JP5993763B2 - Composite nickel particles - Google Patents
Composite nickel particles Download PDFInfo
- Publication number
- JP5993763B2 JP5993763B2 JP2013061306A JP2013061306A JP5993763B2 JP 5993763 B2 JP5993763 B2 JP 5993763B2 JP 2013061306 A JP2013061306 A JP 2013061306A JP 2013061306 A JP2013061306 A JP 2013061306A JP 5993763 B2 JP5993763 B2 JP 5993763B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- composite nickel
- particles
- composite
- nickel particles
- 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.)
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 542
- 239000002245 particle Substances 0.000 title claims description 310
- 229910052759 nickel Inorganic materials 0.000 title claims description 266
- 239000002131 composite material Substances 0.000 title claims description 218
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 39
- 238000000576 coating method Methods 0.000 claims description 39
- 238000002411 thermogravimetry Methods 0.000 claims description 30
- 238000002441 X-ray diffraction Methods 0.000 claims description 29
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 230000004580 weight loss Effects 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 15
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 28
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 27
- 238000000034 method Methods 0.000 description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000002002 slurry Substances 0.000 description 23
- 239000000460 chlorine Substances 0.000 description 22
- 238000005245 sintering Methods 0.000 description 21
- 238000000921 elemental analysis Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- -1 nickel salt Chemical class 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 13
- 150000003141 primary amines Chemical class 0.000 description 13
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 9
- 238000004220 aggregation Methods 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 8
- 230000000536 complexating effect Effects 0.000 description 8
- 239000013585 weight reducing agent Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 230000009918 complex formation Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002815 nickel Chemical class 0.000 description 7
- 229910001453 nickel ion Inorganic materials 0.000 description 7
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002667 nucleating agent Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 230000032798 delamination Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 4
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LSIWWRSSSOYIMS-UHFFFAOYSA-L copper;diformate;tetrahydrate Chemical compound O.O.O.O.[Cu+2].[O-]C=O.[O-]C=O LSIWWRSSSOYIMS-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-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
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 description 1
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- 239000010955 niobium Substances 0.000 description 1
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- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 150000003057 platinum Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 239000011975 tartaric acid Substances 0.000 description 1
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- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Powder Metallurgy (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
本発明は、焼結性に優れた複合ニッケル粒子に関し、より詳しくは、例えば積層セラミックスコンデンサ（ＭＬＣＣ）の内部電極形成用などの導電ペーストに好適に利用できる複合ニッケル粒子に関する。 The present invention relates to composite nickel particles having excellent sinterability, and more particularly to composite nickel particles that can be suitably used for conductive pastes for forming internal electrodes of multilayer ceramic capacitors (MLCC), for example.
ＭＬＣＣは、セラミックス誘電体と内部電極とを交互に層状に重ねて圧着し、焼成して一体化させたものである。このようなＭＬＣＣの内部電極を形成する際には、内部電極材料である金属ニッケル粒子をペースト化したのち、これをセラミックス基板上に印刷する。次いで、乾燥、積層及び圧着した後、通常、酸素雰囲気下で約２５０〜４００℃に加熱して有機物を除去するための脱バインダー処理を行なう。このような加熱処理を行なうことによって、金属ニッケル粒子は酸化され、それにより体積膨張が起きる。さらにその後、還元性雰囲気下で高温（例えばチタン酸バリウム系セラミックス誘電体では約１２００〜１４００℃）で焼結を行なうが、この焼結により、一旦酸化された金属ニッケル粒子が還元されるとともに、体積の収縮が生じる。 In MLCC, ceramic dielectrics and internal electrodes are alternately layered and pressure-bonded, and fired and integrated. When forming such MLCC internal electrodes, metallic nickel particles, which are internal electrode materials, are made into a paste and then printed on a ceramic substrate. Next, after drying, laminating and press-bonding, a binder removal treatment for removing organic substances is usually performed by heating to about 250 to 400 ° C. in an oxygen atmosphere. By performing such a heat treatment, the metallic nickel particles are oxidized, thereby causing volume expansion. Further, after that, sintering is performed under a reducing atmosphere at a high temperature (for example, about 1200 to 1400 ° C. in the case of a barium titanate ceramic dielectric). By this sintering, once oxidized metal nickel particles are reduced, Volume shrinkage occurs.
このように、ＭＬＣＣの製造工程では、酸化反応や還元反応によって金属ニッケル粒子が膨張・収縮して体積変化が生じる。また、セラミックス誘電体も焼結により膨張・収縮し、体積変化が生じる。ところが、金属ニッケル粒子とセラミックス誘電体とでは、焼結時における膨張・収縮による体積変化の挙動が異なるため、デラミネーションやクラック等の欠陥を生じるおそれがある。 Thus, in the manufacturing process of MLCC, metallic nickel particles expand and contract due to an oxidation reaction or a reduction reaction, resulting in a volume change. The ceramic dielectric also expands and contracts due to sintering, resulting in a volume change. However, since the behavior of volume change due to expansion / contraction during sintering differs between the metallic nickel particles and the ceramic dielectric, defects such as delamination and cracks may occur.
このような問題を解決する手段として、金属ニッケル粒子の表面に存在する水酸化物を熱処理により酸化物に変化させて結晶質の酸化被膜を形成した金属ニッケル粒子が提案されている（例えば、特許文献１参照）。このような金属ニッケル粒子は、表面に緻密で厚い酸化被膜が形成されているので、金属ニッケル粒子の内部への酸化の進行は抑制されるものの、焼結時においては、拡散係数の大きな酸化物が、セラミックス誘電体中へ拡散する懸念がある。また、特許文献１のように、粒子表面の被膜が結晶性の高いものであると、脱バインダー工程で粒子の急激な温度上昇を抑制する作用が小さいため、粒子の焼結や凝集を引き起こす原因となりやすい。 As means for solving such a problem, metal nickel particles in which a hydroxide existing on the surface of the metal nickel particles is changed to an oxide by heat treatment to form a crystalline oxide film have been proposed (for example, patents). Reference 1). Since such metal nickel particles have a dense and thick oxide film formed on the surface, the progress of oxidation to the inside of the metal nickel particles is suppressed, but an oxide having a large diffusion coefficient during sintering. However, there is a concern that it may diffuse into the ceramic dielectric. In addition, as in Patent Document 1, when the coating on the particle surface has high crystallinity, the effect of suppressing the rapid temperature rise of the particle in the binder removal step is small, which causes the sintering and aggregation of the particles. It is easy to become.
本発明の目的は、粒子の凝集や融着、脱バインダー時の金属ニッケル粒子の急激な温度上昇を抑制しつつ、耐焼結性を向上させた複合ニッケル粒子を提供することである。 An object of the present invention is to provide composite nickel particles having improved sintering resistance while suppressing rapid temperature rise of the metal nickel particles during particle aggregation and fusion and debinding.
本発明者らは、鋭意研究を重ねた結果、ニッケル粒子の酸化・還元処理時における熱挙動に着目し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have focused on the thermal behavior during the oxidation / reduction treatment of nickel particles and have completed the present invention.
すなわち、本発明の複合ニッケル粒子は、金属ニッケル粒子の表面に、水酸化物の被膜を有する複合ニッケル粒子である。この複合ニッケル粒子は、酸素元素を０．２〜２．５質量％の範囲内で含有し、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内であり、かつＸ線回折により結晶質の水酸化ニッケルが観測されないことを特徴とする。 That is, the composite nickel particles of the present invention are composite nickel particles having a hydroxide coating on the surface of the metal nickel particles. The composite nickel particles contain elemental oxygen in the range of 0.2 to 2.5% by mass, and the weight loss in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere. The rate is in the range of 0.5 to 3%, and crystalline nickel hydroxide is not observed by X-ray diffraction.
本発明の複合ニッケル粒子は、塩化ニッケルを還元して得られるものであってもよい。 The composite nickel particles of the present invention may be obtained by reducing nickel chloride.
本発明の複合ニッケル粒子は、前記複合ニッケル粒子の走査型電子顕微鏡観察による平均粒子径が２０〜２５０ｎｍの範囲内であり、粒子径の変動係数（標準偏差／平均粒子径）が０．２以下であってもよい。 The composite nickel particles of the present invention have an average particle diameter in the range of 20 to 250 nm as observed with a scanning electron microscope of the composite nickel particles, and a variation coefficient (standard deviation / average particle diameter) of the particle diameter of 0.2 or less. It may be.
本発明の複合ニッケル粒子は、水酸化物の被膜を有し、酸素元素を０．２〜２．５質量％の範囲内で含有する。この水酸化物の被膜は、Ｘ線回折により結晶質の水酸化ニッケルが観測されないアモルファス状態の被膜であり、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内に制御されている。このことにより、脱バインダー工程で水酸化物の被膜が速やかに脱水されて酸化物の被膜に変化する。この脱水反応により、粒子の急激な温度上昇を抑制し、４００℃以下の低温での粒子の焼結や凝集を防ぐことができる。また、このように生成した酸化物の被膜により、焼結時には複合ニッケル粒子の内部への急激な酸化を抑制することができるので、デラミネーションやクラック等の欠陥の発生を防ぐことができる。このような複合ニッケル粒子は、例えば積層セラミックコンデンサの内部電極の材料として好適に用いることができる。 The composite nickel particles of the present invention have a hydroxide coating and contain an oxygen element in the range of 0.2 to 2.5 mass%. This hydroxide film is an amorphous film in which no crystalline nickel hydroxide is observed by X-ray diffraction, and is measured in a temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere. Is controlled within a range of 0.5 to 3%. As a result, the hydroxide film is quickly dehydrated in the binder removal step to change to an oxide film. By this dehydration reaction, the rapid temperature rise of the particles can be suppressed, and the sintering and aggregation of the particles at a low temperature of 400 ° C. or less can be prevented. Further, since the oxide film thus generated can suppress rapid oxidation of the composite nickel particles into the interior during sintering, it is possible to prevent the occurrence of defects such as delamination and cracks. Such composite nickel particles can be suitably used as a material for an internal electrode of a multilayer ceramic capacitor, for example.
［複合ニッケル粒子］
本実施の形態の複合ニッケル粒子は、金属ニッケル粒子の表面に、水酸化物の被膜を有する複合ニッケル粒子である。この複合ニッケル粒子は、酸素元素を０．２〜２．５質量％の範囲内で含有するとともに、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内であり、かつＸ線回折により結晶質の水酸化ニッケルが観測されないという特徴を有している。
[Composite nickel particles]
The composite nickel particles of the present embodiment are composite nickel particles having a hydroxide coating on the surface of the metal nickel particles. This composite nickel particle contains elemental oxygen in the range of 0.2 to 2.5% by mass, and the weight in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere. The reduction rate is in the range of 0.5 to 3%, and crystalline nickel hydroxide is not observed by X-ray diffraction.
本実施の形態の複合ニッケル粒子は、ニッケル元素を含有する。ニッケル元素の含有量は、その使用目的に応じて適宜選択すればよいが、ニッケル元素の量を、複合ニッケル粒子１００質量部に対し、好ましくは９０質量部以上、より好ましくは９５質量部以上とすることがよい。ニッケル以外の金属としては、例えば、チタン、コバルト、銅、クロム、マンガン、鉄、アルミニウム、ナトリウム、カリウム、マグネシウム、ジルコニウム、スズ、タングステン、モリブデン、バナジウム、バリウム、カルシウム、ストロンチウム、シリコン、アルミニウム、リン等の卑金属、金、銀、白金、パラジウム、イリジウム、オスミウム、ルテニウム、ロジウム、レニウム、ネオジウム、ニオブ、ホロニウム、ディスプロヂウム、イットリウム等の貴金属、希土類金属を挙げることができる。これらは、単独で又は２種以上含有していてもよく、また水素、炭素、窒素、硫黄、ボロン等の金属元素以外の元素を含有していてもよいし、これらの合金であってもよい。 The composite nickel particles of the present embodiment contain a nickel element. The content of nickel element may be appropriately selected according to the purpose of use, but the amount of nickel element is preferably 90 parts by mass or more, more preferably 95 parts by mass or more with respect to 100 parts by mass of the composite nickel particles. It is good to do. Examples of metals other than nickel include titanium, cobalt, copper, chromium, manganese, iron, aluminum, sodium, potassium, magnesium, zirconium, tin, tungsten, molybdenum, vanadium, barium, calcium, strontium, silicon, aluminum, and phosphorus. Base metals such as gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium, neodymium, niobium, holonium, dysprodium, yttrium and the like, and rare earth metals. These may be contained alone or in combination of two or more, may contain elements other than metal elements such as hydrogen, carbon, nitrogen, sulfur and boron, and may be alloys thereof. .
本実施の形態の複合ニッケル粒子は、酸素元素を含有している。複合ニッケル粒子における酸素元素の含有量は０．２〜２．５質量％の範囲内であり、好ましくは０．５〜２．０質量％の範囲内がよい。酸素元素の含有量が、０．２質量％未満であると、複合ニッケル粒子の表面活性を抑制する効果が小さくなる傾向があり、２．５質量％を超えると、焼結時に体積変化が生じやすくなる傾向がある。この酸素元素の含有量は、複合ニッケル粒子の元素分析により確認することができる。このような酸素元素の含有量は、複合ニッケル粒子の表面に部分的に存在する水酸化物の被膜に含有される酸素元素に由来するものと考えられる。このことは、複合ニッケル粒子における水酸化物の被膜の厚みが、平均粒子径の大小によらず殆ど大差がないのに対し、複合ニッケル粒子の平均粒子径が小さくなるにつれ、酸素元素の含有量が高くなる傾向があることから推察される。すなわち、複合ニッケル粒子の平均粒子径が小さいほど、その総表面積（全ての複合ニッケル粒子の合計の表面積）が大きいので、複合ニッケル粒子全体に占める酸素元素の含有量が相対的に大きくなると考えられる。 The composite nickel particles of the present embodiment contain an oxygen element. The content of oxygen element in the composite nickel particles is in the range of 0.2 to 2.5% by mass, and preferably in the range of 0.5 to 2.0% by mass. If the content of oxygen element is less than 0.2% by mass, the effect of suppressing the surface activity of the composite nickel particles tends to be small, and if it exceeds 2.5% by mass, a volume change occurs during sintering. It tends to be easier. The oxygen element content can be confirmed by elemental analysis of the composite nickel particles. The content of such an oxygen element is considered to be derived from the oxygen element contained in the hydroxide film partially existing on the surface of the composite nickel particle. This is because the thickness of the hydroxide coating film on the composite nickel particles is almost the same regardless of the average particle size, but as the average particle size of the composite nickel particles decreases, the content of oxygen element Is presumed to be higher. That is, the smaller the average particle diameter of the composite nickel particles, the larger the total surface area (the total surface area of all composite nickel particles), and therefore the oxygen element content in the entire composite nickel particles is considered to be relatively large. .
本実施の形態の複合ニッケル粒子は、複合ニッケル粒子の表面に存在する水酸化物の被膜として、例えば水酸化ニッケル（Ｎｉ（ＯＨ）２）の被膜が形成されている。このような被膜は、複合ニッケル粒子を構成する金属ニッケルの表面に部分的に存在する被膜でもよいし、該粒子の全表面に亘る被膜でもよい。なお、水酸化物の被膜には、金属ニッケルの表面に存在する吸着水を含んでいてもよい。このような水酸化物の被膜により、複合ニッケル粒子の表面活性が抑制され、脱バインダー工程におけるバインダーの低温燃焼又は急激な熱分解を抑制することができる。このとき、水酸化物の被膜が脱水によって酸化物の被膜となり、複合ニッケル粒子の焼結が抑制されると考えられる。また、還元雰囲気下での熱処理により、複合ニッケル粒子における水酸化物の被膜が還元されて存在しなくなると、複合ニッケル粒子の焼結が開始される。 In the composite nickel particles of the present embodiment, for example, a nickel hydroxide (Ni (OH) 2 ) coating is formed as a hydroxide coating on the surface of the composite nickel particles. Such a coating may be a coating partially existing on the surface of the metallic nickel constituting the composite nickel particles, or may be a coating covering the entire surface of the particles. The hydroxide coating may contain adsorbed water present on the surface of the metallic nickel. By such a hydroxide coating, the surface activity of the composite nickel particles is suppressed, and low temperature combustion or rapid thermal decomposition of the binder in the debinding process can be suppressed. At this time, it is considered that the hydroxide film becomes an oxide film by dehydration, and sintering of the composite nickel particles is suppressed. Further, when the hydroxide coating on the composite nickel particles is reduced and no longer exists by heat treatment in a reducing atmosphere, sintering of the composite nickel particles is started.
水酸化物の被膜は、Ｘ線回折により結晶質の水酸化ニッケルが観測されないという特徴を有している。このことは、本実施の形態の複合ニッケル粒子において、水酸化物の被膜が、結晶性が低いアモルファス状の水酸化ニッケルによって構成されているか、又は、水酸化物の被膜が、Ｘ線回折によって検出できないレベルのものであることを意味している。水酸化物の被膜がアモルファス状又はＸ線回折による検出限界以下とすることによって、結晶性の高い水酸化物の被膜に比べて脱バインダー工程において脱水がスムーズに行われる。すなわち、低酸素雰囲気で約２５０〜４００℃に加熱処理される脱バインダー工程では、金属ニッケルを被覆する水酸化物の被膜から水分が揮発し、除去されて酸化物の被膜に変化する。このような脱水反応は、水酸化物の被膜の結晶性が高い場合よりも、アモルファス状又はＸ線回折による検出限界以下である場合の方が速やかに進行しやすい。そして、金属ニッケルを被覆する水酸化物の被膜からの水分の揮発は、気化熱によって金属ニッケルの急激な温度上昇を抑制して、４００℃以下の低温での焼結や凝集を防ぐ作用を有している。 The hydroxide coating is characterized in that crystalline nickel hydroxide is not observed by X-ray diffraction. This is because, in the composite nickel particles of the present embodiment, the hydroxide film is composed of amorphous nickel hydroxide having low crystallinity, or the hydroxide film is formed by X-ray diffraction. It means that the level is undetectable. By making the hydroxide film amorphous or less than the detection limit by X-ray diffraction, dehydration can be performed more smoothly in the debinding step than the highly crystalline hydroxide film. That is, in the binder removal step in which the heat treatment is performed at about 250 to 400 ° C. in a low oxygen atmosphere, moisture is volatilized and removed from the hydroxide film covering the metallic nickel, and changes to an oxide film. Such a dehydration reaction is more likely to proceed more rapidly in the amorphous state or below the detection limit by X-ray diffraction than in the case where the hydroxide film has high crystallinity. The volatilization of moisture from the hydroxide coating covering the metallic nickel has the effect of suppressing the rapid temperature rise of the metallic nickel by the heat of vaporization and preventing sintering and aggregation at a low temperature of 400 ° C. or lower. doing.
本実施の形態の複合ニッケル粒子は、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内であり、好ましくは１〜３％の範囲内である。このような温度領域での重量減少は、上記水酸化物の被膜からの脱水によって酸化物の被膜に変化することに起因するものであるが、複合ニッケル粒子の表面に有機物や吸着水が存在している場合もこの温度領域で重量減少が確認される。これらを考慮し、このような重量減少率を０．５〜３％の範囲内に制御することで、脱バインダー工程での急激な温度上昇を抑制しながら、酸化物の被膜が必要以上に厚くなることを抑制し、焼結時の体積の急激な減少を回避することができる。重量減少率が、０．５％未満であると、複合ニッケル粒子の表面活性を抑制する効果が小さくなるばかりでなく、分散性が低下し、３％を超えると、ペーストとしての複合ニッケル粒子の含有量を十分に高めることが困難となるばかりでなく、脱ガス量の増加によりデラミネーションの原因となりやすい。 The composite nickel particles of the present embodiment preferably have a weight reduction rate in the temperature range of 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere in the range of 0.5 to 3%. Is in the range of 1-3%. The weight loss in such a temperature range is due to the change from the hydroxide coating to the oxide coating by dehydration, but there are organic substances and adsorbed water on the surface of the composite nickel particles. In this case, weight reduction is confirmed in this temperature range. Considering these, by controlling the weight reduction rate within the range of 0.5 to 3%, the oxide film becomes thicker than necessary while suppressing a rapid temperature increase in the binder removal step. It is possible to prevent the sudden decrease in volume during sintering. When the weight reduction rate is less than 0.5%, not only the effect of suppressing the surface activity of the composite nickel particles becomes small, but also the dispersibility decreases, and when it exceeds 3%, the composite nickel particles as a paste Not only is it difficult to sufficiently increase the content, but delamination tends to occur due to an increase in the amount of degassing.
水酸化物の被膜の平均厚みは、複合ニッケル粒子の凝集を効果的に抑制する観点から、例えば１〜６ｎｍの範囲内が好ましく、２〜５ｎｍの範囲内であることがより好ましい。水酸化物の被膜の平均厚みが１ｎｍ未満では、脱バインダー時の凝集抑制効果が十分に得られず、６ｎｍを超える場合は、焼結時の収縮が大きくなり過ぎる。 From the viewpoint of effectively suppressing aggregation of the composite nickel particles, the average thickness of the hydroxide coating is preferably in the range of 1 to 6 nm, and more preferably in the range of 2 to 5 nm. If the average thickness of the hydroxide coating is less than 1 nm, the effect of suppressing aggregation during debinding is not sufficiently obtained, and if it exceeds 6 nm, shrinkage during sintering becomes too large.
本実施の形態の複合ニッケル粒子は、炭素元素を含有していてもよい。複合ニッケル粒子の炭素元素の量は、複合ニッケル粒子に対し、好ましくは０．１〜１．５質量％の範囲内であり、より好ましくは０．５〜１．０質量％の範囲内である。この炭素元素の量は、複合ニッケル粒子の元素分析により確認することができる。炭素元素は、複合ニッケル粒子の表面に存在する有機化合物に由来するものであるが、炭素元素の一部が複合ニッケル粒子の内部に存在していてもよい。複合ニッケル粒子の表面に存在する炭素元素は、複合ニッケル粒子の凝集を抑制し、分散性向上に寄与し、複合ニッケル粒子に含有する酸素元素の還元を促進させる。従って、炭素元素が０．１質量％未満では、複合ニッケル粒子の凝集が生じやすくなり、１．５質量％を超えると、焼結時に炭化して残炭となり、これがガス化することによって粒子の膨れの原因となる。 The composite nickel particles of the present embodiment may contain a carbon element. The amount of carbon element in the composite nickel particles is preferably in the range of 0.1 to 1.5% by mass, more preferably in the range of 0.5 to 1.0% by mass with respect to the composite nickel particles. . The amount of this carbon element can be confirmed by elemental analysis of the composite nickel particles. The carbon element is derived from an organic compound present on the surface of the composite nickel particle, but a part of the carbon element may be present inside the composite nickel particle. The carbon element present on the surface of the composite nickel particle suppresses the aggregation of the composite nickel particle, contributes to the improvement of dispersibility, and promotes the reduction of the oxygen element contained in the composite nickel particle. Therefore, if the carbon element is less than 0.1% by mass, aggregation of the composite nickel particles tends to occur, and if it exceeds 1.5% by mass, carbonization occurs during sintering to become residual carbon, which is gasified by gasification. Causes blistering.
本実施の形態の複合ニッケル粒子は、塩化ニッケルを還元して得られるものであることが好ましい。塩化ニッケルを原料とすることによって、複合ニッケル粒子の主成分である金属ニッケルの結晶性を高くすることができる。また、別の観点から、複合ニッケル粒子の一次粒子径に対して、その結晶子径が２０％以上とすることが好ましい。このように、結晶性を高め、結晶子径を大きくすることにより、アモルファス性の金属ニッケルを主体とする複合ニッケル粒子に比べて、低温焼結を抑制する効果が大きくなる。このような高い結晶性を得るため、原料として用いるニッケル前駆体の５０質量％以上が塩化ニッケルであることが好ましい。なお、複合ニッケル粒子を製造する方法については、後述する。 The composite nickel particles of the present embodiment are preferably obtained by reducing nickel chloride. By using nickel chloride as a raw material, the crystallinity of metallic nickel, which is the main component of the composite nickel particles, can be increased. From another viewpoint, the crystallite diameter is preferably 20% or more with respect to the primary particle diameter of the composite nickel particles. As described above, by increasing the crystallinity and enlarging the crystallite diameter, the effect of suppressing low-temperature sintering is increased as compared with composite nickel particles mainly composed of amorphous metallic nickel. In order to obtain such high crystallinity, it is preferable that 50% by mass or more of the nickel precursor used as a raw material is nickel chloride. The method for producing composite nickel particles will be described later.
本実施の形態の複合ニッケル粒子は、塩化ニッケルを原料として好ましく製造されるが、塩化ニッケルを原料として用いると、複合ニッケル粒子中に塩素元素が残留する場合がある。塩素元素の含有量は、９００質量ｐｐｍ未満であることが好ましく、１００質量ｐｐｍ未満であることがより好ましい。複合ニッケル粒子中の塩素は、複合ニッケル粒子の酸化を促進させ該粒子の劣化の原因となるばかりでなく、導電ペーストを形成した際の経時劣化や、該粒子を用いてＭＬＣＣの電極を形成した場合にその特性に影響する可能性があり、極力低減することが好ましい。複合ニッケル粒子に含有される塩素は、複合ニッケル粒子を酸処理することによって除去することができる。この酸処理の方法については後述する。 The composite nickel particles of the present embodiment are preferably manufactured using nickel chloride as a raw material, but when nickel chloride is used as a raw material, chlorine element may remain in the composite nickel particles. The content of chlorine element is preferably less than 900 mass ppm, more preferably less than 100 mass ppm. Chlorine in the composite nickel particles not only promotes oxidation of the composite nickel particles and causes deterioration of the particles, but also deteriorates over time when forming the conductive paste, and forms MLCC electrodes using the particles. In some cases, the characteristics may be affected, and it is preferable to reduce as much as possible. Chlorine contained in the composite nickel particles can be removed by acid treatment of the composite nickel particles. This acid treatment method will be described later.
本実施の形態に係る複合ニッケル粒子は、走査型電子顕微鏡観察による平均粒子径が２０〜２５０ｎｍの範囲内、好ましくは４０〜１５０ｎｍの範囲内がよい。別の観点から、ＢＥＴ測定による平均粒子径が２０〜２５０ｎｍの範囲内、好ましくは４０〜１５０ｎｍの範囲内がよい。複合ニッケル粒子の平均粒子径が上記下限値を下回ると、脱バインダー時の加熱で複合ニッケル粒子同士が凝集又溶融しやすくなり、また酸素を取り込みやすくなるため、複合ニッケル粒子の体積膨張や収縮変化が大きくなる。一方、複合ニッケル粒子の平均粒子径が上記上限値を上回ると、最小径の粒子及び最大径の粒子の分布幅が大きくなり、複合ニッケル粒子をＭＬＣＣの電極に利用した場合に、巨大粒子の存在によりショート不良を起こしやすい。 The composite nickel particles according to the present embodiment have an average particle diameter in the range of 20 to 250 nm, preferably in the range of 40 to 150 nm, as observed by a scanning electron microscope. From another viewpoint, the average particle diameter by BET measurement is in the range of 20 to 250 nm, preferably in the range of 40 to 150 nm. If the average particle diameter of the composite nickel particles is below the above lower limit value, the composite nickel particles are likely to aggregate or melt by heating during debinding, and more easily take in oxygen. Becomes larger. On the other hand, when the average particle diameter of the composite nickel particles exceeds the above upper limit, the distribution width of the minimum diameter particles and the maximum diameter particles becomes large, and when the composite nickel particles are used as an MLCC electrode, the presence of large particles It is easy to cause a short circuit.
本実施の形態に係る複合ニッケル粒子は、粒子径の変動係数（ＣＶ）が０．２以下であることが好ましい。変動係数を０．２以下とすることで、ペースト塗布後の乾燥塗膜の表面平滑性が得られやすい。 The composite nickel particles according to the present embodiment preferably have a coefficient of variation (CV) in particle diameter of 0.2 or less. By setting the coefficient of variation to 0.2 or less, it is easy to obtain the surface smoothness of the dried coating film after applying the paste.
［複合ニッケル粒子の製造方法］
次に、本実施の形態の複合ニッケル粒子の製造方法について説明する。
[Production method of composite nickel particles]
Next, the manufacturing method of the composite nickel particle of this Embodiment is demonstrated.
本実施の形態の複合ニッケル粒子は、気相法や液相法などの方法により得られるが、その製造方法については特に限定されない。気相法では、例えば、気化部、反応部、冷却部を有する反応装置を用いるとともに、原料として塩化ニッケルを用い、この塩化ニッケルを気化部で加熱気化した後にキャリアガスで反応部に移送し、ここで水素と接触させることによって粒子状に金属を析出させ、その後、得られた複合ニッケル粒子を冷却部で冷却するようにして得ることができる。反応温度は、例えば９５０℃〜１１００℃程度に制御すればよい。 The composite nickel particles of the present embodiment can be obtained by a method such as a gas phase method or a liquid phase method, but the production method is not particularly limited. In the vapor phase method, for example, using a reaction apparatus having a vaporization section, a reaction section, and a cooling section, and using nickel chloride as a raw material, the nickel chloride is heated and vaporized in the vaporization section and then transferred to the reaction section with a carrier gas, Here, the metal can be deposited in a particulate form by contacting with hydrogen, and then the obtained composite nickel particles can be cooled in the cooling section. What is necessary is just to control reaction temperature to about 950 degreeC-1100 degreeC, for example.
この方法における複合ニッケル粒子の粒径制御は、例えばキャリアガスの流速を制御することによって実施できる。一般に、キャリアガスの流速を上昇させれば、得られる複合ニッケル粒子の粒径は小さくなる傾向がある。また、得られた複合ニッケル粒子は、例えば遠心力を用いた分級手段などを用いることによって変動係数を制御することもできる。 The particle diameter control of the composite nickel particles in this method can be carried out, for example, by controlling the flow rate of the carrier gas. Generally, if the flow rate of the carrier gas is increased, the particle diameter of the obtained composite nickel particles tends to be small. In addition, the coefficient of variation of the obtained composite nickel particles can be controlled by using, for example, classification means using centrifugal force.
気相法は液相法に比べて製造コストが高価になりがちであるので、液相法を適用することは有利である。液相法のなかでも、粒子径分布が狭い複合ニッケル粒子を短時間で容易に製造する方法として、下記の工程Ａ〜Ｃ；
Ａ）金属ニッケルの前駆体であるニッケル塩を有機溶媒に溶解して、ニッケル錯体を生成させた錯化反応液を得る工程、
Ｂ）錯化反応液を、マイクロ波照射によって加熱して、複合ニッケル粒子のスラリーを得る工程、
Ｃ）複合ニッケル粒子のスラリーから複合ニッケル粒子を単離する工程、
を具える方法が好ましい。
Since the gas phase method tends to be expensive to produce compared to the liquid phase method, it is advantageous to apply the liquid phase method. Among the liquid phase methods, as a method for easily producing composite nickel particles having a narrow particle size distribution in a short time, the following steps A to C;
A) A step of obtaining a complexing reaction solution in which a nickel salt, which is a precursor of metallic nickel, is dissolved in an organic solvent to form a nickel complex,
B) A step of heating the complexing reaction solution by microwave irradiation to obtain a slurry of composite nickel particles,
C) isolating the composite nickel particles from the composite nickel particle slurry;
A method comprising
マイクロ波照射による錯化反応液の加熱は、該反応液内の均一加熱を可能とし、かつエネルギーを媒体に直接与えることができるため、急速加熱を行なうことができる。これにより、反応液全体を所望の温度に均一にすることができ、ニッケル錯体（又はニッケルイオン）の還元、核生成、核成長各々の過程を溶液全体において同時に生じさせ、結果として粒子径分布の狭い単分散な粒子を短時間で容易に製造することができる。特に、走査型電子顕微鏡観察による平均粒子径が２０〜１５０ｎｍの範囲内にある複合ニッケル粒子を製造するのに好適である。 Heating of the complexing reaction solution by microwave irradiation enables uniform heating in the reaction solution and can directly apply energy to the medium, so that rapid heating can be performed. As a result, the entire reaction solution can be made uniform at a desired temperature, and the processes of reduction, nucleation, and nucleation of the nickel complex (or nickel ions) occur simultaneously in the entire solution. Narrow monodisperse particles can be easily produced in a short time. In particular, it is suitable for producing composite nickel particles having an average particle diameter in the range of 20 to 150 nm by observation with a scanning electron microscope.
工程Ａ）錯化反応液生成工程：
ニッケル前駆体（ニッケル塩）としては、例えば塩化ニッケル、硝酸ニッケル、硫酸ニッケル、炭酸ニッケル、カルボン酸ニッケル、Ｎｉ（ａｃａｃ）２（β−ジケトナト錯体）、ステアリン酸ニッケル等を挙げることができる。これらの中でも、塩化ニッケル（II）が最も好ましい。例えば、塩化ニッケル六水和物（ＮｉＣｌ２・６Ｈ２Ｏ）は、錯体であるｔｒａｎｓ―[ＮｉＣｌ２（Ｈ２Ｏ）４]と、それに弱く結合した２個の水分子からなり、６個の水分子のうち４個のみが直接ニッケルと結合した構造を有している。このような構造のニッケル六水和物の水分子は容易にアミンなどによって置換され得るため、アミンと混合することで容易にアミン錯体を形成することができる。ニッケル前駆体の一部もしくは全部として塩化ニッケル（II）を用いることで、結晶性が高い金属ニッケルを生成することができる。また、塩化ニッケルは、カルボン酸ニッケルなどを用いる場合に比べ、アミド由来の水分の副生成を抑制することができる。
Step A) Complexation reaction solution generation step:
Examples of the nickel precursor (nickel salt) include nickel chloride, nickel nitrate, nickel sulfate, nickel carbonate, nickel carboxylate, Ni (acac) 2 (β-diketonato complex), and nickel stearate. Of these, nickel (II) chloride is most preferred. For example, nickel chloride hexahydrate (NiCl 2 · 6H 2 O) is composed of a complex, trans- [NiCl 2 (H 2 O) 4 ], and two water molecules weakly bound thereto. Only four of the water molecules have a structure directly bonded to nickel. Since the water molecule of nickel hexahydrate having such a structure can be easily replaced by an amine or the like, an amine complex can be easily formed by mixing with an amine. By using nickel (II) chloride as part or all of the nickel precursor, metallic nickel having high crystallinity can be generated. In addition, nickel chloride can suppress by-product generation of moisture derived from amide, compared to the case of using nickel carboxylate or the like.
また、ニッケル前駆体として、上記塩化ニッケルとともに、還元過程での解離温度（分解温度）が比較的低いカルボン酸ニッケルを用いることが好ましい。カルボン酸ニッケルとしては、例えば炭素数が１〜１２のカルボン酸ニッケルを用いることができる。カルボン酸ニッケルは、カルボキシ基が１つのモノカルボン酸であってもよく、カルボキシ基が２つ以上のカルボン酸であってもよい。また、非環式カルボン酸であってもよく、環式カルボン酸であってもよい。好ましいカルボン酸ニッケルとして、例えばギ酸ニッケル、酢酸ニッケル等を用いることができるが、還元温度が低く、複合ニッケル粒子の生成のための核を生じさせる作用も併有するギ酸ニッケルを用いることがより好ましい。 Moreover, it is preferable to use nickel carboxylate having a relatively low dissociation temperature (decomposition temperature) in the reduction process together with the nickel chloride as the nickel precursor. As nickel carboxylate, for example, nickel carboxylate having 1 to 12 carbon atoms can be used. The nickel carboxylate may be a monocarboxylic acid having one carboxy group or may be a carboxylic acid having two or more carboxy groups. Moreover, acyclic carboxylic acid may be sufficient and cyclic carboxylic acid may be sufficient. As nickel carboxylate, for example, nickel formate, nickel acetate, and the like can be used. However, it is more preferable to use nickel formate that has a low reduction temperature and also has a function of generating nuclei for producing composite nickel particles.
複合ニッケル粒子の結晶性を高くするために、原料として用いるニッケル前駆体の５０質量％以上が塩化ニッケルであることが好ましく、５０〜９５質量％の範囲内が塩化ニッケルであることがより好ましく、別途、核剤（ニッケル前駆体となりうるものを除く）を添加する場合には、ニッケル前駆体の全部（１００質量％）が塩化ニッケルであることが最も好ましい。 In order to increase the crystallinity of the composite nickel particles, 50% by mass or more of the nickel precursor used as a raw material is preferably nickel chloride, more preferably in the range of 50 to 95% by mass, nickel chloride. Separately, when a nucleating agent (excluding those that can become nickel precursors) is added, it is most preferable that the entire nickel precursor (100% by mass) is nickel chloride.
有機溶媒は、ニッケル塩を溶解できるものであれば、特に限定されず、例えばエチレングリコール、アルコール類、有機アミン類、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、アセトン等が挙げられるが、金属塩に対して還元作用があるエチレングリコール、アルコール類、有機アミン類等の有機溶媒が好ましい。このなかでも特に、１級の有機アミン（以下、「１級アミン」と略称する。）は、ニッケル塩との混合物を溶解することにより、ニッケルイオンとの錯体を形成することができ、ニッケル錯体（又はニッケルイオン）に対する還元能を効果的に発揮しやすく、加熱による還元温度が高温のニッケル塩に対して有利に使用できる。１級アミンは、ニッケルイオンとの錯体を形成できるものであれば、特に限定するものではなく、常温で固体又は液体のものが使用できる。ここで、常温とは、２０℃±１５℃をいう。 The organic solvent is not particularly limited as long as it can dissolve the nickel salt, and examples thereof include ethylene glycol, alcohols, organic amines, N, N-dimethylformamide, dimethyl sulfoxide, acetone, and the like. On the other hand, organic solvents such as ethylene glycol, alcohols and organic amines having a reducing action are preferred. Among these, primary organic amines (hereinafter abbreviated as “primary amines”) can form a complex with nickel ions by dissolving a mixture with a nickel salt. It is easy to effectively exhibit the reducing ability for (or nickel ions), and can be advantageously used for nickel salts whose reduction temperature by heating is high. The primary amine is not particularly limited as long as it can form a complex with nickel ions, and can be a solid or liquid at room temperature. Here, room temperature means 20 ° C. ± 15 ° C.
常温で液体の１級アミンは、ニッケル錯体を形成する際の有機溶媒としても機能する。なお、常温で固体の１級の有機アミンであっても、加熱によって液体であるか、又は有機溶媒を用いて溶解するものであれば、特に問題はない。 The primary amine that is liquid at room temperature also functions as an organic solvent for forming the nickel complex. Even if it is a primary organic amine that is solid at room temperature, there is no particular problem as long as it is liquid by heating or can be dissolved using an organic solvent.
１級アミンは、芳香族１級アミンであってもよいが、反応液におけるニッケル錯体形成の容易性の観点からは脂肪族１級アミンが好適である。脂肪族１級アミンは、例えばその炭素鎖の長さを調整することによって生成する複合ニッケル粒子の粒径を制御することができる。複合ニッケル粒子の粒径を制御する観点から、脂肪族１級アミンは、その炭素数が６〜２０程度のものから選択して用いることが好適である。炭素数が多いほど得られる複合ニッケル粒子の粒径が小さくなる。このようなアミンとして、例えばオクチルアミン、トリオクチルアミン、ジオクチルアミン、ヘキサデシルアミン、ドデシルアミン、テトラデシルアミン、ステアリルアミン、オレイルアミン、ミリスチルアミン、ラウリルアミン等を挙げることができる。 The primary amine may be an aromatic primary amine, but an aliphatic primary amine is preferred from the viewpoint of easy nickel complex formation in the reaction solution. The aliphatic primary amine can control the particle diameter of the composite nickel particles produced, for example, by adjusting the length of the carbon chain. From the viewpoint of controlling the particle diameter of the composite nickel particles, the aliphatic primary amine is preferably selected from those having about 6 to 20 carbon atoms. The larger the carbon number, the smaller the particle size of the resulting composite nickel particles. Examples of such amines include octylamine, trioctylamine, dioctylamine, hexadecylamine, dodecylamine, tetradecylamine, stearylamine, oleylamine, myristylamine, and laurylamine.
１級アミンは、還元反応後の生成した複合ニッケル粒子の固体成分と溶剤または未反応の１級アミン等を分離する洗浄工程における処理操作の容易性の観点からは室温で液体のものが好ましい。更に、１級アミンは、ニッケル錯体を還元して複合ニッケル粒子を得るときの反応制御の容易性の観点からは還元温度より沸点が高いものが好ましい。１級アミンの量は、ニッケル塩１ｍｏｌに対して２ｍｏｌ以上用いることが好ましく、２．２ｍｏｌ以上用いることがより好ましい。１級アミンの量が２ｍｏｌ未満では、得られる複合ニッケル粒子の粒子径の制御が困難となり、粒子径がばらつきやすくなる。また、１級アミンの量の上限は特にはないが、例えば生産性の観点からは２０ｍｏｌ以下とすることが好ましい。 The primary amine is preferably liquid at room temperature from the viewpoint of ease of processing operation in the washing step for separating the solid component of the composite nickel particles produced after the reduction reaction and the solvent or unreacted primary amine. Further, the primary amine preferably has a boiling point higher than the reduction temperature from the viewpoint of ease of reaction control when the nickel complex is reduced to obtain composite nickel particles. The amount of the primary amine is preferably 2 mol or more, more preferably 2.2 mol or more, relative to 1 mol of the nickel salt. When the amount of the primary amine is less than 2 mol, it is difficult to control the particle diameter of the obtained composite nickel particles, and the particle diameter tends to vary. The upper limit of the amount of primary amine is not particularly limited, but is preferably 20 mol or less from the viewpoint of productivity, for example.
均一溶液での反応をより効率的に進行させるために、１級アミンとは別の有機溶媒を新たに添加してもよい。使用できる有機溶媒としては、１級アミンとニッケルイオンとの錯形成を阻害しないものであれば、特に限定するものではなく、例えば炭素数４〜３０のエーテル系有機溶媒、炭素数７〜３０の飽和又は不飽和の炭化水素系有機溶媒、炭素数８〜１８のアルコール系有機溶媒等を使用することができる。また、マイクロ波照射による加熱条件下でも使用を可能とする観点から、使用する有機溶媒は、沸点が１７０℃以上のものを選択することが好ましく、より好ましくは２００〜３００℃の範囲内にあるものを選択することがよい。このような有機溶媒の具体例としては、例えばテトラエチレングリコール、ｎ−オクチルエーテル等が挙げられる。 In order to proceed the reaction in a homogeneous solution more efficiently, an organic solvent other than the primary amine may be newly added. The organic solvent that can be used is not particularly limited as long as it does not inhibit the complex formation between the primary amine and the nickel ion. For example, the organic solvent having 4 to 30 carbon atoms, 7 to 30 carbon atoms, and the like. A saturated or unsaturated hydrocarbon organic solvent, an alcohol organic solvent having 8 to 18 carbon atoms, or the like can be used. Moreover, from the viewpoint of enabling use even under heating conditions by microwave irradiation, it is preferable to select an organic solvent having a boiling point of 170 ° C. or higher, more preferably in the range of 200 to 300 ° C. It is better to choose one. Specific examples of such an organic solvent include tetraethylene glycol and n-octyl ether.
錯形成反応は室温に於いても進行することができるが、十分且つ、より効率の良い錯形成反応を行うために、例えば１００℃〜１６５℃の範囲内に加熱して反応を行う。この加熱は、後に続くニッケル錯体（又はニッケルイオン）のマイクロ波照射による加熱還元の過程と確実に分離し、前記の錯形成反応を完結させるという観点から、上記上限を適宜設定することができる。なお、この加熱の方法は、特に制限されず、例えばオイルバスなどの熱媒体による加熱であっても、マイクロ波照射による加熱であってもよい。 Although the complex formation reaction can proceed even at room temperature, in order to perform a sufficient and more efficient complex formation reaction, for example, the reaction is performed by heating within a range of 100 ° C. to 165 ° C. This heating can be appropriately set from the viewpoint of separating from the subsequent heat reduction process by microwave irradiation of the nickel complex (or nickel ions) and completing the complex formation reaction. The heating method is not particularly limited, and may be heating by a heat medium such as an oil bath or heating by microwave irradiation.
ニッケル塩として塩化ニッケルを用いる場合、錯化反応液には、複合ニッケル粒子を構成する金属ニッケルを生成する際の核となる物質（核剤）を配合することが好ましい。核剤としては、核形成が可能な物質であれば特に制限なく使用可能であり、上述のギ酸ニッケルを利用できるほか、例えばギ酸銅、硝酸銀、硝酸銅、パラジウム塩、白金塩、金塩等を用いることができる。これらの核剤を用いることで、塩化ニッケルから結晶性の高い金属ニッケルを効率よく生成させることができる。 When nickel chloride is used as the nickel salt, the complexing reaction liquid preferably contains a substance (nucleating agent) that serves as a nucleus when producing metallic nickel constituting the composite nickel particles. As the nucleating agent, any substance capable of nucleation can be used without particular limitation. In addition to the above-mentioned nickel formate, for example, copper formate, silver nitrate, copper nitrate, palladium salt, platinum salt, gold salt, etc. Can be used. By using these nucleating agents, metallic nickel having high crystallinity can be efficiently generated from nickel chloride.
核剤の配合量は、塩化ニッケルに対して、０．１〜５０モル％の範囲内が好ましい。核剤の配合量が塩化ニッケルに対して０．１モル％未満では、塩化ニッケルから金属ニッケルの生成を促す効果が得られず、塩化ニッケルに対して５０モル％を超えると、核が多く生成しすぎる結果、複合ニッケル粒子の粒子径が小さくなる傾向がある。なお、核剤は、工程Ａ（錯化反応液生成工程）に限らず、工程Ｂ（複合ニッケル粒子スラリー生成工程）におけるマイクロ波照射の前までに配合すればよい。 The blending amount of the nucleating agent is preferably in the range of 0.1 to 50 mol% with respect to nickel chloride. If the blending amount of the nucleating agent is less than 0.1 mol% with respect to nickel chloride, the effect of promoting the formation of nickel metal from nickel chloride cannot be obtained, and if it exceeds 50 mol% with respect to nickel chloride, many nuclei are produced. As a result, the particle diameter of the composite nickel particles tends to be small. In addition, what is necessary is just to mix | blend a nucleating agent before the microwave irradiation in not only the process A (complexation reaction liquid production | generation process) but the process B (composite nickel particle slurry production | generation process).
工程Ｂ）複合ニッケル粒子スラリー生成工程：
本工程では、ニッケル塩と有機溶媒との錯形成反応によって得られた錯化反応液を、マイクロ波照射によって加熱し、錯化反応液中のニッケルイオンを還元して金属ニッケルを生成させ、複合ニッケル粒子のスラリーを得る。マイクロ波照射によって加熱する温度は、得られる複合ニッケル粒子の形状のばらつきを抑制するという観点から、好ましくは１７０℃以上、より好ましくは１８０℃以上とすることがよい。加熱温度の上限は特にないが、処理を効率的に行う観点からは例えば２７０℃以下とすることが好適である。なお、マイクロ波の使用波長は、特に限定するものではなく、例えば２．４５ＧＨｚである。
Process B) Composite nickel particle slurry production process:
In this step, the complexing reaction solution obtained by the complex formation reaction between the nickel salt and the organic solvent is heated by microwave irradiation, and nickel ions in the complexing reaction solution are reduced to produce metallic nickel, which is combined. A slurry of nickel particles is obtained. The temperature for heating by microwave irradiation is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, from the viewpoint of suppressing variation in the shape of the obtained composite nickel particles. The upper limit of the heating temperature is not particularly limited, but is preferably 270 ° C. or less, for example, from the viewpoint of efficiently performing the treatment. In addition, the use wavelength of a microwave is not specifically limited, For example, it is 2.45 GHz.
均一な粒径を有する複合ニッケル粒子を生成させるには、錯化反応液生成工程の加熱温度を特定の範囲内で調整し、複合ニッケル粒子スラリー生成工程におけるマイクロ波による加熱温度よりも確実に低くしておくことで、粒径・形状の整った粒子が生成し易い。例えば、錯化反応液生成工程で加熱温度が高すぎるとニッケル錯体の生成とニッケル(０価)への還元反応が同時に進行し異種の金属種が発生することで、複合ニッケル粒子スラリー生成工程での粒子形状の整った粒子の生成が困難となるおそれがある。また、複合ニッケル粒子スラリー生成工程の加熱温度が低すぎるとニッケル(０価)への還元反応速度が遅くなり核の発生が少なくなるため粒子が大きくなるだけでなく、複合ニッケル粒子の収率の点からも好ましくはない。 In order to produce composite nickel particles having a uniform particle size, the heating temperature in the complexing reaction liquid production process is adjusted within a specific range, and is surely lower than the heating temperature by microwaves in the composite nickel particle slurry production process. By doing so, particles having a uniform particle diameter and shape are easily generated. For example, if the heating temperature is too high in the complexing reaction liquid generation process, the formation of a nickel complex and the reduction reaction to nickel (zero valence) proceed simultaneously and different metal species are generated. It may be difficult to produce particles having a uniform particle shape. Also, if the heating temperature in the composite nickel particle slurry production step is too low, the reduction reaction rate to nickel (zero valence) is slowed and the generation of nuclei is reduced, so that not only the particles become larger but also the yield of the composite nickel particles It is not preferable also from a point.
複合ニッケル粒子スラリー生成工程においては、必要に応じ、前述した有機溶媒を加えてもよい。なお、前記したように、錯形成反応に使用する１級アミンを有機溶媒としてそのまま用いることは、本発明の好適な実施の形態である。 In the composite nickel particle slurry generation step, the organic solvent described above may be added as necessary. As described above, it is a preferred embodiment of the present invention to use the primary amine used in the complex formation reaction as an organic solvent as it is.
工程Ｃ）複合ニッケル粒子単離工程：
本工程では、マイクロ波照射によって加熱して得られる複合ニッケル粒子スラリーを、例えば、静置分離し、上澄み液を取り除いた後、適当な溶媒を用いて洗浄し、乾燥することで、複合ニッケル粒子が得られる。
Step C) Composite nickel particle isolation step:
In this step, the composite nickel particle slurry obtained by heating by microwave irradiation is, for example, statically separated, and after removing the supernatant liquid, the composite nickel particle slurry is washed and dried using an appropriate solvent. Is obtained.
上記にようにして結晶性の高い金属ニッケルを有する複合ニッケル粒子を製造することができるが、例えば複合ニッケル粒子スラリーの状態で有機溶媒中に所定時間保持することや、複合ニッケル粒子スラリーを低酸素状態で乾燥させることなどによって、複合ニッケル粒子の表面に所定の水酸化物の被膜を形成することができる。 Composite nickel particles having metallic nickel with high crystallinity can be produced as described above. For example, the composite nickel particle slurry can be kept in an organic solvent for a predetermined time, or the composite nickel particle slurry can be reduced in oxygen content. A predetermined hydroxide film can be formed on the surface of the composite nickel particles by, for example, drying in a state.
また、本実施の形態では、複合ニッケル粒子に対し、さらに、酸処理を行うことが好ましい。酸処理によって、ニッケル前駆体である塩化ニッケル由来の塩素元素が除去され、塩素元素の含有量を好ましくは９００質量ｐｐｍ未満、より好ましくは１００質量ｐｐｍ未満に低下させることができる。また、酸処理には、複合ニッケル粒子の表面に付着した微粒子などを除去したり、酸素元素の含有量を調節したりする作用もある。複合ニッケル粒子の酸処理に使用可能な酸としては、弱酸が好ましく、例えば、炭酸などの無機酸や、酢酸、プロピオン酸、酒石酸、マロン酸、コハク酸、アスコルビン酸、クエン酸などの有機酸を用いることができる。酸処理は、例えば複合ニッケル粒子を酸溶液で洗浄する方法、複合ニッケル粒子のスラリー中にガス化した酸（例えば炭酸ガス）を吹き込む方法などにより行うことができる。複合ニッケル粒子を酸溶液で洗浄する方法では、複合ニッケル粒子を例えばｐＨ３．５〜６．５の範囲内、好ましくはｐＨ４．５〜６．０の酸溶液で洗浄することが好ましい。酸溶液がｐＨ３．５未満であると、複合ニッケル粒子の表面の酸化や溶解が進み、焼結しやすくなるばかりでなく、粒子を球状にすることが困難となる。酸溶液がｐＨ６．５を超える場合は、酸処理の効果が十分に得られない。 In the present embodiment, it is preferable to further perform acid treatment on the composite nickel particles. By the acid treatment, the chlorine element derived from nickel chloride, which is the nickel precursor, is removed, and the content of the chlorine element can be reduced to preferably less than 900 mass ppm, more preferably less than 100 mass ppm. The acid treatment also has an action of removing fine particles adhering to the surface of the composite nickel particles and adjusting the content of oxygen element. The acid that can be used for the acid treatment of the composite nickel particles is preferably a weak acid, for example, an inorganic acid such as carbonic acid, or an organic acid such as acetic acid, propionic acid, tartaric acid, malonic acid, succinic acid, ascorbic acid, or citric acid. Can be used. The acid treatment can be performed by, for example, a method of washing the composite nickel particles with an acid solution, a method of blowing a gasified acid (for example, carbon dioxide) into the slurry of the composite nickel particles, and the like. In the method of washing the composite nickel particles with an acid solution, the composite nickel particles are preferably washed with an acid solution having a pH in the range of 3.5 to 6.5, preferably 4.5 to 6.0. When the acid solution has a pH of less than 3.5, the surface of the composite nickel particles is oxidized and dissolved, and it becomes easy to sinter, and it becomes difficult to make the particles spherical. When the acid solution exceeds pH 6.5, the effect of acid treatment cannot be sufficiently obtained.
以上のようにして製造される複合ニッケル粒子は、水酸化物の被膜を有し、酸素元素を０．２〜２．５質量％の範囲内で含有する。この水酸化物の被膜は、Ｘ線回折により結晶質の水酸化ニッケルが観測されないアモルファス状態の被膜であり、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内に制御されている。脱バインダー時には、前記被膜から速やかに水分が揮発し、脱水されることにより、粒子の急激な温度上昇を抑制し、４００℃以下の低温での粒子の焼結や凝集を防ぐことができる。また、脱水によって、水酸化物の被膜は酸化物の被膜に変化する。このように生成した酸化物の被膜により、焼結時には複合ニッケル粒子の内部への急激な酸化を抑制することができるので、デラミネーションやクラック等の欠陥の発生を回避できる。このような複合ニッケル粒子は、例えば積層セラミックコンデンサの内部電極の材料として好適に用いることができる。 The composite nickel particles produced as described above have a hydroxide coating and contain oxygen element in the range of 0.2 to 2.5 mass%. This hydroxide film is an amorphous film in which no crystalline nickel hydroxide is observed by X-ray diffraction, and is measured in a temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere. Is controlled within a range of 0.5 to 3%. At the time of debinding, moisture is volatilized and dehydrated quickly from the coating, so that the rapid temperature rise of the particles can be suppressed, and sintering and aggregation of the particles at a low temperature of 400 ° C. or lower can be prevented. Further, the hydroxide film changes to an oxide film by dehydration. Since the oxide film thus generated can suppress rapid oxidation of the composite nickel particles into the interior during sintering, it is possible to avoid the occurrence of defects such as delamination and cracks. Such composite nickel particles can be suitably used as a material for an internal electrode of a multilayer ceramic capacitor, for example.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。なお、以下の実施例において、特にことわりのない限り各種測定、評価は下記によるものである。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.
［平均粒子径の測定］
ＳＥＭ（走査電子顕微鏡）により試料の写真を撮影して、その中から無作為に２００個を抽出してそれぞれの粒子径を求め、平均粒子径を算出した。具体的には、抽出した微粒子のそれぞれについて面積を求め、真球に換算したときの粒子径を個数基準として一次粒子の平均粒子径とした。
また、ＢＥＴ測定による平均粒子径（ＢＥＴ換算径）は、ニッケルナノ粒子の単位重量当たりの表面積（ＢＥＴ値）を実測し、そのＢＥＴ値から下記式を用いてＢＥＴ換算径を算出した。
ＢＥＴ換算径(ｎｍ)＝｛［６÷ＢＥＴ値(ｍ２／ｇ)］÷真密度(ｇ／ｃｍ３)｝×１０００
また、ＣＶ値（変動係数）は、（標準偏差）÷（平均粒子径）によって算出した。なお、ＣＶ値が小さいほど、粒子径がより均一であることを示す。
[Measurement of average particle size]
A photograph of the sample was taken with an SEM (scanning electron microscope), 200 samples were randomly extracted from the sample, and the respective particle sizes were determined to calculate the average particle size. Specifically, the area of each of the extracted fine particles was obtained, and the average particle size of the primary particles was determined based on the particle size when converted to a true sphere.
Moreover, the average particle diameter (BET conversion diameter) by BET measurement measured the surface area (BET value) per unit weight of nickel nanoparticle, and calculated the BET conversion diameter from the BET value using the following formula.
BET equivalent diameter (nm) = {[6 ÷ BET value (m 2 / g)] ÷ true density (g / cm 3 )} × 1000
The CV value (coefficient of variation) was calculated by (standard deviation) / (average particle diameter). In addition, it shows that a particle diameter is so uniform that a CV value is small.
［複合ニッケル粒子の結晶子径］
粉末Ｘ線回折（ＸＲＤ）結果からシェラーの式により算出した。
[Crystal diameter of composite nickel particles]
It calculated from the X-ray powder diffraction (XRD) result according to Scherrer's equation.
［熱機械分析（ＴＭＡ）、熱重量分析（ＴＧＡ）、５％熱収縮温度］
試料を５Φ×２ｍｍの円柱状成型器に入れ、プレス成型して得られる成型体を作製し、窒素ガス（水素ガス３％含有）の雰囲気下で、熱機械分析（ＴＭＡ）および熱重量分析（ＴＧＡ）を行った。また、熱機械分析装置（ＴＭＡ）により測定される５％熱収縮の温度を５％熱収縮温度とした。
[Thermomechanical analysis (TMA), thermogravimetric analysis (TGA), 5% heat shrinkage temperature]
A sample is put into a 5Φ × 2 mm cylindrical molding machine, and a molded body obtained by press molding is prepared. Under an atmosphere of nitrogen gas (containing 3% hydrogen gas), thermomechanical analysis (TMA) and thermogravimetric analysis ( TGA). Moreover, the temperature of 5% heat shrinkage measured by a thermomechanical analyzer (TMA) was taken as 5% heat shrinkage temperature.
［昇温脱離分析試験］
真空中で複合ニッケル粒子を加熱し、脱離する気体を質量分析計で測定した。
[Temperature desorption analysis test]
The composite nickel particles were heated in a vacuum, and the desorbed gas was measured with a mass spectrometer.
［脱バインダー時微分ピーク温度］
脱バインダー時微分ピーク温度は、窒素下でＴＧＡを測定し、その減少率の微分から燃焼のピーク温度を算出し、そのピーク温度位置を微分ピーク温度とした。
[Differential peak temperature at binder removal]
The differential peak temperature at the time of debinding was obtained by measuring TGA under nitrogen, calculating the peak temperature of combustion from the differential of the decrease rate, and setting the peak temperature position as the differential peak temperature.
実施例１−１
＜溶解工程＞
酢酸ニッケル四水和物６０．０ｇ（２４１．１ｍｍｍｏｌ）にオレイルアミン６９０ｇ（２．５８ｍｏｌ）を加え、窒素フロー下で１４０℃、２０分間加熱することによって酢酸ニッケルをオレイルアミンに溶解させた。
＜還元工程＞
次いで、その溶液にマイクロ波を照射して２５０℃まで加熱し、その温度を５分保持することによって複合ニッケル粒子スラリーを得た。
＜洗浄・乾燥工程＞
複合ニッケル粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンとメタノールを用いて３回洗浄し、７０℃に維持される真空乾燥機で６時間乾燥して複合ニッケル粒子を得た。元素分析の結果、Ｃ；０．５、Ｏ；１．３（単位は質量％）であった。
＜炭酸水調製＞
純水にＣＯ２ガスをバブリングさせて、ｐＨが４．５となるように炭酸水を調製した。
＜炭酸洗浄＞
得られた複合ニッケル粒子１０ｇに炭酸水１００ｇを加えて１回洗浄を行い、メタノールでさらに１回洗浄した後、７０℃に維持される真空乾燥機で６時間乾燥して複合ニッケル粒子を得た。元素分析の結果、Ｃ；０．６、Ｏ；１．６（単位は質量％）であった。また、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は２．０％であった。複合ニッケル粒子の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。得られた複合ニッケル粒子（ＢＥＴ値；８．４ｍ２／ｇ、真密度；８．６ｇ／ｃｍ３）の平均粒子径、ＣＶ値を表１に、５％熱収縮温度、及び脱バインダー時の温度変化の微分ピークを表２に示した。また、この複合ニッケル粒子の結晶子径は、２２ｎｍであった。
Example 1-1
<Dissolution process>
To 60.0 g (241.1 mmol) of nickel acetate tetrahydrate, 690 g (2.58 mol) of oleylamine was added, and nickel acetate was dissolved in oleylamine by heating at 140 ° C. for 20 minutes under a nitrogen flow.
<Reduction process>
Next, the solution was irradiated with microwaves and heated to 250 ° C., and the temperature was maintained for 5 minutes to obtain a composite nickel particle slurry.
<Washing and drying process>
The composite nickel particle slurry was allowed to stand and separated, and the supernatant liquid was removed, followed by washing with toluene and methanol three times and drying for 6 hours in a vacuum dryer maintained at 70 ° C. to obtain composite nickel particles. As a result of elemental analysis, it was C; 0.5, O; 1.3 (unit: mass%).
<Preparation of carbonated water>
Carbonated water was prepared by bubbling pure water with CO 2 gas so that the pH was 4.5.
<Carbonated cleaning>
100 g of carbonated water was added to 10 g of the obtained composite nickel particles, washed once, further washed once with methanol, and then dried for 6 hours in a vacuum dryer maintained at 70 ° C. to obtain composite nickel particles. . As a result of elemental analysis, it was C; 0.6, O; 1.6 (unit: mass%). Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere was 2.0%. In the hydroxide coating on the surface of the composite nickel particles, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). The average particle diameter and CV value of the obtained composite nickel particles (BET value: 8.4 m 2 / g, true density: 8.6 g / cm 3 ) are shown in Table 1, 5% heat shrink temperature, and at the time of debinding The differential peak of the temperature change is shown in Table 2. Moreover, the crystallite diameter of this composite nickel particle was 22 nm.
［実施例１−２］
＜溶解工程＞
ギ酸ニッケル二水和物６．０ｇ（３２．６ｍｍｍｏｌ）と塩化ニッケル六水和物５４．０ｇ（２２７．８ｍｍｏｌ）にオレイルアミン６９０g（２．５８ｍｏｌ）を加え、窒素フロー下で１４０℃、２０分間加熱することによって、ギ酸ニッケルと塩化ニッケルをオレイルアミンに溶解させた。
＜還元工程＞
次いで、その溶液にマイクロ波を照射して２５０℃まで加熱し、その温度を５分間保持することによって、複合ニッケル粒子スラリーを得た。
＜洗浄・乾燥工程＞
複合ニッケル粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンとメタノールを用いて３回洗浄し、７０℃に維持される真空乾燥機で６時間乾燥して複合ニッケル粒子を得た。元素分析の結果、Ｃ；０．４、Ｏ；１．３、Ｓ；＜０．０１、Ｃｌ；０．１３（単位は質量％）であった。また、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．６％であった。複合ニッケル粒子の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。得られた複合ニッケル粒子（ＢＥＴ値；８．５ｍ２／ｇ、真密度；８．７ｇ／ｃｍ３）の平均粒子径、ＣＶ値を表１、５％熱収縮温度、及び脱バインダー時微分ピーク温度を表２に示した。また、この複合ニッケル粒子の結晶子径は、３０ｎｍであった。
[Example 1-2]
<Dissolution process>
Add 690 g (2.58 mol) of oleylamine to 6.0 g (32.6 mmol) of nickel formate dihydrate and 54.0 g (227.8 mmol) of nickel chloride hexahydrate, and heat at 140 ° C. for 20 minutes under nitrogen flow. By doing so, nickel formate and nickel chloride were dissolved in oleylamine.
<Reduction process>
Next, the solution was irradiated with microwaves and heated to 250 ° C., and the temperature was maintained for 5 minutes to obtain a composite nickel particle slurry.
<Washing and drying process>
The composite nickel particle slurry was allowed to stand and separated, and the supernatant liquid was removed, followed by washing with toluene and methanol three times and drying for 6 hours in a vacuum dryer maintained at 70 ° C. to obtain composite nickel particles. As a result of elemental analysis, it was C; 0.4, O; 1.3, S; <0.01, Cl; 0.13 (unit: mass%). The weight reduction rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere was 1.6%. In the hydroxide coating on the surface of the composite nickel particles, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). The average particle diameter and CV value of the obtained composite nickel particles (BET value: 8.5 m 2 / g, true density: 8.7 g / cm 3 ) are shown in Table 1, 5% heat shrinkage temperature, and debinding time differential peak. The temperature is shown in Table 2. The crystallite diameter of the composite nickel particles was 30 nm.
［実施例１−３］
＜炭酸水調製＞
純水にＣＯ２ガスをバブリングさせて、ｐＨが４．５となるように炭酸水を調製した。
＜炭酸洗浄＞
実施例１−２で得られた複合ニッケル粒子１０ｇに炭酸水１００ｇを加えて１回洗浄を行い、メタノールでさらに１回洗浄した後、７０℃に維持される真空乾燥機で６時間乾燥して複合ニッケル粒子を得た。元素分析の結果、Ｃ；０．６、Ｏ；２．０、Ｓ；＜０．０１、Ｃｌ；＜０．０１（単位は質量％）であった。また、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．４％であった。複合ニッケル粒子の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。得られた複合ニッケル粒子（ＢＥＴ値；８．５ｍ２／ｇ、真密度；８．７ｇ／ｃｍ３）の平均粒子径、ＣＶ値を表１に、５％熱収縮温度、及び脱バインダー時微分ピーク温度を表２に示した。
[Example 1-3]
<Preparation of carbonated water>
Carbonated water was prepared by bubbling pure water with CO 2 gas so that the pH was 4.5.
<Carbonated cleaning>
100 g of carbonated water was added to 10 g of the composite nickel particles obtained in Example 1-2, washed once, further washed once with methanol, and then dried for 6 hours in a vacuum dryer maintained at 70 ° C. Composite nickel particles were obtained. As a result of elemental analysis, it was C; 0.6, O; 2.0, S; <0.01, Cl; <0.01 (unit: mass%). The weight reduction rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere was 1.4%. In the hydroxide coating on the surface of the composite nickel particles, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). The average particle diameter and CV value of the obtained composite nickel particles (BET value: 8.5 m 2 / g, true density: 8.7 g / cm 3 ) are shown in Table 1. 5% heat shrinkage temperature and debinding time differential The peak temperature is shown in Table 2.
比較例１−１
実施例１−２で得られた複合ニッケル粒子１０ｇに水１００ｇを加えて５回洗浄して塩素を除去し、メタノールでさらに１回洗浄した後、７０℃に維持される真空乾燥機で６時間乾燥して複合ニッケル粒子を得た。元素分析の結果、Ｃ；０．５、Ｏ；３．５、Ｓ；＜０．１、Ｃｌ；＜０．０４（単位は質量％）であった。また、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は４．２％であった。複合ニッケル粒子の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。得られた複合ニッケル粒子（ＢＥＴ値；８．８ｍ２／ｇ、真密度；７．８ｇ／ｃｍ３）の平均粒子径、ＣＶ値を表１に、５％熱収縮温度、及び脱バインダー時微分ピーク温度を表２に示した。
Comparative Example 1-1
100 g of water was added to 10 g of the composite nickel particles obtained in Example 1-2, washed 5 times to remove chlorine, further washed once with methanol, and then 6 hours in a vacuum dryer maintained at 70 ° C. By drying, composite nickel particles were obtained. As a result of elemental analysis, it was C; 0.5, O; 3.5, S; <0.1, Cl; <0.04 (unit: mass%). The weight reduction rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere was 4.2%. In the hydroxide coating on the surface of the composite nickel particles, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). The average particle diameter and CV value of the obtained composite nickel particles (BET value: 8.8 m 2 / g, true density: 7.8 g / cm 3 ) are shown in Table 1. 5% heat shrinkage temperature and debinding time differential The peak temperature is shown in Table 2.
実施例１−１〜１−３の複合ニッケル粒子は、酸素元素を０．２〜２．５質量％の範囲内で含有するものであり、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内であり、かつＸ線回折により結晶質の水酸化ニッケルが観測されなかった。代表的に、実施例１−１で得られた複合ニッケル粒子の被膜をＸＰＳで測定した結果を図１に、ＸＲＤで測定した結果を図２に、窒素雰囲気下での熱重量分析の結果を図３に、昇温脱離試験の結果を図４に、それぞれ示した。なお、熱重量分析では、比較対象として、試薬の水酸化ニッケルを用いた。これらの結果から、複合ニッケル粒子の被膜は、結晶性が低く、水分を脱離しやすいアモルファス構造の水酸化物であることが確認された。このような特徴によって、実施例１−１−１〜３の複合ニッケル粒子は、脱バインダー時の微分ピーク温度が高く、脱バインダー時の重量減少の急激な変動がより高温側にシフトしており、良好な挙動を示した。つまり、脱バインダー工程で水酸化物の被膜が速やかに脱水されて酸化物の被膜に変化することにより、粒子の急激な温度上昇を抑制し、３００℃以下の低温での粒子の焼結や凝集を防ぐことができると考えられる。また、生成した酸化物の被膜により、焼結時には複合ニッケル粒子の内部への急激な酸化を抑制することができるので、デラミネーションやクラック等の欠陥の発生を抑制できるものと考えられる。一方、比較例１−１の複合ニッケル粒子は、水洗を繰り返したことによって複合ニッケル粒子の表面の酸化被膜が増膜して厚くなっており、酸素元素の含有量が多いため、焼結時の熱収縮が大きくなった。 The composite nickel particles of Examples 1-1 to 1-3 contain the oxygen element in the range of 0.2 to 2.5 mass%, and are measured by thermogravimetric analysis under a nitrogen atmosphere. The weight loss rate in the temperature range from 0 to 300 ° C. was in the range of 0.5 to 3%, and no crystalline nickel hydroxide was observed by X-ray diffraction. Typically, FIG. 1 shows the result of measuring the composite nickel particle coating obtained in Example 1-1 by XPS, FIG. 2 shows the result of XRD measurement, and the result of thermogravimetric analysis in a nitrogen atmosphere. FIG. 3 shows the results of the temperature programmed desorption test and FIG. In thermogravimetric analysis, the reagent nickel hydroxide was used as a comparison target. From these results, it was confirmed that the coating film of the composite nickel particles has a low crystallinity and has an amorphous structure that easily releases moisture. Due to such characteristics, the composite nickel particles of Examples 1-1 to 1-3 have a high differential peak temperature at the time of binder removal, and the rapid fluctuation in weight reduction at the time of binder removal is shifted to a higher temperature side. Showed good behavior. In other words, the hydroxide film is quickly dehydrated and changed to an oxide film in the binder removal step, thereby suppressing the rapid temperature rise of the particles and sintering or agglomeration of the particles at a low temperature of 300 ° C. or lower. Can be prevented. Further, since the generated oxide film can suppress rapid oxidation inside the composite nickel particles during sintering, it is considered that generation of defects such as delamination and cracks can be suppressed. On the other hand, the composite nickel particles of Comparative Example 1-1 were thickened by increasing the thickness of the oxide film on the surface of the composite nickel particles due to repeated washing with water, and the content of oxygen element was large. Heat shrinkage increased.
また、図２から、実施例１−１の複合ニッケル粒子は、ＸＲＤチャートの金属ニッケル結晶を示すピークの幅（半値幅）が狭く、結晶性が高いことが確認された。 Further, from FIG. 2, it was confirmed that the composite nickel particles of Example 1-1 had a narrow peak width (half-value width) indicating a metal nickel crystal of the XRD chart and high crystallinity.
［実施例２−１］
塩化ニッケル六水和物１２９７ｇ（５．４７ｍｏｌ）とギ酸ニッケル二水和物２２６．４ｇ（１．２３ｍｏｌ）にオレイルアミン７０８７g（２６．５ｍｏｌ）を加え、窒素フロー下で１２０℃、１２０分間加熱することによって、塩化ニッケルとギ酸ニッケルのアミン錯体を形成させた。
[Example 2-1]
Add 7087 g (26.5 mol) of oleylamine to 1297 g (5.47 mol) of nickel chloride hexahydrate and 226.4 g (1.23 mol) of nickel formate dihydrate, and heat at 120 ° C. for 120 minutes under a nitrogen flow. To form an amine complex of nickel chloride and nickel formate.
次いで、上記アミン錯体を含む溶液を、マイクロ波を用いて２５０℃まで加熱し、その温度を５分間保持することによって、複合ニッケル粒子１を含むスラリーを得た。収率は１００％であった。 Next, the solution containing the amine complex was heated to 250 ° C. using a microwave, and the temperature was maintained for 5 minutes, whereby a slurry containing the composite nickel particles 1 was obtained. The yield was 100%.
得られたスラリーを静置分離し、上澄み液を取り除いた後、トルエンとメタノールを用いて３回洗浄した後、７０℃に維持される真空乾燥機で６時間乾燥して、複合ニッケル粒子１（平均粒子径；１５０ｎｍ、ＣＶ値；０．１９、５％熱収縮温度；４２０℃、結晶子径；４０ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子１の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は０．７％であった。複合ニッケル粒子１の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．３、Ｏ；１．０、Ｃｌ；０．１０（単位は質量％）であった（Ｃ／Ｏ比＝０．３０）。実施例２−１で得られた複合ニッケル粒子１のＳＥＭ写真（×５万倍）を図５に示した。また、複合ニッケル粒子１のＴＭＡのチャートを図６に示した。 The resulting slurry was allowed to stand and separated, the supernatant was removed, washed three times with toluene and methanol, and then dried in a vacuum dryer maintained at 70 ° C. for 6 hours to obtain composite nickel particles 1 ( Average particle diameter; 150 nm, CV value; 0.19, 5% heat shrink temperature; 420 ° C., crystallite diameter; 40 nm). The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 1 under a nitrogen atmosphere was 0.7%. In the hydroxide coating on the surface of the composite nickel particle 1, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 0.3, O; 1.0, Cl; 0.10 (unit: mass%) (C / O ratio = 0.30). The SEM photograph (x50,000 times) of the composite nickel particle 1 obtained in Example 2-1 is shown in FIG. Further, a TMA chart of the composite nickel particle 1 is shown in FIG.
上記の複合ニッケル粒子１の１０ｇに、炭酸水（純水にＣＯ２ガスをバブリングさせて、ｐＨが４．５となるように炭酸水を調製したもの）の１００ｇを加えて１回洗浄を行い、メタノールでさらに１回洗浄した後、７０℃に維持される真空乾燥機で６時間乾燥して、複合ニッケル粒子１’を得た。元素分析の結果、Ｃ；０．３、Ｏ；１．２、Ｃｌ；＜０．０１（単位は質量％）であった（Ｃ／Ｏ比＝０．２５）。 To 10 g of the above composite nickel particle 1, 100 g of carbonated water (carbonated water prepared by bubbling CO 2 gas into pure water and adjusting the pH to 4.5) was added and washed once. Then, after further washing with methanol, it was dried for 6 hours in a vacuum dryer maintained at 70 ° C. to obtain composite nickel particles 1 ′. As a result of elemental analysis, it was C; 0.3, O; 1.2, Cl; <0.01 (unit: mass%) (C / O ratio = 0.25).
［実施例２−２］
塩化ニッケル六水和物１２９７ｇ（５．４７ｍｏｌ）、ギ酸ニッケル二水和物１６６ｇ（０．９ｍｏｌ）、及びオレイルアミン１０７００g（４０ｍｏｌ）を使用したこと以外、実施例２−１と同様にして、複合ニッケル粒子２（平均粒子径；１２０ｎｍ、ＣＶ値；０．１６、５％熱収縮温度；３９０℃、結晶子径；３９ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子２の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は０．９％であった。複合ニッケル粒子２の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．３、Ｏ；０．６、Ｃｌ；０．０９（単位は質量％）であった（Ｃ／Ｏ比＝０．５０）。実施例２−２で得られた複合ニッケル粒子２のＳＥＭ写真（×５万倍）を図７に示した。また、複合ニッケル粒子２のＴＭＡのチャートを図８に示した。
[Example 2-2]
Composite nickel was obtained in the same manner as in Example 2-1, except that 1297 g (5.47 mol) of nickel chloride hexahydrate, 166 g (0.9 mol) of nickel formate dihydrate, and 10700 g (40 mol) of oleylamine were used. Particles 2 (average particle size; 120 nm, CV value; 0.16, 5% heat shrink temperature; 390 ° C., crystallite size; 39 nm) were obtained. The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 2 under a nitrogen atmosphere was 0.9%. In the hydroxide coating on the surface of the composite nickel particle 2, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 0.3, O; 0.6, Cl; 0.09 (unit: mass%) (C / O ratio = 0.50). The SEM photograph (x50,000 times) of the composite nickel particle 2 obtained in Example 2-2 is shown in FIG. Further, a TMA chart of the composite nickel particles 2 is shown in FIG.
［実施例２−３］
塩化ニッケル六水和物５８１ｇ（２．４５ｍｏｌ）、ギ酸ニッケル二水和物１９３ｇ（１．０５ｍｏｌ）、及びドデシルアミン９３６０g（３５ｍｏｌ）を使用したこと以外、実施例２−１と同様にして、複合ニッケル粒子３（平均粒子径；８０ｎｍ、ＣＶ値；０．１５、５％熱収縮温度；３４５℃、結晶子径；３２ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子３の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．１％であった。複合ニッケル粒子３の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．８、Ｏ；１．６、Ｃｌ；０．１２（単位は質量％）であった（Ｃ／Ｏ比＝０．５０）。実施例２−３で得られた複合ニッケル粒子３のＳＥＭ写真を図９に示した。また、複合ニッケル粒子３のＴＥＭ写真を図１０Ａ示した。また、図１０Ｂは、図１０Ａに示した複合ニッケル粒子３の結晶格子を模式的に示した説明図であり、一点鎖線の斜線は結晶格子模様を表している。図１０Ａでは、図１０Ｂに示したように、結晶格子模様がはっきりと観察されており、単結晶に近いことが推測された。
[Example 2-3]
Compound as in Example 2-1, except that 581 g (2.45 mol) of nickel chloride hexahydrate, 193 g (1.05 mol) of nickel formate dihydrate, and 9360 g (35 mol) of dodecylamine were used. Nickel particles 3 (average particle diameter; 80 nm, CV value; 0.15, 5% heat shrink temperature; 345 ° C., crystallite diameter; 32 nm) were obtained. The yield was 100%. Further, the weight loss rate in the temperature region from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 3 under a nitrogen atmosphere was 1.1%. In the hydroxide coating on the surface of the composite nickel particle 3, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). In addition, as a result of elemental analysis, it was C; 0.8, O; 1.6, Cl; 0.12 (unit: mass%) (C / O ratio = 0.50). An SEM photograph of the composite nickel particles 3 obtained in Example 2-3 is shown in FIG. A TEM photograph of the composite nickel particle 3 is shown in FIG. 10A. FIG. 10B is an explanatory diagram schematically showing the crystal lattice of the composite nickel particle 3 shown in FIG. 10A, and the dashed line of the alternate long and short dash line represents the crystal lattice pattern. In FIG. 10A, as shown in FIG. 10B, the crystal lattice pattern was clearly observed, and it was estimated that it was close to a single crystal.
［実施例２−４］
塩化ニッケル六水和物１８９６ｇ（８ｍｏｌ）とギ酸ニッケル二水和物３６８ｇ（２ｍｏｌ）にオレイルアミン１０７００g（４０ｍｏｌ）を加え、窒素フロー下で１２０℃、１２０分間加熱することによって、塩化ニッケルとギ酸ニッケルのアミン錯体を形成させた。
[Example 2-4]
By adding 10700 g (40 mol) of oleylamine to 1896 g (8 mol) of nickel chloride hexahydrate and 368 g (2 mol) of nickel formate dihydrate, and heating at 120 ° C. for 120 minutes under a nitrogen flow, nickel chloride and nickel formate An amine complex was formed.
次いで、上記アミン錯体を含む溶液を９０℃まで冷却して、硝酸銀８．５ｇ（０．０５ｍｏｌ）を添加して、３０分間撹拌して硝酸銀を溶解した後、マイクロ波を用いて２５０℃まで加熱し、その温度を５分間保持することによって、複合ニッケル粒子４を含むスラリーを得た。収率は１００％であった。 Next, the solution containing the amine complex is cooled to 90 ° C., 8.5 g (0.05 mol) of silver nitrate is added, stirred for 30 minutes to dissolve the silver nitrate, and then heated to 250 ° C. using microwaves. And the slurry containing the composite nickel particle 4 was obtained by hold | maintaining the temperature for 5 minutes. The yield was 100%.
実施例２−１と同様にして、得られたスラリーを乾燥して、複合ニッケル粒子４（平均粒子径；９０ｎｍ、ＣＶ値；０．１６、５％熱収縮温度；３６０℃、結晶子径；２５ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子４の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．１％であった。複合ニッケル粒子４の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．４、Ｏ；１．２、Ｃｌ；０．１２（単位は質量％）であった（Ｃ／Ｏ比＝０．３３）。 The obtained slurry was dried in the same manner as in Example 2-1, and composite nickel particles 4 (average particle diameter; 90 nm, CV value; 0.16, 5% heat shrink temperature; 360 ° C., crystallite diameter; 25 nm). The yield was 100%. Further, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 4 in a nitrogen atmosphere was 1.1%. As for the hydroxide film on the surface of the composite nickel particle 4, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 0.4, O; 1.2, Cl; 0.12 (unit: mass%) (C / O ratio = 0.33).
［実施例２−５］
塩化ニッケル六水和物２１３３ｇ（９ｍｏｌ）、ギ酸ニッケル二水和物１８４ｇ（１ｍｏｌ）、硝酸銀０．８５ｇ（０．００５ｍｏｌ）及びドデシルアミン１３３７５g（５０ｍｏｌ）を使用したこと以外、実施例２−４と同様にして、複合ニッケル粒子５（平均粒子径；１３０ｎｍ、ＣＶ値；０．１７、５％熱収縮温度；４１５℃、結晶子径；３８ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子５の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は０．９％であった。複合ニッケル粒子５の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．３、Ｏ；０．７、Ｃｌ；０．１１（単位は質量％）であった（Ｃ／Ｏ比＝０．４３）。実施例２−５で得られた複合ニッケル粒子５のＳＥＭ写真を図１１に示した。
[Example 2-5]
Example 2-4 with the exception that 2133 g (9 mol) of nickel chloride hexahydrate, 184 g (1 mol) of nickel formate dihydrate, 0.85 g (0.005 mol) of silver nitrate and 13375 g (50 mol) of dodecylamine were used. Similarly, composite nickel particles 5 (average particle diameter; 130 nm, CV value; 0.17, 5% heat shrink temperature; 415 ° C., crystallite diameter; 38 nm) were obtained. The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 5 in a nitrogen atmosphere was 0.9%. In the hydroxide coating on the surface of the composite nickel particles 5, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). In addition, as a result of elemental analysis, it was C; 0.3, O; 0.7, Cl; 0.11 (unit: mass%) (C / O ratio = 0.43). An SEM photograph of the composite nickel particles 5 obtained in Example 2-5 is shown in FIG.
［実施例２−６］
塩化ニッケル六水和物１６５９ｇ（７ｍｏｌ）、ギ酸ニッケル二水和物５５２ｇ（３ｍｏｌ）、硝酸銀２．５５ｇ（０．０１５ｍｏｌ）及びオレイルアミン１０７００ｇ（４０ｍｏｌ）を使用したこと以外、実施例２−４と同様にして、複合ニッケル粒子６（平均粒子径；７０ｎｍ、ＣＶ値；０．１５、５％熱収縮温度；３６０℃、結晶子径；２５ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子６の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．３％であった。複合ニッケル粒子６の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．８、Ｏ；１．６、Ｃｌ；０．０７（単位は質量％）であった（Ｃ／Ｏ比＝０．５０）。実施例２−６で得られた複合ニッケル粒子６のＳＥＭ写真を図１２に示した。
[Example 2-6]
Example 2-4, except that 1659 g (7 mol) of nickel chloride hexahydrate, 552 g (3 mol) of nickel formate dihydrate, 2.55 g (0.015 mol) of silver nitrate and 10700 g (40 mol) of oleylamine were used. Thus, composite nickel particles 6 (average particle diameter; 70 nm, CV value; 0.15, 5% heat shrink temperature; 360 ° C., crystallite diameter; 25 nm) were obtained. The yield was 100%. Further, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 6 under a nitrogen atmosphere was 1.3%. In the hydroxide coating on the surface of the composite nickel particles 6, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 0.8, O; 1.6, Cl; 0.07 (unit: mass%) (C / O ratio = 0.50). An SEM photograph of the composite nickel particles 6 obtained in Example 2-6 is shown in FIG.
［実施例２−７］
塩化ニッケル六水和物１８９６ｇ（８ｍｏｌ）、ギ酸ニッケル二水和物３６８ｇ（２ｍｏｌ）、及びドデシルアミン１６０５０ｇ（６０ｍｏｌ）を使用したこと以外、実施例２−１と同様にして、複合ニッケル粒子７（平均粒子径；９０ｎｍ、ＣＶ値；０．１７、５％熱収縮温度；４３０℃、結晶子径；３２ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子７の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．０％であった。複合ニッケル粒子７の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．６、Ｏ；１．３、Ｃｌ；０．１３（単位は質量％）であった（Ｃ／Ｏ比＝０．４６）。
[Example 2-7]
In the same manner as in Example 2-1, except that 1896 g (8 mol) of nickel chloride hexahydrate, 368 g (2 mol) of nickel formate dihydrate, and 16050 g (60 mol) of dodecylamine were used, composite nickel particles 7 ( Average particle diameter; 90 nm, CV value; 0.17, 5% heat shrink temperature; 430 ° C., crystallite diameter; 32 nm). The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 7 in a nitrogen atmosphere was 1.0%. In the hydroxide coating on the surface of the composite nickel particle 7, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 0.6, O; 1.3, Cl; 0.13 (unit: mass%) (C / O ratio = 0.46).
［実施例２−８］
塩化ニッケル六水和物２１３３ｇ（９ｍｏｌ）、ギ酸ニッケル二水和物１８４ｇ（１ｍｏｌ）、硝酸銀５．１ｇ（０．０３ｍｏｌ）及びドデシルアミン１６０５０ｇ（６０ｍｏｌ）を使用したこと以外、実施例２−４と同様にして、複合ニッケル粒子８（平均粒子径；６０ｎｍ、ＣＶ値；０．１５、５％熱収縮温度；４２０℃、結晶子径；３０ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子８の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．６％であった。複合ニッケル粒子８の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；１．２、Ｏ；１．８、Ｃｌ；０．１４（単位は質量％）であった（Ｃ／Ｏ比＝０．６７）。
[Example 2-8]
Example 2-4 except that 2133 g (9 mol) of nickel chloride hexahydrate, 184 g (1 mol) of nickel formate dihydrate, 5.1 g (0.03 mol) of silver nitrate and 16050 g (60 mol) of dodecylamine were used. Similarly, composite nickel particles 8 (average particle size: 60 nm, CV value: 0.15, 5% heat shrink temperature: 420 ° C., crystallite size: 30 nm) were obtained. The yield was 100%. Further, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 8 under a nitrogen atmosphere was 1.6%. In the hydroxide coating on the surface of the composite nickel particle 8, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 1.2, O; 1.8, Cl; 0.14 (unit: mass%) (C / O ratio = 0.67).
［実施例２−９］
塩化ニッケル六水和物１２９７ｇ（５．４７ｍｏｌ）とギ酸銅四水和物 １８９ｇ（１．２３ｍｏｌ）にオレイルアミン７０８７g（２６．５ｍｏｌ）を加え、窒素フロー下で１２０℃、１２０分間加熱することによって、塩化ニッケルとギ酸ニッケルのアミン錯体を形成させた。
[Example 2-9]
7087 g (26.5 mol) of oleylamine was added to 1297 g (5.47 mol) of nickel chloride hexahydrate and 189 g (1.23 mol) of copper formate tetrahydrate, and heated at 120 ° C. for 120 minutes under a nitrogen flow. An amine complex of nickel chloride and nickel formate was formed.
次いで、上記アミン錯体を含む溶液を、マイクロ波を用いて２５０℃まで加熱し、その温度を５分間保持することによって、複合ニッケル粒子９を含むスラリーを得た。収率は１００％であった。 Next, the solution containing the amine complex was heated to 250 ° C. using a microwave, and the temperature was maintained for 5 minutes to obtain a slurry containing the composite nickel particles 9. The yield was 100%.
得られたスラリーを静置分離し、上澄み液を取り除いた後、トルエンとメタノールを用いて３回洗浄した後、７０℃に維持される真空乾燥機で６時間乾燥して、複合ニッケル粒子９（平均粒子径；１７０ｎｍ、ＣＶ値；０．１７、５％熱収縮温度；４００℃、結晶子径；３８ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子９の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は０．６％であった。複合ニッケル粒子９の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．４、Ｏ；１．３、Ｃｌ；０．０８（単位は質量％）であった（Ｃ／Ｏ比＝０．３１）。実施例２−９で得られた複合ニッケル粒子９のＳＥＭ写真を図１３に示した。 The resulting slurry was allowed to stand and separated, the supernatant was removed, washed three times with toluene and methanol, and then dried for 6 hours in a vacuum dryer maintained at 70 ° C. to obtain composite nickel particles 9 ( Average particle size: 170 nm, CV value: 0.17, 5% heat shrink temperature: 400 ° C., crystallite size: 38 nm). The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 9 under a nitrogen atmosphere was 0.6%. As for the hydroxide coating on the surface of the composite nickel particles 9, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). As a result of elemental analysis, it was C; 0.4, O; 1.3, Cl; 0.08 (unit: mass%) (C / O ratio = 0.31). An SEM photograph of the composite nickel particles 9 obtained in Example 2-9 is shown in FIG.
［実施例２−１０］
塩化ニッケル六水和物１２９７ｇ（５．４７ｍｏｌ）、ギ酸ニッケル二水和物７４ｇ（０．４ｍｏｌ）、及びオレイルアミン１０７００g（４０ｍｏｌ）を使用したこと以外、実施例２−１と同様にして、複合ニッケル粒子１０（平均粒子径；１８０ｎｍ、ＣＶ値；０．１９、５％熱収縮温度；４３０℃、結晶子径；４１ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子１０の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は０．５％であった。複合ニッケル粒子１０の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．４、Ｏ；１．１、Ｃｌ；０．０８（単位は質量％）であった（Ｃ／Ｏ比＝０．３６）。
[Example 2-10]
Compound nickel was obtained in the same manner as in Example 2-1, except that 1297 g (5.47 mol) of nickel chloride hexahydrate, 74 g (0.4 mol) of nickel formate dihydrate, and 10700 g (40 mol) of oleylamine were used. Particles 10 (average particle diameter; 180 nm, CV value; 0.19, 5% heat shrink temperature; 430 ° C., crystallite diameter; 41 nm) were obtained. The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 degreeC to 300 degreeC measured by the thermogravimetric analysis of the composite nickel particle 10 in nitrogen atmosphere was 0.5%. In the hydroxide coating on the surface of the composite nickel particle 10, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). Moreover, it was C; 0.4, O; 1.1, Cl; 0.08 (a unit is the mass%) as a result of the elemental analysis (C / O ratio = 0.36).
［実施例２−１１］
塩化ニッケル六水和物１２９７ｇ（５．４７ｍｏｌ）、ギ酸ニッケル二水和物８２８ｇ（４．５ｍｏｌ）、及びオレイルアミン１０７００g（４０ｍｏｌ）を使用したこと以外、実施例２−１と同様にして、複合ニッケル粒子１１（平均粒子径；８５ｎｍ、ＣＶ値；０．１７、５％熱収縮温度；４１０℃、結晶子径；２７ｎｍ）を得た。収率は１００％であった。また、複合ニッケル粒子１１の窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率は１．１％であった。複合ニッケル粒子１１の表面の水酸化物の被膜は、Ｘ線回折（ＸＲＤ）で結晶質の水酸化ニッケルは観測されなかった。また、元素分析の結果、Ｃ；０．８、Ｏ；１．１、Ｃｌ；０．１１（単位は質量％）であった（Ｃ／Ｏ比＝０．７３）。
[Example 2-11]
Composite nickel was obtained in the same manner as in Example 2-1, except that 1297 g (5.47 mol) of nickel chloride hexahydrate, 828 g (4.5 mol) of nickel formate dihydrate, and 10700 g (40 mol) of oleylamine were used. Particles 11 (average particle diameter; 85 nm, CV value; 0.17, 5% heat shrink temperature; 410 ° C., crystallite diameter; 27 nm) were obtained. The yield was 100%. Moreover, the weight loss rate in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis of the composite nickel particles 11 under a nitrogen atmosphere was 1.1%. In the hydroxide coating on the surface of the composite nickel particle 11, crystalline nickel hydroxide was not observed by X-ray diffraction (XRD). In addition, as a result of elemental analysis, it was C; 0.8, O; 1.1, Cl; 0.11 (unit: mass%) (C / O ratio = 0.73).
上記実施例２−１〜２−１１で原料として用いた塩化ニッケル及びギ酸塩に含まれる全金属換算の金属元素１００モル部に対するギ酸塩のモル部並びに硝酸銀のモル部と、各実施例で得られたニッケル粒子の物理的特性を表３〜表４に示した。なお、ＭＬＣＣの内部電極用途に使用するニッケル粒子の物理的特性は、例えば以下のとおりである。平均粒子径は３０〜２００ｎｍの範囲内が好ましく、ＣＶ値は０．２以下であることが好ましい。さらに、十分な耐焼結性を確保する観点から、５％熱収縮温度は３００℃以上であることが好ましく、結晶子径は出来るだけ大きい方が好ましいが、例えば２５〜６０ｎｍの範囲内であればよい。 Obtained in each example, the molar part of formate and the molar part of silver nitrate with respect to 100 molar parts of metal elements in terms of all metals contained in nickel chloride and formate used as raw materials in Examples 2-1 to 2-11. The physical properties of the obtained nickel particles are shown in Tables 3 to 4. The physical characteristics of nickel particles used for MLCC internal electrode applications are as follows, for example. The average particle diameter is preferably in the range of 30 to 200 nm, and the CV value is preferably 0.2 or less. Furthermore, from the viewpoint of ensuring sufficient sintering resistance, the 5% heat shrinkage temperature is preferably 300 ° C. or higher, and the crystallite diameter is preferably as large as possible, but for example within the range of 25 to 60 nm. Good.
表３〜表４から、実施例２−１〜２−１１では、粒子径が２００ｎｍ以下に制御され、結晶性が高く、低温焼結が抑制されていた。 From Tables 3 to 4, in Examples 2-1 to 2-11, the particle diameter was controlled to 200 nm or less, the crystallinity was high, and low-temperature sintering was suppressed.
以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはなく、種々の変形が可能である。
As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment, A various deformation | transformation is possible.
Claims (4)
前記複合ニッケル粒子は、酸素元素を０．２〜２．５質量％の範囲内で含有し、窒素雰囲気下での熱重量分析によって測定される２４０℃から３００℃までの温度領域での重量減少率が０．５〜３％の範囲内であり、かつＸ線回折により結晶質の水酸化ニッケルが観測されないことを特徴とする複合ニッケル粒子。 Composite nickel particles having a hydroxide coating on the surface of the metal nickel particles,
The composite nickel particles contain elemental oxygen in the range of 0.2 to 2.5% by mass, and the weight loss in the temperature range from 240 ° C. to 300 ° C. measured by thermogravimetric analysis under a nitrogen atmosphere. A composite nickel particle, characterized in that the rate is in the range of 0.5 to 3%, and crystalline nickel hydroxide is not observed by X-ray diffraction.
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