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WO1989001999A1 - Fil hybride - Google Patents

Fil hybride Download PDF

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Publication number
WO1989001999A1
WO1989001999A1 PCT/US1987/002156 US8702156W WO8901999A1 WO 1989001999 A1 WO1989001999 A1 WO 1989001999A1 US 8702156 W US8702156 W US 8702156W WO 8901999 A1 WO8901999 A1 WO 8901999A1
Authority
WO
WIPO (PCT)
Prior art keywords
fibre
filaments
yarn
tow
stretch
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.)
Ceased
Application number
PCT/US1987/002156
Other languages
English (en)
Inventor
Kirk Leon Tradewell
George Edward Tradewell
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.)
Heltra Inc
Original Assignee
Heltra Inc
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 Heltra Inc filed Critical Heltra Inc
Priority to EP19880902069 priority Critical patent/EP0327600A1/fr
Priority to JP88502090A priority patent/JPH02500605A/ja
Priority to PCT/US1987/002156 priority patent/WO1989001999A1/fr
Publication of WO1989001999A1 publication Critical patent/WO1989001999A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D02G3/045—Blended or other yarns or threads containing components made from different materials all components being made from artificial or synthetic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B15/00—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08—Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
    • D01G1/00—Severing continuous filaments or long fibres, e.g. stapling
    • D01G1/06—Converting tows to slivers or yarns, e.g. in direct spinning
    • D01G1/08—Converting tows to slivers or yarns, e.g. in direct spinning by stretching or abrading
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01G—PRELIMINARY TREATMENT OF FIBRES, e.g. FOR SPINNING
    • D01G13/00—Mixing, e.g. blending, fibres; Mixing non-fibrous materials with fibres
    • 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
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2793/00—Shaping techniques involving a cutting or machining operation
    • B29C2793/0081—Shaping techniques involving a cutting or machining operation before shaping
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch

Definitions

  • This invention relates to hybrid yarns comprising a blend of two or more different fibres one of which com ⁇ prises reinforcing fibre.
  • reinforcing material such as carbon fibre
  • a matrix material such as. a resin
  • the carbon fibre and resin are incorporated as separate components.
  • the carbon fibre may be woven into a fabric which is then impregnated with resin .to form a prepreg.
  • both carbon fibre and thermoplastic fibre may be woven together into a fabric, the carbon fibre being the weft, for example, and the thermoplastic fibre the warp. Both these constructions have the disadvantage that the two components are not in an intimate mixture and when they are consolidated into a fabric there exists discrete regions of carbon fibre and thermoplastic matrix.
  • Hybrid yarns have been suggested; for example UK Patent 2 .105 247 B describes a yarn consisting of a core of carbon fibre wrapped with thermoplastic fibre, and-NASA ' report number NASA-CR-3849 NASA1 26:3849 b M.E. Ketterer describes a hybrid yarn produced by intimately- intermixing a tow of continuous carbon filaments with a tow of continuous thermoplastic filaments.
  • these hybrid yarns may to some extent overcome the problem of inadequate mixing, they have the added disadvantage that the yarns, being a combination of two tows, are bulky. Summary of the Invention
  • the present invention provides a method for th manufacture of a hybrid yarn which includes the step of blending two or more types of fibre, at least one of which comprises reinforcing fibre, using a stretch-breaking process.
  • the method according to the invention is used to blend two types of fibre, especially reinforcing fibre, for example carbon fibre and matrix fibre, for example thermoplastic fibre.
  • reinforcing fibre for example carbon fibre and matrix fibre, for example thermoplastic fibre.
  • the method can also be used to blend two different reinforcing fibre types, such as carbon and glass fibre.
  • Stretch-breaking is a well-known technique for processing synthetic textile fibres such as acrylic fibre.
  • the process is adapted to enable a tow of reinforcing filaments, such as carbon, to be stretch-broken simultaneously with a tow of another fibre type such as matrix filaments, then a hybrid yarn comprising a well-blended mixture of the two fibre types can be produced. After being stretch-broken, the fibre can be drafted down to the desired yarn denier ' .
  • the process also has the advantage that hybrid yarns of low denier, for example 500 denier or less can be produced. Higher yar deniers can, of course, also be produced.
  • stretch-breaking process is carried out by the following method:-
  • the carbon tow and thermoplastic tow are preferably fed directly from their packages into the stretch-breaking zone via the first pair- of nip rollers, although some pre-tensioning that is relatively gentle may be included, for example by passing one or both of the tows through a series of pre-tensioning bars.
  • a guide may be positioned in front of the first pair of nip rollers.
  • the guide generally has a slit or indentation through which the tow or tows pass, the width of the slit or indentation being slightly wider than the width of the flattened, spread tow.
  • a spread tow is preferred in order to avoid bunching of the filaments during stretch-breaking which leads to uneven drafting and inconsistent processing. If pre-tensioning bars are used then these aid in spreading out the tows and an additional guide may be omitted.
  • the carbon tow is fed through a series of pre- tensioning bars and the thermoplastic tow is passed through a guide.
  • the two tows are preferably superposed upon each other prior to being fed through the first pair of nip rollers so that good mixing of the two fibres is achieved when they are broken and drafted.
  • the ratio of surface speeds of the first and second pairs of nip rollers must be set so that the filaments are broken in the stretch-breaking zone. In addition the ratio is preferably set so that the fibres are drafted to the desired yarn denier.
  • the second pair of nip rollers is set to have a surface speed of between 6 and 35 times faster than the first pair, preferably between 8 and 25 times faster.
  • a restraining. means is advantageously positioned in the stretch-breaking zone to prevent -recoil of the more elastic thermoplastic filaments when they break. It has been found that recoil can be prevented by interposing the tow of the thermoplastic filaments between the carbon tow and the restraining means which is conveniently in the form of a plate, for example a metal plate. This method is beneficial as the carbon fibre does not have to come into contact with the restraining means which otherwise may damage the fibre.
  • the restraining means is positioned below the thermoplastic tow so that 'it exerts a light upward supporting pressure on the thermoplastic filaments; and the tensioned carbon tow is above the thermoplastic tow so that it simultaneously exerts a slight downward pressure on the thermoplastic filaments.
  • the ratch which is the distance between the first and second pairs of nip rollers, is preferably set at the 5 maximum distance that is mechanically permitted. Typically this is 150mm to 250mm, although this distance may vary depending upon the machinery used. The longer ratch enables longer staple lengths to be obtained which gives a higher reinforcing strength in the resulting Q composite.
  • the fibres After being stretch-broken the fibres are drafted, condensed and passed through the second pair of nip rollers.
  • the condensing is preferably aided by a condensing guide.
  • the process of the invention is advantageously a direct tow-to-yarn process, in which filaments are stretch-broken and drafted to a yarn having the desired denier in one stage, ie it is a continuous process with no intermediate collection of a sliver.
  • the tow is drafted to a sliver and then the sliver further drafted to a yarn as a separate stage.
  • the fibres are preferably drafted to the desired denier of the resulting hybrid yarn, usually between 100 and 1400 denier, frequently between 100 and 800 denier.
  • the fibres After passing through the second pair of nip rollers the fibres can be formed directly into a yarn as a continuous process by inserting a twist, for example using a ring and traveller system, ' and winding into a package.
  • the stretch-broken fibres can be passed through a hollow spindle and wrapped with another yarn, for example a thermoplastic fibre yarn such as a polyetherketone, eg polyetheretherketone (PEEK) .
  • a thermoplastic fibre yarn such as a polyetherketone, eg polyetheretherketone (PEEK)
  • PEEK polyetheretherketone
  • the present invention also includes a hybrid yarn comprising a blend of at least two different types of stretch-broken fibre, at least one of which comprises refinforcing fibre.
  • the hybrid yarn comprises a blend of stretch-broken reinforcing fibre and stretch-broken matrix fibre, the latter preferably being thermoplastic fibre.
  • the proportion of reinforcing fibre to matrix fibre in the hybrid yarn depends upon the required end use of the fibre, but in general the proportion is between 55 to 99%, preferably 60 to 80%, reinforcing fibre and 45% to 5 1%, preferably 40 to 20%, matrix fibre by weight based on the total weight of the yarn.
  • reinforcing fibres and matrix fibres can be used.
  • other reinforcing fibres include glass fibre ' , aramid fibre, oxidised polyacrylonitrile fibre, multi-filament ceramic fibres, for example silicon carbide fibre and graphite-, plastics- or metal-coated carbon
  • thermoplastics for the matrix fibre include polyketones such as a polyetherketone and polyetheretherketone (PEEK), polytetrafluoroethlyene, polyamides such as nylon, polyesters such as poly(ethylene terephthalate) and poly-(butylene terephthalate) ,
  • polyimides such as polyetherimide, polyolefins such as polyethylene, polypropylene and copolymers of ethylene and propylene and, polysul- phones such as polyethersulphone.
  • the hybrid yarn may be assembled in a variety of ways prior to consolidating into a composite wherein the
  • the yarn is fused to surround and embed the reinforcing fibre component.
  • the yarn may be assembled into bundles, warps, arrays or windings.
  • the yarn is preferably assembled
  • the fibrous fabric may be a woven, knitted, braided, non-woven or pile fabric.
  • the ability of the method of the invention to produce low denier yarns enables highly drapable fabrics to be formed which facilitate the formation of shaped composite products.
  • the present invention includes fabrics and composite products formed from the hybrid yarn.
  • Figure 1 shows, diagrammatically, a .process for manufacture of a hybrid yarn using stretch-breaking
  • Figure 2 is a cross-sectional view- along the line X-X of the guide used in the process shown in Figure 1.
  • Description of Preferred Embodiment A 12,000 filament, 7320 denier carbon fibre tow 2 is unwound from a package 4 and fed via a guiding roller 6 through a cascade of rollers 8. This cascade 8 pre-tensions the carbon fibre and spreads it out to a substantially flat tow. After passing through further guiding rollers 10, the tow 2 is fed through a- first pair of nip rollers 12a and 12b. Both the rollers have a smooth surface, the upper roller 12a having a synthetic rubber surface and the lower roller 12b a steel surface.
  • a 900 filament, 3800 denier PEEK fibre tow 14 (PEEK fibre is available from Celanese Corporation) is unwound from a package (not shown) and fed, via a guiding roller
  • thermoplastic tow 14 Prior to passing through the nip rollers 12a and 12b, the thermoplastic tow 14 travels over a guide 18.' Referring to Figure 2, this guide 18 consists of an aluminium block
  • the tow 14 is passed over the groove 102 which is just wide enough to allow the tow 14 to spread to a flat tow without creating voids between the filaments.
  • the tows 2 and 14 After passing through the first pair of nip rollers 12a and 12b, the tows 2 and 14 enter the stretch-breaking zone which is the zone between the first pair of nip rollers 12a and 12b and a second pair of nip rollers 20a and 20b.
  • the ratio of surface speeds between the first and second pairs of nip rollers is set at 1:8, and the ratch distance is 200 mm.
  • the tows 2 and 14 are fed from the first pair of nip rollers 12a and 12b through the second pair of nip rollers 20a and 20b. Again both rollers have smooth surfaces, the upper roller 20a having a synthetic rubber surface and the lower roller 20b a steel surface.
  • the faster speed of the second pair of nip rollers causes the filaments in both tows to stretch and break in the stretch-breaking zone.
  • thermoplastic filaments Because of the elastic nature of the thermoplastic filaments, they tend to recoil when stretch-broken. To prevent this a restraining means which consists of a rectangular aluminium plate 22 is positioned under the thermoplastic tow 14 in the middle of the stretch-breaking zone where the breaking of the filaments occurs. Because the carbon tow 2 is superposed above the thermoplastic tow 14, the thermoplastic tow is sandwiched between the carbon tow 2 and the plate 22, and the combination of forces exerted on the thermoplastic tow 14 by the carbon tow 2 and the plate 22 prevents recoil of the thermoplastic filaments when they break.
  • a restraining means which consists of a rectangular aluminium plate 22 is positioned under the thermoplastic tow 14 in the middle of the stretch-breaking zone where the breaking of the filaments occurs. Because the carbon tow 2 is superposed above the thermoplastic tow 14, the thermoplastic tow is sandwiched between the carbon tow 2 and the plate 22, and the combination of forces exerted on the thermoplastic tow 14 by the carbon to
  • the filaments are drafted, with the aid of a 3.2mm wide condenser guide (not shown), directly to a 200 denier yarn by the second pair of nip rollers 20a and 20b.
  • the condenser -guide is pivotally fixed in the stretch-breaking zone to allow lateral movement of the tows which facilitates the passage of the tows through the stretch-breaking zone.
  • the combination of stretch- breaking and drafting thoroughly mixes the carbon fibre with the thermoplastic fibre.
  • twist is inserted in the yarn using a conventional ring and traveller system (not shown) and the resulting multi- filament hybrid yarn 26 is collected on a bobbin 28.
  • the proportion of carbon and PEEK fibre in the resulting yarn is 65% carbon fibre and 35% PEEK fibre by weight based on the total weight of the yarn.
  • stretch- breaking of the carbon fibre tow 2 may be initiated before the thermoplastic tow 14 is fed through the nip rollers 12a and 12b.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Preliminary Treatment Of Fibers (AREA)

Abstract

Procédé de fabrication d'un fil hybride (26) consistant à appliquer un procédé de craquage pour mélanger deux types différents de fibres ou davantage, dont l'une est une fibre de renfort. Les câbles de filaments (2, 14), par exemple un câble de filaments de carbone et un câble de filaments en matière thermoplastique, sont amenés ensemble dans une zone de craquage (à 22), où ils se rompent par étirage entre deux paires de rouleaux à contact linéaire (12a, 12b: 20a, 20b), sont étirés et transformés en fil (26). On obtient de la sorte des fils hybrides bien mêlés de divers deniers, notamment d'un petit nombre de deniers. Ces fils peuvent être utilisés pour former des produits composites.
PCT/US1987/002156 1987-08-26 1987-08-26 Fil hybride Ceased WO1989001999A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP19880902069 EP0327600A1 (fr) 1987-08-26 1987-08-26 Fil hybride
JP88502090A JPH02500605A (ja) 1987-08-26 1987-08-26 ハイブリツドヤーン
PCT/US1987/002156 WO1989001999A1 (fr) 1987-08-26 1987-08-26 Fil hybride

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1987/002156 WO1989001999A1 (fr) 1987-08-26 1987-08-26 Fil hybride

Publications (1)

Publication Number Publication Date
WO1989001999A1 true WO1989001999A1 (fr) 1989-03-09

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1987/002156 Ceased WO1989001999A1 (fr) 1987-08-26 1987-08-26 Fil hybride

Country Status (3)

Country Link
EP (1) EP0327600A1 (fr)
JP (1) JPH02500605A (fr)
WO (1) WO1989001999A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0395036A3 (fr) * 1989-04-26 1991-05-29 E.I. Du Pont De Nemours And Company Procédé pour fabriquer des matières composites avec des fibres alignées, rompues par étirage et produit obtenu
KR970070267A (ko) * 1996-04-09 1997-11-07 악커만, 루츠 위르겐 저수축율 혼방사, 이의 제조방법 및 용도
WO2004015175A1 (fr) * 2002-08-07 2004-02-19 Albany International Techniweave, Inc. Tissus en graphite a base de brai et feutre poinçonne et aiguillete pour substrats a couche de diffusion gazeuse pour pile a combustible et composites renforces a conductivite thermique elevee
WO2006020404A1 (fr) * 2004-08-06 2006-02-23 Stowe-Pharr Mills, Inc. File de fibres haute resistance produit a partir de filaments continus de module eleve, et procede de fabrication de ce file
EP1609891A3 (fr) * 1999-06-14 2007-02-28 E.I.Du pont de nemours and company Procédé et produit de rupture par étirage
WO2007062617A1 (fr) * 2005-12-02 2007-06-07 Gert Wagener Procede de fabrication d’un materiau de renfort a partir de filaments extrudes impregnes et enduits d’une matiere thermoplastique
EP1846600A4 (fr) * 2005-02-10 2012-08-01 Supreme Elastic Corp Melange de fibres haute performance et produits constitues de ce melange
EP2531638A2 (fr) * 2010-02-05 2012-12-12 University Of Leeds Fil en fibre de carbone et son procédé de production
ITBS20130157A1 (it) * 2013-10-31 2015-05-01 Filtes Internat S R L Con Soc Io Unico Filato per tessuti di protezione, e procedimento di fabbricazione

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2262872A (en) * 1938-06-01 1941-11-18 Celanese Corp Method of preparing textile materials
AU476167B2 (en) * 1974-08-02 1974-10-24 Brunswick Corporation Method of forming fiber composite
GB2084977A (en) * 1980-08-28 1982-04-21 Secr Defence Fibres having a cross-section approximating a polygon
US4369622A (en) * 1980-03-24 1983-01-25 Riegel Textile Corporation Method and apparatus for drawing and blending textile materials

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2262872A (en) * 1938-06-01 1941-11-18 Celanese Corp Method of preparing textile materials
AU476167B2 (en) * 1974-08-02 1974-10-24 Brunswick Corporation Method of forming fiber composite
US4369622A (en) * 1980-03-24 1983-01-25 Riegel Textile Corporation Method and apparatus for drawing and blending textile materials
GB2084977A (en) * 1980-08-28 1982-04-21 Secr Defence Fibres having a cross-section approximating a polygon

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0395036A3 (fr) * 1989-04-26 1991-05-29 E.I. Du Pont De Nemours And Company Procédé pour fabriquer des matières composites avec des fibres alignées, rompues par étirage et produit obtenu
KR970070267A (ko) * 1996-04-09 1997-11-07 악커만, 루츠 위르겐 저수축율 혼방사, 이의 제조방법 및 용도
EP1621650A3 (fr) * 1999-06-14 2007-05-23 E.I.Du pont de nemours and company Procédé et produit de rupture par étirage
EP1609891A3 (fr) * 1999-06-14 2007-02-28 E.I.Du pont de nemours and company Procédé et produit de rupture par étirage
EP1621653A3 (fr) * 1999-06-14 2007-02-28 E. I. du Pont de Nemours and Company Procédé et produit de rupture par étirage
EP1621651A3 (fr) * 1999-06-14 2007-02-28 E.I.Du pont de nemours and company Procédé de rupture par étirage
RU2318932C2 (ru) * 2002-08-07 2008-03-10 Олбани Интернэшнл Текнивив, Инк. Графитовые ткани на основе пека и прошитые иглами войлоки для подложек газодиффузионного слоя топливного элемента, и армированные композиты с высокой теплопроводностью
CN100402716C (zh) * 2002-08-07 2008-07-16 阿尔巴尼国际纺织技术有限公司 一种沥青基石墨织物及其制造方法
WO2004015175A1 (fr) * 2002-08-07 2004-02-19 Albany International Techniweave, Inc. Tissus en graphite a base de brai et feutre poinçonne et aiguillete pour substrats a couche de diffusion gazeuse pour pile a combustible et composites renforces a conductivite thermique elevee
KR100870194B1 (ko) 2004-08-06 2008-11-24 스토우-파 밀즈, 인코포레이티드 고탄성률 연속 필라멘트로부터 제조된 고강도 방적사, 및그의 제조 방법
US7188462B2 (en) 2004-08-06 2007-03-13 Stowe-Pharr Mills, Inc. High-strength spun yarn produced from continuous high-modulus filaments, and process for making same
WO2006020404A1 (fr) * 2004-08-06 2006-02-23 Stowe-Pharr Mills, Inc. File de fibres haute resistance produit a partir de filaments continus de module eleve, et procede de fabrication de ce file
EP1846600A4 (fr) * 2005-02-10 2012-08-01 Supreme Elastic Corp Melange de fibres haute performance et produits constitues de ce melange
WO2007062617A1 (fr) * 2005-12-02 2007-06-07 Gert Wagener Procede de fabrication d’un materiau de renfort a partir de filaments extrudes impregnes et enduits d’une matiere thermoplastique
EP2531638A2 (fr) * 2010-02-05 2012-12-12 University Of Leeds Fil en fibre de carbone et son procédé de production
ITBS20130157A1 (it) * 2013-10-31 2015-05-01 Filtes Internat S R L Con Soc Io Unico Filato per tessuti di protezione, e procedimento di fabbricazione
EP2868787A1 (fr) * 2013-10-31 2015-05-06 Filtes International S.r.l. Con Socio Unico Fil pour textiles de protection et sa méthode de fabrication
US9856584B2 (en) 2013-10-31 2018-01-02 FILTES INTERNATIONAL S.r.l. CON SOCIO UNICO Yarns for protective textiles, and manufacturing methods thereof

Also Published As

Publication number Publication date
JPH02500605A (ja) 1990-03-01
EP0327600A1 (fr) 1989-08-16

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