EP0230161B1 - Process for manufacturing, by thermal shrinkage, tubular textile articles consisting at least partly of carbon fibres - Google Patents

Process for manufacturing, by thermal shrinkage, tubular textile articles consisting at least partly of carbon fibres Download PDF

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Publication number
EP0230161B1
EP0230161B1 EP19860402505 EP86402505A EP0230161B1 EP 0230161 B1 EP0230161 B1 EP 0230161B1 EP 19860402505 EP19860402505 EP 19860402505 EP 86402505 A EP86402505 A EP 86402505A EP 0230161 B1 EP0230161 B1 EP 0230161B1
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EP
European Patent Office
Prior art keywords
fibres
fabric
carbonizable
fibers
tubular
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
Application number
EP19860402505
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German (de)
French (fr)
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EP0230161A1 (en
Inventor
Paul Rebut
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.)
D'applications Et Realisations De Tissus Industriels Sarti Ste
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D'applications Et Realisations De Tissus Industriels Sarti Ste
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Publication of EP0230161A1 publication Critical patent/EP0230161A1/en
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Publication of EP0230161B1 publication Critical patent/EP0230161B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/14—Processes for the fixation or treatment of textile materials in three-dimensional forms

Definitions

  • the invention relates to a method for manufacturing by thermal shrinkage woven tubular parts, composed at least in part of carbon fibers.
  • a method of manufacturing a woven tubular part, formed at least in part from carbon fibers characterized in that it consists in manufacturing in a single weaving a tubular fabric with fibers of which at least some are carbonizable, then heating this fabric to a temperature at least equal to the carbonization temperature of the carbonizable fibers, so as to obtain a shrinkage of these carbonizable fibers, accompanied by an increase in the density of fibers in the fabric .
  • carbonizable fibers designates here any fiber formed of a material capable of transforming into carbon under the effect of heating. This material can in particular be a preoxidized material. More specifically, mention will be made of cellulosic and phenolic fibers, as well as polyacrylonitrile (PAN) fibers or the like.
  • PAN polyacrylonitrile
  • the tubular fabric is placed on a shaped piece before heating, thus, the fabric can be given a particular shape, within the limit of the maximum shrinkage of the fibers during their transformation carbon.
  • This shrinkage is approximately 24% in the three directions for a fabric formed only, of carbonizable fibers.
  • the shaped part limiting the withdrawal of the fibers, causes a tensioning thereof, which also leads to an improvement in the mechanical strength of the part obtained and to a reorganization of the arrangement of the fibers.
  • a three-dimensional tubular fabric is made from weft threads forming several layers generally oriented in a circumferential direction and warp threads alternately passing through all the layers of weft threads and extending from one end to the other of the part, at least the weft threads being formed of carbonizable fibers.
  • a tubular fabric formed of PAN fibers oriented in at least two different directions is produced in a single weaving. This fabric is then installed on a shaped part, made of refractory material whose shape and external dimensions correspond to the shape and internal dimensions of the part to be produced.
  • a rise in temperature to a temperature between 800 ° C and 1800 ° C leads to the transformation of PAN fibers into carbon fibers.
  • the fibers shrink until the dimensions and shape defined by the shaped part are reached. This shrinkage is accompanied by a sharp increase in the density of the fibers.
  • the end of the withdrawal being hampered by the shaped part, a reorganization of the orientation of the fibers, as well as an improvement in their mechanical strength are also obtained.
  • a three-dimensional tubular fabric is placed on the shaped part, made seamlessly in a single weaving.
  • a fabric may in particular be formed of weft threads forming several layers generally oriented in a circumferential direction and of warp threads passing alternately in one and the other direction all the layers of weft threads and extending in a end to end of the room.
  • the weft threads are made of PAN fibers.
  • the warp threads can also be made of PAN fibers if a withdrawal in the three orthogonal directions is desired. They can also be made of a refractory material such as graphite, silica, ceramic, etc.
  • This technique can in particular be used to manufacture rocket elements, tire belts, protective bellows, filter elements, piston and cylinder reinforcements for automobile engines, etc.
  • the thickness of the tubular piece to be produced is greater than that of the three-dimensional tubular fabric, several fabrics of this type on the same shaped part.
  • a complementary refractory device such as bundles of graphite, boron wires, etc. can then be inserted between two tubular fabrics. Maintaining this device before the temperature rise is ensured for example by means of a honeycomb or multitubular tissue designed to disappear during heating.
  • This fabric can in particular be a cotton fabric with a low ash rate.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Woven Fabrics (AREA)

Description

L'invention concerne un procédé permettant de fabriquer par retrait thermique des pièces tubulaires tissées, composées au moins en partie de fibres de carbone.The invention relates to a method for manufacturing by thermal shrinkage woven tubular parts, composed at least in part of carbon fibers.

Le document JP-A-5 969 410 ainsi que le brevet US-A-3 856 593 enseignent la réalisation de pièces épaisses de formes diverses, comprenant une armature formée d'un empilement de plusieurs couches de tissus, éventuellement cousues. Le tissu est formé de fibres de carbone, et ses interstices sont ensuite remplis de carbone par différents procédés, pour former des composites carbone-carbone.The document JP-A-5,969,410 as well as the patent US-A-3,856,593 teach the production of thick pieces of various shapes, comprising a frame formed by a stack of several layers of fabric, possibly sewn. The fabric is formed of carbon fibers, and its interstices are then filled with carbon by various processes, to form carbon-carbon composites.

Par ailleurs, l'article de D. ROBBINS intitulé «A Retrospect of Carbon Fibre Composites» et publié dans la revue «Textile Institute and Industry», vol. 14, n ° 12, déc. 1976, pages 376-379, décrit la fabrication de tissus de fibres de carbone à partir de fibres de cellulose, de bitume ou de polyacrylonitrile (PAN), ces matériaux constituant des «précurseurs» du carbone, disponibles sous forme de fibres. Pour fabriquer un tissu de carbone, des fibres d'un précurseur du carbone peuvent d'abord être tissées. Le précurseur est ensuite transformé en carbone par chauffage du tissu. Au cours de cette opération, il est indiqué que le retrait des fibres doit être empêché, afin notamment que l'orientation moléculaire à l'intérieur des fibres soit satisfaisante.Furthermore, the article by D. ROBBINS entitled "A Retrospect of Carbon Fiber Composites" and published in the journal "Textile Institute and Industry", vol. 14, n ° 12, dec. 1976, pages 376-379, describes the manufacture of carbon fiber fabrics from cellulose, bitumen or polyacrylonitrile (PAN) fibers, these materials constituting carbon "precursors", available in the form of fibers. To make a carbon fabric, fibers of a carbon precursor can first be woven. The precursor is then transformed into carbon by heating the fabric. During this operation, it is indicated that the withdrawal of the fibers must be prevented, in particular so that the molecular orientation inside the fibers is satisfactory.

Ainsi, l'effet de retrait qui accompagne la transformation en carbone de fibres de matériaux précurseurs est considéré depuis de nombreuses années comme un inconvénient, lorsque cette trasnforma- tion est effectuée après tissage des fibres. C'est probablement pour cette reaison que les armatures utilisées dans la réalisation de pièces épaisses sont toujours réalisées directement à partir de tissus de fibres de carbone.Thus, the shrinkage effect which accompanies the carbon transformation of fibers of precursor materials has been considered for many years as a drawback, when this transformation is carried out after weaving the fibers. It is probably for this reaison that the reinforcements used in the production of thick pieces are always made directly from carbon fiber fabrics.

Conformément à l'invention, et contrairement au préjugé selon lequel le retrait des fibres qui se produit lors de la transformation en carbone constitue un inconvénient lorsque ces fibres sont tissées, il est proposé d'utiliser cet effet de retrait pour fabriquer des pièces tubulaires tissées présentant une densité de fibres plus importante et, le cas échéant, pour donner à ces pièces des profils et/ou des dimensions variés.In accordance with the invention, and contrary to the prejudice that the withdrawal of fibers which occurs during carbon transformation constitutes a drawback when these fibers are woven, it is proposed to use this withdrawal effect to manufacture woven tubular parts having a higher fiber density and, if necessary, to give these parts various profiles and / or dimensions.

A cet effet, il est proposé un procédé de fabrication d'une pièce tubulaire tissée, formée au moins en partie de fibres de carbone, caractérisé en ce qu'il consiste à fabriquer en un seul tissage un tissu tubulaire avec des fibres dont au moins certaines sont carbonisables, puis à chauffer ce tissu à une température au moins égale à la température de carbonisation des fibres carbonisables, de façon à obtenir un retrait de ces fibres carbonisables, s'accompagnant d'un accroissement de la densité de fibres dans le tissu.To this end, there is provided a method of manufacturing a woven tubular part, formed at least in part from carbon fibers, characterized in that it consists in manufacturing in a single weaving a tubular fabric with fibers of which at least some are carbonizable, then heating this fabric to a temperature at least equal to the carbonization temperature of the carbonizable fibers, so as to obtain a shrinkage of these carbonizable fibers, accompanied by an increase in the density of fibers in the fabric .

L'expression «fibres carbonisables» désigne ici toute fibre formée d'un matériau apte à se transformer en carbone sous l'effet d'un chauffage. Ce matériau peut notamment être un matériau préoxydé. Plus précisément, on citera les fibres cellulosiques et phénoliques, ainsi que les fibres de polyacrylonitrile (PAN) ou équivalents.The expression “carbonizable fibers” designates here any fiber formed of a material capable of transforming into carbon under the effect of heating. This material can in particular be a preoxidized material. More specifically, mention will be made of cellulosic and phenolic fibers, as well as polyacrylonitrile (PAN) fibers or the like.

Dans un mode de réalisation particulaire de l'invention, on place le tissu tubulaire sur une pièce de forme avant de procéder au chauffage, ainsi, on peut donner au tissu une forme particulière, dans la limite du retrait maximum des fibres lors de leur transformation en carbone. (Ce retrait est d'environ 24% dans les trois directions pour un tissu formé uniquement, de fibres carbonisables). La pièce de forme, On limitant le retrait des fibres, provoque une mise en tension de celle-ci, ce qui conduit par ailleurs à une amélioration de la tenue mécanique de la pièce obtenue et à une réorganisation de l'arrangement des fibres.In a particular embodiment of the invention, the tubular fabric is placed on a shaped piece before heating, thus, the fabric can be given a particular shape, within the limit of the maximum shrinkage of the fibers during their transformation carbon. (This shrinkage is approximately 24% in the three directions for a fabric formed only, of carbonizable fibers). The shaped part, limiting the withdrawal of the fibers, causes a tensioning thereof, which also leads to an improvement in the mechanical strength of the part obtained and to a reorganization of the arrangement of the fibers.

Dans le cas particulier de la fabrication d'une pièce tubulaire épaisse, on fabrique un tissu tubulaire tridimensionnel à partir de fils de trame formant plusieurs couches orientées généralement selon une direction circonférentielle et de fils de chaîne traversant alternativement toutes les couches de fils de trame et s'étendant d'une extrémité à l'autre de la pièce, au moins les fils de trame étantformés de fibres carbonisables.In the particular case of the production of a thick tubular piece, a three-dimensional tubular fabric is made from weft threads forming several layers generally oriented in a circumferential direction and warp threads alternately passing through all the layers of weft threads and extending from one end to the other of the part, at least the weft threads being formed of carbonizable fibers.

Différents exemples mettant en oeuvre les principes de l'invention vont maintenant être décrits.Various examples implementing the principles of the invention will now be described.

Dans un premier exemple de mise en oeuvre de l'invention, on réalise en un seul tissage un tissu tubulaire formé de fibres de PAN orientée selon au moins deux directions différentes. On installe ensuite ce tissu sur une pièce de forme, en matériau réfractaire dont la forme et les dimensions extérieures correspondent à la forme et aux dimensions intérieures de la pièce à réaliser.In a first example of implementation of the invention, a tubular fabric formed of PAN fibers oriented in at least two different directions is produced in a single weaving. This fabric is then installed on a shaped part, made of refractory material whose shape and external dimensions correspond to the shape and internal dimensions of the part to be produced.

Une montée en température à une température comprise entre 800°C et 1800°C conduit à la transformation des fibres de PAN en fibres de carbone. Au cours du chauffage, les fibres se rétractent jusqu'à ce que les dimensions et la forme définies par la pièce de forme soient atteintes. Ce retrait s'accompagne d'une forte augmentation de la densité des fibres. De plus, la fin du retrait étant entravée par la pièce de forme, une réorganisation de l'orientation des fibres, ainsi qu'une amélioration de leur tenue mécanique sont aussi obtenues.A rise in temperature to a temperature between 800 ° C and 1800 ° C leads to the transformation of PAN fibers into carbon fibers. During heating, the fibers shrink until the dimensions and shape defined by the shaped part are reached. This shrinkage is accompanied by a sharp increase in the density of the fibers. In addition, the end of the withdrawal being hampered by the shaped part, a reorganization of the orientation of the fibers, as well as an improvement in their mechanical strength are also obtained.

Dans un deuxième exemple proche du précédent, on place sur la pièce de forme un tissu tridimensionnel tubulaire, réalisé sans couture en un seul tissage. Un tel tissu peut notamment être formé de fils de trame formant plusieurs couches orientées généralement selon une direction circonférentielle et de fils de chaîne traversant alternativement dans l'un et l'autre sens toutes les couches de fils de trame et s'étendant d'une extrémité à l'autre de la pièce. Les fils de trame sont réalisés en fibres de PAN. Les fils de chaîne peuvent être également en fibres de PAN si un retrait dans les trois directions orthogonales est souhaité. Ils peuvent aussi être réalisés en un matériau réfractaire tel que graphite, silice, céramique, etc...In a second example close to the previous one, a three-dimensional tubular fabric is placed on the shaped part, made seamlessly in a single weaving. Such a fabric may in particular be formed of weft threads forming several layers generally oriented in a circumferential direction and of warp threads passing alternately in one and the other direction all the layers of weft threads and extending in a end to end of the room. The weft threads are made of PAN fibers. The warp threads can also be made of PAN fibers if a withdrawal in the three orthogonal directions is desired. They can also be made of a refractory material such as graphite, silica, ceramic, etc.

Un chauffage de montage entre 800 ° C et 18000C conduit ici encore aux effets énoncés précédemment. Cette technique peut notamment être utilisée pour fabriquer des éléments de fusées, des ceintures de pneumatiques, des soufflets de protection, des éléments de filtres, des renforts de pistons et cylindres pour moteurs d'automobiles, etc.A mounting heater between 800 ° C and 18000C again leads to the effects stated above. This technique can in particular be used to manufacture rocket elements, tire belts, protective bellows, filter elements, piston and cylinder reinforcements for automobile engines, etc.

En variante, lorsque l'épaisseur de la pièce tubulaire à réaliser est supérieure à celle du tissu tridimensionnel tubulaire, on superpose plusieurs tissus de ce type sur une même pièce de forme. Un dispositif réfractaire complémentaire tel que des faisceaux de fils de graphite, bore, etc. peut alors être inséré entre deux tissus tubulaires. Le maintien de ce dispositif avant la montée en température est assuré par exemple au moyen d'un tissu alvéolé ou multitubulaire conçu pour disparaître lors du chauffage. Ce tissu peut notamment être un tissu de coton à faible taux de cendres.As a variant, when the thickness of the tubular piece to be produced is greater than that of the three-dimensional tubular fabric, several fabrics of this type on the same shaped part. A complementary refractory device such as bundles of graphite, boron wires, etc. can then be inserted between two tubular fabrics. Maintaining this device before the temperature rise is ensured for example by means of a honeycomb or multitubular tissue designed to disappear during heating. This fabric can in particular be a cotton fabric with a low ash rate.

De façon générale, on voit que le retrait de fibres qui accompagne leur transformation en fibres de carbone permet d'obtenir des pièces tubulaires tissées présentant une densité de fibres très accrue. De plus, ce retrait permet la mise en forme et/ou à dimension des pièces, grâce à l'utilisation d'éléments ou pièces de forme, en matériaux réfractaires (graphite, porcelaine, etc.) ou en matériaux destructibles (technique de fonderie).In general, it can be seen that the withdrawal of fibers which accompanies their transformation into carbon fibers makes it possible to obtain woven tubular pieces having a very increased fiber density. In addition, this shrinkage allows the shaping and / or dimensioning of the parts, through the use of elements or shaped parts, in refractory materials (graphite, porcelain, etc.) or in destructible materials (foundry technique ).

Claims (5)

1. Process for the production of a woven tubular part or piece, at least partly formed from carbon fibres, characterized in that it comprises producing in a single weaving operation a tubular fabric having fibres, whereof at least some are carbonizable, then heating said fabric to a temperature at least equal to the carboniszation temperature of the carbonizable fibres, in order to obtain a shrinkage of said carbonizable fibres acompanied by an increase in the density of the fibres in the fabric.
2. Process according to claim 1, characterized in that before heating the fabric, the latter is placed on at least one shaping member.
3. Process according to either of the claims 1 and 2 adapted to the production of a thick tubular part or piece, characterized in that a three-dimensional tubular fabric is produced from weft thread forming sever- allayers generally oriented in a circumferential direction and warp threads alternatively passing through all the layers of weft threads and extending from one end of the part to the other, whereby at least the weft threads are formed from carbonizable fibres.
4. Process according to claim 3, characterized in that prior to heating, several three-dimensional tubular fabrics are superimposed, whilst inserting between two adjacent fabrics a complimentary refractory device.
5. Process according to any one of the preceding claims, characterized in that the carbonizable threads are preoxidized threads chosen from among cellulose fibres, phenolic fibres and polyacrylonitrile fibres.
EP19860402505 1985-11-15 1986-11-12 Process for manufacturing, by thermal shrinkage, tubular textile articles consisting at least partly of carbon fibres Expired EP0230161B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8517116 1985-11-15
FR8517116A FR2590287B1 (en) 1985-11-15 1985-11-15 USES OF THE THREE-DIMENSIONAL WITHDRAWAL OF A PREOXIDATED OR OTHER TISSUE DURING ITS CONVERSION TO CARBON. RESULTING PRODUCTS

Publications (2)

Publication Number Publication Date
EP0230161A1 EP0230161A1 (en) 1987-07-29
EP0230161B1 true EP0230161B1 (en) 1989-10-18

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EP19860402505 Expired EP0230161B1 (en) 1985-11-15 1986-11-12 Process for manufacturing, by thermal shrinkage, tubular textile articles consisting at least partly of carbon fibres

Country Status (3)

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EP (1) EP0230161B1 (en)
DE (1) DE3666466D1 (en)
FR (1) FR2590287B1 (en)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4823793B1 (en) * 1968-06-17 1973-07-16
US3856593A (en) * 1972-05-23 1974-12-24 Haveg Industries Inc Expanded porous substrate for fibrous graphite structure
US4318948A (en) * 1979-07-25 1982-03-09 Fordath Limited Article comprising carbon fibres and method of producing the article
JPS5734085A (en) * 1980-08-06 1982-02-24 Toho Beslon Co Manufacture of carbon fiber reinforced carbon composite material
GB8334560D0 (en) * 1983-12-29 1984-02-01 Cc Developments Ltd Carbonisable fabrics

Also Published As

Publication number Publication date
EP0230161A1 (en) 1987-07-29
DE3666466D1 (en) 1989-11-23
FR2590287B1 (en) 1988-06-17
FR2590287A1 (en) 1987-05-22

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