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From Audio Basics, July, 1982 Hello again, I am glad that the feedback I am getting from many of you indicates that you are happy with the information and ideas I have been describing. Some of you have complained that you want more "meat" - technical information on audio equipment. So, this month we will get a bit more technical and go through the operation of a vacuum tube amplifier, what it does, what it cannot do, and what you can do about it. The data will pertain to vacuum tube amplifiers in general, and the Dyna St-70 specifically, as we get so many requests for information on how to modify them. VACUUM TUBE AMPLIFIERS Any audio amplifier can essentially be modeled as a two stage device; a voltage amplifier (which amplifies the amplitude of the signal) followed by a current amplifier (which supplies the drive current to drive the now large amplitude signal into a low impedance load - the speaker system). Although many tube circuits will also have voltage gain in the current amplifier section, that is not important to the discussion that follows. The closed loop gain of the amplifier is determined by a voltage divider which sends a portion of the output signal back to the input of the voltage amplifier out of phase. The amplifier then does not amplify the input signal, it amplifies a signal being the difference between input and feedback signal. If the voltage amplifier and current amplifier were perfectly linear, the difference between the input and feedback signal would be only a small version of the input signal and the results would be "perfect." In theory, any difference between input and output is supposed to be eliminated by feedback. The feedback signal, which is a duplicate of the output signal, when subtracted from the input signal, should create a "difference signal" which is "pre-distorted" by the amount of distortion in the circuits, but out of phase with the circuit's distortion. The "pre-distortion" in the "difference" signal, when added out of phase to the actual distortion in the circuits, cancels exactly, giving a "perfect" output signal. That is the way it is supposed to work. By the way, there ain't no such thing as a no feedback amplifier! There are many different feedback schemes. One can choose to use lots of local feedback in each stage and little overall loop feedback, but each device in itself (whether it is transistor or tube) has internal feedback. If one attempts to make an amplifier with "no feedback" except for that inherent in the devices themselves then the design becomes absolutely dependent of the characteristics of each independent device. No two tubes or transistors, even of the same type, are identical. Even if you painstakingly select and bias each individual device one at a time, its characteristics will change with variations in temperature, current, voltage, and age. It will be impossible to make any two channels the same and to keep them the same. The main characteristics of a so called "no feedback" amplifier are: very high cost (each unit is essentially a one off), very hot running as the devices have to be biased on very hard, unstable operation as the unit changes characteristics with age and temperature, no two samples will sound the same as they are device dependent, and lots of "blow-ups." Obviously, repairs will be expensive as a repair is essentially a re-engineering of that unit with new devices and re-biasing of each device. I can live without it. The "wonderful" sound of a "no feedback" amplifier is the wonderful sound of lots of instabilities and underdamped oscillations. You may like it, I don't, it isn't music. Thus, those that choose to build stable, repeatable, and rationally priced amplifiers will use some feedback. The catch is in knowing what the feedback can and cannot do in the real world, and to use the feedback properly, so that the unit does not only measure well, but actually performs well under transient conditions in the real world. Now, back to that vacuum tube amplifier. Remember we mentioned that if the voltage amplifier and the current amplifier were perfect, everything would be just fine. Sorry folks, the internal circuits are not perfect and that is where the troubles start. Inasmuch as the feedback is supposed to compensate for any non-linearities between input and output, it is nice to know what non-linearities exist. First of all each individual active device is nonlinear. Its transfer characteristics are exponential, not linear, be it tube, FET, or transistor. Refer to the sketches below. If the device was perfect, its transfer function would be a straight line, and the slope would remain the same at all frequencies. The actual characteristics are shown in the second and third sketches. Note that the characteristics are actually exponential. The device is only very linear near the center-line of its operation, and the harder it is "worked", the less linear it becomes, finally becoming 100% nonlinear when its absolute limitations are reached. In addition, the slope of the transfer function becomes less at higher frequencies as the gain of the device reduces. Thus if one attempts to get the same output from any given device at higher frequency, one will drive it into gross non-linearity sooner, as its headroom is less. In a similar fashion, at very low frequencies (approaching DC) the device becomes more nonlinear and its gain drops. In addition, because the slope changes with frequency, a kind of phase distortion is introduced which is not measured in standard IHF distortion tests, which measure only single frequency performance.
Obviously, to optimize internal linearity, it is very desirable to operate each device within as narrow a bandwidth and as limited an amplitude range as possible while still covering the audio frequency range of interest. In a vacuum tube amplifier another major non-linearity is the output transformer. The output transformer's primary coil is just that-a very large coil (inductor) in series with the output tubes. Obviously the coil becomes very resistive as the frequency goes up, and in an audio amplifier this happens well within the audio range, rolling off the high frequency output. At very low frequencies the core of the transformer saturates giving very nonlinear bass performance. If one wants good high frequency performance then one must have very small output transformers so that the coil inductance is low. If one wants good low frequency performance one must have very large transformers so the core does not saturate. These requirements are mutually self exclusive. These requirements become more difficult to meet as the power rating goes up. If one attempts to "get around" this by designing a tube amplifier without output transformers, then one is faced with the problem that output tubes have very high output impedance and will not drive normal loudspeaker loads (8 s nominal) without severe non-linearities. Since the output transformer is a very narrow band and nonlinear device, it is obviously necessary to not feed into the transformer a signal that it cannot handle-the bandwidth of the amplifier must be limited to within the bandwidth of the output transformer. You cannot stuff 10 pounds in a 1 pound sack. The power supply is another source of distortion. The power supply can be considered to be in series with and part of the output circuit. All current that flows through the output circuit and speaker load first must flow through the power supply. The frequency limits of a power supply are real. It can be modeled as an inductor in series with a capacitor. Obviously at DC the capacitor's impedance is infinitely high, and at high frequencies the inductance is infinitely high. Thus, at very low and very high frequencies, the power supply is not capable at all. Unless great care is used in the power supply design, it may have multiple resonances, and actually be high impedance at many frequencies within the audio range. Consider also that since the power supply is part of the output circuit, if somebody offers a "wonderful" vacuum tube amplifier with a "wonderful" solid state power supply, you no longer have a vacuum tube amplifier, but a solid state amplifier, so how can it be a "wonderful" tube amplifier? Of course the power supply is also attached to the voltage amplifier section. Consider that all current draw by the output section causes a signal to show up on the power supply feeds. Any given device or circuit will work best when its supply is absolutely stable. Circuits are designed to reject power supply variations, but the supply rejection isn't absolute. Thus the more signal that shows up on the power supply feed to the voltage amplifier, the more distortion and instabilities there will be, as this is a signal injected into the circuit at the wrong place. Since we already know that the power supply is less effective at very high and very low frequencies, obviously the power supply related distortions will be greater at very high and very low frequencies. Again, a very good reason to bandwidth limit the amplifier to within the capability of its power supply. Understand of course that we are considering basic ground rules in general. There are many different kinds of voltage amplifier and current amplifier configurations that work fairly well, some simple, some complex. The important thing to know is that unless the circuits are executed to obey the guidelines established above the distortion will be very high under real world conditions, no matter what the linearity of each section is and no matter how high a quality of parts are used. Another common problem with vacuum tube amplifiers is the value chosen for the interstage coupling capacitors. In the case of the Dynaco St-70 for example (see attached schematic) coupling capacitors C10 and C11 are 0.1 uF. This introduces another large low frequency roll-off within the feedback loop. Since the amplifier actually amplifies the difference between input and feedback, and since the feedback is the difference between input and feedback, and since the feedback is taken off the output of the amplifier, at low frequencies the difference signal becomes very large partially due to the roll-off caused by the 0.1 uF coupling capacitors. Now remember that we have shown that any circuit becomes less linear with increasing amplitude and at the frequency extremes. The roll-off caused by the small value interstage coupler makes the front end work very hard to generate a large low frequency correction signal. This causes the front end to run in a very nonlinear mode at low frequencies. You hear it as "muddy bass." The "cure" is quite simple, make the interstage capacitor large enough in value so that the loop roll-off is minimized, thus reducing the correction required, and letting the front end run in a more linear mode. The low frequency correction signal is easy to see on an oscilloscope. Using a low frequency square wave as a source (20 Hz is fine) look at the signal on the output side of the interstage coupler. Note that it looks much like the input signal. Now look at the signal on the input side of the coupler. You will find the circuit is generating a signal with a large bass boost! (This is true in most tube preamps too!) What is happening is that the "flat" input signal is rolled off by the interstage coupling capacitor. Then the rolled off signal is fed back to the input and a correction signal is generated with a large bass boost to make up for the roll-off. The boosted signal is then rolled off again by the coupling capacitor and its output looks just fine. But the "monkey motion" has ruined the voltage amplifier's linearity at low frequencies. Now let's look at what is wrong with the original Dyna St-70 in detail. Refer to the audio channel schematic again, keeping in mind that the "dashed" section is our addition, the original has the input connected to V2 directly with a piece of wire. What we have is a typical vacuum tube amplifier with unlimited bandwidth input acceptance (DC coupled) but with limited bandwidth output transformers and small interstage coupling capacitors. The power supply is also limited bandwidth, being pretty feeble at both low and high frequencies. A very low frequency signal is rolled off by the interstage coupling capacitors, turned into a "lump" as the output transformer core saturates, and is further distorted as the power supply runs out of steam. The feedback signal, being taken off after all the disasters occur is very different from the input signal. This generates an enormous "difference" signal which drives the front end into 100% distortion trying to make an impossible correction. Inasmuch as the circuits are underdamped too, the "blob" makes the amp ring for a few cycles attempting to digest the mess. Some people call these distortions and ringing, which extends up into the mid-range, "concert hall sound." Sorry, it isn't concert hall sound, it is distortion. If you like it you have bad taste. At high frequencies the compensation in the voltage amplifier rolls off the signal, the active devices roll it off further, and the output transformers attenuate the highs further yet. This generates another huge correction signal at high frequencies, again more than the headroom of the front end, clipping the correction signal once again. Of course the high impedance of the supply has further compounded the problems. The amp is driven into hard slew limiting and all signal entering the amp while any internal device is slewing is erased. Gobs of high frequency distortion are added and part of the music is forever lost. It is very strange to think that some people use the St-70 to drive tweeters when it doesn't "tweet" at all-it does kind of "squeak." Obviously the power supply of the St-70 must be much improved. NO! Not necessarily! Think a minute. Consider that the power bandwidth of the power supply must be greater than the bandwidth of the audio circuit. There are two ways to get this ratio in proper order. The expensive (and stupid) way is to build a huge power supply-and if the amp has DC coupled inputs you can never make it big enough. The easy and smart way is to limit the bandwidth of the circuit to within the capabilities of the existing power supply, especially if it is absolutely necessary to bandwidth limit the inputs anyway to make the input bandwidth within the capabilities of the output transformers. As mentioned earlier, the interstage coupling capacitors, C10 and C11 are too small. Note that as long as the input is DC coupled, it is not possible to make C10 and C11 big enough, as even a very large capacitor will have an inside the loop roll off when compared to DC input acceptance. To install the input bandwidth limited filter on the St-70 you will need 8 parts: (2) 10,000 resistors, (2) 470,000 resistors (5% carbon film 1/4 watt parts from Radio Shack are just fine, and it would be better if you could use a meter and "pair" them, so they are matched within 1%.) You will also need (2) 1000 pF capacitors (mica, polystyrene, or mylar are O.K., of about 100 volt rating - the capacitors used should be physically small) and (2) 0.02 uF capacitors (film) 100 volt rating, again physically as small as possible. Again, Radio Shack will have adequate parts and if you can match them on a precision capacitance meter it will be helpful. The capacitor values suggested are not absolute. Anything from about 0.02 to 0.033 uF is O.K. for the larger cap, and 800 to 1200 pF for the smaller capacitor. The new 6 dB per octave low pass and high pass filter is installed on the input jacks on the bottom inside of the chassis. We suggest that the mono-stereo switch wiring be eliminated as the performance is poorer when bridged mono because of the difference between the two channels (no two output tubes or output transformers are identical). If you decide to eliminate the mono-stereo switch, then do the following: 1. Remove all the wires from the input jack and mono-stereo switch except for the two wires going directly from the input jack ground lugs to the PC card (these are actually extensions of the leads of two 10 resistors mounted on the card). These remain. Also remove the two original 470,000 resistors from the jack and switch. 2. Remove the two wires running from the hot lugs of the input jack to eyelets 7 and 17 on the PC card. 3. Connect a 10,000 resistor in series with a 0.02 uF capacitor and connect the capacitor end of the series set to the left channel hot input jack and the resistor end to eyelet 7 on the PC card. 4. Connect another 10,000 resistor in series with a 0.02 uF capacitor and connect the capacitor end to the right channel hot input jack and the resistor end to eyelet 17 on the PC card. 5. Connect a 1000 pF capacitor in parallel with a 470,000 resistor and install the resistor between the left channel ground lug and eyelet 7 on the PC card. 6. Connect another 1000 pF capacitor in parallel with a 470,000 resistor and connect the resistor from the right channel ground lug on the input jack to eyelet 17 on the PC card. If you must keep the mono-stereo switch option, do the following instead of the last set of instructions: 1. Remove the two wires running from the left and right channel hot lugs on the input jacks to eyelets 7 and 17 on the PC card. 2. Connect a 10,000 resistor in series with a 0.02 uF capacitor and connect the capacitor end to the left channel hot input lug and the resistor end to eyelet 7 on the PC card. 3. Connect another 10,000 resistor in series with a 0.02 uF capacitor and connect the capacitor end to the right channel hot input lug and the resistor end to eyelet 17 on the PC card. 4. Install a 1000 pF capacitor in parallel with each of the two existing 470,000 resistors on the input jack and mono-stereo switch. For mono operation, the amp is switched to mono, only one input jack is used (either left or right, but not both). Connect a jumper wire from the left output ground to the right output ground terminal. Connect a jumper wire from the left 16 tap to the right 16 tap (for 8 speakers). Take the output from the same channel that you have the input jack connected to, using the 16 and ground terminals (for 8 speakers). To use 4 speakers connect the jumper from the left 8 output tap to the right 8 output jack and connect the load from ground to 8 on the channel used. This arrangement parallels the two channels for somewhat higher power, but lower definition performance. Now that the input bandwidth is set to a rational, finite limit, it is possible to make the interstage coupling capacitors "big enough." You will need to acquire four 1 uF at 400 volt film capacitors (mylar, polypropylene, or whatever). Again Radio Shack will have adequate parts. Locate and remove the four large identical black tubular 0.1 uF at 400 volt capacitors from the PC card. They are positioned parallel with the front of the chassis, one at each corner of the PC card. Replace each with a 1.0 uF at 400 volt capacitor. The exact value of the replacements is not critical. They can be anything between 0.8 uF to 2.0 uF at 400 volts or higher. It is important that all four new capacitors be exactly the same. Further detail improvements can be made to the St-70. The bias supply capacitors in old St-70 amps should be replaced. We suggest that the two original 50 uF capacitors (C3 and C4, located on the 7 lug terminal strip under the chassis) be replaced with new 100 uF at 80 volt electrolytic capacitors (again, available at Radio Shack). Note that the positive end of each cap is connected to ground. Do not use a larger capacitor in this application or the supply will come up too slowly, over-biasing the output tubes at turn on. Although the original power supply is now adequate, further reductions in hum and noise can be made by installing an additional 100 uF at 500 volt electrolytic capacitor (a 450 volt rated cap with a 500+ volt surge rating is adequate unless you have high line voltage) from pin 8 of the power supply tube (V1-5AR4) to chassis ground at the ground lug near the quad filter. The positive end of the cap goes to the tube socket, the negative end to ground. Inasmuch as the perceived "image" and "depth" of an audio system is dependent upon both channels having exactly the same gain and phase response, and because the resistors in the St-70 (and other tube amps) may have drifted out of specification over the years, it is helpful to replace all of the resistors with new tight tolerance parts. The gain determining resistors especially should be matched to each other within 1%. The RN60D and RL42S metal film resistors shown on the attached St-70 parts list are a good choice. However using 1/2 watt carbon film resistors for the RN60s and 2 watt carbon film resistors for the RL42S types is just fine, except you will have to sort more of them to get a tight channel-to-channel match. Because selenium rectifiers (the small little finned block located in the bottom middle of the chassis) become resistive with age, you may be able to increase the voltage to your bias supply by substituting a lN4004 silicon diode for this part (Dl). Because the negative voltage to the bias supply will now be higher than stock, it probably will also be necessary to change the value of Rl (10,000 2 watt resistor) to 18,000 2 watt to allow the amp to bias adjust at 1.56 volts DC across R20 in the center of rotation of P1 and P2. The St-70 and other tube amplifiers run very hot. This tends to make solder joints deteriorate with time. Re-solder all solder connections in the amplifier, including all parts, leads, and the tube sockets on the PC card. Clean the input jacks, output terminals, the bias pots, and all the tube sockets with DeoxIT-D5 (we have 5 oz. spray cans available for $20). Usually lightly "crimping" the hot (inner) terminals of the input jacks will eliminate patch cable dropouts. In the St-70 the noise characteristics, gain, power, and slew rate are dependent upon having high quality tubes in the unit. We have SovtEC EL34G+ output tubes available at $80 per set of four plus $6 shipping and a SovtEC 12X4 rectifier tube available for $15 plus $6 shipping. We do not have 7199 tubes available. Refer to the attached schematic and parts list for other service and adjustment notes on the St-70. I assume you have noticed we have not spent much time on the inner details of the circuit topography of the St-70. There may, or may not be "better" input, phase inverter, and output circuits available. The point is that almost all tube amps are mistakenly DC coupled and whatever the internal circuits are, they are driven into gross nonlinearities. The important concept is that any tube amp in which the input is limited to within the internal capabilities of the circuit will outperform any tube amp that can be driven into internal overload, no matter how expensive or complex the circuits may be. And the final limitations of a tube amplifier are the output transformers. Lots of money spent trying to achieve a "better" drive circuit probably is of little value, because the output transformers still are the limits of performance. THINGS YOU SHOULD NOT DO TO YOUR VACUUM TUBE AMPLIFIER (AND WHY). DO NOT install a solid state diode bridge to replace the vacuum tube rectifier. The supply is operating at 500 volts with line surges over 1000 volts! There are no reliable diodes available to operate at this voltage. You will be in great danger of blowing the diode bridge and damaging your power transformer and filter capacitor. In addition, the solid state supply will "turn on" instantly, and the full B+ voltage will be fed to the tubes before the heaters have warmed up and turned the tubes on. This will tend to over voltage the quad filter capacitor and capacitors downstream, which may damage them. The output tubes will run hotter than normal and have a short service life. There are no useful redeeming advantages to a solid state diode bridge. DO NOT install solid state regulators. The "aftermarket" circuits we have seen use transistors with inadequate voltage ratings (operating in the "blow-up" mode) and have severe slew rate limitations. Remember, the bandwidth of your power supply must be greater than the audio circuits, and a series bipolar regulator is bog slow! It will change the sound, it makes it much worse! DO NOT add external power capacitors. The long hookup wires will have lots of inductance and impair the high frequency performance. DO NOT rewire the amplifier internally with "magic wire." The chances are you will screw up the lead routings, add longer lead runs than the original and increase stray inductances. The probabilities of internal short circuits and bad connections increase as the wires are too large for reliable termination. DO NOT replace your capacitors with high priced and physically large "wonder caps." The larger the physical size of a given value capacitor, the greater its inductance will be, and the more trash it will dump into the circuit. Magic "wonder caps" do change the sound, they make it worse! DO NOT use polystyrene capacitors near heat generating components. They change value with temperature, and near an output tube they may even melt. DO NOT ship your vacuum tube amplifier to us to fix if you screw it up unless you CALL US FIRST at 651 330-9871. Output tubes don't survive shipping, tube amps are heavy and expensive to ship, and their performance is limited. One of the "joys" of owning a vacuum tube amplifier is learning how to fix it yourself. If you don't want to do this, you shouldn't own a vacuum tube amplifier.   2005 Note:
We can get much better results now with our complete $449 Ultimate 70 Rebuild
Kit. It includes a new motherboard with all new audio circuits
(using the information contained herein and much more), a new
B+ supply built of modern PC-card-mounted high efficiency, high
reliability capacitors, and a new bias supply. It also includes
new tubes to replace the now obsolete 7199 tubes. A new Input/Output
jack set kit is available too for $65
with gold plated input jacks and high quality Pomona 5-way binding
post output jacks. No cutting or drilling is required and step-by-step
instructions, schematics, parts lists, and wiring diagrams are
provided. The kit instruction manual and bare PC card are available
for $149
if you want to provide your own parts. The price of the manual
and PC card can be applied to the later purchase of the rest of
the kit as long as they are current. The sonic quality is really
special.
Formula to Solve 6 dB/Octave High & Low Pass Filter Such as Recommended for the St-70
Service Notes Examining the 1.56 volt biaset test point on the St-70 can tell you much about the condition of the amplifier. If the output tubes are old, it may be impossible to adjust the bias pots to bring the voltage up high enough. Replace the output tubes. A shorted output tube may cause the bias reading to run away high. 7199 tubes are best selected by examining the output of the amp on a scope. A low gain or noisy 7199 will show excess output hum and/or not make full power. Fuse blowing can be caused by two problems. A hard blow soon after turn-on indicates a power supply short, either a defective 5AR4 tube or a shorted quad filter cap. A fuse that blows soft or after a few minutes of operation indicates a problem with the audio circuits - probably a bad 6CA7 tube. Note that the bias setting will vary with AC line voltage so the value isn't an absolute. It is possible to swap tubes channel to channel (except the 5AR4) one at a time to locate a defective tube. The new input filter circuit provides -3 dB poles at 16 Hz and 17 KHz which keeps the audio circuit working within the limits of the output transformers. The larger C10 and C11 effectively takes them out of circuit for AC signal purposes after the input filters have been installed. It is much more important to install the new input filter circuits than to replace all of the resistors and capacitors. Match R and C values channel to channel for a good gain match between the channels. Dyna St-70 Amplifier Suggested Modifications Parts List
C1 0.02 uF 1000V disc P1 10 k bias trimpot
C2 0.02 uF 1000V disc P2 10 k bias trimpot
C3 100 uF 80V electrolytic R1 10 k 2W
C4 100 uF 80V electrolytic R2 10 k 2W
C5A 30 uF 525V electrolytic R3 6.8 k 2W
C5B 20 uF 525V electrolytic R4 22 k 2W
C5C 20 uF 525V electrolytic R5 10 k 0.5W
C5D 20 uF 525V electrolytic R6 475 k 0.5W
C6 0.02 uF 50V film R7 10 ohm 0.5W
C7 1000 pF 50V film R8 330 k 2W
C8 0.05 uF 400V film R9 1.5 M 0.5W
C8 0.05 uF 400V film R10 270 k 2W
C10 1 uF 400V film R11 620 0.5W
C11 1 uF 400V film R12 47 0.5W
C12 390 pF 500V mica R13 18 k 0.5W
D1 1N4003 or 1N4004 silicon
diode R14 47 k 2W matched within 1% of
R15
V1 5AR4 rectifier tube R15 47 k 2W matched with 1% of R14
V2 7199 pentode, triode tube R16 1 k 2W
V3 6CA7/EL34 pentode tube R17 270 k 0.5W matched within 1%
of R18
V4 6CA7/EL34 pentode tube R18 270 k 0.5W matched within 1%
of R17
L1 choke, Dynaco C-354 R19 1 k 0.5W
S1 power switch, SPST R20 15.6 1W
F1 fuse, 3 ampere slo-blo 3AG R21 1 k 0.5W
T1 power transformer, Dynaco
PA-060 T2 output transformer, Dynaco A-470
Schematic
Note: Input circuit (C6, R5, C7, and R6) is new and replaces the original direct coupled input circuit. All wiring is removed from the input jacks except R7 leads and then the new input circuit is installed. The stereo-mono switch should be eliminated. C3, C4, C10, and C11 are revised values. Adjust bias (P1 & P2) for 1.56 volts across R20. L1 can be replaced with a 30 10 watt resistor to make amplifier operational if L1


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Influence of ultrasound on the processing and structure of polypropylene during extrusion, Cover Story, Jobwerx.com
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Cover Story
Influence
of ultrasound on the processing and structure of polypropylene during
extrusion
INSIGHT
The effects of ultrasonic irradiation on extrusion processing and crystallization
behavior of polypropylene (PP) are examined. The results show that appropriate
irradiation intensity can prominently decrease die pressure and apparent
viscosity, increase output, reduce extrudate swell, and improve apparent
quality of PP. DSC and WAX analysis demonstrate that the crystalline structure
of PP is changed and the content of the beta crystalline increases through
ultrasonic vibration. Special effects can be induced by ultrasound, such
as strong stress, shatter and vibration, which alter the growth of PP
crystals and may favor a special crystal transformation (alpha -> beta).
INTRODUCTION
Recently, some new processing
techniques have been emerging, such as the direct application of physical
(mechanical) fields on polymer melts. The route can be realized by introducing
mechanical or ultrasonic vibrations. Compared with low-intensity vibration,
ultrasonic waves are widely employed to influence a medium through shatter,
cavitation, chemical and mechanical action, with low noise. Lemelson (1)
described an apparatus and method for controlling the internal structure
of plastics in a mold. By applying ultrasonic energy to the solidifying
material, the apparatus can control well the crystalline structure formed
during solidification. Pendleton (2) also described an ultrasonic process
to modify the crystalline structure of blown polyolefin films. Khamad
(3) reported that imposition of ultrasound on HDPE melts containing a
small amount of butyl rubber resulted in increase of cystallinity, reduction
of structural defects, and enhancement of mechanical properties. Isayev
and Levin (4-7) introduced ultrasonic vibrations to an extruder by which
they accomplished reclaiming rubber from old tires and found improvements
of some mechanical properties of the extrudate, such as strain at break
and Young's modulus. However, there is little study on crystalline structure
of PP for the case when ultrasound is employed at the die entrance.
This article studies PP extrusion
with parallel superposition of ultrasonic waves upon the die. The effects
of ultrasound vibrations during extrusion on improving processability
and crystallization of PP melts are described. EXPERIMENTAL
Materials and Experimental Setup
PP, 2401, with a melt index of
2.5 g/10 min and a density of 0.905 g/cm^sup 3^ at 25 deg C, was commercially
obtained from Yanshan Petrochemical Co., Beijing, China.
The Ultrasound-Extrusion experimental
setup consists of a single- screw extruder (d = 20 mm, L/D = 25), with
a variable cross-section capillary having high-temperature pressure transducer
and ultrasonic generator (Fig. 1). The ultrasonic frequency is 20 kHz
and power ranges from 0 to 300W. The direction of ultrasonic vibration
coincides with that of the melt flow. Samples used for all tests were
directly from extruded strands, which are short and very near to the die.
Different samples were extruded one by one at the same rotation speed,
die temperature (200 deg C) and different ultrasonic intensity. They were
then all cooled at the same room temperature.
MFI
The melt flow index of samples
was measured on an American CS- 127 Melt Flow Index measuring device at
230 deg C with a load of 2160 g.
Differential Scanning Calorimetry
RESULTS AND DISCUSSION
Die Temperature
Figure 2 shows a prominently exponential
ascendance in die temperature by introducing ultrasonic vibration during
extrusion of PP. In presence of 250 W ultrasonic intensity, die temperature
at 5 rpm jumped 10 deg C higher than without ultrasonic vibration. This
is because part of the sound energy is converted into heat energy by the
internal friction between the melt molecules. For a given shear rate,
the temperature rise is a function of ultrasonic intensity. The higher
the intensity, the more violent the molecular motion, and the greater
the temperature rise.
Die Pressure and Throughput
The dependence of die pressure
on ultrasonic intensity at different screw speed was examined. Figure
3 shows that higher ultrasonic intensity and lower rotation speed both
contribute to a larger reduction of pressure, indicating that the pressure
drop depends on the intensity and duration of ultrasonic treatment. An
increase of both factors gives the melt the chance to obtain stronger
energy from ultrasound. In addition, ultrasonic vibration during extrusion
affects the throughput of extrudate; the flow rate increases with an increase
in the ultrasonic wave intensity, as shown in Fig. 4. All of the above-mentioned
characteristics demonstrate that ultrasonic treatment will significantly
improve the extrusion efficiency.
Apparent Viscosity
The prominent pressure drops after
the introduction of ultrasound into melts are surely related to molecular
chain structure, which can be reflected in viscosity data. Figure 5 shows
the dependence of apparent viscosity on ultrasonic intensity at various
rotation speeds. Ultrasonic motions result in a sharp decrease of viscosity
of the melt. Since higher screw speed means shorter residence time, the
decrease of apparent viscosity of PP is also a function of ultrasonic
intensity and time, just like the pressure reduction. Further, Fig. 6
demonstrate that MFR increases after application of ultrasound under the
same extrusion conditions. But with low- intensity ultrasound, MFR changes
very little-from 4.2 g/10 min (OW) to 4.7 g/ 10 min (100 W). It may be
concluded that appropriate ultrasonic irradiation can accelerate molecular
motion and make long entangled macromolecular chains unravel with a low
degree of degradation.
Die Swell
The swelling of the extrudate
in capillary extrusion is a manifestation of the elastic properties and
the fading memory of the melt, and is a result of unrelaxed deformations
generated during the extrusion process. Figure 7 shows that die swell
ratios D/D^sub 0^ decrease with increasing ultrasonic irradiation power.
Since swelling is a relaxation process, energy from ultrasonic irradiation
can affect the relaxation of polymer melts by shortening the relaxation
time of chain segments, thus decreasing the elasticity of the melt at
the die entrance. It is also observed that ultrasonic waves contribute
to a smoother appearance of extrudates.
Crystalline Structure
Ultrasound can greatly improve
the processing of PP, and this effect must be a result of structural changes
of the PP chain. At the same time, PP is well known for its different
crystalline forms: alpha, beta and gamma forms. So the ultrasonic irradiation
probably induces the change of the crystal structure. To verify this hypothesis,
samples were analyzed by DSC and WAXD. Table 1 summarizes the values obtained
from DSC thermograms. T^sub c^ is the crystallization temperature, T^sub
onset^ is the temperature at the cross point of the megathermic tangent
line and the base line at angle of alpha. Si, the tangent of alpha, is
a measure of the rate of nucleation. (T^sub onset^-T^sub c^) is a measure
of overall rate of crystallization of the system, which decreases with
the increase of the crystallization rate (11). It has been found that
with the use of ultrasonic vibration, (T^sub onset^-- T^sub c^), Si and
crystallinity are lower than their respective values for a sample without
ultrasonic treatment. This indicates that ultrasound prevents nucleation
as well as accelerating the growth of PP crystal, and the decreased rate
of nucleation may lead to lower crystallinity. Furthermore, it is also
noted from Fig. 8 that in the case of ultrasound, the peak occurring at
lower temperature, which corresponds to fusion of beta-form (temperature
of the peak is about 145 deg C), becomes stronger and the enthalpy is
higher. The other hightemperature peak due to fusion of the alpha-form
is correspondingly weaker. These investigations may imply that processing
PP with ultrasound causes a preference for the growth of the beta-form
relative to that of the alpha-form.
Table 1.
It can be seen from the X-ray
diffraction patterns that PP samples with and without ultrasonic treatment
are different (Fig. 9 and Table 2). By introducing ultrasonic effects,
peaks at theta = 16 deg, 21.3 deg increase and become markedly wider (Mg.
9). In addition, Table 2 shows the values of the increase of K. According
to Turner-Jones (9), these indicate an increase of the beta-forms of polypropylene.
Moreover, the data listed in Table 2 show that nearly all the d spacing
of crystal planes of PP decrease and values of S increase with ultrasonic
treatment. The maximum contribution (K = 29.5%) and maximum order (S =
47.9%) of the beta phase are in the samples affected by ultrasonic power
of 180 W. All the above imply that ultrasonic vibrations can shorten the
distances between molecular chains and decrease the crystal defects and
disordered structure, so that the lattices of PP have an increased order.
The enhancement of the beta-form combined with the decrease of crystallinity
implies that the polymorphic transitions alpha -> beta of PP may exist
in the system.
CONCLUSION
The application of ultrasound
to extrusion can improve the processing of PP by raising the die temperature
and decreasing pressure and viscosity, thus enhancing the throughput and
appearance of extrudate\s.
The results show that this ultrasonic
process can modify the structure of crystallizable thermoplastic materials
like PP during extrusion. Ultrasonic irradiation results in a reduction
of the crystallinity of extruded PP. Ultrasound also shows a selective
effect on the growth of different crystal forms of PP, which causes an
increase of the relative amount and order of the beta-form as well as
transitions of the alpha-form to the beta-form.
ACKNOWLEDGMENT
This paper is based on results
from the subject supported by the Special Funds for Major State Basic
Research Projects (G1999064809).
Table 2.
REFERENCE
1. J. Lemelson, U.S. Patent 4,288,398
(1981).
2. J. W. Pendleton, U.S. Patent
3,298,065 (1965).
3. SI Khamad, EN Popova,
and Z. I. Salina, Deposited Doc. (RUSS), VINITI, 1829 (1984).
4. A. 1. Isayev, CM along,
and X. Zeng, Adv. Polym TechnoL, 31, 10 (1990).
5. AI Isayev and J. Chen, Rubber
Chemistry and Technology, 68, 267 (1995).
6. AI Isayev, S. P. Yushanov,
and J. Chen, J. Appl. Polym. ScL, 59, 803 (1996).
7. V. Yu. Levin and S. H. Kim,
Rubber Chemistry and Techno/ogy, 70, 120 (1997).
8. M. A. Gomez, H. Tanaka, and
A. E. Tonelli, Polymer, 28, 2227 (1987).
9. A. Tuner-Jones, J. M. Aizlewood,
and DR Beckett, MakromoL Chem., 75, 136 (1964).
10. G. Zhou, Z. He, J. Yu, Z.
Han, and G. Shi, MakromoL Chem., 187, 633 (1986).
11. AK Gupta and VB


Fantasy Marching Arts - Forums - Marching Arts Discussion - Your Marching Band Show?
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Marching Arts Discussion
Your Marching Band Show?
1
Cinman2
88
37
August 17th, 2010 8:08pm
I'm not in high school anymore but I do like to follow and learn from around the country from other Marching Bands and their marching shows?
What is your competitive marching show you are performing this fall?
So I don't just limit this to just high schoolers, For people not in a marching band, what is a show you WISH you were performing this fall?
Executive Director of the CAI Performing Ensembles:
Northgate Marching Band
The Generals Drum and Bugle Corps
Generals Guard
Generals Drums
bando
598
1211
August 17th, 2010 8:29pm
My college is doing The Planets as their marching band show. :)
Auditions are on Friday actually.
Clarinet 1 part makes me cry a little inside.
EDIT:
My old hs is doing Robin Hood: Prince of thieves, and their ballad is Training Montage from Highlander.
Proud Member of CLASS
Founder of the IIEA
http://iiea.bravesites.com/
Eagle Regiment A, B | Night Area HS Performing Ensembles
ashfire
131
114
August 17th, 2010 9:49pm
Angola is performing 'through the golden door'. the music is phenominal i must say.
Favorite Composer: Richard Saucedo
Favorite Orchestrated piece: Motion (Brian Balmages)
Favorite Mainstream Piece: FireFlies (Owl City)
BlueDevils
407
233
August 17th, 2010 11:23pm
My school is doing La Dolce Vita. It has Con Te Partiro, Pines of Rome, and some third one I don't remember right now.
DC: Blue Demons Corps
Placement:
S1: 18, S2: 39, S3: 53, S4: 36, S5: 20, S6: 25, S7: 25, S8: 31, S9: 38, S10: 5, S11: 11, S12: 1, S13: X S14: ?
TrumpetVinny
667
146
August 19th, 2010 12:03am
My school is Into the Blue and Beyond. We've got
I. Birds of Thunder
II. Claire de Lune
III. Waverider/Right Stuff Theme
The Azure Arts have officially gone [unspecified].
Vinny is currently on the BOD
ismensink
433
62
August 19th, 2010 2:09am
my schools show is entitled every dark cloud and involves eric whitacre's equus and lux arumque
hi
JacobCaffrey
73
20
August 25th, 2010 9:50am
My school is doing a New Mexico Native American theme where we bring in all our state symbols into our show and we use teepees about 12 feet tall as props.
The show is called KeeVA.
Repertoire-
-Becoming One of the People from Avatar
-Pursuit from Ka by Cirque du Soleil
-Battlefield from Ka by Cirque du Soleil
gmbande94
415
75
August 25th, 2010 11:17am
My school General McLane is doing Elvis featuring:
Can't Help Falling In Love Opener
Burning Love
CC Rider
Love Me Tender
Jailhouse Rock
Can't Help Falling In Love Closer
Music arranged by Jay Dawson
RWB
"It's all for Love L-O-V-E" - Michael Jackson
katkatastrophe
81
150
August 29th, 2010 9:50pm
My schools show is called Inner Turmoil
and we're using Tchaivoiskys (I cannot spell his name for the life of me!) 1812 Overture, Symphony 2,3, and 4 I believe.
Proud Director Of
Infinity Sound Drum and Bugle Corps (D2)
Infinity Winterguard (D2)
Storm Indoor Drumline (D2)
Westwood Academy Marching Band (D2)
rocketfan86
913
48
September 13th, 2010 6:35pm
Although I have graduated from my high school some 6 years ago, I know that their show is called "Classical Elements."
In the Hall of the Mountain King
Fire of Eternal Glory
The Firebird Suite
Member of the Mid-West Combine
ashfire
131
114
September 13th, 2010 9:27pm
our band (high school Class C) swept the competition last saturday. we took home all the captions and led our division by 4 points!
Favorite Composer: Richard Saucedo
Favorite Orchestrated piece: Motion (Brian Balmages)
Favorite Mainstream Piece: FireFlies (Owl City)
coolbaridude
49
5
September 23rd, 2010 12:50pm
My College band is doing a show comprised of songs about/from america
Lead bari- Racine Scouts- 2008
2nd bari- Carolina Crown- 2009-2010
animal
149
163
September 23rd, 2010 1:33pm
I'm just an alum that techs with the battery from time to time, but their show is "The Hero: The Battle of Good vs. Evil," featuring original arrangements of music from X-men, "One Day I'll Fly Away" from Moulin Rouge, Batman, Superman, and I think one other source that I can't recall. It's their best show design I've ever seen (and I'm jealous). They're gonna clean house in Single-A around their neck of the woods. . .
aNiMaL
CLASS VP of Administration
Member of IIEA
Inferno- 21st
Div. I
Rhythm Q- 3rd Div. III
HCHS Marching Tigers- 8th Div. III
HCHS Winter Guard- 6th Div. III
TonyWolcott
78
7
February 13th, 2011 8:52am
http://www.youtube.com/watch?v=jm1qg56fSPY
Sprayberry High School Marching Band of Gold presents: "Super Cosmoes"
Carolina Crown, here I come in 2013, 2014, and 2015
BlueDevils
407
233
February 13th, 2011 3:42pm
http://www.youtube.com/watch?v=S8lDlp6M5OQ&feature=related
My band's marching show: La Dolce Vita
I'm the euphonium soloist and singer in the 4th movement. =)
DC: Blue Demons Corps
Placement:
S1: 18, S2: 39, S3: 53, S4: 36, S5: 20, S6: 25, S7: 25, S8: 31, S9: 38, S10: 5, S11: 11, S12: 1, S13


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Frances Loeb Library
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SPECIAL COLLECTIONS PUBLICATIONS
Special Collections Finding Aids Available in Print Format:
A Guide to the Special Collections of
the Frances Loeb Library /
Mary Daniels. Harvard Graduate School of Design.
Reference Desk
The CIAM Collection: A Descriptive Inventory
of the Archival Holdings in the Frances Loeb Library / Mary
Daniels. Cambridge, MA, 1990. Ref Z675.A83 F732x
The Curutchet Collection: A Descriptive Inventory
of the Archival Holdings in the Frances Loeb Library / Mary
Daniels. Cambridge, MA, 1990. Ref Z675.A83 F733x
The Ferrari Hardoy Archive:
A Descriptive Inventory of the Archival Holdings in the Frances
Loeb Library / Inés Zalduendo. Cambridge, MA, 2002. Ref NA839.F466 A3
The Architecture of Ulrich Franzen:
A Descriptive Inventory of the Archival Holdings in the Frances
Loeb Library / Inés Zalduendo. Cambridge, MA, 2005. Ref NA737.F72 A3
The John Charles Olmsted Collection: A Descriptive
Inventory of the Archival Holdings in the Frances Loeb Library / Mary Daniels. Cambridge, MA, 1990. Ref Z675.A83 F734x
The Josep Lluís Sert Collection: A Descriptive
Inventory of the Archival Holdings in the Frances Loeb Library / Mary Daniels. Cambridge, MA, 1990. Ref Z675.A83 F735x
The Arthur A. and Sidney N. Shurcliff Collection:
A Descriptive Inventory of the Archival Holdings in the Frances
Loeb Library / Mary Daniels. Cambridge, MA, 1990. Ref Z675.A83 F731x
The Alison and Peter Smithson Archive:
A Descriptive Inventory of the Archival Holdings in the Frances
Loeb Library / Inés Zalduendo. Cambridge, MA, 2005. Ref NA997.S54 Z9
In addition to the titles cited above, individual inventories
may be available for other collections. Please consult Special Collections
staff.
Special Collections Articles and Papers:
"The Josep Lluís Sert Collection: An Experiment
in the On-Line Processing of an Architectural Archive",
Mary F. Daniels. Bibliotecas de Arte, Arquitectura y Diseño:
Perspectivas Actuales / Art, Architecture and Design Libraries:
Current Trends. Barcelona, 1993; Munchen, K.G. Saur, 1995. Special Collections
"The Making of Two Americans: European
Traditions and Practices expressed in the Henry Hobson Richardson
and Eleanor Raymond Collections of Harvard University's Graduate School of Design", Mary F. Daniels. International
Confederation of Architectural Museums, New York, 1998. Special Collections
"Shaping and Reshaping Latin American Cities: Josep Lluís Sert and Town Planning Associates",
Mary F. Daniels. ReVista, Harvard Review of Latin America, Cambridge, 2003. Special Collections
"Buenos Aires: Through the Architectural Archive of Jorge Ferrari Hardoy",
Inés Zalduendo. ReVista, Harvard Review of Latin America, Cambridge, 2003. Special Collections
"Arrangement and Description of Architectural Collections -in paper!",
Inés Zalduendo. Museum Archivist, Vol. 17, No. 2, Fall 2004. Special Collections
"Jaqueline Tyrwhitt's Correspondence Courses: Town Planning in the Trenches",
Inés Zalduendo. Presented at the Society of Architectural Historians Annual Meeting, Vancouver, April 2005. Special Collections
"Access and Preservation of Landscape Architecture Collections -in Digital!",
Inés Zalduendo. Presented at the International Confederation of Architectural Museums / United States, Philadelphia, October 2009. Special Collections
"Jaqueline Tyrwhitt's Correspondence Courses for Members of the Allied Forces",
Inés Zalduendo. Presented at War Perspectives Conference, Politecnico di Milano, Italy, January 2010. Special Collections
"Buenos Aires: La Ciudad Frente al Rio",
Inés Zalduendo. Presented at the Society of Architectural Historians Annual Meeting, Chicago


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Order This Book
Elephant Manby Nomi Baumgartl and Chris Gallucci, with an introduction by Daniel Opitz
Click to view a larger image
Firefly Books
World rights (English)
09/12/2008
Book Website
160 pages, 10 1/4" x 11 1/2"
160 color photos
EAN: 9781554074228ISBN: [ 1554074223 ]
hardcover with jacket
39.95 CDN / 39.95 US
The story of an unusual relationship -- and how an unruly giant healed a broken man.
Chris Gallucci ran away from home at 12. By 16 he was in prison for the first time, but not the last. His life was playing out on the fringes of society, characterized by rebellion and aggression. Change seemed unlikely until he happened upon the film set of Roar, a movie featuring Hollywood actress Tippi Hedren (The Birds) and her daughter, Melanie Griffith, as well as a variety of lions, pumas, tigers and elephants. Chriswas immediately fascinated by Timbo, the gigantic bull elephant known for its misbehavior, and applied for a job as an elephant trainer on the small ranch that was its home. To win Timbo's trust, Chris chained himself up in the elephant's enclosure and tossed away the key. It was the start of a 30-year relationship that would tame the savage in Chris.
Powerful photos capture the essence of elephant man Chris Gallucci's life: the small world of the ranch, walks with Timbo on the edge of the Mojave Desert, his training regime with the huge bull. Extracts from Chris's diary provide a window into his soul.
Elephant Man inspires with the silent power of an intense spiritual connection between animal and man.
Nomi Baumgartl is an internationally acclaimed photographer specializing in images that show the connection between man and nature. Her work has received prestigious awards, and her pictures are frequently published and exhibited.
Chris Gallucci, author, biker and elephant trainer, lives in Acton, California. Since Timbo's death, Chris has continued to work as preserve supervisor at Shambala, the wild animal reserve on the edge of the Mojave Desert.
Daniel Opitz is an award-winning filmmaker and founder of Ocean Mind, an independent film, photo and television production company. His work includes The Elephant Man (also called Tusks and Tattoos), which has been shown worldwide at film festivals and on television (Animal Planet).
Sorry, no table of contents exists for this entry.
Foreword by Daniel Opitz
"I love you" and "I could kill you." The world the Elephant Man grew up in was mean and hard. He left home when he was only twelve. Throughout his teens he was involved with the violent biker culture that developed in and around Los Angeles in the late sixties. Thanks to a falsified ID and too much pride to admit it, he found himself in jail for the first time at the tender age of seventeen.
His only true philosophy in those days was to show no weakness. While this mantra fueled the flames of his rebellion and brought him nothing but trouble, it also led to his eventual salvation: Timbo was a five-ton grey giant, who at nearly fifty years of age was North America's biggest and oldest African elephant bull. As stubborn as Chris himself, he too was unpredictable, fearless and always ready for a fight.
Chris was not looking for anything more than a job and perhaps some excitement when he rode his chopper into Acton, California, a small town on the edge of the Mojave Desert in 1975. He found a job as a welder on the insane set of the movie Roar, which starred over 100 wild lions, cougars, tigers and two elephants, as well as Hollywood diva and Hitchcock actress Tippi Hedren and her daughter Melanie Griffith.
When filming was completed, Chris and Tippi stayed behind with the wild animals. Together they converted what was left of the movie set into "Shambala -- The Roar Foundation," a non-profit organization dedicated to providing the animals the best life possible. Chris, who was drawn to gigantic Timbo from the very start, asked if he could be the elephant's new trainer. He got the job.
To understand what it felt like to be an elephant, Chris spent the first night with Timbo, attaching himself to Timbo's chain and throwing away the key. To gain Timbo's trust, Chris learned to control his own demons. "See," he says, "The more relaxed and at ease I am, the more I allow Timbo to be free." In the nearly 30 years they spent together, neither Chris nor Timbo got into serious trouble again.
You do not come across people like Chris Gallucci simply by chance; you get caught in their gravitational field. Chris and I got to know each other in the Bahamas in 2000, during a photo shoot with Nomi Baumgartl. A model had invited him along for his first vacation in nearly 30 years. After just a few days, however, Chris cut his Caribbean trip short. He simply could not bear the thought that due to his absence, Timbo would be again be confined and chained. Chris returned to his own small world and self-imposed prison at Shambala.
I have always been drawn to people who have pushed the envelope throughout their lives, personalities who thrive on enormous challenge. A year later, when I arrived in Shambala with my film crew to document "The Elephant Man," Chris was in the midst of a huge personal crisis. For the first time he regretted his lonely life, confined to a ranch in the desert with Timbo. He shaved his long beard, sold his beloved chopper and stopped polishing his meticulously sharpened knives. But Chris would not be Chris if he did not manage to pull himself out of this deep depression. As filming progressed, he gradually found his balance again. He started his journal again, grew his beard back and bought a new motorcycle and a '57 Chevy Bel Air that he had always wanted. We finished the film and became fast friends.
I valued Chris' simplicity, his attitude and way of looking at things, his entire essence, even Chris just being Chris. He never seemed to need such modern amenities as credit cards, computers or cell phones. Not because he was adverse to them, but because he was busy with other more important things. To me, he represented a sort of primal creature with an instinctive kind of wisdom and yes, an undertone of aggression. In a strange way, Chris became for me what Timbo was to him.
When photographer Nomi Baumgartl gets involved with a new subject it is not only with her camera, but also with her heart and entire being. Nomi was part of our film crew in Shambala. At one point she found herself in the middle of a fallow field with a five-ton elephant hurtling toward her. "Don't move!" Chris shouted, "Don't move!" Nomi closed her eyes and all was still. Suddenly she felt a moist, warm trunk in her face, and a suction so strong it felt as if she was being sucked into a wind tunnel. "Now he trusts you." At that moment she experienced the wondrous spiritual link between man and animal, Chris and Timbo.
Elephant Man is the inspiring story of how a wild animal tamed a wild man. Told through potent pictures and diary excerpts, it reflects on the powerful bond that can occur between humans and animals. Elephant Man describes their training regimen, walks through the fields together and the author's pleasure in watching Timbo play in the water.
- Katy Scope  Katy Lifestyles & Homes  2009 06
Elephant Man is an intriguing diary of two stubborn individuals with personality. It is a remarkable, if somewhat insane story that will keep you coming back.
- Randy Midzain  Winnipeg Free Press  2008 12 07
This is a story of redemption, of how a difficult animal made a human being out of a man.
- Bill Robertson  Saskatoon Star Phoenix  2008 12 13
[Gallucci's] diary forms most of the text, though Baumgartl's sensitive and moving photographs--of both man and beast--are the book's core.
-   The Globe and Mail  2008 12 06
Animal lovers will cherish this love story between Chris Gallucci, an ex-biker, and Timbo, a five-ton grey African elephant bull.... Baumgard's photographs of the two show an amazing similarity in their eyes, facial wrinkles, even their expressions. These photos show less wildness in Gallucci than intelligence and sensitivity to Timbo. Some close ups could easily be of either one. Timbo


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Main lectures 42 microsymposium
Main lectures
1 2 3
4 5 6 7 8 9 10
ML01
CHEMILUMINESCENCE COMBINED WITH THERMAL ANALYSIS FOR
STUDYING POLYMER OXIDATION
N.C. BILLINGHAMa, P.K. FEARONa,
M.N. GRIGGa, S.W. BIGGERb
aDepartment of Chemistry, University of Sussex,
Brighton, BN1 9QJ, UK
bVictoria University of Technology, P.O. Box 14428,
Melbourne 8001, Australia
Because of the effectiveness of modern stabilisers,
accelerated ageing tests must be used to evaluate their
performance. Oven ageing testing is the most reliable but is time
consuming. Differential Scanning Calorimetry (DSC) has been
widely used for measuring oxidation induction times (OIT) but is
usually (mis)used at temperatures above the melting point of the
polymer.
Many polymers emit light (chemiluminescence, CL) during
oxidation. CL offers an alternative method to monitor oxidation,
its advantage being very high sensitivity. CL imaging of
oxidative degradation has recently been made possible by the
development of low noise, high sensitivity cameras, which allow
multiple sampling, reducing experimental times and cost. Imaging
also allows study of inhomogeneity.
In collaboration with Mettler Toledo, we have combined CL
measurement with DSC in a single instrument. The combination has
obvious advantages where oxidation occurs simultaneously with
other thermal events, e.g. melting, since the CL is sensitive
only to oxidation. CL in inert atmospheres can easily detect the
presence of peroxides at concentrations well below those
detectable by DSC.
Measurements on unstabilised samples of polypropylene show
good correlation of CL with heat flow data, with kinetics
consistent with the Russell mechanism for CL. Studies of the
formation of carbonyl groups show that the relation of CL to C=O
content is also consistent with the Russell mechanism.
For stabilised samples OITs measured by both CL and DSC are
similar. It is easier to operate the CL at very high sensitivity
and CL can easily detect OITs above 70 h. Increased oxygen
pressures allow analysis by CL under conditions where DSC signals
are noisy. There is good correlation between CL values measured
by single-sample CL and imaging detection.
Multiple detection needs some care in order to avoid cross
sample contamination but allows major economy of equipment time.
Some applications of the DSC/CL method will be discussed,
including the assessment of stabiliser performance and the
correlation of OIT and oven ageing.
ML02
RADIATION AGEING OF POLYMER MATERIALS
J.L. GARDETTE, A. RIVATON
Laboratoire de Photochimie Moléculaire et Macromoléculaire,
UMR CNRS 6505, Université Blaise Pascal, 63177 Aubière cedex
France
The modifications of structure and properties of polymeric
materials resulting of the ageing initiated by ionising
radiations have been a subject of interest as soon as nuclear
programs began. Exposure of polymers to radiative environments
causes indeed a deterioration of their properties. It has been
approximately 50 years since researchers first began studying the
effects of ionising radiations on polymers. The main
radiation-induced changes consist in scissions and/or
crosslinking of the macromolecular chains, formation of gaseous
products such as hydrogen or low molecular weight hydrocarbons,
accumulation of oxidation products, loss and/or formation of
unsaturations.
Among the numerous studies devoted to the radiochemical ageing
of polymers, many of them report on the mechanism of the -initiated degradation of polyolefins.
This presentation concerns the behaviour of EPDM copolymers,
which are composed of ethylene (PE), propylene (PP) and diene
monomer (5-ethylidene 2-norbornene (ENB) in this study). These
polymers find numerous applications and are often used as wire
insulators or joints. If the mechanisms of photo- and
thermo-oxidations of EPDM can be considered as well known, the
radiation induced degradation of these polymers has only received
little attention.
On the basis of a recent study involving the identification of
the various products that are formed, a mechanism accounting for
the radiochemical degradation of EPDM has been proposed, with a
peculiar attention given to the role played by oxygen and by the
ENB termonomer. Two main processes are involved in the
radiooxidation of EPDM. The random -radiolysis
of the polymer provides a constant source of macroalkyl radicals
mainly formed on ethylene units. The secondary radicals so formed
are likely to initiate a selective oxidation of the polymer
through free-radicals reactions involving the abstraction of
labile hydrogen atoms. In particular, the decomposition of
hydroperoxydes and the degradation of the ENB moieties, this
latter being the most oxidisable site and the source of
crosslinking, may result from hydrogen abstraction by radicalar
species.4
ML03
OVERVIEW AND PARTICULARITIES IN DEGRADATION OF POLYOLEFINS
DERIVED FROM FISCHER-TROPSCH SYNTHESIS
I. TINCUL
Sasol Technology, PO Box 1, Sasolburg, 1947, South Africa
Polyolefins are without doubt the largest volume family of
commercially polymers and a vast literature is dedicated to this
field in the last half of century. The most complex pool of
monomers is available from the Fischer Tropsch process that is
gaining momentum as a major market source. When compared with
ethylene oligomerization processes the main advantage of the
Fischer Tropsch process is the production of odd carbon number
linear and branched olefins that showed new application
possibilities in both the polyethylene and polypropylene
families. We prepared a large number of new polyolefins with
Fischer Tropsch derived alpha olefins that have particular
microstructures and morphology according to the type of branch,
length of branch and number of branches / 1000 carbons.
It is known that steric factors may play an important role in
polyolefin degradation and that tertiary carbon is labile to
oxidative attack. A decrease in crystallinity with the increase
of comonomer content may favour auto-oxidation due to higher
oxygen absorbtion. Very little literature on degradation of
polyolefins prepared with Fisher Tropsch derived olefins is
available. In this paper is presented and discussed some
particularities on the degradation of polyolefins Fischer Tropsch
derived.
The manifestation of oxidation weather by temperature or aging
concerning polymer appearance as discoloration, loss of optical
properties, loss of mechanical properties and surface cracks were
observed. This behaviour was similar to known polyolefins.
Oxidation induction time as measured by DSC varies with the
number of branch and length of branch introduced in the polymer
chain by a certain comonomer. The thermal stability was measured
also by thermogravimetry and compared with the polymer structure
and thermal behaviour. The degradation temperature increases with
an increase of carbon number of the comonomer. Investigation for
a series of ethylene co-polymers and ter-polymers with linear and
branched alpha olefins showed an increase of pre-exponential
factor as a function of carbon number in an Arrhenius type
equation. A decomposition kinetic study showed that the
activation and the rate constant is also related to the size and
type of branch. Rheological investigation showed a similar
pattern. It was concluded that while polyolefins obtained with
Fischer Tropsch derived olefins showed a behaviour similar with
known polyolefins, particularities in degradation does exist and
are related to the number and type of branch.
ML04
ESSENTIAL CRITERIA FOR THE SUCCESSFUL RECOVERY OF PLASTICS
N. MAYNE
Association of Plastics Manufacturers in Europe, Avenue E. Van
Nieuwenhuyse 4, Box 3, B – 1160 Brussels
E-mail address: neil.mayne apme.org
Of the many options for recovery of plastics at the
end-of-life, mechanical recycling is in principle the preferred
route. There is an increasing understanding of the mechanisms,
which affect the degradation of polymers or physical property
enhancement by increasing their compatibility with other
polymers. While many laboratory scale experiments demonstrate the
potential for high levels of recycling, in practice the levels
achieved on an industrial scale with post-consumer plastics can
be viewed as disappointingly low. In addition to economic
considerations, this is because there are a limited number of
applications allowing closed loop recycling and there is a
mismatch between the supply of recyclate and demand from the
market. New developments will increase the potential, but such
recycling will nevertheless remain limited.
Feedstock recycling technologies offer versatility and many
large scale processes have been developed and demonstrated.
Logistics and supply commitments are key factors in determining
viability. To date, fully commercial plants are only operational
in Germany and Japan. A number of active developments are,
however, currently underway in a number of European countries.
Energy recovery will become an increasingly important recovery
option as it is also being stimulated by restrictions on the
landfilling of waste. Even if the full potential of mechanical
recycling were to be realized, the major part of total plastics
waste would still be available for use as an alternative fuel.
This means that with the expected growth of plastics, this
represents an increasingly important source of energy, equivalent
to millions of tonnes of imported oil each year.
The challenge for the successful recovery of plastics is to
identify and use the optimum combination of options, underpinned
by continuing innovation in process, product and recovery
technologies in order to increase the resource efficiency of
products throughout their whole life-cycle.
ML05
OPTIMISAZION OF PROCESSING CONDITIONS IN THE RECYCLING OF
POLYCONDENSATION POLYMERS
F.P. LA MANTIA, R. SCAFFARO
Dipartimento di Ingegneria Chimica dei Processi e dei
Materiali
Università di Palermo, Viale delle Scienze, 90128, Palermo,
Italy
Mechanical recycling of polymers is a very complex and
difficult process because repetitive melt processing can lead to
severe degradation of these materials with subsequent
deterioration of all the properties. For condensation polymers,
the degradation rate is much faster in the presence of water that
induces depolymerization reactions, having also a synergistic
effect with thermomechanical degradation and exalting the loss of
properties. Indeed, a careful drying prior to processing can
drastically reduce the degradation phenomena but increasing the
complexity of the process and its cost.
The aim of this work is to study the effect of the
reprocessing of some polycondensation polymers with and in
absence of water. Moreover, the possibility to process wet
polymer in the presence of proper stabilisers to avoid the drying
step has been studied too.
The materials chosen for the study have been polyamide 6,
polycarbonate and polyethyleneterephtalate.
The results indicate that for the three different systems
considered, the wet processing causes, as expected, a strong
reduction of the mechanical properties and of the molecular
weight, as evidenced by rheological and thermal measurements.
If a degassing stage is added to the processing apparatus, a
certain improvement of the properties is observed. This can be
explained in terms of humidity removing with consequent reduction
of the hydrolytic chain scission.
When nitrogen flow is added to the degassing, both humidity
and oxygen are practically eliminated from the system, and a
further improvement of the properties is observed. This can be
explained with the further reduction of the humidity but it also
suggests that degradation mechanism involves reactions.
The presence small amounts (500 ppm) of a particular
antioxidant has a positive effect in all the cases. In
particular, the adding of antioxidant can substitute the drying
stage as it is able to protect the macromolecules from
hydrolysis. This behaviour can be explained considering that this
antioxidant is more prone to hydrolysis than the polymer, thus
removing the water from the melt and decreasing the degradation
rate. Such consideration has been proved using different
antioxidants with different tendency to hydrolysis: using
antioxidants with theoretical reduced hydrolysis tendency caused
a parallel reduction of the protection with consequent loss of
properties.
The positive effect of the presence of the antioxidant has
been also verified for several reprocessing steps (up to five).
The results indicate that the presence of the antioxidant still
have positive effects also after several recycling operation.
It can be concluded that the mechanical recycling of
condensation polymers can be effectuated with practically any
loss of properties if an adequate removal of humidity from the
system is performed. A valid alternative to the complex and
expensive pre-drying operation can be the adding of antioxidants
that undergo hydrolysis in vice of the polymers.
ML06
FEEDSTOCK RECYCLING OF PLASTICS IN JAPAN
A.OKUWAKI
Tohoku University, Graduate School of Environmental Studies,07
Aoba, Sendai, 980-8579
Various commercial plants for feedstock recycling of waste
plastics have started up in Japan. In 1999, only Niigata
liquefaction plant was operated. Now they are liquefaction at
Sapporo, and Mikasa, Blast Furnace application by NKK, Coke Oven
application by Nippon Steel Corp., Gasification by EBARA-UBE, and
Glycolysis of PET bottles by Teijin. Separated PET bottles are
now used as raw material for polyester fibers, 30,000t/y in
capacity from April, 2002, and the two commercial plants for the
Bottle to Bottle recycling are under construction for the first
time in the world.
Clearly this is related to the practical implementation of the
Containers and Packaging Recycling Law carried out in 1997 for
PET bottles and in 2000 for the other plastics. This law affords
allocating the cost for feedstock recycling of waste plastics
separated only in homes. It has created attractive markets and
thus, they say that the separated waste plastics are even in
short supply in Japan. Recovery of PET bottles increases
successfully since 1997, but that of plastics increases
dramatically since 2000 when the law has carried out.
On the other hand, their cost for recycling decreases
gradually. At present, their recycling fees are quite expensive
compared to the cost for treatment of industrial waste plastics.
However, it is expected that the cost will continue to drop. This
trend suggests that the active competitions among various
techniques proceed including the improvement of collection
system. This situation creates big chances for the world
recycling technologies in the Japanese market and refine
necessarily both techniques and logistic systems.
The Home Appliances Recycling Law came into full force in
April 2001 is to be revised within a few years. In such process,
they say, not only the recycling of their plastics cases, but
also that of printed circuit boards are introduced to elevate the
recycling degree.
In addition, the Law for Recycling of End-of-Life Vehicles has
passed through the Parliament, July 2002. They say, an average
cost per car will be 20,000 Yen, namely 151Euro. Clearly this law
should proceed the recycling of automotive shredder residue.
These environmental policy of Japanese Government are sure to
promote more the recycling of waste plastics in Japan