EP1454003B1 - Process for imparting permanence to a shaped non thermoplastic fibrous material - Google Patents

Process for imparting permanence to a shaped non thermoplastic fibrous material Download PDF

Info

Publication number
EP1454003B1
EP1454003B1 EP02797187A EP02797187A EP1454003B1 EP 1454003 B1 EP1454003 B1 EP 1454003B1 EP 02797187 A EP02797187 A EP 02797187A EP 02797187 A EP02797187 A EP 02797187A EP 1454003 B1 EP1454003 B1 EP 1454003B1
Authority
EP
European Patent Office
Prior art keywords
fibrous material
fiber
shaped non
electromagnetic field
non thermoplastic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02797187A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP1454003A2 (en
Inventor
Serge Rebouillat
Nicolas Pont
Benoit Steffenino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1454003A2 publication Critical patent/EP1454003A2/en
Application granted granted Critical
Publication of EP1454003B1 publication Critical patent/EP1454003B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B6/00—Heating by electric, magnetic or electromagnetic fields
    • H05B6/64—Heating using microwaves
    • H05B6/78—Arrangements for continuous movement of material
    • H05B6/788—Arrangements for continuous movement of material wherein an elongated material is moved by applying a mechanical tension to it
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/20—Combinations of two or more of the above-mentioned operations or devices; After-treatments for fixing crimp or curl
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
    • D02J13/001—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass in a tube or vessel
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/003—Treatment with radio-waves or microwaves

Definitions

  • the present invention relates to a process to impart permanence to a shaped non thermoplastic fibrous material comprising amino groups. It also relates to permanently shaped fibrous material obtainable from that process.
  • Twisting is the process of combining filaments into yarn by arranging them according to a helix pattern or combining two or more parallel single yarns into plied yarns or cords. Twist is generally expressed as the number of turns around the longitudinal axis of the fiber per unit length of the fiber; i.e. turns per meter abbreviated as tpm.
  • Multi-filament yarn twisting is generally considered as a processing aid providing high cohesion to the yarn. It is also considered as a suitable filament arrangement for an optimum load sharing.
  • Twisting is also used to impart to the yarn surface a uniform morphology allowing for a better anchoring of the matrix, such as a rubber, which in turn contributes to a more efficient stress transfer and a better mechanical adhesion between the matrix and the reinforcing fiber. Therefore twisting is generally employed to increase strength, smoothness and uniformity or to obtain specific effects in the yarn.
  • high-modulus, high-strength non thermoplastic fibrous material, and more generally crystalline fibers, such as aramid fibers, are difficult to stabilize at moderate and high twist levels because they have a natural tendency to untwist readily.
  • Microwave heating is a well known technology with industrial as well as domestic applications.
  • US 5, 175, 239 and US 5, 146, 058 disclose the use of a microwave to heat treat para-aramid fibers in order to obtain fibers showing internal cracks through the filament cross-section.
  • One aspect of the invention is a process of imparting permanence to a shaped fibrous non thermoplastic material comprising amino groups comprising submitting said shaped non thermoplastic fibrous material under low tension to a constant and uniformly distributed electromagnetic field generated by a single mode Transverse Magnetic 010 mode cylindrical resonant cavity microwave reactor, the rate of increase in temperature of the material being less than 300°C/s.
  • a preferred embodiment of the invention is a process to impart permanence to a twisted para-aramid fiber comprising submitting said fiber, under a tension of less than 0.2 gpd, to a constant and uniformly distributed electromagnetic field produced by a single mode Transverse Magnetic 010 mode cylindrical resonant cavity microwave reactor,
  • a permanent shape for a non thermoplastic fibrous material may be required for special applications such as imparting to a fiber a stretch factor independant from the elastomeric nature of the fiber.
  • a permanently shaped fiber may be used in a rubber composite in order to decrease the elongation gradient between the fiber and the rubber.
  • the process of the invention it is possible to impart to a non thermoplastic fiber a permanent twist of up to the maximum operational twist level.
  • the maximum operational twist level is generally considered as a twist level which will not65e fracture or rupture of the filaments composing the twist assembly.
  • this permanent twist level can reach 1000 tpm for a 1670 dtex yarn made of para-aramid fiber.
  • the fiber shows no internal crack such as the one which could appear through the filament cross-section like described in US 5, 175, 239. It has a high cohesion and a high stability.
  • This high stabilization may be operated for any twist level necessary for any subsequent processing such as spiraling, knitting, weaving, braiding, felting or embedding in an elastomer matrix or a composite matrix.
  • Such a permanently twisted non thermoplastic fiber may be used as a sewing thread, a fiber to reinforce various matrixes or a woven or knitted fabric, making it possible to achieve high cohesion and stability in a woven or knitted structure.
  • the woven or knitted structure made of a permanently twisted non thermoplastic fiber of the invention is highly stable dimensionally and will not present residual torque effect. Such a structure is also stretchable.
  • the process of the invention also has the advantage of eliminating intermediate steps which would be necessary to processes of the prior art to maintain the shape of a fibrous material.
  • fiber 11 from supply tension regulated roll 12 is fed over rolling guide 13 to assure the desired alignment of the fiber.
  • the fiber is fed to the pretreatment unit 14 where it can be watered so that the amount of water content in the fiber is at least 0.05 weight %.
  • the water pretreatment can be optional in the case of a never-dried fiber having already more than 0.05 weight % water.
  • the pretreatment unit 14 can alternatively be a dewatering unit to tailor the amount of water contained in the supply fiber 11. It can also be a temperature adjusting pretreatment and/or a coating or plasma or any suitable treatment.
  • the pretreatment unit can be a twisting unit or any texturizing unit imparting a filament deformation.
  • the fiber is fed to tension-control roll 15 and then passes into the microwave resonant cavity reactor 16.
  • the process can be tailored to include several resonant cavity reactors in any suitable arrangement in series or in parallel.
  • the microwave electromagnetic field is controlled through the microwave control 17.
  • the fiber is maintained in the cavity at a relatively low tension, preferably suitable to maintain the shape of the fibrous material, preferably less than 0.2 g/denier.
  • the fiber is fed to a tension-control roll 18 and then to a guide 19.
  • the fiber is then fed to rolling guide 20 to assure the desired alignment of the fiber.
  • the fiber is fed to the post-treatment unit 21 where it can be further heated, dried or surface treated by coating or plasma treatment for instance or by any other suitable post treatment.
  • the use of the post-treatment unit is optional.
  • the fiber then passes through a rolling-tension guide 22. Finally, the fiber is wound using a tension controlled precision winder 23.
  • Fig. 1 The process of Fig. 1 can be further modified to allow the treatment of several fibers run in parallel.
  • a cylindrical microwave resonant cavity reactor indicated generally as 30 suitable for use in the present invention is depicted.
  • the reactor comprises a cavity defined by a cylinder 31 designed to support a TM010 (Transverse Magnetic 010) mode and the desired resonant condition at the center frequency which is generally set for industrial applications at 915 MHz or 2450 MHz.
  • TM010 Transverse Magnetic 010
  • Suitable dimension for a 915 MHz resonant condition are provided on Fig. 2 .
  • Typical units are 915 MHz, 400 W amplifier coupled to a 28 VDC, 53 A switching power supply or 915 MHz, 800 W amplifier coupled to a 28 VDC, 107 A power supply.
  • the circular cross section reactor combines the radially symmetric electromagnetic field distributions and the well defined axial electromagnetic field profile.
  • circular cross section is meant herein a circular or an oval cross section.
  • a microwave source 32 initiates the microwave.
  • the fiber 11 is fed through inlet port 33 and exits through outlet port 34.
  • the fiber path is linear.
  • a cylindrical microwave resonant cavity reactor 40 is depicted, similar to the one shown in FIG. 2 but comprising in addition ceramic guides 41 allowing the fiber path to be sinuso ⁇ dal.
  • Fibrous material includes endless fibers such as filaments, short fibrous structures, short cut fibers, microfibers, multifilaments, cords, yarns, fibers, felt, fabric, woven, knitted, braided, spiraled, felted structures or nonwoven forms.
  • the fibers may be made into yarns of short fibrous structures which are spun into staple fibers, into yarns of endless fibers or into stretchbroken yarns which can be described as intermediate yarns between staple and continuous yarns.
  • the yarn, fiber, fabric, woven, knitted, braided, spiraled, felted structure or nonwoven form may be made of continuous filaments, short fibers or pulp.
  • Shaped fibrous material includes any fiber, fabric, textile, garment, fibrous structure or finished product made of the fibrous material as defined above, having been submitted to any shaping process such as twisting, weaving, braiding, crimping, plying, knitting, spiraling, felting, unidirectionally laying down or any other deformation.
  • Aqueous composition includes water, solvents, and/or mixture thereof under the form of a solution, an emulsion or a dispersion. It can contain salts, polymers, or other emulsified, dispersed or dissolved chemical compounds.
  • the aqueous composition is water. This aqueous composition may be present within the fibrous material under the free form and/or under the bound form. In a preferred embodiment of the invention, the aqueous composition is present under both forms, free and bound.
  • Thermoplastic material means a material that softens when exposed to heat and returns to its original condition when cooled to room temperature. A non thermoplastic material does not soften when exposed to heat.
  • the non thermoplastic fibrous material suitable in the present invention includes any natural or man made non thermoplastic fibrous material comprising at least one polymeric structure comprising amino groups.
  • “Amino groups”, as used herein, includes amine groups, amide groups and/or amino-acid groups.
  • Man made and natural fibrous material include polyamides, polyamines, polyimides such as polybenzimidazole (PBI), polyphenylenebenzobisoxazole (PBO), natural silk, spider silk, hair and all natural fibers presenting amino-acid sequences. These groups can be part of a linear or branched, cyclic or heterocyclic, saturated or unsaturated, aliphatic or aromatic chemical structure.
  • Preferred polymeric structures comprising amino groups include polyamides, polyamines, polyimides, aramids, blends and mixtures thereof.
  • the polymeric structure comprising amino groups is an aramid.
  • Aramids are polymers that are partially, preponderantly or exclusively composed of aromatic rings, which are connected through carbamide bridges or optionally, in addition also through other bridging structures.
  • the structure of such aramids may be elucidated by the following general formula of repeating units: (-NH-A1-NH-CO-A2-CO)n wherein A1 and A2 are the same or different and signify aromatic and/or polyaromatic and/or heteroaromatic rings, that may also be substituted.
  • A1 and A2 may independently from each other be 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'-diylen, 2,5-pyridylene and 2,6-quinolylene which may or may not be substituted by one or more substituents which may comprise halogen, C1-C4-alkyl, phenyl, carboalkoxyl, C1-C4-alkoxyl, acyloxy, nitro, dialkylamino; thioalkyl, carboxyl and sulfonyl.
  • the -CONH-group may also be replaced by a carbonyl-hydrazide (-CONHNH-) group, azo-or azoxygroup
  • aramids are generally prepared by polymerization of diacid chloride, or the corresponding diacid, and diamine.
  • aramids are poly-m-phenylene-isophthalamide and poly-p-phenylene-terephthalamide.
  • Additional suitable aromatic polyamides are of the following structure: (-NH-Ar1-X-Ar2-NH-CO-Ar1-X-Ar2-CO-)n in which X represents O, S, SO2, NR, N2, CR2, CO.
  • R represents H, C1-C4-alkyl and Ar1 and Ar2 which may be same or different are selected from 1,2-phenylene, 1,3-phenylene and 1,4-phenylene and in which at least one hydrogen atom may be substituted with halogen and/or C1-C4-alkyl.
  • aramid is a copolyamide in which preferably at least 80% by mole of the total A1 and A2 are 1,4-phenylene and phenoxyphenyl-3,4'-diylene which may or may not be subsituted and the content of phenoxyphenyl-3,4'-diylene is 10% to 40% by mole.
  • Additives may be used with the aramid and, in fact, it has been found that up to as much as 10% by weight, of other polymeric materials may be blended with the aramid or that copolymers may be used having as much as 10% of other diamine substituted for the diamine of the aramid or as much as 10% of other diacid chloride substituted for the diacid chloride of the aramid.
  • the non thermoplastic fibrous material of the invention may also comprise at least one thermoplastic polymer.
  • thermoplastic polymer includes polyvinylchloride, nylon, polyfluorocarbon, polyethylene, polypropylene and mixtures thereof.
  • Constant and uniformly distributed electromagnetic field means an electromagnetic field which is radially symmetric and axially invariant. Such an electromagnetic field may be produced by a microwave reactor.
  • Microwave as used herein, means electromagnetic radiation in the range of frequency from 5 MHz to 500 GHz. Because of Government regulation and the present availability of magnetron power sources, the frequency normally is 915 or 2450 MHz for industrial applications.
  • the microwave reactor suitable for the present invention is a single mode microwave reactor with a cylindrical geometry. In such a geometry, when the fibrous material is a fiber, the electromagnetic field is predictable, uniformly distributed around the fiber.
  • This circular cross section reactor depicted in figures 2 and 3 combines the radially symmetric electromagnetic field distributions and the well defined axial electromagnetic field profile.
  • An example of a particularly suitable reactor for the invention is the single mode TM010 (Transverse Magnetic 010 mode) cylindrical resonant cavity, described in A.C. Metaxas and R.J. Meredith, Industrial Microwave Heating, Peter Peregrinus Ltd., London, England, 1983, pp. 183-193 , equipped with an American Microwave Technology (AMT) solid-state amplifier as microwave power source, 32.7 cm wavelength, powered from a 28 VDC power supply and with a maximum power level of 400W, with dimensions of an inner length (L) of 30 cm and an inner radius (R) of 12.5 cm and generating a resonant frequency of 915 MHz.
  • AMT American Microwave Technology
  • Under low tension means substantially very low tension.
  • the fibrous material is any fibrous structure but a fiber, it is preferably submitted to no tension at all.
  • the tension is preferably less than 0.2 gpd (grams per denier).
  • the permanently shaped non thermoplastic fibrous material obtained through the process of the invention is "unshaped” : in other words, the basic fibrous material composing the permanently shaped fibrous material is taken back to the original linear position it had before it was ever imparted a shape. For instance, if the permanently shaped fibrous material is a twisted fiber, it is untwisted; if it is a crimped fiber, it is uncrimped; if it is a knitted fabric, it is unknitted so that the fibrous material is extented in its original linear position.
  • This "unshaping process” must be done under a certain tension because of the natural elasticity acquired by the fibrous material through the process of the invention.
  • the fibrous material is completely unshaped, ie once it is back to its linear original position, it is relieved of any tension and freed to come back to the shape it had before the "unshaping" process.
  • the percentage of shape retention of the fibrous material is the permanence of the shape.
  • the permanence is at least 30%, preferably at least 50%, and more preferably at least 70%. That means that a shaped fibrous material submitted to the process of the invention retains at least 30% of its shape after "unshaping".
  • the fiber When the shaped fibrous material 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 twist imparted, this twist being measured as described in the examples below.
  • Tpm 960 1.1 / tex - 1 / 2
  • the fibrous material is a fiber.
  • "Fiber”, as used herein, means a fibrous material having a length at least 1000 times its diameter or width.
  • the fibers are preferably polyamide fibers and more preferably aramid fibers. Fibers which are exclusively composed of aromatic polyamides are preferred. Para-aramid fibers which are formed of poly(p-phenylene terephthalamide) are more preferred.
  • the fiber has a modulus of about 10 to about 2500 g/den, preferably of about 1000 to about 2500 g/den, and a tenacity of about 3 to about 50 g/den, preferably of about 3 to about 38 g/den.
  • the modulus and the tenacity are measured according to the ASTM D 885-98 method.
  • the fibers are generally spun from an anisotropic spin dope using an air gap spinning process such as is well known and is described in United States Patent No. 3,767,756 or 4,340,559 .
  • Fibers are spun from an anisotropic spin dope at about 80°C, through an air gap, into an aqueous coagulating bath of about 5°C, and through an aqueous rinse and wash.
  • the resulting fibers are so-called "never-dried” and include at least 0.05% by weight, preferably from 0.05 to 400%, by weight, water, this water content being measured according to ASTM D885-98 for the moisture regain level. This water is uniformly distributed along the length of the fiber.
  • fibers comprising mixtures of the above materials including hybrid fibers, blends of different fibers such as natural and man made fibers.
  • two-component fibers may also be used in accordance with the invention, for instance fibers in which the core consists of a different material from the skin or in which the various filaments are from different nature.
  • the fibers suitable for the present invention may be round, flat or may have another cross-sectional shape or they may be hollow fibers.
  • the shaped fibrous material is a twisted fiber.
  • the shaped fibrous material preferably the twisted fiber, is processed through the constant and uniformly distributed electromagnetic field at a speed which may be adjusted between 0.01 and 2000 m/min. Typical speeds are 60 m/min for the fibrous material treatment other than during the spinning process, and 800 m/min for the speed during the manufacturing of the fibrous material.
  • the fibrous material is maintained at a very low tension. It preferably undergoes no tension at all.
  • the tension is preferably less than 0.2 g/d.
  • the rate of the increase of temperature of the fibrous material is less than 300°C/s during the time it is submitted to the electromagnetic field.
  • the dwell time of the fibrous material in the microwave reactor is more than 0.1 s, and more preferably it is the necessary time so that the difference between the temperature of the outcoming fibrous material and the temperature of the incoming fibrous material is less than 300°C.
  • the temperature of the incoming fibrous material may be selected and is only limited by the temperature resistance of the components, this being valid for very low as well as very high temperatures. Nonetheless a range of 10 °C to 100 °C is preferred, with a range of from 15 °C to 45 °C being more preferred.
  • the fiber path may be a linear trajectory perfectly coinciding with the reactor main central axis, as shown on fig 2 .
  • the fiber path may alternatively be sinusoidal as shown in figure 3 : in such a case, one obtains a periodically varying electromagnetic profile along the fiber which can result in special fiber mechanical and chemical properties uniformly distributed along the fiber length.
  • the sinusoidal fiber path can be offset from the geometric center of the reactor producing similar effects.
  • inserts placed appropriately in the reactor can be engineered to produce a similar periodic fiber treatment. Additionally, such inserts, with for example variable thickness, can be used to produce a gradient distribution of the axial electromagnetic field matching the variation of absorbency of the fiber from its entry in the reactor to its outlet.
  • nitrogen or air can be circulated through the reactor to evacuate water vapor.
  • the temperature of the outcoming fibrous material is preferably less than 100°C, and more preferably less than 45°C.
  • the fibrous material may undergo an additional treatment.
  • it may be further heated or surface treated or coated with various polymeric solutions, like epoxy-latex formulations for a pneumatic production line. It can also be subject to a plasma, an electrostatic discharge, or a corona treatment.
  • the fiber which initially has a fixed microwave loss factor along its length, is exposed to the same electromagnetic field strength over its entire length, except for the inlet and outlet which are special boundaries.
  • the fiber therefore undergoes an isotropic treatment all along its length and therefore shows constant properties as regards tenacity, modulus, residual water content, twist uniformity and permanent shaping.
  • the permanently shaped fibers obtained through the process of the present invention show no internal cracks. Their morphology and density remain almost unchanged. They exhibit no shrinkage during the process They usually have a specific breaking strength of about 2.65 to about 33.5 cN/dtex (about 3 to about 38 g/den, preferably about 15 to about 38 g/den) and a specific modulus of about 8.83 to about 2297 cN/dtex (about 10 to about 2500 g/den, preferably about 1000 to about 2500 g/den).
  • Kevlar® 29 para-aramid yarn made of 1000 filaments of 1.5 denier per filament, equivalent to a total of 1670 dtex linear density, has been used as a feed material for all the examples cited below. This material is thereafter referred to as K29.
  • the moisture content measured on K29 using ASTM D885-98 is 5.9 weight percent.
  • K29 yarn A sufficient amount of K29 yarn has been twisted, using a SAURER ALLMA® elasto-twister AZB 200/240 Kevlar® set at 500 tpm, and directly wound on plastic cylindrical tubes, which tubes are known to resist to water exposure without appreciable swelling or shrinkage.
  • the twisted 500 tpm K29 yarn is thereafter referred to as M3D.
  • the real tpm was confirmed to be 609 tpm which is quite a usual divergence vs. the set point of 500 tpm since it is a high twist level using a manual control of the twisting machine.
  • a 50 cm sample of M3D is freed to relax and let untwist to its natural equilibrium level.
  • the relaxed sample of M3D is untwisted completely to measure the residual twist.
  • the zero twist level is confirmed by driving a pin through the middle and along the axis of the filament bundle.
  • the residual twist level was measured to be 309 tpm , i.e. 51% of the initial twist. The permanence is therefore 51%.
  • the water content of the relaxed sample remains unchanged at about 5.9 weight percent.
  • Fig. 4 shows the cross section of a bundle of filaments of M3D and Fig. 4a of the unaltered cross section of a single filament of M3D.
  • unaltered cross section is meant that the cross section is undamaged, in other words that there are no cracks across the section.
  • K29 yarn A sufficient amount of K29 yarn has been twisted, using a SAURER ALLMA® elasto-twister AZB 200/240 Kevlar® set at 500 tpm, and directly wound on plastic cylindrical tubes, which tubes are known to resist to water exposure without appreciable swelling or shrinkage.
  • the twisted 500 tpm K29 yarn is thereafter referred to as M3D.
  • the real tpm was confirmed to be 617 tpm which is quite a usual divergence vs. the set point of 500 tpm since it is a high twist level using a manual control of the twisting machine.
  • M1500 A sufficient number of bobbins of M3D were immersed for 48 hours in a recipient containing de-ionised water; the resulting fiber is hereinafter referred to as M1500.
  • the moisture content measured on M1-500 using ASTM D885-98 is 22.1 weight percent.
  • a 50 cm sample of M1-500 is freed to relax and let untwist to its natural equilibrium level.
  • Using a twist counter the relaxed sample of M1-500 is untwisted completely to measure the residual twist.
  • the zero twist level is confirmed by driving a pin through the middle and along the axis of the filament bundle.
  • the residual twist level was measured to be 409 tpm , i.e. 66 % of the initial twist. The permanence is therefore 66%.
  • Fig. 5 shows the cross section of a bundle of filaments of M1-500 and Fig. 5a of the unaltered cross section of a single filament of M1-500.
  • K29 yarn A sufficient amount of K29 yarn has been twisted, using a SAURER ALLMA® elasto-twister AZB 200/240 Kevlar® set at 500 tpm, and directly wound on plastic cylindrical tubes, which tubes are known to resist to water exposure without appreciable swelling or shrinkage.
  • the twisted 500 tpm K29 yarn is thereafter referred to as M3D.
  • the real tpm was confirmed to be 611 tpm which is quite a usual divergence vs. the set point of 500 tpm since it is a high twist level using a manual control of the twisting machine.
  • a sufficient number of bobbins of M3D were immersed for 48 hours in a recipient containing de-ionised water.
  • a bobbin was taken off the recipient and was fed at 6 meters per minute to the off-line treatment unit of figure 1 .
  • the corresponding resident time in the cylindrical TM010 resonant cavity was 3 seconds.
  • the resonant cylindrical cavity is depicted on Fig. 2 which also provides its dimensions.
  • the fiber temperature entering the cavity was about 20 degree centigrade compared to less than 40 degree centigrade for the "treated" fiber exiting the cavity.
  • the water content, using ASTM D885-98 method, of the fiber entering the cavity was 22.1 weight percent compared to 18.8 weight percent for the "treated" fiber exiting the cavity.
  • the exiting fiber referred thereinafter as to M3A, was wound onto cylindrical plastic tubes.
  • a 50 cm sample of M3A is freed to relax and let untwist to its natural equilibrium level.
  • Using a twist counter the relaxed sample of M3A is untwisted completely to measure the residual twist.
  • the zero twist level is confirmed by driving a pin through the middle and along the axis of the filament bundle.
  • the residual twist level was measured to be 589 tpm , i.e. 96 % of the initial twist. The permanence is therefore 96%.
  • Fig. 6 shows the cross section of a bundle of filaments of M3A and Fig. 6a of the unaltered cross section of a single filament of M3A.
  • K29 yarn A sufficient amount of K29 yarn has been twisted, using a SAURER ALLMA® elasto-twister AZB 200/240 Kevlar® set at 500 tpm, and directly wound on plastic cylindrical tubes, which tubes are known to resist to water exposure without appreciable swelling or shrinkage.
  • the twisted 500 tpm K29 yarn is thereafter referred to as M3D.
  • the real tpm was confirmed to be 604 tpm which is quite a usual divergence vs. the set point of 500 tpm since it is a high twist level using a manual control of the twisting machine.
  • a bobbin of M3D was fed at 6 meters per minute to the off-line treatment unit of figure 1 .
  • the corresponding resident time in the cylindrical TM010 resonant cavity was 3 seconds.
  • the resonant cylindrical cavity is depicted on Fig. 2 which also provides its dimensions.
  • the fiber temperature entering the cavity was about 20 degree centigrade compared to less than 40 degree centigrade for the "treated" fiber exiting the cavity.
  • the water content, using ASTM D885-98 method, of the fiber entering the cavity was 5.9 weight percent compared to 1.5 weight percent for the "treated" fiber exiting the cavity.
  • the exiting fiber referred thereinafter as to M3C, was wound onto cylindrical plastic tubes.
  • a 50 cm sample of M3C is freed to relax and let untwist to its natural equilibrium level.
  • Using a twist counter the relaxed sample of M3C is untwisted completely to measure the residual twist.
  • the zero twist level is confirmed by driving a pin through the middle and along the axis of the filament bundle.
  • the residual twist level was measured to be 483 tpm, i.e. 80 % of the initial twist. The permanence is therefore 80%.
  • Fig. 7 shows the cross section of a bundle of filaments of M3C and picture Fig. 7a of the unaltered cross section of a single filament of M3C.
  • K29 yarn A sufficient amount of K29 yarn has been twisted, using a SAURER ALLMA® elasto-twister AZB 200/240 Kevlar® set at 500 tpm, and directly wound on plastic cylindrical tubes, which tubes are known to resist to water exposure without appreciable swelling or shrinkage.
  • the twisted 500 tpm K29 yarn is thereafter referred to as M3D.
  • the real tpm was confirmed to be 583 tpm which is quite a usual divergence vs. the set point of 500 tpm since it is a high twist level using a manual control of the twisting machine.
  • a sufficient number of bobbins of M3D were immersed for 48 hours in a recipient containing de-ionised water.
  • a bobbin was taken off the recipient and was fed at 50 meters per minute to the off-line treatment unit of figure 1 .
  • the corresponding resident time in the cylindrical TM010 resonant cavity was 0.4 seconds.
  • the resonant cylindrical cavity is depicted on Fig. 2 which also provides its dimensions.
  • the fiber temperature entering the cavity was about 20 degree centigrade compared to less than 40 degree centigrade for the "treated" fiber exiting the cavity.
  • the water content, using ASTM D885-98 method, of the fiber entering the cavity was 22.1 weight percent. An almost unchanged weight percent for the "treated" fiber exiting the cavity was found.
  • the exiting fiber referred thereinafter as to M4A, was wound onto cylindrical plastic tubes.
  • a 50 cm sample of M4A is freed to relax and let untwist to its natural equilibrium level.
  • Using a twist counter the relaxed sample of M4A is untwisted completely to measure the residual twist.
  • the zero twist level is confirmed by driving a pin through the middle and along the axis of the filament bundle.
  • the residual twist level was measured to be 357 tpm , i.e. 61 % of the initial twist. The permanence is therefore 61%.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Treatment Of Fiber Materials (AREA)
EP02797187A 2001-12-06 2002-12-04 Process for imparting permanence to a shaped non thermoplastic fibrous material Expired - Lifetime EP1454003B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US33843801P 2001-12-06 2001-12-06
US338438P 2001-12-06
PCT/US2002/038748 WO2003050345A2 (en) 2001-12-06 2002-12-04 Process for imparting permanence to a shaped non thermoplastic fibrous material

Publications (2)

Publication Number Publication Date
EP1454003A2 EP1454003A2 (en) 2004-09-08
EP1454003B1 true EP1454003B1 (en) 2012-04-11

Family

ID=23324821

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02797187A Expired - Lifetime EP1454003B1 (en) 2001-12-06 2002-12-04 Process for imparting permanence to a shaped non thermoplastic fibrous material

Country Status (9)

Country Link
EP (1) EP1454003B1 (ko)
JP (1) JP4527400B2 (ko)
KR (1) KR100899760B1 (ko)
CN (2) CN1285794C (ko)
AU (1) AU2002362057A1 (ko)
BR (1) BR0214444B1 (ko)
CA (1) CA2468336C (ko)
MX (1) MXPA04005374A (ko)
WO (1) WO2003050345A2 (ko)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008150644A2 (en) * 2007-05-31 2008-12-11 Dow Global Technologies Inc. Microwave applicator equipment for rapid uniform heating of receptive polymer systems
CN101970197A (zh) * 2007-11-29 2011-02-09 陶氏环球技术公司 控制并优化塑料板材微波加热的方法
US9240259B2 (en) 2011-10-07 2016-01-19 E I Du Pont De Nemours And Company Liquid compositions used as insulating and heat transfer means, electrical devices containing said compositions and preparation method for such compositions
JP6872177B2 (ja) * 2015-08-18 2021-05-19 ユニバーシティ オブ マサチューセッツ アマースト アラミド繊維の改質方法

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4875846A (ko) * 1972-01-21 1973-10-12
GB1482755A (en) * 1975-07-07 1977-08-17 Electricity Council Methods of and apparatus for microwave heating threads or yarns
JPS5936777A (ja) * 1982-08-23 1984-02-29 小松精練株式会社 合成繊維材料の処理方法
JPS6039436A (ja) * 1983-08-10 1985-03-01 旭化成株式会社 糸状体加熱装置
JPS60198212A (ja) * 1984-03-21 1985-10-07 Toyobo Co Ltd 誘電体のマイクロ波加熱延伸および／または熱処理法
SE451228B (sv) * 1985-12-30 1987-09-14 Stiftelsen Inst Mikrovags Mikrovagsapplikator for verming av fremst vesentligen strengformade eller langstreckta kroppar
US5151142A (en) * 1986-01-13 1992-09-29 Bridgestone Corporation Heavy duty pneumatic radial tires using rubber reinforcing fiber cords with improved adhesion
JPH01111031A (ja) * 1987-10-26 1989-04-27 Toyo Bussan Kk 羊毛又は羊毛製品の捲縮法
JPH01207472A (ja) * 1988-02-13 1989-08-21 Anmin Kogyo Kk 詰綿体
JP2560837B2 (ja) * 1989-06-07 1996-12-04 東レ株式会社 ポリアミド系繊維
JP2728507B2 (ja) * 1989-07-06 1998-03-18 帝人株式会社 耐熱性紡績糸の処理方法
US5175239A (en) 1990-12-27 1992-12-29 E. I. Du Pont De Nemours And Company Process for making para-aramid fibers having high tenacity and modulus by microwave annealing
JPH04361666A (ja) * 1991-06-10 1992-12-15 Toyo Bussan Kk 繊維の加工法
DE4128256C1 (ko) * 1991-08-27 1993-04-15 H. Krantz Gmbh & Co, 5100 Aachen, De
US5262099A (en) * 1992-04-01 1993-11-16 E. I. Du Pont De Nemours And Company Process of making high tenacity polyamide monofilaments
JPH0657628A (ja) * 1992-08-03 1994-03-01 Kanebo Ltd 獣毛繊維構造物の改質加工方法
JPH06272158A (ja) * 1993-03-19 1994-09-27 Suzutora Seisen Kojo:Kk 繊維製品の湿熱処理装置
JPH0782658A (ja) * 1993-09-13 1995-03-28 Teijin Ltd 繊維の表面改質法
JPH09159706A (ja) * 1995-12-08 1997-06-20 Mitsubishi Heavy Ind Ltd マイクロ波共振器
KR100201165B1 (ko) * 1996-05-16 1999-06-15 신형인 마이크로파를 이용하여 타이어 아라미드 코드의 고무와의 접착력을 향상시키는 방법
US5794428A (en) * 1996-05-29 1998-08-18 Rhodes; Cheryl Elizabeth Method of bulking and heat-setting a moving, continuous length of twisted thermoplastic yarn
JPH11195500A (ja) * 1997-12-31 1999-07-21 Anelva Corp 表面処理装置
JP4363700B2 (ja) * 1999-05-21 2009-11-11 東レ株式会社 複合紡績糸およびそれを用いてなる布帛
MXPA02004821A (es) * 1999-11-19 2002-08-30 Kimberly Clark Co Metodo para mejorar la resistencia al deslizamiento de un compuesto de substrato.

Also Published As

Publication number Publication date
CN1602375A (zh) 2005-03-30
BR0214444B1 (pt) 2013-04-09
BR0214444A (pt) 2004-09-14
MXPA04005374A (es) 2004-09-27
CA2468336C (en) 2011-05-03
JP4527400B2 (ja) 2010-08-18
KR20050044721A (ko) 2005-05-12
CN1285794C (zh) 2006-11-22
KR100899760B1 (ko) 2009-05-27
AU2002362057A8 (en) 2003-06-23
JP2005511915A (ja) 2005-04-28
CN1840772A (zh) 2006-10-04
CN100425764C (zh) 2008-10-15
WO2003050345A2 (en) 2003-06-19
WO2003050345A3 (en) 2004-04-15
CA2468336A1 (en) 2003-06-19
AU2002362057A1 (en) 2003-06-23
EP1454003A2 (en) 2004-09-08

Similar Documents

Publication Publication Date Title
US5879800A (en) Low -shrinkage hybrid yarns production thereof and use thereof
JPH11189916A (ja) アラミド繊維およびその製造方法
EP1454003B1 (en) Process for imparting permanence to a shaped non thermoplastic fibrous material
FI92943C (fi) Paperikoneen huovat
JPS6242061B2 (ko)
KR100903701B1 (ko) 폴리에스테르 이수축 혼섬사의 제조방법
CN111902574A (zh) 用于制造高强度纱线的纺丝组件及纱线制造设备和方法
WO2005003416A1 (ja) ゴム補強用合成繊維すだれ織物及びそれを用いた空気入りタイヤ
JP4902375B2 (ja) ゴム補強用合成繊維すだれ織物及びそれを用いた空気入りタイヤ
KR102166023B1 (ko) 내피로도가 우수한 파라-아라미드 섬유 및 이의 제조방법
JP2003082540A (ja) 仮撚加工糸
JP2005154963A (ja) ゴム補強用合成繊維すだれ織物及びそれを用いた空気入りタイヤ
KR101933372B1 (ko) 방적용 단섬유 및 그 제조방법
JPS6035449B2 (ja) 補強用織物
KR20160079159A (ko) 발수 성능이 향상된 고강도 폴리에스테르 원사와 그 제조방법
KR840001629B1 (ko) 폴리에스테르 섬유
JP4180976B2 (ja) ゴム補強用合成繊維すだれ織物及びそれを用いた空気入りタイヤ
JP4205526B2 (ja) ゴム補強用合成繊維コード
JP2007009375A (ja) ポリトリメチレンテレフタレート系特殊捲縮糸およびその製造方法
JP2003166120A (ja) 樹脂補強用ポリフェニレンサルファイド繊維
JPH07324240A (ja) ポリエステル複合糸
JP2019085676A (ja) ポリエステル複合仮撚糸
JP2005042263A (ja) ゴム補強用合成繊維すだれ織物及びそれを用いた空気入りタイヤ
JP2003342845A (ja) ゴム補強用嵩高糸、その製造方法及び繊維補強ゴム製品
JPH0369622A (ja) 長手方向に染着差を有する制電性仮撚加工糸およびその製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20040603

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO

17Q First examination report despatched

Effective date: 20070510

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: D02J 13/00 20060101ALI20110913BHEP

Ipc: D06M 10/00 20060101AFI20110913BHEP

Ipc: D02G 1/20 20060101ALI20110913BHEP

Ipc: H05B 6/78 20060101ALI20110913BHEP

GRAC Information related to communication of intention to grant a patent modified

Free format text: ORIGINAL CODE: EPIDOSCIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 60242653

Country of ref document: DE

Effective date: 20120606

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20130114

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 60242653

Country of ref document: DE

Effective date: 20130114

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20131127

Year of fee payment: 12

Ref country code: GB

Payment date: 20131204

Year of fee payment: 12

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20131210

Year of fee payment: 12

Ref country code: FR

Payment date: 20131209

Year of fee payment: 12

Ref country code: NL

Payment date: 20131210

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60242653

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20150701

REG Reference to a national code

Ref country code: NL

Ref legal event code: V1

Effective date: 20150701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20141204

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20150831

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141204

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141204