JPH0379402B2 - - Google Patents
Info
- Publication number
- JPH0379402B2 JPH0379402B2 JP59133852A JP13385284A JPH0379402B2 JP H0379402 B2 JPH0379402 B2 JP H0379402B2 JP 59133852 A JP59133852 A JP 59133852A JP 13385284 A JP13385284 A JP 13385284A JP H0379402 B2 JPH0379402 B2 JP H0379402B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- metal
- dispersion
- alloy
- alloys
- 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
- 239000000843 powder Substances 0.000 claims description 79
- 229910052751 metal Inorganic materials 0.000 claims description 48
- 239000002184 metal Substances 0.000 claims description 48
- 150000002736 metal compounds Chemical class 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 239000000956 alloy Substances 0.000 claims description 27
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 20
- 238000010298 pulverizing process Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000011247 coating layer Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 8
- 238000009703 powder rolling Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000010419 fine particle Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 3
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 3
- 229910001080 W alloy Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000000788 chromium alloy Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 239000002245 particle Substances 0.000 description 26
- 229910052786 argon Inorganic materials 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 description 11
- 150000004692 metal hydroxides Chemical class 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000009864 tensile test Methods 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000013522 chelant Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 for example Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000003779 heat-resistant material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017767 Cu—Al Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NREVZTYRXVBFAQ-UHFFFAOYSA-N propan-2-ol;yttrium Chemical compound [Y].CC(C)O.CC(C)O.CC(C)O NREVZTYRXVBFAQ-UHFFFAOYSA-N 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000004720 acetoacetic acids Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010273 cold forging Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- GONBZNBMLOZYAM-UHFFFAOYSA-K yttrium(3+);triformate Chemical compound [Y+3].[O-]C=O.[O-]C=O.[O-]C=O GONBZNBMLOZYAM-UHFFFAOYSA-K 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、分散強化型合金用粉末の製造方法に
関するものであり、より詳しくは引張強度、延
性、硬度、靭性、耐熱性、電気的特性及び耐中性
子照射性に優れた分散強化型合金用を得るための
粉末の製造方法に関するものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing powder for dispersion-strengthened alloys, and more specifically relates to tensile strength, ductility, hardness, toughness, heat resistance, and electrical properties. The present invention also relates to a method for producing powder for obtaining dispersion-strengthened alloys with excellent neutron irradiation resistance.
従来、分散強化型合金用粉末を製造する方法と
しては、基地金属となる金属粉末と酸化物、炭化
物、窒化物又は炭窒化物等からなる硬質粒子とを
混合し、これをメカニカルアロイング法により粉
砕合金化して合金粉末を得るという方法が行わ
れ、既に一部で実用化されている。
Conventionally, the method for producing powder for dispersion-strengthened alloys is to mix metal powder as a base metal with hard particles made of oxides, carbides, nitrides, carbonitrides, etc., and then to process the mixture using a mechanical alloying method. A method of obtaining alloy powder by pulverization and alloying has been carried out, and has already been put into practical use in some areas.
前記従来法においては、基地金属に硬質粒子を
均一に分散させるには長時間の粉砕を必要とする
という問題がある。また、この方法による場合、
硬質粒子そのものは粉砕工程で粉砕されることが
少ないので、最初から微細な硬質粒子を使用する
必要があるが、このような微細な硬質粒子は大量
生産が困難なために非常に高価なものになるとい
う問題もある。
The above-mentioned conventional method has a problem in that a long period of pulverization is required to uniformly disperse the hard particles in the base metal. Also, if you use this method,
Since the hard particles themselves are rarely crushed during the crushing process, it is necessary to use fine hard particles from the beginning, but such fine hard particles are difficult to mass produce and are therefore very expensive. There is also the issue of becoming.
本発明者は、前記従来法の欠点を除去、改善し
た新たな分散強化型合金用粉末の製造方法を完成
したのである。 The present inventor has completed a new method for producing powder for dispersion-strengthened alloys that eliminates and improves the drawbacks of the conventional method.
本発明に係る分散強化型合金用粉末の製造方法
は、金属化合物の加水分解工程、金属化合物と金
属粉末との混合による被覆工程、被覆層を非晶質
若しくは微細粒子の金属酸化物とするための熱処
理工程、機械粉砕混合法若しくは粉末圧延粉砕混
合法による被覆金属粉末の粉砕工程の全ての工程
を含むことを特徴とするものである。
The method for producing powder for dispersion-strengthened alloys according to the present invention includes a hydrolysis step of a metal compound, a coating step by mixing a metal compound and a metal powder, and a step of forming a coating layer of an amorphous or fine-particle metal oxide. The present invention is characterized in that it includes all the steps of heat treatment, and pulverization of the coated metal powder by a mechanical pulverization and mixing method or a powder rolling and pulverization and mixing method.
先ず、金属化合物の加水分解工程について説明
する。この加水分解工程を経ることにより、金属
化合物が金属水酸化物若しくは金属水和物に変化
させられる。この加水分解工程は、金属化合物と
金属粉末との混合による被覆工程の前に行つて
も、或いは、後に行つてもよい。 First, the process of hydrolyzing a metal compound will be explained. Through this hydrolysis step, the metal compound is changed into a metal hydroxide or a metal hydrate. This hydrolysis step may be performed before or after the coating step by mixing the metal compound and the metal powder.
加熱等により金属化合物が加水分解された場
合、金属化合物がアルコキシド等のときには遊離
炭素が残らないが、有機金属化合物等のときには
遊離炭素が残ることがある。これを除去する必要
がある場合には、水分を含む空気中または水分を
含むアルゴン中、窒素中、酸素中、水素中で加水
分解処理をして、金属化合物を金属水酸化物若し
くは金属水和物に変化させた後、さらに、加熱処
理を行えばよい。なお、この熱処理温度は、約
100℃から融点近くまでの温度で行うのが好まし
い。 When a metal compound is hydrolyzed by heating or the like, no free carbon remains if the metal compound is an alkoxide or the like, but free carbon may remain if the metal compound is an organometallic compound or the like. If it is necessary to remove this, hydrolysis treatment is performed in air containing moisture, argon containing moisture, nitrogen, oxygen, or hydrogen to convert the metal compound into metal hydroxide or metal hydrate. After changing into a product, heat treatment may be further performed. Note that this heat treatment temperature is approximately
Preferably, the reaction is carried out at a temperature from 100°C to close to the melting point.
金属化合物の中には、室温程度の低い温度で、
急速に加水分解により金属水酸化物若しくは金属
水和物に変化するものもある。このような物質
は、化合物の粒子が大きく成長し、分散強化粒子
も粗大化するので、理想的な強度は得られない。
そのため、被覆助剤等を添加することにより、反
応速度を遅くして金属粉末表面に対する密着性を
よくし、徐々に反応を進行させる必要がある。 Some metal compounds, at temperatures as low as room temperature,
Some rapidly transform into metal hydroxides or metal hydrates by hydrolysis. In such a substance, the compound particles grow large and the dispersion-strengthening particles also become coarse, so that ideal strength cannot be obtained.
Therefore, it is necessary to slow down the reaction rate and improve adhesion to the surface of the metal powder by adding a coating aid or the like, so that the reaction progresses gradually.
また、例えば、一部のアセチルアセトナート化
合物のように反応の進行が遅い金属化合物の場合
には、遊離炭素が残るが、この遊離炭素の残留に
より特に焼結性が悪くなるときには、湿水素雰囲
気中等での加熱により前記金属化合物を加水分解
し、金属水酸化物若しくは金属水和物に変化させ
る必要がある。その際、加熱速度が速いか又は加
熱温度が高い場合には、粗大化した酸化物粒子と
なるため、比較的低い温度で徐々に加熱を行う必
要がある。この場合の加熱温度は、100℃から700
℃程度が好ましい。銅、ニツケル、銀等の金属粉
末を加熱焼結する場合には、遊離炭素が含まれて
いると焼結性が特に悪くなる為、遊離炭素を充分
に除去してから金属水酸化物若しくは金属水和物
にする必要がある。 In addition, for example, in the case of metal compounds whose reaction progresses slowly, such as some acetylacetonate compounds, free carbon remains, and when the sinterability is particularly poor due to the residual free carbon, it is necessary to use a wet hydrogen atmosphere. It is necessary to hydrolyze the metal compound by heating at a moderate temperature and convert it into a metal hydroxide or metal hydrate. At this time, if the heating rate is fast or the heating temperature is high, the oxide particles will become coarse, so it is necessary to gradually heat the particles at a relatively low temperature. The heating temperature in this case is from 100℃ to 700℃.
The temperature is preferably about ℃. When heating and sintering metal powders such as copper, nickel, and silver, the sinterability will be particularly poor if free carbon is included, so remove the free carbon sufficiently before sintering metal hydroxide or metal powder. Needs to be hydrated.
次に、金属化合物と金属粉末との混合による被
覆工程について説明する。この工程を経ることに
より、金属粉末の表面に金属化合物の被覆層が形
成される。被覆工程を前記加水分解工程を経る前
に行うときには、被覆層を構成する金属化合物
は、化学変化を起こす前のものであるが、被覆工
程を前記加水分解工程を経た後に行うときには、
被覆層を構成する金属化合物は、金属水酸化物若
しくは金属水和物に変化したものとなつている。 Next, a coating process by mixing a metal compound and metal powder will be described. Through this step, a coating layer of a metal compound is formed on the surface of the metal powder. When the coating step is performed before the hydrolysis step, the metal compound constituting the coating layer has not undergone any chemical change, but when the coating step is performed after the hydrolysis step,
The metal compound constituting the coating layer has been transformed into a metal hydroxide or a metal hydrate.
被覆層を形成するに際し、加水分解前の金属化
合物が常温で液状の有機金属化合物である場合は
そのまま適用し、常温で固体状若しくは粉末状の
有機金属化合物である場合は加熱溶融して適用す
る。 When forming the coating layer, if the metal compound before hydrolysis is an organometallic compound that is liquid at room temperature, it is applied as is; if it is a solid or powdery organometallic compound at room temperature, it is applied after being heated and melted. .
上記何れの場合も、溶媒に有機金属化合物を溶
解させるか、或いは、被覆助剤を添加した溶媒に
有機金属化合物を溶解させておいてもよい。この
ような溶媒としては、例えばアルコール類、ベン
ゼン、アセトン、エーテルなどの有機溶媒を使用
する。被覆助剤としては、アセト酢酸類、グリコ
ール類、エチレングリコール類などが好ましい。 In any of the above cases, the organometallic compound may be dissolved in a solvent, or the organometallic compound may be dissolved in a solvent to which a coating aid has been added. As such a solvent, for example, organic solvents such as alcohols, benzene, acetone, and ether are used. Preferred coating aids include acetoacetic acids, glycols, and ethylene glycols.
一方、加水分解前の金属化合物が無機金属化合
物である場合には、加水分解によつて無機金属化
合物をゲル状又はゾル状にした後、水又は溶媒に
溶かして金属粉末表面に被覆する。 On the other hand, when the metal compound before hydrolysis is an inorganic metal compound, the inorganic metal compound is made into a gel or sol by hydrolysis, and then dissolved in water or a solvent and coated on the surface of the metal powder.
前記被覆工程を経ることにより得られた被覆金
属粉末の被覆層は自然乾燥するものもあるが、金
属化合物の種類や溶媒の存在などに起因して乾燥
処理工程を経る必要がある場合もある。この場合
は、次工程の熱処理工程の前に乾燥工程が行われ
る。 The coating layer of the coated metal powder obtained through the coating step may be naturally dried, but it may also be necessary to undergo a drying process depending on the type of metal compound, the presence of a solvent, etc. In this case, a drying step is performed before the next heat treatment step.
次に、被覆層を非晶質若しくは微細粒子の金属
酸化物とするための熱処理工程について説明す
る。被覆層を熱処理することにより、該被覆層
は、非晶質若しくは微細粒子の金属酸化物に変化
する。この熱処理温度としては、各金属粉末によ
り異なるが、200℃以上1000℃以下が好ましい。
この熱処理の雰囲気は、真空中、アルゴン中、水
素雰囲気中或いは窒素雰囲気中でもよい。なお、
被覆層が金属塩化物又は酸性の金属塩の場合に
は、アンモニアガス雰囲気等のアルカリ雰囲気中
で処理を行う。 Next, a heat treatment step for forming the coating layer into an amorphous or fine-grained metal oxide will be described. By heat-treating the coating layer, the coating layer changes into an amorphous or fine-grained metal oxide. The heat treatment temperature varies depending on each metal powder, but is preferably 200°C or more and 1000°C or less.
The atmosphere for this heat treatment may be vacuum, argon, hydrogen atmosphere, or nitrogen atmosphere. In addition,
When the coating layer is a metal chloride or an acidic metal salt, the treatment is performed in an alkaline atmosphere such as an ammonia gas atmosphere.
次に、機械粉砕混合法若しくは粉末圧延粉砕混
合法による被覆金属粉末の粉砕工程について説明
する。この粉砕工程を経ることにより、被覆金属
粉末は粉砕され、被覆層を構成する金属が金属粉
末内部に均一に分散させられる。粉砕工程は、湿
式又は乾式ボールミル、コロイダルミル、ブレン
ダー、振動ミルやアトライター等の一以上を用い
て行われる。 Next, the process of pulverizing the coated metal powder using the mechanical pulverization mixing method or the powder rolling pulverization mixing method will be described. Through this pulverization process, the coated metal powder is pulverized, and the metal constituting the coating layer is uniformly dispersed inside the metal powder. The grinding process is performed using one or more of a wet or dry ball mill, a colloidal mill, a blender, a vibratory mill, an attritor, and the like.
なお、粉末圧延粉砕混合法により被覆金属粉末
を粉砕する場合は、被覆金属粉末を少量ずつ断続
的に供給し、強圧延により粉末を強薄片化し、機
械的に被覆層を構成する金属を金属粉末粒内に強
制挿入させる。一回の粉末強制圧延粉砕混合で所
期の目的が達成されない場合は、複数回繰り返
す。その後、さらに振動ミル、アトライター等に
より粉砕微粉化を行うこともできる。 In addition, when pulverizing the coated metal powder by the powder rolling pulverization mixing method, the coated metal powder is intermittently fed in small amounts, the powder is made into strong flakes by strong rolling, and the metal constituting the coating layer is mechanically transformed into metal powder. Forcibly insert it into the grain. If the intended purpose is not achieved by one time of forced rolling, pulverization and mixing of the powder, repeat the process multiple times. Thereafter, further pulverization may be performed using a vibrating mill, an attritor, or the like.
本発明において使用する金属化合物は、無機金
属化合物若しくは有機金属化合物であり、この金
属化合物に含まれる金属は、AI、Ti、Cu、Fe、
Mo、Ｗ、Au、Ag、Si、Nb、Ｖ、Zr、Ta、Ｙ、
Cr、Ｂ及び希土類元素の中から選ばれる一種以
上である。 The metal compound used in the present invention is an inorganic metal compound or an organic metal compound, and the metals contained in this metal compound include AI, Ti, Cu, Fe,
Mo, W, Au, Ag, Si, Nb, V, Zr, Ta, Y,
One or more selected from Cr, B, and rare earth elements.
これらの金属を含む金属化合物は、前記した通
り、加水分解によつて金属水酸化物若しくは金属
水和物とされるが、加水分解前の金属化合物とし
ては、金属塩化物例えば塩化アルミニウム、塩化
ジルコニウム、塩化バナジウム、塩化ニオブ、塩
化ケイ素、塩化イツトリウムや塩化セリウムなど
のR.E（希土類元素）塩素化合物、金属の錯化合
物例えばアセチルアセトナトキレート、トリメチ
レンジアミンキレート、プロピレンジアミンキレ
ート等のキレート化合物、アルコキシド例えばメ
トキシド、エトキシド、プロポキシド、ブトキシ
ド、フエノキシド等、金属塩例えばナフテン酸金
属塩、オクチル酸金属塩、カプリル酸金属塩、カ
ルボン酸金属塩、又は有機金属脂肪酸等である。 As mentioned above, metal compounds containing these metals are converted into metal hydroxides or metal hydrates by hydrolysis, but metal compounds before hydrolysis include metal chlorides such as aluminum chloride and zirconium chloride. , RE (rare earth element) chlorine compounds such as vanadium chloride, niobium chloride, silicon chloride, yttrium chloride and cerium chloride, metal complex compounds such as chelate compounds such as acetylacetonate chelate, trimethylene diamine chelate, propylene diamine chelate, alkoxides such as Methoxide, ethoxide, propoxide, butoxide, phenoxide, etc., metal salts such as naphthenic acid metal salts, octylic acid metal salts, caprylic acid metal salts, carboxylic acid metal salts, or organometallic fatty acids.
本発明に使用する金属粉末は、銅、銅合金、ニ
ツケル、ニツケル合金、銀、銀合金、クロム、ク
ロム合金、鉄、鉄合金、アルミニウム、アルミニ
ウム合金、マグネシウム、マグネシウム合金、チ
タン、チタン合金、モリブデン、モリブデン合
金、タングステン及びタングステン合金の中から
選ばれる一種以上である。銅、ニツケル、銀、ク
ロム、鉄、アルミニウム、マグネシウム、チタ
ン、モリブデン及びタングステンの各合金には、
主成分以外に鉄、クロム、ニツケル、チタン、モ
リブデン、ニオブ、バナジウム、コバルト、銅、
アルミニウム、マグネシウム、ジルコニウム、
銀、鉛、タンタル等を合金元素として含むか、又
は、粉末として加えて合金化を行うものとする。 The metal powder used in the present invention includes copper, copper alloy, nickel, nickel alloy, silver, silver alloy, chromium, chromium alloy, iron, iron alloy, aluminum, aluminum alloy, magnesium, magnesium alloy, titanium, titanium alloy, molybdenum. , molybdenum alloy, tungsten, and tungsten alloy. Copper, nickel, silver, chromium, iron, aluminum, magnesium, titanium, molybdenum and tungsten alloys include
In addition to the main ingredients, iron, chromium, nickel, titanium, molybdenum, niobium, vanadium, cobalt, copper,
aluminum, magnesium, zirconium,
Silver, lead, tantalum, etc. shall be included as alloying elements, or alloyed by adding them as powder.
なお、金属化合物の添加量は、その化合物中に
含まれる金属の量、目的とする合金組成により決
定されるが、金属化合物として金属粉末の50重量
％以下が好適である。それ以上加えてもよいが、
均一微細に分散させることが困難となるばかりで
なく、基地となる金属の有する固有の機械的或い
は化学的特性が希薄となり過ぎるので不利なこと
が多い。 The amount of the metal compound added is determined by the amount of metal contained in the compound and the intended alloy composition, but it is preferable that the amount of the metal compound is 50% by weight or less of the metal powder. You can add more, but
Not only is it difficult to uniformly and finely disperse the metal, but it is often disadvantageous because the inherent mechanical or chemical properties of the base metal are too diluted.
本発明に係る分散強化型合金用粉末の製造方法
は、以上の構成よりなるので、次のような効果を
奏することができる。
Since the method for manufacturing a dispersion-strengthened alloy powder according to the present invention has the above-described configuration, it can achieve the following effects.
即ち、本発明に係る分散強化型合金用粉末の製
造方法においては、加水分解工程を経ることによ
つて、被覆金属粉末の被覆層が金属水酸化物若し
くは金属水和物に変化し、熱処理工程を経ること
によつて、前記金属水酸化物若しくは金属水和物
が均一・微細な金属酸化物に変化しているので、
粉砕工程を得た分散強化型合金用粉末は、金属酸
化物の分散粒子が均一且つ微細な薄膜状粒子とな
る。この分散強化型合金用粉末を用いて成型・焼
結すれば、引張強度の強い分散強化合金を得るこ
とができる。 That is, in the method for producing powder for dispersion-strengthened alloys according to the present invention, the coating layer of the coated metal powder is changed into a metal hydroxide or metal hydrate through the hydrolysis step, and the heat treatment step As the metal hydroxide or metal hydrate is transformed into a uniform and fine metal oxide through the process,
In the dispersion-strengthened alloy powder obtained through the pulverization process, the dispersed particles of the metal oxide become uniform and fine thin film-like particles. By molding and sintering this dispersion-strengthened alloy powder, a dispersion-strengthened alloy with high tensile strength can be obtained.
従つて、本発明の方法により得られた分散強化
型合金用粉末は、引張強度、延性、硬度、靭性、
耐熱性、電気的特性及び耐中性子照射性に優れた
分散強化合金を得るための粉末として有用なもの
である。本発明の方法により得られた分散強化型
合金用粉末を用いて製造される分散強化型合金の
用途としては次のようなものが考えられる。 Therefore, the dispersion-strengthened alloy powder obtained by the method of the present invention has high tensile strength, ductility, hardness, toughness,
It is useful as a powder for obtaining dispersion-strengthened alloys with excellent heat resistance, electrical properties, and neutron irradiation resistance. The following are possible uses of the dispersion-strengthened alloy produced using the dispersion-strengthened alloy powder obtained by the method of the present invention.
銅合金：電気接点材料、バネ材、スポツト溶接用
チツプ、耐熱性材料、超電導用導電線
ニツケル合金：耐熱性材料、高温ガス炉用材料
銀合金：電気接点材料（継電気、スイツチ、遮断
器、マイクロスイツチ）
鉄合金：耐熱性材料、中性子遮蔽材料、原子炉用
構造用材料
アルミニウム合金：自動車用部品、エンジン部品
マグネシウム合金：航空機材料
また、本発明に係る分散強化型合金用粉末の製
造方法においては、機械粉砕混合法若しくは粉末
圧延粉砕混合法による被覆金属粉末の粉砕工程を
経るので、従来法に比べて短時間で容易に分散強
化型合金用粉末を製造することができる。Copper alloys: Electrical contact materials, spring materials, spot welding chips, heat-resistant materials, conductive wires for superconducting Nickel alloys: Heat-resistant materials, materials for high-temperature gas furnaces Silver alloys: Electrical contact materials (relays, switches, circuit breakers, microswitch) Iron alloys: heat-resistant materials, neutron shielding materials, structural materials for nuclear reactors Aluminum alloys: automobile parts, engine parts Magnesium alloys: aircraft materials In addition, in the method for producing powder for dispersion-strengthened alloys according to the present invention Since the coated metal powder is pulverized by a mechanical pulverization mixing method or a powder rolling pulverization mixing method, powder for a dispersion-strengthened alloy can be easily produced in a shorter time than in conventional methods.
以下、本発明の実施例を示す。 Examples of the present invention will be shown below.
実施例 １
90℃の蒸溜水中にアルミニウムイソアミラート
をゆつくり滴下し、加水分解を行つた。加水分解
生成物である金属水酸化物は、AIO（OH）ゲル
のＸ線回析パターンを示し、約50Åの微細粒子か
らなつていた。前記金属水酸化物を20時間熟成
後、5Wt％を平均粒径2μｍの電解銅粉に被覆し
た。これを110℃で乾燥した後、水素気流中30分
間400℃で熱処理をして非晶質AI2O3を導粉末表
面に生成させた。次いで、2ton／cm2の圧力で粉末
圧延粉砕した後、振動ミルで５時間粉砕合金化し
て分散強化型合金用銅粉末を得た。この粉末には
0.9Wt％のAI2O3が含まれていた。Example 1 Aluminum isoamylate was slowly dropped into distilled water at 90°C to perform hydrolysis. The hydrolysis product, metal hydroxide, showed an X-ray diffraction pattern of AIO(OH) gel and was composed of fine particles of about 50 Å. After aging the metal hydroxide for 20 hours, 5 Wt% was coated on electrolytic copper powder with an average particle size of 2 μm. After drying this at 110°C, it was heat-treated at 400°C for 30 minutes in a hydrogen stream to generate amorphous AI 2 O 3 on the surface of the conductive powder. Next, the powder was rolled and pulverized at a pressure of 2 ton/cm 2 , and then ground and alloyed in a vibration mill for 5 hours to obtain copper powder for dispersion-strengthened alloy. This powder has
It contained 0.9Wt % AI2O3 .
実験例 １
実施例１によつて得られた銅合金粉末をプレス
成型した後、アルゴン気流中で1000℃、１時間焼
結した。これを冷間で鍛造後、アルゴン気流中で
1000℃で30分間熱処理し、５mm×10mm×0.5mmの
形状に仕上げ、引張試験を行つた。その結果、室
温で45Kg／mm2、600℃で15Kg／mm2の引張強度を得
た。Experimental Example 1 The copper alloy powder obtained in Example 1 was press-molded and then sintered at 1000° C. for 1 hour in an argon stream. After cold forging this, it is placed in an argon stream.
It was heat treated at 1000°C for 30 minutes, finished into a shape of 5 mm x 10 mm x 0.5 mm, and subjected to a tensile test. As a result, a tensile strength of 45 Kg/mm 2 was obtained at room temperature and 15 Kg/mm 2 at 600°C.
実施例 ２
ジルコニウム塩とイツトリウム塩を５：１の割
合に混合した水溶液にアンモニアを加えて加水分
解してＹ、Zr（OH）4の共沈ゾルを作り、それの
5Wt％を平均粒径5μｍの銀粉末に表面被覆した。
その後、振動ミルで10時間粉砕合金化した。次い
で、700℃１時間アルゴン気流中で加熱処理をし
た結果、（Ｙ、Zr）2O3の微粒子を0.3Wt％分散し
た分散強化型合金用銀粉末を得た。Example 2 Ammonia was added to an aqueous solution of zirconium salt and yttrium salt mixed at a ratio of 5:1 to hydrolyze it to produce a coprecipitated sol of Y and Zr(OH) 4 .
5 Wt% was coated on the surface of silver powder with an average particle size of 5 μm.
Thereafter, it was ground and alloyed in a vibrating mill for 10 hours. Next, heat treatment was performed at 700° C. for 1 hour in an argon stream to obtain a silver powder for dispersion-strengthened alloys in which 0.3 Wt% of (Y, Zr) 2 O 3 fine particles were dispersed.
実験例 ２
実施例２によつて得られた銀粉末を用いて、押
し出し加工によつて成型体となし、900℃１時間
アルゴン気流中で焼結し、ビツカース硬度測定を
行なつたところ次の結果を得た。Experimental Example 2 Using the silver powder obtained in Example 2, a molded body was formed by extrusion processing, sintered at 900°C for 1 hour in an argon stream, and the Vickers hardness was measured. Got the results.
常温 300℃ 500℃ 700℃
硬さ(HV) 110 60 40 20
実施例 ３
塩化セリウムにアンモニアを加えて加水分解し
たゾル状のCe（OH）4をベンゼン溶液に溶解し、
それを平均粒径5μｍのチタン粉末にCe
（OH）43Wt％の割合で表面被覆した後、アトライ
ターで10時間粉砕混合し、さらに500℃で１時間
アルゴン気流中で加熱してCe2O3の超微粒子が
0.3Wt％分散したチタン粉末を得た。 Room temperature 300℃ 500℃ 700℃ Hardness (HV) 110 60 40 20 Example 3 Ce(OH) 4 in the form of a sol obtained by adding ammonia to cerium chloride and hydrolyzing it was dissolved in a benzene solution.
Ce to titanium powder with an average particle size of 5 μm.
After coating the surface at a ratio of (OH) 4 3Wt%, it was pulverized and mixed with an attritor for 10 hours, and then heated at 500℃ for 1 hour in an argon stream to form ultrafine particles of Ce 2 O 3 .
Titanium powder dispersed at 0.3 Wt% was obtained.
実験例 ３
実施例３で得られたチタン粉末をプレス成型し
た後、800℃１時間加熱し、さらにそれをプレス
成型して引張強度を測定した結果、室温で50Kg／
mm2、600℃で30Kg／mm2の引張強度を得た。Experimental Example 3 The titanium powder obtained in Example 3 was press-molded, heated at 800°C for 1 hour, and then press-molded to measure its tensile strength.
mm 2 , a tensile strength of 30 Kg/mm 2 was obtained at 600°C.
実施例 ４
加水分解したギ酸イツトリウムを水に溶解し、
さらにそれをエチルアルコールを混合した溶液を
平均粒径10μｍのニツケル粉末に表面被覆した
後、粉末圧延混合法により粉砕した。その後、
500℃１時間アンモニアガス気流中で加熱処理を
し、Y2O3微粒子が0.4Wt％分散したニツケル合金
粉末を作製した。Example 4 Hydrolyzed yttrium formate was dissolved in water,
Further, the surface of nickel powder having an average particle size of 10 μm was coated with a solution containing ethyl alcohol, and the powder was pulverized by a powder rolling mixing method. after that,
A heat treatment was performed at 500° C. for 1 hour in an ammonia gas stream to produce a nickel alloy powder in which 0.4 Wt% of Y 2 O 3 fine particles were dispersed.
実験例 ４
実施例４で得られたニツケル粉末をプレス成型
した後、1000℃１時間アルゴン気流中で焼成し
た。生成物の引張強度を測定したところ、室温で
75Kg／mm2、800℃で70Kg／mm2の引張強度を得た。Experimental Example 4 The nickel powder obtained in Example 4 was press-molded and then fired at 1000°C for 1 hour in an argon stream. When the tensile strength of the product was measured, it was found that at room temperature
A tensile strength of 75Kg/mm 2 and 70Kg/mm 2 at 800°C was obtained.
実施例 ５
被覆助剤としてのアセト酢酸エチルをベンゼン
に5Wt％添加した溶媒にイツトリウムイソプロポ
キシドを溶かしたものを、平均粒径10μの鉄−13
％クロム粉末に表面被覆した後、200℃で加熱し
て加水分解し、Y2（OH）3の非晶質被膜を鉄−13
％クロム粉末表面に被覆した。この粉末をアトラ
イターで10時間粉砕した後、アルゴン気流中で
600℃で加熱した結果、0.3Wt％の微細なY2O3が
含まれていた。Example 5 Yttrium isopropoxide was dissolved in a solvent containing benzene with 5 wt% of ethyl acetoacetate as a coating aid.
% chromium powder and then heated at 200℃ to hydrolyze it to form an amorphous coating of Y2 (OH) 3 into iron-13
% chromium powder coated on the surface. This powder was ground in an attritor for 10 hours, then in an argon stream.
As a result of heating at 600°C, it contained 0.3 Wt% of fine Y 2 O 3 .
実験例 ５
実施例５によつて得られた鉄−クロム粉末をプ
レス成型した後、アルゴン気流中で1000℃で１時
間焼結した。これを600℃の熱間で圧延後、５mm
×10mm×0.5mmの形状に仕上げ、引張試験を行な
つた。その結果、室温で50Kg／mm2、600℃で35
Kg／mm2の引張強度を得た。Experimental Example 5 The iron-chromium powder obtained in Example 5 was press-molded and then sintered at 1000° C. for 1 hour in an argon stream. After hot rolling this at 600℃, 5mm
It was finished into a shape of x10mm x 0.5mm and subjected to a tensile test. As a result, 50Kg/mm 2 at room temperature and 35Kg/mm 2 at 600℃
A tensile strength of Kg/mm 2 was obtained.
実施例 ６
平均粒径10μｍのNi粉末にイツトリウムイソプ
ロポキシドをNi粉末に対し3Wt％ベンゼンに溶
解したものを表面被覆した後、室温で加水分解し
たものを振動型ボールミルで５時間粉砕処理をし
た。その後600℃でアルゴン気流中で処理をした
結果、0.5Wt％の超微粒Y2O3を分散したNi粉末
を得た。Example 6 After coating the surface of Ni powder with an average particle size of 10 μm with yttrium isopropoxide dissolved in benzene at 3 Wt% of the Ni powder, the mixture was hydrolyzed at room temperature and pulverized in a vibrating ball mill for 5 hours. did. Thereafter, treatment was carried out at 600°C in an argon stream to obtain Ni powder in which 0.5 Wt% of ultrafine Y 2 O 3 was dispersed.
実験例 ６
実施例６によつて得られたNi粉末を5tの圧力
で静水圧成型（CIP）した後、水素中1000℃で１
時間焼結した。その後、加工して引張試験を行な
つた結果、室温で55Kg／mm2、600℃で35Kg／mm2の
引張強度を得た。Experimental Example 6 After subjecting the Ni powder obtained in Example 6 to isostatic pressing (CIP) at a pressure of 5 tons, it was
Sintered for hours. Thereafter, as a result of processing and tensile testing, the tensile strength was 55 Kg/mm 2 at room temperature and 35 Kg/mm 2 at 600°C.
実施例 ７
ジルコニウムに10Wt％のイツトリウムを含む
イソプロポキシドをベンゼンに溶解したものを平
均粒径10μｍの銀粉末に表面被覆した後、室温、
空気中で加水分解し、それを500℃で加熱した後、
粉末圧延粉砕した結果、非晶質（Zr、Ｙ）2O3が
0.4Wt％分散した銀粉末を得た。Example 7 Silver powder with an average particle size of 10 μm was coated with isopropoxide containing 10 wt% yttrium in zirconium dissolved in benzene, and then heated at room temperature.
After hydrolyzing in air and heating it at 500℃,
As a result of powder rolling and crushing, amorphous (Zr, Y) 2 O 3
Silver powder dispersed at 0.4 Wt% was obtained.
実験例 ７
実施例７によつて得られた銀粉末を800℃で
HIP成型した後、硬度測定をした結果、ビツカー
ス硬さ130であり、電気比抵抗は2.5μΩ−cmであ
り、800℃１時間熱処理をしても硬度変化は認め
られず、電気接点材料として有用なものであつ
た。Experimental Example 7 The silver powder obtained in Example 7 was heated at 800°C.
After HIP molding, we measured the hardness and found that the Vickers hardness was 130 and the electrical resistivity was 2.5 μΩ-cm. No change in hardness was observed even after heat treatment at 800°C for 1 hour, making it useful as an electrical contact material. It was something.
実施例 ８
平均粒径5μｍの電解銅粉末に、電解銅粉末に
対して3Wt％アルミニウムイソプロポキシドを石
油エーテルに溶解した溶液を表面被覆した。次い
で、湿水素中300℃で加水分解した後、３回の粉
末圧延粉砕混合を行ない、次いでアトライターで
乾式粉砕混合を10時間行なつて分散強化型銅粉末
を得た。Example 8 Electrolytic copper powder having an average particle size of 5 μm was coated with a solution in which aluminum isopropoxide was dissolved in petroleum ether in an amount of 3 wt% based on the electrolytic copper powder. Next, after hydrolysis at 300° C. in wet hydrogen, the powder was rolled, pulverized and mixed three times, and then dry pulverized and mixed in an attritor for 10 hours to obtain a dispersion-strengthened copper powder.
実験例 ８
実施例８によつて得られた銅粉末を粉末押し出
しをして直径10mm、長さ30mmの円筒状成型体を作
り、アルゴン気流中で1000℃60分加熱焼成した。
得られた成型体を熱間鍛造して巾10mm、厚さ0.5
mmの板状試験片として引張試験を行なつた。その
結果、室温で引張強度55Kg／mm2、伸び10.1％、
600℃で20Kg／mm2、伸び15％を得た。また、電気
抵抗は室温で1.72μΩ−cmであり、耐熱導伝性材
料として有用であつた。Experimental Example 8 The copper powder obtained in Example 8 was extruded into a cylindrical molded body with a diameter of 10 mm and a length of 30 mm, which was then heated and fired at 1000°C for 60 minutes in an argon stream.
The obtained molded body is hot forged to a width of 10 mm and a thickness of 0.5 mm.
A tensile test was conducted using a plate-shaped specimen of mm. As a result, the tensile strength was 55Kg/mm 2 and the elongation was 10.1% at room temperature.
20Kg/mm 2 and elongation of 15% were obtained at 600°C. Furthermore, the electrical resistance was 1.72 μΩ-cm at room temperature, making it useful as a heat-resistant conductive material.
実施例 ９
平均粒径20μｍのチタン粉末に、ジルコニウム
アセチルアセトナート3Wt％と酢酸エチル1Wt％
とを混合した溶液を表面被覆した。その後、湿水
素気流中100℃で加水分解して前記被覆物をZr
（OH）4とした。その後、さらに500℃で30分アル
ゴン気流中で熱処理を行なつてチタン粉末表面に
Zr2O3を生成させた。次いで、３回の粉末圧延粉
砕により薄片化し、その後アトライターにより１
時間微粉化して分散強化型チタン合金粉末を得
た。Example 9 Titanium powder with an average particle size of 20 μm was added with 3 Wt% of zirconium acetylacetonate and 1 Wt% of ethyl acetate.
The surface was coated with a mixed solution of Thereafter, the coating was hydrolyzed at 100°C in a stream of wet hydrogen to remove Zr.
(OH) It was set to 4 . After that, heat treatment was performed at 500℃ for 30 minutes in an argon stream to form the surface of the titanium powder.
Zr 2 O 3 was produced. Next, it was made into a thin section by powder rolling and crushing three times, and then it was made into a thin section by an attritor.
Dispersion-strengthened titanium alloy powder was obtained by time-pulverization.
実験例 ９
実施例９によつて得られたチタン合金粉末を用
いて、HIPで900℃１時間成型をした。得られた
成型体を冷間鍛造で巾10mm、厚さ0.5mmの板状試
料として引張試験を行なつた。その結果、室温で
85Kg／mm2、伸び15％、600℃で75Kg／mm2、伸び20
％であつた。Experimental Example 9 The titanium alloy powder obtained in Example 9 was molded by HIP at 900°C for 1 hour. The obtained molded body was cold forged into a plate-like sample with a width of 10 mm and a thickness of 0.5 mm, and a tensile test was conducted. As a result, at room temperature
85Kg/mm 2 , elongation 15%, 75Kg/mm 2 at 600℃, elongation 20
It was %.
実施例 10
平均粒径10μｍのアルミニウム粉末に、アルミ
ニウム粉末に対し3Wt％のジルコニウムプロポキ
シドを被覆助剤としてアセト酢酸エチル1Wt％添
加したベンゼン溶解した溶液を表面被覆した。次
いで、加水分解し、アトライターで５時間粉砕混
合した後、500℃で１時間アルゴン気流中で加熱
し、ZrO2を分散させた。Example 10 Aluminum powder having an average particle size of 10 μm was coated with a benzene-dissolved solution containing 3 wt % zirconium propoxide as a coating aid and 1 wt % ethyl acetoacetate added to the aluminum powder. Next, the mixture was hydrolyzed, pulverized and mixed with an attritor for 5 hours, and then heated at 500° C. for 1 hour in an argon stream to disperse ZrO 2 .
実験例 10
実施例10によつて得られた試料を粉末圧延成型
した後、500℃１時間アルゴン気流中で焼成し、
引張試験をした結果、室温で40Kg／mm2、600℃で
15Kg／mm2の引張強度を得た。Experimental Example 10 The sample obtained in Example 10 was powder-rolled and then calcined at 500°C for 1 hour in an argon stream.
As a result of tensile test, it was 40Kg/mm 2 at room temperature and 600℃.
A tensile strength of 15Kg/mm 2 was obtained.
実施例 11
平均粒径10μｍのアルミニウム粉末に、アルミ
ニウム粉末に対し3Wt％のイツトリウムアセチル
アセトナートをアセト酢酸メチルに溶解した溶液
を表面被覆した。次いで、300℃で湿水素中で加
水分解したものをさらに500℃で加熱し、Y2O3被
膜とした後、振動型ボールミルで10時間粉砕し、
Y2O3の超微粒子の分散しているアルミニウム粉
末を得た。Example 11 Aluminum powder having an average particle size of 10 μm was coated with a solution of 3 Wt % of yttrium acetylacetonate dissolved in methyl acetoacetate based on the aluminum powder. Next, the product was hydrolyzed in wet hydrogen at 300°C, further heated at 500°C to form a Y 2 O 3 coating, and then ground in a vibrating ball mill for 10 hours.
An aluminum powder in which ultrafine particles of Y 2 O 3 were dispersed was obtained.
実験例 11
実施例11によつて得られた粉末をHIPで500℃、
5tで加圧成型した後、引張強度を測定した結果、
室温で35Kg／mm2、600℃で20Kg／mm2の引張強度を
得た。Experimental Example 11 The powder obtained in Example 11 was heated at 500°C by HIP.
As a result of measuring the tensile strength after pressure molding with 5 tons,
A tensile strength of 35 Kg/mm 2 was obtained at room temperature and 20 Kg/mm 2 at 600°C.
比較例 １
アルミニウムイソアミラート5Wt％を平均粒径
2μｍの電解銅粉に被覆した。これ水素気流中600
℃で30分間加熱した。次いで、実施例１に準じ、
2ton／cm2の圧力で粉末圧延粉砕した後、振動ミル
で５時間粉砕合金化して銅合金粉末を得た。この
銅合金粉末には、約0.9Wt％のAl2O3が含まれて
いた。Comparative Example 1 Average particle size of aluminum isoamylate 5Wt%
It was coated with 2 μm electrolytic copper powder. This is 600 in hydrogen flow.
Heat at ℃ for 30 minutes. Then, according to Example 1,
The powder was rolled and pulverized at a pressure of 2 tons/cm 2 , and then pulverized and alloyed in a vibration mill for 5 hours to obtain a copper alloy powder. This copper alloy powder contained approximately 0.9 Wt% Al 2 O 3 .
得られた銅合金粉末を用いて実施例１に記載の
方法で成型・焼結して試験片を作製し、引張試験
を行つた。その結果、室温での引張強さは10Kg／
mm2に過ぎなかつた。 Using the obtained copper alloy powder, a test piece was prepared by molding and sintering according to the method described in Example 1, and a tensile test was conducted. As a result, the tensile strength at room temperature was 10Kg/
It was only mm 2 .
比較例 ２
塩化セリウム0.5Wt％を平均粒径5μｍのチタン
粉末に被覆した後、500℃１時間アルゴン気流中
で加熱してチタン粉末を得た。このチタン粉末に
は、約0.3Wt％のCe2O3が含まれていた。Comparative Example 2 Titanium powder having an average particle size of 5 μm was coated with 0.5 Wt% of cerium chloride, and then heated at 500° C. for 1 hour in an argon stream to obtain titanium powder. This titanium powder contained approximately 0.3 Wt% Ce 2 O 3 .
得られたチタン粉末を用いて実施例５に記載の
方法で成型・焼結して試験片を作製し、引張試験
を行つた。その結果、室温での引張強さは７Kg／
mm2に過ぎなかつた。 Using the obtained titanium powder, a test piece was prepared by molding and sintering according to the method described in Example 5, and a tensile test was conducted. As a result, the tensile strength at room temperature was 7Kg/
It was only mm 2 .
参考例 １
硝酸アルミニウム（Al（NO3）3・9H2O）を約
500mlの蒸留水中に溶解し、得られた溶液を
325US篩サイズより細かい平均粒径を有する微粉
状銅粉末約2724Kg中に加えて混練した。しかる
後、液状分散媒中の金属銅粒子の懸濁状態を維持
するために連続撹拌しながら、すべての水分が除
去されるまで、この水分除去中、懸濁液中に上澄
液層が形成されないようにしながら、この水性ス
ラリーを約95℃に加熱した。このようにした得た
乾燥粉末混合物を約１時間空気中で約100℃で乾
燥し、更に12時間真空下に放置した。この乾燥作
業の後、得られた粉末混合物にイソプロピルアル
コールを加えて１時間ボールミルで粉砕した後、
さらに空気中で乾燥した。この空気乾燥した混合
物を水素中で３時間、800℃で加熱し、これを粉
砕した後、250μｍの開口を有する篩にて篩別し
て篩をさせることにより、Cu粉の表面に0.9Wt％
のAl2O3粒子が付着したCu−Al2O3粉を得た。こ
のAl2O3粉の粒径は約1000Åであつた。Reference example 1 Aluminum nitrate (Al(NO 3 ) 3・9H 2 O)
Dissolve the resulting solution in 500ml of distilled water.
It was added and kneaded into about 2724 kg of finely divided copper powder having an average particle size smaller than the 325 US sieve size. Then, with continuous stirring to maintain suspension of the metallic copper particles in the liquid dispersion medium, a supernatant liquid layer forms in the suspension during this water removal until all the water is removed. The aqueous slurry was heated to about 95° C. while ensuring that it was not heated. The dry powder mixture thus obtained was dried in air at about 100° C. for about 1 hour and left under vacuum for a further 12 hours. After this drying operation, isopropyl alcohol was added to the resulting powder mixture and the mixture was ground in a ball mill for 1 hour.
It was further dried in the air. This air-dried mixture was heated in hydrogen at 800°C for 3 hours, pulverized, and then sieved through a sieve with 250 μm openings, so that 0.9 Wt% was added to the surface of the Cu powder.
Cu-Al 2 O 3 powder to which Al 2 O 3 particles were attached was obtained. The particle size of this Al 2 O 3 powder was about 1000 Å.
得られたCu−Al2O3粉を実験例１に記載の方法
で成型・焼結して試験片を作製し、引張試験を行
つたところ、室温での引張強さは26Kg／mm2であつ
た。 A test piece was prepared by molding and sintering the obtained Cu-Al 2 O 3 powder using the method described in Experimental Example 1, and a tensile test was performed. The tensile strength at room temperature was 26 kg/mm 2 . It was hot.
Claims (1)
属粉末との混合による被覆工程、被覆層を非晶質
若しくは微細粒子の金属酸化物とするための熱処
理工程、機械粉砕混合法若しくは粉末圧延粉砕混
合法による被覆金属粉末の粉砕工程の全ての工程
を含むことを特徴とする分散強化型合金用粉末の
製造方法。 ２ 金属化合物の加水分解工程が、金属化合物と
金属粉末との混合による被覆工程の前に行われる
特許請求の範囲第１項に記載の分散強化型合金用
粉末の製造方法。 ３ 金属化合物の加水分解工程が、金属化合物と
金属粉末との混合による被覆工程の後に行われる
特許請求の範囲第１項に記載の分散強化型合金用
粉末の製造方法。 ４ 被覆層を非晶質若しくは微細粒子の金属酸化
物とするための熱処理工程より前に乾燥工程が行
われる特許請求の範囲第１項〜第３項に記載の分
散強化型合金用粉末の製造方法。 ５ 金属化合物に含まれる金属が、AI、Ti、
Cu、Fe、Mo、Ｗ、Au、Ag、Si、Nb、Ｖ、Zr、
Ta、Ｙ、Cr、Ｂ及び希土類元素の中から選ばれ
る一種以上である特許請求の範囲第１項〜第４項
の何れかに記載の分散強化型合金用粉末の製造方
法。 ６ 金属粉末が、銅、銅合金、ニツケル、ニツケ
ル合金、銀、銀合金、クロム、クロム合金、鉄、
鉄合金、アルミニウム、アルミニウム合金、マグ
ネシウム、マグネシウム合金、チタン、チタン合
金、モリブデン、モリブデン合金、タングステン
及びタングステン合金の中から選ばれる一種以上
である特許請求の範囲第１項〜第５項の何れかに
記載の分散強化型合金用粉末の製造方法。 ７ 被覆層を形成するに際し、被覆助剤を添加し
た溶媒に金属化合物を溶解させたものが使用され
る特許請求の範囲第１項〜第６項の何れかに記載
の分散強化型合金用粉末の製造方法。[Claims] 1 Hydrolysis process of a metal compound, coating process by mixing the metal compound and metal powder, heat treatment process to make the coating layer into an amorphous or fine particle metal oxide, mechanical pulverization mixing method Alternatively, a method for producing a powder for a dispersion-strengthened alloy, comprising all steps of pulverizing coated metal powder by a powder rolling pulverizing mixing method. 2. The method for producing a dispersion-strengthened alloy powder according to claim 1, wherein the step of hydrolyzing the metal compound is performed before the step of coating by mixing the metal compound and the metal powder. 3. The method for producing a dispersion-strengthened alloy powder according to claim 1, wherein the step of hydrolyzing the metal compound is performed after the step of coating by mixing the metal compound and the metal powder. 4. Production of powder for dispersion-strengthened alloys according to claims 1 to 3, wherein a drying step is performed before the heat treatment step to make the coating layer amorphous or fine-particle metal oxide. Method. 5 The metal contained in the metal compound is AI, Ti,
Cu, Fe, Mo, W, Au, Ag, Si, Nb, V, Zr,
The method for producing a powder for dispersion-strengthened alloy according to any one of claims 1 to 4, wherein the powder is one or more selected from Ta, Y, Cr, B, and rare earth elements. 6 The metal powder is copper, copper alloy, nickel, nickel alloy, silver, silver alloy, chromium, chromium alloy, iron,
Any one of claims 1 to 5, which is one or more selected from iron alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, titanium, titanium alloys, molybdenum, molybdenum alloys, tungsten, and tungsten alloys. A method for producing a dispersion-strengthened alloy powder as described in . 7. Powder for dispersion-strengthened alloys according to any one of claims 1 to 6, in which a metal compound dissolved in a solvent to which a coating aid is added is used when forming the coating layer. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59133852A JPS6112801A (en) | 1984-06-27 | 1984-06-27 | Production of powder for dispersion-strengthened alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59133852A JPS6112801A (en) | 1984-06-27 | 1984-06-27 | Production of powder for dispersion-strengthened alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6112801A JPS6112801A (en) | 1986-01-21 |
| JPH0379402B2 true JPH0379402B2 (en) | 1991-12-18 |
Family
ID=15114534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59133852A Granted JPS6112801A (en) | 1984-06-27 | 1984-06-27 | Production of powder for dispersion-strengthened alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6112801A (en) |
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| US6335393B1 (en) * | 1998-02-12 | 2002-01-01 | Samsung Display Devices Co., Ltd. | Precursor composition for metal oxide and preparation method therefor |
| CN107201435B (en) * | 2017-04-29 | 2019-01-11 | 天津大学 | The preparation method of ferrous alloy with nanocluster and dislocation, twins sub-structure |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS503908A (en) * | 1973-04-20 | 1975-01-16 | ||
| JPS5510655A (en) * | 1978-07-10 | 1980-01-25 | Hitachi Ltd | Terminal pressure controller |
| JPS5773103A (en) * | 1980-10-27 | 1982-05-07 | Res Dev Corp Of Japan | Production of high strength heat resistant metallic material |
| JPS5779137A (en) * | 1980-09-04 | 1982-05-18 | Gen Electric | Dispersion reinforced type copper alloy, stock powdery copper mixture thereof and production thereof |
| JPS5836660A (en) * | 1981-08-31 | 1983-03-03 | Fuji Xerox Co Ltd | Multiphase electric field curtain device |
-
1984
- 1984-06-27 JP JP59133852A patent/JPS6112801A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS503908A (en) * | 1973-04-20 | 1975-01-16 | ||
| JPS5510655A (en) * | 1978-07-10 | 1980-01-25 | Hitachi Ltd | Terminal pressure controller |
| JPS5779137A (en) * | 1980-09-04 | 1982-05-18 | Gen Electric | Dispersion reinforced type copper alloy, stock powdery copper mixture thereof and production thereof |
| JPS5773103A (en) * | 1980-10-27 | 1982-05-07 | Res Dev Corp Of Japan | Production of high strength heat resistant metallic material |
| JPS5836660A (en) * | 1981-08-31 | 1983-03-03 | Fuji Xerox Co Ltd | Multiphase electric field curtain device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6112801A (en) | 1986-01-21 |
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