JP2006037195A - Method for producing nickel powder - Google Patents
Method for producing nickel powder Download PDFInfo
- Publication number
- JP2006037195A JP2006037195A JP2004221852A JP2004221852A JP2006037195A JP 2006037195 A JP2006037195 A JP 2006037195A JP 2004221852 A JP2004221852 A JP 2004221852A JP 2004221852 A JP2004221852 A JP 2004221852A JP 2006037195 A JP2006037195 A JP 2006037195A
- Authority
- JP
- Japan
- Prior art keywords
- nickel powder
- nickel
- gas
- sulfur
- powder
- 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.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 206
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 49
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011593 sulfur Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 85
- 230000009467 reduction Effects 0.000 claims description 40
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 33
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 33
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 9
- 239000012808 vapor phase Substances 0.000 claims description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 6
- 150000002816 nickel compounds Chemical class 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 41
- 239000003985 ceramic capacitor Substances 0.000 abstract description 25
- 230000001603 reducing effect Effects 0.000 abstract description 20
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000006722 reduction reaction Methods 0.000 description 45
- 239000000843 powder Substances 0.000 description 30
- 239000002245 particle Substances 0.000 description 26
- 229910052751 metal Inorganic materials 0.000 description 25
- 239000002184 metal Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 20
- 239000012298 atmosphere Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 230000032798 delamination Effects 0.000 description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000011946 reduction process Methods 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 oxynitrate Chemical compound 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005118 spray pyrolysis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011362 coarse particle 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010574 gas phase reaction 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Abstract
Description
本発明は、導電ペースト用に好適な金属ニッケル粉末の製造方法に係り、特に積層セラミックコンデンサ内部電極に用いられ、耐酸化還元性と焼結特性に優れた金属ニッケル粉末の製造方法に関する。 The present invention relates to a method for producing a metal nickel powder suitable for a conductive paste, and more particularly to a method for producing a metal nickel powder which is used for an internal electrode of a multilayer ceramic capacitor and has excellent oxidation-reduction resistance and sintering characteristics.
従来、銀、パラジウム、白金または金などの貴金属粉末、あるいはニッケル、コバルト、鉄、モリブデン、またはタングステンなどの卑金属粉末は、電子材料用の導電ペーストとして、特に積層セラミックコンデンサの内部電極用として用いられている。一般に、積層セラミックコンデンサは、誘電体セラミック層と内部電極として使用される金属層とを交互に積層し、誘電体セラミック層の両端に、内部電極の金属層に接続される外部電極が接続された構成となっている。ここで、誘電体層として使用されるセラミックとしては、チタン酸バリウム、チタン酸ストロンチウム、酸化イットリウムなどの誘電率の高い材料を主成分とするものが用いられている。 Conventionally, noble metal powders such as silver, palladium, platinum or gold, or base metal powders such as nickel, cobalt, iron, molybdenum or tungsten have been used as conductive pastes for electronic materials, especially for internal electrodes of multilayer ceramic capacitors. ing. In general, in a multilayer ceramic capacitor, dielectric ceramic layers and metal layers used as internal electrodes are alternately stacked, and external electrodes connected to the metal layers of the internal electrodes are connected to both ends of the dielectric ceramic layers. It has a configuration. Here, as a ceramic used as the dielectric layer, a ceramic having a high dielectric constant material such as barium titanate, strontium titanate, yttrium oxide or the like is used.
一方、内部電極を構成する金属としては、前述の貴金属粉末あるいは卑金属粉末が使用されるが、最近はより安価な電子材料が要求されるため、卑金属を利用した積層セラミックコンデンサの開発が盛んに行われており、特にニッケル粉末が代表的なものである。 On the other hand, as the metal constituting the internal electrode, the above-mentioned noble metal powder or base metal powder is used, but recently, a cheaper electronic material is required, and therefore, the development of multilayer ceramic capacitors using base metal is actively carried out. In particular, nickel powder is typical.
積層セラミックコンデンサの一般的な製造方法としては、チタン酸バリウム等の誘電体粉末を有機バインダと混合し懸濁させ、ドクターブレード法によりシート状に成形して誘電体グリーンシートを作成する。一方、内部電極とする金属粉末を有機溶剤、可塑剤、有機バインダ等の有機化合物と混合し、金属粉末ペーストを形成して、これを上記グリーンシート上にスクリーン印刷法で印刷する。その後、乾燥、積層および圧着を順次行い、加熱処理にて有機成分を除去した後、１３００℃前後またはそれ以上の温度で焼成する。その後両端に外部電極を焼き付けて、積層セラミックコンデンサを得る。 As a general manufacturing method of a multilayer ceramic capacitor, dielectric powder such as barium titanate is mixed and suspended with an organic binder, and formed into a sheet by a doctor blade method to produce a dielectric green sheet. On the other hand, a metal powder used as an internal electrode is mixed with an organic compound such as an organic solvent, a plasticizer, and an organic binder to form a metal powder paste, which is printed on the green sheet by a screen printing method. Thereafter, drying, lamination, and pressure bonding are sequentially performed, and organic components are removed by heat treatment, followed by baking at a temperature of about 1300 ° C. or higher. Thereafter, external electrodes are baked on both ends to obtain a multilayer ceramic capacitor.
上記積層セラミックコンデンサの製造工程においては、誘電体グリーンシートに金属ペーストを印刷し、積層および圧着を行った後、加熱処理にて有機成分を蒸発除去するが、この加熱処理は通常大気中で２５０〜４００℃で行われる。このように、酸化雰囲気中で加熱処理が行われると、金属粉末は酸化し、それにより金属粉末の体積が膨張する。また、上記加熱処理による有機成分蒸発除去は還元雰囲気中で行われる場合もあり、この場合は、金属粉末は還元されて収縮する。さらにこの有機成分除去のための加熱処理の後、さらに高温に加熱し焼結するが、この焼結は水素ガス雰囲気等の還元性雰囲気で行う。これにより、金属粉末は体積の収縮が起きる。 In the manufacturing process of the above multilayer ceramic capacitor, a metal paste is printed on a dielectric green sheet, laminated and pressure-bonded, and then organic components are evaporated and removed by heat treatment. Performed at ~ 400 ° C. As described above, when the heat treatment is performed in an oxidizing atmosphere, the metal powder is oxidized, thereby expanding the volume of the metal powder. The organic component evaporative removal by the heat treatment may be performed in a reducing atmosphere. In this case, the metal powder is reduced and contracts. Further, after the heat treatment for removing the organic components, the mixture is further heated to a high temperature and sintered. This sintering is performed in a reducing atmosphere such as a hydrogen gas atmosphere. As a result, the metal powder undergoes volume shrinkage.
このように、積層セラミックコンデンサを製造する工程においては、酸化還元反応により金属粉末に膨張・収縮が起こって体積変化が生じる。一方、誘電体自身も焼結により体積変化が生じるが、誘電体と金属粉末という異なった物質を同時に焼結するため、焼結過程でのそれぞれの物質の膨張・収縮の体積変化などの焼結挙動が異なる。このため、金属ペースト層に歪みが生じ、結果としてクラックまたは剥離などデラミネーションといわれる層状構造の破壊が起きるという問題があった。 Thus, in the process of manufacturing a multilayer ceramic capacitor, expansion and contraction occur in the metal powder due to the oxidation-reduction reaction, resulting in a volume change. On the other hand, the dielectric itself also undergoes volume changes due to sintering, but because different materials, dielectric and metal powder, are sintered at the same time, sintering such as volume changes of expansion and contraction of each material during the sintering process. The behavior is different. For this reason, there has been a problem that the metal paste layer is distorted, and as a result, the layered structure, which is called delamination such as cracking or peeling, is destroyed.
具体的には、例えばチタン酸バリウムを主成分とする誘電体は、１０００℃以上、通常１２００〜１３００℃で焼結が始まるのに対し、内部電極に用いられる金属粉末の焼結は、それよりも低い温度、例えばニッケル粉末の場合、通常４００〜５００℃で焼結が始まる。このような焼結挙動（焼結開始温度）の違いがデラミネーション発生の一つの大きな要因となっている。 Specifically, for example, a dielectric containing barium titanate as a main component starts sintering at 1000 ° C. or higher, usually 1200 to 1300 ° C., whereas metal powder used for the internal electrode is more sintered. In the case of a lower temperature, for example, nickel powder, sintering usually starts at 400 to 500 ° C. This difference in sintering behavior (sintering start temperature) is one major factor in the occurrence of delamination.
上記のようなデラミネーションの問題を解決する手段としては、種々の方法が提案されている。例えば特許文献１には、特定の粒径に対するタップ密度（一定条件で容器をタッピングして得られる粉体のかさ密度）がある規定値以上を有するニッケル粉末が開示されている。また、特許文献２には、平均粒径が０．２〜０．５μｍで、平均粒径の２倍以上の粗粒子の存在率が個数基準で０．１％以下であるニッケル超微粉が開示されている。上記特許文献１に開示されたニッケル超微粉は、積層セラミックコンデンサの内部電極として使用した際のクラック、剥離等の内部欠陥の発生を抑制することを目的とするものである。また、上記特許文献２に開示されたニッケル超微粉も、積層セラミックコンデンサの内部電極のショートの発生や、クラック、剥離を抑制することを課題とするものである。
Various methods have been proposed as means for solving the above delamination problem. For example, Patent Document 1 discloses nickel powder having a tap density (a bulk density of a powder obtained by tapping a container under a certain condition) with respect to a specific particle size having a specified value or more.
しかしながら、上記の従来の方法は、粗粉の発生を抑制してデラミネーションの発生をある程度改善しているが、酸化・還元挙動あるいは焼結挙動に基づく積層セラミックコンデンサのデラミネーションを防止する方法としては十分ではなく、さらなる改善が要求されていた。 However, the above conventional method has improved the occurrence of delamination to some extent by suppressing the generation of coarse powder, but as a method to prevent delamination of multilayer ceramic capacitors based on oxidation / reduction behavior or sintering behavior. Was not enough and further improvements were required.
よって本発明は、積層セラミックコンデンサの製造工程において優れた酸化挙動、還元挙動および焼結挙動を示し、結果として積層セラミックコンデンサのデラミネーションを防止することができる導電ペースト用、特に積層セラミックコンデンサ用に適したニッケル粉末の製造方法を提供することを目的としている。 Therefore, the present invention shows excellent oxidation behavior, reduction behavior and sintering behavior in the production process of multilayer ceramic capacitors, and as a result, for conductive pastes that can prevent delamination of multilayer ceramic capacitors, especially for multilayer ceramic capacitors. It aims at providing the manufacturing method of suitable nickel powder.
本発明は上記状況に鑑みてなされたものであり、本発明のニッケル粉末の製造方法は、ニッケル粉末を硫黄ガスまたは硫黄化合物含有ガスにより処理することによって、ニッケル粉末の表面にニッケルと硫黄を含む化合物層を設けることを特徴としている。 This invention is made | formed in view of the said situation, and the manufacturing method of the nickel powder of this invention contains nickel and sulfur on the surface of nickel powder by processing nickel powder by sulfur gas or sulfur compound containing gas. It is characterized by providing a compound layer.
本発明のニッケル粉末の製造方法によれば、ニッケル粉末の表面にニッケルおよび硫黄を含む化合物層が設けられているので、酸化雰囲気中または還元雰囲気中におけるニッケルの酸化還元反応を抑制することができ、ニッケル粉末の酸化還元開始温度が高温化する。また、この化合物層が存在する間は焼結が開始されず、焼結開始温度も高温化する。このため、ニッケル粉末の収縮率減少等の酸化挙動、還元挙動および焼結挙動が改善される。その結果、積層セラミックコンデンサの製造工程において、デラミネーションの発生を抑制することができる。 According to the nickel powder manufacturing method of the present invention, since the compound layer containing nickel and sulfur is provided on the surface of the nickel powder, the oxidation-reduction reaction of nickel in an oxidizing atmosphere or a reducing atmosphere can be suppressed. The oxidation-reduction starting temperature of the nickel powder is increased. Moreover, while this compound layer exists, sintering is not started and the sintering start temperature is also increased. For this reason, oxidation behavior, reduction behavior and sintering behavior such as reduction in shrinkage rate of nickel powder are improved. As a result, it is possible to suppress the occurrence of delamination in the manufacturing process of the multilayer ceramic capacitor.
以下、本発明の好適な実施の形態について詳細に説明する。
本発明のニッケル粉末は、気相法や液相法など公知の方法により製造することができるが、特に塩化ニッケルガスと還元性ガスとを接触させることによりニッケル粉末を生成させる気相還元法、あるいは熱分解性のニッケル化合物を噴霧して熱分解する噴霧熱分解法が、生成する金属微粉末の粒子径を容易に制御することができ、さらに球状の粒子が効率よく製造することができるという点において好ましい方法である。このような気相還元法によるニッケル粉末の製造装置の模式図を図１に示す。
Hereinafter, preferred embodiments of the present invention will be described in detail.
The nickel powder of the present invention can be produced by a known method such as a vapor phase method or a liquid phase method, and in particular, a vapor phase reduction method in which nickel powder is produced by contacting a nickel chloride gas with a reducing gas, Alternatively, the spray pyrolysis method in which a thermally decomposable nickel compound is sprayed and thermally decomposed can easily control the particle diameter of the metal fine powder to be produced, and spherical particles can be efficiently produced. This is a preferable method. A schematic diagram of an apparatus for producing nickel powder by such a gas phase reduction method is shown in FIG.
ニッケル粉末気相還元法においては、気化させた塩化ニッケルのガスと水素等の還元性ガスとを反応させるが、固体の塩化ニッケルを加熱し蒸発させて塩化ニッケルガスを生成させてもよい。しかしながら、塩化ニッケルの酸化または吸湿防止またエネルギー効率を考慮すると、金属ニッケルに塩素ガスを接触させて塩化ニッケルガスを連続的に発生させ、この塩化ニッケルガスを還元工程に直接供給し、次いで還元性ガスと接触させ塩化ニッケルガスを連続的に還元してニッケル微粉末を製造する方法が有利である。 In the nickel powder vapor phase reduction method, vaporized nickel chloride gas is reacted with a reducing gas such as hydrogen, but solid nickel chloride may be heated and evaporated to generate nickel chloride gas. However, in consideration of oxidation or moisture absorption prevention and energy efficiency of nickel chloride, nickel chloride gas is continuously generated by bringing chlorine gas into contact with metallic nickel, and this nickel chloride gas is directly supplied to the reduction process, and then the reducing property is reduced. A method of producing nickel fine powder by contacting with gas and continuously reducing nickel chloride gas is advantageous.
気相還元反応によるニッケル粉末の製造過程では、塩化ニッケルガスと還元性ガスとが接触した瞬間にニッケル原子が生成し、ニッケル原子同士が衝突・凝集することによって超微粒子が生成し、成長してゆく。そして、還元工程での塩化ニッケルガスの分圧や温度等の条件によって、生成されるニッケル微粉末の粒径が決まる。上記のようなニッケル粉末の製造方法によれば、塩素ガスの供給量に応じた量の塩化ニッケルガスが発生するから、塩素ガスの供給量を制御することで還元工程へ供給する塩化ニッケルガスの量を調整することができ、これによって生成するニッケル微粉末の粒径を制御することができる。 In the production process of nickel powder by gas phase reduction reaction, nickel atoms are generated at the moment when the nickel chloride gas and the reducing gas come into contact with each other, and ultrafine particles are generated and grown by collision and aggregation of the nickel atoms. go. And the particle diameter of the nickel fine powder produced | generated is determined by conditions, such as the partial pressure of nickel chloride gas in a reduction | restoration process, temperature. According to the nickel powder manufacturing method as described above, an amount of nickel chloride gas corresponding to the supply amount of chlorine gas is generated. Therefore, the amount of nickel chloride gas supplied to the reduction process is controlled by controlling the supply amount of chlorine gas. The amount can be adjusted, and the particle diameter of the nickel fine powder produced | generated by this can be controlled.
さらに、金属塩化物ガスは、塩素ガスと金属との反応で発生するから、固体金属塩化物の加熱蒸発により金属塩化物ガスを発生させる方法と異なり、キャリアガスの使用を少なくすることができるばかりでなく、製造条件によっては使用しないことも可能である。したがって、気相還元反応の方が、キャリアガスの使用量低減とそれに伴う加熱エネルギーの低減により、製造コストの低減を図ることができる。 Furthermore, since metal chloride gas is generated by the reaction of chlorine gas and metal, unlike the method of generating metal chloride gas by heating and evaporation of solid metal chloride, the use of carrier gas can be reduced. In addition, it may not be used depending on manufacturing conditions. Therefore, in the gas phase reduction reaction, the manufacturing cost can be reduced by reducing the amount of carrier gas used and the accompanying heating energy.
また、塩化工程で発生した塩化ニッケルガスに不活性ガスを混合することにより、還元工程における塩化ニッケルガスの分圧を制御することができる。このように、塩素ガスの供給量もしくは還元工程に供給する塩化ニッケルガスの分圧を制御することにより、ニッケル粉末の粒径を制御することができ、よってニッケル粉末の粒径を安定させることができるとともに、粒径を任意に設定することができる。 Moreover, the partial pressure of the nickel chloride gas in the reduction process can be controlled by mixing an inert gas with the nickel chloride gas generated in the chlorination process. Thus, by controlling the supply amount of chlorine gas or the partial pressure of nickel chloride gas supplied to the reduction process, the particle size of nickel powder can be controlled, and thus the particle size of nickel powder can be stabilized. In addition, the particle size can be arbitrarily set.
上記のような気相還元法によるニッケル粉末の製造条件は、平均粒径１μｍ以下になるように任意に設定するが、例えば、出発原料である金属ニッケルの粒径は約５〜２０ｍｍの粒状、塊状、板状等が好ましく、また、その純度は慨して９９．５％以上が好ましい。この金属ニッケルを、まず塩素ガスと反応させて塩化ニッケルガスを生成させるが、その際の温度は、反応を十分進めるために８００℃以上とし、かつニッケルの融点である１４５３℃以下とする。反応速度と塩化炉の耐久性を考慮すると、実用的には９００℃〜１１００℃の範囲が好ましい。 The production conditions of the nickel powder by the gas phase reduction method as described above are arbitrarily set so that the average particle diameter is 1 μm or less. For example, the particle diameter of the metallic nickel as a starting material is about 5 to 20 mm, A lump shape, a plate shape, and the like are preferable, and the purity is preferably 99.5% or more. The nickel metal is first reacted with chlorine gas to produce nickel chloride gas, and the temperature at that time is set to 800 ° C. or higher and 1453 ° C. or lower, which is the melting point of nickel, to sufficiently advance the reaction. Considering the reaction rate and the durability of the chlorination furnace, the range of 900 ° C. to 1100 ° C. is preferable for practical use.
次いで、この塩化ニッケルガスを還元工程に直接供給し、水素ガス等の還元性ガスと接触反応させるが、窒素やアルゴン等の不活性ガスを、塩化ニッケルガスに対し１〜３０モル％混合し、この混合ガスを還元工程に導入してもよい。また、塩化ニッケルガスとともに、または独立に塩素ガスを還元工程に供給することもできる。このように塩素ガスを還元工程に供給することによって、塩化ニッケルガスの分圧が調整でき、生成するニッケル粉末の粒径を制御することが可能となる。還元反応の温度は反応完結に十分な温度以上であればよいが、固体状のニッケル粉末を生成する方が取扱いが容易であるので、ニッケルの融点以下が好ましく、経済性を考慮すると９００℃〜１１００℃が実用的である。 Next, this nickel chloride gas is directly supplied to the reduction step and brought into contact with a reducing gas such as hydrogen gas, but an inert gas such as nitrogen or argon is mixed in an amount of 1 to 30 mol% with respect to the nickel chloride gas, This mixed gas may be introduced into the reduction step. Moreover, chlorine gas can also be supplied to a reduction process with nickel chloride gas or independently. By supplying chlorine gas to the reduction process in this way, the partial pressure of nickel chloride gas can be adjusted, and the particle size of the nickel powder to be produced can be controlled. The temperature of the reduction reaction may be at least a temperature sufficient for the completion of the reaction, but since it is easier to handle the production of solid nickel powder, it is preferably below the melting point of nickel. 1100 ° C. is practical.
このように還元反応を行いニッケル粉末を生成させたら、次は生成ニッケル粉末を冷却する。冷却の際、生成したニッケルの一次粒子同士の凝集による二次粒子の生成を防止して所望の粒径のニッケル粉末を得るために、還元反応を終えた１０００℃付近のガス流を４００〜８００℃程度まで窒素ガス等の不活性ガスを吹き込むことにより急速冷却させることが望ましい。その後、生成したニッケル粉末を、例えばバグフィルター等により分離、回収する。 After the reduction reaction is performed in this way to produce nickel powder, the produced nickel powder is then cooled. In cooling, in order to obtain the nickel powder having a desired particle size by preventing the formation of secondary particles due to the aggregation of the primary particles of the generated nickel, the gas flow around 1000 ° C. after finishing the reduction reaction is 400 to 800. It is desirable to cool rapidly by blowing an inert gas such as nitrogen gas to about 0 ° C. Thereafter, the produced nickel powder is separated and collected by, for example, a bag filter or the like.
また、噴霧熱分解法によるニッケル粉末の製造方法では、熱分解性のニッケル化合物を原料とするが、具体的には、硝酸塩、硫酸塩、オキシ硝酸塩、オキシ硫酸塩、塩化物、アンモニウム錯体、リン酸塩、カルボン酸塩、アルコキシ化合物などの１種または２種以上である。このニッケル化合物を含む溶液を噴霧して、微細な液滴を作るが、このときの溶媒としては、水、アルコール、アセトン、エーテル等が用いられる。また、噴霧の方法は、超音波または二重ジェットノズル等の噴霧方法により行う。このようにして微細な液滴とし、高温で加熱して金属化合物を熱分解し、ニッケル粉末を生成させる。このときの加熱温度は、使用される特定のニッケル化合物が熱分解する温度以上であり、好ましくは金属の融点付近である。 In addition, in the method for producing nickel powder by the spray pyrolysis method, a heat decomposable nickel compound is used as a raw material. Specifically, nitrate, sulfate, oxynitrate, oxysulfate, chloride, ammonium complex, phosphorus 1 type or 2 types or more, such as an acid salt, a carboxylate, and an alkoxy compound. The solution containing the nickel compound is sprayed to form fine droplets. As the solvent at this time, water, alcohol, acetone, ether or the like is used. The spraying method is performed by a spraying method such as ultrasonic or double jet nozzle. In this way, fine droplets are formed and heated at a high temperature to thermally decompose the metal compound to produce nickel powder. The heating temperature at this time is equal to or higher than the temperature at which the specific nickel compound used is thermally decomposed, and is preferably near the melting point of the metal.
液相法による金属微粉末の製造方法では、硫酸ニッケル、塩化ニッケルあるいはニッケル錯体を含むニッケル水溶液を、水酸化ナトリウムなどのアルカリ金属水酸化物中に添加するなどして接触させニッケル水酸化物を生成させ、次いでヒドラジンなどの還元剤でニッケル水酸化物を還元し金属ニッケル粉末を得る。このように生成した金属ニッケル粉末は、均一な粒子を得るために必要に応じて解砕処理する。 In a method for producing fine metal powder by a liquid phase method, nickel hydroxide containing nickel sulfate, nickel chloride or a nickel complex is contacted by adding it to an alkali metal hydroxide such as sodium hydroxide. Next, the nickel hydroxide is reduced with a reducing agent such as hydrazine to obtain metallic nickel powder. The metallic nickel powder thus produced is crushed as necessary to obtain uniform particles.
以上のようにして得られたニッケル粉末は、炭酸水溶液中に懸濁させ処理することが望ましい。炭酸水溶液で処理することにより、ニッケル表面に付着している塩素などの不純物が十分に除去されるとともに、ニッケル粉末の表面に存在する水酸化ニッケルなどの水酸化物や粒子同士の摩擦などにより表面から剥離して形成された微粒子が除去され、均一な酸化ニッケルの被膜を形成することができる。 The nickel powder obtained as described above is preferably suspended and treated in an aqueous carbonate solution. By treating with an aqueous carbonate solution, impurities such as chlorine adhering to the nickel surface are sufficiently removed, and the surface of the nickel powder is caused by hydroxide such as nickel hydroxide or friction between particles. The fine particles formed by peeling off the film are removed, and a uniform nickel oxide film can be formed.
炭酸水溶液中に懸濁して処理する際、気相還元法、噴霧熱分解法によるニッケル粉末の製造方法では、生成したニッケル粉末を通常純水で洗浄するが、その洗浄を炭酸水溶液で行う方法、あるいは純水洗浄後の水スラリー中に炭酸ガスを吹き込むか、あるいは炭酸水溶液を添加して処理することもできる。特に、気相還元法を採用した場合、純水洗浄の途中あるいは後に、スラリー状態において炭酸水溶液と接触して処理することが、製造工程の簡略化の面において有利である。 When processing by suspending in an aqueous carbonate solution, the nickel powder produced by vapor phase reduction or spray pyrolysis is usually washed with pure water, but the washing is performed with an aqueous carbonate solution, Alternatively, carbon dioxide gas can be blown into the water slurry after washing with pure water, or an aqueous carbonate solution can be added for treatment. In particular, when the vapor phase reduction method is employed, it is advantageous in terms of simplifying the production process that the treatment is performed in contact with the aqueous carbonate solution in the slurry state during or after the pure water cleaning.
この炭酸水溶液での処理は、ｐＨ５．５〜６．５の範囲、好ましくはｐＨ５．５〜６．０である。炭酸水溶液中での処理をｐＨ５．５未満で行った場合には、ニッケル粉末の表面に不均一な酸化皮膜が生成しニッケル粉末の焼結性を低下させることになる。また、ニッケル粉末自体が溶解し、表面の荒れが生じる。ｐＨ６．５を超えて行った場合には、ニッケル粉末の表面に付着、もしくは吸着した水酸化物を除去することができず、乾燥後に残存した水酸化物が不均一な酸化皮膜となる。 The treatment with the aqueous carbonate solution is in the range of pH 5.5 to 6.5, preferably pH 5.5 to 6.0. When the treatment in the carbonic acid aqueous solution is performed at a pH of less than 5.5, a non-uniform oxide film is formed on the surface of the nickel powder, and the sinterability of the nickel powder is lowered. In addition, the nickel powder itself dissolves and the surface becomes rough. When the pH exceeds 6.5, the hydroxide adhered or adsorbed on the surface of the nickel powder cannot be removed, and the hydroxide remaining after drying becomes a non-uniform oxide film.
このようにしてニッケル粉末を炭酸処理した後、そのニッケル粉末を乾燥する。乾燥方法は公知の方法を採用することができ、具体的には高温のガスと接触させ乾燥する気流乾燥、加熱乾燥および真空乾燥などが挙げられる。これらのうち、気流乾燥は粒子同士の接触による酸化皮膜の摩耗がないため、好ましい方法である。また、ニッケル粉末の表面に均質な酸化皮膜を形成させるためには、短時間に水分を除去して乾燥することが望ましい。 After the nickel powder is carbonized in this manner, the nickel powder is dried. As the drying method, a known method can be adopted, and specific examples include air-flow drying, heating drying, and vacuum drying in which the drying is performed by contacting with a high-temperature gas. Of these, air drying is a preferred method because there is no wear of the oxide film due to contact between the particles. In order to form a uniform oxide film on the surface of the nickel powder, it is desirable to remove moisture in a short time and dry it.
具体的には、ニッケル粉末が水スラリーの状態もしくは水分が約５０質量％の状態から、水分が０．１質量％以下になるまでの時間は、１分以内、好ましくは３０秒以内、より好ましくは１０秒以内である。このような短時間でニッケル粉末を乾燥することができるという点でも、気流乾燥方法は数秒での乾燥が可能であり、好ましい方法である。この気流乾燥では高温の窒素ガスなどと接触させるが、このときの温度は２００〜３００℃、好ましくは２５０℃前後のガスを接触させる。 Specifically, the time from when the nickel powder is in a water slurry state or when the water content is about 50% by mass to when the water content becomes 0.1% by mass or less is within 1 minute, preferably within 30 seconds, more preferably Is within 10 seconds. In view of the fact that the nickel powder can be dried in such a short time, the air flow drying method is preferable because it can be dried in a few seconds. In this air flow drying, the gas is brought into contact with a high-temperature nitrogen gas or the like. The temperature at this time is 200 to 300 ° C., preferably about 250 ° C.
本発明のニッケル粉末は、上記炭酸水溶液による処理の後、乾燥し、次いで大気中または酸素ガス雰囲気などの酸化性雰囲気中で加熱処理することが好ましく、特に好ましくは炭酸水溶液による処理を行い、次いで気流乾燥を行って水分を０．１質量％以下にした後、酸化性雰囲気中で加熱処理を行うことである。 The nickel powder of the present invention is preferably dried after the treatment with the carbonic acid aqueous solution, and then heat-treated in an oxidizing atmosphere such as air or an oxygen gas atmosphere, particularly preferably treated with the carbonic acid aqueous solution, It is to perform heat treatment in an oxidizing atmosphere after air drying to reduce the moisture to 0.1% by mass or less.
ニッケル粉末の焼結開始温度については、以下の事実が知られている。すなわち、ニッケル粉末表面に酸化皮膜等の皮膜が存在する間は焼結が開始されないが、焼成温度の上昇に伴い、酸化皮膜が還元されて存在しなくなると、ニッケル粉末の焼結が開始される。ニッケル粉末は通常２００〜３００℃で焼結が始まるので、２００〜３００℃以上に加熱されても還元されないよう、均質で安定な酸化皮膜を形成することにより、ニッケル粉末の耐還元性が向上し、このため焼結開始温度をより高温側に移行することが可能となる。このように、耐還元性を向上させることが可能な均質で安定した酸化皮膜を形成するには、上記酸化性雰囲気での加熱処理温度を、１００〜４００℃とすることが好ましく、より好ましくは２００〜３００℃、特に好ましくは２００〜２５０℃である。また、加熱処理時間は、通常３０分〜１０時間であり、ニッケル粉末中の酸素含有量が０．３〜２．０質量％になるように処理を行う。 The following facts are known about the sintering start temperature of nickel powder. That is, sintering does not start while a film such as an oxide film is present on the surface of the nickel powder, but when the oxide film is reduced and no longer exists as the firing temperature increases, sintering of the nickel powder starts. . Since nickel powder usually starts sintering at 200-300 ° C, the reduction resistance of nickel powder is improved by forming a homogeneous and stable oxide film so that it is not reduced even when heated to 200-300 ° C or higher. For this reason, the sintering start temperature can be shifted to a higher temperature side. Thus, in order to form a homogeneous and stable oxide film capable of improving the reduction resistance, the heat treatment temperature in the oxidizing atmosphere is preferably 100 to 400 ° C., more preferably 200-300 degreeC, Most preferably, it is 200-250 degreeC. Moreover, heat processing time is 30 minutes-10 hours normally, and it processes so that the oxygen content in nickel powder may be 0.3-2.0 mass%.
次に、上記のようにして得られたニッケル粉末に硫黄ガスまたは硫黄含有ガスを接触させることにより処理する。硫黄ガスまたは硫黄含有ガスにより処理することによって、ニッケル粉末の表面にＮｉ−ＳやＮｉ−Ｓ−Ｏのような硫黄とニッケルを含有する層が生じ、ニッケル耐還元性および焼結挙動等の熱挙動を改善することができる。硫黄含有化合物ガスとしては、硫化水素ガス、亜硫酸ガス等を挙げることができ、また、硫化ニッケル等の硫黄含有化合物を加熱蒸発させて生成したものを使用することも可能である。これら硫黄含有ガスは、例えば水素−窒素混合ガス等の還元性ガスと混合して使用すると、ニッケル粉末表面に硫黄含有化合物層が形成されるだけでなく、ニッケル粉末表面の酸素量を調製し酸化皮膜を均質化することができ、また、塩化物等の不純物を除去することが可能となり、より効果的である。 Next, the nickel powder obtained as described above is treated by contacting with sulfur gas or sulfur-containing gas. By treating with sulfur gas or sulfur-containing gas, a layer containing sulfur and nickel, such as Ni-S and Ni-S-O, is formed on the surface of the nickel powder, and heat such as nickel reduction resistance and sintering behavior. The behavior can be improved. Examples of the sulfur-containing compound gas include hydrogen sulfide gas, sulfurous acid gas, and the like, and it is also possible to use a gas produced by heating and evaporating a sulfur-containing compound such as nickel sulfide. When these sulfur-containing gases are used in combination with a reducing gas such as a hydrogen-nitrogen mixed gas, not only a sulfur-containing compound layer is formed on the nickel powder surface, but also the amount of oxygen on the nickel powder surface is adjusted and oxidized. The film can be homogenized, and impurities such as chloride can be removed, which is more effective.
ニッケル粉末を硫黄ガスまたは硫黄含有ガスで処理する際の温度範囲は２０〜３００℃、好ましくは１５０〜２５０℃であり、処理時間は５〜６０分、好ましくは１０〜１５分である。硫黄ガスまたは硫黄含有ガスの導入量は、処理後のニッケル粉末中の硫黄含有量で０．０１〜１質量％、好ましくは０．０５〜０．８質量％となるように調整する。ニッケル粉末表面の硫黄含有量が０．０１質量％未満では、ニッケル粉末の還元挙動および焼結挙動改善の効果が得られない。また、ニッケル粉末表面の硫黄含有量が１質量％を超えると、積層セラミックコンデンサの電気特性を劣化させるという問題が生じる。本発明のニッケル粉末の製造方法においては、平均粒径が１μｍ以下、好ましくは０．０５〜１μｍ、より好ましくは０．１〜０．５μｍであり、ＢＥＴによる比表面積が１〜２０ｍ２／ｇであるニッケル粉末を硫黄ガスまたは硫黄化合物含有ガスで処理するとより効果的である。 The temperature range when nickel powder is treated with sulfur gas or sulfur-containing gas is 20 to 300 ° C., preferably 150 to 250 ° C., and the treatment time is 5 to 60 minutes, preferably 10 to 15 minutes. The amount of sulfur gas or sulfur-containing gas introduced is adjusted so that the sulfur content in the treated nickel powder is 0.01 to 1% by mass, preferably 0.05 to 0.8% by mass. If the sulfur content on the surface of the nickel powder is less than 0.01% by mass, the effect of improving the reduction behavior and sintering behavior of the nickel powder cannot be obtained. Moreover, when the sulfur content on the surface of the nickel powder exceeds 1% by mass, there arises a problem that the electrical characteristics of the multilayer ceramic capacitor are deteriorated. In the method for producing nickel powder of the present invention, the average particle size is 1 μm or less, preferably 0.05 to 1 μm, more preferably 0.1 to 0.5 μm, and the specific surface area by BET is 1 to 20 m 2 / g. It is more effective to treat nickel powder that is a sulfur gas or a sulfur compound-containing gas.
ニッケル粉末を塩化ニッケルガスと還元性ガスの気相反応法によって製造する場合、塩化ニッケルガスの還元性ガスによる還元反応を、硫黄ガスあるいは硫黄化合物ガス雰囲気中で行うことによって硫黄を含むニッケル粉末を製造する方法、または塩化ニッケルガスを還元する還元ガスに硫黄ガスあるいは硫黄化合物ガスを含有させることによって硫黄を含むニッケル粉末を製造することも可能である。しかしながら、このような方法でニッケル粉末を製造した場合、硫黄含有化合物層形成の制御が困難であるため、
（１）硫黄が生成したニッケル粒子の内部にまで存在してしまう、
（２）均質な硫黄化合物層が得られない、
（３）硫黄化合物層が厚くなり過ぎる、
等の問題が生じる。このような問題点が生じると、ニッケル粉末の還元挙動および焼結挙動を逆に低下させてしまったり、あるいは焼結性を低下させてしまうことになる。さらに、このように硫黄あるいは硫黄化合物ガス含有雰囲気中で塩化ニッケルガスを還元して製造したニッケル粉末は、
（４）塩素含有量が高い、
（５）洗浄しても塩素が落ち難い、すなわち洗浄効率が極めて悪い
という問題も生じる。ニッケル粉末中に塩素等のハロゲン化物が残留すると、ニッケル粉末の酸化を促進して錆を誘発し、さらには導電ペーストとして内部電極に使用した場合、マイグレーションと呼ばれる金属イオンの移動を引き起こし、内部電極の破損を生じさせるため好ましくない。
When nickel powder is produced by a gas phase reaction method of nickel chloride gas and reducing gas, nickel powder containing sulfur is obtained by performing a reduction reaction of nickel chloride gas with a reducing gas in an atmosphere of sulfur gas or sulfur compound gas. It is also possible to produce nickel powder containing sulfur by including a sulfur gas or a sulfur compound gas in a reducing gas for reducing nickel chloride gas. However, when nickel powder is produced by such a method, it is difficult to control the formation of the sulfur-containing compound layer.
(1) Sulfur is present even inside the nickel particles generated,
(2) A homogeneous sulfur compound layer cannot be obtained.
(3) The sulfur compound layer becomes too thick,
Such problems arise. If such a problem arises, the reduction behavior and sintering behavior of the nickel powder will be reduced, or the sinterability will be reduced. Furthermore, the nickel powder produced by reducing nickel chloride gas in an atmosphere containing sulfur or sulfur compound gas in this way,
(4) high chlorine content,
(5) Chlorine is difficult to be removed even after washing, that is, the washing efficiency is extremely poor. If halides such as chlorine remain in the nickel powder, the nickel powder promotes oxidation and induces rust, and when used as an internal electrode as a conductive paste, it causes migration of metal ions called migration. This is not preferable because it causes damage.
これに対し、本発明のニッケル粉の製造方法、すなわち、気相還元法、噴霧熱分解法、あるいは液相法等によって製造したニッケル粉末を、硫黄または硫黄化合物含有ガスで処理してニッケル粉末表面にニッケルと硫黄を含む化合物層を形成させる製造方法は、還元挙動および焼結挙動に優れ、かつ塩素等の残留ハロゲン化物の少ないニッケル粉末を得ることができる。 On the other hand, the nickel powder surface of the nickel powder produced by the method for producing the nickel powder of the present invention, that is, the nickel powder produced by the gas phase reduction method, the spray pyrolysis method, or the liquid phase method is treated with sulfur or a sulfur compound-containing gas. The manufacturing method in which the compound layer containing nickel and sulfur is formed can provide a nickel powder that is excellent in reduction behavior and sintering behavior and has little residual halide such as chlorine.
また、上記硫黄または硫黄化合物含有ガスで処理する前に、ニッケル粉末を解砕処理することによって、還元挙動および焼結挙動をより向上させることができる。 Further, the reduction behavior and the sintering behavior can be further improved by crushing the nickel powder before the treatment with the sulfur or sulfur compound-containing gas.
本発明の製造方法によるニッケル粉末は、これを内部電極に用いた積層セラミックコンデンサの製造工程において有機成分を除去するために酸化性雰囲気で加熱処理した際の重量変化が少ない。また、還元性雰囲気で加熱処理した際には、還元開始温度がより高温であり、加熱処理中における急激な重量減少が生じ難い、等の耐還元性に優れるものである。さらには、焼結開始温度が高く、焼結開始による体積変化が少ない。これは、前記したように、積層セラミックコンデンサの焼成時にデラミネーションが発生し難くなることを意味する。したがって、本発明の製造方法によるニッケル粉末は、積層セラミックコンデンサの製造工程において優れた酸化挙動、還元挙動および焼結挙動を示し、デラミネーションが生じにくくなるという効果が奏される。 The nickel powder produced by the production method of the present invention has little change in weight when heat-treated in an oxidizing atmosphere in order to remove organic components in the production process of the multilayer ceramic capacitor using the nickel powder as an internal electrode. In addition, when heat treatment is performed in a reducing atmosphere, the reduction start temperature is higher, and a rapid weight loss is less likely to occur during the heat treatment. Furthermore, the sintering start temperature is high and the volume change due to the start of sintering is small. As described above, this means that delamination hardly occurs during the firing of the multilayer ceramic capacitor. Therefore, the nickel powder produced by the production method of the present invention exhibits excellent oxidation behavior, reduction behavior, and sintering behavior in the production process of the multilayer ceramic capacitor, and has an effect that delamination hardly occurs.
以下、実施例を挙げて本発明の効果をより具体的に説明する。なお、本明細書において、ニッケル粉末の平均粒径、硫黄濃度、塩素濃度、還元挙動および焼結挙動は下記の方法で調べた。 Hereinafter, an example is given and the effect of the present invention is explained more concretely. In the present specification, the average particle diameter, sulfur concentration, chlorine concentration, reduction behavior and sintering behavior of nickel powder were examined by the following methods.
ａ．平均粒径
電子顕微鏡によりニッケル粉末の写真を撮影し、その写真から粒子２００個の粒径を測定してその平均値を算出した。なお、粒径は粒子を包み込む最小円の直径とした。
a. Average Particle Size A photograph of nickel powder was taken with an electron microscope, and the particle size of 200 particles was measured from the photograph, and the average value was calculated. The particle diameter was the diameter of the smallest circle enclosing the particles.
ｂ．硫黄濃度
株式会社堀場製作所製ＥＭＧＡ−５２０ＳＰを使用して、燃焼−赤外線吸収法により測定した。ニッケル粉末０．５ｇと金属錫および金属タングステンをアルミナるつぼに入れ、酸素気流中で高周波電流によって加熱、燃焼させ、発生したＳＯ２を赤外線により検出、定量し、ニッケル粉末中の硫黄濃度とした。
b. Sulfur concentration The sulfur concentration was measured by a combustion-infrared absorption method using EMGA-520SP manufactured by Horiba, Ltd. Nickel powder 0.5 g, metal tin, and metal tungsten were placed in an alumina crucible, heated and burned with a high-frequency current in an oxygen stream, and the generated SO 2 was detected and quantified by infrared rays to obtain the sulfur concentration in the nickel powder.
ｃ．塩素濃度
ニッケル粉末を硝酸に溶解し、硝酸銀溶液で滴定する硝酸銀滴定法により求めた。なお、硝酸銀滴定は、ＪＩＳ Ｈ１６１５−１９９７に準拠して行った。
c. Chlorine concentration Nickel powder was dissolved in nitric acid and determined by a silver nitrate titration method in which titration was performed with a silver nitrate solution. The silver nitrate titration was performed according to JIS H1615-1997.
ｄ．還元挙動
熱重量−示差熱分析機（ＴＧ−ＤＴＡ、ＴＧ８１２０：株式会社リガク社製）にて、弱還元性雰囲気（１．５％水素−９８．５％窒素）中で５℃／分の昇温速度で７００℃まで加熱し、その際の重量変化を測定した。
d. Reduction behavior Increased by 5 ° C / min in a weakly reducing atmosphere (1.5% hydrogen-98.5% nitrogen) with a thermogravimetric-differential thermal analyzer (TG-DTA, TG8120: manufactured by Rigaku Corporation). It heated to 700 degreeC with the temperature rate, and the weight change in that case was measured.
ｅ．焼結挙動
ニッケル粉末１ｇ、樟脳３重量％およびアセトン３重量％を混合し、この混合物を、内径５ｍｍ、高さ１０ｍｍの円柱状金属に充填し、面圧０．１７トンの荷重をかけて試験ピースを作製した。この試験ピースの焼結開始温度を、熱膨張収縮挙動測定装置（ＴＭＡ−８３１０：株式会社リガク社製）を用いて、弱還元性雰囲気（１．５％水素−９８．５％窒素混合ガス）の下、昇温速度５℃／分の条件で測定した。
e. Sintering behavior 1 g of nickel powder, 3% by weight of camphor and 3% by weight of acetone were mixed, and this mixture was filled into a cylindrical metal having an inner diameter of 5 mm and a height of 10 mm, and a test was conducted with a surface pressure of 0.17 tons Pieces were made. Sintering start temperature of this test piece was measured using a thermal expansion / shrinkage behavior measuring device (TMA-8310: manufactured by Rigaku Corporation), and a weakly reducing atmosphere (1.5% hydrogen-98.5% nitrogen mixed gas). The temperature was measured under the condition of a heating rate of 5 ° C./min.
[実施例]
Ａ．ニッケル粉末の調製
図１に示すニッケル粉末製造装置の塩化炉１内に、出発原料である平均粒径５ｍｍの金属ニッケルショットＭを充填するとともに、加熱手段１１で炉内雰囲気温度を１１００℃とした。次いで、ノズル１２から塩化炉１内に塩素ガスを供給し、金属ニッケルショットＭを塩化して塩化ニッケルガスを発生させ、この後、ノズル１３から供給した窒素ガスを塩化ニッケルガスに混合した。そして、塩化ニッケルガスと窒素ガスとの混合ガスを、加熱手段２１で１０００℃の炉内雰囲気温度とした還元炉２内に、ノズル２２から流速２．３ｍ／秒（１０００℃換算）で導入した。
[Example]
A. Preparation of Nickel Powder In the chlorination furnace 1 of the nickel powder production apparatus shown in FIG. 1, metal nickel shot M having an average particle diameter of 5 mm, which is a starting material, is filled and the furnace atmosphere temperature is set to 1100 ° C. . Next, chlorine gas was supplied from the
これと同時に、ノズル２３から還元炉２０内に水素ガスを流速７Ｎｌ／分で供給して塩化ニッケルガスを還元し、ニッケル粉末Ｐを得た。さらに、還元工程にて生成したニッケル粉末Ｐに、ノズル２４から供給した窒素ガスを接触させ、ニッケル粉末Ｐを冷却した。この後、ニッケル粉末Ｐを分離回収して湯洗洗浄し、ニッケル粉末スラリー中に炭酸ガスを吹き込んでｐＨ５．５とし、常温下においてニッケル粉末を炭酸水溶液中で６０分処理した。その後、気流乾燥機で乾燥処理した後、大気中２００℃で３０分間加熱処理を行った後、ジェットミル解砕処理を行い、乾燥ニッケル粉末を得た。
At the same time, hydrogen gas was supplied from the
Ｂ．ニッケル粉末の硫化処理
上記のようにして得られた乾燥ニッケル粉末１３０ｇを容器に入れ、１８０℃に加熱した。ニッケル粉末の下方向より硫化水素ガスと１．５％水素−窒素混合ガスをそれぞれ０．１Ｌ／分、１０Ｌ／分で導入し、１０分間硫化処理した。
B. Sulfurization treatment of nickel powder 130 g of the dry nickel powder obtained as described above was placed in a container and heated to 180 ° C. Hydrogen sulfide gas and 1.5% hydrogen-nitrogen mixed gas were introduced at 0.1 L / min and 10 L / min, respectively, from below the nickel powder and subjected to sulfiding treatment for 10 minutes.
[比較例１]
実施例の「Ａ.ニッケル粉末の調製」と同様にして得られた乾燥ニッケル粉末で、硫化処理を行わないものを比較例１のニッケル粉末とした。
上記実施例および比較例１のニッケル粉末につき、平均粒径、硫黄濃度を上記の方法で測定し、その結果を表１に示す。また、実施例および比較例１のニッケル粉末の還元挙動および焼結挙動を上記の方法で調べた。実施例および比較例１のニッケル粉末の還元挙動を図２に、焼結挙動を図３に示す。
[Comparative Example 1]
The dry nickel powder obtained in the same manner as in “A. Preparation of nickel powder” in the examples and not subjected to sulfiding treatment was used as the nickel powder of Comparative Example 1.
With respect to the nickel powders of Examples and Comparative Example 1, the average particle diameter and sulfur concentration were measured by the above methods, and the results are shown in Table 1. Further, the reduction behavior and sintering behavior of the nickel powders of Examples and Comparative Example 1 were examined by the above method. FIG. 2 shows the reduction behavior of the nickel powder of Example and Comparative Example 1, and FIG. 3 shows the sintering behavior.
図２から明らかなように、比較例１のニッケル粉末は２２０℃近辺で重量減が生じ始め、７００℃まで加熱した際の重量減少率が約−１．８％である。これに対し、本発明のニッケル粉末は比較例よりも高温の２５０℃付近から重量減が始まっており、７００℃における重量減少率は約−１．２％である。これは、本発明のニッケル粉末は還元開始温度が高く、重量減少率が小さい、すなわち耐還元性に優れることを意味している。 As is apparent from FIG. 2, the nickel powder of Comparative Example 1 begins to lose weight around 220 ° C., and the weight reduction rate when heated to 700 ° C. is about −1.8%. In contrast, the nickel powder of the present invention begins to lose weight at around 250 ° C., which is higher than the comparative example, and the weight reduction rate at 700 ° C. is about −1.2%. This means that the nickel powder of the present invention has a high reduction start temperature and a small weight loss rate, that is, excellent resistance to reduction.
また、図３から明らかなように、比較例のニッケル粉末が２５０℃付近において体積変化が生じ、これは焼結の開始点と認められ、６００℃付近での収縮率が−１６％近くに達している。これ対し、本発明のニッケル粉末は４５０℃付近まで体積変化がなく、６００℃付近まで加熱した際の収縮率も−８％前後である。これらの結果から、本発明のニッケル粉末は、従来のニッケル粉末よりも焼結挙動に優れることが判る。 As is clear from FIG. 3, the nickel powder of the comparative example undergoes a volume change near 250 ° C., which is recognized as the starting point of sintering, and the shrinkage rate near 600 ° C. reaches nearly −16%. ing. On the other hand, the nickel powder of the present invention has no volume change up to around 450 ° C., and the shrinkage rate when heated to around 600 ° C. is around −8%. From these results, it can be seen that the nickel powder of the present invention is superior in sintering behavior to the conventional nickel powder.
[比較例２]
実施例の「Ａ．ニッケル粉末の調製」において、塩化ニッケルガスを水素ガスで還元する際、水素ガスとともに硫化水素ガスを０．４Ｎｌ／分で供給し、硫黄含有ニッケル粉末を得た。さらに、還元工程にて生成したニッケル粉末に、ノズル２４から供給した窒素ガスを接触させ、硫黄含有ニッケル粉末を冷却した。この後、硫黄含有ニッケル粉末を分離回収して湯洗洗浄し、気流乾燥機で乾燥処理した後、大気中２００℃で３０分間加熱処理を行い、比較例２の硫黄含有ニッケル粉末を得た。実施例で実施した炭酸洗浄処理は行わなかった。また、実施例で行った「Ｂ．ニッケル粉末の硫化処理」は行わなかった。
[Comparative Example 2]
In “A. Preparation of nickel powder” in the examples, when nickel chloride gas was reduced with hydrogen gas, hydrogen sulfide gas was supplied at 0.4 Nl / min together with hydrogen gas to obtain sulfur-containing nickel powder. Furthermore, the nitrogen powder supplied from the
実施例および比較例２のニッケル粉末の塩素濃度および焼結挙動を上記方法により調べた結果を表２に示す。表２は、実施例および比較例２のニッケル粉末を上記焼結挙動測定方法によって測定し、得られた収縮率曲線において、７００℃まで加熱した際の収縮率を示したものである。 Table 2 shows the results of examining the chlorine concentration and sintering behavior of the nickel powders of Examples and Comparative Example 2 by the above method. Table 2 shows the shrinkage ratio when the nickel powders of Examples and Comparative Example 2 were measured by the above-described sintering behavior measurement method and heated to 700 ° C. in the obtained shrinkage ratio curves.
表２から明らかなように、本発明のニッケル粉末（気相還元法により得られたニッケル粉末を炭酸処理し、乾燥、加熱処理した後、硫化水素ガスで硫化処理することにより得られた、ニッケル−硫黄化合物層を有するニッケル粉末）は、比較例２のニッケル粉末（塩化ニッケルガスを水素ガスで気相還元してニッケル粉末を製造する際に、水素ガスとともに硫化水素ガスを導入して得られた硫黄含有ニッケル粉）と比べ、塩素含有量が低く、また、硫黄含有量はほぼ同じであるが７００℃まで加熱した際の収縮率が小さいものであることがわかる。すなわち、本発明の製造方法によるニッケル粉末は、収縮率が極めて小さい、すなわち焼結挙動に優れたものであることを示している。 As is apparent from Table 2, the nickel powder of the present invention (the nickel powder obtained by carbonizing nickel powder obtained by the vapor phase reduction method, drying and heating, and then sulfurating with hydrogen sulfide gas. -Nickel powder having a sulfur compound layer) is obtained by introducing hydrogen sulfide gas together with hydrogen gas when producing nickel powder by vapor phase reduction of nickel chloride gas with hydrogen gas in Comparative Example 2 It can be seen that the chlorine content is lower than that of the sulfur-containing nickel powder, and the sulfur content is substantially the same, but the shrinkage rate when heated to 700 ° C. is small. That is, the nickel powder produced by the production method of the present invention has an extremely small shrinkage rate, that is, an excellent sintering behavior.
以上の結果から、本発明のニッケル粉末では、積層セラミックコンデンサの製造工程において優れた酸化挙動、耐還元性および焼結挙動を示し、結果としてデラミネーションの防止に極めて有効なものであることが実証された。 From the above results, the nickel powder of the present invention demonstrates excellent oxidation behavior, reduction resistance and sintering behavior in the production process of multilayer ceramic capacitors, and as a result, is proved to be extremely effective in preventing delamination. It was done.
本発明のニッケル粉末の製造方法によれば、表面にニッケルと硫黄を含有する化合物層が形成されるので、積層セラミックコンデンサの製造工程において優れた酸化挙動、還元挙動および焼結挙動を示し、結果として積層セラミックコンデンサのデラミネーションを防止することができる導電ペースト用、特に積層セラミックコンデンサ用に適したニッケル粉末を製造することが可能である。 According to the method for producing nickel powder of the present invention, since a compound layer containing nickel and sulfur is formed on the surface, excellent oxidation behavior, reduction behavior and sintering behavior are shown in the production process of the multilayer ceramic capacitor. As a result, it is possible to produce nickel powder suitable for a conductive paste, particularly for a multilayer ceramic capacitor, which can prevent delamination of the multilayer ceramic capacitor.
１ 塩化炉
１１ 加熱手段
１２ 塩素ガス供給ノズル
１３ 窒素ガス供給ノズル
２ 還元炉
２１ 加熱手段
２２ 塩化ニッケル移送ノズル
２３ 水素ガス供給ノズル
２４ ノズル
Ｍ 原料のニッケル粉末
Ｐ 製造されたニッケル粉末
DESCRIPTION OF SYMBOLS 1 Chlorination furnace 11 Heating means 12 Chlorine
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004221852A JP4394535B2 (en) | 2004-07-29 | 2004-07-29 | Method for producing nickel powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004221852A JP4394535B2 (en) | 2004-07-29 | 2004-07-29 | Method for producing nickel powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2006037195A true JP2006037195A (en) | 2006-02-09 |
| JP4394535B2 JP4394535B2 (en) | 2010-01-06 |
Family
ID=35902502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004221852A Active JP4394535B2 (en) | 2004-07-29 | 2004-07-29 | Method for producing nickel powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4394535B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1972397A2 (en) | 2007-03-12 | 2008-09-24 | Shoei Chemical Inc. | Nickel powder, method for manufacturing same, conductor paste, and multilayer ceramic electronic component using same |
| JP2014122368A (en) * | 2012-12-20 | 2014-07-03 | Jfe Mineral Co Ltd | Nickel ultrafine powder, conductive paste and method of producing nickel ultrafine powder |
| JP2014196531A (en) * | 2013-03-29 | 2014-10-16 | 住友金属鉱山株式会社 | Nickel powder and production method therefor |
| KR20150070362A (en) | 2012-11-20 | 2015-06-24 | 제이에프이미네라르 가부시키가이샤 | Nickel powder, conductive paste, and laminated ceramic electronic component |
-
2004
- 2004-07-29 JP JP2004221852A patent/JP4394535B2/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1972397A2 (en) | 2007-03-12 | 2008-09-24 | Shoei Chemical Inc. | Nickel powder, method for manufacturing same, conductor paste, and multilayer ceramic electronic component using same |
| US8128725B2 (en) | 2007-03-12 | 2012-03-06 | Shoei Chemical Inc. | Nickel powder, method for manufacturing same, conductor paste, and multilayer ceramic electronic component using same |
| US8734562B2 (en) | 2007-03-12 | 2014-05-27 | Shoei Chemical Inc. | Nickel powder, method for manufacturing same, conductor paste, and multilayer ceramic electronic component using same |
| KR20150070362A (en) | 2012-11-20 | 2015-06-24 | 제이에프이미네라르 가부시키가이샤 | Nickel powder, conductive paste, and laminated ceramic electronic component |
| JP2014122368A (en) * | 2012-12-20 | 2014-07-03 | Jfe Mineral Co Ltd | Nickel ultrafine powder, conductive paste and method of producing nickel ultrafine powder |
| JP2014196531A (en) * | 2013-03-29 | 2014-10-16 | 住友金属鉱山株式会社 | Nickel powder and production method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4394535B2 (en) | 2010-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4740839B2 (en) | Nickel powder and method for producing the same | |
| JP4286220B2 (en) | Metallic nickel powder and method for producing the same | |
| JP5626217B2 (en) | Nickel fine powder and method for producing the same | |
| JP6876001B2 (en) | Nickel powder manufacturing method | |
| JP3787032B2 (en) | Metallic nickel powder | |
| JP6559118B2 (en) | Nickel powder | |
| JP5141983B2 (en) | Nickel fine powder and method for producing the same | |
| JP4960210B2 (en) | Nickel powder and method for producing nickel powder | |
| JP4394535B2 (en) | Method for producing nickel powder | |
| JP6082278B2 (en) | Method for surface modification of nickel nanoparticles | |
| JP4276031B2 (en) | Titanium compound-coated nickel powder and conductive paste using the same | |
| WO2004067211A1 (en) | Fine metal powder, process for producing the same, and conductive paste containing the fine metal powder | |
| JP5060227B2 (en) | Method for producing nickel powder | |
| JP2009013456A (en) | Nickel alloy powder production method | |
| JP2005248198A (en) | Nickel powder, and electrically conductive paste and laminated ceramic capacitor using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070719 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20090630 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090702 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090805 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090924 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20091015 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4394535 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121023 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121023 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121023 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121023 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131023 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131023 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131023 Year of fee payment: 4 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |