JPH0211646B2 - - Google Patents
Info
- Publication number
- JPH0211646B2 JPH0211646B2 JP59086919A JP8691984A JPH0211646B2 JP H0211646 B2 JPH0211646 B2 JP H0211646B2 JP 59086919 A JP59086919 A JP 59086919A JP 8691984 A JP8691984 A JP 8691984A JP H0211646 B2 JPH0211646 B2 JP H0211646B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- coating layer
- molded body
- metal powder
- forming
- 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 - Lifetime
Links
- 239000002184 metal Substances 0.000 claims description 147
- 229910052751 metal Inorganic materials 0.000 claims description 147
- 239000000843 powder Substances 0.000 claims description 100
- 238000005245 sintering Methods 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 53
- 239000011247 coating layer Substances 0.000 claims description 34
- 230000001070 adhesive effect Effects 0.000 claims description 26
- 239000012779 reinforcing material Substances 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 14
- -1 acrylate ester Chemical class 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 10
- 229920000620 organic polymer Polymers 0.000 claims description 9
- 229910045601 alloy Inorganic materials 0.000 claims description 8
- 239000000956 alloy Substances 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 5
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 229920001567 vinyl ester resin Polymers 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000002075 main ingredient Substances 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 229920000058 polyacrylate Polymers 0.000 description 12
- 239000010953 base metal Substances 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000006023 eutectic alloy Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001289 polyvinyl ether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229910017086 Fe-M Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000007965 phenolic acids Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Description
【発明の詳細な説明】
この発明は金属粉末およびこの粉末を結合する
有機質結合剤を含む金属粉末成形本体と耐熱性補
強材とからなる低収縮性金属粉末成形体を用いて
金属母材面に金属被覆層を形成する方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION This invention uses a low-shrinkage metal powder molded body consisting of a metal powder molded body containing metal powder and an organic binder for binding the powder, and a heat-resistant reinforcing material to form a metal powder on the surface of a metal base material. The present invention relates to a method of forming a metallization layer.
従来、金属母材面に特別な性質たとえば耐摩耗
性あるいは耐腐食性などを付与するために、これ
らの性質にすぐれた金属被覆層を母材面に形成す
ることがよく行われている。 Conventionally, in order to impart special properties, such as wear resistance or corrosion resistance, to the surface of a metal base material, it has been common practice to form a metal coating layer having excellent properties on the surface of the base material.
金属被覆は、多くの場合、金属粉末とこの粉末
を結合する有機質結合剤とからなる柔軟な粉末成
形体を金属母材面に貼着してから焼結することに
よつて母材面に層状に形成され、この焼結した金
属被覆層は母材面に冶金学的に結合される。 In many cases, metal coating is made by attaching a flexible powder compact made of metal powder and an organic binder that binds the powder to the metal base material surface, and then sintering it to form a layer on the base material surface. The sintered metallization layer is metallurgically bonded to the base metal surface.
ところで、粉末成形体は、これを金属母材面に
貼着しその後焼結して上記母材面に冶金学的に結
合させる場合、上記母材面の曲面に対してもクラ
ツク発生などの実用性を阻害する要因を生起させ
ることなく追随変形させうる良好な柔軟性を有し
ていることが必要である。 By the way, when a powder compact is adhered to a metal base material surface and then sintered to be metallurgically bonded to the base metal surface, cracks may occur even on the curved surface of the base material. It is necessary that the material has good flexibility so that it can be deformed without causing any factors that impede its properties.
また、この種の粉末成形体は、上記追随変形性
の如き賦形性にすぐれた良好な柔軟性を有するう
えに、当然のことながら、その取り扱い上充分な
強度を有し、しかも焼結にあたつては巣と指称す
る穴など生じさせることなく密度の高い金属層を
与えうるものであることが要求される。 In addition, this type of powder compact not only has good flexibility with excellent formability such as the above-mentioned conformable deformability, but also has sufficient strength for handling, and is also resistant to sintering. In general, it is required that a metal layer with high density can be provided without forming holes called cavities.
従来、この種の粉末成形体として、たとえば特
開昭49−91910号公報、同56−35703号公報、特公
昭45−21167号公報などに代表されるように、ポ
リビニルエーテル、メチル繊維素系樹脂の如き樹
脂類を主剤としてこれにジブチルフタレート、グ
リセリン、ワツクス類などの揮散性の可塑剤を粉
末成形体の柔軟性向上剤として配合したものが知
られている。 Conventionally, as this type of powder compact, polyvinyl ether and methyl cellulose resins have been used, as typified by, for example, JP-A No. 49-91910, JP-A No. 56-35703, and JP-A No. 45-21167. It is known that resins such as the following are used as a main ingredient, and volatile plasticizers such as dibutyl phthalate, glycerin, and waxes are blended therein as a flexibility improver for powder compacts.
しかるに、このような金属粉末に主剤と柔軟性
向上剤とを包含する結合剤を配合してなる粉末成
形体は、焼結時に面方向に約20％前後収縮する欠
点がある。このため、この種の粉末成形体を金属
母材面に貼着して焼結するにあたつては、焼結後
に規定寸法が得られるように予め焼結前の成形体
の寸法を上記収縮率を見込んだ寸法に設定してお
く必要がある。 However, a powder compact formed by blending such a metal powder with a binder containing a base material and a flexibility improver has the disadvantage that it shrinks by about 20% in the planar direction during sintering. Therefore, when attaching this type of powder compact to the metal base material surface and sintering it, the dimensions of the compact before sintering must be adjusted as described above to obtain the specified dimensions after sintering. It is necessary to set the dimensions taking into account the ratio.
ところが、このような寸法設定は、実際上非常
に煩わしくて実用性に欠け、しかも粉末成形体の
厚みや金属粉末とこれを結合する有機質結合剤と
の混合割合などのバラツキによる収縮率の変動を
どうしてもさけられないため、焼結後の寸法を必
ずしも規定寸法どおりに設定しにくいという難点
がある。特に粉末成形体の寸法が大きくなると収
縮率の変動もそれだけ大きくなるため、上記難点
が顕著となる。 However, this kind of dimension setting is actually extremely troublesome and impractical, and furthermore, it is difficult to adjust the shrinkage rate due to variations in the thickness of the powder compact or the mixing ratio of the metal powder and the organic binder that binds it together. Since this cannot be avoided, it is difficult to necessarily set the dimensions after sintering to the specified dimensions. In particular, as the size of the powder compact increases, the variation in shrinkage rate also increases accordingly, making the above-mentioned difficulties more pronounced.
また、粉末成形体を金属母材面に貼着して焼結
する場合、上記焼結時の収縮が下記の如き問題を
招く。すなわち、金属母材面が凹部などを有する
場合にこれに粉末成形体を貼着して焼結すると、
成形体の収縮によつて上記凹部などの母材内面と
焼結形成された金属被覆層との間に大きな空隙が
形成され、母材と金属被覆層との間の密着性が著
しく損なわれてしまうという不都合がある。 Furthermore, when a powder compact is adhered to a metal base material surface and sintered, the shrinkage during sintering causes the following problems. In other words, when the metal base material surface has a recess or the like, if a powder compact is attached to this and sintered,
Due to the shrinkage of the molded body, large gaps are formed between the inner surface of the base material such as the above-mentioned recesses and the sintered metal coating layer, and the adhesion between the base material and the metal coating layer is significantly impaired. There is the inconvenience of putting it away.
この発明は、かかる従来技術に鑑み鋭意研究の
結果完成されたものであつて、特に焼結後に密度
の高い金属層が原形と実質的に近似の大きさで焼
結形成されうる低収縮性金属粉末成形体を用いて
金属母材面に上記良好な特性を有する金属被覆層
を焼結形成する方法を提供せんとするものであ
る。 The present invention has been completed as a result of intensive research in view of the prior art, and is particularly a low-shrinkage metal that can be sintered to form a high-density metal layer in a size substantially similar to the original shape after sintering. It is an object of the present invention to provide a method for sintering and forming a metal coating layer having the above-mentioned favorable properties on the surface of a metal base material using a powder compact.
すなわち、この発明は、金属母材面に、金属粉
末およびこの粉末を結合する有機質結合剤を含む
金属粉末成形本体とこの本体の表面または内部に
設けられた焼結時の面方向収縮を抑制する塑性変
形性の金属箔または穿孔金属箔よりなる耐熱性補
強材とからなる低収縮性金属粉末成形体を、上記
本体を介して直接あるいは間接的に貼着したの
ち、非酸化雰囲気下で加熱昇温して上記本体を焼
結することにより、金属母材面に金属被覆層を形
成することを特徴とする金属被覆層の形成方法に
係るものである。 That is, the present invention provides a metal powder molded body containing a metal powder and an organic binder for bonding the powder on the metal base material surface, and a metal powder molded body provided on the surface or inside of this body to suppress in-plane shrinkage during sintering. A low-shrinkage metal powder molded body made of a heat-resistant reinforcing material made of plastically deformable metal foil or perforated metal foil is adhered directly or indirectly to the body, and then heated and raised in a non-oxidizing atmosphere. The present invention relates to a method for forming a metal coating layer, characterized in that a metal coating layer is formed on a surface of a metal base material by heating and sintering the main body.
この発明で用いる低収縮性金属粉末成形体は、
金属粉末成形本体の表面または内部に焼結時の面
方向収縮を抑制する耐熱性補強材を設けた構成と
しているため、この成形体を金属母材面に貼着し
て焼結させたときの焼結時の面方向への収縮を10
％以下、好態として５％以下に抑えることができ
る。すなわち、原形と実質的に近似する大きさで
焼結を完了させることができるという特徴を有す
る。したがつて、従来のように焼結前の寸法を焼
結時の収縮を考慮した大きさに厳密に設定しなく
とも、ほぼ規定寸法どおりの寸法安定性良好な金
属被覆層を得ることができる。 The low shrinkage metal powder compact used in this invention is
Heat-resistant reinforcing material is provided on the surface or inside of the metal powder molded body to suppress in-plane shrinkage during sintering, so when this molded body is attached to the metal base material surface and sintered, Shrinkage in the plane direction during sintering is 10
% or less, preferably 5% or less. That is, it has the characteristic that sintering can be completed in a size that is substantially similar to the original shape. Therefore, it is possible to obtain a metal coating layer with good dimensional stability that has almost the specified dimensions without strictly setting the dimensions before sintering to a size that takes into account shrinkage during sintering, as is the case in the past. .
また、この発明で用いる低収縮性金属粉末成形
体は、上記収縮抑制用の耐熱性補強材として特に
塑性変形しうる材質のものを選択していることに
よつて、この種の成形体を焼結に際して曲面状の
金属母材面に追随変形させたときに、上記補強材
がこれら変形に対する復元力に抗してその変形状
態を焼結完了まで保持する機能を発揮し、その結
果母材面との接着が不充分となるといつた不都合
が解消されるという特徴をも有している。 In addition, the low-shrinkage metal powder compact used in this invention is made of a material that can be particularly plastically deformed as the heat-resistant reinforcing material for suppressing shrinkage. When the curved metal base metal surface is deformed during sintering, the reinforcing material exerts the function of resisting the restoring force against these deformations and maintaining the deformed state until the completion of sintering, and as a result, the base metal surface It also has the feature of eliminating the inconvenience caused by insufficient adhesion.
さらに、この発明の如く上記特定の成形体を用
いてこれを金属母材面に貼着したのち焼結処理す
る方法によれば、上記成形体が上述の如く低収縮
性であることによつて、この成形体を曲面状の金
属母材面、特に凹部を有する金属母材面に貼着す
る場合でも、焼結後に母材と金属被覆層との間に
従来の如き収縮に起因した大きな空隙を生じさせ
る必配が全くない。このため、金属母材面に対す
る金属被覆層の密着性を大幅に改善することが可
能となる。 Furthermore, according to the method of the present invention, in which the above-mentioned specific molded body is used and is sintered after being adhered to the surface of the metal base material, since the above-mentioned molded body has low shrinkage as described above, Even when this molded body is attached to a curved metal base material surface, especially a metal base material surface having a recessed part, there is no large gap between the base material and the metal coating layer due to conventional shrinkage after sintering. There is no necessity for this to occur. Therefore, it is possible to significantly improve the adhesion of the metal coating layer to the surface of the metal base material.
この発明で用いる低収縮性金属粉末成形体にお
いて、金属粉末成形本体を構成する金属粉末とし
ては、金属母材面に付与すべき性質に応じて各種
の金属粉末を使用することができる。たとえば自
溶性合金粉末や耐摩耗性合金粉末などの各種合金
粉末を好適なものとして例示することができる。 In the low-shrinkage metal powder molded body used in this invention, various metal powders can be used as the metal powder constituting the metal powder molded body depending on the properties to be imparted to the metal base material surface. For example, various alloy powders such as self-fusing alloy powder and wear-resistant alloy powder can be exemplified as suitable.
金属母材面に付与すべき性質の代表的な例とし
て、耐摩耗性の向上が挙げられるが、かかる目的
を達成しうる耐摩耗性合金粉末として、Fe−Ｍ
−Ｃ系の多元共晶合金粉末を挙げることができ
る。上記のＭはMo、ＢおよびＰのうちいずれか
少なくとも一種を主成分とし、副次的な元素とし
てCr、Ｖ、Ｗ、Nb、Ta、Tiを含むことがあり、
また他の元素としてSi、Ni、Mnなどを含むこと
ができる。かかる多元共晶合金粉末は焼結温度が
比較的低く、一般に1000〜1150℃の温度範囲で液
相が10〜50容量％となり、しかもこの液相は母材
に対して濡れ性が優れているという特徴を有して
いる。 A typical example of the properties that should be imparted to the metal base material surface is improvement of wear resistance, and Fe-M is a wear-resistant alloy powder that can achieve this purpose.
-C-based multi-component eutectic alloy powder can be mentioned. The above M has at least one of Mo, B, and P as a main component, and may include Cr, V, W, Nb, Ta, and Ti as secondary elements,
Moreover, Si, Ni, Mn, etc. can be included as other elements. Such multi-component eutectic alloy powder has a relatively low sintering temperature, and generally has a liquid phase of 10 to 50% by volume in the temperature range of 1000 to 1150°C, and this liquid phase has excellent wettability to the base material. It has the following characteristics.
なお、これらの合金粉末の粉末粒度としては、
これが焼結後の気孔率に影響するため、一般に
150メツシユ以下であるのが好ましい。これより
大きくなると密度の高い合金層を形成しにくくな
るため、好ましくない。 The particle size of these alloy powders is as follows:
This affects the porosity after sintering, so it is generally
Preferably, it is 150 meshes or less. If it is larger than this, it becomes difficult to form a dense alloy layer, which is not preferable.
かかる金属粉末を結合して金属粉末成形本体を
構成させるための有機質結合剤としては、たとえ
ばメチルまたはエチル繊維素、ポリテトラフルオ
ロエチレン、ポリビニルアルコール、ポリビニル
エーテル、ポリブチラール、ポリアクリル、天然
または合成ゴムなどの主剤単独、またはこれにジ
ブチルフタレート、グリセリン、ワツクス類の如
き柔軟性向上剤などを使用してなるものが使用さ
れる。 Examples of organic binders for binding such metal powders to form a metal powder molded body include methyl or ethyl cellulose, polytetrafluoroethylene, polyvinyl alcohol, polyvinyl ether, polybutyral, polyacrylic, and natural or synthetic rubber. These base ingredients may be used alone or in combination with a flexibility improver such as dibutyl phthalate, glycerin, or waxes.
有機質結合剤の配合量は、金属粉末成形本体中
に占める割合が一般に１〜15重量％、好適には２
〜10重量％の範囲となるような割合とされる。こ
の配合量が過少では金属粉末成形本体の物理的強
度に劣り、逆に過多となると焼結後の金属層の密
度が低くなつたり、焼結処理中にガス化する樹脂
成分などによつて焼結炉内を汚染したりすること
があるので好ましくない。 The content of the organic binder is generally 1 to 15% by weight, preferably 2% by weight in the metal powder molded body.
The proportion is set to be in the range of ~10% by weight. If this amount is too small, the physical strength of the metal powder molded body will be poor; if it is too large, the density of the metal layer after sintering may become low, or the resin components that gasify during the sintering process may cause sintering. This is not desirable as it may contaminate the inside of the furnace.
有機質結合剤として、特に常温で感圧接着性を
有するゴム系や合成樹脂系の有機質ポリマーを主
剤としたものを用いると、可撓性にすぐれ、二次
元以上の形状に追随変形せしめても、クラツクな
どの発生を生じない金属粉末成形本体が得られる
ので好ましい。 When using an organic binder based on a rubber-based or synthetic resin-based organic polymer that has pressure-sensitive adhesive properties at room temperature, it has excellent flexibility and can be deformed to a two-dimensional or more shape. This is preferable because a metal powder molded body that does not cause cracks or the like can be obtained.
さらに、上記常温で感圧接着性を有する有機質
ポリマーとして、特に（メタ）アクリル酸アルキ
ルエステルの単独重合体または（メタ）アクリル
酸アルキルエステルとこれと共重合可能な官能性
モノマーおよび／またはビニルエステルモノマー
との共重合体からなるアクリル系重合体を用いる
と、後述するようなすぐれた特徴を有する金属粉
末成形本体が得られる。 Furthermore, as the organic polymer having pressure-sensitive adhesive properties at room temperature, in particular, a homopolymer of (meth)acrylic acid alkyl ester or (meth)acrylic acid alkyl ester and a functional monomer copolymerizable therewith and/or vinyl ester. When an acrylic polymer made of a copolymer with a monomer is used, a metal powder molded body having excellent characteristics as described below can be obtained.
上記（メタ）アクリル酸アルキルエステルとし
ては、脂肪族アルコールのアルキル基がメチル
基、エチル基、ブチル基、イソブチル基、ヘキシ
ル基、ヘプチル基、オクチル基、イソオクチル
基、２−エチルヘキシル基などからなるアルキル
基の平均炭素数が３〜12個のアクリル酸もしくは
メタクリル酸のアルキルエステルが挙げられる。 The above (meth)acrylic acid alkyl esters include alkyl groups of aliphatic alcohols such as methyl, ethyl, butyl, isobutyl, hexyl, heptyl, octyl, isooctyl, and 2-ethylhexyl groups. Examples include alkyl esters of acrylic acid or methacrylic acid having an average number of carbon atoms of 3 to 12.
かかる（メタ）アクリル酸アルキルエステル
は、金属粉末成形本体を高温加熱処理して焼結さ
せたときのガス発生量を少なくして焼結後の金属
層の膨れなどが発生するのを防止する働きを有す
る。アルキル基の平均炭素数が３に満たないかあ
るいは12を超えてしまうといずれも粘着結合性に
劣ると共に柔軟性に欠けるなどの問題があるので
好ましくない。 This (meth)acrylic acid alkyl ester works to reduce the amount of gas generated when the metal powder molded body is sintered by high-temperature heat treatment, thereby preventing the metal layer from blistering after sintering. has. If the average number of carbon atoms in the alkyl group is less than 3 or more than 12, it is undesirable because there are problems such as poor adhesive bonding properties and lack of flexibility.
上記（メタ）アクリル酸アルキルエステルと共
重合可能な官能性モノマーとしては、たとえば官
能基としてカルボキシル基を有する（メタ）アク
リル酸、クロトン酸、マレイン酸、イタコン酸、
フエノール酸、フマル酸などのα−モノまたはジ
オレフインカルボン酸が、また官能基として水酸
基を有する（メタ）アクリル酸−２−ヒドロキシ
エチル、（メタ）アクリル酸−２−ヒドロキシプ
ロピル、（メタ）アクリル酸−１−メチル−２−
ヒドロキシエチル、２−ヒドロキシビニルエーテ
ルなどが、また官能基としてエポキシ基を有する
グリシジル（メタ）アクリレートやメチロール基
を有するＮ−メチロール（メタ）アクリルアミド
などが、さらに官能基としてアミノ基を有する
Ｎ・Ｎ−ジメチルアミノエチル（メタ）アクリレ
ート、Ｎ−ターシヤリーブチルアミノエチル（メ
タ）アクリレート、Ｎ−ターシヤリーブチルアミ
ノブチル（メタ）アクリレートなどの官能性モノ
マーが挙げられる。また前記（メタ）アクリル酸
アルキルエステルと共重合可能なビニルエステル
モノマーとしては、プロピオン酸ビニル、酢酸ビ
ニル、（メタ）アクリロニトリルなどが挙げられ
る。 Examples of the functional monomer copolymerizable with the above (meth)acrylic acid alkyl ester include (meth)acrylic acid, crotonic acid, maleic acid, itaconic acid, which has a carboxyl group as a functional group,
α-mono- or diolefincarboxylic acids such as phenolic acid and fumaric acid, and 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid having a hydroxyl group as a functional group. acid-1-methyl-2-
Hydroxyethyl, 2-hydroxy vinyl ether, etc., glycidyl (meth)acrylate having an epoxy group as a functional group, N-methylol (meth)acrylamide having a methylol group, etc., and N/N- having an amino group as a functional group. Functional monomers such as dimethylaminoethyl (meth)acrylate, N-tertiarybutylaminoethyl (meth)acrylate, and N-tertiarybutylaminobutyl (meth)acrylate can be mentioned. Examples of vinyl ester monomers copolymerizable with the (meth)acrylic acid alkyl ester include vinyl propionate, vinyl acetate, and (meth)acrylonitrile.
これら共重合モノマーを用いる場合の使用量と
しては、前記（メタ）アクリル酸アルキルエステ
ル80〜99.5重量％、好ましくは90〜98重量％に対
して、上記の官能性モノマーおよび／またはビニ
ルエステルモノマーが通常20〜0.5重量％、好ま
しくは10〜２重量％となるようにするのがよい。 When using these copolymerizable monomers, the amount of the above functional monomer and/or vinyl ester monomer is 80 to 99.5% by weight, preferably 90 to 98% by weight of the (meth)acrylic acid alkyl ester. The amount is usually 20 to 0.5% by weight, preferably 10 to 2% by weight.
このような（メタ）アクリル酸アルキルエステ
ルの単独重合体または共重合体からなるアクリル
系重合体は、その重量平均分子量が５〜150万、
好ましくは30〜120万で、ガラス転移温度が−10
〜−70℃、好ましくは−25〜−65℃であるのがよ
く、また25℃での弾性率が0.05〜50Kg／cm2、好ま
しくは0.2〜30Kg／cm2に設定されているのが望ま
しい。金属粉末に対する結合力向上、焼結後の高
密度化、賦形に耐え得る柔軟性の付与および賦形
時のクラツク防止などの点で好ましい結果を与え
るからである。 The acrylic polymer consisting of a homopolymer or copolymer of such (meth)acrylic acid alkyl ester has a weight average molecular weight of 50,000 to 1,500,000,
Preferably 300,000 to 1,200,000, with a glass transition temperature of -10
The temperature is preferably -70°C, preferably -25 to -65°C, and the elastic modulus at 25°C is preferably set to 0.05 to 50 Kg/cm 2 , preferably 0.2 to 30 Kg/cm 2 . This is because it provides favorable results in terms of improved bonding strength to metal powder, higher density after sintering, provision of flexibility that can withstand shaping, and prevention of cracks during shaping.
なお、上記弾性率とは、測定温度25℃におい
て、試料をチヤツク間距離50mmで300mm／分の速
度で引き伸ばしたときの接線モジユラスの値を意
味する。その計算式は下記の通りである。 The above elastic modulus means the value of the tangent modulus when the sample is stretched at a speed of 300 mm/min with a distance between chucks of 50 mm at a measurement temperature of 25°C. The calculation formula is as follows.
＜計算式＞弾性率＝Ｆ／Ｓ
但し
Ｆ：試料を100％伸ばした点上と接線との交点の
力（Kg／cm2）
Ｓ：試料の断面積
また、上記のアクリル系重合体には、接着性付
与樹脂を含ませることができる。この接着性付与
樹脂は主に金属粉末成形本体の常温での接着力の
向上に寄与する。併用割合は、アクリル系重合体
50〜99.8重量％に対して接着性付与樹脂が50〜
0.2重量％とするのがよく、接着性付与樹脂の使
用量が少ないと上記の効果が得られず、また多く
なりすぎるとアクリル系重合体の前記特性が損な
われるため好ましくない。 <Calculation formula> Elastic modulus = F/S However, F: Force at the intersection of the point at which the sample is stretched 100% and the tangent line (Kg/cm 2 ) S: Cross-sectional area of the sample In addition, the above acrylic polymer , an adhesion-imparting resin may be included. This adhesion-imparting resin mainly contributes to improving the adhesive strength of the metal powder molded body at room temperature. The combined ratio is acrylic polymer
Adhesion imparting resin is 50~99.8% by weight
The amount is preferably 0.2% by weight; if the amount of the adhesion-imparting resin used is too small, the above effects cannot be obtained, and if it is too large, the properties of the acrylic polymer will be impaired, which is not preferable.
このような接着性付与樹脂の具体例としては、
アルキルフエノール系樹脂、クマロンインデン系
樹脂、ポリテルペン系樹脂、ロジン系樹脂、石油
系樹脂などを挙げることができる。 Specific examples of such adhesion-imparting resins include:
Examples include alkylphenol resins, coumaron indene resins, polyterpene resins, rosin resins, and petroleum resins.
このような常温で感圧接着性を有するアクリル
系重合体を主剤としたものを結合剤として用いる
と、前述の如き柔軟性向上剤の如き可塑化物を使
用することなく、曲面に対してクラツクの発生な
く追随変形させうるだけでなく、1.5〜7.0重量％
という少量で良好な金属粉末成形本体が得られ、
しかも焼結後の金属層も高密度なものが得られる
という特徴を有する。 If an acrylic polymer that has pressure-sensitive adhesive properties at room temperature is used as a binder, it will not crack on curved surfaces without using plasticizers such as the aforementioned flexibility improvers. Not only can it be followed by deformation without generation, but also 1.5 to 7.0% by weight
A good metal powder molded body can be obtained with a small amount of
Furthermore, the metal layer after sintering has the characteristic of being able to have a high density.
この発明における金属粉末成形本体は、たとえ
ば上記の有機質結合剤をアセトン、トルエン、メ
チルエチルケトンなどの適宜の有機溶剤を用いた
溶液とし、この溶液中に上記結合剤の固型分含量
が金属粉末100重量部に対して多くとも17.7重量
部（15重量％）を超えない割合、好ましくは３〜
15重量部（約３〜13重量％）の割合となるように
前記金属粉末を加えて混練し、これを一般に離型
紙を被せた型枠上に流し込み、溶剤を蒸発させた
のち、圧延ロールに通すなどして厚さ0.3〜５mm
程度のシート状その他の形状に成形することによ
り、得ることができる。また、上記結合剤と金属
粉末とを溶剤を用いることなく必要に応じて加熱
下または加熱真空下で上記同様の混合割合で混合
して加圧成形することにより、得ることもでき
る。 The metal powder molded body according to the present invention can be produced by preparing a solution of the above-mentioned organic binder in an appropriate organic solvent such as acetone, toluene, methyl ethyl ketone, etc., and in which the solid content of the above-mentioned binder is 100% by weight of the metal powder. at most 17.7 parts by weight (15% by weight), preferably from 3 to
The metal powder is added and kneaded in a proportion of 15 parts by weight (approximately 3 to 13% by weight), poured onto a formwork generally covered with release paper, and after the solvent has evaporated, it is placed on a rolling roll. Thickness 0.3 to 5 mm by passing it through etc.
It can be obtained by molding it into a sheet shape or other shape. It can also be obtained by mixing the above-mentioned binder and metal powder at the same mixing ratio as above under heating or under heating vacuum as necessary without using a solvent, and then press-molding the mixture.
この発明で用いる低収縮性金属粉末成形体は、
上記の如くして得られる金属粉末成形本体の表面
または内部に焼結時の面方向への収縮を抑制する
耐熱性補強材を設けたことをもつとも大きな特徴
とするものである。 The low shrinkage metal powder compact used in this invention is
Another major feature is that a heat-resistant reinforcing material is provided on the surface or inside of the metal powder molded body obtained as described above to suppress shrinkage in the surface direction during sintering.
一般に、前記金属粉末成形本体の焼結時の収縮
は、この本体を構成する前記結合剤の加熱分解
（通常250〜400℃以上）と共に開始する。したが
つて、上記収縮抑制用の耐熱性補強材としては少
なくとも上記結合剤の分解温度以上の耐熱性を有
するものが用いられる。 In general, shrinkage of the metal powder molded body during sintering begins with thermal decomposition (usually at 250 to 400° C. or higher) of the binder constituting the body. Therefore, as the heat-resistant reinforcing material for suppressing shrinkage, one having heat resistance at least equal to or higher than the decomposition temperature of the binder is used.
また、一般に金属母材面に金属被覆層を形成す
ることの意味は、母材自体に目的とする性質、た
とえば耐摩耗性などの性質を付与することにあ
り、この目的を達成するために用いられる金属粉
末はその焼結温度が高いものが選択される。すな
わち、一般に焼結開始温度が約700℃以上で、焼
結温度が約900℃以上のものが使用されるのが普
通である。 In general, the purpose of forming a metal coating layer on the surface of a metal base material is to impart desired properties to the base material itself, such as wear resistance, and it is used to achieve this purpose. The metal powder used is selected to have a high sintering temperature. That is, in general, those having a sintering start temperature of about 700°C or higher and a sintering temperature of about 900°C or higher are usually used.
したがつて、かかる高温で焼結開始または焼結
する金属粉末を用いてなる金属粉末成形本体の収
縮を抑制するための耐熱性補強材としては、その
溶融温度が前記結合剤の分解温度以上であること
はもちろんのこと上記本体の焼結温度近傍あるい
はそれ以上、実質的には焼結温度を起点にして−
50〜1000℃の範囲にあることが望まれる。これよ
り低い耐熱性を有するものでは充分な収縮抑制効
果が得られない。溶融温度の上限は、一般的に経
済的理由から決められる。 Therefore, as a heat-resistant reinforcing material for suppressing the shrinkage of a metal powder molded body made of a metal powder that starts sintering or sinters at such high temperatures, it is recommended to use a material whose melting temperature is higher than the decomposition temperature of the binder. It goes without saying that there is a temperature close to or above the sintering temperature of the main body, essentially starting from the sintering temperature.
It is desired that the temperature is in the range of 50 to 1000°C. If the heat resistance is lower than this, a sufficient shrinkage suppressing effect cannot be obtained. The upper limit of melting temperature is generally determined for economic reasons.
このような耐熱性を備えた補強材としては、
Fe、Cu、Ni、Ti、Ｗなどの金属またはこれらの
合金を材質とし、厚みが10〜100μｍ程度の箱ま
たは穿孔箱からなる、焼結時の収縮を抑制する物
理的強度を有するとともに、それ自体塑性変形性
を有するものが用いられる。 As a reinforcing material with such heat resistance,
It is made of metals such as Fe, Cu, Ni, Ti, W, or alloys thereof, and is made of a box or perforated box with a thickness of about 10 to 100 μm, and has physical strength to suppress shrinkage during sintering. A material having plastic deformability itself is used.
すなわち、耐熱性補強材として塑性変形性を有
するものを用いたときには、この発明の成形体を
その焼結に先立つて母材面に追随変形させるなど
の賦形を行う場合にこれら変形状態を上記補強材
の塑性変形性によつて良好に保持させることがで
き、その結果焼結前の取り扱い時または焼結中に
形崩れしたり、形崩れに起因する母材面との接着
不良を生じるおそれがないという利点が得られ
る。 That is, when a material having plastic deformability is used as a heat-resistant reinforcing material, when the molded article of the present invention is subjected to shaping such as deformation following the base material surface prior to sintering, the deformation state is The plastic deformability of the reinforcing material allows for good retention, and as a result, there is a risk that the reinforcing material may lose its shape during handling before sintering or during sintering, or may cause poor adhesion to the base metal surface due to deformation. The advantage is that there is no
この発明において上記構成の耐熱性補強材を金
属粉末成形本体の表面または内部に設ける手段は
特に限定されない。たとえば予め成形された前記
金属粉末成形本体の表面に前記結合剤に関して記
述したと同様の常温で感圧接着性を有する有機質
ポリマーなどからなる接着剤を用いてあるいは溶
着などの接着手段を用いて耐熱性補強材を接着す
る方法、金属粉末およびこの粉末を結合する有機
質結合剤を含む成形前の混練物を耐熱性補強材に
塗設および／または含浸させるなどの付着手段を
用いて金属粉末成形本体の成形と同時に補強材を
一体化させる方法、その他金属粉末成形本体と耐
熱性補強材とを重ね合わせて加熱加圧する加圧手
段によつて一体化させる方法などを採用すること
ができる。 In the present invention, the means for providing the heat-resistant reinforcing material having the above structure on the surface or inside of the metal powder molded body is not particularly limited. For example, a heat-resistant adhesive such as an organic polymer having pressure-sensitive adhesive properties at room temperature or a heat-resistant adhesive such as welding may be used on the surface of the pre-formed metal powder molded body, as described for the binder. A metal powder molded body is formed using an adhesion method such as applying and/or impregnating a heat-resistant reinforcing material with a kneaded material containing metal powder and an organic binder that binds the powder before molding to the heat-resistant reinforcing material. It is possible to adopt a method in which the reinforcing material is integrated at the same time as molding, or a method in which the metal powder molded main body and the heat-resistant reinforcing material are overlapped and integrated using a pressing means that heats and presses them.
なお、耐熱性補強材を金属粉末成形本体の表面
に設けるかあるいは内部に設けるか、また表面に
設ける場合でも一面側だけに設けるか両面側に設
けるかは、焼結方法や金属粉末成形本体の種類、
厚みその他用途目的などに応じて適宜決定すれば
よい。しかし、一般には成形本体の片面または内
部に設けるようにするのが望ましい。内部に設け
る場合の耐熱性補強材としては特に穿孔金属箔を
用いるのが好ましい。 Note that whether the heat-resistant reinforcing material is provided on the surface or inside the metal powder molded body, and even if it is provided on the surface, whether it is provided only on one side or on both sides, depends on the sintering method and the metal powder molded body. kinds,
It may be determined as appropriate depending on the thickness and other purposes. However, it is generally desirable to provide it on one side or inside the molded body. It is particularly preferable to use perforated metal foil as the heat-resistant reinforcing material when provided inside.
つぎに、このようにして得られるこの発明の低
収縮性金属粉末成形体を用いて金属母材面に金属
被覆層を形成する方法につき説明する。 Next, a method for forming a metal coating layer on the metal base material surface using the low-shrinkage metal powder compact of the present invention obtained in this manner will be explained.
この方法においては、まず上記成形体をこの成
形体を構成する金属粉末成形本体を介して金属母
材面に貼着する。ここで、金属粉末成形本体を介
しての意味は、片面に耐熱性補強材が設けられた
ものではこの補強材が外側、つまり成形本体が内
側となつてこの本体が母材面と接触するように貼
着することを意味するものである。 In this method, the molded body is first adhered to the metal base material surface via the metal powder molded body that constitutes the molded body. Here, the meaning of "through the metal powder molded body" means that if a heat-resistant reinforcing material is provided on one side, this reinforcing material is on the outside, that is, the molded body is on the inside, and this body is in contact with the base metal surface. It means to be attached to.
この貼着に際して、金属母材面が平坦である場
合はもちろんのこと凹部などの曲面を有する場合
でも、この曲面形状に沿つて上記成形体を追随変
形させることにより、この成形体を母材面に対し
て密着性良好に貼着させることができる。特に成
形体を構成する耐熱性補強材として塑性変形性を
有するものが用いられていることにより、上記変
形状態を良好に保持させることができるから、焼
結前の取扱い時または焼結中に形崩れしたり、形
崩れに起因する母材面との接着不良を生じるおそ
れは全くない。 At the time of this adhesion, even when the metal base metal surface is flat or has a curved surface such as a recess, the molded body is deformed along the shape of the curved surface so that the molded body can be attached to the base metal surface. It can be attached with good adhesion to. In particular, by using a material with plastic deformability as the heat-resistant reinforcing material constituting the compact, the above deformed state can be maintained well, so the shape can be shaped during handling before sintering or during sintering. There is no risk of collapse or poor adhesion to the base metal surface due to deformation.
上記の如き貼着は、金属母材面が平坦である場
合などでは、成形本体の表面の平滑性または弱粘
着性を利用して直接行うことができる。しかし、
母材面が傾斜していたり、焼結処理が振動状態下
などで行われたりする場合などでは、常温で感圧
接着性を有する有機質ポリマーを主剤とした接着
剤を用いて行うのが好ましい。 When the metal base material surface is flat, the above-described adhesion can be directly performed by utilizing the smoothness or weak adhesiveness of the surface of the molded body. but,
In cases where the base material surface is inclined or the sintering process is performed under vibration conditions, it is preferable to use an adhesive based on an organic polymer that has pressure-sensitive adhesive properties at room temperature.
特に、上記の有機質ポリマーが、前記結合剤に
ついで述べたのと同様の（メタ）アクリル酸アル
キルエステルの単独重合体、または（メタ）アク
リル酸アルキルエステルとこれと共重合可能な官
能性モノマーおよび／またはビニルエステルモノ
マーとの共重合体からなるものを使用し、この接
着剤を50μｍ以下の厚みで介在させて用いると、
焼結時の炉内の昇温に従つて、上記ポリマーが熱
分解重縮合反応をおこしてタールピツチ状の粘性
物を生成し、これが粉末成形体が焼結し始める温
度付近まで母材への接着固定能を維持するので好
都合である。 In particular, the above-mentioned organic polymer is a homopolymer of (meth)acrylic acid alkyl ester similar to the above-mentioned binder, or a (meth)acrylic acid alkyl ester and a functional monomer copolymerizable therewith. / or a copolymer with a vinyl ester monomer is used, and this adhesive is used with a thickness of 50 μm or less,
As the temperature rises in the furnace during sintering, the above polymer undergoes a thermal decomposition polycondensation reaction to produce a tar pitch-like viscous substance, which adheres to the base material until the powder compact starts to sinter. This is advantageous because it maintains fixation ability.
このようにして貼着したのち、金属粉末成形本
体の金属粉末の種類に応じた適宜の温度条件下に
一定速度で加熱昇温して焼結処理を行う。この処
理は、金属粉末の酸化劣化を防止するために、
N2、Arの如き不活性ガス雰囲気、H2の如き還元
性雰囲気、真空雰囲気などの非酸化性雰囲気下で
行われる。 After pasting in this manner, a sintering process is performed by heating and increasing the temperature at a constant rate under appropriate temperature conditions depending on the type of metal powder in the metal powder molded body. This treatment is used to prevent oxidative deterioration of metal powder.
It is carried out under a non-oxidizing atmosphere such as an inert gas atmosphere such as N 2 or Ar, a reducing atmosphere such as H 2 , or a vacuum atmosphere.
このように焼結処理することにより、金属母材
面に密度が高く母材面の耐摩耗性や耐腐食性など
の向上に寄与する金属被覆層が形成される。この
被覆層は縦横の面方向の長さが原形の10％以下、
好態として５％以下の実質的に焼結前の成形体と
同一または近似の大きさを有するものであり、焼
結処理中の面方向収縮が良好に抑えられているこ
とにより、母材面が凹部などを有する曲面形状で
ある場合でも、この母材面と金属被覆層との間に
空隙を生じることはない。すなわち、母材と金属
被覆層との密着性に非常にすぐれたものとなる。 By performing the sintering treatment in this manner, a metal coating layer is formed on the metal base material surface, which has a high density and contributes to improving the wear resistance, corrosion resistance, etc. of the base material surface. The length of this coating layer in the vertical and horizontal directions is 10% or less of the original shape.
Preferably, it has a size of 5% or less, which is substantially the same as or similar to that of the compact before sintering, and the shrinkage in the plane direction during the sintering process is well suppressed, so that the base material surface Even when the base metal surface has a curved shape with recesses or the like, no voids are created between the base metal surface and the metal coating layer. In other words, the adhesion between the base material and the metal coating layer is extremely excellent.
なお、上記焼結処理により形成された金属被覆
層の表面に残存する耐熱性補強材は、必要に応じ
て研磨などの手段により除去することができる。 Note that the heat-resistant reinforcing material remaining on the surface of the metal coating layer formed by the above-mentioned sintering process can be removed by means such as polishing, if necessary.
以上詳述したとおり、この発明の上記特定の低
収縮性金属粉末成形体を用いてこれを上述の如く
焼結処理することにより、工具、機械、電気、自
動車などの金属母材面に対し表面改質用の良質の
金属被覆層を密着性および寸法安定性良好にかつ
容易に形成できるものである。 As detailed above, by using the specific low-shrinkage metal powder compact of the present invention and sintering it as described above, the surface of the metal base material of tools, machines, electricity, automobiles, etc. A high-quality metal coating layer for modification can be easily formed with good adhesion and dimensional stability.
つぎに、この発明の実施例を記載してより具体
的に説明する。なお、以下に部とあるのは重量部
を意味する。 Next, examples of the present invention will be described in more detail. Note that parts below mean parts by weight.
実施例 １
粒度200メツシユ以下のSUS302（＃250）粉末
100部とポリビニルブチラール８部とにトルエン
80部を加えて湿式混練し、ロール圧延によつて、
厚さが1.5mmになるようにシート化して金属粉末
成形本体とした。Example 1 SUS302 (#250) powder with particle size of 200 mesh or less
Toluene to 100 parts and 8 parts of polyvinyl butyral
80 parts were added, wet kneaded, and rolled by roll.
It was made into a sheet with a thickness of 1.5 mm to form a metal powder molded body.
このシート状本体の両面に、２−エチルヘキシ
ルアクリレート93部、エチルアクリレート２部、
アクリル酸５部および酢酸エチル100部からなる
重合原料を共重合させてなる常温で感圧接着性を
有するアクリル系重合体の溶液を、乾燥後の厚み
が20μｍとなるように塗布乾燥し、20mm×20mmの
大きさに切断した。 93 parts of 2-ethylhexyl acrylate, 2 parts of ethyl acrylate,
A solution of an acrylic polymer that has pressure-sensitive adhesive properties at room temperature, which is obtained by copolymerizing a polymerization raw material consisting of 5 parts of acrylic acid and 100 parts of ethyl acetate, is applied and dried to a thickness of 20 μm after drying. It was cut into a size of 20 mm.
つぎに、この切断片の片面に、溶融温度が1530
℃で、厚みが50μｍのFe箔（大きさ20mm×20mm）
を貼り合せて低収縮性金属粉末成形体とした。こ
の成形体を上記Fe箔とは反対側の面を内側にし
て曲率半径が100mmの金属母材面に貼着し、真空
雰囲気下で1350℃で焼結して金属被覆層を形成し
た。 Next, one side of this cut piece is coated with a melting temperature of 1530.
℃, Fe foil with a thickness of 50 μm (size 20 mm × 20 mm)
were bonded together to form a low-shrinkage metal powder compact. This molded body was adhered to a metal base material surface having a radius of curvature of 100 mm with the surface opposite to the Fe foil inside, and was sintered at 1350° C. in a vacuum atmosphere to form a metal coating layer.
この金属被覆層の両方向への収縮率は前記切断
片原寸の約５％であつた。なお、Fe箔を貼り合
わせていない前記切断片のみを上記同様に焼結し
たときの面方向への収縮率は約15％であつた。 The contraction rate of this metal coating layer in both directions was about 5% of the original size of the cut piece. Incidentally, when only the cut pieces to which Fe foil was not bonded were sintered in the same manner as above, the shrinkage rate in the plane direction was about 15%.
実施例 ２
Mo10.5重量％、Cr2.5重量％、P2.4重量％、
C3.5重量％、残部Feの組成を有し、粒度が150メ
ツシユ以下の三元共晶合金粉末48.5重量％と、粒
度150メツシユ以下のSUS410粉末48.5重量％と、
アクリル酸エステル−アクリル酸共重合体からな
る常温で感圧接着性を有するアクリル系共重合体
３重量％とに、トルエンを上記アクリル系重合体
100部に対して200部加えて混練し、ロール圧延し
て、密度4.8ｇ／cm3、厚み1.5mmのシート状の金属
粉末成形本体とした。Example 2 Mo10.5% by weight, Cr2.5% by weight, P2.4% by weight,
48.5% by weight of a ternary eutectic alloy powder having a composition of 3.5% by weight of C and the balance being Fe, with a particle size of 150 mesh or less, and 48.5% by weight of SUS410 powder with a particle size of 150 mesh or less,
Add toluene to 3% by weight of an acrylic copolymer consisting of an acrylic acid ester-acrylic acid copolymer and having pressure-sensitive adhesive properties at room temperature.
200 parts to 100 parts were added, kneaded, and rolled to form a sheet-shaped metal powder molded body having a density of 4.8 g/cm 3 and a thickness of 1.5 mm.
このシート状本体を20mm×20mmの大きさに切断
したのち、切断片の片面に溶融温度が1455℃、厚
みが40μｍの上記切断片と同じ大きさのニツケル
箔を加圧により貼り合せて低収縮性金属粉末成形
体とした。この成形体を上記ニツケル箔とは反対
側の面を内側にして曲率半径が100mmの金属母材
面に貼着し、H2ガス雰囲気下で1090℃で焼結し
て金属被覆層を形成した。 After cutting this sheet-like body into a size of 20 mm x 20 mm, a nickel foil of the same size as the cut piece with a melting temperature of 1455°C and a thickness of 40 μm is attached to one side of the cut piece by pressure to reduce shrinkage. It was made into a metal powder compact. This molded body was attached to a metal base material surface with a radius of curvature of 100 mm with the surface opposite to the nickel foil inside, and was sintered at 1090°C in an H 2 gas atmosphere to form a metal coating layer. .
この金属被覆層の面方向への収縮率は前記切断
片原寸の約２％であつた。なお、ニツケル箔を貼
り合せていない切断片のみを上記同様に焼結した
ときの収縮率は約17％であつた。 The shrinkage rate of this metal coating layer in the plane direction was about 2% of the original size of the cut piece. Note that when only the cut pieces to which the nickel foil was not bonded were sintered in the same manner as above, the shrinkage rate was about 17%.
実施例 ３
実施例２で使用したものと同一の三元共晶合金
粉末47.5重量％と粒度150メツシユ以下のSUS410
粉末47.5重量％と実施例２で使用したものと同一
の常温で感圧接着性を有するアクリル系重合体５
重量％とを、上記重合体100部に対して200部のト
ルエンを用いて混練し、ロール圧延して厚み1.2
mm、密度4.35ｇ／cm3のシート状の金属粉末成形本
体とした。Example 3 SUS410 with 47.5% by weight of the same ternary eutectic alloy powder used in Example 2 and a particle size of 150 mesh or less
47.5% by weight of powder and the same acrylic polymer 5 that has pressure-sensitive adhesive properties at room temperature as used in Example 2
% by weight using 200 parts of toluene per 100 parts of the above polymer, and rolled to a thickness of 1.2
A sheet-shaped metal powder molded body with a density of 4.35 g/cm 3 and a density of 4.35 g/cm 3 was obtained.
このシート状本体を20mm×20mmの大きさに切断
したのち、切断片の片面に10μｍ厚の上記同様の
常温で感圧接着性を有するアクリル系重合体から
なる接着剤を介して融点1455℃、厚み40μｍで穿
孔率80％の上記切断片と同じ大きさのNi箔を貼
り合せてこの発明の低収縮性金属粉末成形体とし
た。 This sheet-like main body was cut into a size of 20 mm x 20 mm, and then a 10 μm thick adhesive made of an acrylic polymer with a melting point of 1455°C and a pressure-sensitive adhesive property at room temperature was attached to one side of the cut piece. A Ni foil of the same size as the above-mentioned cut piece having a thickness of 40 μm and a perforation rate of 80% was laminated to form a low-shrinkage metal powder compact of the present invention.
つぎに、この成形体のNi箔とは反対側の面に
上記同様の常温で感圧接着性を有するアクリル系
重合体からなる接着剤を20μｍ厚に塗布したの
ち、この塗布面を内側にして曲率半径が100mmの
金属母材面に貼着し、真空雰囲気下で1090℃で焼
結して金属被覆層を形成した。 Next, a 20 μm thick adhesive made of an acrylic polymer that has pressure-sensitive adhesive properties at room temperature was applied to the surface of this molded body opposite to the Ni foil, and then the coated surface was turned inside. It was attached to a metal base material surface with a radius of curvature of 100 mm and sintered at 1090°C in a vacuum atmosphere to form a metal coating layer.
この金属被覆層の面方向への収縮率は前記切断
片原寸の約２％であつた。なお、Ni箔を貼り合
せていない前記切断片を上記同様にして金属母材
面に貼着して焼結させたときの収縮率は約20％で
あつた。 The shrinkage rate of this metal coating layer in the plane direction was about 2% of the original size of the cut piece. Note that when the cut piece to which the Ni foil was not attached was attached to the metal base material surface and sintered in the same manner as described above, the shrinkage rate was about 20%.
実施例 ４
ブチルアクリレート98部、ヒドロキシエチルア
クリレート２部および酢酸エチル100部からなる
重合原料を共重合させてなる重量平均分子量45万
の常温で感圧接着性を有するアクリル系重合体の
溶液に、その固型分100部に対してレゾール系フ
エノール樹脂を30部添加混合して、ガラス転移温
度が−56℃で、25℃での弾性率が1.4Kg／cm2の結
合剤溶液を得た。Example 4 A solution of an acrylic polymer having a weight average molecular weight of 450,000 and having pressure-sensitive adhesive properties at room temperature, which is obtained by copolymerizing polymerization raw materials consisting of 98 parts of butyl acrylate, 2 parts of hydroxyethyl acrylate, and 100 parts of ethyl acetate, 30 parts of resol type phenolic resin was added and mixed with respect to 100 parts of the solid content to obtain a binder solution having a glass transition temperature of -56°C and an elastic modulus of 1.4 Kg/cm 2 at 25°C.
この結合剤溶液の固型分６部に、還元鉄粉
（＃250）100部を添加して混練し、ロール圧延に
よつて厚さ1.8mmとなるようにシート化して金属
粉末成形本体とした。 100 parts of reduced iron powder (#250) was added to 6 parts of the solid content of this binder solution, kneaded, and rolled into a sheet with a thickness of 1.8 mm to form a metal powder molded body. .
このシート状本体を20mm×20mmの大きさに切断
し、この切断片の片面に、溶融温度が1672℃、厚
みが30μｍでかつ穿孔率が20％である上記切断片
と同じ大きさのTi製穿孔箔を加圧により貼り合
せて低収縮性金属粉末成形体とした。 This sheet-like main body is cut into a size of 20 mm x 20 mm, and one side of this cut piece is made of Ti with the same size as the above cut piece with a melting temperature of 1672 ° C, a thickness of 30 μm, and a perforation rate of 20%. The perforated foils were bonded together under pressure to form a low-shrinkage metal powder compact.
この成形体を、上記穿孔箔とは反対側の面に上
記同様の常温で感圧接着性を有するアクリル系重
合体からなる接着剤を20μｍ厚に塗布したのち、
この塗布面を内側にして曲率半径が100mmの金属
母材面に貼着し、H2ガス雰囲気下で1400℃で焼
結して金属被覆層を形成した。 After applying an adhesive made of an acrylic polymer having pressure-sensitive adhesive properties at room temperature to a thickness of 20 μm on the surface of this molded body opposite to the perforated foil,
This coated surface was attached to a metal base material surface with a radius of curvature of 100 mm, and sintered at 1400° C. in an H 2 gas atmosphere to form a metal coating layer.
この金属被覆層の面方向への収縮率は前記切断
片原寸の約９％であつた。なお、穿孔箔を貼り合
せていない前記切断片のみを上記同様に焼結した
ときの収縮率は22％であつた。 The shrinkage rate of this metal coating layer in the plane direction was about 9% of the original size of the cut piece. Note that when only the cut pieces to which no perforated foil was attached were sintered in the same manner as above, the shrinkage rate was 22%.
Claims (1)
合する有機質結合剤を含む金属粉末成形本体とこ
の本体の表面または内部に設けられた焼結時の面
方向収縮を抑制する塑性変形性の金属箔または穿
孔金属箔よりなる耐熱性補強材とからなる低収縮
性金属粉末成形体を、上記本体面を介して貼着し
たのち、非酸化性雰囲気下で加熱昇温して上記本
体を焼結することにより、金属母材面に金属被覆
層を形成することを特徴とする金属被覆層の形成
方法。 ２ 金属粉末が合金粉末である特許請求の範囲第
１項記載の金属被覆層の形成方法。 ３ 有機質結合剤が常温で感圧接着性を有する有
機質ポリマーを主剤として含む特許請求の範囲第
１項または第２項記載の金属被覆層の形成方法。 ４ 常温で感圧接着性を有する有機質ポリマーが
（メタ）アクリル酸アルキルエステルの単独重合
体または（メタ）アクリル酸アルキルエステルと
これと共重合可能な官能性モノマーおよび／また
はビニルエステルモノマーとの共重合体からなる
特許請求の範囲第３項記載の金属被覆層の形成方
法。 ５ 金属粉末成形本体中の有機質結合剤量が１〜
15重量％である特許請求の範囲第１〜４項のいず
れかに記載の金属被覆層の形成方法。 ６ 耐熱性補強材の溶融温度が金属粉末成形本体
の焼結温度近傍あるいはそれ以上である特許請求
の範囲第１〜５項のいずれかに記載の金属被覆層
の形成方法。 ７ 低収縮性金属粉末成形体を金属母材面に貼着
するにあたり常温で感圧接着性を有する有機質ポ
リマーを主剤とした接着剤を使用する特許請求の
範囲第１〜６項のいずれかに記載の金属被覆層の
形成方法。 ８ 接着剤を構成する常温で感圧接着性を有する
有機質ポリマーが（メタ）アクリル酸アルキルエ
ステルの単独重合体または（メタ）アクリル酸ア
ルキルエステルとこれと共重合可能な官能性モノ
マーおよび／またはビニルエステルモノマーとの
共重合体からなる特許請求の範囲第７項記載の金
属被覆層の形成方法。[Claims] 1. A metal powder molded body containing metal powder and an organic binder for bonding the powder on the metal base material surface, and a metal powder molded body provided on the surface or inside of this body to suppress in-plane shrinkage during sintering. A low-shrinkage metal powder molded body made of a heat-resistant reinforcing material made of plastically deformable metal foil or perforated metal foil is attached via the main body surface, and then heated to raise the temperature in a non-oxidizing atmosphere. A method for forming a metal coating layer, comprising: forming a metal coating layer on a metal base material surface by sintering the main body. 2. The method for forming a metal coating layer according to claim 1, wherein the metal powder is an alloy powder. 3. The method for forming a metal coating layer according to claim 1 or 2, wherein the organic binder contains as a main ingredient an organic polymer having pressure-sensitive adhesive properties at room temperature. 4 The organic polymer having pressure-sensitive adhesive properties at room temperature is a homopolymer of an alkyl (meth)acrylate ester or a copolymer of an alkyl (meth)acrylate and a functional monomer and/or a vinyl ester monomer copolymerizable therewith. A method for forming a metal coating layer according to claim 3, which is made of a polymer. 5 The amount of organic binder in the metal powder molded body is 1~
The method for forming a metal coating layer according to any one of claims 1 to 4, wherein the amount is 15% by weight. 6. The method for forming a metal coating layer according to any one of claims 1 to 5, wherein the melting temperature of the heat-resistant reinforcing material is close to or higher than the sintering temperature of the metal powder molded body. 7. Any one of claims 1 to 6 in which an adhesive based on an organic polymer having pressure-sensitive adhesive properties at room temperature is used to adhere the low-shrinkage metal powder compact to the metal base material surface. The method for forming the metal coating layer described above. 8 The organic polymer having pressure-sensitive adhesive properties at room temperature constituting the adhesive is a homopolymer of (meth)acrylic acid alkyl ester or (meth)acrylic acid alkyl ester and a functional monomer copolymerizable therewith and/or vinyl. 8. The method for forming a metal coating layer according to claim 7, which comprises a copolymer with an ester monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8691984A JPS60230910A (en) | 1984-04-28 | 1984-04-28 | Metallic powder molding having low shrinkability and formation of metallic coating layer using said molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8691984A JPS60230910A (en) | 1984-04-28 | 1984-04-28 | Metallic powder molding having low shrinkability and formation of metallic coating layer using said molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60230910A JPS60230910A (en) | 1985-11-16 |
| JPH0211646B2 true JPH0211646B2 (en) | 1990-03-15 |
Family
ID=13900261
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8691984A Granted JPS60230910A (en) | 1984-04-28 | 1984-04-28 | Metallic powder molding having low shrinkability and formation of metallic coating layer using said molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60230910A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS613806A (en) * | 1984-06-19 | 1986-01-09 | Honda Motor Co Ltd | Raw material sheet for sintered metallic body and its production |
| JPS613804A (en) * | 1984-06-19 | 1986-01-09 | Honda Motor Co Ltd | Raw material sheet for sintered metallic body and its production |
| CN111085688B (en) * | 2019-12-04 | 2021-08-13 | 西安交通大学 | Tungsten/silicon nitride/tungsten symmetrical layered gradient composite material and rapid preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4917390A (en) * | 1972-06-12 | 1974-02-15 | ||
| JPS54112706A (en) * | 1978-02-24 | 1979-09-03 | Fujikoshi Kk | Production of liquid phase sintered alloy |
| JPS54132412A (en) * | 1978-03-31 | 1979-10-15 | Fujikoshi Kk | Production of sintered body for brazing use |
| JPS5519283A (en) * | 1978-07-24 | 1980-02-09 | Merck & Co Inc | Alphaaethynylamino acid and ester |
| JPS605807A (en) * | 1983-06-24 | 1985-01-12 | Sumitomo Metal Ind Ltd | Sintering method of metallic powder molding |
-
1984
- 1984-04-28 JP JP8691984A patent/JPS60230910A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4917390A (en) * | 1972-06-12 | 1974-02-15 | ||
| JPS54112706A (en) * | 1978-02-24 | 1979-09-03 | Fujikoshi Kk | Production of liquid phase sintered alloy |
| JPS54132412A (en) * | 1978-03-31 | 1979-10-15 | Fujikoshi Kk | Production of sintered body for brazing use |
| JPS5519283A (en) * | 1978-07-24 | 1980-02-09 | Merck & Co Inc | Alphaaethynylamino acid and ester |
| JPS605807A (en) * | 1983-06-24 | 1985-01-12 | Sumitomo Metal Ind Ltd | Sintering method of metallic powder molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60230910A (en) | 1985-11-16 |
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