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1. A process for manufacturing nylon-66 yarn having a tenacity of at least 10 grams per denier comprising:

Description: BACKGROUND OF THE INVENTION

Although nylon-66 filaments today find uses in many end products because of their extraordinarily high tenacity, much research effort is devoted to improve the tensile strength of such filaments. For example, within the last decade the strength of nylon-66 filaments used to reinforce pneumatic tires has been increased from about 7 grams per denier to a present high of 9.5 grams per denier. A desideratum of long standing has been to produce nylon-66 filaments having at least 10 grams per denier by an economically feasible process. The present invention provides the art with such a process.

SUMMARY OF THE INVENTION

Nylon-66 filaments are melt spun from a high molecular weight polymer indicated by a formic relative viscosity of at least 50. The spinning conditions are selected to induce the formation of a low crystalline order in the yarn as spun. Immediately or at the latest within four hours after spinning the yarn is molecularly drawn. During any appreciable interval between spinning and drawing the yarn must be stored in a low humidity environment. From the drawing step the yarn is packaged at inordinately high tensions of about 1.0-1.5 g/denier or higher. The packaged filaments are stored in a low humidity environment from 1 to 10 days during which time a slowly increasing, maximum tenacity of at least 10 grams per denier is attained. Thereafter the filaments may be repackaged under normal, lower tension of 0.12-1.0 grams per denier and employed in conventional procedures for making textile products where strength of the yarn is an important factor.

DETAILED DESCRIPTION

In accordance with the present invention nylon-66 yarn having a tenacity of at least 10 grams per denier is produced when yarn is melt spun to have a low crystalline order and is then processed under critical conditions of drawing and storage. Factors shown to be important in producing low crystalline order spun yarn are such things as employment of conditions that rapidly quench the molten polymer into filaments and maintaining a melt pool residence time of long duration. Other process conditions can also be varied to insure the presence of low crystallinity in the yarn. The yarn quench rate can be varied by know techniques including lowering the temperature of the quenching medium which usually is air, increasing the flow of the quenching medium across the filaments undergoing spinning, and producing filaments of lower individual denier. Nylon-66 usually undergoes rather rapid crystallization. The degree of crystallization of unoriented nylon-66 filaments as a factor ultimately influencing the maximum obtainable tenacity was not heretofore considered important.

It is difficult to determine the absolute crystallinity of unoriented nylon-66 filaments with good precision. The application of known x-ray diffraction techniques gives satisfactory values of relative crystallinity. In determining crystallinity the first step is to set up a relative crystallinity index as follows: reference samples of the least crystalline nylon-66 filament and the most crystalline filament obtainable are prepared and X-ray diffraction patterns of these samples are made. In applying the X-ray diffraction technique to the undrawn filaments herein, it was found that the crystalline order thereof was so poorly developed that no significant difference between the sample and the selected standard nylon-66 filament of low crystallinity was determinable. Therefore, for all practical purposes the crystallinity of the present filaments as spun have crystallinity index values that approach zero.

The polymer from which the filaments of the present invention are spun must have a high formic acid relative viscosity (R.V.) of 50 or more. Polymer of high viscosities of 50-80 are most preferred. Relative viscosity is the ratio of absolute viscosity at 25 C. (in centipoises) of the solution of nylon in 90 percent formic acid (10 percent water and 90 percent formic acid) to the absolute viscosity at 25 C. (in centipoises) of the 90 percent formic acid. An 8.4 percent (by weight) solution of the nylon is used in the determination.

The effect of lag time between spinning of the filaments and drawing of the filaments is significant. The improved tenacities of 10 grams per denier and higher are not obtained when this lag time exceeds four hours. After four hours of storage the crystallinity of the filaments will have increased to an undesirably high level. In nylon filament production it is common practice to spin the filaments and without inducing much orientation therein to wind the filaments on a bobbin. The bobbin of undrawn filaments is stored for many hours under controlled temperature and humidity conditions, for example 75-80 F. and 7075 percent relative humidity. Another common practice involves spinning nylon filaments and

immediately drawing them. The procedure is known as spin-draw and can be conveniently modified to adapt the present concept. In spin-draw the drawing takes place within a second or so after spinning. Hence, observing the less than normal lag time requirement does not present a large problem.

Some orientation of the polymer molecules occurs during the spinning process. As is well known the degree of orientation is a function of spinning speed, polymer viscosity, quenching conditions, snubbing produced by yarn guides, etc. Such orientation is kept to minimal value by proper control of these factors affecting the orientation during spinning to provide the source of substantially molecularly unoriented yarn herein. Such orientation can be measured by determining the birefringence in filaments of the spun yarn in accordance with a well known testing technique. The birefringence of the undrawn source yarn of the present invention will normally be from 0.00 to 0.040.

Drawing the filaments involves increasing the length of the filaments and produces a more tenacious structure. When carried out below the softening temperature of the filaments, the drawing is often termed cold-drawing. Many drawing conditions and the thermal and mechanical treatments encountered during drawing will affect the tenacity and elongation of the draw filaments. In accordance with the present invention, the filaments are subjected to a thermomechanical experience so as to produce a yarn having a uniformly high tenacity and low elongation. To accomplish this drawing may be carried out in one or more stages with a total draw of about 4.5 x to 6.0 x at ambient temperature. The conditions are selected so that the drawn yarn has an elongation at break at about 11-20 percent and a tenacity of at least 8.5 up to 9.8 grams per denier. Elongations and tenacities herein are determined by ASTM Test D1380-62T.

One of the most important requirements for the high strength is that the drawn yarn be stored on a core under sufficient tensile stress of about 1.0-1.5 grams per denier. The actual stress cannot be measured directly after the yarn has been packaged. When the yarn is drawn and packaged on a drawtwister, the balloon tension as measured above the pigtail guide is taken. When the yarn is wound without twist, the tension measurement is made at the accessible location nearest the package.

It is important to control the temperature and the humidity in all stages of the process (spinning, drawing and yarn storage). The relative humidity during storage should not exceed 40 percent but may be as low as 10 percent. This is accomplished by controlling the humidity in the areas where these operations are carried out. One should employ a finish having a low moisture content. Normally, the finish is applied just before drawing is accomplished. During storage the moisture on the yarn should be about 1.1 - 2.3 percent. The temperature at which the drawn yarn is stored should be about 15-40 C.

EXAMPLE I

This example illustrates the practice of the invention. Nylon-66 was prepared in a conventional manner. The polymerization in an auto, clave was permitted to proceed until the polymer had a relative viscosity of 50. Chips were prepared from the polymer and melted using a standard grid-spinning apparatus. Thirty-five filaments having an ultimate drawn denier of 214 were extruded through a spinning chimney having a cross flow of air at 25 C. The flow across the filament was 150 cubic feet per minute, 50 percent more than normally considered optimum for spinning of such filaments. X-ray diffractometer scans were made in the freshly-spun yarn. The crystalline order was so poorly developed that the crystallinity index was estimated to be 0. A finish composed of an emulsion of water and oil was applied to the filaments during spinning just prior to take up on a spin bobbin. The amount of application of the finish was restricted to a minimum required for drawing the filaments without intolerable amount of breaks and filament wraps. Within 1 hour the filaments were drawtwisted using a draw ratio of 5.7. An extraordinarily heavy traveller was used during take up of the drawn filaments to insure that the filaments were packaged at high tensions. The balloon tension was measured to be 250 grams on the average. The tenacity was determined immediately and found to be 9.6 grams per denier. The tenacity was again measured at the end of 24 hours and was found to have increased to 10.8 grams per denier. Measurements then were made daily. Maximum tenacity of 11.0 grams per denier was obtained after 5 days of high tension storage. During spinning, drawing and storage the relative humidity was maintained at 35 percent. Crystallinity studies showed that the level of crystallinity of the stored filaments increased significantly as compared to the crystallinity of the freshly-drawn product.

EXAMPLE II

This example illustrates the importance of following the prescribed conditions of the present invention. Nylon-66 polymer of 46 relative viscosity was spun using a grid melter to produce 35 filaments having an ultimate total denier of 214. The cross flow of the air at 25 C. was 100 cubic feet per minute. A finish emulsion composed of water and oil was applied to the filaments. After 72 hours the filaments were drawn on a standard drawtwister at a ratio of 5.2. The balloon tension on the yarn was 150 grams on the average. The tenacity of the freshly drawn yarn was measured to be 9.1 grams per denier. After 5 days the tenacity had remained the same with no increase being noted. The spinning, drawing and storage of the filaments was at 65 percent relative humidity.

Other spinnings and drawings were conducted following this example but changing the relative viscosity to above 50 and some improvement in tenacity was noted. It was also observed that when the balloon tension was raised to 250 grams while using the high viscosity polymer, the tenacity increased

significantly after 5 days of being stored under such tension. Furthermore, as the lag time was reduced to four hours and the relative humidity of the ambient air to 35 percent while using the high viscosity polymer and high windup tension, yarns having tenacities in excess of 10 grams per denier were made. This illustrates that the process conditions set forth herein as critical are additive and very important in attaining the yarn of high tenacity.

There are numerous advantages associated with the present invention. First, one is able to produce nylon-66 yarn having extraordinarily high tenacity. Yarn of high tenacity can be effectively used in the construction of fabrics such as that used in building tires. Little modification of existing spinning and drawing equipment is required to practice the present process.

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ETHOD OF MAKING IMPROVED NOSE CAPS FOR MISSILES AND ROCKETS

United States Patent 3716610 Ads by Google Fiber Reinforcemt Open Mesh Laid Scrim Multi-Axial Warp Knitted Fabric www.kurabo.co.jp/english/ A method of making missile nose caps for extremely high temperature perfonce is disclosed. The method utilizes a typical material such as reinforcement fibers of silica or glass fiber tape inpregnated with a phenolic resin to form a panel. The panel which provides the proper orientation of the reinforcement fibers from a shingle angle to a perpendicular angle is shaped to a preform. The preform is placed in a mold and molded to a final shape and dimension required for the nose cap. If a rosette or rod tip is required, the tip is molded integrally with the nose cap. Ads by Google Carbon Fiber Lines Harper offers complete carbon fiber lines to produce carbon fiber www.harperintl.com Nylon Wrapping Tapes Home of AMOTAPES(R), the most durable wrappers you can find. www.amohr.com Carbon Fibre Tubes Ltd Suppliers of composite tubes. parallel/tapered, many finishes etc carbonfibretubes.co.uk Used Injection Machines Used injection molding machines JSW, Toyo, Fanuc, Sumitomo, Nissei www.esta-tech.com US Patent References: N/A Andersen et al. - April 1972 - 3655863

METHOD FOR FABRICATION OF ABLATIVE COMPONENTS Vasterling - October 1970 - 3532784

Method of making hollow articles of helically wound fibrous tape impregnated with resin Trimble - September 1968 - 3402085

Method and apparatus for forming a rocket nozzle structure Bluck - February 1968 - 3367817

Extrusion process for orienting fibers in molding material Barnett - June 1967 - 3328501

Application Number: 05/133921 Publication Date: 02/13/1973 Filing Date: 04/14/1971 Export Citation: Click for automatic bibliography generation Primary Class: 264/152 Other Classes:

156/195, 264/108, 264/294 International Classes: B29C69/00; B29C70/30; B29C70/34; B64G1/58; F42B15/34; B29C69/00; B29C70/04; B64G1/22; F42B15/00; (IPC1-7): B29D3/02; B32B1/10; B32B31/18 View Patent Images: Download PDF 3716610 PDF help Warnken

US Patent References:3081705 Articles having laminated walls March 1963

Ads by Google GRP Profiles and Gratings THE alternative to Steel From producer, from stock www.fibrolux.com Masking products Masking products: caps, plugs, polyester tapes and discs. www.global-mask.com Commissioning Engineering Preservation, functional, test mechanical, acceptance, start-up www.seaoil.com.br Primary Examiner: White, Robert F. Assistant Examiner: Sokal, Allen M. Claims: I claim

1. A method of making a nose cap for a missile or a rocket to achieve controlled orientation of reinforcement fibers of the impregnated tape used to construct said nose cap, said method comprising the steps of:

2. Method of claim 1 wherein said step of forming a panel is accomplished by wrapping said tape edgewise at a perpendicular angle to centerline of said first mandrel, said first mandrel being cylindrically shaped.

3. Method of claim 2 wherein prior to said step of placing preform in said suitable mold, a rosette or rod tip is properly positioned and molded integrally with the nose cap.

4. Method of claim 1 wherein said step of forming a panel is accomplished by wrapping said tape edgewise at a conical angle to centerline of said first mandrel, said first mandrel being cylindrically shaped.

5. Method of claim 4 wherein prior to step of placing preform in said suitable mold, a rosette or rod tip is properly positioned and molded integrally with the nose cap.

Description: BACKGROUND OF THE INVENTION

Ablative heat shielding is one of the most effective means for providing thermal protection to bodies exposed to extremely high temperatures and high heat fluxes such as are encountered in atmospheric re-entry of ballistic missile nose cones and space vehicles.

Various types of materials, which may be classified as glassy, subliming or intumescent, have been used for ablative cooling, and normally more than one of these types have been employed in combination with one another as a composite ablator. The most widely used composite has been comprised of silica fiber or glass fiber tape impregnated with phenolic resin.

A major problem has been related to flowoff, which term is applied to the loss of liquid mass. When the ablative material melts a glassy layer is formed which flows under the action of aerodynamic shear. When a surface indentation occurs by spalling of the char surface, a liquid glass flows into the hole and smooths the surface again. Therefore, it has been necessary to provide reinforcement fibers to anchor the molten glassy layer and char surface to the underlying unaffected material. To accomplish the anchoring effect for the highest degree of efficiency, it has been shown that the reinforcement fibers should be oriented at an angle from a shingle angle to a perpendicular angle to the surface of the nose cap or missile structure.

Present methods of achieving proper orientation of the reinforcement fiber involve:

A. Stacking circular discs of resin-impregnated cloth (comprised of silica or glass fibers) and molding into a cylindrical billet which is subsequently cured and then, machined to shape. This procedure provides perpendicular orientation of the reinforcement fibers; or

B. Stacking cone shaped discs of resin-impregnated cloth into a billet and molding, followed by machining to shape. This procedure gives shingled orientation; or

C. Tape wrapping an impregnated tape onto a conical mandrel and molding to shape. The tape can be wrapped on end to give a perpendicular orientation, or a shingle angle orientation.

The tip of the nose cap can be formed by rosetting or by a rod molded or bonded in place in the center of the nose cap. The rod can be wrapped from cloth, or can be formed of parallel filaments.

Desirable would be a method for forming a nose cap for a missile or rocket which method does not involve using a series of fiber discs to form a cylindrical billet which requires time consuming machining to shape.

Therefore, an object of this invention is to provide a method for forming a nose cap for a missile or rocket to obtain proper orientation of the reinforcement fibers without the need for stacking of fiber discs to form a cylindrical billet.

Another object of this invention is to provide a method for making a nose cap for a missile or rocket to enable substantially all machining to be accomplished prior to final molding of the nose cap (with or without a rosette or a rod tip) to its required geometrical shape.

A further object of this invention is to provide a method for making a nose cap for a missile or a rocket having increased strength due to helical formation of tape.

Still, a further object of this invention is to provide a method for making a nose cap for a missile or rocket which method results in a considerable savings in material and labor utilized.

SUMMARY OF THE INVENTION

The method of this invention comprises the formation of a panel by wrapping tape on a cylindrical mandrel, slitting, and removing the panel from the mandrel. The panel is constituted of a tape that is impregnated with a material selected from organic resins and ceramics or combinations thereof (e.g. phenolic resin, silica or glass fibers, or the like). The panel is uncured at this stage which permits the reshaping of the panel by heating below its cure temperature (e.g. curing temperatures and catalysts to promote curing are well established in the art) coupled with pressure to also densify if necessary. The panel may be shaped to a predetermined geometrical contour by the described procedure to follow. The panel is wrapped spirally around a suitable mandrel which defines the inside contour of the nose cap. At this stage of processing the material is known as a preform. The preform may be machined or cut to adjust the weight and dimension for proper molding. The preform is then placed in a mold (along with a rosette or rod tip if required) and molded to the final shape and dimensions required for the outside contour of the nose cap.

BRIEF DESCRIPTION OF THE DRAWINGS

Selected stages of the method of this invention are illustrated in the drawings as follows wherein:

FIG. 1 shows the formation of a panel on a mandrel;

FIG. 2 shows a panel being removed after slitting; FIG. 3 shows a panel removed and in a flexible bag; FIG. 4 shows a panel being wrapped spirally around a mandrel; FIG. 5 shows a panel which is termed a "preform" for molding; FIGS. 6 A, B, and C show a rosette tip in various stages of formation along with a cross section of a nose cap with a rosette tip moulded in place; FIGS. 7 A, B, and C show rod tip types along with a cross section of a nose cap with a rod tip molded in place;

FIG. 8 shows a completed nose cap with a rod tip molded in place (prior to trimming the excess length of the rod); FIG. 9 shows a completed nose cap with a portion cut away to show perpendicular orientation of reinforcement fibers; and FIG. 10 shows a completed nose cap with a portion cut away to show shingle angle orientation of reinforcement fibers.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The missile or rocket nose cap of this invention provides the most pointed section of the missile or rocket which is subjected to the most extreme heat as the missile or rocket re-enters the atmosphere. The cap may be fabricated with or without a rosette or rod tip which makes up the outermost tip of the cap. A rosette is formed from a convolute wrap of layers of silica or glass fiber tape which is impregnated with phenolic resin. The convolute wrap is generally distorted into a conical shape for filling out the outermost tip of a missile or rocket nose cap. A rod tip may be made of a rod shaped member formed from wrapped impregnated tape or parallel filaments arranged in a rod shape. The rod tip is used in a similar fashion to the rosette tip to fill out the outermost portion of the nose cap. The excess of rosette tip or rod tip may be trimmed to the desired finish and contour.

References to the accompanying drawings are made wherein the first stage formation, 10 of FIG. 1, of a panel on a mandrel, begins by the selecting of a suitable mandrel 12 followed by the wrapping of silica fiber or glass fiber woven tape impregnated with a ceramic or an organic resin 13 to form a panel 14 on the mandrel. The number 15 of FIGS. 1, 1A, 2A, 2B, and 3 designates a typical tape weave of fibers which

is shown as 15 (exclusive of the impregnation material, ceramic or resin) in FIG. 1A which is an enlarged view for clarity. The tape is oriented with its width either perpendicular to (edgewise) or at a conical angle to the mandrel centerline, depending on whether the nose cap is to have perpendicular or shingle angle orientation of the reinforcement. After the required length of winding (L) is attained (determined by the cone angle and desired helical wrapping angle required for a particular nose cap), the tape, wrapped edgewise at a perpendicular angle to the mandrel, is slit in a length-wise direction of the mandrel and the panel 14 is removed as shown in FIG. 2 A. FIG. 2 B shows the tape, with winding length (L), after being wrapped edgewise at a conical angle to the mandrel 12 and after being slit in a lengthwise direction of the mandrel to remove the panel 14. The panel will have perpendicular angle oriented reinforcement fibers or shingle angle oriented reinforcement fibers depending upon whether the plane of the tape was perpendicular to (edgewise) or at a conical angle to the mandrel centerline respectively, during the previous wrapping operation. The preceding statement describes the results achieved from slitting a woven tape which has been wrapped as described. Further, it follows that slitting a woven tape which has been wrapped as noted will cause the fibers to be oriented in both a substantially vertical and horizontal arrangement in the panel 14. The substantially vertically arranged fibers of the panel will be either perpendicular or shingle angle oriented when further processed as described. Also, the substantially horizontally arranged fibers of the panel will have circumferential orientation when further processed as described. The panel is uncured at this stage of method. The uncured panel may be cut to the required geometrical shape, and the panel may be densified by subjecting it to heat below the cure temperature coupled with pressure. One means for applying pressure is by enclosing the panel in a sealed flexible bag (shown as 16 in FIG. 3) and exhausting the air from the bag, thus applying approximately 15 psi pressure to the panel 14.

The number 17 of FIGS. 1, 1A, 2A, 2B, 3, 4, 5, 6A, 7A, and 8 depicts typical reinforcement fiber ends.

FIG. 4 shows an uncured panel 14 being wrapped spirally around a mandrel 18 which defines the inside contour of the nose cap. A rod tip 20 is shown fitted to the mandrel. After the wrapping operation is performed the nose cap at this stage is termed a preform as illustrated by 22 of FIG. 5. The uncured preform may be easily machined at this stage, to adjust its weight and dimensions for proper molding. The preform is then placed in a suitable mold (not shown) and molded to final shape and dimensions required for the outside contour of the nose cap. If a rosette or rod tip is required, the tip can be molded integrally with the nose cap during the molding to final shape and dimensions.

FIG. 6 A shows a rosette tip 19 in a convolute wrap. FIG. 6 B shows a rosette tip 19 in a convolute wrap distorted into a conical shape. FIG. 6 C shows a cross sectional view of a nose cap 24 with shingle angle orientation of the reinforcement fibers 28 and with a rosette 19 molded in place.

FIG. 7 A shows the type of rod tip generally referred to as cloth wrapped rod 21. FIG. 7 B shows the type of rod tip generally referred to as a parallel filiament rod 23. FIG. 7 C shows a cross sectional view of a nose cap 25 with perpendicular orientation of the reinforcement fibers 26 and with a rod tip 23 molded in place.

FIG. 8 shows a substantially completed nose cap 25 with a rod tip 20 molded in place (prior to trimming the excess length of the rod).

FIG. 9 shows a completed nose cap 24 having a portion cutaway and enlarged to show reinforcement fibers 26 which are oriented at a perpendicular angle.

FIG. 10 shows a completed nose cap 24 having a portion cutaway and enlarged to show reinforcement fibers 28 which are oriented at a shingle angle.

The advantages of the method of this invention over the prior art method for making nose caps are: 1. Reduced cost due to speedy tape wrap as compared to stacking discs. 2. Greatly increased strength due to helical formation of tape. Helical formation of tape eliminates weak resin planes perpendicular to the axis of the nose cap. 3. Any necessary machining is done prior to final molding, when material is easily machined. The method of this invention is suitable for all variations in tape weave and tape material, all variations in organic resins, as well as ceramic compositions used to impregnate tape, and for all variations in nose cap geometry, helix angle of wrap, etc.

Nylon 66 Nylon 66 adalah rekayasa semi-kristal termoplastik dengan aplikasi universal. Karakteristik utama dari Nylon 66 adalah: Ia memiliki sifat baik geser

Sangat abrasi tahan Tahan terhadap minyak banyak, gemuk, diesel, bensin, cairan pembersih Kuat dan tangguh Kaku Isolasi elektrik Mudah machined Mudah dilas dan berikat Bidang disukai untuk penggunaan Nylon 66 adalah:, mekanik otomotif rekayasa, transportasi dan teknologi konveyor, tekstil, kemasan dan pengolahan kertas mesin, pencetakan dan minuman mengeluarkan mesin, peralatan rumah tangga, listrik teknik, mesin bangunan, dan mesin pertanian aplikasi Populer untuk penggunaan Nylon 66 adalah: Gear roda Gesekan strip Semak-semak, spindle kacang Piston panduan Kastor Dampak piring Gesekan bantalan Conveyor sekrup Cam disk Rope pulley Plug bagian Redaman piring Nylon 66 is a Semi-crystalline engineering thermoplastic with universal applications.

The main characteristics of Nylon 66 are : - It has good sliding properties - Is very abrasion resistant. - Resistant to many oils, greases, diesel, petrol, cleaning fluids - Strong and tough - Rigid - Electrically insulating - Easily machined - Easily welded and bonded The preferred fields for the use of Nylon 66 are : mechanical engeenering, automotive engeenering, transport and conveyor technology, textile, packing and paper processing, machinery, printing and drinks dispensing machinery, household articles, electrical engeenering, building machinery, and agricultural machinery. Popular applications for the use of nylon 66 are : Gear wheels Friction strips Bushes, spindle nuts Piston guides Castotrs Impact plates Friction bearings Conveyor screws Cam discs Rone pulley Plug parts Damping plates

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Nylon
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In 1928 E. I. du Pont de Nemours & Company (Du Pont) launched one of its first basic research programs and hired Wallace Hume Carothers to run it. He was brought to Du Pont in part because his fellow researchers at Harvard University and the University of Illinois had called him the best

Figure 1.

Figure 2. An amide unit.

synthetic chemist they knew. The program he supervised was designed to investigate the composition of natural polymers such as silk, cellulose, and rubber. Many of Carothers's efforts related to condensation polymers were based on his deduction that if a monofunctional reactant reacted in a certain manner in forming a small molecule, then similar reactions that employed a comparable reactant, but with two reactive groups, would form polymers. (See Figure 1.)

The amide unit (found in polyamides) shown in Figure 2 is the same connective grouping that is found in proteins.

Although the Carothers group had worked with both polyesters and polyamides, they initially emphasized their work on the polyesters, as polyesters were more soluble and easier to work with. Julian Hill, a member of the Carothers team, noticed that he could form fibers if he separated a portion of a soft polyester material using a glass stirring rod and pulled it away from the clump. But because the polyesters had softening points that were too low for their use as textiles, the group returned to its work with the polyamides. The researchers found that fibers could also be formed from the polyamides, similar to those formed from the polyesters. The strength of these fibers approached, and in some cases surpassed, the strengths of natural fibers. This new miracle fiber (nylon) was introduced at the 1939 New York World's Fair, in an exhibit that announced the synthesis of a wonder fiber from "coal, air, and water" an exaggeration but nevertheless eye-catching. When the nylon stockings were first offered for sale in New York City, on May 15, 1940, over four million pairs were sold in the first few hours. Nylon stocking sales took a large drop during World War II when it became publicized that nylon was needed to make parachutes.

The polyamides (nylons) were given a special naming system. Nylons made from diamines and dicarboxylic acids are designated by two numbers, the first representing the number of carbons in the diamine chain (a) and the second the number of carbons in the di carboxylic acid (b). (See Figure 3.)

The nylon developed by Carothers at Du Pont was nylon 6,6. Because of the importance of starting out with equal amounts of the two reactants, salts of the diamine and of the diacid are made and then used in the commercial synthesis of nylon 6,6. (See Figure 4.) STEPHANIE KWOLEK (1923 )

Stephanie Kwolek has seventeen patents, the first of which is for Kevlar. After creating a new polymer, she would spin them into fibers for strength and flexibility testing. Material for fibers of Kevlar was cloudy white instead of molasses brown, the first indication that she had uncovered an exceptional polymer.

Valerie Borek

Nylon 6,6 (or simply nylon 66) is the largest volume nylon used as fiber, film, and plastic. About 1,134 million kilograms (2,500 million pounds) of nylon 66 were produced for fiber applications in 2000. Nylon 66 is used to make tire cord, rope, clothing, thread, hose, undergarments, rug filament,

Figure 3.

socks, dresses, and more. Because of the presence of polar units in nylons, similar to the presence of polar units in proteins, materials made from nylon have a nice "feel" to them. Nylon materials also attract odors (many everyday odors are polar in nature) and are easily stained. Most textile and fabric products are treated to repel unwanted odors and stainmaking materials.

Nylon 66 was the first engineering thermoplastic, and up until 1953 represented all of engineering thermoplastic sales. The term "thermoplastic" denotes a material that can be melted through heating. The term "engineering thermoplastics" describes a plastic material that can be cut, drilled, or machined. About 680.4 million kilograms (1,500 million pounds) of nylons were produced in the United States in 2000 for thermoplastic use. Nylon 66 plastic is tough and rigid. It has a relatively high use temperature (to about 270C or 518F), and is used in the manufacture of products ranging from automotive gears to

hairbrush handles. Molded nylon 66 is used to make skate wheels, motorcycle crank cases, bearings, tractor hood extensions, skis for snowmobiles, lawnmower blades, bicycle wheels, and so on.

Most polymers, when heated, progress from a glasslike solid to a softer solid, and then to a viscous "taffylike" material that is most amenable to heat-associated fabrication. In the case of nylon 66, the transition from the solid to the soft stage is abrupt, requiring that fabrication be closely watched.

The presence in nylons of polar groups results in materials that have a relatively high glass transition temperature (T g , the point at which segmental mobility begins) and high melting point (the point at which entire polymer chain mobility begins), so that, unlike many vinyl polymers such as polyethylene and polypropylene (which must be at temperatures above their glass transition temperatures to possess needed flexibility), nylons, and many other condensation polymers, function best in contexts in which strength, and not flexibility, is the desired attribute.

Figure 4.

Figure 5.

Because they have these polar groups that also allow for hydrogen bonding , nylons and most condensation polymers are also stronger, more rigid and brittle, and tougher in comparison to most vinyl polymers. Nylons are also "lubrication-free," meaning they do not need lubricant for easy mobility; thus they can be used to make mechanical bearings and gears that do not need periodic lubrication.

During the early 1950s George deMestral, after walking in the Swiss countryside, noticed that he had cockleburs caught in his jacket. He examined the cockleburs and noticed that they had tiny "hooks." His cotton jacket had loops that "held" the cockleburs. He began playing with his observations and making combinations of materials one having rigid hooks and the other having flexible loops or eyes. Today, Velcro, the name given to the nylon-based hook-and-eye combination, uses nylon as both the hook material and the eye material. Polyester is sometimes blended with the nylon to make it stronger.

(Polyesters have also been used to make hook-andeye material.) Velcro is used to fasten shoes, close space suits, and it has many other applications.

Nylon 6, produced via the ring-opening reaction of the compound caprolactam is structurally similar to nylon 66 and has similar properties and uses. It is widely used in Europe in place of nylon 66, but not in the United States. (See Figure 5.)

Nylon 6,10 and nylon 6,12 are also commercially available. Because of the presence of the additional methylene ( CH 2 ) groups that are hydrophobic (water-hating), these nylons are more resistant to moisture and more ductile than nylon 66.

DSM (once called Dutch State Mines) introduced nylon 4,6 (Stanyl) in 1990. It is produced via the condensation reaction between adipic acid and 1,4-diaminobutane, produced from renewable resources. Stanyl can withstand temperatures up to about 300C (570F), allowing it to occupy a niche position between conventional nylons and high-performance materials. (See Figure 6.)

Figure 6.

Figure 7.

Several new commercial ventures are based on using natural, renewable starting materials (instead of petrochemicals). These products are known as "green" products because they are made from renewable resources and can be composted. The compound 1,4-butanediamine, used to produce nylon 4,6 from natural material, is such a green product.

In general, more crystalline nylons are fibrous whereas less crystalline nylon materials are more plastic in behavior.

Several aromatic polyamides, called aramids, have been produced. These materials are strong, are stable at high temperatures, and have good flame-resistance properties. Nomex (made from m diaminobenzene and isophthalic acid) is used to make flame-resistant clothing and the thin pads used in space shuttles to protect sintered silica-fiber mats from stress and vibration during flight. Kevlar (made from p -diaminobenzene and terephthalic acid) is structurally similar to Nomex and by weight is stronger than steel. It is used in the manufacture of so-called bullet-resistant clothing. Because of its outstanding strength to weight ratio, it was used as the skin covering of the human-powered Gossamer Albatross, flown over the English Channel.

Aramids are also widely used as the fibers that are part of space-age composites and in the manufacture of tire cord and tread. (See Figure 7.)

SEE ALSO C AROTHERS , W ALLACE ; M ATERIALS S CIENCE ; P OLYMERS , S YNTHETIC .

Charles E. Carraher Jr. Bibliography

Allcock, Harry R.; Lampe, Frederick W.; and Mark, James E. (2003). Contemporary Polymer Chemistry, 3rd edition. Upper Saddle River, NJ: Pearson/Prentice Hall.

Amato, Ivan (1997). Stuff: The Materials the World Is Made Of. New York: Basic Books.

Campbell, Ian M. (2000). Introduction to Synthetic Polymers, 2nd edition. New York: Oxford University Press.

Carraher, Charles E., Jr. (2003). Giant Molecules: Essential Materials for Everyday Living and Problem Solving, 2nd edition. Hoboken, NJ: Wiley.

Carraher, Charles E., Jr. (2003). Polymer Chemistry, 6th edition. New York: Marcel Dekker.

Collier, Billie J., and Tortora, Phyllis G. (2000). Understanding Textiles. Upper Saddle River, NJ: Prentice Hall.

Craver, Clara E., and Carraher, Charles E., Jr. (2000). Applied Polymer Science: 21st Century. New York: Elsevier.

Elias, Hans-Georg (1997). An Introduction to Polymer Science. New York: Wiley.

Morawetz, Herbert (1985). Polymers: The Origins and Growth of a Science. New York: Wiley.

Morgan, Paul W., and Kwolek, Stephanie L. (1959). "The Nylon Rope Trick." Journal of Chemical Education 36:182 184.

Rodriguez, Ferdinand (1996). Principles of Polymer Systems, 4th edition. Washington, DC: Taylor & Francis.

Salamone, Joseph C., ed. (1996). Polymeric Materials Encyclopedia. Boca Raton, FL: CRC Press.

Stevens, Malcolm P. (1990). Polymer Chemistry: An Introduction, 2nd edition. New York: Oxford University Press.

Thrower, Peter (1996). Materials in Today's World, 2nd edition. New York: McGraw-Hill.

Tonelli, Alan E. (2001). Polymers from the Inside Out: An Introduction to Macromolecules. New York: Wiley-Interscience. Ads by Google

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