JPH0411664B2 - - Google Patents
Info
- Publication number
- JPH0411664B2 JPH0411664B2 JP26365386A JP26365386A JPH0411664B2 JP H0411664 B2 JPH0411664 B2 JP H0411664B2 JP 26365386 A JP26365386 A JP 26365386A JP 26365386 A JP26365386 A JP 26365386A JP H0411664 B2 JPH0411664 B2 JP H0411664B2
- Authority
- JP
- Japan
- Prior art keywords
- fibers
- fiber
- inorganic
- crystalline
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000012784 inorganic fiber Substances 0.000 claims description 68
- 239000000835 fiber Substances 0.000 claims description 67
- 239000002131 composite material Substances 0.000 claims description 41
- 239000012783 reinforcing fiber Substances 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000000919 ceramic Substances 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000010410 layer Substances 0.000 claims description 12
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 10
- -1 whiskers Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000011882 ultra-fine particle Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003733 fiber-reinforced composite Substances 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 229920003023 plastic Polymers 0.000 claims description 6
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 5
- 229910010272 inorganic material Inorganic materials 0.000 claims description 5
- 239000011147 inorganic material Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 13
- 229910010271 silicon carbide Inorganic materials 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 8
- 235000019646 color tone Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229920003257 polycarbosilane Polymers 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000003779 heat-resistant material Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052574 oxide ceramic Inorganic materials 0.000 description 2
- 239000011224 oxide ceramic Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000011226 reinforced ceramic Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- 229910026551 ZrC Inorganic materials 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000011074 autoclave method Methods 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009730 filament winding Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009787 hand lay-up Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、内部層と表面とからなり色調の豊か
な強化用繊維及びそれで強化された複合体に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a reinforcing fiber with a rich color tone, consisting of an inner layer and a surface, and a composite reinforced with the reinforcing fiber.
（従来の技術及びその問題点）
従来、各種複合体の強化用繊維として、炭素繊
維及び炭化珪素繊維が用いられてきた。(Prior Art and its Problems) Conventionally, carbon fibers and silicon carbide fibers have been used as reinforcing fibers for various composites.
これらの繊維はいずれも色調が黒色であり、こ
のためこれら繊維で強化された複合体も黒色ない
し灰黒色を呈し、複合体の表面を塗布するか、あ
るいはこの複合体に他の樹脂を積層するかしない
限り、種々の色調を有する美麗な外観の複合体を
得ることができなかつた。 All of these fibers are black in color, so composites reinforced with these fibers also have a black or grayish-black color and can be coated onto the surface of the composite or laminated with other resins. Unless this process is carried out, it is not possible to obtain a composite material having a beautiful appearance and having various color tones.
繊維で強化された金属又はプラスチツクは、強
度と軽量性とを要求される製品、例えば、テニス
ラケツト、釣竿、スキーストツク、スキーエツ
ジ、レーシングカー、パイプ等から航空機、自動
車に亘る広範囲の製品として使用される。これら
の用途には、機械的強度は勿論のこと外観の美し
さ、フアツシヨン性も重要な因子として同時に要
求される。従来知られていた強化用無機繊維では
充分な機械的強度及び美麗な外観の二つの要求を
同時に満足させることができない。 Fiber-reinforced metals or plastics are used in a wide range of products that require strength and lightness, such as tennis rackets, fishing rods, ski stocks, ski wedges, racing cars, pipes, etc., as well as aircraft and automobiles. For these uses, not only mechanical strength but also beautiful appearance and fashionability are required as important factors. Conventionally known reinforcing inorganic fibers cannot simultaneously satisfy the two requirements of sufficient mechanical strength and beautiful appearance.
また、繊維で強化されたセラミツクは各種機械
部品、構造材料として使用されている。これらの
分野においても用途に応じて外観の美しい複合体
が要求されている。公知の繊維強化セラミツクは
この要求を満足させるものではない。 Fiber-reinforced ceramics are also used as various mechanical parts and structural materials. In these fields as well, composites with a beautiful appearance are required depending on the application. Known fiber-reinforced ceramics do not meet this requirement.
さらに、公知の無機繊維を使用して得られる複
合体は、その製造過程で強化用繊維がかたよりや
すく、複合体中で繊維の分布が粗な部分と密な部
分とが生ずる。そのため、複合体中の繊維体積率
の制御が困難であり、特に繊維体積率が小さい場
合には、強化用繊維が均一に複合体中に分散せ
ず、目的とする高い機械特性を有する複合体が得
られない。 Furthermore, in composites obtained using known inorganic fibers, the reinforcing fibers tend to become uneven during the manufacturing process, resulting in areas where the fiber distribution is coarse and areas where the fibers are dense. Therefore, it is difficult to control the fiber volume fraction in the composite, and especially when the fiber volume fraction is small, the reinforcing fibers are not uniformly dispersed in the composite, resulting in a composite that has the desired high mechanical properties. is not obtained.
無機繊維のみで強化した複合体では強度の異方
性が大きく、繊維の長さ方向の強度は大きく、そ
れと直角方向の強度は極めて小さくなる。短繊維
のみを使用した複合体は等方性ではあるが、その
強度は一般に小さい。 A composite reinforced only with inorganic fibers has a large anisotropy of strength, with the strength in the longitudinal direction of the fibers being high, but the strength in the direction perpendicular to it being extremely low. Composites using only short fibers are isotropic, but their strength is generally low.
複合体に使用する強化用繊維として連続繊維又
は長繊維と短繊維又はウイスカとを組み合わせて
使用する方法も提案されている。例えば、複合体
部材の内側には長繊維を使用し、外側には短繊維
を使用する方法がある。この方法においても、長
繊維と短繊維とを部材の内側で使い分ける方法は
製造工程が煩雑となり、さらに得られる複合体の
強度も充分ではない。また、プリプレグ製造時に
長繊維と短繊維とを混在させる方法は、長繊維束
中の表面に刷毛等により短繊維を付着させること
はできるものの、内部の長繊維の一本一本の表面
に均一に付着させることが困難であり、繊維体の
品質が不均一になる。 It has also been proposed to use a combination of continuous fibers or long fibers and short fibers or whiskers as reinforcing fibers for composites. For example, there is a method of using long fibers on the inside of the composite member and short fibers on the outside. Even in this method, the method of using long fibers and short fibers separately inside the member complicates the manufacturing process, and furthermore, the strength of the resulting composite is not sufficient. In addition, in the method of mixing long fibers and short fibers during prepreg manufacturing, short fibers can be attached to the surface of the long fiber bundle with a brush, etc., but the surface of each long fiber inside is uniformly coated. It is difficult to adhere to the fibers, resulting in uneven quality of the fibers.
（発明の目的）
本発明の目的は、美麗な色調を有し、かつ複合
体中に連続繊維を均一に分散させて繊維体積率を
制御でき、複合体の機械的特性を向上させること
ができる強化用無機繊維を提供することにある。(Objective of the Invention) The object of the present invention is to have a beautiful color tone, uniformly disperse continuous fibers in the composite, control the fiber volume percentage, and improve the mechanical properties of the composite. The purpose of the present invention is to provide reinforcing inorganic fibers.
本発明の別の目的は、上記強化用無機繊維で強
化された優れた機械特性及び美しい外観を有する
複合体を提供することにある。 Another object of the present invention is to provide a composite reinforced with the above-mentioned reinforcing inorganic fibers and having excellent mechanical properties and a beautiful appearance.
（発明の要旨）
本発明によれば、連続無機繊維と該連続無機繊
維との間に介在する耐熱性物質の短繊維、ウイス
カ又は粉末とからなる強化用繊維であつて、該連
続無機繊維が
() Si、Ｃ及びＯからなる非晶質物質、又は
() 粒径が500Å以下のβ−SiCからなる結晶質
超微粒子と非晶質のSiO2とからなる集合体、
又は、
() 上記（）の非晶質物質と上記（）の結
晶質超微粒子集合体の混合系、
からなる珪素、炭素及び酸素を含有する無機質
物質からなる内部層と、
() Si及びＯからなる非晶質物質、
() 結晶質のSiO2からなる集合体、又は
() 上記（）の非晶質物質と上記（）の結
晶質重合体の混合系
からなる珪素及び酸素を含有する無機質物質から
なる表面層とからなることを特徴とする強化用無
機繊維が提供される。(Summary of the Invention) According to the present invention, there is provided a reinforcing fiber comprising continuous inorganic fibers and short fibers, whiskers or powder of a heat-resistant substance interposed between the continuous inorganic fibers, wherein the continuous inorganic fibers are () An amorphous substance consisting of Si, C and O, or () an aggregate consisting of crystalline ultrafine particles consisting of β-SiC with a particle size of 500 Å or less and amorphous SiO 2 ,
or () an inner layer made of an inorganic material containing silicon, carbon, and oxygen, consisting of a mixed system of the amorphous material of the above () and the crystalline ultrafine particle aggregate of the above (); an amorphous substance consisting of () an aggregate consisting of crystalline SiO 2 , or () a mixed system of the above () amorphous substance and the above () crystalline polymer containing silicon and oxygen Provided is a reinforcing inorganic fiber characterized by comprising a surface layer made of an inorganic substance.
また、本発明によれば、金属、セラミツク、プ
ラスチツク等のマトリツクスが上記強化用無機繊
維で強化された複合体が提供される。 Further, according to the present invention, there is provided a composite in which a matrix of metal, ceramic, plastic, etc. is reinforced with the above-mentioned reinforcing inorganic fibers.
（発明の具体的説明）
本発明における連続無機繊維の大部分を占める
内部層は、
() Si、Ｃ及びＯからなる非晶質物質、又は
() 粒径が500Å以下のβ−SiCからなる結晶質
超微粒子と非晶質のSiO2とからなる集合体、
又は、
() 上記（）の非晶質物質と上記（）の結
晶質超微粒子集合体の混合系、
からなる珪素、炭素及び酸素を含有する無機質
物質からなつている。(Detailed Description of the Invention) The inner layer that occupies most of the continuous inorganic fiber in the present invention is () made of an amorphous material made of Si, C, and O, or () made of β-SiC with a particle size of 500 Å or less. An aggregate consisting of crystalline ultrafine particles and amorphous SiO 2 ,
or () A mixed system of the amorphous material described in () above and the crystalline ultrafine particle aggregate described in () above, consisting of an inorganic material containing silicon, carbon, and oxygen.
また、本発明における連続無機繊維の表面層
は、
() Si及びＯからなる非晶質物質、
() 結晶質のSiO2からなる集合体、又は
() 上記（）の非晶質物質と上記（）の結
晶質重合体の混合系
からなる珪素及び酸素を含有する無機質物質から
なつている。 In addition, the surface layer of the continuous inorganic fiber in the present invention is () an amorphous substance made of Si and O, () an aggregate made of crystalline SiO 2 , or () the above amorphous substance in () and the above It is made of an inorganic material containing silicon and oxygen, which is a mixed system of crystalline polymers ().
上記（）及び（）の非晶質物質は不可避不
純物を含んでいてもよい。また、上記の表面層は
５重量％以下の炭素を含んでいてもよい。 The above amorphous substances () and () may contain unavoidable impurities. Further, the above surface layer may contain 5% by weight or less of carbon.
上記の連続無機繊維は、例えば、まず内部層と
同一の組成を有する無機繊維を調製した後、この
繊維を酸化性雰囲気中で加熱して表面層を形成さ
せることによつて得ることができる。 The above-mentioned continuous inorganic fiber can be obtained, for example, by first preparing an inorganic fiber having the same composition as the inner layer, and then heating this fiber in an oxidizing atmosphere to form a surface layer.
内部層と同一の組成を有する無機繊維は、例え
ば、下記方法に従つて調製することができる。 Inorganic fibers having the same composition as the inner layer can be prepared, for example, according to the method below.
側鎖に少なくとも１個のアルキル基を有するポ
リシランを、触媒の存在下又は不存在下に加熱し
て、ポリカルボシランを生成させる第１工程と、
上記ポリカルボシランの紡糸原液を造り紡糸する
第２工程と、該紡糸繊維を張力あるいは無張力下
で不融化する第３工程と、不融化した前記紡糸繊
維を真空中あるいは不活性ガス雰囲気中で800〜
1800℃の範囲の温度で焼成する第４工程から、実
質的にSi、Ｃ及びＯからなる連続無機繊維を製造
することができる。 A first step of heating a polysilane having at least one alkyl group in a side chain in the presence or absence of a catalyst to produce a polycarbosilane;
a second step of preparing and spinning a spinning dope of the polycarbosilane; a third step of infusibleizing the spun fiber under tension or no tension; and a step of infusibilizing the spun fiber in a vacuum or an inert gas atmosphere. 800〜
From the fourth step of firing at a temperature in the range of 1800°C, continuous inorganic fibers consisting essentially of Si, C and O can be produced.
無機繊維中の各元素の割合は、通常 Si：30〜60重量％、 Ｃ：25〜40重量％、 Ｏ：0.01〜30重量％ である。 The proportion of each element in inorganic fibers is usually Si: 30-60% by weight, C: 25-40% by weight, O: 0.01-30% by weight It is.
こうして得られる連続無機繊維を通常500〜
1600℃の範囲の温度で酸化性雰囲気下に加熱する
ことによつて、表面層が形成され、本発明におけ
る連続無機繊維が得られる。酸化性雰囲気として
は、空気、純酸素、オゾン、水蒸気、炭酸ガス等
の雰囲気が挙げられる。 The continuous inorganic fibers obtained in this way are usually
By heating in an oxidizing atmosphere at a temperature in the range of 1600°C, a surface layer is formed and the continuous inorganic fiber of the present invention is obtained. Examples of the oxidizing atmosphere include atmospheres such as air, pure oxygen, ozone, water vapor, and carbon dioxide gas.
この処理により、無機繊維に種々の色調、例え
ば、赤、紫、青、緑、橙、茶、桃等の色調が付与
される。無機繊維の色調は、酸化性雰囲気での加
熱条件を変化させて表面層の厚さ及び構造を調整
することによつて任意に変えることができる。一
例をあげると、酸化条件が穏やかであると赤色な
いし紫色になり、順次酸化条件を厳しくするに従
つて、青色、緑色になる。色調の調整は上記教示
に従つて当業者が容易に行うことができる。 This treatment imparts various colors to the inorganic fibers, such as red, purple, blue, green, orange, brown, and peach. The color tone of the inorganic fiber can be arbitrarily changed by changing the heating conditions in an oxidizing atmosphere and adjusting the thickness and structure of the surface layer. For example, when the oxidation conditions are mild, the color becomes red or purple, and as the oxidation conditions are made more severe, the color becomes blue or green. Adjustment of color tone can be readily accomplished by those skilled in the art in accordance with the above teachings.
こうして得られる連続無機繊維の内部層の各元
素の割合は実質的に上記と変わらず、表面層の各
元素の割合は、通常
Si：40〜65重量％、
Ｏ：30〜55重量％、
Ｃ：０〜５重量％
である。 The proportions of each element in the inner layer of the continuous inorganic fiber thus obtained are substantially the same as above, and the proportions of each element in the surface layer are usually Si: 40-65% by weight, O: 30-55% by weight, C. :0 to 5% by weight.
本発明における連続無機繊維の内部層の直径は
通常２〜20μｍであり、表面層の厚さは通常0.01
〜5μｍである。 The diameter of the inner layer of continuous inorganic fibers in the present invention is usually 2 to 20 μm, and the thickness of the surface layer is usually 0.01 μm.
~5μm.
この連続無機繊維は繊維そのものを単軸方向、
多軸方向に配向させる方法、あるいは平織、朱子
織、模様織、綾織、からみ織、らせん織物、三次
元織物等の各模織物にして使用する方法、又はチ
ヨツプドストランドフアイバーとして使用する方
法等がある。 This continuous inorganic fiber is oriented in a uniaxial direction.
A method in which the fiber is oriented in multiple axes, a method in which it is used as a fabric with various patterns such as plain weave, satin weave, patterned weave, twill weave, leno weave, spiral fabric, three-dimensional fabric, etc., or a method in which it is used as a chopped strand fiber. etc.
連続無機繊維の繊維間隙に介在させる短繊維、
ウイスカ又は粉末を構成する耐熱性物質として
は、炭化珪素、窒化珪素、アルミナ、シリカ、シ
リカ−アルミナ、ジルコニア、ベリリア、炭化硼
素、炭化チタンのようなセラミツク、金属、金属
間化合物が挙げられる。耐熱性物質の短繊維、ウ
イスカ又は粉末の割合は、連続無機繊維に対して
0.5〜500容量％であることが好ましい。 Short fibers interposed between fiber gaps of continuous inorganic fibers,
Heat-resistant substances constituting whiskers or powders include ceramics, metals, and intermetallic compounds such as silicon carbide, silicon nitride, alumina, silica, silica-alumina, zirconia, beryllia, boron carbide, and titanium carbide. The ratio of short fibers, whiskers or powder of heat-resistant material to continuous inorganic fibers is
It is preferably 0.5 to 500% by volume.
本発明におけるマトリツクスとしては、金属、
プラスチツク又はセラミツクをあげることができ
る。 The matrix in the present invention includes metal,
Plastic or ceramic may be mentioned.
金属マトリツクスの例としては、アルミニウ
ム、マグネシウム、チタン、又はこれらの合金が
挙げられる。 Examples of metal matrices include aluminum, magnesium, titanium, or alloys thereof.
プラスチツクマトリツクスの例としては、エポ
キシ樹脂、変性エポキシ樹脂、ポリエステル樹
脂、ポリイミド樹脂、フエノール樹脂、ポリウレ
タン樹脂、ポリアミド樹脂、ポリカーボネート樹
脂、シリコン樹脂、フエノキシ樹脂、ポリフエニ
レンサルフアイド樹脂、フツ素樹脂、炭化水素樹
脂、含ハロゲン樹脂、アクリル酸系樹脂、ABS
樹脂、超高分子量ポリエチレン、変性ポリフエニ
レンオキサイド、ポリスチレン等が挙げられる。 Examples of plastic matrices include epoxy resin, modified epoxy resin, polyester resin, polyimide resin, phenolic resin, polyurethane resin, polyamide resin, polycarbonate resin, silicone resin, phenoxy resin, polyphenylene sulfide resin, fluorine resin, Hydrocarbon resin, halogen-containing resin, acrylic acid resin, ABS
Examples include resin, ultra-high molecular weight polyethylene, modified polyphenylene oxide, and polystyrene.
セラミツクマトリツクスの例としては、炭化珪
素、炭化チタン、炭化ジルコニウム、炭化ニオ
ブ、炭化タンタル、炭化ホウ素、炭化クロム、炭
化タングステン、炭化モリブデン等の炭化物セラ
ミツク；窒化珪素、窒化チタン、窒化ジルコニウ
ム、窒化バナジウム、窒化ニオブ、窒化タンタ
ル、窒化ホウ素、窒化アルミニウム、窒化ハフニ
ウム等の窒化物セラミツク；アルミナ、シリカ、
マグネシア、ムライト、コージライト等の酸化物
セラミツク；ホウ珪酸ガラス、リチウムシリケー
ト系ガラス等のガラスが挙げられる。これらの中
でも、複合体の色調の面から酸化物セラミツク及
びガラスが好ましく使用される。 Examples of ceramic matrices include carbide ceramics such as silicon carbide, titanium carbide, zirconium carbide, niobium carbide, tantalum carbide, boron carbide, chromium carbide, tungsten carbide, and molybdenum carbide; silicon nitride, titanium nitride, zirconium nitride, and vanadium nitride. , nitride ceramics such as niobium nitride, tantalum nitride, boron nitride, aluminum nitride, hafnium nitride; alumina, silica,
Examples include oxide ceramics such as magnesia, mullite, and cordierite; glasses such as borosilicate glass and lithium silicate glass. Among these, oxide ceramics and glass are preferably used from the viewpoint of the color tone of the composite.
本発明の強化用無機繊維の製法については特に
制限はなく、例えば電着法、流動床を用いる方
法、吹きつけ法、懸濁浸漬法等を採用することが
できる。簡便さ及び適用範囲の広さ等の観点から
懸濁浸漬法が好適に採用されうる。 There are no particular limitations on the method for producing the reinforcing inorganic fibers of the present invention, and for example, electrodeposition, a method using a fluidized bed, a spraying method, a suspension dipping method, etc. can be employed. The suspension dipping method can be suitably employed from the viewpoints of simplicity and wide applicability.
懸濁浸漬法の一例としては、ボビン等に巻きつ
けた連続無機繊維又は適当数の連続無機繊維を束
ねた連続無機繊維束を巻戻して、あるいは連続無
機繊維の織物を、短繊維、ウイスカ又は粉末の少
なくとも１種を懸濁した液体中に浸漬し、連続無
機繊維又は織物の繊維の各々の表面に短繊維、ウ
イスカ又は粉末を付着させる方法が挙げられる。 An example of the suspension dipping method is to unwind continuous inorganic fibers wound around a bobbin or a continuous inorganic fiber bundle made by bundling an appropriate number of continuous inorganic fibers, or to unwind a continuous inorganic fiber woven fabric with short fibers, whiskers or Examples include a method in which short fibers, whiskers, or powder are attached to the surface of each continuous inorganic fiber or fiber of a textile by immersing it in a liquid in which at least one kind of powder is suspended.
繊維数の多い連続無機繊維束又は織物を浸漬す
る場合には、超音波により振動を与えて、短繊
維、ウイスカ又は粉末を各繊維に均一に付着させ
ることが好ましい。超音波の振動数は10〜2000K
Hz程度が便利である。 When dipping a continuous inorganic fiber bundle or fabric with a large number of fibers, it is preferable to apply vibration using ultrasonic waves to uniformly adhere short fibers, whiskers, or powder to each fiber. The frequency of ultrasonic waves is 10-2000K
A value around Hz is convenient.
懸濁液は水でもよいが、有機溶剤、例えばエタ
ノール、メタノール、アセトンが好ましく使用さ
れる。 The suspension may be water, but organic solvents such as ethanol, methanol, acetone are preferably used.
これら連続無機繊維は必要に応じてサイジング
処理することができる。サイジング剤としては、
無機繊維のサイジング剤として公知のものをすべ
て使用することができ、その例としては、ポリエ
チレンオキサイド、ポリスチレンオキサイド、ポ
リメチレン、ポリビニルアルコール、エポキシ樹
脂等が挙げられる。サイジング剤の割合は連続無
機繊維と次に述べる耐熱性物質の短繊維、ウイス
カ又は粉末との合計に対して0.5〜50容量％であ
ることが好ましい。連続無機繊維のサイジング処
理は、耐熱性物質の短繊維、ウイスカ又は粉末を
介在させるに先立つて行つてもよく、耐熱性物質
の短繊維、ウイスカ又は粉末の介在と同時に行つ
てもよい。 These continuous inorganic fibers can be subjected to sizing treatment if necessary. As a sizing agent,
All known sizing agents for inorganic fibers can be used, examples of which include polyethylene oxide, polystyrene oxide, polymethylene, polyvinyl alcohol, and epoxy resin. The proportion of the sizing agent is preferably 0.5 to 50% by volume based on the total of the continuous inorganic fibers and short fibers, whiskers, or powder of the heat-resistant material described below. The sizing treatment of the continuous inorganic fibers may be performed prior to intervening the short fibers, whiskers, or powder of the heat-resistant substance, or may be performed simultaneously with the interposition of the short fibers, whiskers, or powder of the heat-resistant substance.
懸濁液中の短繊維、ウイスカ又は粉末の濃度は
特に制限されないが、過度に小さいと連続無機繊
維に均一に付着せず、過度に多いと付着量が多く
なりすぎるため、0.5〜30ｇ／であることが好
ましい。 The concentration of short fibers, whiskers, or powder in the suspension is not particularly limited, but if it is too small, it will not adhere uniformly to the continuous inorganic fibers, and if it is too large, the amount of adhesion will be too large. It is preferable that there be.
こうして得られた強化用無機繊維から、それ自
体公知の方法に従つて本発明の各種複合体が製造
される。 Various composites of the present invention are produced from the reinforcing inorganic fibers thus obtained according to methods known per se.
金属複合体は、金属複合材料の製法として公知
の方法、例えば、拡散結合法、液体浸透法、溶射
法、電析法、押出し及びホツトロール法、化学気
相析出法又は焼結法に従つて製造することができ
る。 The metal composite is manufactured according to known methods for manufacturing metal composite materials, such as diffusion bonding, liquid infiltration, thermal spraying, electrodeposition, extrusion and hot rolling, chemical vapor deposition, or sintering. can do.
プラスチツク複合体の製法としてはそれ自体公
知の方法、例えば、ハンドレイアツプ法、マツチ
ドメタルダイ法、ブレークアウエイ法、フイラメ
ントワインデイング法、ホツトプレス法、オート
クレーブ法、連続引抜き法等が挙げられる。 Methods for producing plastic composites include methods known per se, such as a hand lay-up method, a mated metal die method, a breakaway method, a filament winding method, a hot press method, an autoclave method, and a continuous drawing method.
また、セラミツク複合体は、セラミツク粉状母
材とあるいはこれと公知のセラミツク結合剤との
混合物に強化用繊維を埋没させる方法、セラミツ
ク粉状母材と強化用繊維あるいは上記混合物とを
交互に配設する方法、又は予め強化用繊維を配置
しておきその間隙にセラミツク粉状母材あるいは
上記混合物を充填する方法等により、セラミツク
粉状母材と強化用繊維との集合体を作成し、この
集合体をラバープレス、金型プレス等により加圧
成形した後に焼結する方法、あるいは上記集合体
をホツトプレスする方法等によつて、製造するこ
とができる。必要に応じて、得られるセラミツク
複合体を減圧下で有機珪素化合物又は有機珪素重
合体の溶融液、あるいは必要により上記物質の有
機溶剤溶液に浸漬して、該溶融液又は溶液を焼結
体の粒界及び気孔に含浸させ、この後焼結体を加
熱することにより、より高密度のセラミツク複合
体を得ることができる。この処理は不活性ガス雰
囲気下に通常800〜2500℃の温度で行われる。上
記処理は２回以上行うこともできる。 Ceramic composites can also be produced by embedding reinforcing fibers in a ceramic powder matrix or a mixture of this and a known ceramic binder, or by alternately arranging the ceramic powder matrix and reinforcing fibers or the above mixture. An aggregate of the ceramic powder base material and the reinforcing fibers is created by placing the reinforcing fibers in advance, or by filling the gaps with the ceramic powder base material or the above-mentioned mixture. It can be manufactured by a method in which the aggregate is pressure-formed using a rubber press, a mold press, etc., and then sintered, or by a method in which the aggregate is hot-pressed. If necessary, the obtained ceramic composite is immersed under reduced pressure in a melt of an organosilicon compound or an organosilicon polymer, or if necessary, an organic solvent solution of the above substance, and the melt or solution is used to form a sintered body. By impregnating the grain boundaries and pores and then heating the sintered body, a ceramic composite with higher density can be obtained. This treatment is usually carried out at a temperature of 800-2500°C under an inert gas atmosphere. The above process can also be performed two or more times.
本発明の各種強化複合体中の強化用繊維の割合
は、複合体に対して10〜70体積％であることが好
ましい。強化用繊維の割合を過度に高くしても、
相対的にマトリツクスの量が少なくなり、強化用
繊維を間隙を充分にマトリツクスで充填すること
ができなくなつて、複合則に従つた強度が発揮さ
れなくなる。また、強化用繊維の割合が過度に低
いと、機械的特性の良好な複合体が得られにくく
なる。 The proportion of reinforcing fibers in the various reinforced composites of the present invention is preferably 10 to 70% by volume based on the composite. Even if the proportion of reinforcing fibers is excessively high,
The amount of matrix becomes relatively small, and the spaces between the reinforcing fibers cannot be sufficiently filled with the matrix, so that the strength according to the law of compositeness cannot be exhibited. Furthermore, if the proportion of reinforcing fibers is too low, it becomes difficult to obtain a composite with good mechanical properties.
（実施例） 以下に実施例を示す。(Example) Examples are shown below.
実施例 １
ジメチルジクロロシランを金属ナトリウムで脱
塩素縮合して合成されるポリジメチルシラン100
重量部に対しポリボロシロキサン３重量部を添加
し、窒素中、350℃で熱縮合して、式−（Si−CH2
−）のカルボシラン単位から主としてなる主鎖骨格
を有し、該カルボシラン単位の珪素原子に水素原
子及びメチル基を有しているポリカルボシランを
得た。このポリマーを溶融紡糸し、空気中190℃
で不融化処理し、さらに引き続いて窒素中1200℃
で焼成して、繊維径13μｍ、引張強度250Kg／mm2、
引張弾性率14t／mm2の主として珪素、炭素及び酸
素からなる無機繊維を得た。この無機繊維はSi、
Ｃ及びＯからなる非晶質物質と、粒径が50Åのβ
−SiC及び非晶質のSiO2からなる集合体との混合
系からなつていた。Example 1 Polydimethylsilane 100 synthesized by dechlorination condensation of dimethyldichlorosilane with metallic sodium
3 parts by weight of polyborosiloxane were added to each part by weight, and heat condensation was carried out at 350°C in nitrogen to form the formula -(Si-CH 2
-) A polycarbosilane having a main chain skeleton mainly composed of carbosilane units and having a hydrogen atom and a methyl group on the silicon atom of the carbosilane unit was obtained. This polymer was melt spun and spun in air at 190°C.
infusible at 1200°C in nitrogen.
The fiber diameter is 13 μm and the tensile strength is 250 Kg/mm 2 .
An inorganic fiber consisting mainly of silicon, carbon and oxygen with a tensile modulus of 14 t/mm 2 was obtained. This inorganic fiber is Si,
An amorphous substance consisting of C and O and β with a particle size of 50 Å
- It consisted of a mixed system with an aggregate consisting of SiC and amorphous SiO 2 .
上記無機繊維を900℃の空気中で１時間加熱処
理することにより、鮮やかな青色の反射光を発す
る連続無機繊維［Ｉ］を得た。この連続無機繊維
［Ｉ］は、繊維径13.0μｍ、引張強度245Kg／mm2、
引張弾性率14t／mm2の機械的特性を有しており、
繊維表面に0.2μｍの非晶質のガラス層を有してい
た。 The above inorganic fibers were heat-treated in air at 900° C. for 1 hour to obtain continuous inorganic fibers [I] that emit bright blue reflected light. This continuous inorganic fiber [I] has a fiber diameter of 13.0 μm, a tensile strength of 245 Kg/mm 2 ,
It has mechanical properties with a tensile modulus of 14t/ mm2 ,
It had an amorphous glass layer of 0.2 μm on the fiber surface.
炭化珪素ウイスカ（平均直径0.2μｍ、平均長さ
100μｍ）５ｇをエタノール１の入つた処理槽
に投入した後、超音波振動を与えて懸濁させ、懸
濁液を調製した。 Silicon carbide whiskers (average diameter 0.2 μm, average length
100 μm) was put into a treatment tank containing ethanol 1, and then suspended by applying ultrasonic vibration to prepare a suspension.
無機繊維［Ｉ］の繊維束（800本糸）をボビン
から巻戻し、浸漬時間が約15秒となるように可動
ロールによつて調節し、上記懸濁液中に浸漬し、
ついで加圧ロールにより押圧した後、ボビンに巻
取り、室温、大気中で乾燥した。得られた強化用
無機繊維［Ａ］は、無機繊維［Ｉ］の繊維間及び
繊維束間にウイスカが介在しており、ウイスカの
付着量は無機繊維束10ｍ当たり0.03ｇであつた。 A fiber bundle (800 threads) of inorganic fiber [I] is unwound from the bobbin, the immersion time is adjusted to about 15 seconds using a movable roll, and immersed in the suspension,
The material was then pressed with a pressure roll, wound up onto a bobbin, and dried at room temperature in the atmosphere. The obtained reinforcing inorganic fiber [A] had whiskers interposed between the fibers and fiber bundles of the inorganic fiber [I], and the amount of whiskers attached was 0.03 g per 10 m of the inorganic fiber bundle.
実施例 ２
無機繊維を空気中で1100℃で30分間加熱処理し
た以外は実施例１におけると同様にして、緑色の
反射光を発する連続無機繊維［］を得た。こ無
機繊維［］は、繊維径13.0μｍ、引張強度240
Kg／mm2、引張弾性率13.6t／mm2の機械的特性を有
しており、繊維表面に0.3μmmの非晶質のガラス層
を有していた。Example 2 Continuous inorganic fibers [ ] that emit green reflected light were obtained in the same manner as in Example 1 except that the inorganic fibers were heat-treated in air at 1100° C. for 30 minutes. This inorganic fiber [ ] has a fiber diameter of 13.0 μm and a tensile strength of 240
It had mechanical properties of Kg/mm 2 and tensile modulus of 13.6 t/mm 2 , and had an amorphous glass layer of 0.3 μmm on the fiber surface.
連続無機繊維［］を実施例１におけると同様
にして炭化珪素ウイスカの懸濁液で処理して、無
機繊維［］の繊維束間及び繊維間にウイスカが
介在した強化用繊維［Ｂ］を得た。ウイスカの付
着量は無機繊維束10ｍ当たり0.03ｇであつた。 Continuous inorganic fibers [] were treated with a suspension of silicon carbide whiskers in the same manner as in Example 1 to obtain reinforcing fibers [B] in which whiskers were interposed between fiber bundles and between fibers of inorganic fibers []. Ta. The amount of whiskers attached was 0.03 g per 10 m of the inorganic fiber bundle.
実施例 ３
炭化珪素ウイスカに代えて炭化珪素粒子（平均
直径0.28μｍ）50ｇを使用した懸濁液を用いて連
続無機繊維［］を処理した以外は実施例１と同
様の方法を繰り返して、無機繊維［Ｉ］の繊維束
間及び繊維間に炭化珪素粒子が介在した強化用繊
維［Ｃ］を得た。炭化珪素の付着量は無機繊維束
10ｍ当たり0.03ｇであつた。Example 3 The same method as in Example 1 was repeated except that continuous inorganic fibers [] were treated with a suspension containing 50 g of silicon carbide particles (average diameter 0.28 μm) instead of silicon carbide whiskers. A reinforcing fiber [C] in which silicon carbide particles were interposed between the fiber bundles and between the fibers of the fiber [I] was obtained. The amount of silicon carbide adhered to is the inorganic fiber bundle.
It was 0.03g per 10m.
実施例 ４
強化用繊維［Ａ］の繊維束（800本糸）を長さ
150mmに切断して50本束ね、鋼製パイプ中に挿入
した。上記パイプを窒素ガス雰囲気中で760℃に
予熱し、ついで鋳造型に配置して、760℃に加熱
した純アルミニウムの溶湯を注入し、パンチを用
いて500Kg／cm2で60秒加圧して、繊維強化複合体
を得た。Example 4 Fiber bundle (800 threads) of reinforcing fiber [A]
They were cut into 150mm pieces, bundled into 50 pieces, and inserted into a steel pipe. The above pipe was preheated to 760°C in a nitrogen gas atmosphere, then placed in a casting mold, molten pure aluminum heated to 760°C was injected, and pressurized at 500 kg/cm 2 for 60 seconds using a punch. A fiber reinforced composite was obtained.
得られた複合体の連続繊維の繊維軸線に対して
直角方向の断面を走査型電子顕微鏡で観察したと
ころ、炭化珪素ウイスカが連続繊維間隙に多数介
在し、またマトリツクスである母材金属中に均一
に分散して、無機繊維は複合体中で互いに接する
ことなく分散していることが認められた。 When a cross section of the continuous fibers of the obtained composite in a direction perpendicular to the fiber axis was observed using a scanning electron microscope, it was found that many silicon carbide whiskers were interposed between the continuous fibers, and that silicon carbide whiskers were uniform in the matrix of the base metal. It was observed that the inorganic fibers were dispersed in the composite without touching each other.
さらに、上記複合体の表面は、強化用繊維から
発せられる鮮やかな青色の反射光とマトリツクス
である金属の自然な光沢とが融和して、美麗な色
調を示した。 Furthermore, the surface of the composite exhibited a beautiful color tone due to the combination of the bright blue reflected light emitted from the reinforcing fibers and the natural luster of the metal matrix.
実施例 ５
強化用繊維［Ｂ］を一軸方向に引き揃え、これ
に市販のビスフエノールＡ型エポキシ樹脂を含浸
させ、予備硬化させて、厚さ0.15mmのプリプレグ
を得た。これを積層した後、170℃、７Kg／cm2で
４時間ホツトプレスして、厚さ２mmの複合体を得
た。Example 5 Reinforcing fibers [B] were aligned in a uniaxial direction, impregnated with a commercially available bisphenol A type epoxy resin, and precured to obtain a prepreg with a thickness of 0.15 mm. After laminating these layers, they were hot pressed at 170° C. and 7 kg/cm 2 for 4 hours to obtain a composite with a thickness of 2 mm.
この複合体の断面を走査型電子顕微鏡で観察し
たところ、炭化珪素ウイスカが無機繊維界面に一
部付着し、またマトリツクスである樹脂中に均一
に分散して、無機繊維は複合体中で互に接するこ
となく分散していることが認められた。この複合
体の繊維含有量は55容量％であつた。複合体の引
張強度は145Kg／mm2、層間剪断強度は8.5Kg／mm2で
あつた。 When a cross section of this composite was observed using a scanning electron microscope, it was found that silicon carbide whiskers were partially attached to the interface of the inorganic fibers, and were also uniformly dispersed in the resin matrix, indicating that the inorganic fibers were interwoven with each other in the composite. It was observed that they were dispersed without touching each other. The fiber content of this composite was 55% by volume. The composite had a tensile strength of 145 Kg/mm 2 and an interlaminar shear strength of 8.5 Kg/mm 2 .
複合体の表面は強化用繊維自体の表面反射光を
反映して、美麗な緑色の色調を示した。 The surface of the composite exhibited a beautiful green tone reflecting the light reflected from the surface of the reinforcing fiber itself.
実施例 ６
平均粒径44μｍのコーニングガラス製のホウ珪
酸ガラス（7740）粉末に45容量％の強化用繊維
［Ｃ］を10mmの長さに切断したチヨツプドフアイ
バーを添加し、イソプロパノール中でよく分散さ
せ混合したスラリーと、強化用繊維［Ｃ］を一方
向に均一に配列させたものとを、交互に積層させ
て、乾燥した後、ホツトプレス装置により1300
℃、750Kg／cm2で約10分間アルゴン雰囲気下に処
理して、無機繊維強化複合体を得た。Example 6 A chopped fiber obtained by cutting 45% by volume reinforcing fiber [C] into a length of 10 mm was added to borosilicate glass (7740) powder manufactured by Corning Glass with an average particle size of 44 μm, and the mixture was stirred in isopropanol. The well-dispersed and mixed slurry and the reinforcing fibers [C] uniformly arranged in one direction were alternately layered, dried, and then heated using a hot press machine for 1300 m
The inorganic fiber-reinforced composite was obtained by treatment at 750 Kg/cm 2 at 750 Kg/cm 2 for about 10 minutes under an argon atmosphere.
この複合体の断面を走査型電子顕微鏡で観察し
たところ、マトリツクスのホウ珪酸ガラス中に強
化用繊維が互い接することなく分散していること
が認められた。複合体の室温抗折強度は14.1Kg／
mm2であつた。 When the cross section of this composite was observed with a scanning electron microscope, it was found that the reinforcing fibers were dispersed in the borosilicate glass matrix without coming into contact with each other. The room temperature bending strength of the composite is 14.1Kg/
It was warm in mm2 .
複合体の表面は繊維自体の反射光を反映して、
美麗な青色を示した。 The surface of the composite reflects the light reflected from the fiber itself,
It showed a beautiful blue color.
Claims (1)
する耐熱性物質の短繊維、ウイスカ又は粉末とか
らなる強化用繊維であつて、該連続無機繊維が () Si、Ｃ及びＯからなる非晶質物質、又は () 粒径が500Å以下のβ−SiCからなる結晶質
超微粒子と非晶質のSiO2とからなる集合体、
又は () 上記（）の非晶質物質と上記（）の結
晶質超微粒子の混合系、 からなる珪素、炭素及び酸素を含有する無機質
物質からなる内部層と、 () Si及びＯからなる非晶質物質、 () 結晶質のSiO2からなる集合体、又は () 上記（）の非晶質物質と上記（）の結
晶質重合体の混合系 からなる珪素及び酸素を含有する無機質物質から
なる表面層とからなることを特徴とする強化用無
機繊維。 ２ 連続無機繊維に対する耐熱性物質の短繊維、
ウイスカ又は粉末の体積率が0.5〜500％であるこ
とを特徴とする特許請求の範囲第１項に記載の強
化用無機繊維。 ３ 連続無機繊維と該連続無機繊維との間に介在
する耐熱性物質の短繊維、ウイスカ又は粉末とか
らなる強化用繊維でマトリツクスが強化されてい
る複合体であつて、該連続無機繊維が () Si、Ｃ及びＯからなる非晶質物質、又は () 粒径が500Å以下のβ−SiCからなる結晶質
超微粒子と非晶質のSiO2とからなる集合体、
又は () 上記（）の非晶質物質と上記（）の結
晶質超微粒子の混合系、 からなる珪素、炭素及び酸素を含有する無機質
物質からなる内部層と、 () Si及びＯからなる非晶質物質、 () 結晶質のSiO2からなる集合体、又は () 上記（）の非晶質物質と上記（）の結
晶質重合体の混合系 からなる珪素及び酸素を含有する無機質物質から
なる表面層とからなることを特徴とする繊維強化
複合体。 ４ マトリツクスが金属であることを特徴とする
特許請求の範囲第３項に記載の繊維強化複合体。 ５ マトリツクスがプラスチツクであることを特
徴とする特許請求の範囲第３項に記載の繊維強化
複合体。 ６ マトリツクスがセラミツクであることを特徴
とする特許請求の範囲第３項に記載の繊維強化複
合体。[Scope of Claims] 1. A reinforcing fiber consisting of continuous inorganic fibers and short fibers, whiskers, or powder of a heat-resistant substance interposed between the continuous inorganic fibers, wherein the continuous inorganic fibers include () Si, An amorphous substance consisting of C and O, or () an aggregate consisting of crystalline ultrafine particles consisting of β-SiC with a particle size of 500 Å or less and amorphous SiO 2 ,
or () an inner layer made of an inorganic material containing silicon, carbon, and oxygen, consisting of a mixed system of the amorphous material of the above () and the crystalline ultrafine particles of the above (); A crystalline substance, () an aggregate consisting of crystalline SiO 2 , or () an inorganic substance containing silicon and oxygen consisting of a mixed system of the above () amorphous substance and the above () crystalline polymer A reinforcing inorganic fiber characterized by comprising a surface layer. 2 Short fibers of heat-resistant substances for continuous inorganic fibers,
The reinforcing inorganic fiber according to claim 1, wherein the volume percentage of whiskers or powder is 0.5 to 500%. 3 A composite whose matrix is reinforced with reinforcing fibers consisting of continuous inorganic fibers and short fibers, whiskers or powder of a heat-resistant substance interposed between the continuous inorganic fibers, wherein the continuous inorganic fibers are ( ) an amorphous substance consisting of Si, C and O, or () an aggregate consisting of crystalline ultrafine particles consisting of β-SiC with a particle size of 500 Å or less and amorphous SiO2 ,
or () an inner layer made of an inorganic material containing silicon, carbon, and oxygen, consisting of a mixed system of the amorphous material of the above () and the crystalline ultrafine particles of the above (); A crystalline substance, () an aggregate consisting of crystalline SiO 2 , or () an inorganic substance containing silicon and oxygen consisting of a mixed system of the above () amorphous substance and the above () crystalline polymer A fiber-reinforced composite comprising a surface layer. 4. The fiber reinforced composite according to claim 3, wherein the matrix is metal. 5. The fiber reinforced composite according to claim 3, wherein the matrix is plastic. 6. The fiber reinforced composite according to claim 3, wherein the matrix is ceramic.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26365386A JPS63120169A (en) | 1986-11-07 | 1986-11-07 | Reinforcing inorganic fiber and reinforced composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26365386A JPS63120169A (en) | 1986-11-07 | 1986-11-07 | Reinforcing inorganic fiber and reinforced composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63120169A JPS63120169A (en) | 1988-05-24 |
| JPH0411664B2 true JPH0411664B2 (en) | 1992-03-02 |
Family
ID=17392459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26365386A Granted JPS63120169A (en) | 1986-11-07 | 1986-11-07 | Reinforcing inorganic fiber and reinforced composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63120169A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63277730A (en) * | 1987-03-11 | 1988-11-15 | Toyota Central Res & Dev Lab Inc | Fiber body for composite material and its production |
| JPS63250430A (en) * | 1987-04-06 | 1988-10-18 | Toyota Central Res & Dev Lab Inc | Inorganic fiber reinforced composite metallic body |
| JPS63216936A (en) * | 1987-03-04 | 1988-09-09 | Toshiba Corp | Manufacture of metal-base composite material |
-
1986
- 1986-11-07 JP JP26365386A patent/JPS63120169A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63120169A (en) | 1988-05-24 |
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