CA1279033C - Producing composite materials from high voltage electrostatically charged fibres by impregnation - Google Patents
Producing composite materials from high voltage electrostatically charged fibres by impregnationInfo
- Publication number
- CA1279033C CA1279033C CA000491615A CA491615A CA1279033C CA 1279033 C CA1279033 C CA 1279033C CA 000491615 A CA000491615 A CA 000491615A CA 491615 A CA491615 A CA 491615A CA 1279033 C CA1279033 C CA 1279033C
- Authority
- CA
- Canada
- Prior art keywords
- fibers
- electric current
- induced
- matrix
- time interval
- 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 - Fee Related
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
- B29C70/14—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat oriented
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- 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
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
- B29C70/20—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length oriented in a single direction, e.g. roofing or other parallel fibres
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- 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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/38—Automated lay-up, e.g. using robots, laying filaments according to predetermined patterns
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/38—Textile inserts, e.g. cord or canvas layers, for tyres; Treatment of inserts prior to building the tyre
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0048—Fibrous materials
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/82—Asbestos; Glass; Fused silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/248—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using pre-treated fibres
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/24—Electrodes for alkaline accumulators
- H01M4/26—Processes of manufacture
- H01M4/28—Precipitating active material on the carrier
- H01M4/29—Precipitating active material on the carrier by electrochemical methods
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/70—Carriers or collectors characterised by shape or form
- H01M4/80—Porous plates, e.g. sintered carriers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
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- 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
- B29B15/10—Coating or impregnating independently of the moulding or shaping step
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- 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
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/04—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam
- B29C35/045—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould using liquids, gas or steam using gas or flames
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
- C04B2235/5248—Carbon, e.g. graphite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/605—Making or treating the green body or pre-form in a magnetic field
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- C—CHEMISTRY; METALLURGY
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/616—Liquid infiltration of green bodies or pre-forms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2915—Rod, strand, filament or fiber including textile, cloth or fabric
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2916—Rod, strand, filament or fiber including boron or compound thereof [not as steel]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/292—In coating or impregnation
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Disintegrating Or Milling (AREA)
- Battery Electrode And Active Subsutance (AREA)
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Abstract
Canada APPLICANT: MICHEL BERGER
INVENTOR: MICHEL BERGER
TITLE: PROCESS FOR PREPARING COMPOSITE
MATERIALS AND PRODUCTS OBTAINED WITH
SAID PROCESS
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the preparation of a composite material wherein the element used to reinforce the composite material is subjected to an electrostatic field induced by a high voltage electric current, said element being then impregnated with a liquid matrix material or precursor of matrix, while still under the influence of said field, and to the composite materials obtained by carrying out said process.
INVENTOR: MICHEL BERGER
TITLE: PROCESS FOR PREPARING COMPOSITE
MATERIALS AND PRODUCTS OBTAINED WITH
SAID PROCESS
ABSTRACT OF THE DISCLOSURE
The present invention relates to a process for the preparation of a composite material wherein the element used to reinforce the composite material is subjected to an electrostatic field induced by a high voltage electric current, said element being then impregnated with a liquid matrix material or precursor of matrix, while still under the influence of said field, and to the composite materials obtained by carrying out said process.
Description
1.~'7'~
The present lnvention relates to a process for preparing composite materials; it also relates to the intermediate or finished products which can be obtained with sa$d process.
Composite materials are materials comprised of reinforcing elements (mostly fibers - or filaments - such as glass fibers, carbon fibers, boron or polyamide fibers, etc...) and of a matrix (constituted either by a resin or a resistant material such as metal or ceramics).
The properties of composite materials are particularly dependent, as we know, on:
- the orientation of the reinforcing elements:
~ - the good distribution of the matrix throughout the volume ; between the reinforcing elements:
- and of any bonds which may be induced between said reinforcing elements and said matrix.
It is therefore an advantage to use a technique wherein the above parameters can be worked in such a way as to optimize the properties of the product as a function of the aim in view, and this is precisely the ob~ect of the present invention.
~, According to one of its aspects, the present invention provides a process for the preparation of a composite material that includes fibers used to reinforce the composite material comprising the steps of:
~ sub~ecting the fibers to an electrostatic field induced ;~ by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of the , ~ ; fibers; and .~ :
.., ~, . ~q~
~ ,, s , . ~: , . . : "
~'; " ' " ' ' '~ ' ' ' :~ ' ' .
~:~ , , ' ' "' .
. ' . - ' ' ~' ' ' ' . . .
': ' ' , - ' . " ' ' ': ' ' ' ' ~ ' , , ~
:. ' . ' . . , . , ,' ' ,, ' ' , ' .' .
.' ' . ' , : . ' , . .
.~'7~30;~
la impregnating the fibers after the elapse of the time interval with a llquid matrix material or precursor of matrix, while the $ibers are electrostatically charged.
According to another of its aspects, the present invention provides a process for the preparation of a composite material that includes fibers used to reinforce the composite material comprising the steps of:
subjecting the fibers to a first electrostatic field that is induced by a first high-voltage electric current for a first time interval:
sub;ecting the fibers to a second electrostatic field different from the first electrostatic field that is induced by a second h~gh-voltage electric current for a second time interval after sub~ecting the fibers to the first electrostatic field; one of the first and second electrostatic fields being induced by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of the fibers.
Thus, it has been found that the reinforcing elements (i.e. the fibers) may be advantageously sub~ected to an electrostatic field induced by a very high voltage current, and then impregnated with the liquid matrix, using the known techniques, while the elements are electrostatically charged.
Thus, the present process encompasses (i) the case where the electrostatic field has been stopped or removed but the fibers are still charged, and (ii) the case where the electrostatic field is maintained during impregnation.
By high voltage current-induced electrostatic field is meant a field at least equal to the filed obtained by applying between two electrodes 20 mm apart, a voltage equal to at least 20,000 volts in alternating current and to at least 40,000 volts in direct current. The reinforcing elements, and in particular the fibers, fibrils or roves used, are then positioned . ..
; ~., :, i~, .- '` `. 1" ,. : ~
., . ~ : . .
'-''',,' ' ' '' ~-. '' :. ,.
:'~':- ,''. :. ' -': ' '' .... . . .
. ~: , : - .
: . : - -. . . ..
.
~. - ~ - - .
., , - .
between the electrodes subjected to the very high voltage current.
According to the invention, any type of fibers can be used as reinforcing elements, but they must be in a dielectric material, namely a material which, when under the effect of the field, becomes electrically charged and remains charged for a certain time. This is the case for example with polyami~e fibers (of NYLON or KEVLAR type), glassfibers, fibers in ce~rtain metallic oxides, fibers in complex materials (metaloxide) and with carbon fibers. On the contrary, conducting fibers, such as for example metallic fibers or surface-metallized fibers are-more aifficult to use in the process according to the invention.
The reinforcing fibers are placed between the electrodes, and the very high voltage current is applied between said electrodes for a period long enough to charge said fibers, then, the charged fibers, taken out of the field, are impregnated with the matrix material or with a precursor of the matrix material, which is in liquid form.
The charged fibers having a tendency to push one another back, a bed of fibers is obtained at the output of the field, of which the thickness is - ;25 between two and four times the thickness of the bed of ~-fibers initially introduced between the electrodes, and `~;it is when the fibers are in that "swollen" state that they should be impregnated.
Any one ofthe currently known and used matrix materials is suitable for the process according to the invention, for example resins ~epoxy or polyamide resins or hardened carbon mixtures) or silica-based mixtures capable of forming ceramics, and metals.
When the fibers have been impregnated - ~35 by the liquid matrix material (or its liquid precursor), ,~the resulting product can either be sold as is (normally ,"~
.-: - - . . . . - ~. , :
. ... - ~ . - , -: - . . .
~ ~ . . . . .
:-., - ~ ,: ' .~ . ' ' after a first solification) or it can be transformed by molding and solidification of the matrix. And as known, the matrix itself can be charged.
It has been found that with the process according to the invention, the reinforcing elements (fibers) become thoroughly impregnated by the matrix.
sut it is also possible to bring to the process according to the invention certain particular-ly advantageous alterations.
If the electrostatic field is produced with a direct current, it is noted that, besides the swelling action of the bundle of initial fibers, there occurs a complementary orientation of said fibers.
This orientation will permit the preparation of a compo-site material having specific properties.
It is àlso possible, as we know, to ob-tain that same orientation for certain fibers, by the slmultaneous or prlor use of another field such as for example a magnetic field.
If the electrostatic field is produced with an alternating current, it is noted that besides the swelling action of the bundle of fibers described hereinabove, localized discharges occur between the ~ ~ fibrils, causing, principally in the presence of oxygen, ~ - 25 a modification of the surface of the fibers. This modification (which is probably an oxidation), stimulates the properties of the final material insofar as it makes it possible to obtain consolidated bonding between the fiber and the matrix.
~ It is conceivably possible, according to the invention, to use successively an A.C. electro-static field (swelling and surface treatment) and a D.C.
electrostatic field (swelling and orientation).
The invention will be more readily 35~ understood on reading the following description of a non-:, ., :. , , ~ ~
~ restrictlve xample, with reference to the accompanying Figures 1 to 9, in which:
Figure 1 represents a schematic view of anelectrostatic field inducing apparatus through whi~h the reinforcing element bundle is charged;
Figure 2 represents a fragmentary view of a bundle of elements prior to electrostatic char~e;
Figure 3 represents a fragmentary view similar to Figure 2 but showing the bundle after electrostatic charge;
Figure 4 represents a microscopic fragmentary view of a fibril prior to treatment;
Figure 5 represents a microscopic fragmentary view of a fibril after treatment;
Figure 6 illustrates a disorderly fibril bundle prior to treatment;
Figure 7 illustrates the bundle shown in Figure 6 but after treatment;
Figure 8 illustrates another form of fibril bundle prior to treatment; anà
Figure 9 represents a schematic view of means for treating the bundle shown in Figure 8 with a high voltage field.
Referring first to Figure 1, this shows a casing in insulating material 1 resting on insulating support members 2, and containing, in position between wedge members 3 and resting on an insulating base 4 : a first plate-shaped lower electrode 5, a first dielectric 6, a gap 7, a second dielectric 8 and a second, equally plate-shaped electrode 9. The fibrous bundle 10 is placed between the two dielectrics. The two electrodes 5 and 9 are connected to a generator of direct current of voltage about 100,000 volts. The assembly is charged for about 10 mins. for fibrils of between 5 and 6 mm thickness. Figure 2 shows the bundle before being charged, and Figure 3 shows the bundle after a 10-minute charging treatment.
It is found after successive experiments that the volume has virtually doubled, hence, doubling the , .
volume between the fibrils, the actual volume of the fibrils remaining unchanged.
:
.... : . - : - .
:: . . . . `- - ' ~ : . , , ' ' `
'7~
Figure 4 shows a microscopic view of a fibril before the treatment, and Figure S shows the same fibril as ground after the treatment.
From a practical standpoint, it has been found that the fact of subjecting the whole bundle of fibrils to a first A.C. field in order to obtain a more efficient etching with alternating current, and then subjecting it to a D.C. field in order to create an expansion, greatly con~ributes to obtaining a ground, expanded and tidy bundle. Indeed, a third effect noted is that a rather disorderly bundle, such as illustrated in Figure 6, becomes perfectly orderly after a treatment in a high voltage D.C.electrostatic field, as illustrated in Figure 7.
Another application, this time using A.C.
voltage, consists in injecting short fibers between the ` two electrodes, as illustrated in Figure`8;-and subjècting them to a high voltage A.C. field, as illustrated in Figure 9. It is found then that a bundle of short fibers is obtained in which the fibers are arranged somewhat random~y but homogeneously, which is very a~dvantageous in the case of short fiber composites, since sequencing always gives breaking points, hence weak points.
.,~, ',;
. ,~
. . . . .
.
,~ ~ - . - - . ,
The present lnvention relates to a process for preparing composite materials; it also relates to the intermediate or finished products which can be obtained with sa$d process.
Composite materials are materials comprised of reinforcing elements (mostly fibers - or filaments - such as glass fibers, carbon fibers, boron or polyamide fibers, etc...) and of a matrix (constituted either by a resin or a resistant material such as metal or ceramics).
The properties of composite materials are particularly dependent, as we know, on:
- the orientation of the reinforcing elements:
~ - the good distribution of the matrix throughout the volume ; between the reinforcing elements:
- and of any bonds which may be induced between said reinforcing elements and said matrix.
It is therefore an advantage to use a technique wherein the above parameters can be worked in such a way as to optimize the properties of the product as a function of the aim in view, and this is precisely the ob~ect of the present invention.
~, According to one of its aspects, the present invention provides a process for the preparation of a composite material that includes fibers used to reinforce the composite material comprising the steps of:
~ sub~ecting the fibers to an electrostatic field induced ;~ by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of the , ~ ; fibers; and .~ :
.., ~, . ~q~
~ ,, s , . ~: , . . : "
~'; " ' " ' ' '~ ' ' ' :~ ' ' .
~:~ , , ' ' "' .
. ' . - ' ' ~' ' ' ' . . .
': ' ' , - ' . " ' ' ': ' ' ' ' ~ ' , , ~
:. ' . ' . . , . , ,' ' ,, ' ' , ' .' .
.' ' . ' , : . ' , . .
.~'7~30;~
la impregnating the fibers after the elapse of the time interval with a llquid matrix material or precursor of matrix, while the $ibers are electrostatically charged.
According to another of its aspects, the present invention provides a process for the preparation of a composite material that includes fibers used to reinforce the composite material comprising the steps of:
subjecting the fibers to a first electrostatic field that is induced by a first high-voltage electric current for a first time interval:
sub;ecting the fibers to a second electrostatic field different from the first electrostatic field that is induced by a second h~gh-voltage electric current for a second time interval after sub~ecting the fibers to the first electrostatic field; one of the first and second electrostatic fields being induced by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of the fibers.
Thus, it has been found that the reinforcing elements (i.e. the fibers) may be advantageously sub~ected to an electrostatic field induced by a very high voltage current, and then impregnated with the liquid matrix, using the known techniques, while the elements are electrostatically charged.
Thus, the present process encompasses (i) the case where the electrostatic field has been stopped or removed but the fibers are still charged, and (ii) the case where the electrostatic field is maintained during impregnation.
By high voltage current-induced electrostatic field is meant a field at least equal to the filed obtained by applying between two electrodes 20 mm apart, a voltage equal to at least 20,000 volts in alternating current and to at least 40,000 volts in direct current. The reinforcing elements, and in particular the fibers, fibrils or roves used, are then positioned . ..
; ~., :, i~, .- '` `. 1" ,. : ~
., . ~ : . .
'-''',,' ' ' '' ~-. '' :. ,.
:'~':- ,''. :. ' -': ' '' .... . . .
. ~: , : - .
: . : - -. . . ..
.
~. - ~ - - .
., , - .
between the electrodes subjected to the very high voltage current.
According to the invention, any type of fibers can be used as reinforcing elements, but they must be in a dielectric material, namely a material which, when under the effect of the field, becomes electrically charged and remains charged for a certain time. This is the case for example with polyami~e fibers (of NYLON or KEVLAR type), glassfibers, fibers in ce~rtain metallic oxides, fibers in complex materials (metaloxide) and with carbon fibers. On the contrary, conducting fibers, such as for example metallic fibers or surface-metallized fibers are-more aifficult to use in the process according to the invention.
The reinforcing fibers are placed between the electrodes, and the very high voltage current is applied between said electrodes for a period long enough to charge said fibers, then, the charged fibers, taken out of the field, are impregnated with the matrix material or with a precursor of the matrix material, which is in liquid form.
The charged fibers having a tendency to push one another back, a bed of fibers is obtained at the output of the field, of which the thickness is - ;25 between two and four times the thickness of the bed of ~-fibers initially introduced between the electrodes, and `~;it is when the fibers are in that "swollen" state that they should be impregnated.
Any one ofthe currently known and used matrix materials is suitable for the process according to the invention, for example resins ~epoxy or polyamide resins or hardened carbon mixtures) or silica-based mixtures capable of forming ceramics, and metals.
When the fibers have been impregnated - ~35 by the liquid matrix material (or its liquid precursor), ,~the resulting product can either be sold as is (normally ,"~
.-: - - . . . . - ~. , :
. ... - ~ . - , -: - . . .
~ ~ . . . . .
:-., - ~ ,: ' .~ . ' ' after a first solification) or it can be transformed by molding and solidification of the matrix. And as known, the matrix itself can be charged.
It has been found that with the process according to the invention, the reinforcing elements (fibers) become thoroughly impregnated by the matrix.
sut it is also possible to bring to the process according to the invention certain particular-ly advantageous alterations.
If the electrostatic field is produced with a direct current, it is noted that, besides the swelling action of the bundle of initial fibers, there occurs a complementary orientation of said fibers.
This orientation will permit the preparation of a compo-site material having specific properties.
It is àlso possible, as we know, to ob-tain that same orientation for certain fibers, by the slmultaneous or prlor use of another field such as for example a magnetic field.
If the electrostatic field is produced with an alternating current, it is noted that besides the swelling action of the bundle of fibers described hereinabove, localized discharges occur between the ~ ~ fibrils, causing, principally in the presence of oxygen, ~ - 25 a modification of the surface of the fibers. This modification (which is probably an oxidation), stimulates the properties of the final material insofar as it makes it possible to obtain consolidated bonding between the fiber and the matrix.
~ It is conceivably possible, according to the invention, to use successively an A.C. electro-static field (swelling and surface treatment) and a D.C.
electrostatic field (swelling and orientation).
The invention will be more readily 35~ understood on reading the following description of a non-:, ., :. , , ~ ~
~ restrictlve xample, with reference to the accompanying Figures 1 to 9, in which:
Figure 1 represents a schematic view of anelectrostatic field inducing apparatus through whi~h the reinforcing element bundle is charged;
Figure 2 represents a fragmentary view of a bundle of elements prior to electrostatic char~e;
Figure 3 represents a fragmentary view similar to Figure 2 but showing the bundle after electrostatic charge;
Figure 4 represents a microscopic fragmentary view of a fibril prior to treatment;
Figure 5 represents a microscopic fragmentary view of a fibril after treatment;
Figure 6 illustrates a disorderly fibril bundle prior to treatment;
Figure 7 illustrates the bundle shown in Figure 6 but after treatment;
Figure 8 illustrates another form of fibril bundle prior to treatment; anà
Figure 9 represents a schematic view of means for treating the bundle shown in Figure 8 with a high voltage field.
Referring first to Figure 1, this shows a casing in insulating material 1 resting on insulating support members 2, and containing, in position between wedge members 3 and resting on an insulating base 4 : a first plate-shaped lower electrode 5, a first dielectric 6, a gap 7, a second dielectric 8 and a second, equally plate-shaped electrode 9. The fibrous bundle 10 is placed between the two dielectrics. The two electrodes 5 and 9 are connected to a generator of direct current of voltage about 100,000 volts. The assembly is charged for about 10 mins. for fibrils of between 5 and 6 mm thickness. Figure 2 shows the bundle before being charged, and Figure 3 shows the bundle after a 10-minute charging treatment.
It is found after successive experiments that the volume has virtually doubled, hence, doubling the , .
volume between the fibrils, the actual volume of the fibrils remaining unchanged.
:
.... : . - : - .
:: . . . . `- - ' ~ : . , , ' ' `
'7~
Figure 4 shows a microscopic view of a fibril before the treatment, and Figure S shows the same fibril as ground after the treatment.
From a practical standpoint, it has been found that the fact of subjecting the whole bundle of fibrils to a first A.C. field in order to obtain a more efficient etching with alternating current, and then subjecting it to a D.C. field in order to create an expansion, greatly con~ributes to obtaining a ground, expanded and tidy bundle. Indeed, a third effect noted is that a rather disorderly bundle, such as illustrated in Figure 6, becomes perfectly orderly after a treatment in a high voltage D.C.electrostatic field, as illustrated in Figure 7.
Another application, this time using A.C.
voltage, consists in injecting short fibers between the ` two electrodes, as illustrated in Figure`8;-and subjècting them to a high voltage A.C. field, as illustrated in Figure 9. It is found then that a bundle of short fibers is obtained in which the fibers are arranged somewhat random~y but homogeneously, which is very a~dvantageous in the case of short fiber composites, since sequencing always gives breaking points, hence weak points.
.,~, ',;
. ,~
. . . . .
.
,~ ~ - . - - . ,
Claims (6)
1. Process for the preparation of a composite material that includes fibers used to reinforce the composite material comprising the steps of:
subjecting the fibers to an electrostatic field induced by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of said fibers; and impregnating said fibers after the elapse of said time interval with a liquid matrix material or precursor of matrix, while the fibers are electrostatically charged.
subjecting the fibers to an electrostatic field induced by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of said fibers; and impregnating said fibers after the elapse of said time interval with a liquid matrix material or precursor of matrix, while the fibers are electrostatically charged.
2. A process for the preparation of a composite material that includes fibers used to reinforce the composite material comprising the steps of:
subjecting the fibers to a first electrostatic field that is induced by a first high-voltage electric current for a first time interval;
subjecting the fibers to a second eleotrostatic field different from said first electrostatic field that is induced by a second high-voltage electric current for a second time interval after subjecting the fibers to said first electrostatic field;
one of said first and second electrostatic fields being induced by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of said fibers; and impregnating said fibers with a liquid matrix or precursor of matrix, after the elapse of said two time intervals, while the fibers are electrostatically charged.
subjecting the fibers to a first electrostatic field that is induced by a first high-voltage electric current for a first time interval;
subjecting the fibers to a second eleotrostatic field different from said first electrostatic field that is induced by a second high-voltage electric current for a second time interval after subjecting the fibers to said first electrostatic field;
one of said first and second electrostatic fields being induced by a high-voltage alternating electric current for a time interval sufficient to cause a modification of the surface of said fibers; and impregnating said fibers with a liquid matrix or precursor of matrix, after the elapse of said two time intervals, while the fibers are electrostatically charged.
3. The process as claimed in claim 2, wherein the other of said first and second fields is induced by a D.C. electric current.
4. The process as claimed in claim 3, wherein said D.C.
electric current is at a voltage equal to at least 20,000 volts.
electric current is at a voltage equal to at least 20,000 volts.
5. The process as claimed in claim 3, wherein said fibers are a dielectric material selected from the group consisting of polyamide fibers, glass fibers, metallic oxide fibers, carbon fibers, and combinations thereof.
6. Composite materials obtained by carrying out the process as claim 1.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR84.14800 | 1984-09-26 | ||
FR8414800A FR2570646B1 (en) | 1984-09-26 | 1984-09-26 | PROCESS FOR THE PREPARATION OF COMPOSITE MATERIALS WITH ORIENTED REINFORCING ELEMENTS AND PRODUCTS OBTAINED |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1279033C true CA1279033C (en) | 1991-01-15 |
Family
ID=9308107
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000491615A Expired - Fee Related CA1279033C (en) | 1984-09-26 | 1985-09-26 | Producing composite materials from high voltage electrostatically charged fibres by impregnation |
Country Status (13)
Country | Link |
---|---|
EP (1) | EP0179688B1 (en) |
JP (1) | JPS6184210A (en) |
AT (1) | ATE39079T1 (en) |
AU (1) | AU578740B2 (en) |
BR (1) | BR8504704A (en) |
CA (1) | CA1279033C (en) |
DE (1) | DE3566632D1 (en) |
DK (1) | DK162334C (en) |
ES (1) | ES8800635A1 (en) |
FR (4) | FR2570646B1 (en) |
IE (1) | IE57205B1 (en) |
PT (1) | PT81185B (en) |
ZA (1) | ZA857143B (en) |
Cited By (1)
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---|---|---|---|---|
US9528002B2 (en) | 2011-04-11 | 2016-12-27 | Solvay Sa | Manufacture and use of a composite material comprising fibres and at least one vinyl chloride polymer |
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IT1178518B (en) * | 1984-09-28 | 1987-09-09 | Alusuisse Italia Spa | PROCEDURE FOR THE PRODUCTION OF CARBON BODIES |
JPH02501996A (en) * | 1987-01-23 | 1990-07-05 | プラドム・リミテッド | Methods for manufacturing composite materials, including vulcanized products such as tires, ceramics, electrodes, etc., and products manufactured by the methods |
US5218012A (en) * | 1987-12-11 | 1993-06-08 | Pradom Limited | Process for coating fibers and applications thereof to the production of composite materials |
FR2636683B2 (en) * | 1988-02-26 | 1990-12-28 | Berger Michel | HANGING ASSEMBLY SYSTEM HAVING HANGING ELEMENTS FORMED BY CURVILINE RIBS PROVIDED WITH ELASTICALLY DEFORMABLE LIPS |
FR2655036B1 (en) * | 1989-11-27 | 1993-07-09 | Pradom Ltd | COMPLEX COMPOSITE MATERIALS WITH ORGANIC-METAL MATRIX, MANUFACTURING METHOD THEREOF AND USE THEREOF FOR THE MANUFACTURE OF HIGH TECHNOLOGY PRODUCTS INTENDED IN PARTICULAR FOR AEROSPATIAL OR HIGH-SPEED VEHICLES, SUCH AS TGV. |
GB9124816D0 (en) * | 1991-11-22 | 1992-01-15 | Rolls Royce Plc | Method of manufacturing a composite material |
GB9124822D0 (en) * | 1991-11-22 | 1992-01-15 | Rolls Royce Plc | Method of manufacturing a composite material |
AT410073B (en) * | 1997-12-17 | 2003-01-27 | Klaus Dipl Ing Dr Hummel | METHOD FOR IMPROVING THE ADHESION OF RUBBER VOLCANISANS TO COPPER ALLOYS |
EP1525969A1 (en) * | 2003-10-21 | 2005-04-27 | Materials Technics Holding | Process and device for mixing, dispersing and/or homogenizing powder material |
EP1526214A1 (en) * | 2003-10-21 | 2005-04-27 | Materials Technics Holding Société Anonyme | Process and device for impreganting a fibre network with powder material in an electrostatic field with alternating current |
JP5233600B2 (en) * | 2008-11-06 | 2013-07-10 | 株式会社ニコン | Method for producing particle-containing resin |
CN106104858B (en) * | 2014-03-10 | 2020-07-31 | 麦斯韦尔技术股份有限公司 | Method, apparatus and system for fibrillating binder component of electrode film |
US10151026B2 (en) | 2016-08-05 | 2018-12-11 | Honeywell International Inc. | Vibration assisted densification of a carbon fiber preform |
EP3661712A1 (en) * | 2017-08-01 | 2020-06-10 | SABIC Global Technologies B.V. | Method and system for producing unidirctional carbon fiber tape as well as method for surface treating carbon fibers |
US11273598B2 (en) | 2020-03-18 | 2022-03-15 | Powder Motion Labs, LLC | Powder bed recoater |
US11407172B2 (en) | 2020-03-18 | 2022-08-09 | Powder Motion Labs, LLC | Recoater using alternating current to planarize top surface of powder bed |
US11612940B2 (en) | 2020-03-18 | 2023-03-28 | Powder Motion Labs, LLC | Powder bed recoater |
CN112793188A (en) * | 2021-04-13 | 2021-05-14 | 若宇检具股份有限公司 | Carbon fiber simulation block based on die extrusion molding and molding method |
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US3073732A (en) * | 1959-03-23 | 1963-01-15 | U S Plastic And Chemical Corp | Plastic articles and method of producing same |
NL6617660A (en) * | 1966-01-11 | 1967-07-12 | ||
US3575789A (en) * | 1966-12-27 | 1971-04-20 | Owens Corning Fiberglass Corp | Fiber ceramic composites and method of producing same |
US3668014A (en) * | 1968-06-10 | 1972-06-06 | Leesona Corp | Electrode and method of producing same |
US3626041A (en) * | 1968-11-13 | 1971-12-07 | Monsanto Co | Apparatus and process for making continuous filament |
GB1296686A (en) * | 1968-11-13 | 1972-11-15 | ||
US3660888A (en) * | 1969-07-24 | 1972-05-09 | Brunswick Corp | Process for making electrical energy sources |
US3676253A (en) * | 1969-11-20 | 1972-07-11 | Cambridge Thermionic Corp | Process of making flocked plate structure for electric batteries |
DE2022164B1 (en) * | 1970-05-06 | 1971-12-30 | Messerschmitt Boelkow Blohm | Process for increasing the strength of molded parts |
FR2096585B1 (en) * | 1970-06-30 | 1974-04-26 | Ibm | |
US3767505A (en) * | 1971-02-19 | 1973-10-23 | Monsanto Co | Producing ordered composites by application of magnetic forces |
US3771202A (en) * | 1971-03-31 | 1973-11-13 | Us Agriculture | Method for electrostatic yarn bulking and impregnating |
US3919437A (en) * | 1972-02-22 | 1975-11-11 | Owens Corning Fiberglass Corp | Method for electrostatically impregnating strand |
SE415550B (en) * | 1977-02-04 | 1980-10-13 | Forbo Forshaga Ab | PROCEDURE FOR COATING WITH PLASTIC MATERIAL OF A SUBSTANCE THAT WILL UNDERSTAND CONDITIONAL CHANGE |
NL7806452A (en) * | 1978-06-14 | 1979-12-18 | Tno | PROCESS FOR THE TREATMENT OF AROMATIC POLYAMIDE FIBERS SUITABLE FOR USE IN CONSTRUCTION MATERIALS AND RUBBERS, AS WELL AS FIBERS THEREFORE TREATED AND PREPARED PRODUCTS ARMED WITH THESE FIBERS. |
US4256792A (en) * | 1980-01-25 | 1981-03-17 | Honeywell Inc. | Composite electronic substrate of alumina uniformly needled through with aluminum nitride |
DE3127017C2 (en) * | 1981-07-09 | 1984-08-23 | Messerschmitt-Bölkow-Blohm GmbH, 8000 München | Process for the production of a component from short fiber prepregs |
US4838843A (en) * | 1982-04-16 | 1989-06-13 | The Gates Rubber Company | Toothed belt |
FR2529215B1 (en) * | 1982-06-28 | 1987-05-07 | Electricite De France | PROCESS FOR THE PREPARATION OF POLYMER NETWORKS OF HOMOGENEOUS INTERPENETRATED STRUCTURE |
SU1143716A1 (en) * | 1982-10-20 | 1985-03-07 | Московский Ордена Трудового Красного Знамени Инженерно-Строительный Институт Им.В.В.Куйбышева | Conveyer method for manufacturing fibrous heat-insulating materials |
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-
1984
- 1984-09-26 FR FR8414800A patent/FR2570646B1/en not_active Expired
-
1985
- 1985-09-18 ZA ZA857143A patent/ZA857143B/en unknown
- 1985-09-23 EP EP85401836A patent/EP0179688B1/en not_active Expired
- 1985-09-23 IE IE2335/85A patent/IE57205B1/en not_active IP Right Cessation
- 1985-09-23 AT AT85401836T patent/ATE39079T1/en active
- 1985-09-23 DE DE8585401836T patent/DE3566632D1/en not_active Expired
- 1985-09-24 PT PT81185A patent/PT81185B/en not_active IP Right Cessation
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- 1985-09-25 ES ES547269A patent/ES8800635A1/en not_active Expired
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- 1985-09-26 AU AU47919/85A patent/AU578740B2/en not_active Ceased
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1987
- 1987-01-23 FR FR878700797A patent/FR2609934B2/en not_active Expired - Lifetime
- 1987-02-18 FR FR878702106A patent/FR2611086B2/en not_active Expired - Lifetime
- 1987-02-18 FR FR878702105A patent/FR2610922B2/en not_active Expired - Lifetime
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9528002B2 (en) | 2011-04-11 | 2016-12-27 | Solvay Sa | Manufacture and use of a composite material comprising fibres and at least one vinyl chloride polymer |
Also Published As
Publication number | Publication date |
---|---|
AU578740B2 (en) | 1988-11-03 |
DE3566632D1 (en) | 1989-01-12 |
ES8800635A1 (en) | 1987-12-01 |
EP0179688B1 (en) | 1988-12-07 |
DK162334C (en) | 1992-03-09 |
FR2611086A2 (en) | 1988-08-19 |
ATE39079T1 (en) | 1988-12-15 |
EP0179688A1 (en) | 1986-04-30 |
DK162334B (en) | 1991-10-14 |
FR2570646A1 (en) | 1986-03-28 |
ES547269A0 (en) | 1987-12-01 |
PT81185A (en) | 1985-10-01 |
IE57205B1 (en) | 1992-06-03 |
FR2610922A2 (en) | 1988-08-19 |
FR2611086B2 (en) | 1994-09-09 |
DK434585A (en) | 1986-03-27 |
JPS6184210A (en) | 1986-04-28 |
AU4791985A (en) | 1986-04-10 |
FR2570646B1 (en) | 1987-10-30 |
DK434585D0 (en) | 1985-09-25 |
BR8504704A (en) | 1986-07-22 |
FR2609934A2 (en) | 1988-07-29 |
FR2610922B2 (en) | 1993-08-20 |
DE3566632T (en) | 1989-01-12 |
FR2609934B2 (en) | 1992-09-04 |
ZA857143B (en) | 1986-05-28 |
IE852335L (en) | 1986-03-26 |
PT81185B (en) | 1987-08-19 |
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