EP0342197A1 - Process for preparing a composite material - Google Patents
Process for preparing a composite materialInfo
- Publication number
- EP0342197A1 EP0342197A1 EP88901042A EP88901042A EP0342197A1 EP 0342197 A1 EP0342197 A1 EP 0342197A1 EP 88901042 A EP88901042 A EP 88901042A EP 88901042 A EP88901042 A EP 88901042A EP 0342197 A1 EP0342197 A1 EP 0342197A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fibers
- matrix
- electric current
- electrostatic field
- induced
- 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.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000011159 matrix material Substances 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 80
- 230000008569 process Effects 0.000 claims abstract description 74
- 230000005686 electrostatic field Effects 0.000 claims abstract description 53
- 239000000919 ceramic Substances 0.000 claims abstract description 42
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 239000000835 fiber Substances 0.000 claims description 215
- 230000003014 reinforcing effect Effects 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 229920002647 polyamide Polymers 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000151 deposition Methods 0.000 claims description 10
- 230000008021 deposition Effects 0.000 claims description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000271 Kevlar® Polymers 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004761 kevlar Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 9
- 239000012783 reinforcing fiber Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- 239000003989 dielectric material Substances 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000004073 vulcanization Methods 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 claims description 2
- ZUMMKALUNVXLCS-UHFFFAOYSA-N O=[Ag]=O Chemical compound O=[Ag]=O ZUMMKALUNVXLCS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012700 ceramic precursor Substances 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229920003051 synthetic elastomer Polymers 0.000 claims description 2
- 239000005061 synthetic rubber Substances 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000011282 treatment Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 230000008961 swelling Effects 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000011149 active material Substances 0.000 description 5
- 230000005684 electric field Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003570 air Substances 0.000 description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229940050410 gluconate Drugs 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000284 resting effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000914 Metallic fiber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- -1 for example Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000012705 liquid precursor Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000019612 pigmentation Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
- 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
- C04B20/02—Treatment
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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
- 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
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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
- 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
- C04B35/016—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 manganites
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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
- 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
- C04B35/03—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite
- C04B35/04—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 magnesium oxide, calcium oxide or oxide mixtures derived from dolomite based on magnesium oxide
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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
- 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
- C04B35/10—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 aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
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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
- 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
- C04B35/14—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 silica
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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
- 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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- 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
- 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
- C04B35/453—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Definitions
- the present invention relates to a process for preparing composite materials ; it also relates to the intermediate or finished products which can be obtained with said process, notably vulcanized products, in particular tires, ceramics and electrodes.
- Composite materials are materials constituted of reinforcing elements (mostly fibers - or filaments - such as glass fibers, carbon fibers, boron or poly amide 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 : of :
- the invention provides a main 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 still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
- this process for the preparation of a composite material that includes fibers used to reinforce the composite material comprises the steps of : subjecting the fibers to an electrostatic field induced by a high voltage direct electric current for a first time interval sufficient to cause charging said fibers ; subjecting the fibers to an electrostatic field induced by a high voltage alternating electric current for a second time interval sufficient to cause a modification of the surface of the fibers ; after the elapse of said two time intervals, impregnating said fibers with a liquid matrix or precursor of matrix, while still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
- this process for the preparation of a composite material that includes fibers used to reinforce the composite material comprises the successive steps of : subjecting the fibers to an electrostatic field induced by a high voltage alternating electric current for a first time interval sufficient to cause a modification of the surface of the fibers ; subj ecting the fibers to an electrostatic field induced by a high voltage direct electric current for a second time interval sufficient to cause charging said fibers ; after the elapse of said two time intervals, impregnating said fibers with a liquid matrix or precursor of matrix, while still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
- high voltage current-induced electrostatic field is meant a field at least equal to the field obtained by applying between two electrodes 20 mm apart, a voltage equal to at least 20,000 volts in alternating current and to a least 40,000 volts in direct current.
- the reinforcing elements, and in particular the fibers, fibrils or roves used, are then positioned between the electrodes subjected to the very high voltage current.
- 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.
- 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 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 of the currently known and used matrix material 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.
- the resulting product can either be sold as is (normally after a first solidification) 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 above process according to the invention, called main or basic process, the reinforcing elements (fibers) become thoroughly impregnated by the matrix.
- 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 composite material having specific properties.
- a preferred embodiment comprises using first a D.C. electrostatic field and secondly a A.C. electrostatic field.
- the present invention according to a second object relates to a use of the above main process for preparing composite materials with oriented reinforcing elements, to the vulcanization and production of tires, and also the vulcanized products, in particular tires , obtained according to said process .
- the present invention therefore relates to a use of the invention main process such as above-described to vulcanization, and in particular to the production of tires, such a as radial-ply tires.
- the invention concerns a process for the manufacture of a vulcanized composite material having improved mechanical and wear properties, the composite material having reinforced fibers that reinforce a vulcanizable matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a vulcanizable liquid matrix or precursor of vulcanizable matrix while still under the influence of said electrosatic field thereby consolidating bonding between the fibers and the matrix ; and vulcanizing the imprenated fibers/matrix composite, thereby obtaining said vulcanized composite material.
- said electrostatic field includes time sequential first and second fields that are induced by high voltage electric currents.
- one of said fields is induced by an A.C. electric current and the other of said fields is induced by a O.C. electric current.
- the first of said fields is induced by D.C. electric current and the second one of said fields is induced by A.C. electric current.
- it is further including the step of shaping the impregnated fibers/matrix composite into a vehicle tire to obtain a vehicle tire as the vulcanized composite material.
- the fibers used as reinforcing elements are selected from the group consisting of polyamide fibers, plant fibers and glass fibers.
- the matrix is selected from the group consisting of polyurethane elastomer, natural rubber, synthetic rubber, rhodorsil, silicon, thermoplastic elastomer, and mixtures thereof.
- woven Kevlar fibers as reinforcing fibers are used with polyurethane elastomer as matrix, the relative proportion being about 40 % by weight of woven Kevlar fibers with about 60 % by weight of polyurethane elastomer.
- the D.C. electric current is about a 40,000 V D.C. electric current and the A.C. electric current is about a 20 ,000 V electric current.
- the D.C. electric current is about a 100, 000 V D.C. electric current and the A.C. electric current is about a 25,000 V electric current.
- said fibers are of a dielectric material, which can be advantageously selected from the group consisting of polyamide fibers, glass fibers, metallic oxide fibers, carbon fibers and mixtures thereof.
- the invention also concerns a process for the manufacture of a composite material usable as a vehicle tire having improved mechanical and wear properties, the composite material having tire reinforcing fibers that reinforce a tire matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a liquid matrix or precursor of matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and vulcanizing the impregnated fibers/matrix composite so that the resulting vulcanized material is usable as a vehicle tire.
- this process includes the step of shaping the impregnated fibers/matrix composite into a vehicle tire.
- an A.C. type high-voltage electrostatic field causes a roughness of the fibers surface, thus radically and totally unexpectedly improving the surface bonding strength of the elastomer vulcanized on the surface of the fibers, thereby radically improving the mechanical properties of the vulcanized products and in particular of tires, such as radial-ply tires.
- the present invention also relates to the vulcanized products obtained according to said process, such as tires, and preferably radial-ply tires.
- the present invention according to a third object relates to a use of the above main process for the preparation of composite materials with oriented reinforcing elements, in the manufacture of ceramic composites and the ceramic composites obtained with said process.
- the invention concerns a process for the manufacture of a ceramic composite material having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce a ceramic or ceramic precursor matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a ceramic matrix or precursor of ceramic matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and baking the impregnated fibers/matrix composite, thereby obtaining said ceramic composite material.
- the present invention therefore relates to a use of the above-said main process using electrostatic fields in the production of ceramic composites notably of the ceramic-ceramic type or of the mixed ceramic and different fibers type.
- One particular embodiment of the invention consists in producing a ceramic in which the ceramic matrix is of the zirconium type and the fibers are silicium carbide fibers, which are advantageously long fibers, woven or non-woven, the length of which is identical or near to the length of the piece to be produced.
- Another particular embodiment of the invention consists in using alumina as ceramic matrix, the fibers being also in alumina and being advantageously long but non-woven fibers.
- the present invention also covers the ceramic composites obtained according to said process.
- the present invention according to a fourth object relates to a use of the above main process for the preparation of composite materials with oriented reinforcing elements, in the production of electrodes, as well as the electrodes obtained according to said process and electrochemical generators equipped with such electrodes. It has now been found, quite unexpectedly, that the use of the invention process has given totally unexpected results in the production of electrodes and that it was therefore especially advantageous for producing electrodes which can be used in electrochemical generators, such as accumulator batteries, primary cells, fuel cells, etc.
- the electrodes produced according to these methods have a relatively poor lamination resistance because of the poor quality interface bonding between active material and conducting fibers. Moreover, the active surface/apparent surface ratio is relatively low and has to be improved in order to improve efficiency.
- the solution proposed is also meant to be particularly simple.
- the present invention further relates to a use of the invention process as above-described in the manufacture of electrodes as well as those electrodes.
- the invention thus concerns a process for the manufacture of a composite electrode having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce a conducting adhesive forming matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with an electroactive conducting matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; optionally compressing said impregnated fibers (matrix composite) thereby obtaining said composite electrodes.
- fibers capable of receiving, by electrolytic deposition, negative active materials for producing the anodes, or positive active materials for producing cathodes, therefore said fibers will have to be either conducting or made to be conducting by metal deposition, such as for example of "electroless" type.
- carbon or boron fibers are preferably used as conducting fibers, the preferred ones being graphite fibers, and advantageously in the form of weaves of fibers, out to the size of the electrodes to be produced.
- negative electrodes are produced by deposition of a metal selected from the group consisting advantageously of zinc, lithium, magnesium, cadmium. According to yet another embodiment of the invention for producing negative electrodes, it is preferably proceeded to a deposition of manganese dioxide, nickel oxide, silver dioxide, titanium dioxide.
- the invention also covers the eletrodes obtained according to said process as well as the electrochemical generators equipped with such electrodes, namely accumulator batteries, primary cells, fuel cells, etc.
- FIG. 1 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
- figure 3 shows the bundle after a 10-minute charging treatment.
- Figure 4 shows a microscopic view of a fibril before the treatment
- Figure 5 shows the same fibril as ground after the treatment. From a practical standpoint, it has been found that the fact of subj ecting the whole bundle of fibrils to a first A.C. field in order to obtain a more effecient etching with alternating current, and then subjecting it to a D.C. field in order to create an expansion , greatly contributes 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.
- Woven Kevlar fibers are placed between the plates of an electrostatic field generating device, which plates can be fed with a high-voltage alternating or direct current.
- an alternative current at a voltage of preferably at least 20,000 volts is applied for a few minutes, in order to obtain a roughness of the fibers surface due to an etching effect created on the surface by localized discharges when the electrostatic field is modified by reversing the polarity of the electric field.
- Kevlar fibers While the Kevlar fibers are still under the influence of the electrostatic field, said fibers are embedded in a polyurethane elastomer which may contain one or more of the conventional vulcanizing agents, such as sulphur, in a relative proportion of 40 % by weight of Kevlar fibers and 60 % by weight of polyurethane elastomer.
- a polyurethane elastomer which may contain one or more of the conventional vulcanizing agents, such as sulphur, in a relative proportion of 40 % by weight of Kevlar fibers and 60 % by weight of polyurethane elastomer.
- the conventional vulcanizing treatment which may comprise a shaping in order to obtain a tire.
- the process may be carried out so as to obtain a radial-ply tire in a quite conventional way.
- the resulting vulcanized product is found to have mechanical properties which are radically improved over the conventionally vulcanized products which have not been submitted to the process described in the French patent namely through a treatment by a high-voltage A.C. or D.C. electric field.
- the procedure is the same as in Example 1, except that the fibers used are KEVLAR type polyamide fibers woven at 60 % lengthwise and at 40 % widthwise. These fibers are subjected for 10 minutes to a direct current of 100,000 V, then for 15 minutes to an alternating current of 25,000 V.
- Each one of these two electrostatic treatments consisting in causing first a stream of hot air at 90°C followed by a stream of hotter air, at more than 100°C, for example around 130°C, to flow between the plates, then the treated fibers are impregnated, while still under the influence of an electrostatic discharge, with a soft matrix composed of a polyurethane elastomer containing an adhesive bond constituted by a phenolic resin of the "Rhone-Poulenc" A.R.P. 27 type.
- the resulting material is then put under a pressure of 2 t/dm 2 and baked by polymerisation at 140°C for four hours, then heating is stopped and the resulting product is allowed to cool for 24 hours.
- the resulting vulcanized elastomer can be used as vehicle tire and is found to have the following characteristics : Characteristics :
- the matrix used here may be replaced for example by natural rubber. It is also possible for various applications to obtain the same supple products with pre-treated vegetable fibers (such as for example, fibers pre-treated in phenol-based solutions).
- Said fibers are then subjected to a treatment by the electrostatic process described in the French patent 84 14800, preferably conducted as follows :
- a high D.C. voltage of at least 40,000 volts is applied to the plates, preferably 100,000 volts, for a few minutes, preferably 10 minutes, so as to space out the fibers and cause them to swell, the thickness of the fibers assembly then reaching between two and four times the thickness of the bed of fibers initially introduced between the plates forming electrodes, as described in the French patent.
- an A.C. voltage at least equal to 20,000 volts, and preferably around 25,000 volts, is then applied for a few minutes, preferably about 10 minutes, in order to obtain a roughness of the fibers surface by a stripping effect on the surface, or by etching, resulting from localized discharges when the electrostatic field is modified by reversing the polarity of the electric field.
- This treatment of the fibers is advantageously carried out under a stream of hot air heated to a temperature exceeding 100°C, and preferably equal to about 130°C.
- the silicium carbide fibers are coated with a ceramic matrix which in this case is preferably composed of ZrO 2 (70 % by weight) and of SiO 2 (30 % by weight), which matrix can contain an adhesive binder and, advantageously, an activating binder, in the relative proportion given hereunder, in % by weight : % by weight
- a second baking operation is then conducted in the same conventional oven using ambient air, by raising the temperature progressively of 150°C every hour, until a temperature of 1050°C is reached ;
- said third baking operation is conducted in an oven with a neutral or reducing atmosphere, such as for example Xenon or H 2 . Thereagain, the temperature is raised progressively of 150°C every hour , for two hours ;
- the heating is then turned off and the product is cooled slowly for 24 hours.
- the ceramic composites prepared in this way which are known as of the "zirconia-silicium carbide” type, exhibits the following characteristics :
- the matrix contains an adhesive binder such as of "CONTRONICS" RTC 70 type, the relative proportions being the same as in Example 1.
- the invention also covers the ceramic composites obtained according to said process. Therefore, the two examples given hereinabove form an integral part of the invention.
- long fibers fibers of which the length is not preset.
- the length of these fibers is adapted to the length of the piece to be produced.
- the length of the fibers is normally chosen to be either identical or near to the length of the piece. There is therefore no restriction of size for the fibers, contrary to what was the case in prior art processes. This then constitutes a particularly unexpected advantage of the present invention.
- the fibers used as reinforcing elements may be of different types without departing from the scope of the invention.
- they may be in silicium carbide, boron, alumina, carbon and polyamides, in any forms.
- the matrix may also be different type provided that it leads to the formation of a ceramic type material. It will advantageously be a matrix of ZrO 2 ; ZrO 2 SiO ; SiO 2 ; Al 2 O 3 ; SiO 2 Al 2 O 3 ; LiO ; TiO 2 ; ZnO ; MnO ; CaO ; CeO 2 ; MgO 5 ; Al 2 TiO 5 ; NiSiO 2 and mixtures thereof in all proportions.
- ZrO 2 ZrO 2 SiO ; SiO 2 ; Al 2 O 3 ; SiO 2 Al 2 O 3 ; LiO ; TiO 2 ; ZnO ; MnO ; CaO ; CeO 2 ; MgO 5 ; Al 2 TiO 5 ; NiSiO 2 and mixtures thereof in all proportions.
- a first step consists in cutting elements from a weave of graphite fibers, to the size of the electrodes.
- cut fibers in woven form, are then placed between the plates of an electrical field generating device, which plates can be fed with a high A.C. or D.C. voltage.
- the plates receive for a few minutes, preferably about 15 minutes, a high-voltage direct current of at least 40,000 V, preferably around 100,000 V, for spacing and swelling up the fibers, the thickness of the fibers assembly then reaching between two and four times the thickness of the bed of fibers initially introduced between the plates forming electrodes. Then, preferably, an alternating current at least equal to 20,000 V, and preferably to 25,000 V, is applied for a few minutes, preferably 15 minutes, in order to obtain a roughness of the fiber surface by surface stripping effect, or etching, resulting from localized discharges when the electrostatic field is modified by reversing the polarity of the electric field.
- a high-voltage direct current of at least 40,000 V, preferably around 100,000 V
- these two treatments by an electrostatic field are preferably conducted after heating the fibers in an oven, at about 350°C, said treatments being conducted by causing a steam of hot air to pass between the plates at a temperature of about 150°C.
- another step consists in placing on each side of a metal grid in stainless steel, such as of the GANTOIS R. 0.25 type, a bulky and treated weave, then still under the effect of the electrostatic field, and coating these weaves with a view to bonding them, with a conducting adhesive forming matrix, such as for example an M. Ag type conducting adhesive, sold by the company 3M.
- Said adhesive having been left to test as prescribed in the notice of use thereof, it is then proceeded, in an electrolytic bath, to the deposition of a metal, in this case zinc, on the swollen and etched fibers, according to the following method.
- a metal in this case zinc
- the electrolytic bath is prepared as follows, for 2 1 of solution :
- the pH of the obtained solution is brought to between 2 and 5.5 with KOH.
- the electrolytic bath solution can be used serveral times on condition that 20 g of gluconate are added in after each filtration, said gluconate being preferably sodium gluconate.
- Electrolytic deposition of zinc is performed conventionally, a slight strirring being kept up throughout the deposition.
- the intensity is preferably under 7 A. In the case where the intensity is below 7 A, it suffices to clean the zinc plates every two hours, whereas if the intensity is higher than 7 A, the zinc plastes must be cleaned every hour.
- the same process can be used in particular to produce anodes in zinc, in cadmium, in lithium, in magnesium, as well as to produce cathodes in nickel, in silver, in cobalt, in titanium and in manganese.
- the invention corresponds to an important technical progress which was totally unexpected for any one skilled in the art.
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Abstract
Procédé de préparation d'un matériau composite, dans le cadre duquel l'élément utilisé pour renforcer le matériau composite est soumis à un champ électrostatique induit par un courant électrique de haute tension, ledit élément, alors qu'il est encore soumis à ce champ, étant ensuite imprégné d'un matériau matrice liquide ou d'un précurseur de la matrice. L'invention porte également sur les matériaux composites obtenus par ledit procédé, surtout des produits vulcanisés, pneus, céramiques et électrodes en particulier.Process for the preparation of a composite material, in which the element used to reinforce the composite material is subjected to an electrostatic field induced by a high voltage electric current, said element, while it is still subjected to this field , then being impregnated with a liquid matrix material or a matrix precursor. The invention also relates to the composite materials obtained by said process, especially vulcanized products, tires, ceramics and electrodes in particular.
Description
PROCESS FOR PREPARING A COMPOSITE MATERIAL
The present invention relates to a process for preparing composite materials ; it also relates to the intermediate or finished products which can be obtained with said process, notably vulcanized products, in particular tires, ceramics and electrodes. Composite materials are materials constituted of reinforcing elements (mostly fibers - or filaments - such as glass fibers, carbon fibers, boron or poly amide 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 : of :
- 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 object of the present invention.
To this effect, it has been unexpectedly found that composite materials of highly improved mechanical properties can be obtained when the reinforcing elements are subjected to an electrostatic field induced by a very high voltage current, and then impregnated with the liquid matrix, using the known techniques, while said elements are still under the influence of said field.
According to a first object, the invention provides a main 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 still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
According to an advantageous embodiment, this process for the preparation of a composite material that includes fibers used to reinforce the composite material comprises the steps of : subjecting the fibers to an electrostatic field induced by a high voltage direct electric current for a first time interval sufficient to cause charging said fibers ; subjecting the fibers to an electrostatic field induced by a high voltage alternating electric current for a second time interval sufficient to cause a modification of the surface of the fibers ; after the elapse of said two time intervals, impregnating said fibers with a liquid matrix or precursor of matrix, while still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
According to another embodiment, this process for the preparation of a composite material that includes fibers used to reinforce the composite material comprises the successive steps of : subjecting the fibers to an electrostatic field induced by a high voltage alternating electric current for a first time interval sufficient to cause a modification of the surface of the fibers ; subj ecting the fibers to an electrostatic field induced by a high voltage direct electric current for a second time interval sufficient to cause charging said fibers ; after the elapse of said two time intervals, impregnating said fibers with a liquid matrix or precursor of matrix, while still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
By high voltage current-induced electrostatic field is meant a field at least equal to the field obtained by applying between two electrodes 20 mm apart, a voltage equal to at least
20,000 volts in alternating current and to a least 40,000 volts in direct current. The reinforcing elements, and in particular the fibers, fibrils or roves used, are then positioned 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 polyamide fibers (of NYLON or KEVLAR type), glassfibers, fibers in certain 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 difficult to use in the process according to the invention. The reinforcing elements 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 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 of the currently known and used matrix material 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 by the liquid matrix material (or its liquid precursor), the resulting product can either be sold as is (normally after a first solidification) 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 above process according to the invention, called main or basic process, the reinforcing elements (fibers) become thoroughly impregnated by the matrix.
But it is also possible to bring to this main process according to the invention certain particularly advantageous alteration or improvement.
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 composite material having specific properties.
It is also possible, as we know, to obtain that same orientation for certain fibers, by the simultaneous or prior 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, 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. electrostatic field (swelling and surface treatment) and a D.C. electrostatic field (swelling and orientation). A preferred embodiment comprises using first a D.C. electrostatic field and secondly a A.C. electrostatic field.
The present invention according to a second object relates to a use of the above main process for preparing composite materials with oriented reinforcing elements, to the vulcanization and production of tires, and also the vulcanized products, in particular tires , obtained according to said process .
Indeed, it has been found that the application of this process causes unexpected effects during a vulcanization treatment, and that it was most advantageous for the production of
tires and in particular radial-ply tires.
The present invention therefore relates to a use of the invention main process such as above-described to vulcanization, and in particular to the production of tires, such a as radial-ply tires.
In this respect, the invention concerns a process for the manufacture of a vulcanized composite material having improved mechanical and wear properties, the composite material having reinforced fibers that reinforce a vulcanizable matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a vulcanizable liquid matrix or precursor of vulcanizable matrix while still under the influence of said electrosatic field thereby consolidating bonding between the fibers and the matrix ; and vulcanizing the imprenated fibers/matrix composite, thereby obtaining said vulcanized composite material. According to a particular feature, said electrostatic field includes time sequential first and second fields that are induced by high voltage electric currents.
According to another feature, one of said fields is induced by an A.C. electric current and the other of said fields is induced by a O.C. electric current.
According to a specific feature, the first of said fields is induced by D.C. electric current and the second one of said fields is induced by A.C. electric current.
According to another feature, it is further including the step of shaping the impregnated fibers/matrix composite into a vehicle tire to obtain a vehicle tire as the vulcanized composite material.
According to a particular feature, the fibers used as reinforcing elements are selected from the group consisting of polyamide fibers, plant fibers and glass fibers.
According to a specific feature, the matrix is selected from the group consisting of polyurethane elastomer, natural rubber, synthetic rubber, rhodorsil, silicon, thermoplastic elastomer, and mixtures thereof. According to another feature, woven Kevlar fibers as reinforcing fibers are used with polyurethane elastomer as matrix, the relative proportion being about 40 % by weight of woven Kevlar fibers with about 60 % by weight of polyurethane elastomer.
According to an interesting feature, the D.C. electric current is about a 40,000 V D.C. electric current and the A.C. electric current is about a 20 ,000 V electric current.
According to another feature, the D.C. electric current is about a 100, 000 V D.C. electric current and the A.C. electric current is about a 25,000 V electric current. According to another feature, said fibers are of a dielectric material, which can be advantageously selected from the group consisting of polyamide fibers, glass fibers, metallic oxide fibers, carbon fibers and mixtures thereof.
The invention also concerns a process for the manufacture of a composite material usable as a vehicle tire having improved mechanical and wear properties, the composite material having tire reinforcing fibers that reinforce a tire matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a liquid matrix or precursor of matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and vulcanizing the impregnated fibers/matrix composite so that the resulting vulcanized material is usable as a vehicle tire. Preferably, this process includes the step of shaping the impregnated fibers/matrix composite into a vehicle tire. In this particular application of the process described
hereinabove, it has been found that the application of an A.C. type high-voltage electrostatic field, causes a roughness of the fibers surface, thus radically and totally unexpectedly improving the surface bonding strength of the elastomer vulcanized on the surface of the fibers, thereby radically improving the mechanical properties of the vulcanized products and in particular of tires, such as radial-ply tires.
The present invention also relates to the vulcanized products obtained according to said process, such as tires, and preferably radial-ply tires.
The present invention according to a third object relates to a use of the above main process for the preparation of composite materials with oriented reinforcing elements, in the manufacture of ceramic composites and the ceramic composites obtained with said process.
Accordingly, the invention concerns a process for the manufacture of a ceramic composite material having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce a ceramic or ceramic precursor matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a ceramic matrix or precursor of ceramic matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and baking the impregnated fibers/matrix composite, thereby obtaining said ceramic composite material. It has been unexpectedly found that the use of said process could produce unexpected effects in the manufacture of ceramic composites and that it was therefore especially advantageous for the production of ceramic composites, whether of the ceramic-ceramic type or of the mixed ceramic and fibers type. Indeed, the advantages of the ceramic materials lie in
their mechanical strength, their resistance to very high temperatures, their resistance to corrosive agents, etc.. and are wellknown. Yet, the weak point of all these ceramics is their brittleness. Attempts have then been made, to create ceramic composites imitating the known composites, but major difficulties have been encountered, particularly as regards the introduction of the matrix into the fibers, due to the viscosity of that matrix and to the interface bonding between matrix and fibers.
Now, the use of the invention main process as above-described has solved simultaneously all the aforesaid difficulties due to the fact that the electrostatic treatment process described in that patent enables the swelling of the fibers, which helps the introduction of the matrix, the orientation of the fibers which enables the use of long fibers necessary in order to obtain a good mechanical strength whereas the etching procures excellent interface bonding conditions.
It is therefore the object of the present invention to solve another technical problem by proposing a solution permitting the preparation of ceramic composites in which the introduction of the matrix into the fibers is simplified, and the interface bonding is excellent, and which also enables the use of long fibers necessary to obtain a good if not excellent mechanical strength.
This problem is now solved quite satisfactorily and for the first time by the present invention. Once again, the present invention therefore relates to a use of the above-said main process using electrostatic fields in the production of ceramic composites notably of the ceramic-ceramic type or of the mixed ceramic and different fibers type.
One particular embodiment of the invention consists in producing a ceramic in which the ceramic matrix is of the zirconium type and the fibers are silicium carbide fibers, which are advantageously long fibers, woven or non-woven, the length of which is identical or near to the length of the piece to be produced.
Another particular embodiment of the invention consists in using alumina as ceramic matrix, the fibers being also in
alumina and being advantageously long but non-woven fibers.
The present invention also covers the ceramic composites obtained according to said process.
As already indicated, it was found with the main process described above, that the fact of applying a high A.C. voltage electrostatic field, preferably immediately after applying a high-voltage D.C. electrostatic field, was causing a roughness of the fibers surface, preferably after causing a swelling of said fibers, this improving radically, and quite unexpectedly, the impregnation of the fibers by the matrix and the bonding of interface adhesion between matrix and fibers, while improving radically the mechanical properties of the obtained ceramic composites.
The present invention according to a fourth object relates to a use of the above main process for the preparation of composite materials with oriented reinforcing elements, in the production of electrodes, as well as the electrodes obtained according to said process and electrochemical generators equipped with such electrodes. It has now been found, quite unexpectedly, that the use of the invention process has given totally unexpected results in the production of electrodes and that it was therefore especially advantageous for producing electrodes which can be used in electrochemical generators, such as accumulator batteries, primary cells, fuel cells, etc.
It is conventionally known that in any type of electromechanical generators, the efficiency is proportional to the ion exchange surface per unit of apparent surface. But if the aim is to obtain an advantageous weight/mass-energy ratio, it is important for the ion working surface to be equal to the outer surface multiplied by a maximum coefficient. This has led to the production of electrodes in fiber form. A number of patents have already been filed on such production processes, among them : EP 22409 ; FR-863 970, FR-995 222 ; FR-1 598 370 ; FR-2 489 788 ; DE-1 671 761 ; DE-1 915 859, DE-2 407 444 ; US-2 616 165 ;
US-3 375 136 and also GB-2 055 899.
But the electrodes produced according to these methods have a relatively poor lamination resistance because of the poor quality interface bonding between active material and conducting fibers. Moreover, the active surface/apparent surface ratio is relatively low and has to be improved in order to improve efficiency.
It is the object of the present invention to solve this new technical problem with a solution permitting the production of electrodes with an excellent interface banding between the active material and the conducting fibers, thus improving radically the mechanical properties of said electrodes, and with a very large active surface for a small apparent surface, thereby improving radically the efficiency of said electrodes. The solution proposed is also meant to be particularly simple.
Such a problem has now been satisfactorily and unexpectedly solved in a particularly simple way by the present invention.
Accordingly, the present invention further relates to a use of the invention process as above-described in the manufacture of electrodes as well as those electrodes.
The invention thus concerns a process for the manufacture of a composite electrode having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce a conducting adhesive forming matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with an electroactive conducting matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; optionally compressing said impregnated fibers (matrix composite) thereby obtaining said composite electrodes. Among suitable fibers according to the invention, it is
obviously important to use fibers capable of receiving, by electrolytic deposition, negative active materials for producing the anodes, or positive active materials for producing cathodes, therefore said fibers will have to be either conducting or made to be conducting by metal deposition, such as for example of "electroless" type.
According to the invention, carbon or boron fibers are preferably used as conducting fibers, the preferred ones being graphite fibers, and advantageously in the form of weaves of fibers, out to the size of the electrodes to be produced.
According to a particular embodiment of the invention, negative electrodes are produced by deposition of a metal selected from the group consisting advantageously of zinc, lithium, magnesium, cadmium. According to yet another embodiment of the invention for producing negative electrodes, it is preferably proceeded to a deposition of manganese dioxide, nickel oxide, silver dioxide, titanium dioxide.
In this particular application or utilization of the process described in the main patent, it has been found that the fact of applying a high voltage A.C. electrostatic field roughens the surface of the fibers, said A.C. field being preferably applied after the application of a high-voltage A.C. electrostatic field which causes the swelling and alignment of the fibers, thus radically and unexpectedly improving the penetration of the active material into the fibers, and giving an excellent interface bonding between active material and fibers and most unexpectedly, a very large active surface for a small apparent surface.
The invention also covers the eletrodes obtained according to said process as well as the electrochemical generators equipped with such electrodes, namely accumulator batteries, primary cells, fuel cells, etc.
The invention will be more readily understood on reading the following description of a non-restrictive example, with reference to the accompanying figures 1 to 9, and invention
examples .
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.
Figure 4 shows a microscopic view of a fibril before the treatment, and Figure 5 shows the same fibril as ground after the treatment. From a practical standpoint, it has been found that the fact of subj ecting the whole bundle of fibrils to a first A.C. field in order to obtain a more effecient etching with alternating current, and then subjecting it to a D.C. field in order to create an expansion , greatly contributes 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 subjecting 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 randomly but homogeneously, which is very advantageous in the case of short fiber composites, since sequencing always gives
breaking points, hence weak points. EXAMPLE 1
Woven Kevlar fibers are placed between the plates of an electrostatic field generating device, which plates can be fed with a high-voltage alternating or direct current.
First of all a high-voltage direct current of at least 40,000 volts is applied to said plates for a few minutes in order to separate the fibers and to obtain a swelling thereof, the overall thickness of the fibers then reaching between two and four times the thickness of the bed of fibers initially introduced between the plates forming electrodes, as described in the French patent.
Then an alternative current at a voltage of preferably at least 20,000 volts is applied for a few minutes, in order to obtain a roughness of the fibers surface due to an etching effect created on the surface by localized discharges when the electrostatic field is modified by reversing the polarity of the electric field.
While the Kevlar fibers are still under the influence of the electrostatic field, said fibers are embedded in a polyurethane elastomer which may contain one or more of the conventional vulcanizing agents, such as sulphur, in a relative proportion of 40 % by weight of Kevlar fibers and 60 % by weight of polyurethane elastomer.
Then, it is proceeded with the conventional vulcanizing treatment which may comprise a shaping in order to obtain a tire. To this end, the process may be carried out so as to obtain a radial-ply tire in a quite conventional way.
The resulting vulcanized product is found to have mechanical properties which are radically improved over the conventionally vulcanized products which have not been submitted to the process described in the French patent namely through a treatment by a high-voltage A.C. or D.C. electric field. EXAMPLE 2
The procedure is the same as in Example 1, except that the fibers used are KEVLAR type polyamide fibers woven at 60 %
lengthwise and at 40 % widthwise. These fibers are subjected for 10 minutes to a direct current of 100,000 V, then for 15 minutes to an alternating current of 25,000 V. Each one of these two electrostatic treatments consisting in causing first a stream of hot air at 90°C followed by a stream of hotter air, at more than 100°C, for example around 130°C, to flow between the plates, then the treated fibers are impregnated, while still under the influence of an electrostatic discharge, with a soft matrix composed of a polyurethane elastomer containing an adhesive bond constituted by a phenolic resin of the "Rhone-Poulenc" A.R.P. 27 type.
The resulting material is then put under a pressure of 2 t/dm2 and baked by polymerisation at 140°C for four hours, then heating is stopped and the resulting product is allowed to cool for 24 hours. The resulting vulcanized elastomer can be used as vehicle tire and is found to have the following characteristics : Characteristics :
- Density : 2.35
- Color : dark grey - Maximum temperature of use : 150°C
- fibers-matrix delamination :
None after 10,000 helical twistings. The matrix used here may be replaced for example by natural rubber. It is also possible for various applications to obtain the same supple products with pre-treated vegetable fibers (such as for example, fibers pre-treated in phenol-based solutions).
Tests conducted in laboratories have given excellent results with flaw and hemp fibers. The swelling and pigmentation reaction obtained in electrostatic fields is particularly advantageous, because the swelling effect is such that the "blotting effect" permits instant absorption of the different matrices with which said fibers may have been mixed.
EXAMPLE 3
Long woven fibers in silicium carbide, such as for example the MITSUI "Micalon" type, are placed between the plates of an electrostatic field generating device, which plates can be supplied with a high A.C. or D.C. voltage.
Said fibers are then subjected to a treatment by the electrostatic process described in the French patent 84 14800, preferably conducted as follows :
- first a high D.C. voltage of at least 40,000 volts is applied to the plates, preferably 100,000 volts, for a few minutes, preferably 10 minutes, so as to space out the fibers and cause them to swell, the thickness of the fibers assembly then reaching between two and four times the thickness of the bed of fibers initially introduced between the plates forming electrodes, as described in the French patent.
Preferably, an A.C. voltage at least equal to 20,000 volts, and preferably around 25,000 volts, is then applied for a few minutes, preferably about 10 minutes, in order to obtain a roughness of the fibers surface by a stripping effect on the surface, or by etching, resulting from localized discharges when the electrostatic field is modified by reversing the polarity of the electric field.
This treatment of the fibers is advantageously carried out under a stream of hot air heated to a temperature exceeding 100°C, and preferably equal to about 130°C.
Then, while the silicium carbide fibers are still under the effect of the electrostatic field, the silicium carbide fibers are coated with a ceramic matrix which in this case is preferably composed of ZrO2 (70 % by weight) and of SiO2 (30 % by weight), which matrix can contain an adhesive binder and, advantageously, an activating binder, in the relative proportion given hereunder, in % by weight :
% by weight
- Ceramic matrix : ZrO2 (70 % by weight)
SiO2 (30 % by weight) 50
- Adhesive binder, type 940 A from "Cotronics" Adhesive binder, type 940 T from "Cotronics" 20
- Long woven silicium carbide fibers type "Nicalon" MITSUI 30
Then, it is proceeded to the baking operation, as follows : - a first baking in a conventional oven for two hours, using the ambient air heated up to 80°C ;
- then, the heating is turned off, and the product is left to rest for 24 hours ;
- a second baking operation is then conducted in the same conventional oven using ambient air, by raising the temperature progressively of 150°C every hour, until a temperature of 1050°C is reached ;
- the heating is then turned off and the product is cooled slowly for 24 hours ; - finally, a third baking operation is conducted for fritting purposes ;
- said third baking operation is conducted in an oven with a neutral or reducing atmosphere, such as for example Xenon or H2. Thereagain, the temperature is raised progressively of 150°C every hour , for two hours ;
- the heating is then turned off and the product is cooled slowly for 24 hours.
The ceramic composites prepared in this way, which are known as of the "zirconia-silicium carbide" type, exhibits the following characteristics :
- Density : 2.7
- Color : pinkish-white
- Maximum temperature of use : 1800°C
- Water regain : none - Modulus in the flexure : 160 G.Pa
- Modulus of rupture : 860 M.Pa
- Elongation : 0.47
- Mechanical strength towards vibrations : between 0 and 60 KHz.
It is clear from these test results that the characteristics of the ceramic composites obtained with the electrostatic process are quite exceptional, which constitutes an undeniable technical progress, particularly unexpected for any one skilled in the art. EXAMPLE 4 The procedure is the same as in Example 1, but using alumina as matrix and long non-woven fibers of alumina of SUMITOMO type as fibers.
As adhesive binder, the matrix contains an adhesive binder such as of "CONTRONICS" RTC 70 type, the relative proportions being the same as in Example 1.
The ceramic composite material thus obtained exhibits the following characteristics :
- Density : 2.2
- Color : white - Maximum temperature of use : 1700°C
- Modulus of flexure : 140 G.Pa
- Modulus of rupture : 720 M.Pa
- Elongation : 0.38
As already indicated, the invention also covers the ceramic composites obtained according to said process. Therefore, the two examples given hereinabove form an integral part of the invention.
It should be noted that, according to the invention, by long fibers is meant fibers of which the length is not preset. Advantageously, the length of these fibers is adapted to the length of the piece to be produced. Thus, the length of the fibers is normally chosen to be either identical or near to the length of the piece. There is therefore no restriction of size for the fibers, contrary to what was the case in prior art processes. This then constitutes a particularly unexpected advantage of the present
invention.
The fibers used as reinforcing elements may be of different types without departing from the scope of the invention. Advantageously, they may be in silicium carbide, boron, alumina, carbon and polyamides, in any forms.
The matrix may also be different type provided that it leads to the formation of a ceramic type material. It will advantageously be a matrix of ZrO2 ; ZrO2SiO ; SiO2 ; Al2O3 ; SiO2 Al2O3 ; LiO ; TiO2; ZnO ; MnO ; CaO ; CeO2 ; MgO5 ; Al2TiO5 ; NiSiO2 and mixtures thereof in all proportions. EXAMPLE 5
Production of a negative electrode (anode) for use in zinc-nickel accumulator batteries
A first step consists in cutting elements from a weave of graphite fibers, to the size of the electrodes.
These cut fibers, in woven form, are then placed between the plates of an electrical field generating device, which plates can be fed with a high A.C. or D.C. voltage.
First, the plates receive for a few minutes, preferably about 15 minutes, a high-voltage direct current of at least 40,000 V, preferably around 100,000 V, for spacing and swelling up the fibers, the thickness of the fibers assembly then reaching between two and four times the thickness of the bed of fibers initially introduced between the plates forming electrodes. Then, preferably, an alternating current at least equal to 20,000 V, and preferably to 25,000 V, is applied for a few minutes, preferably 15 minutes, in order to obtain a roughness of the fiber surface by surface stripping effect, or etching, resulting from localized discharges when the electrostatic field is modified by reversing the polarity of the electric field.
These two treatments by an electrostatic field are preferably conducted after heating the fibers in an oven, at about 350°C, said treatments being conducted by causing a steam of hot air to pass between the plates at a temperature of about 150°C. In order to obtain a perfect electrical conductibility,
another step consists in placing on each side of a metal grid in stainless steel, such as of the GANTOIS R. 0.25 type, a bulky and treated weave, then still under the effect of the electrostatic field, and coating these weaves with a view to bonding them, with a conducting adhesive forming matrix, such as for example an M. Ag type conducting adhesive, sold by the company 3M.
Said adhesive having been left to test as prescribed in the notice of use thereof, it is then proceeded, in an electrolytic bath, to the deposition of a metal, in this case zinc, on the swollen and etched fibers, according to the following method.
The electrolytic bath is prepared as follows, for 2 1 of solution :
- first 200 g of gluconate are dissolved in one liter of distilled water ; - then 50 g of zinc chloride are dissolved in the resulting solution ;
- and about 15 cm3 of a solution sold under the reference 9211-WH by Ets. Walberg are added thereto ;
- the solution is completed with 2 1 of distilled water, and
- the pH of the obtained solution is brought to between 2 and 5.5 with KOH.
It should be noted that the electrolytic bath solution can be used serveral times on condition that 20 g of gluconate are added in after each filtration, said gluconate being preferably sodium gluconate.
Electrolytic deposition of zinc is performed conventionally, a slight strirring being kept up throughout the deposition. The intensity is preferably under 7 A. In the case where the intensity is below 7 A, it suffices to clean the zinc plates every two hours, whereas if the intensity is higher than 7 A, the zinc plastes must be cleaned every hour.
After proceeding to a deposition of 3 hours, it is proceeded to a rinsing and drying, then the obtained plate iscompressed at the rate of 3 t per dm2, to obtain a porous electrode
of very high capacity with an ion working surface mutiplied by 30 or 40 compared with the currently used electrodes, this fact constituting a totally unexpected technical result.
The same process can be used in particular to produce anodes in zinc, in cadmium, in lithium, in magnesium, as well as to produce cathodes in nickel, in silver, in cobalt, in titanium and in manganese.
Similarly, with cells, it is possible with the invention to obtain an excellent deposition of manganese dioxide, whereas if such an electrode is produced in wound-band form, the tests conducted to-date have shown that it is possible to constitute a very conducting cathode in which the MnO2-graphite ratio is 75 % of MnO2 for only 25 % of conducting material, which is a remarkable achievement. Thus, the obtained cathode is found to have a considerably higher mechanical strength wich is a great improvement over the conventional MnO2 as wellas alkaline or salin cells, and an active material-inert material ratio increased in the proportion of 30 %. These results are due to the swelling of the fibers, by the electrostatic treatment with a direct current, which enables the fibers to admit a large quantity of active material, and to the etching obtained with the alternating current electrostating treatment, which procures good interface bonding between fibers and matrix, hence a perfect electrical conductibility.
Conceivably therefore, the invention corresponds to an important technical progress which was totally unexpected for any one skilled in the art.
Claims
1. 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 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 still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
2. The process of claim 1 comprising the steps of : subjecting the fibers to an electrostatic field induced by a high-voltage direct electric current for a first time interval sufficient to cause charging said fibers ; subjecting the fibers to an electrostatic field induced by a high-voltage alternating electric current for a second time interval sufficient to cause a modification of the surface of the fibers ; after the elapse of said two time intervals, impregnating said fibers with a liquid matrix or precursor of matrix, while still under the influence of said field, thereby consolidating bonding between the fibers and the matrix.
3. The process of claim 1 comprising the successive steps of : subjecting the fibers to an electrostatic field induced by a high-voltage alternating electric current for a first time interval sufficient to cause a modification of the surface of the fibers ; subjecting the fibers to an electrostatic field induced by a high-voltage direct electric current for a second time interval sufficient to cause charging said fibers ; after the elapse of said two time intervals, impregnating said fibers with a liquid matrix or precursor of matrix, while still under the influence of said field, thereby consolidating
bonding between the fibers and the matrix.
4. The process of any one of claim 1 to 3, wherein said direct electric current is at a voltage equal to at least 40,000 volts and said alternating current is at a voltage equal to at least 20,000 volts.
5. The process as claimed in any one of claims 1 to 3, wherein said fibers are made in a dielectric material and are selected from the group consisting of polyamide fibers, glassfibers, metallic oxides fibers, carbon fibers and mixtures thereof.
6. Use of the process of anyone of claims 1 to 5, to vulcanization, preferably for producing tires.
7. A process for the manufacture of a vulcanized composite material having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce a vulcanizable matrix, comprising the steps of : subjecting trie fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a vulcanizable liquid matrix or precursor of vulcanizable matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and vulcanizing the impregnated fibers/matrix composite, thereby obtaining said vulcanized composite material.
8. The process of claim 7, wherein said electrostatic field includes time sequential first and second fields that are induced by high-voltage electric currents.
9. The process of; claim 8, wherein one of said fields is induced by an A.C. electric current and where the other of said fields is induced by a D.C. electric current.
10. The process of claim 7, wherein the first of said fields is induced by D.C. electric current and the second one of said fields is induced by A.C. electric current.
11. The process of claim 7, further including the step of shaping the impregnated fibers/matrix composite into a vehicle tire
to obtain a vehicle tire as the vulcanized composite material.
12. The process of claim 7, wherein the fibers used as reinforcing elements are selected from the group consisting of polyamide fibers, plant fibers and glass fibers.
13. The process of claim 7, wherein the matrix is selected from the group consisting of polyurethane elastomer, natural rubber, synthetic rubber, rhodorsil, silicon, thermoplastic elastomer, and mixtures thereof.
14. The process of claim 7 or 12, wherein woven Kevlar fibers as reinforcing fibers are used with polyurethane elastomer as matrix, the relative proportion being about 40 % by weight of woven Kevlar fibers with about 60 % by weight of polyurethane elastomer.
15. The process of claim 10, wherein the D.C. electric current is about a 40,000 V D.C. electric current and wherein the A.C. electric current is about a 20,000 V electric current.
16. The process of claim 10, wherein the D.C. electric current is about a 100,000 V D.C. electric current and wherein the A.C. electric current is about a 25,000 V electric current.
17. The process of claim 7 or 12, wherein said fibers are of a dielectric material.
18. The process of claim 17, wherein said dielectric material is selected from the group consisting of polyamide fibers, glass fibers, metallic oxide fibers, carbon fibers and mixtures thereof.
19. A process for the manufacture of a composite material usable as a vehicle tire having improved mechanical and wear properties, the composite material having tire reinforcing fibers that reinforce a tire matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a liquid matrix or precursor of matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and vulcanizing the impregnated fibers/matrix composite so
that the resulting vulcanized material is usable as a vehicle tire.
20. Use of the process of any one of claims 1 to 5, in the manufacture of electrodes.
21. A process for the manufacture of composite electrodes having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce electro-active conducting matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with electro-active conducting matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and optionally comprising the impregnated fibers/matrix composite, thereby obtaining said composite electrodes.
22. The process of claim 21, wherein the fibers used are conducting fibers in carbon and/or boron.
23. The process of claim 21, wherein the fibers are non-conducting fibers on which a metal deposition has been carried out.
24. The process of claim 21, wherein to produce negative electrodes, it is proceeded to a deposition of zinc, lithium, magnesium or cadmium.
25. The process of claim 21, wherein to produce positive electrodes, it is proceeded to a deposition of manganese dioxide, nickel oxide, silver dioxide, or titanium dioxide.
26. Use of the process of any one of claims 1 to 5, in the production of ceramic composites, such as of the ceramic-ceramic type or of the ceramic with mixed fibers type.
27. A process for the manufacture of a ceramic composite material having improved mechanical and wear properties, the composite material having reinforcing fibers that reinforce a ceramic or ceramic precursor matrix, comprising the steps of : subjecting the fibers to an electrostatic field that is
induced by a high-voltage electric current to prepare the fibers to be impregnated ; impregnating said fibers with a ceramic matrix or precursor of ceramic matrix while still under the influence of said electrostatic field thereby consolidating bonding between the fibers and the matrix ; and baking the impregnated fibers/matrix composite, thereby obtaining said ceramic composite material.
28. The process of claim 27, wherein the fibers used as reinforcing elements are selected from silicium carbide, boron, alumina, carbon and polyamide in any forms.
29. The process of claim 27, wherein the matrix is selected from the group consisting of alumina, zirconium, particularly a mixture of ZrO2 + SiO2, preferably in a relative proportion by weight of 70 % for 30 %.
30. The process of claim 28, wherein long fibers are used the length of which is preferably identical or near to the length of the piece to be produced.
31. The process of claim 28, wherein woven fibers are used, and advantageously long woven fibers.
32. The process of claim 26, wherein said ceramic composite comprises a matrix selected from the group consisting of alumina, zirconium or a mixture or zirconium and SiO2, whareas the fibers are selected from the group consisting of alumina, silicium carbide, boron, carbon, or polyamides in any form.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8700797 | 1987-01-23 | ||
| FR878700797A FR2609934B2 (en) | 1984-09-26 | 1987-01-23 | APPLICATION OF A PROCESS FOR THE PREPARATION OF COMPOSITE MATERIALS WITH REINFORCING ELEMENTS ORIENTED IN THE MANUFACTURE OF VULCANIZED PRODUCTS SUCH AS TIRES AND VULCANIZED PRODUCTS, PARTICULARLY PNEUMATIC THUS OBTAINED |
| FR8702105 | 1987-02-18 | ||
| FR8702106 | 1987-02-18 | ||
| FR878702105A FR2610922B2 (en) | 1984-09-26 | 1987-02-18 | APPLICATION OR USE OF A PROCESS FOR THE PREPARATION OF COMPOSITE MATERIALS WITH ORIENTED REINFORCING ELEMENTS, FOR THE MANUFACTURE OF COMPOSITE CERAMICS, AND THE COMPOSITE CERAMICS THUS OBTAINED |
| FR878702106A FR2611086B2 (en) | 1984-09-26 | 1987-02-18 | APPLICATION OR USE OF A PROCESS FOR THE PREPARATION OF COMPOSITE MATERIALS WITH ORIENTED REINFORCING ELEMENTS, FOR THE MANUFACTURE OF ELECTRODES, AS WELL AS THE ELECTRODES OBTAINED AND ELECTROCHEMICAL GENERATORS COMPRISING SUCH ELECTRODES |
| US07/027,793 US4857244A (en) | 1984-09-26 | 1987-03-19 | Process of making a composite product, especially a vehicle tire |
| US27793 | 1987-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0342197A1 true EP0342197A1 (en) | 1989-11-23 |
Family
ID=27446556
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88200098A Expired - Lifetime EP0276041B1 (en) | 1987-01-23 | 1988-01-21 | Process for preparing composite material including vulcanized products notably tires, ceramics and electrodes and products obtained with said process |
| EP88901042A Pending EP0342197A1 (en) | 1987-01-23 | 1988-01-21 | Process for preparing a composite material |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP88200098A Expired - Lifetime EP0276041B1 (en) | 1987-01-23 | 1988-01-21 | Process for preparing composite material including vulcanized products notably tires, ceramics and electrodes and products obtained with said process |
Country Status (10)
| Country | Link |
|---|---|
| EP (2) | EP0276041B1 (en) |
| JP (1) | JPH02501996A (en) |
| AU (1) | AU597789B2 (en) |
| BR (1) | BR8807320A (en) |
| DE (1) | DE3869432D1 (en) |
| DK (1) | DK527288D0 (en) |
| ES (1) | ES2031225T3 (en) |
| GR (1) | GR3004197T3 (en) |
| PT (1) | PT86601B (en) |
| WO (1) | WO1988005375A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2747940C2 (en) * | 2016-07-20 | 2021-05-17 | Мануэль ТОРРЕС МАРТИНЕС | Method for processing fibers, installation for processing fibers and resulting tape formed from processed fibers |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US5468357A (en) * | 1994-12-27 | 1995-11-21 | Hughes Missile Systems Company | Densification of porous articles by plasma enhanced chemical vapor infiltration |
| AT410073B (en) * | 1997-12-17 | 2003-01-27 | Klaus Dipl Ing Dr Hummel | METHOD FOR IMPROVING THE ADHESION OF RUBBER VOLCANISANS TO COPPER ALLOYS |
| JP5233600B2 (en) * | 2008-11-06 | 2013-07-10 | 株式会社ニコン | Method for producing particle-containing resin |
| AU2017260086A1 (en) | 2016-05-04 | 2018-11-22 | Somnio Global Holdings, Llc | Additive fabrication methods and devices for manufacture of objects having preform reinforcements |
| CN115852590B (en) * | 2022-09-28 | 2023-10-10 | 青岛德冠超导材料制造有限公司 | Natural antibacterial and antistatic nanofiber membrane and its preparation method and use |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3634220A (en) * | 1968-09-19 | 1972-01-11 | Us Navy | Method for improving graphite fibers for plastic reinforcement and products thereof |
| 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 |
| US4302264A (en) * | 1973-06-04 | 1981-11-24 | The General Tire & Rubber Company | Method for pretreating glass cords which minimizes cord blows |
| US3984366A (en) * | 1973-11-21 | 1976-10-05 | The General Tire & Rubber Company | Bonding glass fibers to rubber |
| FR2570646B1 (en) * | 1984-09-26 | 1987-10-30 | Pradom Ltd | PROCESS FOR THE PREPARATION OF COMPOSITE MATERIALS WITH ORIENTED REINFORCING ELEMENTS AND PRODUCTS OBTAINED |
-
1988
- 1988-01-21 JP JP63501230A patent/JPH02501996A/en active Pending
- 1988-01-21 ES ES198888200098T patent/ES2031225T3/en not_active Expired - Lifetime
- 1988-01-21 BR BR888807320A patent/BR8807320A/en not_active Application Discontinuation
- 1988-01-21 WO PCT/EP1988/000039 patent/WO1988005375A2/en not_active Ceased
- 1988-01-21 AU AU11587/88A patent/AU597789B2/en not_active Ceased
- 1988-01-21 DE DE8888200098T patent/DE3869432D1/en not_active Expired - Fee Related
- 1988-01-21 EP EP88200098A patent/EP0276041B1/en not_active Expired - Lifetime
- 1988-01-21 EP EP88901042A patent/EP0342197A1/en active Pending
- 1988-01-22 PT PT86601A patent/PT86601B/en not_active IP Right Cessation
- 1988-09-22 DK DK527288A patent/DK527288D0/en not_active Application Discontinuation
-
1992
- 1992-03-31 GR GR920400568T patent/GR3004197T3/el unknown
Non-Patent Citations (1)
| Title |
|---|
| See references of WO8805375A2 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2747940C2 (en) * | 2016-07-20 | 2021-05-17 | Мануэль ТОРРЕС МАРТИНЕС | Method for processing fibers, installation for processing fibers and resulting tape formed from processed fibers |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0276041A2 (en) | 1988-07-27 |
| WO1988005375A2 (en) | 1988-07-28 |
| AU597789B2 (en) | 1990-06-07 |
| AU1158788A (en) | 1988-08-10 |
| PT86601B (en) | 1991-12-31 |
| EP0276041A3 (en) | 1988-12-28 |
| EP0276041B1 (en) | 1992-03-25 |
| DE3869432D1 (en) | 1992-04-30 |
| GR3004197T3 (en) | 1993-03-31 |
| WO1988005375A3 (en) | 1988-10-06 |
| ES2031225T3 (en) | 1992-12-01 |
| JPH02501996A (en) | 1990-07-05 |
| DK527288A (en) | 1988-09-22 |
| BR8807320A (en) | 1990-05-22 |
| DK527288D0 (en) | 1988-09-22 |
| PT86601A (en) | 1988-02-01 |
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