JPS62260027A - Manufacture of sintered composite material - Google Patents
Manufacture of sintered composite materialInfo
- Publication number
- JPS62260027A JPS62260027A JP61101995A JP10199586A JPS62260027A JP S62260027 A JPS62260027 A JP S62260027A JP 61101995 A JP61101995 A JP 61101995A JP 10199586 A JP10199586 A JP 10199586A JP S62260027 A JPS62260027 A JP S62260027A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- ceramics
- metal
- composite material
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- 239000000919 ceramic Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 150000001247 metal acetylides Chemical class 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- -1 borides Chemical class 0.000 claims abstract description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 8
- 229930195729 fatty acid Natural products 0.000 claims abstract description 8
- 239000000194 fatty acid Substances 0.000 claims abstract description 8
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 238000002844 melting Methods 0.000 claims abstract description 6
- 230000008018 melting Effects 0.000 claims abstract description 6
- 150000004767 nitrides Chemical class 0.000 claims abstract description 6
- 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 claims abstract description 5
- 229910021332 silicide Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 12
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 150000001734 carboxylic acid salts Chemical class 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000011347 resin Chemical class 0.000 claims description 4
- 229920005989 resin Chemical class 0.000 claims description 4
- 125000005608 naphthenic acid group Chemical group 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008117 stearic acid Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 2
- 235000012054 meals Nutrition 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 23
- 239000011230 binding agent Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000344 soap Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910009043 WC-Co Inorganic materials 0.000 description 4
- 239000011195 cermet Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 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 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020630 Co Ni Inorganic materials 0.000 description 2
- 229910002440 Co–Ni Inorganic materials 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Chemical class CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical class CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Chemical class CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Chemical class CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Chemical class CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Chemical class CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Chemical class CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Chemical class CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical class C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910018499 Ni—F Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Chemical class 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 159000000032 aromatic acids Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- KJDZDTDNIULJBE-QXMHVHEDSA-N cetoleic acid Chemical class CCCCCCCCCC\C=C/CCCCCCCCCC(O)=O KJDZDTDNIULJBE-QXMHVHEDSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 1
- 244000145841 kine Species 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000009700 powder processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、焼結複合材料の製造方法に関するものであり
、特には炭化物、酸化物、窒化物等のセラミクスと結合
相としての全日との焼結複合材料を製造するに際して、
結合相としての金属を従来の金属粉末として使用する方
法に代えて有機酸塩として用いることを特徴とするもの
である。本発明は、一般に超硬合金或いはサーメットと
呼ばれる系列の焼結複合材料全般を対象とするが、特に
周期律表■ａ族金１１（Ｔｌ、ｚｒ、ａｒ）、Ｖａ族金
萬（Ｖ、 Ｎｂ％７’ａ）及び■ａ族金Ｂ４（Ｃｒ ％
Ｍ Ｏ、Ｗ ）の炭化物をＣｏ、Ｎｌ、Ｆｅ等の金属
で焼結結合した超硬合金を好ましい対象例とし、その代
表例は、ＷＣ−Ｃｏ、ＷＣ−Ｔｍ（Ｎｂ）Ｃ−Ｃｏ％Ｗ
Ｃ−Ｔｉｃ−Ｃｏ。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing sintered composite materials, and in particular to sintering of ceramics such as carbides, oxides, nitrides, etc. When manufacturing composite materials,
This method is characterized in that the metal as the binder phase is used as an organic acid salt instead of the conventional method of using metal powder. The present invention is directed to sintered composite materials of the series generally referred to as cemented carbide or cermet, but is particularly directed to sintered composite materials of the series generally referred to as cemented carbide or cermet. %7'a) and ■a group metal B4 (Cr %
A preferred target example is a cemented carbide in which carbides of MO, W) are sintered and bonded with metals such as Co, Nl, and Fe, and typical examples thereof are WC-Co, WC-Tm(Nb)C-Co%W
C-Tic-Co.
ＷＣ−ＴｉＣ−Ｔａ（Ｎｂ）Ｃ−Ｃｏ％ＷＣ−Ｎｉ％Ｗ
Ｃ−Ｃｏ−Ｎｉ％ＷＣ−Ｎｉ−Ｆ・等である。本発明材
料は、これまで超硬合金やサーメットが利用されてきた
チップ、バイト、ミル、ドリル、カッタ等の切削工具、
耐摩耗・耐＠撃工具等全般に有益に用いられるが、特に
最近電気回路基板のスルーホール部の穴明けに用いるマ
イクロドリルのような微細で且つ高い強度や切削性が望
まれる用途に最適である。WC-TiC-Ta(Nb)C-Co%WC-Ni%W
C-Co-Ni%WC-Ni-F. etc. The material of the present invention can be applied to cutting tools such as tips, bits, mills, drills, and cutters in which cemented carbide and cermet have been used,
It is useful for wear-resistant and hammer-resistant tools in general, but it is especially suitable for applications that require fine, high strength and machinability, such as micro drills, which are recently used to drill through-holes in electrical circuit boards. be.
発明の背景
炭化物、酸化物、窒化物、ホウ化物、ケイ化物等の高融
点物質と金属との焼結複合材料はサーメットと呼ばれ、
切削工具、耐摩耗・耐衝撃工具用途に広く使用されてき
た。このうち、炭化物系サーメットに属するものは、超
硬合金と呼ばれ、とりわけ良好な機械的性質を示す。超
硬合金は、前記した通り、周期律表■１族金属（ＴＩ、
Ｚｒ、 Ｈｆ ）、ｖａ族金属（ｖ、 Ｎｂ％Ｔ＆）及
び■ａ族金ｆｉ（Ｃｒ。Background of the Invention A sintered composite material of metal and high melting point substances such as carbides, oxides, nitrides, borides, and silicides is called cermet.
It has been widely used for cutting tools, wear-resistant and impact-resistant tools. Among these, those belonging to carbide-based cermets are called cemented carbides and exhibit particularly good mechanical properties. As mentioned above, cemented carbide is a group 1 metal of the periodic table (TI,
Zr, Hf), va group metals (v, Nb%T&) and group a group metals fi (Cr.
Ｍｏ、’Ｗ）の炭化物粉末の１種以上を結合相とじての
Ｆ・、Ｃｏ％Ｎｉの１種以上の金属で焼結結合した焼結
複合材料として定義することが出来る。It can be defined as a sintered composite material in which one or more carbide powders (Mo, W) are sintered and bonded with one or more metals F., Co%Ni as a binder phase.
こうした焼結複合材料は、ＷＣ−Ｃｏ系を例にとると次
の工程により製造される：
（１）ＷＣの製造工程：
原料タングステン粉末と原料炭素とを混合し、そして混
合物を横型水素炉等の使用により炭化処理する。その後
、炭化物を粉砕しそして分級する。但し、一般にＷＣは
市販されており入手しつる。Taking the WC-Co system as an example, such a sintered composite material is manufactured by the following process: (1) WC manufacturing process: Raw material tungsten powder and raw material carbon are mixed, and the mixture is heated in a horizontal hydrogen furnace, etc. Carbonized by using. The carbide is then crushed and classified. However, in general, WC is commercially available and can be obtained.
（２１ＷＣ＋Ｃｏ混合粉末の処理工程：上記ＷＣ粉末と
Ｃｏ金属粉末（所定粒度）をその地温加物と共にボール
ミル等にて混合し、更に造粒する。(21 WC+Co mixed powder processing step: The above-mentioned WC powder and Co metal powder (predetermined particle size) are mixed together with the geothermal additive in a ball mill or the like, and further granulated.
（３）成形及び焼結工程：
上記造粒物をプレス成形し、適宜予備焼結及び中間加工
を経由して焼結を行う。(3) Molding and sintering process: The above granulated material is press-molded, and sintered via preliminary sintering and intermediate processing as appropriate.
（４）仕上げ工程： この後、研削、検査を経て工具が作製される。(4) Finishing process: After this, the tool is manufactured through grinding and inspection.
従来技術の問題点 近年、微細な切削工具への需要が高まっている。Problems with conventional technology In recent years, demand for fine cutting tools has increased.
例えば、半導体デバイスの進歩に伴い、電気回路基板の
スルーホール部の穴あけに用いるマイク四ドリルは年々
小径化をたどり、しかもその要求性能も益々厳しくなっ
ている。従来技術においてこうした微細な切削工具を製
造する場合、ＷＣ％ＴＩＣ等の炭化物その他の基材が微
粉であることが必要であると共に、結合相となる
Ｃｏ、Ｎｉ及びＦａ等についてもそれらが微粉であるこ
とを必要とする。しかし、現状では、ＷＣ％ＴＸＣ等の
基材のサブミクロン微粉の製造は可能であるが、結合相
とするＣｏやＮｉについてはサブミクロン微粉を工業的
規模で得ることは非輩に困難である。一般に、粉砕工程
において、金属としての性質から、サブミクロン粒度の
ＣｏやＮｉを得ることは非常に難しいとされている。仮
にサブミクロンのＣｏやＮｉが得られたとしても、それ
らは非常に不安定であり、爆発的に燃焼したりまた注意
深い取扱いの下でも徐々に酸化物に変化しやすく、結合
能力を低下する。For example, with the advancement of semiconductor devices, the diameter of microphone drills used for drilling through-holes in electrical circuit boards is becoming smaller year by year, and the required performance is becoming increasingly strict. When manufacturing such fine cutting tools using conventional technology, it is necessary that carbides such as WC%TIC and other base materials are fine powders, and the binder phases such as Co, Ni, and Fa are also fine powders. requires something. However, at present, although it is possible to produce submicron fine powder of base materials such as WC%TXC, it is difficult for non-professionals to obtain submicron fine powder of Co and Ni used as binder phases on an industrial scale. . Generally, it is said that it is very difficult to obtain submicron particle size Co or Ni in the pulverization process due to their properties as metals. Even if submicron Co and Ni could be obtained, they are very unstable and easily burn explosively or gradually change into oxides even under careful handling, reducing their binding ability.
従って、結合相合ａｔ金属粉末として使用する限り、工
具の微細化への対応は限度があり、そうした微細工具を
必要とする用途での大きなネックとなりつつある。Therefore, as long as it is used as a bonded intermetallic powder, there is a limit to its ability to respond to the miniaturization of tools, and this is becoming a major bottleneck in applications requiring such fine tools.
更に、微細工具に限らず、焼結複合材料を使用する工具
その他の部品全般においても、セラミクス基材と結合相
金属との更に一層の親和性即ち結合力を高めることによ
り、一段と大きな強度、切削性、耐摩耗性、耐衝撃性等
の機械的性質を実現することが望まれている。Furthermore, not only fine tools but also tools and other parts that use sintered composite materials can have even greater strength and cutting ability by further increasing the affinity, or bonding strength, between the ceramic base material and the binder phase metal. It is desired to achieve mechanical properties such as hardness, abrasion resistance, and impact resistance.
発明の目的
こうした要望に答えるべく、本発明は、従来技術では得
られない、極めて微密なそしてセラミクス基材に結合用
金属を理想的に一様に分散させた焼結複合材料を製造す
る方法を確立することである。Purpose of the Invention In order to meet these needs, the present invention provides a method for producing a sintered composite material in which bonding metals are ideally and uniformly dispersed in extremely fine particles and in a ceramic substrate, which cannot be obtained using conventional techniques. The goal is to establish
本発明の特定された目的は、マイク四ドリルのような微
細工具の製造を可能ならしめる上記のような焼結複合材
料の製造方法を提供することである。A specific object of the invention is to provide a method for producing a sintered composite material as described above, which allows the production of fine tools such as microphone drills.
発明の概要
本発明者等は、結合相金属を全翼粉末として利用する限
り、上述した固有の障害を克服することは至難と考え、
結合相金属を有機酸塩として導入することを想到し、研
究を重ねた。その結果、これら金属を炭素数６以上のカ
ルボン酸塩の形で導入することにより上記目的の実現に
成功した。Summary of the Invention The present inventors believe that it is extremely difficult to overcome the above-mentioned inherent obstacles as long as the binder phase metal is used as a flying powder.
We came up with the idea of introducing the bonded phase metal as an organic acid salt, and conducted repeated research. As a result, the above objective was successfully achieved by introducing these metals in the form of carboxylates having 6 or more carbon atoms.
こうしたカルボン酸塩は、実用的には、金属石鹸として
市販されているものが多く、脂肪酸、樹脂酸及びナフテ
ン酸の、コバルト、ニッケル及び鉄の金属塩に代表され
る。Practically speaking, many of these carboxylic acid salts are commercially available as metal soaps, and are typified by cobalt, nickel, and iron metal salts of fatty acids, resin acids, and naphthenic acids.
こうして、コバルト、ニッケル及び鉄をカルボン酸塩の
形でセラミクス基材と混合することにより、セラミクス
基材にこれらカルボン酸塩が緊密に絡みあった分散体が
得られ、それらを還元処理して得られるスポンジ状還元
物を粉砕することによりサブミクロン寸法の混合微粉が
容易に得られる。この粉末は爾後の成形、焼結等の工程
を経由して工具その他の物品、特に微細切削工具を製作
するに好適なものである。Thus, by mixing cobalt, nickel, and iron in the form of carboxylates with a ceramic substrate, a dispersion in which these carboxylates are tightly entangled in the ceramic substrate is obtained, which can be reduced and obtained. By pulverizing the sponge-like reduced product, a fine mixed powder of submicron size can be easily obtained. This powder is suitable for manufacturing tools and other articles, especially fine cutting tools, through subsequent processes such as molding and sintering.
斯くして、本発明は、少くとも１８１２の高融点セラミ
クスとコバルト、ニッケル及び鉄のうちから選択される
少くとも１種の結合用金属とから成る混合物を成形及び
焼結することにより焼結複合材料を製造する方法におい
て前記混合物を、前記セラミクスと前記結合用金属の炭
素数６以上のカルボン酸塩との混合物を還元処理するこ
とにより調製することを特徴とする焼結複合材料の製造
方法を提供する。Thus, the present invention provides a sintered composite by forming and sintering a mixture of at least 1812 high melting point ceramic and at least one bonding metal selected from cobalt, nickel and iron. A method for producing a sintered composite material, characterized in that the mixture is prepared by reducing a mixture of the ceramic and the carboxylic acid salt having 6 or more carbon atoms of the bonding metal. provide.
発明の具体的説明
本発明は、２０００〜５５００℃の高融点を持つ酸化物
、炭化物、ホウ化物、窒化物、ケイ化物等のセラミクス
の少くとも１種以上と、Ｃｏ、Ｎｌ及びＦｅのうちから
選択される少くとも１種以上との焼結複合材料を対象と
する。酸化物としては、Ａ １２０３ ＳＺ ｒ ０２
％ Ｔ ｈ Ｏ２、Ｂ ＠ Ｏｓ Ｃｒ ｔＯｓ ％
ＭＪｒ Ｏ等が挙げられ、炭化物としてはＴｉｃ、
ＺｒＣ，１（ｆＣ。DETAILED DESCRIPTION OF THE INVENTION The present invention comprises at least one type of ceramics such as oxides, carbides, borides, nitrides, and silicides having a high melting point of 2000 to 5500°C, and Co, Nl, and Fe. The object is a sintered composite material with at least one selected type. As an oxide, A 1203 SZ r 02
% T h O2, B @ Os Cr tOs %
Examples of carbides include Tic, MJrO, etc.
ZrC,1(fC.
ＶＣ，ＮｂＣ，ＴａＣ，Ｃｒ５Ｃ２、ＭＯＣ％ＷＣ％Ｓ
ＩＣ等が挙げられ、ホウ化物としてはＴ Ｉ Ｂ２ ％
Ｚ ｒ Ｂ２、ＣｒＪ等が挙げられ、窒化物としては
ＴＩＮ％ＴａＮ等が挙げられそしてケイ化物としてはＴ
ｉ Ｓ ｔ、、Ｍｏ Ｓ １２ 、ＷＳ ｉ２等が挙
げられる。特に好ましいものは、一般に超硬合金と呼ば
れる炭化物系サーメットであり、周期律表■ａ族金Ｊ！
＄（’Ｉ’ｉ％Ｚｒ。VC, NbC, TaC, Cr5C2, MOC%WC%S
Examples of borides include T I B2 %
Examples of the nitride include TIN%TaN, and examples of the silicide include T.
i S t, , Mo S 12 , WS i2, and the like. Particularly preferred are carbide-based cermets, generally called cemented carbides, which include metals from group II of the periodic table J!
$('I'i%Zr.
Ｈｆ）、’／ａ族金興（Ｖ、Ｎｂ、Ｔａ）及びＶＩＡ族
金属（Ｃｒ ％ Ｍ Ｏ％ Ｗ ）の炭化物をｃｏ％Ｎ
１ ％ Ｆ ｓ等の金属で焼結結合したものである。Co%N
It is sintered and bonded with a metal such as 1% Fs.
炭化物は表面エネルギーが大きいため金属との濡れ性が
良く、良好な機械的性質を創出しつる。その代表例は、
ＷＣ−ＣＯ％ＷＣ−Ｔａ（Ｎｂ）Ｃ−Ｃｏ、ＷＣ−Ｔｉ
ｃ−Ｃｏ、ＷＣ−ＴｉＣ−Ｔａ（Ｎｂ）Ｃ−Ｃｏ、ＷＣ
−Ｎｉ、ＷＣ−Ｃｏ−Ｎｉ、ＷＣ−Ｎｌ−Ｆｅ％Ｔｉｃ
−Ｃｏ％Ｔｉｃ−Ｎ１、Ｔｉｃ−Ｃｒ３Ｃ２−？’ＬＩ
、Ｃｒ５Ｃ２−ＷＣ−Ｎｉ等である。Carbides have high surface energy, so they have good wettability with metals and create good mechanical properties. A typical example is
WC-CO%WC-Ta(Nb)C-Co, WC-Ti
c-Co, WC-TiC-Ta(Nb)C-Co, WC
-Ni, WC-Co-Ni, WC-Nl-Fe%Tic
-Co%Tic-N1, Tic-Cr3C2-? 'LI
, Cr5C2-WC-Ni, etc.
本発明に従えば、結合用全屈としてのＣｏ、Ｎ１及びＦ
ｅは、炭素数６以上のカルボン酸塩の形で使用される。According to the invention, Co, N1 and F as coupling total bends
e is used in the form of a carboxylate having 6 or more carbon atoms.
こうしたカルボン酸塩は、金属石鹸として市販されてい
るものが多く、脂肪酸、樹脂酸及びナフテン酸の金属塩
に代表される。Many of these carboxylic acid salts are commercially available as metal soaps, and are typified by metal salts of fatty acids, resin acids, and naphthenic acids.
脂肪酸は、カルボキシル基１個をもつカルボン酸ＲＣＯ
ＯＨのうち鎖式構造のものを総称するが、ここではＣ−
以上の、カプロン酸（Ｃ，１口Ｃ００Ｈ）、エナント酸
（Ｃｓ Ｈｌｓ Ｃ００Ｈ） 、カプリル酸（オクチ／
ｌ’ 酸） （（４Ｍｌ ８ Ｃ００Ｈ）、ベラＡ／
：ｆ ン７７９（（４Ｈ１ｒＣＯＯＨ）、カプリン酸（
ＣｏＨｔ＊Ｃ００Ｈ） 、ウンデシル酸（Ｃ１ｏＨｚｔ
ＣＯＯＨ） 、５ ’ｙ ！Ｊ ＞酸（Ｃｔｔ）ｈｓｃ
ＯＯＨ） 、）リゾシル酸（Ｃｌ２Ｈ２１１ＣＯＯＨ）
、ミリスチンｆｉｌｉ（Ｃ１３Ｈ２？ Ｃ００Ｈ） 、
へ＞ タデシｋ 酸（Ｃ１４１’１２９ Ｃ００Ｈ）、
パルミチン酸（Ｃ１ｓ Ｈｓｘ Ｃ００Ｈ）、ヘプタデ
シ／Ｌ／１９（Ｏｌｓ Ｈｓｓ Ｃ００Ｈ）、ステアリ
ン酸（Ｃｔｙ Ｈｓｓ Ｃ００Ｈ）、／ ＋ ｆ ｊｓ
ン’ｒｌｌ （Ｃ１ａ Ｈｓｔ Ｃ００Ｈ） 、アラ
キン醜（Ｃ１ｅ Ｈｓｓ Ｃ００Ｈ）、ベヘン酸（Ｃ２
１Ｈ４３Ｃ０ＯＨ）等の飽和脂肪酸の金属塩が代表的に
使用される。この他、不飽和脂肪酸として、ウンデシル
酸、オレイン酸、エライジン酸、セトレイン酸、エルカ
酸等の金属塩の使用も可能である。Fatty acids are carboxylic acids RCO with one carboxyl group.
Among OH, those with a chain structure are collectively referred to as C-
Above, caproic acid (C, 1 mouth C00H), enanthic acid (Cs Hls C00H), caprylic acid (octyl/
l' acid) ((4Ml 8 C00H), Vera A/
: f 779 ((4H1rCOOH), capric acid (
CoHt*C00H), undecylic acid (C1oHzt
COOH), 5'y! J>Acid(Ctt)hsc
OOH) ,) Lysosylic acid (Cl2H211COOH)
, myristin fili (C13H2? C00H),
to > Tadeshik acid (C141'129 C00H),
Palmitic acid (C1s Hsx C00H), heptadecy/L/19 (Ols Hss C00H), stearic acid (Cty Hss C00H), / + f js
N'rll (C1a Hst C00H), Alachin Ugly (C1e Hss C00H), Behenic acid (C2
Metal salts of saturated fatty acids such as 1H43C0OH) are typically used. In addition, metal salts of undecylic acid, oleic acid, elaidic acid, cetoleic acid, erucic acid, etc. can also be used as unsaturated fatty acids.
樹脂酸は、脂肪族と芳香族とに大別され、脂肪族として
はアビエチン酸、ネオアビエチン９、ｄ−ピマル酸、イ
ソーｄ−ピマル酸等そして芳香族としては安息香酸、ケ
イ皮醗等が存在し、それらの金属塩の使用が考慮される
。Resin acids are broadly classified into aliphatic and aromatic. Aliphatic acids include abietic acid, neoabietin9, d-pimaric acid, iso-d-pimaric acid, etc., and aromatic acids include benzoic acid, cinnamic acid, etc. exist and the use of their metal salts is considered.
ナフテン酸は、石油酸の主成分で、ナフテン核をもつ飽
和カルボン酸類を総称する。単環式、二環式、更に三環
式等が存在し、これらの金属塩が使用されうる。Naphthenic acid is the main component of petroleum acids and is a general term for saturated carboxylic acids with a naphthene nucleus. There are monocyclic, bicyclic, and even tricyclic types, and metal salts of these types can be used.
代表的に使用されるものは、オクチル酸コバルト、オク
チル酸ニッケル、オクチル酸鉄、ナフテン酸コバルト、
ナフテン酸ニッケル、ナフテン酸鉄、ステアリン酸コバ
ルト、ステアリン酸ニッケル、ステアリン醪鉄等である
。尚、金属石鹸を構成する有機酸基が２以上である場合
に各々が同一の有機酸基である必要はない。これらは、
脂肪酸成るいはナフテン酸と、ＮａＯＨと、溶剤とを混
合鹸化し、そこに金属塩溶液を加えて複分解を行い、洗
浄後、固型製品を得るには脱水・脱溶剤を行って成型し
そして液状製品を得るには脱水及び調合を行ったもので
ある。その他の製法としては、脂肪酸等と金属粉末とを
反応させる直接法や脂肪酸等と金属の水酸化物、酸化物
、弱酸塩とを高温で反応させる溶融法等がある。Typically used are cobalt octylate, nickel octylate, iron octylate, cobalt naphthenate,
These include nickel naphthenate, iron naphthenate, cobalt stearate, nickel stearate, and iron stearate. Incidentally, when there are two or more organic acid groups constituting the metal soap, it is not necessary that they are the same organic acid group. these are,
Fatty acid or naphthenic acid, NaOH, and a solvent are mixed and saponified, a metal salt solution is added thereto to perform double decomposition, and after washing, to obtain a solid product, dehydration and solvent removal are performed and molding is performed. The liquid product is obtained by dehydration and blending. Other manufacturing methods include a direct method in which fatty acids and the like are reacted with metal powder, and a melting method in which fatty acids and the like are reacted with metal hydroxides, oxides, and weak acid salts at high temperatures.
カルボン酸の炭素数を６以上としたのは、（１）炭素数
５以下のカルボン酸塩は、有機溶剤に難溶または不溶の
ためか良好な分散が得られないこと、さらには、
（２）炭素数１〜３のカルボン酸塩は、結晶を生成する
ためか、得られる還元金属粉の粒度が粗いこと、
等の理由による。The reason for setting the number of carbon atoms in the carboxylic acid to be 6 or more is that (1) good dispersion cannot be obtained with carboxylic acid salts having 5 or less carbon atoms, perhaps because they are poorly soluble or insoluble in organic solvents; and (2) ) This is because carboxylic acid salts having 1 to 3 carbon atoms form crystals, or the particle size of the resulting reduced metal powder is coarse.
本発明の製造工程についてＷＣ−Ｃｏ系を例にとって説
明する。ＷＣは各種粒径のものが市販入手しうるので、
その適宜のものを出発材料とする。市販品が無い場合に
は、先きに従来技術で説明したようにタングステンと炭
素とを出発材料としてＷＣの製造が可能である。The manufacturing process of the present invention will be explained by taking the WC-Co system as an example. Since WC is commercially available in various particle sizes,
The appropriate material is used as the starting material. If a commercially available product is not available, WC can be manufactured using tungsten and carbon as starting materials, as described above in the prior art.
先ず、ＷＣ粉末と代表例としてＣ０石鹸（例えば、オク
チル酸コバルト）が配合される。カーボンブラック等の
炭素が、使用ＷＣの分析値に従い、必要に応じて補償用
に添加されうる。別途に依存するが、ＷＣ粉末は細いも
のの使用が好ましい。First, WC powder and, as a typical example, CO soap (eg, cobalt octylate) are blended. Carbon, such as carbon black, may be added for compensation as necessary, depending on the analysis of the WC used. Although it depends on the case, it is preferable to use thin WC powder.
一般に４．５μｍ以下の細粉が好ましい。微細工具製造
目的には、１μｍ未満、特にはα３〜α７μｍ１最適に
は０．５μｍ前後のものが好ましい。Generally, fine powder of 4.5 μm or less is preferred. For the purpose of manufacturing fine tools, a thickness of less than 1 μm, particularly α3 to α7 μm1, optimally around 0.5 μm is preferred.
使用するコバルト石鹸もなるたけ高純度のものが好まし
い。コバルト石鹸中のＣｏ純度として９９ｆｆｉｆｆｉ
％以上で、Ｓフリーのものが好ましい。It is preferable that the cobalt soap used be of as high a purity as possible. 99ffiffi as Co purity in cobalt soap
% or more and is S-free.
Ｃｏ石酷の量は、用徐に応じて、Ｃｏ換芦で１〜３０重
盪％、代表的には５〜２０ｆｆｉｆｉ％に相当すく量と
される。The amount of Co stone is set to be equivalent to 1 to 30% by weight, typically 5 to 20% by weight of Co, depending on the usage.
カーボンブラックのような補償用炭素は、全量の０．２
重機％までにおいて必要量添加される。Compensating carbon, such as carbon black, accounts for 0.2 of the total amount.
It is added in the required amount up to % of heavy machinery.
少ｆｉのＴｉｃ、ＴａＣ，ＮｂＣ，ＶＣ，Ｃｒ３Ｃ２を
加えることも多（、ＴｉｃはＷＣ／Ｔ ｓ ｃ ＜ 重
量比）ニア０／３０または５０１５０の複炭化物で添加
されることもある。ＴａＣ，ＮｂＣは単独で或いは複炭
化物の形で添加される。A small amount of Tic, TaC, NbC, VC, Cr3C2 is often added (Tic is WC/T sc < weight ratio) and is sometimes added as a double carbide of near 0/30 or 50150. TaC and NbC may be added alone or in the form of multiple carbides.
次いで、これら混合物は、溶剤として例えばアセトンを
使用して、振動ボールミル、回転ボールミル、遠心ボー
ルミル等のボールミルにおいて充分に混合される。混合
は、充分なる混合をもたらすべく２０〜６０時間もたら
される。溶剤としては、アセトンの池へ午サン、アルコ
ールなどが用いられる。These mixtures are then thoroughly mixed in a ball mill, such as a vibratory ball mill, a rotary ball mill, or a centrifugal ball mill, using for example acetone as a solvent. Mixing is allowed for 20 to 60 hours to provide sufficient mixing. As the solvent, acetone, alcohol, etc. are used.
次は、溶媒分離工程である。これは、真空ライカイ機、
遠心分離機、ウオターバス等の設備を使用して行われる
。溶媒を除去するに充分の温度、一般に７０〜９５℃、
好ましくは８０〜９０°Ｃの温度で実施される。通常、
ステンレス醜製のウス、キネ等で攪拌を行う。Next is the solvent separation step. This is a vacuum laikai machine,
This is done using equipment such as centrifuges and water baths. a temperature sufficient to remove the solvent, generally 70-95°C;
Preferably it is carried out at a temperature of 80-90°C. usually,
Stir with a stainless steel bowl, kine, etc.
その後、混合物は、還元処理を受ける。還元処理は、代
表的には、水素還元炉を使用して７５０〜１０００°Ｃ
の湿度で水素気流を流しつつ実施される。温度、被処理
物証等に応じて充分の還元が行われるよう還元時間が設
定される。The mixture is then subjected to a reduction treatment. Reduction treatment is typically performed at 750 to 1000°C using a hydrogen reduction furnace.
It is carried out with a hydrogen stream flowing at a humidity of . The reduction time is set to ensure sufficient reduction depending on the temperature, material to be treated, etc.
こうして、結合相としてコバルトを均一に分散したスポ
ンジ状ＷＣが得られる。粉砕後、これに、バインダー（
パラフィン、カン７アー、ポリエチレングリコール、ポ
リブテン等）を溶媒（例えばパラフィン溶媒として四塩
化炭素）に溶かした溶液の添加の下で（１〜５重ｆｆｉ
％）、例えば真空ライカイ機を使用して造粒が行われ、
その後篩別を行って目標寸法の粉末を回収する。In this way, a spongy WC in which cobalt is uniformly dispersed as a binder phase is obtained. After grinding, add a binder (
Paraffin, carbon dioxide, polyethylene glycol, polybutene, etc.) in a solvent (e.g. carbon tetrachloride as paraffin solvent) (1 to 5 times ffi
%), granulation is carried out using a vacuum laikai machine, for example,
Thereafter, sieving is performed to collect powder having the target size.
得られた微粉は、その後、通常の成形及び焼結工程に供
せられる。成形は、カム式プレス機、油圧プレス機、静
水圧プレス機等を使用して段階的に圧力を高めて或いは
一定圧力の下で０．５ｔ／ｃｍ２〜４ｔ／ｃｍ２の圧力
において行われる。The resulting fine powder is then subjected to conventional shaping and sintering steps. The molding is carried out at a pressure of 0.5 t/cm 2 to 4 t/cm 2 using a cam press, a hydraulic press, a hydrostatic press, etc., and increasing the pressure stepwise or under a constant pressure.
成形物は、必要に応じ、７００〜１０００℃において予
備焼結されうる。これは、例えば、真空炉において実施
される。その後、中間加工を行ってもよい。The molded product may be pre-sintered at 700 to 1000°C, if necessary. This is carried out, for example, in a vacuum furnace. After that, intermediate processing may be performed.
最後に焼結が行われる。焼結は、１４００〜１５００℃
、通常１４５０℃において１〜４時間行われる。Finally, sintering takes place. Sintering is at 1400-1500℃
, usually at 1450°C for 1 to 4 hours.
以上はＷＣ−Ｃｏ、ｌ＝について述べたが、本発明は結
合相を前述したような有＠酸塩として導入することを特
徴とするものであり、Ｗ Ｃ−Ｃｏ糸量外にも同様の処
理条件を設定しうることは明らかである。The above description has been about WC-Co, l=, but the present invention is characterized by introducing the binder phase as an @ acid salt as described above, and similar It is clear that the processing conditions can be set.
発明の効果
ｔ 従来技術では得られない超硬合金用結合相金属の超
微粉を、所１ｉｎｓｌｔｕ法で容易にかつ安価に得られ
る。Effects of the Invention t Ultrafine powder of binder phase metal for cemented carbide, which cannot be obtained by conventional techniques, can be easily and inexpensively obtained by the 1insltu method.
２ 結合相金属の超微粉は非常に不安定であり、流通商
品として取扱うことは種々制約を生じることが予想され
るが、本発明によれば極めて安全に超硬合金用基材に結
合相金属が理想的なまでに分散した形で得られる。2. Ultrafine powder of binder phase metal is extremely unstable, and it is expected that handling it as a commercial product will be subject to various restrictions. However, according to the present invention, it is possible to extremely safely apply binder phase metal to a base material for cemented carbide. can be obtained in an ideally dispersed form.
五 本発明から得られる超硬合金はその用途を特に限定
するものではないが、従来技術では、ユーザーの要求に
対応出来ないマイクロドリル等微細でかつ強度、切削性
が望まれる用途に最適である。5. The use of the cemented carbide obtained from the present invention is not particularly limited, but it is most suitable for applications that require fineness, strength, and machinability, such as micro drills, where conventional technology cannot meet user requirements. .
実施例１
平均粒径０．５ ｐｍのＷＣα９５ｋｙ、ＴｌＣ５９、
およびＴａＣ１０りの混合物に対し、Ｃｏとして６０り
に相当するオクチル酸Ｃｏとカーボンブラック５りおよ
びアセトン５００−を加えた混合物をボールミルに張込
み、４８Ｈｒ混合した。次いで内容物を真空ライカイ機
に移し、ライカイしながら８０℃に加温しアセトンを留
去した。内容物を取り出し水素還元炉中にセットし本案
気流５００ゴ／ ｍ １ ｍを保ちながら炉内温度を４
００°Ｃとした。還元の開始と共に排気口にオクチル酸
の蒸気が凝縮する。ＪＨｒ後炉内炉内温度００°Ｃとし
２１’Ｉｒ処理した。次にＰ内気流を窒素に切り替え説
水素処理後放冷した。かくして、結合相としてＣｏを均
一に分散したスポンジ状ＷＣが得られ、これをライカイ
機に移しパラフィン１０％を溶解した四塩化炭素を２０
０ゴ加えて４８Ｈｒライカイした後、１００ｍｅｓｈの
ふるいでし別し、通過率９５％微粉を得た。得られた微
粉をカム式プレスを用い、圧力１ｔ／口２の条件で２３
×１６×６×６Ｒ（ｍｍ）の寸法に成型した。この成型
物を真空炉中８００°ＣＸ２４Ｈｒ（ｇ変度１〜５０
ｍｍＨｇ）予備焼結した後、１４５０°ＣＸ２ Ｈｒ
（５〜１０ ） ＸｊＯｒｒｍＨ９の条件で焼結し超硬
合金を得た。この合金を常法によりエツチングした後、
顕微鏡で組織を観察すると非常に緻密かつ理想的な分散
状態にあることが認められた。また、得られた材料につ
いてＪＩＳ−１７７６２、Ｂ−０６０１に規定された硬
度と抗折力を測定し、表−１の結果を得た。Example 1 WCα95ky with an average particle size of 0.5 pm, TlC59,
A mixture of Co octylate corresponding to 60 mol of Co, 5 ml of carbon black, and 500 ml of acetone was charged into a ball mill and mixed for 48 hours. Next, the contents were transferred to a vacuum cleaner and heated to 80°C under vacuum to distill off acetone. The contents were taken out and placed in a hydrogen reduction furnace, and the temperature inside the furnace was raised to 4.5 m while maintaining an air flow of 500 g/m 1 m.
The temperature was 00°C. Octylic acid vapor condenses at the exhaust port as reduction begins. After JHr, the temperature inside the furnace was set to 00°C, and 21'Ir treatment was performed. Next, the air flow inside the P was changed to nitrogen, and after the hydrogen treatment, the reactor was allowed to cool. In this way, a sponge-like WC in which Co was uniformly dispersed as a binder phase was obtained, and this was transferred to a Raikai machine where 20% of carbon tetrachloride in which 10% of paraffin was dissolved was added.
After adding 0.0% of the powder and rinsing for 48 hours, it was sieved through a 100 mesh sieve to obtain a fine powder with a passing rate of 95%. The obtained fine powder was heated using a cam press at a pressure of 1 t/mouth for 23 hours.
It was molded into dimensions of x16 x 6 x 6R (mm). This molded product was placed in a vacuum furnace at 800°C for 24 hours (g variation 1 to 50
mmHg) After pre-sintering, 1450°CX2 Hr
(5-10) A cemented carbide was obtained by sintering under the conditions of XjOrrmH9. After etching this alloy by a conventional method,
When the structure was observed under a microscope, it was found to be extremely dense and in an ideal dispersed state. Further, the hardness and transverse rupture strength of the obtained material as specified in JIS-17762 and B-0601 were measured, and the results shown in Table 1 were obtained.
実施例２
実施例１においてオクチル酸ＣＯに代えてオクチル＠Ｎ
ｌを使用して同じ処理を行い、非強磁性超硬合金を得た
。以下、同様の評価を行なった。Example 2 Octyl@N instead of octylic acid CO in Example 1
The same treatment was carried out using L to obtain a non-ferromagnetic cemented carbide. Similar evaluations were made below.
結果を表−１に示す。The results are shown in Table-1.
実施例３
実施例１においてオクチル酸ｃｏに代えてナフテン酸Ｃ
ｏを用いて同じ処理を行い、同様の結果を得た。以下、
同様の評価を行なった。結果を表−１に示す。Example 3 In Example 1, naphthenic acid C was substituted for octylic acid co.
The same process was performed using o and similar results were obtained. below,
A similar evaluation was conducted. The results are shown in Table-1.
実施例４
実施例１においてオクチルｉ！ｉＩＣｏに代えてステア
リンｆｉ Ｃａを用いて同じ処理を行い、同様の結果を
得た。以下、同様の評価を行なった。結果を表−１に示
す。Example 4 In Example 1, Octyl i! The same treatment was performed using stearin fi Ca instead of iICo and similar results were obtained. Similar evaluations were made below. The results are shown in Table-1.
比較例
実施例１のオクチル酸Ｃｏに代えてコバルト粉末（平均
粒径ｔｏ−ｔｓμｍ）を用いまた、水素還元の工程を経
ない以外は、総て同様にして超硬合金を得た。以下、同
様の評価を行ない、それらの測定結果を表−１に示した
。Comparative Example A cemented carbide was obtained in the same manner as in Example 1 except that cobalt powder (average particle size to-ts μm) was used instead of Co octylate and the hydrogen reduction step was not performed. Similar evaluations were carried out below, and the measurement results are shown in Table 1.
Claims (1)
ケル及び鉄のうちから選択される少くとも１種の結合用
金属とから成る混合物を成形及び焼結することにより焼
結複合材料を製造する方法において、前記混合物を、前
記セラミクスと前記結合用金属の炭素数６以上のカルボ
ン酸塩との混合物を還元処理することにより調製するこ
とを特徴とする焼結複合材料の製造方法。 ２）セラミクスが酸化物、炭化物、ホウ化物、窒化物及
びケイ化物のうちから選択される特許請求の範囲第１項
記載の方法。 ３）セラミクスが周期律表IVａ族金属（Ｔｉ、Ｚｒ、Ｈ
ｆ）、Ｖａ族金属（Ｖ、Ｎｂ、Ｔａ）及びVIａ族金属（
Ｃｒ、Ｍｏ、Ｗ）の炭化物である特許請求の範囲第１項
記載の方法。 ４）炭素数６以上のカルボン酸塩が脂肪酸、樹脂酸及び
ナフテン酸の金属塩から選択される特許請求の範囲第１
項記載の方法。 ５）炭素数６以上のカルボン酸塩が、オクチル酸、ナフ
テン酸及びステアリン酸の金属塩から選択される特許請
求の範囲第１項記載の方法。[Claims] 1) Sintering by forming and sintering a mixture consisting of at least one type of high melting point ceramic and at least one type of bonding metal selected from cobalt, nickel, and iron. A method for producing a composite material, characterized in that the mixture is prepared by reducing a mixture of the ceramic and the carboxylic acid salt having 6 or more carbon atoms of the bonding metal. Method. 2) A method according to claim 1, wherein the ceramic is selected from oxides, carbides, borides, nitrides and silicides. 3) Ceramics contain group IVa metals of the periodic table (Ti, Zr, H
f), Va group metals (V, Nb, Ta) and VIa group metals (
The method according to claim 1, wherein the carbide is a carbide of Cr, Mo, W). 4) Claim 1 in which the carboxylic acid salt having 6 or more carbon atoms is selected from metal salts of fatty acids, resin acids, and naphthenic acids.
The method described in section. 5) The method according to claim 1, wherein the carboxylic acid salt having 6 or more carbon atoms is selected from metal salts of octylic acid, naphthenic acid, and stearic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101995A JPS62260027A (en) | 1986-05-06 | 1986-05-06 | Manufacture of sintered composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61101995A JPS62260027A (en) | 1986-05-06 | 1986-05-06 | Manufacture of sintered composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62260027A true JPS62260027A (en) | 1987-11-12 |
Family
ID=14315406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61101995A Pending JPS62260027A (en) | 1986-05-06 | 1986-05-06 | Manufacture of sintered composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62260027A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003518195A (en) * | 1999-12-22 | 2003-06-03 | エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Powder mixtures and composite powders, their preparation and their use in composites |
| JP2010121192A (en) * | 2008-11-21 | 2010-06-03 | Japan New Metals Co Ltd | Composite powder and method for producing the same |
| WO2017195695A1 (en) | 2016-05-11 | 2017-11-16 | 日立金属株式会社 | Composite member manufacturing method and composite member |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4885406A (en) * | 1972-02-17 | 1973-11-13 | ||
| JPS5024799A (en) * | 1973-07-04 | 1975-03-17 |
-
1986
- 1986-05-06 JP JP61101995A patent/JPS62260027A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4885406A (en) * | 1972-02-17 | 1973-11-13 | ||
| JPS5024799A (en) * | 1973-07-04 | 1975-03-17 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003518195A (en) * | 1999-12-22 | 2003-06-03 | エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシユレンクテル・ハフツング | Powder mixtures and composite powders, their preparation and their use in composites |
| JP4969008B2 (en) * | 1999-12-22 | 2012-07-04 | エイチ・シー・スタルク・ゲゼルシヤフト・ミツト・ベシュレンクテル・ハフツング | Powder mixtures and composite powders, methods for their production and their use in composite materials |
| JP2010121192A (en) * | 2008-11-21 | 2010-06-03 | Japan New Metals Co Ltd | Composite powder and method for producing the same |
| WO2017195695A1 (en) | 2016-05-11 | 2017-11-16 | 日立金属株式会社 | Composite member manufacturing method and composite member |
| US11786967B2 (en) | 2016-05-11 | 2023-10-17 | Proterial, Ltd. | Composite member manufacturing method and composite member |
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