CN1602375A - Method of imparting permanence to shaped non-thermoplastic fibrous materials - Google Patents

Abstract

The present invention relates to a method for imparting permanence to a shaped non-thermoplastic fibrous material, comprising subjecting the shaped non-thermoplastic fibrous material to a constant and uniformly distributed electromagnetic field generated by a single-mode transverse magnetic 010-type cylindrical resonant cavity microwave reactor under low tension, wherein the uniformly distributed electromagnetic field operates at a frequency of 5 MHz to 500 GHz; the shaped non-thermoplastic fibrous material is subjected to the uniformly distributed electromagnetic field at a speed of 0.01 to 1200 m/min; the shaped non-thermoplastic fibrous material is heated at a rate of 300°C/s or less; and the shaped non-thermoplastic fibrous material comprises at least one polymer structure containing amino groups and at least 0.05% by weight of an aqueous composition. The present invention also relates to a permanently shaped non-thermoplastic fibrous material, particularly a permanently twisted fiber, obtained by the method, and to structures comprising such a shaped non-thermoplastic fibrous material.

Description

Method of imparting permanence to shaped non-thermoplastic fibrous materials

field of invention

The present invention relates to a method of imparting permanence to shaped non-thermoplastic fibrous materials containing amino groups. It also relates to permanently shaped fiber materials obtained from this method.

current technology

Much textile processing involves the twisting process of multifilament fibers, which are then fabricated into woven, knitted or braided structures. Twisting is the process of combining filaments into a yarn by arranging them in a helical pattern or by combining two or more parallel individual yarns into a plied thread or rope. Twist is generally expressed as: the number of turns per unit length of fiber around its longitudinal axis, that is, the number of turns per meter, abbreviated as tpm. Multifilament yarn twisting is generally considered a process that helps provide high cohesion to the yarn. It is also believed to be the proper filament arrangement for optimal load distribution. Twisting also serves to impart a uniform morphology to the surface of the yarn for better bonding of the matrix, such as rubber, which in turn contributes to more efficient stress transfer and better mechanical adhesion between the matrix and reinforcing fibers. good. So in general, the twisting process is used to increase strength, smoothness and uniformity, or to achieve specific effects on the yarn.

To this end, it is of interest to provide fibers that are stabilized in a specific shape, for example in twisted form. US Patent 5,794,428 discloses a method of permanently setting the twist of thermoplastic fibers.

However, high modulus, high strength non-thermoplastic fiber materials and, more generally, crystalline fibers such as aramid fibers are difficult to stabilize at medium to high twist levels because of their inherent tendency to untwist rapidly.

For low to medium twist levels it is known to apply so-called S-twist and Z-twist arrangements, a two-step process combining S-twist and Z-twist yarns to form a stable combined system. However, in the case of non-thermoplastic fibers containing amino groups, for high tpm of eg 1670 dtex yarn above one hundred twists per meter, applying this process is impractical, both in terms of productivity and uniformity .

Now, it has been found that by subjecting the shaped fiber material to a constant and uniformly distributed electromagnetic field generated by specific microwaves, permanent properties can be imparted to the shaped fiber material, even if the material is a high modulus or high strength amino group containing Groups of non-thermoplastic materials can do the same.

Microwave heating is a well known process in both industrial and domestic applications. US 5,175,239 and US 5,146,058 disclose the application of microwave heat to treat para-aramid fibers in order to obtain fibers with internal cracks in the cross-section of the filaments.

Summary of the invention

One aspect of the present invention is a method of imparting permanence to a shaped non-thermoplastic fibrous material comprising subjecting the shaped non-thermoplastic fibrous material under low tension to a microwave reactor with a single-mode transverse magnetic type 010 cylindrical resonator ( Single mode Transverse Magnetic 010mode cylindrical resonant cavity cavity microwave reactor) produces a constant and uniformly distributed electromagnetic field,

- The uniformly distributed electromagnetic field operates at a frequency of 5MHz to 500GHz,

- The formed non-thermoplastic fiber material is processed by a uniformly distributed electromagnetic field at a speed of 0.01 to 1200m/min,

- the temperature rise rate of the formed non-thermoplastic fiber material is below 300°C/s,

- The shaped non-thermoplastic fibrous material comprises i) at least one polymeric structure containing amino groups and ii) at least 0.05% by weight of an aqueous composition.

Another aspect of the invention is a permanently shaped non-thermoplastic fibrous material obtainable or obtained by the above method.

Another aspect of the invention is a structure comprising the permanently formed non-thermoplastic fibrous material of the invention. The structure can be woven, knitted, bias knotted, spiral, felted, unidirectional laminated or nonwoven. Nonwoven structures may include webs, wadding, felts.

Another aspect of the invention is a method of imparting permanence to a shaped non-thermoplastic fibrous material comprising subjecting said shaped non-thermoplastic fibrous material to a The action of a constant and uniformly distributed electromagnetic field.

Another aspect of the invention is a method of imparting permanence to twisted para-aramid fibers comprising subjecting said fibers to a single-mode transverse magnetic 010 type cylindrical resonance at a tension of less than 0.2 gpd. The effect of a constant and uniformly distributed electromagnetic field generated by a cavity microwave reactor,

- The uniformly distributed electromagnetic field operates at a frequency of 5MHz to 500GHz,

-The fiber is processed through the microwave reactor at a speed of 0.01～1200m/min,

-The heating rate of the fiber is below 300°C/s,

- the fibers comprise at least 0.05% by weight of an aqueous composition.

The permanent shape of the non-thermoplastic fiber material may be desired for a particular application, for example, to impart a modulus of stretch to the fiber independent of its elastic properties. For example, such permanently shaped fibers can be used in rubber composites in order to reduce the difference in elongation between the fiber and the rubber.

With respect to the method of the present invention, non-thermoplastic fibers can be imparted with permanent twist up to maximum twist processing levels. It is generally considered that the maximum twist processing level is the level of twist that does not induce breakage or breakage of the filaments that make up the twist system. For example, the level of permanent twist can reach 1000 tpm for a 1670 dtex yarn made from para-aramid fiber. The fibers are thus free of internal cracks, such as can occur in the cross-section of the filament, as described in US 5,175,239. The fiber has high cohesion and high stability. In particular, twisted non-thermoplastic fibers can be stabilized in a highly uniform manner with the method of the invention. This high degree of stabilization can be done at any level of twist necessary for any subsequent processing such as spiraling, knitting, weaving, braiding, felting, etc., or for embedding in an elastic or composite matrix.

This permanently twisted non-thermoplastic fiber can be used as sewing thread, as a fiber to reinforce various substrates, or as a fiber in woven or knitted fabrics, enabling high cohesion and stability in woven or knitted structures. Woven or knitted structures made from permanently twisted non-thermoplastic fibers of the present invention are highly dimensionally stable and free from residual torque effects. This structure is also stretchable.

The method of the invention also has the advantage of eliminating the intermediate steps necessary to maintain the shape of the fibrous material in the prior art methods.

Brief description of the drawings

Figure 1 is a schematic diagram of the process according to the invention when the fibrous material is a fibre.

Figure 2 shows a perspective view of a microwave reactor with linear track fiber routing.

FIG. 2 a shows a constant and uniformly distributed electromagnetic field generated by a microwave reactor according to FIG. 2 .

Figure 3 shows a perspective view of a microwave reactor with sinusoidal trajectory fiber routing.

Figure 4 is a scanning electron micrograph of a cross-section of the tow of Example 1 of the present application.

Figure 4a is a related close up view of the monofilament of Figure 4 .

Figure 5 is a scanning electron micrograph of a cross-section of the tow of Example 2 of the present application.

Figure 5a is a related close-up view of the monofilament of Figure 5 .

Figure 6 is a scanning electron micrograph of a cross-section of the tow of Example 3 of the present application.

Figure 6a is a related close up view of the monofilament of Figure 6 .

Figure 7 is a scanning electron micrograph of a cross-section of the tow of Example 4 of the present application.

Figure 7a is a related close up view of the monofilament of Figure 7 .

Figure 8 is a scanning electron micrograph of a cross-section of the tow of Example 5 of the present application.

Figure 8a is a related close up view of the monofilament of Figure 8 .

Detailed description of the drawings

Referring to Figure 1, fibers 11 from tension feed adjustment roll 12 are fed through rolling godet roll 13 to ensure that the fibers are aligned as desired. The fibers are fed to a pretreatment unit 14 where they are soaked with water so that the fibers have a water content of at least 0.05% by weight. The water pretreatment can optionally be carried out in the case of fibers which have not been dried and which already contain more than 0.05% by weight of water. Alternatively, the pretreatment device 14 can be a dehydration device, so that the water content of the raw material fiber 11 meets the requirements. It can also be temperature-regulated pretreatment and/or coating or plasma or any suitable treatment device. Optionally, the pretreatment device can be a twisting device or any texturing device imparting shape to the filament. The fiber is fed from the pretreatment device 14 to the tension control roll 15 and then into the microwave resonant cavity reactor 16 . The process can be modified to include several resonant cavity reactors, in any suitable arrangement, either in series or in parallel. The microwave electromagnetic field is controlled by a microwave controller 17 . The fibers are kept in the lumen at a relatively low tension, preferably a tension suitable for maintaining the shape of the fiber material, preferably a tension of 0.2 g/d or less. The fiber is fed into the tension control roller 18 from the outlet of the microwave resonant cavity reactor, and then to the godet roller 19. Thereafter, the fibers are fed into a roller guide 20 to ensure that the fibers are aligned as desired. The fibers are fed to a post-treatment unit 21 where they can be further heated, dried, or subjected to surface treatment such as coating or plasma treatment, or any other suitable post-treatment. Applying a post-processing device is optional. The fiber is then passed through a rolling tension guide 22. Finally, the fibers are wound using a tension-controlled fine winder 23 .

The Figure 1 process can be further modified to process several fibers simultaneously.

Referring to Figure 2, there is depicted a cylindrical microwave resonant cavity reactor, designated 30, suitable for use in the present invention. The reactor comprises a chamber defined by a cylinder 31 designed to support the required resonance conditions of the TM010 (transverse magnetic 010) type and at a center frequency, typically set at 915 MHz or 2450MHz. Figure 2 provides suitable dimensions for the 915MHz resonant condition. A typical device is a 915MHz, 400W amplifier, which works with a 28VDC, 53A switching power supply, or a 915MHz, 800W amplifier, which works with a 28VDC, 107A power supply.

Circular cross-section reactors combine a radially symmetric electromagnetic field distribution with a well-defined axial electromagnetic field distribution. By "circular cross-section" is meant a circular or inert circular cross-section.

The microwave source 32 excites microwaves. Fibers 11 enter through inlet 33 and exit through outlet 34 . The fiber course is linear.

With respect to Figure 3, a cylindrical microwave resonator reactor 40 is depicted, similar to that shown in Figure 2, but also incorporating a ceramic wire guide 41 to make the fiber path sinusoidal.

detail

The term "fibrous material" as used herein includes uncut fibers such as filaments, staple fiber structures, staple fibers, microfibers, multifilaments, cords, yarns, fibers, felts, fabrics, woven, knitted, braided, spiral , felted structures or non-woven forms. Fibers can be made into staple structural yarns spun into staple fibers, uncut staple yarns, or draft cut yarns that can be described as intermediate yarns between staple and filament yarns. Yarns, fibers, woven, knitted, braided, helical, felted structures or nonwoven forms can be made from filaments, staple fibers or pulp.

The term "shaped fibrous material" as used herein includes fibrous material as defined above which has been subjected to any forming process such as twisting, weaving, braiding, crimping, plying, knitting, spiraling, felting, unidirectional laying or any other deformation etc. Any fibre, fabric, textile, garment, fibrous structure or finished product manufactured.

The term "aqueous composition" as used herein includes water, solvents and/or mixtures thereof, in the form of solutions, emulsions or dispersions. It can contain salts, polymers or other emulsified, dispersed or dissolved compounds. Preferably, the aqueous composition is water. The aqueous composition may be present in the fiber material in free and/or bound form. In a preferred embodiment of the invention, the aqueous composition exists in two forms, ie in free form and in bound form.

The term "thermoplastic" as used herein means a material that is soft when subjected to heat and returns to its original condition when cooled to room temperature. Non-thermoplastic materials do not soften when subjected to heat.

Non-thermoplastic fibrous materials suitable for the present invention include any natural or man-made non-thermoplastic fibrous material comprising at least one polymeric structure containing amino groups. The term "amino group" as used herein includes amine groups, amide groups and/or amino acid groups. Man-made and natural fiber materials including polyamide, polyamine, polyimide and polybenzimidazole (PBI), polyphenylene benzobisoxazole, natural silk, spider silk, hair with amino acid sequences and all natural fibers . These groups can be part of linear or branched, cyclic or heterocyclic, saturated or unsaturated, aliphatic or aromatic chemical structures. Preferred polymer structures containing amino groups include polyamides, polyamines, polyimides, aramids, and blends and mixtures thereof. Preferably, the polymer structure containing amino groups is an aramid.

Aramids are polymers which consist partly, predominantly or entirely of aromatic rings which are connected via urea bridges or optionally also via other bridge structures. These aramid structures can be illustrated by repeating units of the general formula:

(-NH-A1-NH-CO-A2-CO) _n

Wherein: A1 and A2 are the same or different, represent aromatic and/or polyaromatic and/or heteroaromatic rings, and may also be substituted. Typically, A1 and A2 can be independently selected from 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 4,4'-biphenylene, 2,6- Naphthylene, 1,5-naphthylene, 1,4-naphthylene, phenoxyphenyl-4,4'-diyelen, phenoxyphenyl-3,4'-diyelen Subunit (diylen), 2,5-pyridyl and 2,6-quinolinyl, which may or may not be substituted with one or more substituents, which may include halogen, C ₁ to C ₄ Alkyl, phenyl, alkoxycarbonyl, C ₁ -C ₄ -alkoxy, acyloxy, nitro, dialkylamino, thioalkyl, carboxyl and sulfonyl. The -CONH- group may also be substituted for a carboxyhydrazide (-CONHNH-) group, an azo or an azo oxide group.

These aromatic polyamides are generally prepared by polymerizing diacid chlorides, or the corresponding diacids, and diamines.

Examples of aromatic polyamides are poly-m-phenylene isophthalamide and poly-p-phenylene terephthalamide.

Another suitable aramid is the structure:

(-NH-Ar1-X-Ar2-NH-CO-Ar1-X-Ar2-CO) _n

Wherein, X represents O, S, SO ₂ , NR, N2, CR2, CO.

R represents H, C ₁ ~C ₄ -alkyl, Ar1 and Ar2 can be the same or different, selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene, Wherein at least one hydrogen atom may be substituted by halogen and/or C ₁ -C ₄ -alkyl.

Additional useful polyamides are disclosed in U.S. Patent No 4,670,343, wherein the aramid is a copolyamide wherein at least 80 mole percent of all A1 and A2 are 1,4-phenylene and phenoxyphenyl- 3,4'-diylene, which may or may not be substituted, with a phenoxyphenyl-3,4'-diylene content of 10-40 mol%.

Additives can be applied with the aramid, in fact it has been found that as much as 10% by weight of other polymeric materials can be blended with the aramid, or copolymers containing 10 % of other diamines substituted for diamines of aramids, or other diacid chlorides containing as many as 10% of diacid chlorides of aramids.

In addition to at least one polymer structure containing amino groups, the non-thermoplastic fiber material according to the invention may also comprise at least one thermoplastic polymer. Such thermoplastic polymers include polyvinyl chloride, nylon, polyfluorocarbons, polyethylene, polypropylene and mixtures thereof.

The term "constant and uniformly distributed electromagnetic field" as used herein means an electromagnetic field that is radially symmetric but axially invariant. This electromagnetic field can be generated by a microwave reactor. The term "microwave" as used herein means electromagnetic radiation with a frequency in the range of 5 MHz to 500 GHz. Due to government regulations and the current availability of magnetron power sources, for industrial applications, the frequency is typically 915 or 2450 MHz.

Microwave reactors suitable for use according to the invention are single-mode microwave reactors with cylindrical geometry. In this geometry, when the fiber material is a fiber, the electromagnetic field is predictable and uniformly distributed around the fiber.

The circular cross-section reactor depicted in Figures 2 and 3 combines a radially symmetric electromagnetic field distribution with a well-defined axial electromagnetic field distribution.

An example of a reactor particularly suitable for the present invention is the single-mode TM010 (transverse magnetic 010 type) cylindrical resonator described in A.C. Metaxas and R.J. Meredith, Industrial Microwave Heating, Peter Peregrinus Company, London; England , 1983, pp183～193, equipped with American Microwave Technology (AMT) solid-state amplifier as microwave power source, the wavelength is 32.7cm, its power comes from 28VDC power supply, the maximum power level is 400W, the inner length (L) is 30cm, and the inner radius ( R) is 12.5cm, resulting in a resonance frequency of 915MHz.

Parallel connection of the aforementioned cavities, series connection or any combination of suitable assembly methods are considered to be part of the scope of the present invention.

The term "under low tension" as used herein means substantially low tension. When the fibrous material is any fibrous structure other than fibers, it is preferably not subjected to tension at all. When the fiber material is a fiber, it is preferable that the tension is 0.2 gpd (g/d) or less.

The term "permanent" as used herein is determined according to the following test: the permanently formed non-plastic fibrous material obtained by the method of the present invention is deformed: in other words, the basic fibrous material comprising the permanently formed fibrous material The original linear state it had before it was given a shape. For example, if the permanently formed fibrous material is a twisted fiber, it is untwisted; if it is a crimped fiber, it is decrimped; if it is a knitted fabric, it is unraveled; There is linear state extension. This "deshaping process" must be carried out under tension because of the inherent elasticity of the fibrous material passed through the process of the present invention. Where the fibrous material is completely deformed, ie returned to its original linear state, it is not subject to any tension and is free to return to the shape it had before the "deforming" process. By comparing the corresponding levels of shape of the fibrous material before and after the "deforming" process, the percentage of shape retention of the fibrous material can then be determined. This percentage is the shape's permanence. For the method of the invention, the permanent is at least 30%, preferably at least 50%, more preferably at least 70%. This means that the shaped fiber material subjected to the method of the invention retains at least 30% of its shape after the "de-shaping" process. When the formed fiber is a twisted fiber, the fiber retains at least 70%, preferably at least 80%, more preferably at least 90%, and even more preferably at least 96% of the imparted twist as described in the examples below. Measured as described.

The method of the present invention is capable of imparting a permanent high twist to para-aramid fibers which has never been achieved before. For example, for industrial fibers, the optimal twist Tpm (twists per meter) can be calculated using the following relationship given in ASTM D 885-98 by equation (10) for the generally acceptable twist coefficient TM For the case of 1.1.

Tpm＝960(1.1)/(tex) ^-1/2

Taking 1670dtex para-aramid fiber with TM of 1.1 as an example, the optimal calculated twist is about 80tpm. This value is calculated as follows:

Tpm＝(1.1)960(tex) ^-1/2 ＝(1.1)960(167) ^-1/2

In the case of 1670dtex para-aramid fiber with an initial twist of 500tpm, and then through the method of the present invention, it can be observed that the permanent twist is 400tpm.

In one embodiment of the invention the fibrous material is a fiber. The term "fiber" as used herein means a fibrous material having a length at least 1000 times its diameter or width. Preferably the fibers are polyamide fibers, more preferably aramid fibers. Preference is given to fibers consisting entirely of aramid. More preferred are para-aramid fibers formed from poly-p-phenylene terephthalamide.

Preferably, the fiber modulus is about 10 to about 2500 g/d, more preferably about 1000 to about 2500 g/d, and the tenacity is about 3 to about 50 g/d, more preferably about 3 to about 38 g/d. The modulus and strength are measured according to the ASTM D 885-98 method.

Generally, the fibers are spun from anisotropic spinning solutions by the well-known air gap spinning method described in U.S. Patent Nos. 3,767,756 or 4,340,559. The fiber manufacturing process is as follows: spinning from anisotropic spinning solution at about 80°C, the fiber passes through an air gap, enters a water coagulation bath at about 5°C, and then rinses and washes with water. The resulting fibers are so-called "green" and contain at least 0.05% by weight of water, preferably 0.05 to 400% by weight, as measured according to ASTM D885-98 moisture regain. The contained water is evenly distributed along the fiber length.

Undried or partially dried or completely dried fibers can be used as fiber material for the process of the invention: in the case of completely dried fibers it is important to soak the fibers for a few minutes in an aqueous composition prior to microwave treatment. hours, such that it contains at least 0.05% by weight of the aqueous composition.

Fibers comprising mixtures of the above materials can also be used, including multicomponent fibers, blends of different fibers such as natural fibers and man-made fibers. In addition, bicomponent fibers can also be used according to the invention, for example fibers in which the core consists of a different material than the sheath, or fibers in which the various filaments have different properties.

Fibers suitable for use in the present invention may be round, flat, or may have other shaped cross-sections, or they may be hollow fibers.

In a preferred embodiment of the invention, the shaped fiber material is a twisted fiber.

The formed fibrous material, preferably twisted fibers, is processed through a constant and uniformly distributed electromagnetic field at a speed which can be adjusted from 0.01 to 2000 m/min. Typical speeds for fibrous material processing are 60 m/min, as opposed to the spinning process, which is 800 m/min during the manufacture of fibrous material.

During the process of the present invention, the fiber material remains under very low tension. It is preferably completely free from tension. When the fiber material is fiber, the tension is preferably 0.2 g/d or less.

It is very important that the fiber material does not degrade during the process of the invention. From this point of view, during the period of being subjected to the action of the electromagnetic field, the temperature rise rate of the fiber material is below 300°C/s. In a preferred embodiment of the present invention, the residence time of the fiber material in the microwave reactor is more than 0.1s, more preferably the residence time is the time necessary for the temperature difference between the temperature of the fiber material at the outlet and the temperature of the fiber material at the inlet to be below 300°C .

The temperature of the inlet fiber material can be chosen, limited only by the temperature resistance of the components, which is suitable for very low or very high temperatures. Nevertheless, the preferred temperature range is still 10°C to 100°C, and the more preferred temperature range is 15°C to 45°C.

When the fiber material is a fiber, the fiber path can be a linear trajectory that is completely aligned with the main central axis of the reactor, as shown in FIG. 2 . The fiber path may alternatively be a sinusoidal trajectory as shown in Figure 3, in which case the electromagnetic profile varies periodically along the fiber, which enables specific fiber mechanical and fiber chemical properties to be uniformly distributed along the fiber length. Alternatively, the sinusoidal fiber routing can be offset from the geometric center of the reactor to produce a similar effect. Alternatively an insert suitably placed in the reactor can be designed to produce a similar periodic fiber treatment effect. In addition, it is possible to apply such an insert with, for example, a variable thickness, creating a gradient profile of the axial electromagnetic field to match the variation in the absorbency of the fibers from the reactor inlet to its outlet. The latter case can be used for a linear fiber route, still creating a gradient from the inlet to the outlet of the reactor. Other variants, such as sinusoidal fiber paths with variable amplitudes, or, instead of circular but inert circular lumen cross-sections, are possible within the scope of the present invention, which should not be limited to the alternative structures and fiber path shapes described above. .

In a preferred embodiment, nitrogen or air can be circulated through the reactor to vent water vapor.

At the outlet of the microwave reactor, the temperature of the outgoing fiber material is preferably below 100°C, more preferably below 45°C.

At the outlet of the microwave reactor, the fiber material can be subjected to other treatments. For example, it can be further subjected to heating or surface treatment or coated with various polymer solutions, eg epoxy latex formulations for air flow lines. It can also withstand plasma, electrostatic discharge or corona treatment.

By specific design of the inventive process reactor, a fiber initially having a fixed microwave loss rate along its length is exposed to the same electromagnetic field strength throughout its entire length, except for the inlet and outlet as specific boundaries. As a result, the fiber is completely isotropically treated along its length, so that the fiber exhibits constant properties in terms of strength, modulus, residual moisture content, twist uniformity and permanent form.

The permanently shaped fibers obtained by the method of the present invention are free of internal fissures. Its shape and density remain almost unchanged. They do not shrink during processing. Its specific breaking strength is usually about 2.65 to about 33.5cN/dtex (about 3 to about 38g/d, preferably about 15 to about 38g/d), and the specific modulus is about 8.33 to about 2297cN/dtex (about 10 to about 2500g/d). d, preferably about 1000 to about 2500 g/d).

The present invention will now be explained in more detail with reference to the following examples.

Example

Example 1

Plain bobbins of Kevlar® ²⁹ para-aramid yarn, consisting of 1000 filaments of 1.5 d/f and having a total density corresponding to 1670 dtex, were used as the raw material for all the examples below. This material is hereafter referred to as K29. The moisture content of K29 was determined to be 5.9% by weight using ASTM D885-98.

Using a SAURER ^ALLMA® elastic twister (elasto-twister ⁾ AZB 200/240Kevlar® set at 500tpm, a sufficient amount of K29 yarn was twisted and wound directly on a plastic cylindrical bobbin, which is known to be water resistant , no appreciable swelling or shrinkage was observed on exposure to water. The 500 tpm twisted K29 yarn is referred to as M3D hereinafter. The actual tpm was confirmed to be 609 tpm using a twist counter Zeigle D311, which is a fairly common deviation from the 500 tpm set point due to the high twist obtained with the manually controlled twister.

A 50cm M3D sample was allowed to relax freely, allowing it to untwist to its natural equilibrium level. Using a twist counter, the M3D relaxed sample is completely untwisted, and the residual twist is measured. The zero twist level is confirmed by driving the needle through the middle of the tow and along the tow axis. The needle should be able to move freely from one boundary of the sample to the other in the axial direction without the needle being obstructed and stopped. The residual twist was determined to be 309 tpm, or 51% of the initial twist. So permanent is 51%. The water content of the relaxed sample was unchanged at about 5.9% by weight.

SEM (Scanning Electron Microscopy) analysis of the morphology of the M3D samples showed no change in the silk, in particular no cracks parallel to the longitudinal axis of the silk were found. Figure 4 shows a cross-section of an M3D filament bundle, while Figure 4a shows an unchanged cross-section of an M3D single filament. The so-called unaltered cross-section means that the cross-section is not damaged, in other words, the cross-section has no cracks.

Example 2

Using a SAURER ^ALLMA® elastic twister (elasto-twister ⁾ AZB 200/240Kevlar® set at 500tpm, a sufficient amount of K29 yarn was twisted and wound directly on a plastic cylindrical bobbin, which is known to be water resistant , no appreciable swelling or shrinkage was observed on exposure to water. The 500 tpm twisted K29 yarn is referred to as M3D hereinafter. The actual tpm was confirmed to be 617 tpm using a twist counter Zeigle D311, which is a fairly common deviation from the 500 tpm set point due to the high twist obtained with the manually controlled twister.

A sufficient number of M3D bobbins were soaked for 48 hrs in a vessel filled with deionized water, and the resulting fibers were hereinafter referred to as M1-500. The moisture content of M1-500 was determined to be 22.1% by weight using ASTM D885-98.

A 50cm M1-500 sample was allowed to relax freely and untwisted to its natural equilibrium level. Use a twist counter to completely untwist the M1-500 relaxed sample and measure the residual twist. The zero twist level is confirmed by driving the needle through the middle of the tow and along the tow axis. The needle should be able to move freely from one boundary of the sample to the other in the axial direction without the needle being obstructed and stopped. The residual twist was determined to be 409 tpm, or 66% of the initial twist. So permanent is 66%.

SEM (Scanning Electron Microscopy) analysis of the morphology of the M1-500 sample showed no change in the silk, in particular no cracks parallel to the longitudinal axis of the silk were found. Figure 5 shows the cross-section of the M1-500 tow, while Figure 5a shows the unchanged cross-section of the M1-500 single filament.

Example 3

Using a SAURER ^ALLMA® elastic twister (elasto-twister ⁾ AZB 200/240Kevlar® set at 500tpm, a sufficient amount of K29 yarn was twisted and wound directly on a plastic cylindrical bobbin, which is known to be water resistant , no appreciable swelling or shrinkage was observed on exposure to water. The 500 tpm twisted K29 yarn is referred to as M3D hereinafter. The actual tpm was confirmed to be 611 tpm using a twist counter Zeigle D311, which is a fairly common deviation from the 500 tpm set point due to the high twist obtained with the manually controlled twister.

Immerse a sufficient number of M3D cartridges in a container of deionized water for 48hr. Take out the bobbin from the container and feed it into the off-line processing device in Fig. 1 at 6m/min. The corresponding residence time in the cylinder TM010 resonant cavity is 3 seconds. Figure 2 depicts the resonant cylindrical cavity and also provides its dimensions. The temperature of the fiber entering the chamber was about 20°C, while the "treated" fiber exiting the chamber was below 40°C. The water content of the fiber entering the lumen was 22.1% by weight and the "treated" fiber exiting the lumen was 18.8% by weight as determined by ASTM D885-98. The discharged fiber, hereinafter referred to as M3A, is wound on a cylindrical plastic bobbin.

The 50cm M3A sample was allowed to relax freely to untwist to its natural equilibrium level. Use a twist counter to completely untwist the M3A relaxed sample and measure the residual twist. The zero twist level is confirmed by driving the needle through the middle of the tow and along the tow axis. The needle should be able to move freely from one boundary of the sample to the other in the axial direction without the needle being obstructed and stopped. The residual twist was determined to be 589 tpm, or 96% of the initial twist. So permanent is 96%.

SEM (Scanning Electron Microscopy) analysis of the morphology of the M3A sample showed no change in the silk, in particular no cracks parallel to the longitudinal axis of the silk were found. Figure 6 shows a cross-section of an M3A tow, while Figure 6a shows an unchanged cross-section of an M3A single filament.

Example 4

Using a SAURER ^ALLMA® elastic twister (elasto-twister ⁾ AZB 200/240Kevlar® set at 500tpm, a sufficient amount of K29 yarn was twisted and wound directly on a plastic cylindrical bobbin, which is known to be water resistant , no appreciable swelling or shrinkage was observed on exposure to water. The 500 tpm twisted K29 yarn is referred to as M3D hereinafter. The actual tpm was confirmed to be 604 tpm using a twist counter Zeigle D311, which is a fairly common deviation from the 500 tpm set point due to the high twist obtained with the manually controlled twister.

The M3D bobbin is fed into the off-line processing device in Figure 1 at 6m/min. The corresponding residence time in the cylinder TM010 resonant cavity is 3 seconds. Figure 2 depicts the resonant cylindrical cavity and also provides its dimensions. The temperature of the fiber entering the chamber was about 20°C, while the "treated" fiber exiting the chamber was below 40°C. The water content of the fiber entering the lumen was 5.9% by weight as determined by ASTM D885-98 method, while the "treated" fiber exiting the lumen was 1.5% by weight. The discharged fiber, hereinafter referred to as M3C, is wound on a cylindrical plastic bobbin.

A 50cm M3C sample was allowed to relax freely to untwist to its natural equilibrium level. Use a twist counter to completely untwist the loose M3C sample and measure the residual twist. The zero twist level is confirmed by driving the needle through the middle of the tow and along the tow axis. The needle should be able to move freely from one boundary of the sample to the other in the axial direction without the needle being obstructed and stopped. The residual twist was determined to be 483 tpm, or 80% of the initial twist. So permanent is 80%.

SEM (Scanning Electron Microscopy) analysis of the morphology of the M3C samples showed no change in the silk, in particular no cracks parallel to the longitudinal axis of the silk were found. Figure 7 shows a cross-section of an M3C tow, while Figure 7a shows an unchanged cross-section of a single M3C filament.

Example 5

Using a SAURER ^ALLMA® elastic twister (elasto-twister ⁾ AZB 200/240Kevlar® set at 500tpm, a sufficient amount of K29 yarn was twisted and wound directly on a plastic cylindrical bobbin, which is known to be water resistant , no appreciable swelling or shrinkage was observed on exposure to water. The 500 tpm twisted K29 yarn is referred to as M3D hereinafter. The actual tpm was confirmed to be 583 tpm using a twist counter Zeigle D311, which is a fairly common deviation from the 500 tpm set point due to the high twist obtained with the manually controlled twister.

Immerse a sufficient number of M3D cartridges in a container of deionized water for 48hr. Take out the bobbin from the container and feed it into the off-line processing device in Figure 1 at 50m/min. The corresponding dwell time in the cylinder TM010 resonant cavity is 0.4 seconds. Figure 2 depicts the resonant cylindrical cavity and also provides its dimensions. The temperature of the fiber entering the chamber was about 20°C, while the "treated" fiber exiting the chamber was below 40°C. The fiber entering the lumen had a water content of 22.1% by weight as determined by the ASTM D885-98 method, and it was found that there was little change in the water content weight percent of the "treated" fiber exiting the lumen. The discharged fibers, hereinafter referred to as M4A, are wound on plastic cylindrical bobbins.

A 50cm M4A sample was allowed to relax freely to untwist to its natural equilibrium level. Use a twist counter to completely untwist the M4A relaxed sample and measure the residual twist. The zero twist level is confirmed by driving the needle through the middle of the tow and along the tow axis. The needle should be able to move freely from one boundary of the sample to the other in the axial direction without the needle being obstructed and stopped. The residual twist was determined to be 357 tpm, or 61% of the initial twist. So permanent is 61%.

SEM (Scanning Electron Microscopy) analysis of the morphology of the M4A sample showed no change in the silk, in particular no cracks parallel to the longitudinal axis of the silk were found. Figure 8 shows a cross-section of an M4A tow, while Figure 8a shows an unchanged cross-section of an M4A single filament.

sample initial twist Relaxed Residual Twist Permanent % Residual Twist M3D Comparative Example 1 609 309 51 M1-500 Example 2 617 409 66 M3A Example 3 611 589 96 M3C Example 4 604 483 80 Example 5 of MA4 583 357 61

These results show that fibrous materials subjected to the method of the invention are able to retain up to 96% of their shape.

Claims (17)

1. non-thermoplastic fiber's material of giving shaping is with nonvolatil method, comprise that the non-thermoplastic fiber's material that makes described shaping stands the effect by the constant and equally distributed electromagnetic field of singlemode transverse magnetism 010 type cylinder-shaped resonance chamber microwave reactor generation under low-tension

-constant and equally distributed electromagnetic field moves under the frequency of 5MHz～500GHz,

Non-thermoplastic fiber's material of-shaping is handled by constant and equally distributed electromagnetic field with the speed of 0.01～1200m/min,

The programming rate of-non-thermoplastic fiber's material of being shaped be 300 ℃/below the s,

-non-thermoplastic fiber's material of being shaped comprises i) at least a polymer architecture of amino group and the ii) at least 0.05 weight % Aquo-composition of containing.

2. the process of claim 1 wherein that the polymer architecture that contains amino group comprises polyamide, polyamine, polyimides, aromatic polyamides and blend thereof and mixture.

3. the method for claim 2, the polymer architecture that wherein contains amino group is an aromatic polyamides.

4. the method for claim 3, wherein aromatic polyamides comprises poly and PPTA.

5. the process of claim 1 wherein that non-thermoplastic fiber's material also comprises at least a thermoplastic polymer.

6. the process of claim 1 wherein that Aquo-composition is to be present in water in the fibrous material with free form and constraint form.

7. the process of claim 1 wherein that the temperature of the fibrous material of discharging is below 45 ℃.

8. the process of claim 1 wherein that described fibrous material is a fiber.

9. the method for claim 8, wherein said fiber has been twisted.

10. the method for claim 8, wherein said fiber stands the effect of the following tension force of 0.2g/d.

11. non-thermoplastic fiber's material of the permanent shaping that the method by claim 1 obtains.

12. comprise the structure of non-thermoplastic fiber's material of the permanent shaping of claim 11.

13. non-thermoplastic fiber's material of giving shaping, comprises that the non-thermoplastic fiber's material that makes described shaping stands the effect by the constant and equally distributed electromagnetic field of singlemode transverse magnetism 010 type cylinder-shaped resonance chamber microwave reactor generation with nonvolatil method.

14. the para-aramid fiber of giving twisting is with nonvolatil method, comprise the effect that makes described fiber under the tension force below the 0.2gpd (g/d), stand the constant and equally distributed electromagnetic field that produces by singlemode transverse magnetism 010 type cylinder-shaped resonance chamber microwave reactor

-equally distributed electromagnetic field moves under the frequency of 5MHz～500GHz,

-fiber is handled by microwave reactor with the speed of 0.01～1200m/min,

The programming rate of-fiber be 300 ℃/below the s,

-fiber comprises at least 0.05 weight % Aquo-composition.

15. according to the method for claim 14, wherein Aquo-composition is to be present in water in the fiber with free form and constraint form.

16. the permanent twisting para-aramid fiber that the method by claim 14 obtains.

17., permanently be at least 70% according to the fiber of claim 16.

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