JPH0122335B2 - - Google Patents
Info
- Publication number
- JPH0122335B2 JPH0122335B2 JP5262281A JP5262281A JPH0122335B2 JP H0122335 B2 JPH0122335 B2 JP H0122335B2 JP 5262281 A JP5262281 A JP 5262281A JP 5262281 A JP5262281 A JP 5262281A JP H0122335 B2 JPH0122335 B2 JP H0122335B2
- Authority
- JP
- Japan
- Prior art keywords
- fiber
- fibers
- metal
- matrix
- strength
- 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
- 239000000835 fiber Substances 0.000 claims description 69
- 229910052751 metal Inorganic materials 0.000 claims description 53
- 239000002184 metal Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 31
- 239000011159 matrix material Substances 0.000 claims description 29
- 239000012784 inorganic fiber Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002905 metal composite material Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 150000002484 inorganic compounds Chemical class 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-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
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 description 18
- 239000002131 composite material Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- -1 copper metals Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical class Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229940065285 cadmium compound Drugs 0.000 description 1
- 150000001662 cadmium compounds Chemical class 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910001902 chlorine oxide Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002356 single layer Substances 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
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
本発明は無機質繊維を強化材とし、金属または
合金（以下金属類と略称する）をマトリツクスと
する機械強度のすぐれた繊維強化金属複合材料
（以下複合材料と略称する）に関する。
近年、無機質繊維にアルミナ繊維、炭素繊維、
シリカ繊維、シリコンカ―バイド繊維、ボロン繊
維などを用い、マトリツクスにアルミニウム、マ
グネシウム、銅、ニツケル、チタンなどを用いた
複合材料が開発され、多くの産業分野に使用され
始めている。
無機質繊維と金属類を複合化する際溶融または
高温の金属類と無機質繊維界面で反応が生じ、脆
化層が生ずる。このため複合材料の強度は低下
し、理論強度と比較して低い強度を与える場合が
多い。例えば市販の炭素繊維などは大略300Kg／
mm2程度の強度を有しており、繊維含有率を50体積
％としてマトリツクス材料の強度を無視しても炭
素繊維強化複合材料の理論強度は複合則から150
Kg／mm2程度と推定される。事実エポキシ樹脂をマ
トリツクスとした炭素繊維強化複合材料は150
Kg／mm2乃至それ以上の強度を示すが、アルミニウ
ムをマトリツクスとし、溶融金属含浸法を用いて
作られた炭素繊維強化金属複合材料では、たかだ
か30〜40Kg／mm2程度の強度しか与えない。これは
前述した様に繊維が溶融金属と接触することで界
面反応が起こり繊維劣化が起こるためである。か
かる繊維劣化を防止するために種々の方法、例え
ば繊維の表面をコーテイング剤等で処理する方法
などがとられているが、一般に取扱い上の面倒
さ、コスト高などの点から実用化されていない現
状である。例えばシリコンカーバイド繊維の表面
を金属またはセラミツクスのように繊維に対し安
定な物質で被覆した後マトリツクス金属と複合化
するような繊維保護法が考えられている（公開特
許公報昭53−30407号）。しかしこの発明は繊維表
面に均一に金属またはセラミツクを被覆する技術
が難かしく、また多数本の繊維に均一に塗布する
ことも非常に困難であり実用的とは考えられな
い。
一方、特開昭51−70116号公報にはアルミニウ
ムマトリツクス中にリチウムを数％添加する事に
より繊維強化金属複合材料の機械強度が向上する
事を述べている。しかしこの方法は無機繊維がマ
トリツクス金属類と全く濡れないか、反応しない
場合には有効であるが、無機繊維がマトリツクス
金属類と反応して劣化する時には無効である以上
に逆に強度低下をもたらす傾向にある。
以上に示すごとく容易かつ安価な方法で繊維強
化金属複合材料の機械強度を向上させるに到つて
いないのが現状である。
本発明者らはこれらの現状から繊維強化金属複
合材料の強度を向上させるためには無機繊維とマ
トリツクス金属類の界面での反応による無機繊維
の劣化を防止すればよいのであり、それを安易且
つ安価に実施し得る方法を鋭意検討した。その結
果これらの無機繊維より選ばれる少くとも１種の
繊維の表面をカルシウム、カドミウム、スズおよ
びアンチモンの無機化合物または有機化合物から
なる群から選ばれる少くとも１種にて被覆した後
マトリツクスとなる金属類と複合化する事により
無機繊維とマトリツクス金属類との反応による無
機繊維の劣化を防止する事ができ、この金属類を
マトリツクスとした複合材料の機械強度が飛躍的
に向上することを見い出し本発明に到つた。
本発明によれば金属単体では取扱いが難しいも
のでも安定な化合物の形で取扱が出来る事、繊維
表面にごく簡単な方法で被覆でき、かつ高い強度
を有する繊維強化金属複合材料が得られるなどそ
の効果は大きい。
以下に本発明を詳細に説明する。
本発明に用いられる無機質繊維は、炭素繊維、
シリカ繊維、シリコンカーバイド繊維、ボロン繊
維及びアルミナ質繊維である。
本発明複合材料中に含まれる無機質繊維の割合
は特に限定されるものではないが、好ましくは15
〜70容積％の範囲である。15容積％以下では強化
効果が小さく、70容積％以上では、繊維同志の接
触により、かえつて強度が低下する。繊維形状は
長繊維、短繊維いずれをも使用する事ができ、目
的、用途に応じていずれか、または両者を同時に
使用できる。目的とする機械強度または弾性率を
得るために一方向クロスプライ、ランダム配向な
どの配向方法を選択する事が出来る。
これらの無機質強化繊維のうち本発明の金属強
化効果を最も顕著に示しうる繊維は、特公昭51−
13768号に記載されているアルミナ質繊維である。
即ち、一般式
（式中、Ｙは有機残基、ハロゲン、水酸基の１種
または２種以上を示す。）
で表わされる構造単位を有するポリアルミノキサ
ンを原料とし、これに得られるシリカアルミナ繊
維中のシリカ含有量が28％以下であるような量の
ケイ素を含む化合物を１種または２種以上混合
し、該混合物を紡糸して得られる前駆体繊維を焼
成してなるアルミナ質繊維であり、好ましくはシ
リカ含有量が２重量％以上25重量％以下の組成の
ものであり、Ｘ線的構造においてα―Al2O3の反
射を実質的に示さないアルミナ質繊維である。
このアルミナ質繊維は、本発明の効果をそこな
わない範囲でリチウム、ベリリウム、ホウ素、ナ
トリウム、マグネシウム、ケイ素、リン、カリウ
ム、カルシウム、チタン、クロム、マンガン、イ
ツトリウム、ジルコニウム、ランタン、タングス
テン、バウムなどの１種または２種以上の酸化物
などのような耐火性化合物を含有することができ
る。
本発明に用いられるマトリツクス金属類として
好適なものはアルミニウム、マグネシウムおよび
銅金属またはそれらの合金などである。軽量かつ
高強度が要求される場合には、アルミニウムやマ
グネシウム金属またはそれらの合金をマトリツク
スとする系が好適であり、耐熱性かつ高強度を要
求される場合には銅などの金属類をマトリツクス
とする系が好適である。本発明でいうこれらの金
属類は通常の使用にさしつかえない範囲で少量の
不純物元素を含有していてもさしつかえない。
前記無機繊維をカルシウム、カドミウム、スズ
およびアンチモンの無機化合物または有機化合物
からなる群から選ばれる少なくとも１種にて被覆
する事により、この繊維を強化材として用いた繊
維強化金属複合材料の機械強度が向上する機構は
明らかではないが、下記の理由によるものと考え
られる。
ここにあげられている金属元素は金属類に添加
されるとその金属類の表面におけるこれら添加元
素の濃度は平均濃度より高くなる。例えば金属が
アルミニウムの場合、これら金属元素の含まれる
系の表面張力がアルミニウムの表面張力より低く
なる事により知れる。これはGibbsの吸着等温式
によつて示されるように表面部分のこれら添加元
素の濃度がマトリツクス中における平均濃度より
高くなつているためである。微量の前記金属元素
が微量に存在すると、繊維と金属の界面により高
濃度に該金属元素が存在する事になる。該金属元
素類の無機化合物または有機化合物の１種以上で
被覆された繊維と金属類を複合化する時溶融金属
と該化合物とが接触し、一部は分解し、金属元素
単体となり、これが上記機構に従つて繊維表面近
くに高濃度に分布すると考えられる。したがつて
本発明による被覆は繊維表面を均一に被覆する事
なくしても効果を発現できることになり、被覆方
法が大きく簡略化される。
次にこれら金属元素で表面を被覆された無機繊
維と金属類の複合材料の破断面を走査型電子顕微
鏡で観察するとアンチモンの化合物の１種以上で
被覆された繊維の周囲は被覆化合物のない系と比
較して繊維／マトリツクス界面の結合が弱くなつ
ている。繊維の外周面に見られたマトリツクス金
属との反応相が消失するなどの現象が見られ、繊
維―マトリツクス界面での反応が低下しているこ
とが観察される。即ち本発明のこれら金属元素は
界面での反応を制御する働きを有し、従つて複合
材料の強度が飛躍的に向上するものと考えられ
る。
一方カルシウおよびカドミウムの化合物の少く
とも１種で被覆された無機繊維で強化した繊維強
化金属複合材料は被覆化合物のない系と比較して
繊維／マトリツクス界面の結合は弱くなつていな
いにも拘らず繊維の外周面に見られたマトリツク
ス金属との反応相は消失しているなどの現象が見
られる。この複合材料から塩酸水溶液を用いてマ
トリツクス金属を溶解除去して取り出した繊維の
強度を測定したところ複合化前の繊維強度と比較
して該化合物のない系では約半分の強度まで低下
しているのに対し、これらの被覆化合物の存在す
る系では強度の低下は殆んど認められなかつた。
以上の事からこれら化合物中の金属元素は繊維
と単層で反応し、安定な層を形成することによつ
て繊維とマトリツクス金属類との反応を抑制する
働きを有し、従つて複合材料の強度が飛躍的に向
上するものと考えられる。
これらの金属元素の無機化合物または有機化合
物としては種々のものが取り得るが、一例を挙げ
れば、下記のようなものが有効である。
ハロゲン化物、水素化物、酸化物、水酸化物、
硫酸化物、硝酸化物、炭酸化物、塩素酸化物、炭
化物、窒化物、燐酸化物、燐化物、硫化物、アル
キル化物、有機酸化物、アルコラートなどであ
る。
前記無機繊維に前記金属元素無機化合物または
有機化合物の被覆を形成する方法として種々の方
法を取り得る。すなわちその主なものとして(1)電
気メツキ、(2)無電解メツキ、(3)真空蒸着、(4)スパ
ツタリング蒸着、(5)化学蒸着、(6)プラズマスプレ
ー法、(7)溶液浸漬法、(8)デイスパージヨン浸漬法
などが例示される。
これらの方法のうち本発明に特に好適な方法は
(7)溶液浸漬法、(8)デイスパージヨン浸漬法であ
る。適当な溶媒に該金属元素の化合物を溶解又は
懸濁し、その中に無機繊維を浸漬し乾燥した後、
マトリツクスとなる金属類と複合化させる事によ
り高強度な繊維強化金属複合材料が得られる訳で
あり、この方法は他の被覆方法と比較して非常に
簡単且つ安価に実施出来る方法である。
被膜の厚みは好ましくは20Å以上必要である。
被膜の厚みが20Åより薄い場合は効果が顕著に認
められない。
本発明複合材料は、種々の方法によつて製造し
得る。
すなわちその主なものとして、(1)液体金属含浸
法のような液相法、(2)拡散接合のよな固相法、(3)
粉末冶金（焼結、溶結）法、(4)溶射、電析、蒸着
などの沈積法、(5)押出、圧延などの塑性加工法、
(6)高圧凝固鋳造法などが例示される。本発明の効
果が特に顕著に認められる方法は(1)の液体金属含
浸法や(6)の高圧凝固鋳造法などのように溶融金属
と繊維が直接接触する場合であるが、(2)〜(5)に示
される製造方法においても明らかに効果が認めら
れる。
この様にして製造された複合材料は本発明に用
いられる添加金属元素の存在しない場合と比較し
て大幅な機械強度の向上が認められる。また加工
法上も既存の設備、方法を何ら変更することなく
本発明を実行できることは実生産上からも非常に
大きなメリツトである。以下本発明を実施例によ
りさらに詳しく説明するが本発明はこれによつて
限定されるものではない。
実施例 １
無機繊維として、平均繊維径7.5μm、引張強
度300Kg／mm2、引張り弾性率23000Kg／mm2の炭素繊
維、平均繊維径14μm、引張り強度150Kg／mm2、
引張り弾性率23500Kg／mm2のアルミナ質繊維
（Al2O3含有率85重量％、SiO2含有率15重量％）
及び平均繊維径9μm、引張強度600Kg／mm2、引
張り弾性率7400Kg／mm2のシリカ繊維、平均繊維
径15μm、引張り強度220Kg／mm2、引張り弾性率
20000Kg／mm2の遊離炭素を含有するシリコンカー
バイド繊維の４種類を用意した。塩化カルシウ
ム、硫酸カドミウムの２重量％の水溶液および三
塩化アンチモンの２重量％エタノール溶液に第１
表で示される無機繊維／金属化合物の組合わせの
無機繊維を浸漬し、水溶液系については130℃の
熱風乾燥器で３時間乾燥、三塩化アンチモンは
100℃で３時間真空乾燥を行なつた。ついでこれ
らの無機繊維をアルゴン雰囲気下110mmの長さに
切りそろえ束ねてそれぞれ内径４mmの鋳型管に平
行に引き入れた。次いでアルゴンガス雰囲気中で
700℃に保つたアルミニウム（純度99.99％）の溶
融体の中に鋳型管の一端を浸し、他方を真空脱気
しつつ、溶湯表面に50Kg／cm2の圧力をかけて繊維
間へアルミニウムを浸透させ、これを冷却するこ
とによつて繊維強化金属複合材料を得た。繊維体
積含有率は50±１％になるように調整した。また
比較のため金属元素の化合物に浸漬しない無機繊
維を用い、アルミニウムをマトリツクスとして、
全く同じ方法で繊維強化金属複合材料を得た。こ
のようにして作製した繊維強化金属複合材料の常
温での曲げ強度、曲げの弾性率を測定した。結果
を第１表に示すが炭素繊維、アルミナ繊維、シリ
カ繊維、シリコンカーバイド繊維を強化材とした
いずれの場合でも比較例と較べて著しく強度が向
上していた。
The present invention relates to a fiber-reinforced metal composite material (hereinafter referred to as a composite material) having excellent mechanical strength, which uses inorganic fibers as a reinforcing material and a metal or alloy (hereinafter referred to as a metal alloy) as a matrix. In recent years, inorganic fibers such as alumina fiber, carbon fiber,
Composite materials have been developed that use silica fibers, silicon carbide fibers, boron fibers, etc., and matrices of aluminum, magnesium, copper, nickel, titanium, etc., and are beginning to be used in many industrial fields. When inorganic fibers and metals are composited, a reaction occurs at the interface between the molten or high-temperature metals and the inorganic fibers, resulting in the formation of a brittle layer. For this reason, the strength of the composite material decreases, often giving a strength lower than the theoretical strength. For example, commercially available carbon fiber weighs approximately 300 kg/
mm 2 , and even if the fiber content is 50% by volume and the strength of the matrix material is ignored, the theoretical strength of carbon fiber reinforced composite material is 150% from the composite law.
It is estimated to be around Kg/ mm2 . In fact, carbon fiber-reinforced composite materials with epoxy resin matrix are 150
It exhibits a strength of Kg/mm 2 or more, but carbon fiber-reinforced metal composite materials made using aluminum as a matrix and using a molten metal impregnation method only provide a strength of about 30 to 40 Kg/mm 2 at most. This is because, as mentioned above, when the fibers come into contact with the molten metal, an interfacial reaction occurs and the fibers deteriorate. Various methods have been used to prevent such fiber deterioration, such as treating the surface of the fiber with a coating agent, but these methods are generally not put to practical use due to the troublesome handling and high cost. This is the current situation. For example, a fiber protection method has been considered in which the surface of silicon carbide fibers is coated with a material that is stable to the fibers, such as metal or ceramics, and then composited with a matrix metal (Japanese Unexamined Patent Publication No. 53-30407). However, this invention is not considered practical as it is difficult to uniformly coat the fiber surface with metal or ceramic, and it is also very difficult to uniformly coat a large number of fibers. On the other hand, JP-A-51-70116 states that the mechanical strength of fiber-reinforced metal composite materials is improved by adding several percent of lithium to the aluminum matrix. However, although this method is effective when the inorganic fibers do not wet or react with the matrix metals, it is ineffective when the inorganic fibers react with the matrix metals and deteriorate, resulting in a decrease in strength. There is a tendency. As shown above, at present, it has not been possible to improve the mechanical strength of fiber-reinforced metal composite materials by an easy and inexpensive method. The present inventors believe that in order to improve the strength of fiber-reinforced metal composite materials, it is only necessary to prevent the deterioration of inorganic fibers due to the reaction at the interface between inorganic fibers and matrix metals. We worked hard to find a method that could be implemented at low cost. As a result, the surface of at least one type of fiber selected from these inorganic fibers is coated with at least one type selected from the group consisting of inorganic compounds or organic compounds of calcium, cadmium, tin, and antimony, and then the metal that becomes the matrix is coated. It was discovered that by combining inorganic fibers with matrix metals, it is possible to prevent the deterioration of inorganic fibers due to the reaction between the inorganic fibers and matrix metals, and the mechanical strength of composite materials using these metals as a matrix can be dramatically improved. I came up with an invention. According to the present invention, metals that are difficult to handle as single metals can be handled in the form of stable compounds, fiber surfaces can be coated with a very simple method, and fiber-reinforced metal composite materials with high strength can be obtained. The effect is great. The present invention will be explained in detail below. The inorganic fibers used in the present invention include carbon fibers,
They are silica fiber, silicon carbide fiber, boron fiber and alumina fiber. The proportion of inorganic fibers contained in the composite material of the present invention is not particularly limited, but is preferably 15
~70% by volume. If it is less than 15% by volume, the reinforcing effect is small, and if it is more than 70% by volume, the strength will actually decrease due to contact between the fibers. As for the fiber shape, either long fibers or short fibers can be used, and either one or both can be used at the same time depending on the purpose and use. Orientation methods such as unidirectional cross ply and random orientation can be selected to obtain the desired mechanical strength or elastic modulus. Among these inorganic reinforcing fibers, the fiber that can most significantly exhibit the metal reinforcing effect of the present invention is
This is an alumina fiber described in No. 13768. That is, the general formula (In the formula, Y represents one or more of organic residues, halogens, and hydroxyl groups.) A polyaluminoxane having a structural unit represented by is used as a raw material, and the silica content in the silica alumina fiber obtained from this is It is an alumina fiber obtained by mixing one or more compounds containing silicon in an amount of 28% or less, and firing a precursor fiber obtained by spinning the mixture, preferably with a silica content of 28% or less. The fiber has a composition of 2% by weight or more and 25% by weight or less, and is an alumina fiber that substantially shows no reflection of α-Al 2 O 3 in its X-ray structure. The alumina fibers may include lithium, beryllium, boron, sodium, magnesium, silicon, phosphorus, potassium, calcium, titanium, chromium, manganese, yttrium, zirconium, lanthanum, tungsten, Baum, etc. within a range that does not impair the effects of the present invention. It may contain refractory compounds such as one or more oxides of. Preferred matrix metals for use in the present invention include aluminum, magnesium, and copper metals or alloys thereof. When light weight and high strength are required, a matrix made of aluminum, magnesium metals, or their alloys is suitable; when heat resistance and high strength are required, a matrix made of metals such as copper is suitable. A system that does this is preferred. These metals referred to in the present invention may contain small amounts of impurity elements as long as they do not interfere with normal use. By coating the inorganic fibers with at least one selected from the group consisting of inorganic or organic compounds of calcium, cadmium, tin, and antimony, the mechanical strength of the fiber-reinforced metal composite material using the fibers as a reinforcing material can be increased. Although the mechanism of improvement is not clear, it is thought to be due to the following reasons. When the metal elements listed here are added to metals, the concentration of these added elements on the surface of the metal becomes higher than the average concentration. For example, when the metal is aluminum, this is known because the surface tension of a system containing these metal elements is lower than the surface tension of aluminum. This is because the concentration of these added elements on the surface is higher than the average concentration in the matrix, as shown by the Gibbs adsorption isotherm. If a trace amount of the metal element is present, the metal element will be present at a high concentration at the interface between the fiber and the metal. When the fiber coated with one or more inorganic compounds or organic compounds of the metal elements is composited with the metals, the molten metal and the compound come into contact, and a part of the compound decomposes to become a single metal element, which is the above-mentioned compound. According to this mechanism, it is thought that it is distributed in high concentration near the fiber surface. Therefore, the coating according to the present invention can be effective without uniformly coating the fiber surface, and the coating method is greatly simplified. Next, when the fractured surface of a composite material of inorganic fibers and metals whose surface is coated with these metal elements is observed using a scanning electron microscope, the fibers coated with one or more antimony compounds are found to have no coating compound. The bond at the fiber/matrix interface is weaker than that of the fiber/matrix interface. Phenomena such as the disappearance of the reactive phase with the matrix metal observed on the outer peripheral surface of the fibers are observed, and it is observed that the reaction at the fiber-matrix interface is reduced. That is, it is considered that these metal elements of the present invention have a function of controlling the reaction at the interface, and therefore the strength of the composite material is dramatically improved. On the other hand, fiber-reinforced metal composites reinforced with inorganic fibers coated with at least one of calcium and cadmium compounds show that the bond at the fiber/matrix interface is not weakened compared to systems without coating compounds. Phenomena such as the reaction phase with the matrix metal that was observed on the outer peripheral surface of the fiber disappears. When we measured the strength of the fibers extracted from this composite material by dissolving and removing the matrix metal using an aqueous hydrochloric acid solution, we found that the strength of the fibers was reduced to about half that of the fibers before composite formation in a system without this compound. On the other hand, in the systems in which these coating compounds were present, almost no decrease in strength was observed. From the above, the metal elements in these compounds react with the fibers in a single layer, forming a stable layer that suppresses the reaction between the fibers and the matrix metals, and therefore is effective in forming composite materials. It is thought that the strength will be dramatically improved. Although various inorganic or organic compounds of these metal elements can be used, the following are effective as an example. halides, hydrides, oxides, hydroxides,
These include sulfides, nitrides, carbonates, chlorine oxides, carbides, nitrides, phosphorus oxides, phosphides, sulfides, alkylates, organic oxides, and alcoholates. Various methods can be used to form a coating of the metal element, inorganic compound, or organic compound on the inorganic fiber. The main methods are (1) electroplating, (2) electroless plating, (3) vacuum deposition, (4) sputtering deposition, (5) chemical vapor deposition, (6) plasma spray method, and (7) solution immersion method. , (8) dispersion immersion method, etc. Among these methods, the method particularly suitable for the present invention is
(7) solution immersion method, and (8) dispersion immersion method. After dissolving or suspending the compound of the metal element in a suitable solvent and immersing the inorganic fiber therein and drying it,
A high-strength fiber-reinforced metal composite material can be obtained by combining it with metals that serve as a matrix, and this method is extremely easy and inexpensive to implement compared to other coating methods. The thickness of the coating is preferably 20 Å or more.
When the thickness of the coating is less than 20 Å, no significant effect is observed. The composite material of the present invention can be manufactured by various methods. The main methods are (1) liquid phase methods such as liquid metal impregnation, (2) solid phase methods such as diffusion bonding, and (3)
Powder metallurgy (sintering, welding), (4) deposition methods such as thermal spraying, electrodeposition, and vapor deposition, (5) plastic processing methods such as extrusion and rolling,
(6) Examples include high-pressure solidification casting method. The effects of the present invention are particularly noticeable when molten metal and fibers come into direct contact, such as in (1) the liquid metal impregnation method and (6) in the high-pressure solidification casting method. The manufacturing method shown in (5) is also clearly effective. The composite material produced in this way has significantly improved mechanical strength compared to the case where the additive metal element used in the present invention is not present. In addition, the fact that the present invention can be carried out without making any changes to existing equipment or methods is a great advantage in terms of actual production. EXAMPLES The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto. Example 1 Inorganic fibers include carbon fibers with an average fiber diameter of 7.5 μm, a tensile strength of 300 Kg/mm 2 , and a tensile modulus of 23000 Kg/mm 2 , an average fiber diameter of 14 μm, and a tensile strength of 150 Kg/mm 2 .
Alumina fiber with tensile modulus of 23500Kg/ mm2 ( Al2O3 content 85% by weight, SiO2 content 15% by weight)
and silica fiber with average fiber diameter 9 μm, tensile strength 600 Kg/mm 2 , tensile modulus 7400 Kg/mm 2 , average fiber diameter 15 μm, tensile strength 220 Kg/mm 2 , tensile modulus
Four types of silicon carbide fibers containing 20000 Kg/mm 2 of free carbon were prepared. The first solution was added to a 2% by weight aqueous solution of calcium chloride, cadmium sulfate and a 2% by weight ethanol solution of antimony trichloride.
Inorganic fibers of the combinations of inorganic fibers/metal compounds shown in the table are soaked, and aqueous solutions are dried in a hot air dryer at 130°C for 3 hours, and antimony trichloride is
Vacuum drying was performed at 100°C for 3 hours. These inorganic fibers were then cut into lengths of 110 mm under an argon atmosphere, bundled, and drawn in parallel into mold tubes each having an inner diameter of 4 mm. Then in an argon gas atmosphere
One end of the mold tube is immersed in a molten aluminum (99.99% purity) kept at 700℃, and while the other end is vacuum degassed, a pressure of 50Kg/cm 2 is applied to the surface of the molten metal to infiltrate the aluminum between the fibers. By cooling this, a fiber-reinforced metal composite material was obtained. The fiber volume content was adjusted to 50±1%. For comparison, we used inorganic fibers that were not immersed in a compound of metal elements, and used aluminum as a matrix.
A fiber-reinforced metal composite material was obtained using exactly the same method. The bending strength and bending elastic modulus at room temperature of the fiber-reinforced metal composite material thus produced were measured. The results are shown in Table 1, and in all cases where carbon fiber, alumina fiber, silica fiber, or silicon carbide fiber was used as the reinforcing material, the strength was significantly improved compared to the comparative example.
【表】
実施例 ２
実施例１で示した方法により実施例１で用いた
のと同じアルミナ繊維表面を塩化カルシウムで被
覆した。市販の純マグネシウム（純度99.9％）を
黒鉛るつぼ中にとり、アルゴンガス雰囲気下700
℃まで加熱溶融し、実施例１に示した方法により
繊維強化金属複合材料を得た。
次に同様な方法により銅と上記アルミナ繊維を
1100℃にて複合化した。比較のため表面処理をし
ていないアルミナ繊維を用いてマグネシウム、銅
のマトリツクスの繊維強化金属複合材料を得た。
この複合材料の常温での曲げ強度を測定した結果
を第２表に示す。いずれも比較例と較べて高い曲
げ強度を示した。[Table] Example 2 The same alumina fiber surface as used in Example 1 was coated with calcium chloride by the method shown in Example 1. Commercially available pure magnesium (purity 99.9%) was placed in a graphite crucible and heated at 700 °C under an argon gas atmosphere.
The mixture was heated and melted to a temperature of 0.degree. C., and a fiber-reinforced metal composite material was obtained by the method shown in Example 1. Next, copper and the above alumina fibers were added using the same method.
Composite was performed at 1100℃. For comparison, a fiber-reinforced metal composite material with a matrix of magnesium and copper was obtained using alumina fibers without surface treatment.
Table 2 shows the results of measuring the bending strength of this composite material at room temperature. All exhibited higher bending strength than the comparative example.
Claims (1)
ンカーバイド繊維及びアルミナ繊維より選ばれる
少なくとも１種の無機繊維を強化材とし、アルミ
ニウム、マグネシウムおよび銅から選ばれる少な
くとも１種の金属またはそれらの合金からなる繊
維強化金属複合材料において、無機繊維の表面を
カルシウム、カドミウムおよびアンチモンの無機
化合物または有機化合物からなる群から選ばれる
少なくとも１種にて被覆した後、マトリツクスと
なる金属または合金と複合化することを特徴とす
る機械強度に優れる繊維強化金属複合材料の製造
方法。1 Fiber made of at least one metal selected from aluminum, magnesium, and copper or an alloy thereof, reinforced with at least one inorganic fiber selected from carbon fiber, silica fiber, boron fiber, silicon carbide fiber, and alumina fiber. In the reinforced metal composite material, the surface of the inorganic fibers is coated with at least one selected from the group consisting of inorganic compounds or organic compounds of calcium, cadmium, and antimony, and then composited with a metal or alloy to serve as a matrix. A method for manufacturing a fiber-reinforced metal composite material with excellent mechanical strength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5262281A JPS57169039A (en) | 1981-04-07 | 1981-04-07 | Fiber reinforced metallic composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5262281A JPS57169039A (en) | 1981-04-07 | 1981-04-07 | Fiber reinforced metallic composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57169039A JPS57169039A (en) | 1982-10-18 |
| JPH0122335B2 true JPH0122335B2 (en) | 1989-04-26 |
Family
ID=12919899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5262281A Granted JPS57169039A (en) | 1981-04-07 | 1981-04-07 | Fiber reinforced metallic composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57169039A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4941918A (en) * | 1987-12-12 | 1990-07-17 | Fujitsu Limited | Sintered magnesium-based composite material and process for preparing same |
| JP5148820B2 (en) * | 2005-09-07 | 2013-02-20 | 株式会社イーアンドエフ | Titanium alloy composite material and manufacturing method thereof |
-
1981
- 1981-04-07 JP JP5262281A patent/JPS57169039A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57169039A (en) | 1982-10-18 |
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