JPS60238480A - Manufacture of carbon fiber-reinforced metal - Google Patents
Manufacture of carbon fiber-reinforced metalInfo
- Publication number
- JPS60238480A JPS60238480A JP59093681A JP9368184A JPS60238480A JP S60238480 A JPS60238480 A JP S60238480A JP 59093681 A JP59093681 A JP 59093681A JP 9368184 A JP9368184 A JP 9368184A JP S60238480 A JPS60238480 A JP S60238480A
- Authority
- JP
- Japan
- Prior art keywords
- carbon fiber
- metal
- metals
- fibers
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 33
- 239000004917 carbon fiber Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 230000001681 protective effect Effects 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000012808 vapor phase Substances 0.000 claims description 8
- 239000010953 base metal Substances 0.000 claims description 6
- 239000000835 fiber Substances 0.000 abstract description 41
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 9
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229910052719 titanium Inorganic materials 0.000 abstract description 5
- -1 and Co Inorganic materials 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 229910010271 silicon carbide Inorganic materials 0.000 abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- 229910052748 manganese Inorganic materials 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 229910052718 tin Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000007792 gaseous phase Substances 0.000 abstract 2
- 229910052581 Si3N4 Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000155 melt Substances 0.000 abstract 1
- 229910003465 moissanite Inorganic materials 0.000 abstract 1
- 229910052750 molybdenum Inorganic materials 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052715 tantalum Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-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
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0272—Deposition of sub-layers, e.g. to promote the adhesion of the main coating
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は炭素繊維と金属との複合材料の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a composite material of carbon fiber and metal.
更に詳しくはセラミックス、黒鉛、金属等の基板に成長
させた気相法による炭素繊維に複合材料の母材となる金
属または保護膜製被覆することを特徴とする炭素繊維強
化金属の製造方法に関する。More specifically, the present invention relates to a method for manufacturing a carbon fiber reinforced metal, which comprises coating carbon fibers grown on a substrate of ceramics, graphite, metal, etc. by a vapor phase method with a metal or a protective film to serve as a base material of a composite material.
炭素繊維強化金属（ＣＦ ＲＭ）は炭素繊維の特性と金
属の特性を生かした高強度、高弾性率、軽量の耐熱材料
として期待され、研究開発が進められている。Carbon fiber reinforced metal (CF RM) is expected to be a high-strength, high-modulus, lightweight, heat-resistant material that takes advantage of the characteristics of carbon fiber and metal, and research and development is progressing.
本発明は特に優れた特性を有する気相法による炭素繊維
を使用し、しかもこの繊維製造時の特徴を利用して高品
質の炭素繊維強化金属を製造する方法を提供するもので
ある。The present invention provides a method for producing high-quality carbon fiber reinforced metal by using carbon fiber produced by a vapor phase process which has particularly excellent properties, and by utilizing the characteristics during production of this fiber.
一般に炭素繊維はポリアクリロニトリル繊維、ピッチ繊
維等の繊維を焼成して得られているが、近年炭化水素気
体を熱分解させ炭素繊維を製造する方法が研究されてい
る。この方法はセラミックス、金属、黒鉛等の基板上に
分散させた金属触媒粒子を介して炭化水素熱分解を行う
もので、熱分解により生成する炭素は触媒粒子の作用で
一方向に析出し、繊維状になる。この繊維は「気相法に
よる炭素繊維」または「気相成長炭素繊維」と呼ばれる
。Generally, carbon fibers are obtained by firing fibers such as polyacrylonitrile fibers and pitch fibers, but in recent years, research has been conducted on methods of producing carbon fibers by thermally decomposing hydrocarbon gases. This method performs hydrocarbon thermal decomposition via metal catalyst particles dispersed on a substrate made of ceramics, metal, graphite, etc. Carbon produced by thermal decomposition is precipitated in one direction by the action of the catalyst particles, and fibers It becomes like this. This fiber is called "vapor-phase carbon fiber" or "vapor-grown carbon fiber."
通常この繊維は直径２μ＋ｓ〜１０μｍ、長さ１＋ｗｍ
〜１００ｍｍで、基板上に密生する。気相法による炭素
繊維は結晶子の配向が良好で、かつ欠陥が極めて少ない
のでポリアクリロニトリル繊維（ＰＡＮ系）、ピッチ繊
維（ピッチ系）等からの炭素繊維よりはるかに優れた機
械的性質を有する。Usually this fiber has a diameter of 2μ+s~10μm and a length of 1+wm.
~100 mm, densely growing on the substrate. Carbon fiber produced by the vapor phase method has good crystallite orientation and extremely few defects, so it has far superior mechanical properties to carbon fiber made from polyacrylonitrile fibers (PAN type), pitch fibers (pitch type), etc. .
例えば、気相法による炭素繊維と他の方法による炭素繊
維を比較すると表１に示す通りである。For example, Table 1 shows a comparison between carbon fibers produced by the vapor phase method and carbon fibers produced by other methods.
表１
〔発明が解決しようとする問題点〕
ＣＦＲＭは、その優れた特性が期待されているにもかか
わらず、製造上の問題から予想された特性値が得られて
いない。すなわち炭素繊維は金属と濡れにくく、高温で
はアルミニウムやチタンなどとは反応１起し、またニッ
ケルや鉄に溶解する等の原因による。これらの問題を解
決するため、これまで数多くの製造方法が提案されてい
る。例えば炭素繊維表面をＴｉＣ，ＴｉＢ、ＳｉＣ，Ｓ
ｉ３Ｎ、等の無機質保護膜で被覆した後、金属溶湯に浸
漬する溶浸法や、プラズマ・スプレー、メッキ、化学蒸
着、物理蒸着等の方法で繊維に金属を付与し、しかる後
に、金属と炭素繊維が反応しない条件で成形する方法で
ある。しかし、溶浸法の場合は完壁な保護膜が要求され
、プラズマ・スプレー、メッキ、化学蒸着、物理蒸着等
の方法ではできるだけ均一な金属膜が要求される。保護
膜を被覆する場合においても、金属を被覆する場合にお
いても均一な被膜が得られるという点では化学蒸着法お
よびプラズマ化学蒸着法が最も好ましい方法と言える。Table 1 [Problems to be Solved by the Invention] Although CFRM is expected to have excellent properties, expected property values have not been obtained due to manufacturing problems. In other words, carbon fibers are difficult to wet with metals, react with aluminum, titanium, etc. at high temperatures, and dissolve in nickel and iron. Many manufacturing methods have been proposed to solve these problems. For example, the surface of carbon fiber is TiC, TiB, SiC, S.
After coating with an inorganic protective film such as i3N, metal is applied to the fiber by an infiltration method in which the fiber is immersed in molten metal, or by a method such as plasma spray, plating, chemical vapor deposition, physical vapor deposition, etc., and then the metal and carbon are coated. This is a method of molding under conditions where the fibers do not react. However, infiltration methods require a complete protective film, and methods such as plasma spray, plating, chemical vapor deposition, physical vapor deposition, etc. require a metal film that is as uniform as possible. The chemical vapor deposition method and the plasma chemical vapor deposition method are the most preferable methods in that a uniform coating can be obtained both when coating a protective film and when coating a metal.
しかしながら化学蒸着法（ＣＶ Ｄ）およびプラズマ化
学蒸着法（Ｐ−ＣＶ Ｄ）においても、繊維数が多く、
繊維が密集していると、繊維−繊維間に蒸着すべき物質
が入り込まず、繊維束の外周のみが被覆されてしまう。However, even in chemical vapor deposition (CV D) and plasma chemical vapor deposition (P-CV D), the number of fibers is large;
If the fibers are densely packed, the substance to be deposited will not enter between the fibers, and only the outer periphery of the fiber bundle will be coated.
通常ＰＡＮ系、ピッチ系の炭素繊維は５μｍ〜１０μｍ
の繊維が１，０００〜１０，０００本まとまった連続糸
として供給されるためこの繊維束内部まで、無機質保護
膜や金属を被覆することは非常に難しい。Normally PAN-based and pitch-based carbon fibers are 5 μm to 10 μm.
Since 1,000 to 10,000 fibers are supplied as a continuous yarn, it is very difficult to coat the inside of this fiber bundle with an inorganic protective film or metal.
例えば、東しく株）製トレカＴ−３００においては直径
約７μｍの炭素繊維３，０００本が直径１ｍｍ以下の繊
維束として市販されているが、この場合、繊維−繊維間
の平均距離は約８〜９μｍと非常に狭く、よって、この
繊維束内部にまで、蒸着する原子が入り込むことが困難
になるからである。For example, in Toshiku Co., Ltd.'s Trading Card T-300, 3,000 carbon fibers with a diameter of about 7 μm are commercially available as a fiber bundle with a diameter of 1 mm or less, but in this case, the average distance between fibers is about 8 This is because the diameter is very narrow at ~9 μm, making it difficult for atoms to be deposited to enter the inside of this fiber bundle.
他方、基板上に密生している炭素繊維は、基板の面から
遠くなるほど、繊維の発生密度が減少するが、最も密度
が高い基板面上においても、繊維−繊維間の距離は５０
μｍもあるので、蒸着する原子が入り込みやすい。On the other hand, the density of carbon fibers growing densely on a substrate decreases as the distance from the substrate surface increases, but even on the substrate surface where the density is highest, the distance between fibers is 50
Since it has a diameter of μm, it is easy for atoms to be evaporated to enter.
ＣＶＤ装置やＰ、−ＣＶ Ｄ装置で繊維に皮膜を付与し
ている時の装置の断面を示したのが第１図である。通常
、外部より加熱するため、内壁が最も高温となり、この
壁が最も高い速度で蒸着されることになる。つまり、繊
維よりも器壁の方が多く蒸着されてしまうというデメリ
ットがある。第１図においては、１は反応管、２はヒー
ター、３は繊維束である。FIG. 1 shows a cross section of a CVD device or P,-CVD device when a film is applied to fibers. Typically, since heating is done from the outside, the inner wall will be at the highest temperature and will be deposited at the highest rate. In other words, there is a disadvantage that more vapor is deposited on the vessel wall than on the fibers. In FIG. 1, 1 is a reaction tube, 2 is a heater, and 3 is a fiber bundle.
〔問題点を解決するための手段〕 ゛
第２図に気相法による炭素繊維が基板上に成長した時の
状況を示す。炭素繊維は基板に対しほぼ垂直方向に成長
している。通常は、繊維を基板からはがして使用するが
１本発明においては、基板上に成長している炭素繊維を
そのまま使用することに意義がある。すなわち、本発明
では、第２図のような炭素繊維が成長した基板をそのま
ま第１図の装置内に配置して、ＣＶＤまたはＰ−ＣＶＤ
を行って、炭素繊維に無機質保護膜や金属を被覆する。[Means for solving the problem] Fig. 2 shows the situation when carbon fibers are grown on a substrate by the vapor phase method. The carbon fibers grow almost perpendicularly to the substrate. Normally, the fibers are used after being peeled off from the substrate, but in the present invention, it is meaningful to use the carbon fibers grown on the substrate as they are. That is, in the present invention, a substrate on which carbon fibers have been grown as shown in FIG. 2 is placed in the apparatus shown in FIG.
The carbon fibers are coated with an inorganic protective film or metal.
保護膜を被覆した場合は、被覆繊維を基板から引きはが
した後、金属溶湯中に浸漬するかまたは金属粉、金属箔
を付与して加熱加圧する等の方法で金属を付与してＣＦ
ＲＭとする。When a protective film is coated, the coated fibers are peeled off from the substrate and then CF
RM.
母材金属を被覆した場合（あるいは、保護膜被覆した場
合）、被覆繊維を積層、加熱加圧してＣＦＲＭとするこ
とができる。When the base metal is coated (or when it is coated with a protective film), the coated fibers can be laminated, heated and pressed to form a CFRM.
本発明によれば、母材金属中に繊維が均一に分散するの
で、表１に示す様に高性能のＣＦＲＭが得られる。According to the present invention, since the fibers are uniformly dispersed in the base metal, a high performance CFRM can be obtained as shown in Table 1.
本発明においてはＣＶＤ、または、Ｐ−ＣＶＤの方法に
ついてなんら限定されるものではない。In the present invention, there are no limitations on the CVD or P-CVD method.
本発明における無機質保護膜は１元素周期律表ＴＶｂ（
Ｔｉ、Ｚｒ等）Ｖｂ（Ｔａ等）、ｖｒｂ（Ｍ ｏ等）お
よびＳｉの炭化物、窒化物、硼化物、酸化物等であり、
炭素繊維を金属から保護し、金属と濡れるものが好まし
い。無機質保護膜の厚さは、繊維の体積が被覆前に対し
、被覆後で１．５倍以下であるようにすることが好まし
い。あまり無機質保護膜が厚いとＣＦＲＭの強度が低下
することが多い。The inorganic protective film in the present invention is one element of the periodic table TVb (
Ti, Zr, etc.) Vb (Ta, etc.), vrb (Mo, etc.) and Si carbides, nitrides, borides, oxides, etc.
It is preferable to use a material that protects carbon fibers from metal and that can be wetted with metal. The thickness of the inorganic protective film is preferably such that the volume of the fibers after coating is 1.5 times or less than that before coating. If the inorganic protective film is too thick, the strength of the CFRM often decreases.
本発明における母材金属とは、Ａ】、Ｍｇ、Ｔｉ等の軽
金属、Ｚｎ、Ｓｎ、Ｐｂ等の低融点金属、鉄属（ｐｃ、
Ｎｉ、 Ｃｏ）、Ｃｄ、 Ｍｎ、 Ｃｕ。Base metals in the present invention include light metals such as A], Mg, and Ti, low melting point metals such as Zn, Sn, and Pb, iron metals (PC,
Ni, Co), Cd, Mn, Cu.
等の重金属、Ａｕ、 Ａｇ、 Ｐｔ、Ｉｒ、Ｏｓ、Ｐｄ
等の貴金属、Ｔａ、Ｗ、Ｎｂ、Ｍｏ、■、Ｃｒ等の高融
点金属、Ｓｉ’、Ｇｅ等の半導体金属等であり、ＣＦＲ
Ｍにした時の繊維の体積が５〜７５％の範囲内であるこ
とが好ましい。Heavy metals such as Au, Ag, Pt, Ir, Os, Pd
CFR
It is preferable that the volume of the fiber when M is within the range of 5 to 75%.
本発明における無機質または金属を与えるＣＶＤ用原料
としては、有機金属化合物（フルキル金属、アリル金属
、π−コンプレックス、カルボニル金属等）または、無
機金属化合物（ハロゲン化物、水素化物等）が用られ無
機質保護膜を形成するには、炭化水素、窒素（アンモニ
ア）、ハロゲン化硼素、酸素等と反応させて炭化物、窒
化物、硼化物、酸化物等にする。母材金属の膜を形成す
るには。In the present invention, organic metal compounds (fulkyl metal, allyl metal, π-complex, carbonyl metal, etc.) or inorganic metal compounds (halides, hydrides, etc.) are used as raw materials for CVD to provide inorganic substances or metals to protect inorganic substances. To form a film, it is reacted with hydrocarbons, nitrogen (ammonia), boron halides, oxygen, etc. to form carbides, nitrides, borides, oxides, etc. To form a film of base metal.
水素ガスや希ガスを用いてＣ，ＶＤ、又はＰ−ＣＶＤを
行う。C, VD, or P-CVD is performed using hydrogen gas or rare gas.
以下実施例に従って、具体的に説明する。 A detailed description will be given below based on examples.
実施例 １゜
外径５０ｗｎ、内径４４ｍｎ（肉厚３ｍ）、長さ３００
ｍｍのアルミナ２ツ割管（基板）の内壁に、直径１００
人〜３００人の鉄超微粒子を塗布した。これを外径６０
＋＋ｎ＋内径５２画（肉厚４ｎｗｎ）の外部より電気ヒ
ーターで加熱される均熱部長さ６００ｍ＋のアルミナ管
に配置した。Example 1゜Outer diameter 50wn, inner diameter 44mm (thickness 3m), length 300
A diameter of 100mm is placed on the inner wall of a 2-mm alumina tube (substrate).
Ultrafine iron particles were applied to ~300 people. This has an outer diameter of 60
It was placed in an alumina tube with an internal diameter of 52 (wall thickness: 4 nwn) and a soaking section length of 600 m+, which was heated from the outside with an electric heater.
この管内を水素ガスを流通させながら。While hydrogen gas is flowing inside this tube.
１１００℃、２時間、鉄超微粒子を還元した。Ultrafine iron particles were reduced at 1100°C for 2 hours.
しかる後、ベンゼン２体積％を含む水素ガスを１．００
ｍ１／分を導入し、１０９０℃で１時間、、１１８０℃
で２間時気相成長反応を行い、炭素繊維製作成させた。After that, 1.00% of hydrogen gas containing 2% by volume of benzene was added.
m1/min, 1 hour at 1090°C, 1180°C
A vapor phase growth reaction was carried out for 2 hours to produce carbon fiber.
気相成長反応終了後、Ａｒガスを導入して、反応管を１
３００℃に昇温した。温度が安定した後、Ａ「ガス中に
５体積％の四塩化珪素と３体積％のアセチレンを導入し
、３０分間ＣＶＤを行った。反応終了後、Ａｒ雰囲気下
で２００℃まで冷却した後、アルミナ２ツ割管をとり出
し、繊維を基板から引きはがして集めた。この繊維は平
均直径１１μｍであり、内側の直径１０μｍに相当する
部分は炭素で構成されており、外部は炭化珪素より成る
ものであった。After the vapor phase growth reaction is completed, Ar gas is introduced and the reaction tube is
The temperature was raised to 300°C. After the temperature stabilized, 5% by volume of silicon tetrachloride and 3% by volume of acetylene were introduced into the A gas, and CVD was performed for 30 minutes. After the reaction was completed, the temperature was cooled to 200°C under an Ar atmosphere. An alumina split tube was taken out, and the fibers were peeled off from the substrate and collected.The fibers had an average diameter of 11 μm, the inner diameter of which was 10 μm was made of carbon, and the outer part was made of silicon carbide. It was something.
この繊維を７００℃に加熱されたマグネシウム合金（Ａ
Ｚ６１Ａ）の溶湯中に分散させ。These fibers were heated to 700°C to form a magnesium alloy (A
Disperse in the molten metal of Z61A).
ＣＦＲＭとした。このＣＦＲＭは■す１０％で引張強度
３５０ＭＰａのものであった。It was designated as CFRM. This CFRM was 10% thick and had a tensile strength of 350 MPa.
実施例２
実施例１と同じ方法で気相成長炭素繊維を作成した後、
反応管を冷却し、更に、真空排気した。反応管を３００
℃に保持し、絶対圧がＩＰａになった処でＡｒガスを導
入し、１００Ｐａとした後、反応管外部の高周波コイル
より、１３．５６ＭＨｚ、０．２ＫＷ高周波を与え、低
温プラズマ髪発生させた。この雰囲気にＡｌＣｌ３．５
ｉＣ１４を含むＡｒガスを導入し、３００ Ｐａの全ガ
ス圧とし、６０分間、Ｐ−ＣＶＤを行なった。Example 2 After creating vapor grown carbon fibers in the same manner as in Example 1,
The reaction tube was cooled and further evacuated. 300 reaction tubes
℃, and when the absolute pressure reached IPa, Ar gas was introduced to bring the pressure to 100 Pa, and then 13.56 MHz, 0.2 KW high frequency was applied from a high frequency coil outside the reaction tube to generate low-temperature plasma hair. . In this atmosphere, AlCl3.5
Ar gas containing iC14 was introduced, the total gas pressure was 300 Pa, and P-CVD was performed for 60 minutes.
この様にして得られたＡｌ−８ｉ合金被覆炭素繊維をで
きるだけ一方向に引き揃えて真空ホットプレスにて４５
０℃、３０ＭＰａ、２０分の条件で成形し、ＣＦＲＭと
した。このＣＦＲＭは繊維体積３３％を有し、繊維軸方
向の引張強度が８２０ＭＰａ、弾性率が１３０ＧＰａを
示した。The Al-8i alloy-coated carbon fibers obtained in this way were pulled in one direction as much as possible and then heated in a vacuum hot press for 45 minutes.
It was molded under the conditions of 0° C., 30 MPa, and 20 minutes to obtain a CFRM. This CFRM had a fiber volume of 33%, a tensile strength in the fiber axis direction of 820 MPa, and an elastic modulus of 130 GPa.
本発明に従うと、最も繊維密度の高い基板が器壁に接触
し、最も温度が高くなるので、蒸着されやすくなる。従
って、通常蒸着しにくいとされる繊維密度の高い処が蒸
着しゃすなり、結果的には全体が比較的均一に蒸着され
ることになる。According to the present invention, the substrate with the highest fiber density contacts the vessel wall and has the highest temperature, making it easier to deposit. Therefore, the vapor deposition is carried out in areas with high fiber density, which are normally difficult to vapor deposit, and as a result, the entire area is vapor deposited relatively uniformly.
第１図は、ＣＶＤまたはＰ−ＣＶＤ＆、：、よって繊維
に母材金属または保護膜を被覆する装置図である。１は
反応管、２はヒーター、３は繊維束、４は高周波コイル
を示す。
第２図は気相法によって基板１１上に生成した炭素繊維
１２の状態を示すものである。FIG. 1 is a diagram of an apparatus for coating fibers with a base metal or a protective film by CVD or P-CVD. 1 is a reaction tube, 2 is a heater, 3 is a fiber bundle, and 4 is a high frequency coil. FIG. 2 shows the state of the carbon fibers 12 produced on the substrate 11 by the vapor phase method.
Claims (1)
たは保護吸殻被覆することを特徴とする炭素繊維強化金
属の製造方法。A method for producing a carbon fiber-reinforced metal, which comprises coating carbon fibers produced on a substrate by a vapor phase method with a base metal or a protective butt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093681A JPS60238480A (en) | 1984-05-10 | 1984-05-10 | Manufacture of carbon fiber-reinforced metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59093681A JPS60238480A (en) | 1984-05-10 | 1984-05-10 | Manufacture of carbon fiber-reinforced metal |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60238480A true JPS60238480A (en) | 1985-11-27 |
Family
ID=14089142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59093681A Pending JPS60238480A (en) | 1984-05-10 | 1984-05-10 | Manufacture of carbon fiber-reinforced metal |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60238480A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049409A (en) * | 1985-03-20 | 1991-09-17 | Sharp Kabushiki Kaisha | Method for metal or metal compounds inserted between adjacent graphite layers |
| US5273778A (en) * | 1985-03-20 | 1993-12-28 | Sharp Kabushiki Kaisha | Method for producing graphite intercalation compound |
| CN102373389A (en) * | 2011-09-30 | 2012-03-14 | 常熟市星源金属涂层厂 | Preparation method of three-dimensional woven carbon fiber-reinforced magnesium-based composite material |
| CN107723628A (en) * | 2017-08-31 | 2018-02-23 | 宁波市佳利来机械制造有限公司 | A kind of automobile drive electric motor shell |
-
1984
- 1984-05-10 JP JP59093681A patent/JPS60238480A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049409A (en) * | 1985-03-20 | 1991-09-17 | Sharp Kabushiki Kaisha | Method for metal or metal compounds inserted between adjacent graphite layers |
| US5273778A (en) * | 1985-03-20 | 1993-12-28 | Sharp Kabushiki Kaisha | Method for producing graphite intercalation compound |
| US5404837A (en) * | 1985-03-20 | 1995-04-11 | Sharp Kabushiki Kaisha | Method for preparing a graphite intercalation compound having a metal or metal compounds inserted between adjacent graphite layers |
| CN102373389A (en) * | 2011-09-30 | 2012-03-14 | 常熟市星源金属涂层厂 | Preparation method of three-dimensional woven carbon fiber-reinforced magnesium-based composite material |
| CN107723628A (en) * | 2017-08-31 | 2018-02-23 | 宁波市佳利来机械制造有限公司 | A kind of automobile drive electric motor shell |
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