text:
Recruiting date change could slow coaching carousel during bowl season
GLENDALE, Ariz. -- Calvin Magee is leaving West Virginia for Michigan, but not yet.
The Mountaineers' offensive coordinator couldn't walk out on his players with a Tostitos Fiesta Bowl game to be played against Oklahoma.
"I think it's the right thing to do to put closure on it," Magee said. "We went through a tough season together."
The Mountaineers appreciate Magee's dedication to the cause, and to a bond forged through hundreds of hours in winter conditioning and spring ball and summer workouts and a full fall of games.
"I'm glad he did stick around," fullback Owen Schmitt said, "because he's one of those guys who have gotten us this far."
"For him to stay and compete with us says a lot about his commitment to the team," quarterback Pat White said.
Great. Nice. Now here's the elephant-sized question hovering in the room: What about Rod?
What does it say about head coach Rich Rodriguez's commitment to the team, since he's now in Ann Arbor while his players are in the desert? What does it say about an ethically bankrupt system that makes the program architect's abandonment of his team before its biggest game perfectly understandable and increasingly common?
Schmitt sighed when those questions were put to him. He's heard them so many times in the last few weeks, since Rodriguez bolted for Michigan. And nobody is more powerless in these situations than the players.
"The saying of this whole thing is, 'It is what it is,'" Schmitt declared.
"It is what it is" has become the most-favored Sportspeak for "it sucks and it's an absolute travesty, but what are we supposed to do about it?"
Here's what we're supposed to do: Fix it. Change the recruiting calendar, or pass NCAA legislation limiting when coaches can be hired or fired, or fine the shorts off schools for tampering with another school's coach before its season is over. There already is an epidemic of lying intrinsic in the job-search market; the fact that it has intruded so heavily upon the bowl games only makes it worse.
A bundle of bowl games have been reduced to sideshow status, with interim coaches plugged in where head coaches used to be, because nobody wanted to wait until the season was complete before shuffling the deck.
The reason you will hear for why haste is paramount is recruiting. The new coach must get into his new digs and must assemble a staff because they must firm up the old commitments and must secure the new and must raid those who already have committed to other schools. Because signing day is the first Wednesday in February, and of course that date is set in stone and more sacred than Christmas falling on Dec. 25.
Why, exactly, nobody knows. Would the earth stop rotating if they moved signing day to, say, the first Wednesday of March?
Or, would it be criminal to let high school players who have already committed sign letters-of-intent in December, when the junior-college players do it? That's Oklahoma athletic director Joe Castiglione's preferred idea -- though not necessarily for the purpose of slowing the job carousel.
That, he believes, is a hopeless task.
"You could try to pass legislation prohibiting contact," Castiglione said. "But in today's world I don't think we could get to that point legally."
It was only four seasons ago that Urban Meyer stuck it out through Utah's Fiesta Bowl game against Pittsburgh and completed an undefeated season with the Utes. Now that looks like an aberration, waiting until January to move all your boxes to your next job. It all seems accepted now.
"I don't know if it would change anything even if you moved recruiting back," Oklahoma coach Bob Stoops said. "When you're changing jobs, I don't know if the timing is ever very good for it."
It would run counter to human nature -- especially in a competitive business -- to expect schools and coaches not to consider their next move. But shoulder shrugging at what has become an ingrained part of the game is an insufficient response.
Wouldn't it make sense for the alleged intelligentsia of college athletics to find a way to preserve the competitiveness of their precious bowl system by actually making sure the head coaches show up for the games?
Interim and/or lame-duck coaches are 0-6 in bowls so far, with the remaining three all underdogs. That tells you the effect the carousel can have on the marquee portion of the college football schedule.
The only good that has come from Rodriguez's fleeing to Michigan is the chance to meet the charming soul that is Bill Stewart. West Virginia's interim coach is a football lifer who seems to consider himself the luckiest guy on Earth -- and not just because he's the man in charge for the Fiesta Bowl.
He's worked from high school to the CFL with nearly a dozen stops in between, and the journey hasn't soured him a bit. In fact, when Stewart wound up on the podium at media day in University of Phoenix Stadium on Monday, he compared it to working as the dunkee at a dunking booth as Sistersville (W.V.) High School in the mid-1970s.
"It has been a great trip, a great trip," Stewart said of the journey from dunking booth to BCS bowl. "I've had my bride [Karen] most everywhere. She probably thought she married Jim Bridge when she locked onto me. All I ever told her [when changing jobs], 'Are you ready to go?' " And she says two words to me: 'Let's go.' So I am very blessed.
"I tell our young coaches all the time, if you are going to get in this business, get in it because you can't live without it. Don't do it because you love it, because love sometimes strays. If you can't live without it, then you get in football. And then you make sure you have a good gal to roost with you, because it is a long road."
To hear Stewart tell it, he wandered along the wrong side of the street as a kid growing up in New Martinsville, W.V.
"That's the kid right there, the mountains of West Virginia, he stole turnips out of his neighbors' gardens, and I did," he said. "He threw snowballs at cars, and I did. He threw apples at tractor-trailer trucks. I never hit the cab, but I hit the boxcars. We jumped trains. I went to the high school and many a day walked up to the principal and walked out the back door and went fishing. That's all Cub and Boy Scout honor, I did that."
Not exactly high crimes and misdemeanors. Certainly nothing that should keep West Virginia from considering him to be its permanent coach, if the Mountaineers shock the Sooners on Wednesday night.
Stewart doesn't want to hear anything about it right now, but several of the players have spoken out in support of him as their next coach. And at least publicly, they've also gotten past the evacuation by their old coach.
"It's a business, man," said defensive lineman Keilen Dykes. "[Rodriguez] gotta do what he gotta do. When it comes right down to it, it comes down to the almighty dollar."
There's the life lesson the job hoppers have taught their young men: When the money calls, drop everything else and go take it.
Pat Forde is a senior writer for ESPN.com. He can be reached at firstname.lastname@example.com.
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2007 Bowl Season
• Maisel: What a way to geaux
• Wojciechowski: Miles deserves a wa-hooooo
• Forde: Ohio St. buckles under BCS pressure
• Schlabach: Game analysis
• GameDay: Big Ten weak?
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• McShay: BCS breakdown
• Postgame quotes: Jim Tressel
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• LSU celebrates win over Ohio State
BCS Title Game Preview
• Forde/Maisel: 10 reasons Ohio State/LSU will win
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• Maisel: OSU's children of the scorn
• Forde: Destiny's Team tag fits Tigers well
• Wojciechowski: Don't believe the hype
• Forde: Tale of the tape
• Maisel: BCS QBs not stars, but leaders
• Schlabach: 'Ironhead' Heyward's memory alive in son
• Beanie carries the load for Bucks
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• Wojciechowski: Ohio State's motivational DVD
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• Scouts' edge: LSU or Ohio State?
• Forde/Maisel: Breaking down the title game
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• Schlabach: Bucks' WRs key
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• McShay: BCS Championship preview
Fiesta Bowl
• Forde: Stewart nails on-the-job interview
• Forde: Scene of the crime
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• Forde: Picture worth 1,000 words
Rose Bowl
• Schlabach: USC looks like nation's best team
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Sugar Bowl
• Maisel: Seems like old times
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Orange Bowl
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Other Bowl Coverage
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• Low: Liberty Bowl win caps MSU's season
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What To Watch
• Pat Forde: Bowl-der Dash
• Feldman's picks: December | January
• Flash Gallery: Chris Low's impact players
• Heather Dinich: Bowling for the best gifts
BCS Selection Sunday
• Pat Forde: The grateful duo
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• Gene Wojciechowski: Theater of the absurd
More Bowl Coverage
• BCS: Rose | Sugar | Fiesta | Orange
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subset: commoncrawl


text:
A new method for producing high-strength films, fibers and other shaped articles from chitin has been discovered, whereby an anhydrous solution of chitin is made into the desired shape, the chitin is insolubilized with an organic non-solvent for the chitin and the resultant shaped article, if desired, is oriented, by cold drawing until its properties, such as tensile strength, are substantially enhanced. The films, fibers, and other shaped articles capable of being oriented or in oriented form, are novel and useful in such applications as food wrap and surgical sutures.
1. A cold drawn fiber, film or shaped object of renatured chitin containing crystalline chitin.
2. The cold drawn fiber, film or shaped object of claim 1 that has been cold drawn at least 25 percent of one of its original dimensions.
3. The cold drawn fiber, film or shaped object of claim 1 that has been cold drawn at least 25 percent of one of its original dimensions and has a specific gravity above 1.40.
4. The fiber, film or shaped object of renatured chitin characterized by there being present in the renatured chitin characterized by there being present in the renatured chitin renatured fibrils, crystallites or spherulites, showing (1) a Maltese Cross or birefringence with a polarizing microscope, (2) an x-ray pattern with sharp concentric Debye rings, and (3) a specific gravity above 1.40, and in an amount sufficient for said fiber, film or shaped object to be cold drawn at least 25 percent of one of its original dimensions.
5. A method of orienting a shaped object of claim 4 which comprises subjecting it to stress in the solid state.
6. The method of claim 5 wherein the stress is applied by cold drawing, cold rolling, stamping, die extrusion or blowing.
7. The shaped article made by the method of claim 6 wherein the article had been stressed to at least 1.4 times one of its original dimensions.
8. The shaped article made by the method of claim 6 having an x-ray pattern substantially identical to that of oriented fibrous natural alpha-chitin.
9. A method of orienting the shaped object of claim 4 which comprises subjecting it to stress in the solid state until it has been elongated to at least 25 percent greater than its original dimensions.
10. The method of claim 9 wherein the stress is applied by cold drawing, cold rolling, stamping, die extrusion or blowing.
11. A process for the manufacture of the product of claim 4 from natural chitin which comprises forming an anhydrous solution of chitin casting the solution into the shape desired and coagulating the chitin from the solution with an anhydrous coagulating medium to retain the shape desired and to form fibrils, crystallites or spherulites in the coagulated structure.
12. The process of claim 11 wherein the solvent consists of trichloracetic acid, a chlorinated solvent and chloral or chloralhydrate.
13. The process of claim 2 wherein the coagulated renatured chitin is treated with an anhydrous alkaline system to neutralize and/or leach out the acid solvent.
14. The process of claim 13 wherein the anhydrous alkaline system is an alcoholic alkali system.
15. The process of claim 11 wherein the chitin is precipitated from solution with a lower molecular weight ketone.
16. The process of claim 15 wherein the ketone is acetone.
17. An oriented-shaped article from renatured chitin having an X-ray pattern characteristic of an oriented fiber.
18. A shaped article of claim 17 wherein said article is in the form of a fiber, film, tubing or stamping.
19. The shaped article of claim 17 that has been stressed to at least 1.4 times its original dimensions.
The Government of the United States has rights to this invention pursuant to Grant No. 04-3-158-30 with the Department of Commerce.
This invention relates to films and fibers and a process of making same. This invention also relates to solutions of chitin.
Chitin is a cellulose-like material that occurs widely in nature, for example in the cell walls of fungi and the hard shell of insects and crustaceans. The waste from shrimp, lobster and crab seafood industries, now used largely for its protein values in animal feed, contains 10-15 percent chitin and is a readily available source of supply.
More specifically, chitin is a mucopolysaccharide, poly-N-acetyl-D-glucosamine and like cellulose, of relatively high molecular weight. However, in the natural state it occurs only in small flakes or short fibrous material, e.g. from the carapace or tendons of crustaceans; there is no source, as with cotton in the cellulosics, that forms useful shaped articles without solution and reprecipitation or renaturing.
For many years efforts have been made to prepare films and fibers of chitin following cellulose technology, but with limited success. Kunike, Soc. Dyers and Colourists, 42, 318 (1926), prepared chitin films and fibers by its solution in aqueous acids, spinning or casting, and subsequently coagulating with a non-solvent. Even though the filaments were dried under tension their tensile strength was only about that of rayon.
Clark and Smith, J. Phys. Chem., 40, 863 (1936), used aqueous acids or lithium salts for solution and regeneration, but the films produced were readily dispersed in water. Threads extruded from lithium thiocyanate with tension applied during their formation were said to develop orientation, but an x-ray pattern of a chitin sheet supported on a glass plate reprecipitated from lithium thiocyanate solution, showed only the broad diffuse nodes of a strained, noncrystalline material.
Somewhat later, Thor, U.S. Pat. No. 2,168,374 and No. 2,168,375, Aug. 8, 1939, described the preparation of chitin xanthate for regenerating chitin films and fibers. The patents mention the stretching of filaments in the gel state to improve physical properties, but not the drawing of solid chitin, required for fiber orientation. Thor, U.S. Pat. No. 2,217,823, Oct. 15, 1940, discloses some further details of his efforts to produce commercially useful films and fibers from chitin, but covers only homogeneous mixtures of chitin and cellulose coprecipitated from the mixed xanthates. Regenerated chitin films were said to possess good strength in the dry state, but became soft and slimy on wetting, implying a lack of toughness when wet.
Thor and Henderson, Am. Dyestuff Reporter, 29, 489 (1940) describe the preparation of regenerated chitin from chitin xanthate and summarize its properties. It formed films having a tensile strength of 9.49 kg/sq mm (dry) and 1.75 kg/sq mm (wet).
In summary, the prior art discloses attempts to produce useful articles by solution and regeneration of chitin, including stretching during fiber formation, as practiced commercially with rayon technology, but it does not teach how to carry out film or fiber preparation in such a manner as to achieve a tough renatured product capable of high orientation and possessing tensile strength, resistance to water and other outstanding physical properties comparable with native chitin, as indicated in Table 1.
Table 1______________________________________Chitin Properties______________________________________ Ten. Str.Fiber kg/sq mm Reference______________________________________Natural chitin 58 Clark and SmithRegenerated chitin 35 KunikeSilk 35.6 Clark and SmithViscose rayon 25 KunikeWool 14.5 Clark and SmithFilmRegenerated chitin 9.49 Thor and HendersonRegenerated celullose 9.10 Thor and Henderson______________________________________
It is an object of this invention to prepare highly oriented shaped articles from chitin. Further objects are the unsupported films, fibers and other shaped articles themselves, either as cast, extruded or formed, or after having been cold drawn to achieve a high degree of orientation and substantial enhancement of their properties. A further object is to provide a method for producing the shaped articles in such a way that the chitin is laid down with a substantial portion of it in crystalline form, comparable with the well-ordered natural chitins, capable of being cold drawn to enhance its properties. Another object is to provide a superior solution and renaturing process for producing unsupported films, continuous filaments and other shaped articles from chitin, such that those articles shall have physical properties and utility substantially improved over those at the prior art, which are comprised almost wholly of amorphous chitin.
Like certain other natural and synthetic polymers, chitin may occur in amorphous, stretched amorphous, partially crystalline and unoriented, and crystalline, oriented forms. Broadly these are described as different degrees of order or organization. Fibrillar chitin, for example, from the tendons of crustaceans (Clark and Smith) is of the highest natural occurring order; it is highly crystalline as shown by double refraction along the fiber axis and the characteristic Maltese Cross with a polarizing microscope, and its x-ray pattern shows the sharp multi-nodal pattern typical of known crystalline, oriented fibers. Amorphous portions of natural chitin and most reconstituted chitins show no Maltese Cross with a polarizing microscope and only broad, diffuse concentric rings in their x-ray patterns. They may show some double refraction under a polarizing microscope arising from the strain of stretching. Similarly, there are striking differences in the specific gravity of the different forms of chitin, ranging from about 1.35 for the amorphous material to about 1.49 for the highly crystalline fibrils. There are, of course, gradations and overlap in the degree of order or organizations of the chitin, both in the natural and renatured states, and such differences are found in natural chitins even from different areas of the same animal. The distinctions are determined by a combination of physical measurements, such as those indicated above.
The problem confronting the investigator then is to devise a method for converting a solution of chitin, in which the chitin is fully dissolved or dispersed, and without order or organization, into a shaped article with a high or at least controlled degree of crystallinity and/or orientation. We have found that we can accomplish these objectives and produce products of the desired qualities by a multistage process that involves controlling the molecular structure and maximizing the properties of the chitin products. The method comprises the following steps:
1. Chitin is dissolved in a solvent comprising dichloracetic acid or trichloracetic acid, such as the chloracetic acid systems at my co-pending patent application Ser. No. 418,441, filed Nov. 23, 1973, usually in combination with at least one other anhydrous organic solvent.
2. The chitin in the solution of step 1 is coagulated or renatured, in the form of a filament, film, tube or other shape by addition of an excess of an anhydrous organic liquid which is a non-solvent for chitin.
3. The coagulated shaped object is neutralized and/or leached with an alkaline reagent, preferably in an anhydrous system, then washed with water until it is neutral, and then dried.
4. Optionally, the shaped chitin object obtained as described in steps 1, 2, and 3, is oriented by subjecting it to cold drawing in the solid state to a length at least 25% greater than its original dimension.
The following examples illustrate, but in no way limit, the practice of this invention.
Two parts of red crab Opilio chionecetes chitin was dissolved in 87 parts by weight of a solvent system comprised of 40 percent by weight of trichloroacetic acid, 40 percent chloral hydrate and 20 percent methylene chloride, with mechanical agitation for a period of 30 minutes. The solution was very viscous and was filtered through wool felt. A ribbon of the solution was flowed on glass and then immersed in acetone to coagulate it. The acetone was removed and replaced with fresh acetone several times at 15-minute intervals. The clear, coagulated band had substantial tensile strength. It was neutralized and washed with a 5 percent sodium hydroxide and potassium hydroxide mixture in 2-propanol, washed with water and air-dried. The x-ray pattern of this material revealed distinct, concentric Debye rings closely similar to those of natural crystalline, unoriented alpha-chitin (Carlstrom, J. Biophys. Biochem. Cytol., Vol. 3, p. 669-683, 1957) and to the red crab flake from which it was prepared.
The above ribbon was then cold drawn with necking down, to twice its initial length. The resultant oriented ribbon could be tied into a knot and pulled tight without breaking. With further extension, breaking occurred at some imperfection rather than at the knot. This renatured, cold-drawn ribbon had an x-ray diffraction pattern of an oriented fiber, characterized by three main layer lines along the vertical axis (drawn through strong nodal points), two strong row lines laterally, and three weaker though distinct row lines that can be drawn laterally from the center through the less distinct nodal points. This pattern fits well with that of natural fibrous alpha-chitin (Rudall, K. M., Advances in Insect Physiology, Vol. I, Academic Press, New York, 1963). The cold-drawn ribbon on observation with a polarizing microscope was highly birefringent and showed extinction along the fiber axis under crossed Nicols.
Another solution of chitin prepared as described in the forepart of this example was extremely viscous and flowed very slowly to form a film, which was coagulated with excess acetone, neutralized and washed with 5 percent potassium hydroxide-sodium hydroxide mixture, in 2-propanol, and finally washed with water. The use of an alcholic system for neutralization appeared superior to an aqueous system. The film, observed under the microscope showed the presence of many fibrils in an apparently amorphous mat.
A solution of red crab chitin was prepared by dissolving 2 parts (by weight) of chitin in 87 parts of a solvent system comprised of 40 percent (by weight) trichloracetic acid, 40 percent chloral hydrate and 20 percent methylene chloride with mechanical agitation for 30 minutes, followed by filtration through wool felt. A portion of the viscous chitin solution was extruded through an orifice into acetone to yield a monofilament and another portion was poured onto glass in the form of a ribbon, which were then immersed in acetone. In each case the products were washed several times with fresh acetone during a one-hour period, retained acid neutralized by treating with 5 percent by weight sodium hydroxide-potassium hydroxide solution in 2-propanol at room temperature, and washed with water until neutral. The materials were subsequently extracted with methylene chloride for four hours. The samples were then tested with the results given below.
______________________________________ Tensile Stength Elongation N2 Cl2Material kg/sq mm* % % %______________________________________Filament 63 13 5.03 9.45Ribbon 104 44** 5.03 9.45______________________________________ *Break dimension; Instron TT-CM tensile testing machine **Cold draw
It will be noted that the chitin retains solvent tenaciously and that even after neutralization and extraction with methylene chloride the samples contained portions of the original chitin solvents employed as indicated by their chlorine content. Nevertheless, the material could be cold drawn to give a very strong filament, which was birefringent and showed a marked nodal pattern by x-ray diffraction, indicating fiber orientation. The extruded filament was perhaps partially ordered by extrusion stress and showed lower elongation, without the striking enhancement of tensile strength induced by cold drawing.
Two parts of red crab chitin was dissolved in 87 parts of a solvent mixture comprised of 40 percent trichloracetic acid, 40 percent chloral hydrate and 20 percent methylene chloride. Solution was accelerated by gentle warming and stirring for 30 minutes. A very thick, viscous solution was obtained which was filtered through felt.
One portion of the chitin filtrate solution was doctored onto glass to a thickness of about one-sixteenth inch. It was immersed in acetone to coagulate and wash it, and given three successive fresh acetone washes each lasting 15 minutes. It was then neutralized and washed with a 5 percent solution of potassium hydroxide in 2-propanol and finally with water to pH of 7. The film was tough, clear and ductile, and part of it was cold drawn to two times its length. Films neutralized with aqueous potassium hydroxide appeared weaker than those prepared in an anhydrous system. Observation of the undrawn film under a polarizing microscope showed the presence of fibrillar material interspersed in a generally amorphous chitin matrix. The scanning electron microscope revealed small bundles of fibrils embedded in an amorphous mat. The drawn film, above, upon x-ray analysis, showed a marked nodal pattern very similar to that of the drawn ribbon of Example I, although not as intense.
A second portion of the above viscous chitin solution was placed in a vessel with a single fine orifice and the solution was extruded under pressure into an excess of acetone. Fine monofilaments were produced that were clear and coherent and retained their entity with both appreciable strength and elasticity. They were washed successively with acetone, 5 percent potassium hydroxide in 2-propanol, and water as described above for film preparation. The renatured chitin filaments were strong, semi-clear and easily cold drawn to two or three times their initial length. One sample, 0.5 mm. in diameter was drawn to a fiber of 0.25 mm. in diameter. The presence of moisture in the filament facilitated the cold drawing.
Examination of the undrawn extruded filament with the scanning electron microscope revealed surface striations with axial furrows, apparently a collapsed tubular structure. An x-ray analysis of the filament gave a pattern with sharp concentric Debye rings and also nodes at both the vertical and lateral positions, indicating high crystallinity together with some fiber orientation during extrusion.
To 87 parts of 40 percent trichloracetic acid/40 percent chloral hydrate/20 percent methylene chloride solution, 2.0 parts of red crab chitin (Opilio chionecetes) were added. This chitin had been prepulverized to pass through a 24-mesh screen. This solution was magnetically stirred for 45 minutes, adding small portions of methylene chloride as the solution became too viscous to stir until 5-10 parts of methylene chloride had been added. This viscous solution was filtered free of undissolved material through felt and then through glass fiber mat. It was then immediately cast upon glass and doctored to an even thickness. After several acetone (dried with Drierite) washes, reprecipitation of clear, tough films was evident. These films had good strength, pliability and cold drawing capability. They were then extracted for 12 hours in a soxlet apparatus with equal parts by volume of methylene chloride and acetone and were then immersed for storage in acetone (dry) or dried in air for testing. These extracted, dried films maintained their good characteristics and still had cold drawing capability. The specific gravity of these films fell in the 1.46- 1.47 g./ml. range. Elemental analysis showed that they contained 5.10 percent nitrogen and 9.54 percent chlorine. After treatment of a portion of the extracted, dried films in a boiling solution of one percent sodium hydroxide in 2-propanol, elemental analysis revealed that the nitrogen content was 6.56 percent and the chlorine content had dropped to 0.67 percent (pure chitin has a nitrogen content of 6.9 percent); the sp. gr. was 1.42- 1.45.
Viewing the extracted, dried film under the polarizing microscope revealed a high degree of relative birefringence and the existence of Maltese Cross interference patterns, indicative of a high degree of spherultic crystallinity.
X-ray diffraction analysis of the extracted, dried film gave a pattern of concentric Debye rings, visually consistent with that from the source chitin. Mathematical analysis of the d-spacings tabulated below was in good agreement with the source material, confirming that the product approached renatured chitin.
______________________________________d-Spacing (Angstroms)______________________________________Red Crab Chitin Renatured Film Computed______________________________________11.00 11.00 11.0210.34 9.64 9.707.86 7.45 7.856.81 -- 6.815.38 5.47 5.484.87 4.75 4.864.30 4.07 4.323.89 3.82 3.93______________________________________
To evaluate the cold drawing properties of the extracted, dried film, a portion was cold drawn by hand, with an extension of about 85 percent. The hand-drawn film was cut into strips of constant width with a razor blade; the samples were conditioned at ambient temperature and 60 percent relative humidity and were tested for tensile strength and elongation. Based on their original dimensions, their tensile strength varied between 52-58 kg/sq mm; total elongation was approximately 125 percent which included cold drawing by hand and machine. Retesting of these totally drawn materials revealed an average tensile strength of 75 kg/sq mm with one sample at high as 95 kg/sq mm; residual elongation was about 4 percent.
Two parts of red crab chitin, 125 parts of dichloracetic acid and 54 parts of methylene chloride were stirred intermittently for one hour at room temperature to swell and dissolve the chitin. The system became very viscous, but still contained undissolved gel particles that were removed by filtration through wool felt. The clear filtrate was flowed on glass, methylene chloride allowed to evaporate during 20 minutes and acetone added carefully to cover the thickened chitin solution without disturbing its continuity. After 15 minutes the acetone and extracted solvents were decanted and the film covered with fresh acetone. The extraction, decantation and acetone replacement was repeated; the total time of acetone extraction was one hour and the film was stored in acetone, and then dried in air. The air-dried film was treated with 2 percent aqueous sodium carbonate solution at room temperature for 30 minutes and then washed with water. The film was air dried and kept at high humidity, as moisture acts as a plasticizer for the film.
Narrow sections of the chitin film were cold drawn by hand to about 25 percent elongation and showed the following characteristics of crystallinity and orientation: some drawn sections had a dumbell shape, indicating the necking down of cold drawing; broken sections at times left tails of fibrillar chitin; drawn portions appeared more transparent than the original film; over-drawn sections whitened, indicating lack of adequate moisture and resultant inhomogeneities in the drawn film; portions toughened and curled on drawing between tight fingernails; with the polarizing microscope the drawn film showed high birefringence and parallel extinction, and imperfect Maltese Crosses evidenced by characteristic light spots in the film, indicating spherulitic crystallinity.
The examples above were selected to illustrate significant aspects of the invention, but are not to be considered limiting. Thus to one skilled in the art, many variations of the operations and choice of materials will be evident and are considered within the scope of this invention. Several such variations and alternatives are indicated herewith.
Chitin from red crabs has been used in the examples and is a so-called alpha-chitin, but it is known that chitin from other crabs, e.g., blue, rock, ring and Dungeness crabs, and from lobsters, shrimp, crayfish and other crustaceans is of the alpha type and such chitin sources may also be used to prepare the products of this invention. Chitin from other structures such as the cell walls of fungi and the hard shell of insects may be the same or of the beta or gamma type of chitin, which differ mainly in molecular spacial arrangement and only slightly in chemical structure, but since they all revert to a random structure in solution, their conversion (renaturing) to a strong film, fiber or other shaped structure makes any of the chitins, whatever their source, suitable for use in this invention. The chitins may vary slightly chemically, depending on source and method of separation from shell and proteinaceous materials, for example; such variations may include molecular weight, partial hydrolysis of the acetamide group and/or the presence of water of hydration. However, such chitins will still be insoluble in dilute acetic acid, which distinguishes them from the chitosans, obtained from chitins purposely hydrolysed to a substantial degree. Chitins of high molecular weight are preferred in carrying out this invention.
Natural chitin includes an amorphous form, associated or aggregated particles containing spherulitic crystalline material and showing the typical Maltese Cross with a polarizing microscope, fibrils having a spherulitic structure with one very long axis (showing Debye rings with x-ray analysis and parallel extinction under crossed Nicols with a polarizing microscope), and oriented fibers giving characteristic nodal x-ray patterns. There are of course overlaps and gradation in these structures. Each of these forms has its counterpart in reprecipitated or renatured chitin over a range of products including powders, unsupported film, fibrils and oriented fibers.
The specific solvents employed to dissolve the chitin are selected as a matter of convenience and economics. Although such solvents are normally dry, adventitious moisture entering the system as absorbed water in or on the chitin, or as a hydrate or azetrope of one of the solvents is frequently tolerated and may at times be advantageous. Solvents that are particularly useful in combination with the chloracetic acids mentioned above in dissolving chitin include formic acid, acetic acid, glycollic acid, chloral, chloral hydrate, nitromethane, chlorinated aliphatic hydrocarbons such as methylene chloride and stetrachlorethane. The proportions of the chloracetic acids in the solvent mixture can vary widely, amounts ranging from 25 percent to 80 percent by weight of the mixture are suitable. More than one auxillary solvent can be employed in the solvent mixture. Thus, for example, a mixture of 40 percent, by weight, trichloracetic acid, 40 percent chloral hydrate, and 20 percent methylene chloride is especially preferred. The concentration of chitin in the solution can also vary widely. Solutions containing less than 0.5 percent, by weight, to 10 percent are useful. Chitin concentrations of from 1 to 5 percent are preferred.
Because trichloracetic acid and chloral are held so tenaciously by chitin, certain after-treatments may be employed to remove them more completely, such as heating with dilute aqueous ammonia or other alkali or by soaking in such media over a long period. Alternatively, recourse may be taken by the use of other solvents for chitin such as phenol, cresol or other phenolic compound in conjunction with a chlorinated or fluorinated solvent, an amide or a sulfoxide. Some of the fluorinated solvents, although expensive, may be useful as chitin solvents by themselves or in conjunction with one or more of the other solvents mentioned.
Renatured connotes the reforming of chitin from its solution to a solid structure possessing to a substantial degree the organization of natural crystalline chitin. Mere coagulation or precipitation as described in the prior art, or regeneration from the xanthate as indicated in the cited references yields only amorphous chitin showing no crystal structure with x-rays or polarizing microscope, having a low specific gravity and incapable of being cold drawn appreciably without breaking. The stretching of a coagulating fiber may give strain and orientation as indicated by parallel extinction under crossed Nicols, but the x-ray pattern shows the absence of crystalline structure (Clark and Smith, 1936). Fibrous natural chitin has been described by Hackman and Goldberg, 1965, as comprising about 30 percent of crystalline, organized molecular chitin. Such measurements are not precise, but at least a few percent of such organized material is required before a renatured chitin structure can be cold drawn.
The renaturing of the chitin takes place principally in the insolubilization step using a non-solvent for the chitin. Commonly the organic solvent of the chitin is extruded or immersed in acetone or other organic non-solvent for a sufficient time to permit some degree of crystallization-organization of the chitin to take place. There is a time-temperature concentration inter-relationship here that is optimized by suitable pilot trails. It appears that the shaped article may first be "case hardened", that is, a skin is formed around the inner still-soluble system and the insolubilization the crystallization-organization then proceeds by diffusion of non-solvent in through the membrane and the chitin solvent out to the excess of leaching solvent. This action, together with subsequent neutralization (if required) and drying involves some collapse of the structure within its skin because of the reduced volume, with consequent elaboration of a characteristic film or fiber morphology. Suitable coagulating agents include aliphatic ketones; e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, and cyclopentanone; chlorinated aliphatic hydrocarbons; e.g., excess methylene chloride, carbon tetrachloride, trichloroethylene, and tetrahydrofuran; hydrocarbons, e.g., cyclohexane, hexane, and petroleum ether. Alcohols such as ethyl alcohol, isopropyl alcohol, n-butyl alcohol can be used, especially after preliminary coagulation of the chitin has been obtained by means of one of the above-mentioned non-solvents.
With an acid solvent system for the chitin, a neutralization step is usually desirable. If the insolubilization in an organic solvent is essentially complete, then aqueous alkali or ammonia may be used for the neutralization. Depending on time and other processing conditions, however, it may be desirable to neutralize with a nonaqueous system such as alcoholic alkali metal hyroxide, which permits insolubilization and crystallization to continue at the same time. Salts formed during neutralization are finally leached with water to yield the salt-free chitin product. Alkaline materials useful in the neutralization step include sodium carbonate, alkali metal hydroxides; e.g., lithium, sodium and potassium hydroxides, pyridine and ammonia. Preferably the neutralization is carried out with a 1 to 5 percent, by weight, solution of one or more alkali metal hydroxides in an aliphatic alcohol of up to four carbon atoms; e.g., methyl, ethyl, isopropyl and n-butyl alcohol.
Cold drawing is an operation commonly applied to crystalline polymers to orient them and enhance their properties. Thus polyethylene, nylon, polyethylene terephthalate and polyvinylidene chloride are all crystalline polymers capable of being cold drawn and are frequently so oriented as to develop their optimum properties for various uses. For chitin fibers, drawing may be carried out between differential speed rolls, between a snub pin or mandrel and a fiber-advancing roll, or other device that will control their elongation in uniform manner to 25 percent or more of the original length. Drawing to at least 2.0 times the original length gives objects having greatly improved properties. If desired, the filaments may be moistened or humidified with steam. The drawing may be carried out at any temperature below the decomposition point of the fiber, but is customarily drawn between 0� and 150� C. Plasticizers or humectants such as glycerol may be employed to facilitate the drawing.
With chitin film, a one-way stretch may be imparted as described for fiber, but if desired a two-way cold drawing may be carried out, for example, by means of a tenter frame. Drawing of a sheet may also be accomplished by use of a flat-iron shaped mandrel to serve as a focal point for the drawing. Alternatively, a tubing of chitin film may be blown to impart circumferential drawing and orientation, and the blown film used as such or cut to flat film.
Depending upon the nature of the shaped article of chitin, the cold drawing step may be carried out by cold rolling, extrusion and drawing through a constricting die, or by stamping.
As with the crystalline polymers mentioned above, the chitin shaped articles may be conditioned or set in predetermined form by heating them, as such or under tension or restraint in the desired form with or without the presence of moisture. In this way not only tensile strength but residual elongation, elasticity, stiffness, shrinkage, recovery from deformation, and shape can be controlled.
The pliability of the renatured chitin products can be enhanced by incorporation of plasticizers or humectants having a significant degree of compatibility with chitin. Examples of suitable materials for this use include glycerol, ethylene glycol, propylene glycol and sorbitol.
Because of their inertness to water, steam sterilization and storage conditions the films both as formed and as cold drawn are useful in food wrapping, such as sausage casings, oven products and dairy products. The undrawn films are particularly useful where the film is subjected to temporary stress. The fibers, particularly when oriented, are especially adapted to use as sewing thread and decorative fibers where their good dyeability, strength and controlled elongation are advantageous. Use of the chitin as surgical sutures has been described by L. L. Balassa, U.S. Pat. No. 3,632,754, Jan. 4, 1972, in part because of its ability to accelerate wound healing. The oriented chitin fibers of this invention are particularly suited for this purpose because of their enhanced tensile strength and elasticity.
It is apparent that changes and modifications may be made without departing from the invention in its broader aspects. The aim of the appended claims, therefore, is to cover all such changes and modifications as fall within the true spirit and scope of the invention.
Patent Citations
Non-Patent Citations
Referenced by
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Teams: NY Giants
Teams: NY Giants
How to Play With This Team: The Giants are a shadow of the team that has existed the last couple of seasons. They aren't without weapons, however. The addition of Kurt Warner brings precision (coupled with lack of mobility) to the QB position. Then there's Jeremy Shockey, one of the most dominant TEs in the game. Look to him in the I Spread set, and hit him on the 90 Y Qk Slant. It works best against zone, but sometimes you can zing it in when a defender is draped on him, and Shockey will hang on. The I Spread-RO Z Slide to Shockey is another impact play that should remain among your favorites.
Don't be afraid to step up in the pocket if you're getting hassled. Although Warner doesn't throw a pretty ball on the move, he does alright when heading forward, and sometimes that's necessary simply because the O-line isn't all that impressive. If you're looking to run, spread the field and let Tiki scamper outside. He has quite a bit of speed and a suprising amount of tackle-breaking ability. Put a move on someone at the corner, and a big gain will be yours.
How to Beat This Team: If you can get in and rattle Warner a little bit, the game will be yours. He doesn't have enough mobility to create on his own, and if you get a hand in his grill, his accuracy will drop considerably. Bottling up Mr. Barber shouldn't be much of a problem. If you clog the middle of the field and control a player who can roam and track him down on outside runs, you'll be fine.
On the flip side, the Giants don't exactly put up a concrete wall of defense. A balanced attack will allow you to control the clock against the G-Men. Don't force the ball and turn it over, and you should maintain the edge.
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Defending Financial Journalists - and Bloggers [View article]Mar 6, 2009. 02:31 PM | 2 Likes |Link to Comment
I wrote the initial article: "The Case Against Leveraged ETFs". Since then I've done more writing and analysis, and the latest is here:
I also contributed to some of the recent Larry McDonald articles which are very good.
The take aways:
1) the cumulative product of doubled daily returns will almost certainly be lower than the underlying returns because its harder to recover from a doubled loss than the loss itself.
2) you have to pay very close attention to your index exposure because it can very quickly get out of control, making your risk exposure rise and fall dramatically
3) they have a *monster* cost of capital & expenses built in that's simply indefensible - like 7% a year.
Bottom line: Leveraged ETFs are for amateurs. If you want leverage, use options or futures or even margin (with a decent broker) like a professional.
Jan 26, 2009. 01:00 PM | 2 Likes |Link to Comment
Are Index Funds the Only Rational Choice? [View article]
I recommend reading Fama & French's 2007 paper "migration" and his related 2008 paper that investigates the source of the value and size premiums.
Tristan Yates
Author: Enhanced Indexing StrategiesDec 16, 2008. 02:54 PM | 1 Like |Link to Comment
Leveraged ETF Debate Hits the Mainstream [View article]Dec 16, 2008. 02:46 PM | 1 Like |Link to Comment
Fed's Folly: Fooled by Flawed Futures? [View article]Jan 25, 2008. 01:37 PM | 1 Like |Link to Comment
Will it Take a Liquidity Crisis for Intel to Rationalize Capital Spending? [View article]Jun 1, 2007. 08:48 PM | 1 Like |Link to Comment
The Case Against Leveraged ETFs [View article]
msangelbates: It sounds like an interesting trading strategy, though I'm skeptical on the predictive power of SMA lines. The article is aimed more at people who are considering holding these at long term investments, as for example, Bill Donahue from the Street has suggested. Email me and we can talk more in-depth - I'm writing another article on momentum vs mean reversion and have some papers you may be interested in. firstname.lastname@example.com.
But as a trader, you likely have access to better index-linked products anyway, like index and ETF futures and options, which is what I personally use. In a low-volatility market I can leverage the index 5x+ times with a capped 20% downside risk using an in-the-money LEAP call. Why even consider a leveraged ETF then?
david: I used Yahoo adjusted-close prices, which include the effects of dividends. I think SSO keeps the dividends and uses them to pay interest costs, and that adds to the lag.
qftz: You may not be using dividend adjusted prices. On close 6/21, adjusted for dividends, SPY was 123.97 and SSO was 68.32. At yesterday's close, SPY was 152.42 and SSO was 97.67. Gain for SPY is +22.9%, SSO is +43.0%. See the 6.1% lag in the nine month period? (43.0 / (2 x 22.9)). If our fund really doubled the return, we would have expected to make +45.8%.
Note that this math differs from the article because we have some additional days, and I did the straight gain here rather than taking the individual daily SPY prices, doubling them, and comparing them to SSO.May 23, 2007. 01:05 PM | 1 Like |Link to Comment
The Case Against Leveraged ETFs [View article]
Let's say you have $100k to invest and you want to create a 2X S&P 500 index fund. You buy index futures on $200k worth of the index. Every month, you settle and buy more futures. A year later, the index has gone up 10%. Your gains are 20%, or $20,000 right? Not quite. The futures cost you 0.4% x 2 x $100,000 per month, or 4.8% of $200,000 = $9600 for the year. You end up with only $10,400 in gains.
But, because it only takes 5% margin to own a future, you were able to keep $90,000 worth of cash in your account all year earning interest. Invested at 5%, you get an extra $4,500. So your gains are $14,900, or about 15% of your investment. Which is what we'd expect given basic leverage formulas: $2 x 10% - $1 x 5% = 15%.
This is what I mean when I say money costs money. An interest rate is built into any financial derivative you buy, and any leveraged investor has to exceed that cost of capital before they start making money.May 18, 2007. 02:33 AM | 1 Like |Link to Comment
Leveraged ETF Performance YTD [View article]Mar 19, 2009. 12:31 AM | 0 Likes |Link to Comment
Volcker's Capital Idea: Getting Back to Real Banking [View article]Mar 11, 2009. 12:43 AM | 0 Likes |Link to Comment
As Unemployment Grows, Tech Jobs Hang On [View article]Mar 9, 2009. 12:05 AM | 0 Likes |Link to Comment
Mark, I hope you don't mind the debate. As a writer I get lots of positive and negative feedback on my articles and always enjoy it because it means my ideas are out there. I probably helped inspired your article and I'm happy to have done so. Good luck with your research and writing.
Jan 28, 2009. 02:03 PM | 0 Likes |Link to Comment
Quick quiz:
1) If the S&P 500 falls 15%, what percentage increase do you need to recover your losses?
2) Now calculate the same for a double and triple leveraged ETF.
3) If you trade $20,000 of SSO every day and it has a built in 7% expense ratio, calculate how much you would save over a year if you switched to index futures with their built in broker margin rate of under 2%.Jan 26, 2009. 09:35 PM | 0 Likes |Link to Comment
Understanding Levered ETFs and Geometric Returns [View article]Jan 4, 2009. 08:17 PM | 0 Likes |Link to Comment
Direxion's Andy O'Rourke Talks Triple Leverage [View article]Dec 16, 2008. 05:40 PM | 0 Likes |Link to Comment
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product code: 128254
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Join Humpty Dumpty and all of his friends on this fun packed CD which features a bumper 35 favourite nursery rhymes.
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The Big Ship Sails
The Ants Go Marching
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Dance To Your Daddy
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Humpty Dumpty
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1 2 3 4 5
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Polly Put The Kettle On
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Row Row Row Your Boat
See Saw Margery Daw
Sing A Song Of Sixpence
Three Blind Mice
Tom Tom The Piper's Son
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Wind Your Bobbin Up
One Man Went To Mow
The Wheels On The Bus
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London Bridge Is Falling Down
This toy encourages your child to enjoy using their SENSES.
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Hotel Rio
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... excited at the thought! Once siesta time was over for the locals and we had recovered from our, let's be honest, near death, experience we headed to the shops to stock up on wine and cheese! Stopping on the way back for a cheeky little prosseco at an empty bar we were joined minutes later by what must be the only other English people in the area! What a totally random night! We also found out that Lucca, a town which a few people had mentioned was one ...
Day 48 - MSC transfer from Venice to Genoa
... met some great people and shared our travel stories....then conversation turned to about our pets and we started sharing photos. If I had WiFi I would have shown them the awesome video Jesika made of Romeo and Stitch. The receptionist had told us the bus trip from Venice to Genoa was 1hr 45mins. We left at 9am and arrived at the Genoa port terminal at 2pm. I was worried when we stopped for a lunch break on the way to Genoa as to how long ...
Monica from Genoa we LOVE you
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Home » News » Politics » City Hall
Ted Siefer's City Hall: Levasseur comes out swinging with lawsuit against city
Freshman Ward 10 Alderman Bill Barry has been meeting with department heads and will be sitting down with the city clerk and solicitor this week to discuss ideas for a uniform policy for how the city responds to right-to-know requests. Barry expects to have something to present to the Administration Committee later this month.
"Doing police work, you sometimes develop confidential informants," Barry said. "As aldermen, some of the information we get, there's no doubt in my mind, they don't want their name (released)."
Of course, Barry isn't a completely disinterested party in all of this. One of Girard's right-to-know requests concerns communications Levasseur had with critics of the Manchester Dog Park Association, which was founded and is run by Phil Greazzo, whom Barry defeated in November. Greazzo has accused Levasseur of siding with the dog park critics, along with a host of other misdeeds. More on this later.
In his suit, Levasseur accuses Girard of sending the city on a fishing expedition that netted "over 11,000 pages of emails containing Alderman Levasseur's name or email address." Girard insists that he made two very specific requests. And, as it turns out, the first of them originated with a request from, of all people, Levasseur himself.
It's Girard's subsequent request, however, that likely prompted Levasseur to seek an injunction. (Girard has already received the file containing the Union Leader-requested emails.)
- - - - - - -
Greazzo, for his part, is not relenting in his dogged pursuit of Levasseur, even after his censure last month.
But Clark's opinion stands. He told me the section of state law cited by Greazzo is merely "a template" for a municipal charter; Manchester has a different charter, one that lacks any mechanism for the removal of an alderman by his or her colleagues, Clark said.
Ted Siefer is the City Hall reporter for the New Hampshire Union Leader and New Hampshire Sunday News. He may be reached at email@example.com and followed on Twitter @tbsreporter.
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David Guetta
David Guetta, Tiësto, Hardwell Announced as Headliners for Ultimate Music Experience 2015
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Nicki Minaj Takes Over on the New David Guetta Jam, 'Hey Mama': Listen
Afrojack and Ester Dean are also on the track, but it's all about Miss Minaj.
Hear a Teaser of David Guetta, Nicki Minaj & Afrojack's 'Hey Mama'
The song will appear on Guetta's upcoming new album.
David Guetta Hits the Formula 1 Track in 'Dangerous' Video: Watch
The EDM producer realizes his F1 fantasies with real-life driver Romain Grosjean and lots and lots of models.
David Guetta Reveals 'Listen' Tracklist, Featuring Nicki Minaj, Sia, More
David Guetta is one step closer to releasing his next album, winkingly titled Listen.
David Guetta Releases 'Dangerous' Lyric Video, Featuring Sam Martin: Watch
The new track is an evolution in Guetta's sound, sidestepping the EDM bombast for some classic disco elements.
Coop Talks With David Guetta!
David Guetta was on with us this morning debuting his brand new single 'Dangerous'!
Calvin Harris, David Guetta, Avicii: Who is the World's Highest Paid DJ?
Fact: superstar DJs make a lot of money.
Listen to a Tease of David Guetta's New Single, 'Lovers on the Sun'
If the snippet of new song "Lovers of the Sun" is any indication, EDM superstar David Guetta is ready for summer.
Throwback Thursday With David Guetta!
Let's put this French house DJ and producer in the spotlight for Throwback Thursday!!