount of power to the resistive heating element 12 depending on the magnitude of the target value.
[0036] Each VFD 14 in a ventilation system 10 can be arranged to regulate the heating capacity of one or more resistive heating elements 12 . The inventive ventilation system 10 may therefore be used for conditioning, circulating and distributing air through several different isolated cells. Each isolated cell may be provided with individual resistive heating elements 12 so that a plurality of cells may be separately or simultaneously heated to individually selected temperatures to suit the needs or desires of their occupants. Each cell may also comprise thermostatic means to ensure that the ventilation system maintains each cell at a pre-determined temperature. Optionally each VFD 14 may also be arranged to regulate the rotational speed of one or more electric motors located inside the ventilation system 10 or in the vicinity thereof.
[0037] FIG. 2 shows another embodiment of a ventilation system 10 in which a temperature sensor 17 , such as a thermocouple or an infrared camera, is placed in the vicinity of the resistive heating element 12 to measure the temperature of gas passing over the resistive hearing element 12 and provide the VFD controller 16 with information concerning the actual heating capacity of the resistive heating element 12 . The actual temperature is compared to the target temperature and the power being supplied to the resistive heating element 12 is modulated until the actual temperature corresponds to the target temperature. The ventilation system therefore ensures that the VFD 14 is supplying the required to power the resistive heating element 12 and that the components of the ventilation system are working correctly.
[0038] FIG. 3 shows an electric circuit of a variable frequency drive 14 configured for use with single-phase input power (for the sake of clarity), which may be used in carrying out the method according to an embodiment of the present invention. The input section of the VFD 14 contains two diodes 18 arranged as a rectifier bridge to convert AC input power 20 to DC intermediate power. The following section, the DC bus section, sees a fixed DC voltage and filters and smoothes out the waveform. The DC intermediate power is then converted to quasi-sinusoidal AC power using an inverter switching circuit comprising two insulated gate bipolar transistors (IGBTs) 22 . The inverter switching circuit inverts the fixed DC voltage back to a variable AC voltage output by switching the DC bus on and off at specific intervals. This is called pulse width modulation. The variable AC voltage output 24 from the VFD (which can be 230-690 V AC for example) is fed to at least part of the resistive heating element(s) 12 of a ventilation system and consequently varies the heating capacity of the heating element(s) 12 (from 1-50 kW for example as symbolized by the block arrow in FIG. 3 ).
[0039] The rectifier bridge of a VFD is usually a diode bridge but may also be a controlled rectifier circuit. The inverter switching circuit may comprise silicon-controlled rectifiers (SCRs) or semiconductor switches, such as IGBTs as shown in FIG. 3 .
[0040] FIG. 4 schematically shows a matrix converter 23 which utilizes one pole and three throw switches 26 to directly convert an AC input voltage at one frequency to an AC output voltage at another frequency.
[0041] FIG. 5 shows back to back IGBTs and diodes may be used to implement the bi-directional high power semiconductor switches 26 shown in FIG. 4 . The AC input from the three throw switches is converted to a variable AC voltage output 24 . The variable AC voltage output 24 from the matrix drive is then fed to at least is fed to at least part of the resistive heating element(s) 12 of a ventilation system and consequently varies the heating capacity of the heating element(s) 12 .
[0042] Due to the relatively high currents and voltages which these switches must handle, the semiconductor switches are relatively expensive and can limit the reliability of a converter system however a matrix drive avoids the need for a DC link capacitor that constitutes a life-limiting component of a converter and that contributes to the bulk of the converter.
[0043] FIG. 6 is a flow diagram of a method according to an embodiment of the invention, whereby at least some of the steps of the method may be executed by a computer or processor. The method comprises the steps of inputting a target value, such as a desired room temperature, into the controller of a VFD or matrix drive. AC power is then provided by the VFD or matrix drive to resistive heating means so that the resistive heating means will heat up air passing through a ventilation system to the desired temperature. The method also comprises the step of detecting or monitoring a parameter indicative of the heating capacity of the resistive heating means, using a temperature sensor for example. The AC power being supplied to the resistive heating means is continuously modulated until the desired room temperature has been achieved. Once the desired room temperature has been achieved, the AC power is continuously modulated to ensure that the desired room temperature is maintained.
[0044] Further modifications of the invention within the scope of the claims would be apparent to a skilled person. For example, the present invention is also suitable for the regulating the temperature of a liquid that is heated by the resistive heating means of the ventilation system. | Ventilation system ( 10 ) comprising resistive heating means ( 12 ) for heating gas flowing through the ventilation system ( 10 ) and means that are arranged to provide a 5 controlled, continuously variable AC voltage/current to at least part of the resistive heating means ( 12 ) of the ventilation system ( 10 ) to modulate the power ( 24 ) being supplied thereto and to enable continuous regulation of the temperature of gas flowing through the ventilation system ( 10 ). | 5 |
CROSS REFERENCE RELATED TO APPLICATION
This is a continuation-in-part of application Ser. No. 09/389,575 filed on Sep. 3, 1999, now U.S. Pat. No. 6,096,699.
TECHNICAL FIELD
The present invention relates to a solvent that is biodegradable and generally benign to human health, and more particularly to a mixture of a lactate ester and an ester of fatty acid derived from an edible oil; the mixture provides effective solvency for a broad range of tasks. This blended solvent is shown to provide effective performance for paint removal, de-inking, degreasing, and as a general surface cleaning agent that provides for a non-toxic, cost effective alternative to commonly used toxic solvents.
2. Background Art
A solvent is a substance that is generally capable of dissolving another substance, or solute, to form a uniformly dispersed mixture (solution) at the molecular or ionic level. Solvents are either polar (high dielectric constant) or non-polar (low dielectric constant). Water, the most common solvent, is strongly polar having a dielectric constant of 81. Hydrocarbon solvents are non-polar and are comprised of two groups, aliphatics such as alkanes and alcohols, and aromatics, which generally have a higher solvency power than aliphatics. Other organic solvent groups are esters, ethers, ketones, amines, nitrated hydrocarbons and halogenated hydrocarbons.
The chief uses of organic solvents include dissolution of coatings (paints, varnishes, and laquers), industrial and household cleaners, printing inks, and extractive processes. Because many solvents are flammable and toxic to health, there is a need to develop safer solvents for commercial use without sacrificing critical performance.
For decades industrial and household cleaning products have been utilized to provide certain tasks such as paint removers, ink removers, degreasers, etc. Solvents are also used to clean, maintain, and prepare wood, metal, masonry, natural and synthetic fabrics, plastic components, electronic components. Although providing the needs of these many and mission-critical tasks, most solvents generally, are toxic, thus posing a threat to health and to the environment. These environmental and health threats include ozone depleting air pollutants and water pollution that threaten aquatic organisms and drinking water supplies. Many of these solvents are carcinogenic and hazardous to health in general.
Although government, industry and the community at large are all relatively well informed to the dangers of toxic solvents, the dangers associated with the use of such solvents have not dramatically diminished their use. Safer handling, disposal, recycling, recovery and other responsible methods of dealing with toxic substances are improving. However, the availability of safer alternative solvents is still not wide spread, especially in second and third world countries, which is due, primarily, to the high cost of the solvent alternatives and because the majority of the environmentally safer solvent alternatives do not provide satisfactory performance.
In order for an “environmentally friendly” solvent alternative to gain wide spread acceptance, a solvent should meet several criteria. First, it should provide effective performance. Second, it should be economically viable and affordable. Third, it should be widely available and, of course, it should be non-toxic to the environment generally and humans specifically.
Several alternative solvents have been introduced by industry for decades, but in general do not meet the criteria stated above. Further, many of these solvents are not completely biodegradable, just less toxic.
A solvent described hereinafter provides high solvency performance while overcoming the toxicity issues associated with most other organic solvents. In addition, a contemplated solvent is biodegradable.
BRIEF SUMMARY OF THE INVENTION
The present invention contemplates an environmentally friendly solvent. This solvent is biodegradable in normal sewerage treatment plants, and has a low volatile content so that it can be used indoors with minimal ventilation.
A contemplated solvent composition comprises:
(A) about 10 to about 60 weight percent C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less;
(B) about 20 to about 75 weight percent of a C 1 -C 4 ester of lactic acid;
(C) zero to about 20 (preferably zero to about 5) weight percent of a surfactant;
(D) zero to about 20 (preferably zero to about 10) weight percent of a thickener; and
(E) zero to about 50 (preferably zero to about 35 or more preferably zero to about 20) weight percent organic solvent.
The composition is a homogeneous liquid or gel at zero degrees C and has a closed cup flash point in excess of 60° C., and preferably in excess of 60° C.
In one preferred embodiment, the composition comprises:
(A) about 30 to about 60 weight percent of a C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less;
(B) about 30 to about 60 weight percent of a C 1 -C 4 ester of lactic acid;
(C) zero to about 5 weight percent of a surfactant;
(D) zero to about 10 weight percent of a thickener; and
(E) zero to about 35 weight percent organic solvent.
Preferably, in the above embodiment, the weight percent of the lactic acid ester is equal to the weight percent of the fatty acid ester, plus or minus about 5 weight percent.
In another preferred embodiment, the composition comprises:
(A) about 20 to about 40 weight percent of a C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less;
(B) about 20 to about 40 weight percent of a C 1 -C 4 ester of lactic acid;
(C) zero to about 20 (preferably zero to about 5) weight percent of a surfactant;
(D) zero to about 20 (preferably zero to about 10) weight percent of a thickener; and
(E) zero to about 35 (preferably zero to about 20) weight percent organic solvent.
In each of the embodiments of the invention, the particularly preferred C 1 -C 4 ester of a C 16 -C 20 fatty acid is an ester of a mixture of oleic and linoleic acids. The methyl ester is preferred, and the fatty acid mixture is preferably that of soybean oil so that methyl soyate is particularly preferred. The particularly preferred C 1 -C 4 ester of lactic acid is the ethyl ester so that ethyl lactate is also particularly preferred.
The present invention has several benefits and advantages.
One benefit of the invention is that a contemplated composition is much safer than a halogenated organic solvent.
A related advantage is that a contemplated composition can be used in occupied areas. The characteristic odor from traditional solvents makes them unsafe to use indoors.
A benefit of a composition according to the present invention is that it has a closed cup flash point greater than about 60° C.
An additional advantage of the present invention is that the cleaning solvent is miscible with water, and thus can be removed with water rinsing, including high pressure water. This rinsing factor can offer some industrial advantages that do not exist with traditional cleaning solvents.
Yet another benefit of a preferred embodiment of the present invention is that it is biodegradable, non-toxic and is derived from two major crops, corn and soybeans.
Another benefit of a paint-stripping embodiment of the invention is that paint strippers containing a contemplated composition can be scraped off, collected and reused. This can not be done with methylene chloride-based paint strippers, due to the significant product that is lost to evaporation.
A further benefit of a paint-stripping embodiment of the invention is that although a contemplated paint stripper composition took a longer period of time to loosen paint than a conventional paint stripper based on methylene chloride, paint stayed wet and workable for a much longer duration.
This offers many advantages in commercial applications.
A further advantage of an ink- and paint-removing embodiment of the invention in the cleaning of air dry inks and paints is that a contemplated composition cleaned tougher grade inks and often cleaned dried inks and paints, whereas soy methyl ester alone showed no effectiveness.
Still another advantage of an ink-removing embodiment of the invention is that the quantity of the ink-removing composition required to be effective is less than is needed with the corresponding petroleum-based products.
Still further benefits and advantages will be apparent to the skilled worker from the discussion that follows.
DETAILED DESCRIPTION OF THE INVENTION
The present invention contemplates an alternative solvent for a multitude of tasks that are commonly practiced today. Separately, lactate ester based solvents, wholly or in combination with other solvents, thixotropic agents, surfactants, pH adjusters and fragrance have been made. In addition, C 1 -C 4 esters of fatty acids derived from edible oils have been developed for certain solvent and cleaning applications. Both lactate esters and edible oil- derived ester solvents have shown to be successful for many application tasks, but separately do not fulfill all properties desired in a solvent and/or cleaning product.
A contemplated composition broadly comprises a solvent blend of about 10 to about 60 weight percent of a C 1 -C 4 ester of lactic acid and about 20 to about 75 weight percent C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less, the latter fatty acid esters preferably being a mixture of esters linoleic and oleic acid. This blended solvent provides several key beneficial properties not achieved separately nor in combination with other solvent blend candidates.
More specifically, a contemplated composition comprises
(A) about 10 to about 60 weight percent C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less;
(B) about 20 to about 75 weight percent of a C 1 -C 4 ester of lactic acid;
(C) zero to about 20 weight percent of a surfactant;
(D) zero to about 20 (preferably zero to about 10) weight percent of a thickener; and
(E) zero to about 50 (preferably zero to about 35 and more preferably zero to about 20) weight percent organic solvent.
The composition is a homogeneous liquid or gel at zero degrees C and has a closed cup flash point in excess of 60° C., and preferably in excess of 60° C.
One preferred composition comprises
(A) about 30 to about 60 weight percent of a C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less;
(B) about 30 to about 60 weight percent of a C 1 -C 4 ester of lactic acid;
(C) zero to about 20 (preferably zero to about 10) weight percent of a surfactant; and
(D) zero to about 20 weight percent of a thickener; and
(E) zero to about 20 weight percent organic solvent.
Preferably, the weight percent of the lactic acid ester is equal to the weight percent of the fatty acid ester, plus or minus about 5 percent.
Another preferred composition comprises
(A) about 20 to about 40 weight percent of a C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less;
(B) about 20 to about 40 weight percent of a C 1 -C 4 ester of lactic acid;
(C) zero to about 5 weight percent of a surfactant; and
(D) zero to about 5 weight percent of a thickener; and
(E) zero to about 35 weight percent organic solvent.
The above preferred embodiment compositions are homogeneous liquids or gels at zero degrees C and has a closed cup flash point in excess of 60° C. (139° F.) [ASTM D93-90], preferably in excess of 60° C.
A contemplated C 1 -C 4 ester of a C 16 -C 20 fatty acid having a melting point of −10° C. or less is an ester of a fatty acid derived (hydrolyzed) from a so-called “edible” vegetable oil. Vegetable oils are comprised of fatty acid triglyceride esters. Hydrolysis of the vegetable oil esters frees the fatty acids, from which the C 1 -C 4 ester are made. Preferred edible vegetable oils include, without limitation, corn, mustard, niger-seed, olive, peanut, poppy-seed, safflower, rape-seed, sesame, soybean, sunflower-seed and wheat-germ oil.
The C 16 -C 20 fatty acid is preferably comprised of a mixture whose fatty acids are constituted by about 70 to about 90 percent unsaturated fatty acids such as oleic, linoleic erucic and linolenic acids. Fatty acid esters derived from edible vegetable oils containing a mixture of about 70 to about 90 weight percent oleic and linoleic acids are more preferred. Soybean oil, which is comprised principally of oleic and linoleic acids is the source of the preferred C 16 -C 20 fatty acid. A methyl (C 1 ) ester is the preferred C 1 -C 4 group. A particularly preferred contemplated C 1 -C 4 ester of a C 16 -C 20 fatty acid is methyl soyate.
The C 1 -C 4 ester of lactic acid is preferably an ethyl (C 2 ) ester. Exemplary C 1 -C 4 alcohols that can comprise the C 1 -C 4 ester portion of a lactate ester or of a C 16 -C 20 fatty acid ester include methanol, ethanol, propanol, isopropanol, allyl alcohol, butanol, 3-buten-1-ol, t-butanol and sec-butanol.
In some contemplated embodiments, the C 1 -C 4 ester of a C 16 -C 20 fatty acid is present at about 10 to about 60 weight percent and the C 1 -C 4 ester of lactic acid is present at about 20 to about 75 weight percent. In preferred embodiments, each of these two ingredients is present at about 30 to about 60 weight 30 percent.
A contemplated composition can also contain up to about 50 weight percent of an organic solvent. A contemplated solvent is biodegradable and can be illustrated by a solvent including but not limited to mixed methyl esters of C 4 -C 6 dibasic acids, N-methylpyrrolidone (NMP), d-limonene, tetrahydrofurfuryl alcohol (THFA) and di-C 2 -C 3 alkylene glycol mono and di-C 1 -C 6 alkyl ethers such as dipropylene glycol n-butyl ether (DPNB), dipropylene glycol methyl ether, diethylene glycol t-butyl methyl ether and diethylene glycol butyl ether. Preferably, the organic solvent is a C 1 -C 4 ester of a C 3 -C 10 dicarboxylic acid, as discussed below. A contemplated organic solvent is free of halogens. The organic solvent plays a role as a useful bridging solvent, helping to maintain a homogeneous solution and helping to dissolve assorted components.
For use as an organic solvent with the invention, mixed methyl esters of C 3 -C 10 dibasic include C 4 -C 6 dibasic acid esters that are commercially available from DuPont Nylon Intermediates and Specialties, Wilmington, DE under the designation DBE. Seven DBE fractions are available that differ in the amounts of each of three diesters (dimethyl adipate [IC 6 ,] dimethyl glutarate [C 5 ] and dimethyl succinate [C 4 ]) present. Each of the products examined was useful, with the material sold as DBE-3 being preferred. That material is said by its manufacturer to contain 89 weight percent dimethyl adipate, 10 weight percent dimethyl glutarate and 0.2 weight percent dimethyl succinate.
A contemplated composition can also contain up to about 20 weight percent of a surfactant. Lesser amounts of surfactant than the full 20 weight percent are typically present when a surfactant is utilized, as is illustrated by the above-enumerated preferred embodiments and the examples that follow.
Surfactants are named herein following the nomenclature system of the International Cosmetic Ingredient Dictionary, 5 th ed., J. A. Wenninger et al. eds., The Cosmetic, Toiletry, and Fragrance Associaton, Washinton, D.C. (1993), usually followed by a chemical name and a trademark name of a particular product. Exemplary surfactants are isotridecyl alcohol tri-ethoxylate (Surfonic® TDA-3B, Huntsman Corp.), C 9 -C 11 pareth-6 [polyethylene glycol ether of mixed synthetic C 9 -C 11 fatty alcohols having an average of 6 moles of ethoxalate; Neodol® 91.6], C 11 -C 15 pareth-59 [polyethylene glycol ether of mixed synthetic C 11 -C 15 fatty alcohols having an average of 59 moles of ethoxalate; Tergitol® 15-S-59], nonoxynol-6 [polyethylene glycol (6) nonylphenyl ether; Tergitol® NP-6], nonoxynol-9 [polyethylene glycol (9) nonylphenyl ether; Tergitol® NP-9], and a modified alkanolamide alkanolamine [Monamine® 1255].
Surfactants containing aromatic groups, such as nonylphenyl groups, are less preferred because they are not as biodegradable as the others. Preferred surfactants are branched and linear alcohol ethoxylates. Most preferred surfactants are alcohol ethoxylates. The addition of a surfactant to a composition comprising a C 1 -C 4 ester of a C 16 -C 20 fatty is preferred. The addition of a surfactant typically makes the cleaner more effective.
A contemplated solvent composition can also include a thickener that provides a “gel-like” consistency to the composition to minimize drip and running of the composition when applied to an other than horizontal surface. Such a thickened consistency can also be useful in an application to a horizontal surface. It is unknown whether a contemplated thickened composition is technically a gel, but that term is used herein to mean a non-solid composition at room temperature that is spreadable, but barely to non-pourable at room temperature.
Preferred thickeners are polysaccharide derivatives having nonionic functionalities such as alkyl alcohol or ether groups. Exemplary thickeners include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, corn starch, hydroxyethyl corn starch, and hydroxypropyl corn starch. Exemplary preferred thickeners include Propylene Glycol Thickener Klucel®-H and Baragel Methocel® 311.
A contemplated composition can also include a perfume (fragrance) to help mask the odor of the 25 components and a colorant. These inactive ingredients are present, if at all, in minor amounts that do not exceed about 5 weight percent in aggregate. Although such inactive ingredients can be present in any contemplated composition, they are not included in a recitation of a contemplated embodiment as they are inactive as solvents.
Contemplated compositions are substantially miscible with water, unlike many petrochemical-based cleaning solvents. Water miscibility is advantageous, because it is easier to handle the cleaning solutions, dispose of them, dilute them and rinse them off of components. A biodegradable solution of the invention can be degraded in standard sewerage treatment plants, as opposed to special chemical waste handling procedures.
A contemplated composition is substantially free of added water. Thus, although some water can be present as a result of being an impurity of a constituent, water is typically not added to a composition, and a composition typically contains 5 weight percent water or less. The weight percent of the compositions described herein refers to the weight percent of the organic phase, and does not include the mass of any added water. A contemplated composition is also substantially free of halogenated compounds so that only contaminating amounts of such materials are present.
In some embodiments, a contemplated composition discussed above is used as a concentrate, and as such, it can be admixed with up to about 30 weight percent water prior to use. In a preferred concentrate usage, a contemplated composition is admixed with water and emulsified prior to use.
The present invention is illustrated in the non-limiting examples that follow.
EXAMPLE 1
Formulation A, Paint Stripping Gel
Weight
Percent
Ingredient
11.0
Soy Methyl Ester (Methyl Soyate)
CAS No. 67784-80-9
74.0
Ethyl Lactate CAS No. 97-64-3
6.0
Surfactant--6M Nonyl Phenol
6.0
Thickener--Propylene Glycol-Klucel ®-H
or Baragel Methocel ® 311 Methyl
Cellulose (cellulose methyl ether)
CAS NO. 9004-67-5
3.0
Fragrance
Mix ingredients in order listed. Appearance: dark golden thick gel with mild odor.
EXAMPLE 2
Formulation B, Paint Stripper
Weight
Percent
Ingredient
74.0
Ethyl Lactate CAS No. 97-64-3
14.0
Soy Methyl Ester (Methyl Soyate) CAS
NO: 67784-80-9
6.0
Surfactant--Tergitol ® 15-S-59
6.0
Thickener--Propylene Glycol Thickener
Klucel ®-H or Baragel Methocel ® 311
Methyl cellulose (cellulose methyl
ether; CAS NO: 9004-67-5)
Mix ingredients in order listed. Appearance: golden paste.
EXAMPLE 3
Formulation C, Liquid Paint Stripper
Weight %
Ingredient
30
Soy Methyl Ester (Methyl Soyate)
CAS No. 67784-80-9
35.0
Ethyl Lactate CAS 97-64-3
35.0
Organic solvent--Tetrahydrofurfuryl
Alcohol (THFA; QO Chemical)
Mix ingredients in order listed. Appearance: light golden liquid.
EXAMPLE 4
Formulation D, Paint Stripper
Weight
Percent
Ingredient
20.0
Soy Methyl Ester (Methyl Soyate) CAS
No: 67784-80-9
40.0
Ethyl Lactate CAS No. 97-64-3
35.0
Organic solvent--DBE-1
Dimethyl glutarate CAS No: 1119-40-0
Dimethyl adipate CAS No: 627-93-0
Dimethyl succinate CAS No: 106-65-0
5.0
Thickener Blend
Propylene Glycol Thickener Klucel ®-H
or Baragel Methocel ® 311
Methyl Cellulose (cellulose methyl
ether) CAS No: 9004-67-54
Mix ingredients in order listed. Appearance: light golden paste, heavy viscosity, mild odor.
EXAMPLE 5
Formulation E, Fat And Grease Remover
Weight
Percent
Ingredient
35.0
Soy Methyl Ester (Methyl Soyate)
CAS No: 67784-80-9
20.0
Ethyl Lactate CAS No. 97-64-3
30.0
Organic solvent--d-Limonene
(Florida Chemical Co., Inc.)
CAS No: 5989-27-5
15.0
Surfactant Blend
Tergitol ® NP-6 & Tergitol ® NP-9
(Union Carbide Corporation)
Mix ingredients in order listed. Appearance: light golden liquid, mild citrus odor.
EXHIBIT 6
Formulation F, Heavy Grease Remover
Weight
Percent
Ingredient
39.0
Soy Methyl Ester (Methyl Soyate) CAS
No: 67784-80-9
21.0
Ethyl Lactate CAS No. 97-64-3
10.5
Surfactant--Neodol ® 91.6 (Shell
Chemical)
10.5
Surfactant--Monamine ® 1255 (Mona
Corporation)
19.0
Organic solvent--Dipropylene Glycol n-
Butyl Ether (DPNB; Arco Chemical)
Mix ingredients in order listed. Appearance: light amber liquid, mild odor.
EXAMPLE 7
Formulation G, Gel Paint Stripper
Weight
Percent
Ingredient
20
Ethyl Lactate CAS No. 97-64-3
20
Soy Methyl Ester (Methyl Soyate)
CAS NO: 67784-80-9
20
Organic solvent--N-Methylpyrrolidone
30.0
Organic solvent--DBE-3
Dimethyl glutarate CAS NO: 1119-40-0
Dimethyl adipate CAS NO: 627-93-0
Dimethyl succinate CAS NO: 106-65-0
5.0
Thickener Blend
Propylene Glycol Thickener Klucel ® -H
or Baragel Methocel ® 311
Methyl Cellulose (Cellulose Methyl
Ether) CAS NO: 9004-67-54
5.0
Surfactant
6M Nonyl Phenol
Mix ingredients in order listed. Appearance: light golden gel, mild odor.
EXAMPLE 8
Paint Stripping
Ingredients:
Formulation A (Example 1)
Test Panel:
Wood, Oak approximately 90 years
of age.
Paint:
2 Coats of White Latex Paint with
a cure time of over 5 years
Cleaning Method:
Extended Dip, 100% solution of
Formulation A
Environment:
75° F. controlled interior
environment, 50% humidity,
ventilation minimum.
Time:
Test materials was submerged for 2 hours.
The test panel was dipped and submerged in solution. After 2 hours test panel was removed and immediately scrubbed with non-absorbent nylon scrub pad. At conclusion of scrubbing test panel was rinsed with water and permitted to air dry.
When the test panel was removed from solvent bath, it was apparent to the eye that paint was thoroughly attacked and penetrated by solvent. Paint appeared soft and showed significant bubbling at many locations. Upon scrubbing, 80% of paint was immediately removed. Further scrubbing removed remaining paint. A second test on a similar panel provided the same results.
It is apparent there are many applications for a point dip solvent of this type. The thickening agent permits the solvent to be applied directly to material rather than dipped. The dipping procedure was chosen to permit maximum solvent contact without solvent drying or hardening. This was also chosen because it is a common cleaning method within the paint removal and furniture stripping business.
Comparative Test
A traditional paint stripper containing methylene chloride was tested under same conditions. It showed effectiveness at dip times of less than 30 minutes. However, solvent vapors were so strong the test could not be conducted under same test conditions. The test conditions had to be moved to exterior location, for ventilation purposes. Also, safety clothing was necessary. Gloves and goggles were also necessary to handle traditional solvent. Dip times had to be closely monitored due to solvent lost to evaporation. Waste posed some disposal problems because of the large concentrations of methylene chloride. The latex paint presented no disposal problems until mixed with methylene chloride.
EXAMPLE 9
Paint Stripping
Ingredients:
Formulation B (Example 2)
Appearance:
golden paste
Odor:
Slight odor
Test Panel:
Wood, Oak approximately 90 years of
age.
Paint:
2 Coats of White Latex Paint with a cure
time of over 5 years
Cleaning Method:
Brush on 100% solution of
Formulation B
Environment:
75° F. controlled Interior environment,
50% humidity, ventilation minimum
The test panel was brush coated with approximately ⅛-inch thick amount of Formulation B. After 60 minutes, the test panel was scraped with putty knife. At conclusion of scraping, the test panel was rinsed with water and permitted to air dry.
At 15 minutes, it was apparent to the eye that paint was being attacked and penetrated by solvent. The paint appeared soft and showed significant bubbling at many locations. Upon scraping, about 80% of paint was immediately removed. Further scraping removed remaining paint. A second test provided the same results with a second test panel.
The thickening agent permits the solvent to be applied directly to material rather than dipped. This formulation takes a longer time to show effectiveness in loosening paint, compared to traditional high odor paint strippers. However, in applications where time is not an issue this paint remover is superior to traditional methods.
Comparative Test
A traditional paint stripper containing methylene chloride was tested under same conditions. It showed effectiveness at 10 minutes. However, solvent vapors were so strong the test could not be carried out under the same test conditions, and the test had to be moved to exterior location for ventilation purposes. Also, safety clothing was necessary. Gloves and goggles were also necessary to handle traditional solvent. Waiting time had to be closely monitored due to solvent lost to evaporation. Waste posed some disposal problems because of the large concentrations of methylene chloride. The latex paint presented no disposal problems until mixed with methylene chloride.
EXAMPLE 10
Paint Stripping
Ingredients:
Formulation D (Example 4)
Appearance:
Light golden paste
Odor:
mild odor
Test Panel:
Wood, Oak approximately 90 years of
age.
Paint:
2 Coats of White Latex Paint with a
cure time of over 5 years
Cleaning Method:
Extended Dip, 100% solution of
Formulation D
Environment:
75° F. controlled interior environment, 50%
humidity ventilation minimum
The test panel was dipped and submerged in solution. After 2 hours the test panel was removed and immediately scrubbed with non-absorbent nylon scrub pad. At the conclusion of scrubbing lest panel was rinsed with water and permitted to air dry.
When the test panel was removed from solvent bath, it was apparent to the eye that paint was being attacked and penetrated by solvent. Paint appeared soft and showed some bubbling. Upon scrubbing, about 70% of paint was immediately removed. Further scrubbing removed remaining paint. A second test provided the same results using a similar panel.
Comparative Test
A traditional paint stripper containing methylene chloride was tested under same conditions. It showed effectiveness at dip times of less than 30 minutes. However, solvent vapors were so strong test could not be conducted under same test conditions. Test conditions had to be moved to exterior location, for ventilation purposes. Also, safety clothing was necessary. Gloves and goggles were also necessary to handle traditional solvent. Dip times had to be closely monitored due to solvent lost to evaporation. Waste posed some disposal problems because of the large concentrations of methylene chloride. The latex paint presented no disposal problems until mixed with methylene chloride.
EXAMPLE 11
Grease Removal
Ingredients:
Formulation E (Example 5)
Appearance:
Golden liquid.
Odor:
Slight citrus odor.
Test Panel:
Stainless steel with heavy
accumulation of grease.
Cleaning Method:
Spray on 100% solution of
Formulation E
Environment:
75° F. controlled interior environment,
50% humidity, ventilation minimum.
The test panel was mist sprayed with formulation until saturated. After 30 seconds, the test panel was wiped with paper towel. At the conclusion of wiping, the test panel was mist sprayed with water, wiped again and permitted to air dry.
It was immediately apparent to the eye that rease was being attacked and penetrated by solvent. rease began to loosen and returned to a liquid state. When test panel was wiped with paper towel, the grease emulsified with solvent. A water rinse completed the cleaning process. When water was mist sprayed, the solvent and grease emulsification turned white. An emulsification of grease, solvent and water then occurred. Panel was thoroughly cleaned with no grease residues remaining. A second test using a second, similar panel provided the same results.
Comparative Test
A traditional aqueous grease remover was tested containing 2-butoxyethanol (CAS No.: 111-76-2), lauryldimethylamine oxide (CAS No.: 1643-20-5) and water (CAS No.: 7732-18-5). Formulation E was much more effective. The traditional cleaner required multiple applications and extended scrubbing times. The scent of the traditional cleaner was less noticeable. However, for grease removal applications involving heavy accumulations of grease, there was no comparison. Formulation E out performed the traditional cleaner. Formulation E emulsified grease in hard to reach areas where scrubbing could not be performed. In this situation, a concentrated water rinse can replace scrubbing and effectively remove grease. The traditional cleaner showed no effectiveness in these hard to reach areas where scrubbing could not be accomplished.
EXAMPLE 12
Paint Stripping
Ingredients:
Formulation G (Example 7)
Appearance:
Light golden gel.
Odor:
Mild odor.
Test Panel:
Aluminum Panel
Paint:
2 Coats of White Latex Paint with
a cure time of over 5 years
Cleaning Method:
Brush on 100% solution of
Formulation G.
Environment:
75° F. controlled interior environment,
50% humidity, ventilation minimum.
The test panel was brush-coated with an approximately ⅛″ thick amount of Formulation G. At 5 minutes, it was apparent to the eye that paint was being attacked and penetrated by solvent. Paint appeared soft and showed significant bubbling at many locations. After 30 minutes, the test panel was scraped with a putty knife. At the conclusion of scraping, the test panel was rinsed with water and permitted to air dry. Upon scraping, about 95% of paint was immediately removed, further scraping removed remaining paint. A second test provided the same results with a second, similar panel.
The thickening agent present in this formulation permits the solvent to be applied directly to material rather than dipped. The product takes a slightly longer time to show effectiveness in loosening paint, when compared to traditional high odor paint strippers. However, traditional paint strippers tended to dry if not immediately removed. Formulation G did not dry and permitted greater flexibility in setting a removal time.
EXAMPLE 13
Paint Stripping
Formulation H
Ingredients:
46% Ethyl Lactate
46% Methyl Soyate
8% Surfactant - 6M nonyl phenol
Test Panels:
Wood, Oak approximately 90 years of age
Paint:
panel A: 2 coats of latex paint
panel B: varnish
panel C: lead-based oil paint
(all cured over 5 years)
Environment:
75° F. Controlled interior environment,
50% humidity, ventilation minimum.
The ingredients were mixed in order itemized and stirred to first create an environmentally friendly solvent as a concentrate, Formulation H, and then a micro-emulsion within 1 minute of the addition of water (in a water amount equal to 16 weight percent of the concentrate). The micro-emulsion was applied to the test panels.
Time: After maintaining the micro-emulsion in contact with the painted surface for 15 minutes, the test panels were scrubbed with a non-absorbent nylon scrub and rinsed with water.
Results: All paint was completely removed, rinsed and dried.
EXAMPLE 14
Paint Stripping Gel
Formulation J:
40% Ethyl Lactate
40% Methyl Soyate
20% Thickener--Corn Starch
Test Panels:
Wood, Oak over 50 years of age.
Paint:
panel A: baked on enamel
panel B: latex over varnish
(all cured over 5 years)
The ingredients were mixed sequentially and maintained without agitation for 30 minutes forming a stiff gel, Formulation J, that did not run when applied to wood panels in a vertical position.
Time:
Test 1—The gel was permitted to stand on the panel for 30 minutes, then scrubbed with non-absorbent nylon scrub and rinsed with water.
Test 2—The gel was permitted to dry overnight, leaving a white dry “cake frosting” appearance, then scrapped off and rinsed.
Results: The paint was completely removed in both tests. The dry paint stripping powder stripped off in Test 2 was swept up and co nvenien tly discarded as a dry powder.
EXAMPLE 15
Cleaning and Degreasing Solvent
A blend of ethyl lactate and soy methyl ester (50 weight percent of each component, Formulation K) was prepared. The blend has a flash point greater than 140° F. (60° C.). The blend was tested in a Safety-Kleen industrial large parts washer Model No. 81 (Elgin, Ill.) to wash a variety of old, dirty and used parts such as engine blocks, milling machine heads, gears and other machine parts.
At the end of the 10 week test, Formulation K was compared to a commercially available petroleum- based cleaner. The cleaning performance of Formulation K was satisfactory. Less time was required to sufficiently clean the parts with Formulation K as compared to the petroleum-based cleaners, and Formulation K was a more effective cleaner. No new or special operating methods or procedures where required to work with or manage the Formulation K composition.
Formulation K was more effective than the petroleum-based solvents in cleaning large and highly dirty parts. The cleaned parts required more time to dry when Formulation K was used than when the petroleum-based cleaner was used. The odor of Formulation K was more noticeable than the petroleum- based solvent, but not unpleasant.
From the foregoing, it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitation with respect to the specific examples presented is intended or should be inferred. The disclosure is intended to cover by the appended claims all such modifications as fall within the scope of the claims. | A solvent that is biodegradable, provides effective solvency for a broad range of tasks and is generally benign to human health is disclosed. This solvent is a mixture of a lactate ester and an edible oil ester having a closed cup flash point in excess of 60° C., and can include other non-halogenated solvents and surfactants. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of U.S. Ser. No. 10/780,260, filed Feb. 17, 2004 now abandoned, each of which are hereby expressly incorporated by reference herein in their entireties.
FIELD OF THE INVENTION
This invention relates to a device for filling a trench with the dirt previously removed to form the trench.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a rear-perspective view of the device attached to the rear of a pulling vehicle, such as a tractor.
FIG. 2 is a perspective view of the device looking at the right, rear corner of the device.
FIG. 3 is a longitudinal cross sectional view through the device.
FIG. 3 a is the same view as FIG. 3 , but illustrating the location of the dirt being put back into the trench.
FIG. 4 is a plan view of the device.
FIG. 5 is perspective view of the front left corner of the device.
FIG. 6 is a front, perspective view of a portion of the device.
FIG. 7 is a schematic, plan view of an alternate embodiment.
DETAILED DESCRIPTION
Referring to the drawings in detail, and particularly FIG. 1 , reference character 10 generally designates the trench filling device of this invention which is adapted to be towed along a trench by a tractor or the like 12 . In general, the device 10 comprises a frame 14 supporting a pair of rearwardly converging scraper blades 16 ( FIG. 4 ) in the forward end 18 of the frame; a temporary leveling blade 20 ( FIG. 3 ) rearwardly of the blades 16 and a compaction roller 22 in the rearward end 24 of the frame 14 .
As shown in FIGS. 1 and 2 , the frame 14 comprises a pair of side plates 26 interconnected by cross braces 28 and having a skid 30 formed along the lower edge 32 of each side plate.
As shown in FIGS. 3 and 4 , a pair of brackets 34 are secured to the forward end 18 of the frame 14 near each side of the frame, and an upper bracket 38 is provided in the center of the frame for connection with the three point hitch 40 of the tractor 12 . The device 10 can thus be towed as well as raised to an inoperative position by the use of the three point hitch 40 of the tractor 12 .
The forward end 42 of each of the rearwardly converging scraper blades 16 is suitably secured to the forward end 18 of the respective side of the frame 14 by a suitable bracket 44 as shown in FIG. 5 . The rearward end 46 of each rearwardly converging scrape blade 16 is supported horizontally by a suitable adjustable bracket 48 , by means of which the spacing between the rear end portions 46 of the scraper blades 16 may be adjusted as desired. The rear end portion 46 of each scrape blade 16 is secured vertically by a suitable bracket 50 .
As indicated in FIG. 3 , each end of the horizontally extending blade 20 is secured to the respective frame side plate 26 by an adjustable bracket 52 in order that the overall height of the blade 20 may be adjusted as desired by the local conditions. Normally, the blade 20 is positioned about three inches above the level of the skids 30 .
As shown in FIG. 1 , the roller 22 is mounted on a shaft 54 . Each end of the shaft 54 is supported in a bearing 56 suitably secured to the respective side plate 26 by bolts 58 . As indicated in FIG. 2 , two sets of bolt holes 60 are provided in the frame side walls 26 to receive bolts 58 and provide for a vertical adjustment of the height of roller 22 . Normally, the roller 22 is adjusted at a height a short distance above the skids 30 , such as about one and one quarter inches.
An alternate embodiment 10 a is shown schematically in FIG. 7 . This alternate embodiment utilizes a virtually identical frame 14 , as well as the rearwardly converging scraper blades 16 at the forward end of the device, and the roller 22 at the rear end of the device. Rather than the use of a scraper blade extending horizontally across the frame 14 , the alternate embodiment 10 a utilizes a rubber tire 62 for temporarily compressing the dirt moved into the trench by the blades 16 , and a second pair of scraper blades 64 between the rubber tire 62 and the roller 22 to move dirt into the path of the central portion of the roller 22 which is disturbed by the rubber tire 62 . The rubber tire is suitably supported by a linkage 66 from one of the cross frame members 28 utilizing a compression spring 68 and an adjustable jack mechanism or hydraulic cylinder 70 , by means of which the rubber tire 62 will be urged downwardly against dirt moved by the scraper blades 16 , and the amount of the compression provided by the spring 68 may be adjusted by the jack or cylinder 70 to provide the desired force on the dirt moved over the trench by the scraper blades 16 . The secondary scraper blades 64 will be suitably mounted on cross braces 28 in such a manner that the angle of these blades may also be adjusted.
It will be understood by those skilled in the art that the blades 16 and 64 in FIG. 7 may be mounted in the frame 14 using hydraulic cylinders, rather than mechanically, for the convenience of the operator of the device.
OPERATION
The purpose of device 10 is to move the dirt 72 ( FIG. 3 a ) at each side of an open trench 74 into the trench and provide some compaction of the dirt moved back into the trench. As indicated in FIG. 3 a , the scraper blades 16 move the dirt 72 into and over the trench 74 as the device 10 is pulled forwardly with the skids 30 straddling the trench.
The dirt moved by the scraper blades 16 will extend above the level of the ground on each side of the trench and the horizontally extending scraper blade 20 will temporarily level that dirt, before it is contacted and somewhat compressed or compacted by the roller 22 . The level of the dirt behind the device 10 will be a short distance above the ground on each side of the trench, allowing for the dirt to settle in the trench and eventually end up with a relatively level surface where the trench had been.
The modified device 10 A shown in FIG. 7 will provide a first compaction and spreading of the dirt first moved by the scraper blades 16 by operation of the rubber tires 62 , and the dirt disturbed by the rubber tire 62 will be moved back over the center portion of the trench by the small scraper blades 64 . Then the roller 22 will further compact the dirt and leave a surface slightly above the surrounding ground in the same manner as the device shown in the preferred embodiment.
Changes may be made in the combination and arrangement of parts or elements as here to fore set forth in the specification and shown in the drawing without departing from the spirit and scope of the invention as defined in the following claims. | A device for filling an open trench with the dirt previously removed from the trench lying alongside the trench, using a skid-mounted frame having blades to initially fill the trench and leveling the dirt, followed by a compactor. | 4 |
This is a divisional of application Ser. No. 07/447,310, filed Dec. 7, 1989 and now U.S. Pat. No. 4,983,553.
BACKGROUND
The present invention concerns an improved method for preparing aluminum nitride powders. The present invention also concerns an apparatus suitable for use in conjunction with the improved method.
Aluminum nitride exhibits certain physical properties which make it particularly suitable for use in a variety of applications. Some applications, e.g., packaging components for electronic circuitry, require substantially full theoretical density and high thermal conductivity. High quality aluminum nitride powder, when densified by sintering, hot-pressing or other suitable means, generally satisfies these requirements. A number of factors contribute to powder quality. Powder particle size and surface area primarily affect density of the resultant ceramic article. Powder purity plays a major role in determining purity of the resultant ceramic and thereby the magnitude of certain physical properties such as thermal conductivity.
High quality aluminum nitride powder typically has a low oxygen content (less than about 2%), a low carbon content (less than about 0.2%), and low trace metals content (less than a few hundred parts per million). Lower quality aluminum nitride powders, e.g., those with greater oxygen, carbon or trace metals contents, are generally regarded as unsuitable for use in certain electronics applications such as electronic packaging. Sinterable aluminum nitride powders typically have a particle size of from 1.0 to 0.2 micrometers inclusive. The surface area of the powders, being inversely proportional to the particle size, ranges from about 2 to 10 m 2 /g inclusive.
Production of aluminum nitride powder typically follows one of two known methods. One method, known as direct nitridation, involves nitriding of metallic aluminum nitride powder in a nitrogen or ammonia atmosphere at high temperature and pulverizing the resultant nitride. The second method, known as carbothermal reduction, reacts aluminum oxide, carbon and nitrogen at a high temperature. The present invention focuses upon the latter method.
An examination of the carbothermal reduction reaction thermochemistry shows that it has a highly endothermic nature under all conditions. As such, heat must be supplied in an effective and efficient manner if the reaction is to proceed at an acceptable velocity. Adverse effects of an improper supply of heat include an incomplete reaction of starting materials, coarsening or grain growth of the aluminum oxide starting material or the aluminum nitride product or both, and undesirable side reactions to form unwanted byproducts such as aluminum oxynitride.
Complete conversion of the reactants requires both an effective introduction of reactant gases, e.g., nitrogen, into the reacting mass and an efficient removal of product gases such as carbon monoxide therefrom. If reactant gas introduction and product gas removal are not done properly, the resultant aluminum nitride product can contain high levels of oxygen. Excess oxygen indicates that the reaction has achieved an equilibrium position between starting materials and products which lies short of complete conversion to the desired aluminum nitride.
Kuramoto et al. (U.S. Pat. No. 4,618,592) teach the importance of choosing and maintaining high purity in the reactant solids, e.g., aluminum oxide and carbon. They also teach the importance of preparing an intimate mixture of the reactant solids. Their Example 1 discloses a small (30 to 200 gram) scale reaction in an electric furnace operating at about 1600° C. while feeding nitrogen gas into the furnace at a rate of 3 liters per minute. Following a reaction time of 6 hours, the mixture is removed and oxidized in air to remove unreacted carbon.
Reaction conditions suitable for use in conjunction with a laboratory scale reactor may not provide acceptable results in a larger scale apparatus. A small reacting mass allows for relatively efficient gas and thermal transport which, in turn, lead to preparation of high quality powders even under far less than ideal conditions. As the size of the reaction vessel increases to accommodate larger reacting masses, degradation of gas and thermal transport efficiency usually follows. As the depth of a bed of reactant solids increases, difficulties in providing contact between reactant solids and reactant gases and removal of product gases change from minor irritants to major problems. As the bed of reactant solids increases in size, heating of the bed to drive the endothermic reaction toward completion becomes increasingly non-uniform and varies with the distance of a portion of the bed from the source of heat. In other words, the reaction proceeds from the outside of the reactant bed or charge toward its center in response to an external source of heat. The foregoing gas and thermal transport problems give rise to less than ideal reaction conditions in local volumes within a reacting mass and consequent variability in aluminum nitride conversion and quality.
Design and operation of a reactor or process to provide near ideal reaction conditions in the reacting mass, while necessary, are not sufficient for a successful scale-up of aluminum nitride synthesis to industrial scale. Other factors, including raw materials, labor and utilities, must be managed efficiently in order to manufacture a competitive product.
Although operation of a continuous reactor or process may provide a cost effective use of utilities and labor, it also necessarily implies motion or moving parts. The design and operation of a reactor with hot moving parts is limited by the availability and performance of suitable materials. Addressing this limitation, while necessary, may give rise to other problems such as unacceptable loss of reaction control and product quality.
A number of references describe reactors and processes for preparing aluminum nitride. Some suggest the potential for industrial scale reaction of aluminum oxide with carbon and nitrogen. Others address reaction scale without reference to the product quality. Although a few references bring up the need for complete conversion of reactants to a product containing low oxygen, none address industrial scale facilities and processes for preparing high quality aluminum nitride having both low oxygen and fine particle size. Indeed, references which stress scale and product oxygen content necessarily preclude attainment of a fine particle size material.
Kuramoto et al., supra, disclose a process which prepares high quality powder. The process is not, however, suitable for practice on an industrial scale. Static beds of powdered solid reactants are impractical for large scale operations due to problems with product quality and uniformity and uneconomical reaction kinetics. Reaction times of six hours or more are clearly excessive.
Serpek (U.S. Pat. No. 888,044) discloses a method of producing aluminum nitride which consists of heating a mixture of alumina, carbon and a metal capable of forming an alloy with aluminum in a nitrogenous atmosphere to red heat. The resultant product quality is less than desirable because of contamination due to retained metal.
Serpek (U.S. Pat. No. 1,030,929) teaches the use of an electric furnace in which raw material powder mixtures are introduced into a rotary reaction chamber heated by resistance elements. Conversion of the mixtures to aluminum nitride is assisted by a counter flow of gaseous nitrogen. The rotary action of the chamber provides necessary agitation of the powder mixtures. This facilitates both gas and thermal transport. However, it also leads to unacceptable mixing of unreacted, partially reacted and fully reacted materials. If the reactor is operated at feed rates and residence times sufficient to fully convert all of the unreacted materials in such a mixture, the resultant material is still not uniform. The lack of uniformity translates to an unacceptable product.
Serpek (U.S. Pat. No. 1,078,313) teaches incorporation of hydrogen into the nitrogenous reaction atmosphere to induce somewhat faster initial reaction kinetics. However, the best product shown in the examples contains only 8.6 percent nitrogen, an indication of a conversion of approximately 30 percent.
Shoeld (U.S. Pat. No. 1,274,797) teaches a process for producing aluminum nitride which utilizes a vertically situated reaction zone through which briquets of aluminum oxide and carbon and a binder are passed while a nitrogen containing gas is uniformly distributed within. The reacting mass is heated by means of electrodes which cause current to pass through the briquets, heating each directly and uniformly. The configuration and operation of this process places severe demands upon the composition and physical properties of the feed briquets and on the partially and completely reacted briquets as well. In order for the briquets to pass electricity, the composition must be precisely tailored to provide the correct resistance. Unfortunately, the resistance clearly changes in an unpredictable fashion as the material is reacted. This unpredictability leads to inefficient heating of the reacting mass which, in turn, leads to variable reaction kinetics and nonuniform product quality. In addition, a vertical deep bed of briquets places severe constraints on briquet strength. The briquets must have both high unreacted strength and sufficient strength during conversion to avoid disintegration and consequent blinding of the column to flow of gaseous nitrogen. High strength is usually provided by incorporation of large amounts of binder or by the preparation of a denser material. Large amounts of binder compromise the purity of the product or change the course of the reaction whereas denser feed briquets inhibit the necessary gas transport within the briquet resulting in longer reaction times or lower product quality or both.
Perieres et al. (U.S. Pat. No. 2,962,359) teach the importance of maintaining effective control of the atmosphere in flow and composition in all portions of the reacting mass including the volume within individual porous briquets. The briquets consist of aluminum oxide and aluminum oxide in admixture with coke. Perieres et al. also teach the existence of volatile solid byproducts which can clog the reactor and otherwise alter the reaction's critical stoichiometry.
Clair (U.S. Pat. No. 3,032,398) discloses a process for continuously producing aluminum nitride. The process comprises forming a particulate feed material composed of aluminum oxide, carbon and a calcium aluminate binder: continuously passing the particulate material downward into an externally heated elongated reaction zone: passing a countercurrent flow of nitrogen through the descending particulate material: and removing and recovering the aluminum nitride below the reaction zone. The exhaust gases are conducted through an expansion zone to condense any calcium contained in the gases. The volatilized calcium compounds, if not removed, would otherwise clog the reactor. Some calcium remains in the product and represents an undesirable impurity. The binder also causes excessive sintering of particulate material thereby preventing recovery of a fine particle size product. Because nitrogen is consumed in the reaction and carbon monoxide is released, the elongated reaction zone with its axial flow of gas necessarily contains a non-uniform reaction atmosphere. In addition, the mechanical nature of the particulate flow within a stationary tube results in a nonuniform distribution of particle velocities leading to an uncertain residence time. Furthermore, countercurrent gas typically flows via channels within a deep or elongated bed. Such flow patterns contributes to production of a nonuniform product.
Paris et al. (U.S. Pat. No. 3,092,455) disclose a process for producing aluminum nitride wherein aluminum oxide grains are contacted with a reactant gas containing a hydrocarbon as a source of carbon. The process may be used in conjunction with a fixed bed reactor, a moving bed reactor, or a fluidized bed reactor. The introduction of a hydrocarbon into a fixed or moving bed of aluminum oxide grains, in either a co-current or a countercurrent flow, results in a nonuniform distribution of carbon, a critical reactant. The resultant product is expected to be similarly nonuniform. The fluidized bed typically provides for rapid and uniform mixing of the solid and gaseous reactants. However, continuous operation of a fluidized bed mandates continuous removal of product. The product so removed contains a finite, but undesirable, amount of unreacted and partially reacted solids.
SUMMARY OF THE INVENTION
One aspect of the present invention is a method for continuously producing aluminum nitride via carbothermal reduction of aluminum oxide. The method comprises:
a) providing at least one discrete aliquot of solid reactant materials, each aliquot being disposed within a separate container, each container having defined therein a means for receiving gaseous reactants and distributing said gaseous reactants in a generally uniform manner throughout said aliquot, said solid reactants comprising aluminum oxide and, optionally, carbon, said gaseous reactants comprising nitrogen and, optionally, a source of carbon:
b) passing the container(s) at least once through a heated reaction zone at a rate and for a period of time sufficient to heat said aliquot to a temperature sufficient to initiate a reaction between the gaseous reactants and solid reactant materials to produce aluminum nitride:
c) supplying the gaseous reactants to said container at a rate sufficient to convert the solid reactant materials to aluminum nitride:
d) removing gaseous reaction products from the solid reactant materials at a rate sufficient to form aluminum nitride with a controlled particle size and substantially preclude formation of aluminum oxynitride or aluminum oxycarbide.
The solid reactants are suitably in a form which maximizes contact with gaseous reactants and removal of reactant gases. The actual form is immaterial and may be selected from the group consisting of powder, flakes, pellets, agglomerates and the like. The solid reactants are desirably in the form of pellets.
A second aspect of the present invention is an apparatus comprising:
a) means for containing solid reactant materials, said means including a means for receiving gaseous materials and distributing said gaseous materials throughout any solid reactant materials contained therein:
b) means for conveying said container means at least once through a reaction zone:
c) means for supplying gaseous materials to the means for receiving gaseous materials said container means while the container means are conveyed through the reaction zone; and
d) means for removing gaseous reaction products from the reaction zone.
The method and apparatus of the present invention suitably produce high quality aluminum nitride powder on a commercial scale. The resultant aluminum nitride beneficially has an oxygen content equal to or less than about 1.5% by weight, a particle size of equal to or less than about 1.5 microns and a specific surface area of between about 2 m 2 /gms and about 5 m 2 /gms. Sintered aluminum nitride formed from aluminum nitride powder prepared by the method and apparatus of the present invention can be of near theoretical density with a thermal conductivity in excess of about 140 W/m° K.
The above features and other details of the invention, either as steps of the invention or as combinations of parts of the invention, are more particularly described with reference to the accompanying drawings and pointed out in the claims.
Particular embodiments of the invention are shown by way of illustration only and not as a limitation of the invention. Principal features of the invention may be employed in various embodiments without departing from the scope of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cross-sectional side view of a schematic illustration of one embodiment of the apparatus of the present invention
FIG. 2 is a cross-sectional plan view taken along line 2--2 of FIG. 1.
FIG. 3 is a cross-sectional side view of schematic illustration of a means for containing solid, finely-divided materials. The means is adapted to receive gaseous reactants by countercurrent flow thereof.
FIG. 4 is a cross-sectional side view of a schematic illustration of a preferred means for containing solid, finely-divided materials. The means is adapted to receive gaseous reactants via a porous bottom.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1 and 2 schematically depict an apparatus suitable for purposes of the present invention and designated by the reference numeral 10. The apparatus 10 comprises a reaction chamber 20, a plurality of upper reaction chamber conduits 28, a plurality of lower reaction chamber conduits 29, a first tunnel chamber 30, a first tunnel chamber conduit 35, a second tunnel chamber 40, a second tunnel chamber conduit 45, a first air lock 50, a second air lock 55, a container support means (rail, track, path or channel) 60, a plurality of container means, boats or trays 70, a plurality of heating elements 80, a means (not shown) of moving said container means 70 along track 60, a source of reactant gases (not shown) and a means for receiving gaseous reaction products (not shown).
The first tunnel chamber 30 has a first end 31 located proximate to, and in operative communication with, the first air lock 50 by way of inner air lock door 52 and a second end 32 located remote from the first end 31 and proximate to, and in fluid communication with, first end 21 of reaction chamber 20. The first tunnel chamber conduit 35 is connected to, and in fluid communication with, the first tunnel chamber 30.
The second tunnel chamber 40 has a first end 41 located proximate to, and in fluid communication with, second end 22 of reaction chamber 20, and a second end located remote from the first end 41 and proximate to, and in operative communication with, the second air lock 55 by way of inner air lock door 56. The second tunnel chamber conduit 45 is connected to, and in fluid communication with, the second tunnel chamber 40.
The reaction chamber 20 has disposed therein the heating elements 80. The heating elements 80 are arrayed in a manner sufficient to impart heat to contents of container means 70 as said means traverse reaction chamber 20. As shown in FIG. 1, heating elements 80 are arrayed above container means 70. That arrangement may be varied as desired to place the heating elements 80 proximate to the sides of, below, or all around said container means 70 while they are disposed within reaction zone 20.
The placement of heating elements 80 also fixes the first end 21 and the second end 22 of reaction zone 20. As shown in FIG. 1, the first end 21 is proximate to the heating element 80 located closest to the first air lock 50 and the second end 22 is proximate to the heating element 80 located closest to the second air lock 55.
If desired, the heat supplied by heating elements 80 may be supplemented by preheating reactant gases by a means before introducing them into reaction chamber 20. Sweep gases, if used, could also be preheated. Preheating apparatus and the operation thereof are known. Suitable preheat temperatures are readily determined without undue experimentation.
The upper reaction chamber conduits 28 are connected to, and in fluid communication with, reaction zone 20. The lower reaction chamber conduits 29 are connected to the rail, track, path or channel 60 in such a manner that the conduits 29 are in fluid communication with a lower portion of reaction zone 20. At least one of the conduits 29 is beneficially in fluid communication with a gaseous reactant receiving chamber 71 of each container means 70 while said container means 70 is disposed within reaction zone 20. As shown in FIG. 1, and more particularly in FIG. 4, the chamber 71 is suitably a hollowed out lower portion of container means 70. The edges of the hollowed out portion beneficially form a frictional seal with channel 60 sufficient to minimize loss of gaseous reactants (not shown) introduced into chamber 71 via one or more of conduits 29.
The first air lock 50 has an inner air lock door 52 located proximate to, and in operative communication with, the first end 31 of the first tunnel chamber 30 and an outer air lock door 51 located remote from the inner air lock door 52. The second air lock 55 has an inner air lock door 56 located proximate to, and in operative communication with, the second end 42 of second tunnel chamber 40 and an outer air lock door 57 located remote from the inner air lock door 56.
FIG. 2 shows a gap 16 between the sides of container means 70 and sides 11 and 12 of apparatus 10 which constitute the sides of reaction chamber or zone 20, the first tunnel chamber or zone 30 and the second tunnel chamber or zone 40. The gap 16 is not drawn to scale. In actual practice, gap 16 may be quite small where container support means 60 is merely a floor of apparatus 10 rather than a rail, track or defined path. The "small" gap minimizes side-to-side movement of container means 70 as they are moved respectively through first tunnel chamber 30, reaction chamber 20 and second tunnel chamber 40 or vice versa. Such a gap is readily determined without undue experimentation. If container support means 60 is a rail, track, channel or other defined path which restricts side-to-side movement of container means 70, the gap may be larger if desired.
FIG. 3 is a cross-sectional schematic view of an alternate embodiment 70' of a container means 70. In L this embodiment, container means 70' has a solid bottom 74' with no chamber or hollowed-out portion 71 and holds a bed of solid reactant materials 100. Container means 70' beneficially moves along container support means 60 toward a flow of gaseous reactants (not shown). By way of illustration, container means 70', while moving along support means 60 from first air lock 50 (FIG. 1) to second air lock 55 (FIG. 1), would face a countercurrent flow of reactant gases (not shown) introduced via second tunnel chamber conduit 45 (FIG. 1) and exiting via first tunnel chamber conduit 35 (FIG. 1). If desired, the flow of reactant gases could be reversed to provide a co-current flow. As used herein, the term "co-current flow" means a parallel flow or a flow which proceeds in the same direction as container means 70 or 70'. In this embodiment, upper reaction chamber conduits 28 are used to introduce reactant gases (not shown) into apparatus 10. Reaction product gases (not shown) desirably vent through first tunnel chamber conduit 35 (countercurrent flow). In alternate embodiments, reaction product gases could be vented through second tunnel chamber conduit 45 for co-current flow or simultaneously through conduits 35 and 45 for a combination of countercurrent and co-current flow. One or more of conduits 28 (FIG. 1) can be used as sight ports for pyrometer temperature indicators (not shown). In this embodiment, lower reaction chamber conduits 29 (FIG. 1) may be omitted or closed off.
FIG. 4 schematically depicts, in cross-section, a preferred embodiment of container means 70 in conjunction with a partial sectional view of apparatus 10. In this embodiment, container means 70 has a hollowed-out chamber 71 configured so as to be in fluid communication with at least one lower reaction chamber conduit 29. Container means 70 has a porous floor 72. Floor 72 has an upper or solids receiving surface 73 and a lower or gaseous chamber surface 74. The lower surface 74 provides a top or ceiling for chamber 71. The floor 72 has defined therein a plurality of apertures or passageways 75 which are in fluid communication with both the chamber 71 and the solids receiving surface 73. In this manner, gaseous reactants (not shown) which enter chamber 71 via conduit 29 will exit chamber 71 via passageways 75 and be distributed throughout a bed of solid reactant materials 100 which is disposed on surface 73. Excess reactant gases and reaction product gases (not shown) may exit Apparatus 10 via first tunnel chamber conduit 35, second tunnel chamber conduit 45 upper reaction chamber conduits 28 or any combination thereof If desired, reactant gases or an inert sweep gas or an admixture of reactant gases and an inert sweep gas may be introduced into apparatus 10 via conduit 45, conduit 35 or conduits 28 so long as at least one of said conduits 35, 45 or 28 is used to exhaust or vent reaction product gases (not shown). In addition, one or more of lower reaction chamber conduits 29 may be used to vent excess reactant gases or reaction product gases so long as at least one of conduits 28, 29, 35 or 45 is employed to introduce reactant gases into reaction chamber 20. In other words, any combination of conduits may be used to add reactant gases to reaction chamber 20 and exhaust reaction product gases from apparatus 10 so long as at least one conduit is dedicated to each function.
A means for moving container means 70 along container support means 60 is suitably a hydraulic or pneumatic pushing arm. Other means of moving container means 70 from one end of apparatus 10 to the other end and, optionally, back again are readily discernible without undue experimentation
The means for moving container means suitably conveys container means 70 or 70' sequentially from first airlock 50 through first tunnel chamber 30, reaction chamber 20, second tunnel chamber 40 and into second airlock 55. Each container means 70 beneficially contains a bed of solid reactant materials (see, e.g., bed 100 in FIGS. 3 and 4). The means for moving container means advances container means 70 or 70' through reaction chamber 20 at a rate sufficient to convert substantially all of said solid reactants into a desired reaction product The bed of solid reactant materials 100 is heated to a reaction temperature by heating elements 80 while container means 70 or 70' carrying said reactant materials are disposed within reaction chamber 20. Concurrent with heating, reactant gases (not shown) are conveyed from a source (not shown) via lower reaction chamber conduits 29, chamber 71 of container means 70 located above said conduits 29 and passageways 75 of said container means 70 through the bed solid reactant materials 100. Reaction product gases (not shown) and excess reactant gases (also not shown) are exhausted from reaction chamber 20 primarily via first tunnel chamber conduit 35. These gases may also be exhausted or vented through one or more of upper reaction chamber conduits 28, second tunnel chamber conduit 45 and lower reaction chamber conduits 29.
If a stream of reactant gases or inert gases (not shown) flows countercurrent from the second tunnel chamber conduit 45 to the first tunnel chamber conduit 35, or vice versa, some reaction product gases will also be swept from the reaction chamber 20 and out of either conduit 35 or conduit 45 as appropriate. As used herein, the term "inert gases" includes noble gases and other gases which do not react with solid or gaseous reactants under conditions employed to make a particular product, e.g., aluminum nitride, in apparatus 10.
If container means 70' are used in place of container means 70, reactant gases suitably flow as described in the immediately preceding paragraph. In this case, reactant gases will not enter reaction chamber 20 by way of conduits 29.
After container means 70 or 70' enter the second airlock 55, a number of options are available. First, container means 70 or 70' may be returned to first airlock 50 by reversing the direction of travel of the container means. This presumes the presence of a second container support means (not shown) as well as a means (also not shown) of moving said container means onto said second support means. A second option involves simply removing the reaction product from container means 70 or 70' and thereafter reusing said container means. A third option provides an additional passage of solid reactants through apparatus 10 as container means 70 or 70' are removed from second airlock 55 and conveyed by a suitable means (not shown) to first airlock 50. Variations of these options as well as other options are readily determined by those skilled in the art without undue experimentation.
Container means 70 and 70' and container support means 60 are suitably fabricated from graphite. Upper reaction chamber conduits 28 and lower reaction chamber conduits 29 may also be fabricated from graphite. The sides, top and bottom of first tunnel chamber 30, reaction chamber 20 and second tunnel chamber 40 suitably have a four layer structure consisting of an inner layer, a first intermediate layer, a second intermediate layer and an outer layer. The inner layer preferably consists of solid pieces of graphite. The first intermediate layer beneficially contains an insulating material to minimize loss of heat. A variety of insulation materials, including lamp black, and arrangements may be used. The second intermediate layer is desirably made from masonry materials with firebrick being particularly suitable for reaction chamber 20. The outer layer is desirably formed from steel or another suitable structural metal. In addition, other structural materials or features, such as additional intermediate layers, may be added without departing from the scope of the present invention.
Container means used in the following examples either have solid bottoms (70') for countercurrent or co-current configurations (FIG. 3) or perforated bottoms (70) for crosscurrent and combinations of crosscurrent, countercurrent, and co-current configurations (FIG. 4). Container means 70 and 70' are suitably 70 to 72 inches (177.8 to 182.9 centimeters) long by 9 inches (22.9 centimeters) wide by 3 to 4 inches (7.6 to 10.2 centimeters) tall. The actual dimensions are not particularly critical so long as container means 70 or 70' are compatible with mechanical or other means of moving said container means through the combined length of first tunnel chamber 30, reaction chamber 20 and second tunnel chamber 40 without undue difficulties such as those resulting from excess friction or too much play between the sides of container means 70 or 70' and the sides of chambers 20, 30 and 40. The bed of reactant materials 100 suitably has a depth of 0.25 inch (0.64 centimeter) to three inches (7.6 centimeters). If desired, a greater depth may be obtained with deeper container means 70 or 70'.
The particular form, size and physical properties of such a form of solid reactant materials is generally immaterial with a solid bottom container means 70' so long as the solid reactant materials are not swept from the container means by the flow of reactant gases. When using container means 70, the size or shape of solid reactant materials has an additional constraint in that it must be sufficient to substantially preclude loss of solid reactant materials through passageways 75 and subsequent interference with movement of the container means 70 along container support means 60. The solid reactant materials may, for example, be in the form of a powder or a shape selected from the group consisting of pellets, agglomerates, briquettes, tablets, granulates, extrudates or other suitable structure. The solid reactant materials are desirably in the form of pellets. Pellets may be formed by conventional technology, e.g., by extrusion, tabletting, granulation and the like.
Passageways 75 of container means 70 have two primary size constraints. First, they must provide enough open area to handle the anticipated flow of gaseous reactants, e.g., nitrogen, without so much backpressure that container means 70 are lifted, even momentarily, from track 60. Second, as noted hereinabove, they must not be so large that solid reactant materials easily fall therethrough. By way of illustration only, passageways having a diameter of 0.125 inch (0.32 centimeter) with a spacing of 0.625 inch (1.59 centimeters) center to center are used for the following examples. Other suitable sizes and spacing are readily determined without undue experimentation.
Hollowed-out chamber 71 is beneficially a 0.125 inch (0.32 centimeter) deep pocket cut out of the bottom surface of container means 70. The actual dimensions of Chamber 71 are not critical so long the chamber is large enough to handle the anticipated flow of gaseous reactants without causing excessive backpressure.
Heating elements 80 can be heated by flame, electrical elements, or by other heating means. Reaction chamber 20 is suitably heated to a temperature within a range of between about 1500° C. and 1900° C. for preparation of aluminum nitride. Other temperature ranges may be more suitable for other products. With such a temperature, container means 70 and 70' are suitably moved through apparatus 10 at a rate sufficient to provide adequate residence time, e.g. from about 0.25 to about 6 six hours. Illustrative rates vary from as low as 0.5 inches per minute to as high as 20 inches per minute. The actual rate will depend upon constraints such as residence time and size of reaction zone.
The spacing, number and arrangement of lower reaction zone conduits 29 are not particularly critical so long they supply sufficient gaseous reactant to the bed of solid reactant materials 100. Each container means 70 is suitably located over at least one conduit 29 while said container means 70 are situated within reaction zone 20. Accordingly, conduits 29 are beneficially spaced evenly within reaction zone 20. Other arrangements are, however, satisfactory.
The spacing, number and arrangement of upper reaction zone conduits 28, like those of lower reaction zone conduits 29, are not particularly critical. The conduits serve one or more of a number of functions including supply of reactant gases, venting of reaction product gases and providing access for instruments such as pyrometers. The functions desired for a particular process dictate actual quantities and spacing of such conduits.
Airlocks 50 and 55, while not shown to scale in FIGS. 1 and 2, are suitably of a size sufficient to hold, and provide access to, at least one container means 70 or 70'. Airlocks 50 and 55, particularly the latter, also serve as a cooling area. As such, the airlocks should either be large enough to serve that function or be connected to an auxiliary cooling or holding area of sufficient size to allow safe handling of said container means and their contents.
Aluminum nitride produced by the method and apparatus of the present invention beneficially has a specific surface area of between about 2 m 2 /gm and about 5 m 2 /gm Particle size of the aluminum nitride is suitably less than about 1.5 microns. Oxygen content is desirably about 1.5% by weight or less. Iron content within the aluminum nitride particles can be higher but is suitably less than about 35 ppm. The aluminum nitride particles desirably have a silicon content of less than about 250 ppm.
Residual carbon in the aluminum nitride product from apparatus 10 can be removed by exposing the product to air at a temperature of about 700° C. in an apparatus such as a rotary furnace.
The solid reactants which comprise the bed of solid reactant materials or reaction bed 100 are suitably those which yield the aluminum nitride described hereinabove. The solid reactants beneficially include aluminum oxide and carbon. The carbon is desirably present in an amount which is slightly (one to ten mole percent) in excess of the stoichiometric proportion to aluminum oxide so as to produce carbon monoxide gas during reaction of aluminum oxide with nitrogen gas. In terms of weight percent, based upon weight of solid reactant material wherein carbon is a solid reactant, a suitable amount is from about 24 to about 40 weight percent. The bed of solid reactant materials 100 may also comprise up to 1.5 weight percent of calcium oxide, which can act as a catalyst for production of aluminum nitride. Other sources or derivatives of calcium, as well as other materials which are known to function as catalysts for preparation of aluminum nitride, may be substituted for calcium oxide. In addition, sintering aids for subsequent densification of aluminum nitride may also be combined with the solid reactant materials One such sintering aid is yttria.
The solid reactants, aluminum oxide, carbon and, optionally, calcium oxide are suitably combined and formed into pellets prior to loading into container means or trays 70 or 70'. The solid reactants are beneficially dry-milled for about 4 hours and subsequently mixed with water and a binder to form an extrudable mixture. Suitable binders include, for example, polyvinyl alcohol, starch, methyl cellulose, and colloidal alumina, etc. The mixture is extruded into pellets which are beneficially of a size which facilitates the flow of reactant gases through reaction bed 100, does not substantially impede removal of gaseous reaction products from reaction bed 100, and minimizes, if not eliminates, plugging of passageways 75 of preferred container means 70. A suitable diameter is 0.25 inch (0.64 centimeter). The pellets are preferably oven-dried to remove substantially all of their water content prior to loading into container means 70 or 70'.
Instead of forming pellets, the solid reactants can be granulated to produce shapes of high porosity. The porous shapes provide sufficient reaction surface area for formation of aluminum nitride.
Reactant gases used in making materials with apparatus 10 are chosen to produce a desired reaction product. By way of illustration wherein the desired reaction product is aluminum nitride, reactant gases include nitrogen, mixtures of nitrogen and hydrogen, ammonia, mixtures of nitrogen or sources of nitrogen plus gaseous sources of carbon. Other potential sources of reactant gases are known to those skilled in the art.
The apparatus 10 is not restricted to production of aluminum nitride. It should also be suitable for use in producing other materials via carbothermal reduction wherein a gaseous reactant is placed in contact with solid reactants under conditions sufficient to produce the material One such reaction product is silicon nitride
By way of illustration only, a suitable combined length of the first tunnel chamber 30, the reaction chamber 20 and the second tunnel chamber 40 is about 60 feet (18.5 meters), with the reaction chamber itself having a length of about eight feet (2.5 meters). First tunnel chamber 30, reaction chamber 20 and second tunnel chamber 40 each have a width of about 10 inches (25.4 centimeters) and a height of about six inches (15.2 centimeters). Trays 70 or 70' typically have dimensions as described hereinabove Depending upon factors such as rate of movement of trays 70 through the apparatus 10, the amount of solid reactants contained in said trays, the temperature of reaction zone 20 and the rate of flow of gaseous reactants, a production rate from such an apparatus is suitably three pounds per hour or more when the resultant product is aluminum nitride.
The following examples simply illustrate the present invention and are not to be construed, by implication or otherwise, as limiting the scope thereof All parts and percentages are by weight and all temperatures are in ° Celsius (° C.) unless otherwise stated.
EXAMPLE 1 AND COMPARATIVE EXAMPLE A
Using a 27 gallon (102.2 liter) mill containing one-half inch (1.3 centimeters) high density 99.5% alumina milling media, commercially available from Coors Ceramics Company, a 25 pound (11.4 kilogram) batch of the following raw materials is dry milled for 4 hours to prepare an aluminum nitride (AlN) precursor:
1. 72.0 weight percent alumina powder, commercially available from Aluminum Company of America under the trade designation Alcoa A16-SG: and
2. 28.0 weight percent acetylene carbon black, commercially available from Chevron Chemical Company under the trade designation Shawinigan acetylene black.
The alumina powder has a surface area of 9.46 square meters per gram. It has the following impurity levels in parts per million: calcium - 66: silicon - 53: chromium - less than 10: and iron - 80.
A portion of the AlN precursor powder is loaded into one solid bottom tray, hereinafter "Tray A", (see FIG. 3) at a depth of 1/2 inch (1.3 centimeter) to provide a total loading of two kilograms (Example 1). A second portion is loaded into another solid bottom tray, hereinafter "Tray B", at a depth of 11/8 inches (2.8 centimeters) to provide a total loading of five kilograms (Comparative Example A). Because the trays have solid bottoms, there is no upflow of gaseous reactants via lower reaction zone conduits (see. FIG. 1). The trays are then pushed through a furnace having dimensions as detailed hereinabove (see also FIGS. 1 and 2) at a push rate sufficient to give a 96 minute reaction time at a maximum temperature of 1750° C. The reaction time is the estimated total time that the reactants are in a portion of the furnace that is at or greater than the minimum temperature at which the AlN reaction occurs (approximately 1500° C). A countercurrent nitrogen flow of 1,600 cubic feet (45.3 cubic meters) per hour is purged through the furnace while the trays are contained therein. Exhaust gases are vented through first tunnel chamber conduit 35 (see, FIG. 1) The trays contain, following completion of passage through the furnace's reaction zone, aluminum nitride. The resultant AlN product in each tray is sampled in six product bed locations (front top and bottom, middle top and bottom, back top and bottom) and analyzed for weight percent oxygen and surface area. The results are summarized in Table 1.
The oxygen content of the AlN product is used as an indication of reaction completeness. A product oxygen level above 1.5 percent is considered an indication, albeit not absolute, of a poorly converted product.
The data presented in Table 1 show that attempts to convert alumina powder to aluminum nitride powder in a thick bed (Tray B) result in much greater variability of product oxygen content as well as a larger range of resultant oxygen contents than similar attempts with a comparatively thin bed (Tray A). This is believed to be due to heat transfer and gas transport limitations inherent in thicker powder beds. All oxygen contents in Tray A save one are less than 1.5 percent. While this may indicate that a portion of the resultant powder may have an excessively high oxygen content, the
TABLE 1______________________________________ Weight Surface Sample Percent AreaTray Location Oxygen m.sup.2 /g______________________________________A Front Top 1.16 2.81A Front Bottom 1.20 2.92A Middle Top 1.39 2.93A Middle Bottom 1.27 3.10A Back Top 1.76 3.26A Back Bottom 1.36 2.93B Front Top 14.38 4.63B Front Bottom 8.30 2.79B Middle Top 2.78 3.52B Middle Bottom 7.87 3.23B Back Top 4.07 3.47B Back Bottom 8.89 2.75______________________________________
average oxygen content of aluminum nitride powder contained in that tray is clearly acceptable. Conversely, all oxygen contents in Tray B are clearly above, often considerably above, 1.5 percent. As such, the average oxygen content of powder contained in Tray B is also above such a desirable oxygen level.
EXAMPLE 2
Using the procedure and apparatus of Example 1, a 25 pound (11.4 kilogram) batch of aluminum nitride precursor powder is prepared from 71.7 percent of the same alumina as in Example 1, 28.0 percent of the same acetylene carbon black as in Example 1 and 0.3 percent calcium oxide.
The aluminum nitride precursor powder is mixed in a ribbon blender with 30% water and 5% polyvinyl alcohol. The resultant mixture is extruded into 1/4 inch (0.6 centimeter) extrudates or pellets. The pellets are oven dried to a water content of less than 2.0%.
Solid bottom trays (see. FIG. 3) are loaded to a depth of 0.25 inch (0.6 centimeter) with the pellets to provide a total solid reactant charge of two kilograms. The density difference between pellets and powder accounts for a shallower depth of pellets to attain a particular loading. The trays are then pushed through the same furnace as in Example 1 at a rate sufficient to provide a 48 minute reaction time at 1750° C. maximum temperature. A countercurrent N 2 flow of 1500 CFH (42.5 cubic meters per hour) is used. The average oxygen content of the resulting AlN product is 1.26%.
COMPARATIVE EXAMPLE B
The process and composition of Example 2 is duplicated save for increasing the depth of pellets in the trays fourfold to one inch (2.54 centimeters).
The resulting AlN product has an average oxygen content of 20.6%. This indicates an unacceptably low conversion of alumina to AlN. The poor conversion is believed to result from a combination of mass transfer and heat transfer limitations.
The data presented in Example 2 and Comparative Example B show that pellets, like powder, provide a much more acceptable product in shallow bed than in a comparatively thick bed. As such, there is no significant difference in terms of oxygen content in using pelletized, rather than powdered, solid reactants in a solid bottom tray or container means.
EXAMPLE 3
Using a modified furnace wherein lower reaction zone conduits 29 (see, FIG. 1) are used to supply gaseous nitrogen to the hollowed-out chamber 71 of container means 70 (see, FIG. 4), the procedure of Example 2 is duplicated. Exhaust gases are vented through first tunnel chamber conduit 35 as in Example 1. The hollowed-out chamber is a 1/8 inch (0.3 centimeter) deep cavity routed out of the bottom of each tray. The cavity acts as a nitrogen distributor which evenly supplies nitrogen to 1/8 inch (0.3 centimeter) diameter holes which are spaced 5/8 inches (1.6 centimeter) from center to center across the entire floor of the tray. The conduits 29 are actually graphite tubes, each of which has an exit which is flush with the floor 60 of reaction zone 20 of the furnace. The depth of pellets in the trays is one inch (2.5 centimeters) as in Comparative Example B. Gaseous nitrogen flow through conduits 29 is at a rate of 1600 CFH (45.3 cubic meters per hour).
The average oxygen content of the resulting AlN product is 1.22%. The product has a surface area of 3.03 m 2 /gm. These results show a dramatic improvement in conversion over that obtained in Comparative Example B.
EXAMPLE 4 AND COMPARATIVE EXAMPLE C
AlN precursor pellets prepared as in Example 2 are loaded into a solid bottom tray (Comparative Example C) and a perforated bottom tray (Example 4) to a depth of 0.75 inch (1.9 centimeters). The solid bottom tray and the perforated bottom tray are identical, respectively, to those used in Examples 1 and 3. Each of the two trays is pushed through the apparatus at a rate sufficient to provide a reaction time of about 96 minutes with a maximum temperature of 1750 ° C. In the case of the perforated tray, gaseous nitrogen is supplied to the hollowed-out chamber, as in Example 3, at a rate of 1500 CFH (42.5 cubic meters per hour). The AlN product in each tray is sampled in 6 locations, as in Example 1, and analyzed for wt. % oxygen and surface area as determined from Brunauer, Emmet, Teller (B.E.T.) surface area analysis. The results are summarized in Tables 2 and 3.
TABLE 2______________________________________Solid Tray Percent SurfaceSample Location Oxygen Area m.sup.2 /gm______________________________________Front Top 4.32 3.28Front Bottom 11.08 2.99Middle Top 1.25 3.11Middle Bottom 1.44 2.88Back Top 3.55 3.03Back Bottom 7.93 2.98______________________________________
TABLE 3______________________________________Perforated Tray Weight percent SurfaceSample Location Oxygen Area m.sup.2 /gm______________________________________Front Top 1.24 2.99Front Bottom 1.22 2.91Middle Top 1.10 2.63Middle Bottom 1.03 2.81Back Top 1.04 2.70Back Bottom 1.13 2.87______________________________________
A comparison of the data presented in Tables 2 and 3 shows that the perforated tray (Example 4) produces a more uniform product quality than the solid tray (Comparative Example C). Because of the similarity of all factors other than the pattern of flow of gaseous nitrogen, the improved results are believed to follow from a more uniform distribution of the reaction gases. The reaction in the perforated tray also proceeds at a faster rate as evidenced by the lower oxygen values. The product sampled from the bottom layer on the solid tray shows early indications of product coarsening even though the precursor is not fully converted. This may be caused by an insufficient N 2 supply near the bottom of the bed with the solid tray.
Although preferred embodiments have been specifically described and illustrated herein, it will be appreciated that many modifications and variations of the present invention are possible, in light of the above teachings, within the purview of the following claims, without departing from the spirit and scope of the invention. | A reactor for carbothermal reduction is disclosed. By supplying gaseous nitrogen throughout a discrete aliquot of a preferably pelletized mixture of aluminum oxide, carbon and, optionally, calcium oxide during the carbothermal reduction thereof to aluminum nitride and continuously removing gaseous reaction products therefrom, a high quality aluminum nitride is produced. One means of supplying gaseous nitrogen to the mixture of solid reactants is a perforated tray having a hollowed-out bottom. Gaseous nitrogen supplied to the hollowed-out portion flows through the perforations and throughout solid reactants contained in the tray. The carbon may be alternatively supplied, in whole or in part, as a gaseous reactant. | 2 |
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