JPH01139710A - Manufacture of fine granular alloy powder - Google Patents
Manufacture of fine granular alloy powderInfo
- Publication number
- JPH01139710A JPH01139710A JP29770187A JP29770187A JPH01139710A JP H01139710 A JPH01139710 A JP H01139710A JP 29770187 A JP29770187 A JP 29770187A JP 29770187 A JP29770187 A JP 29770187A JP H01139710 A JPH01139710 A JP H01139710A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- particle size
- silver
- alloy powder
- alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 title claims abstract description 65
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 27
- 239000000956 alloy Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 9
- 239000011133 lead Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 11
- 239000012535 impurity Substances 0.000 abstract description 8
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 150000008043 acidic salts Chemical class 0.000 abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 abstract description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 2
- 229910052745 lead Inorganic materials 0.000 abstract 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 229910002855 Sn-Pd Inorganic materials 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002002 slurry Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- 239000010944 silver (metal) Substances 0.000 description 5
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QOGLYAWBNATGQE-UHFFFAOYSA-N copper;gold;silver Chemical compound [Cu].[Au][Ag] QOGLYAWBNATGQE-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010946 fine silver Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229910001174 tin-lead alloy Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は安価で、かつ不純物及び酸化膜の少ない３．０
μｍ以下の鉄より責な金属の合金粉末の製造方法に関す
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention is inexpensive and has less impurities and oxide film.
The present invention relates to a method for producing an alloy powder of a metal smaller than .mu.m in diameter than iron.
電子工業の分野でプリント塗布配線用に銀粉ペーストが
広く使用されている。近年の電子部品の小型化、精密化
および高集積化に伴って、プリント塗布の巾は著しく狭
くなり、銀粉ペーストの銀粉はより微細なものが要求さ
れている。特に、ＩＣ用の導電ペーストには、従来銀粉
とガラス質バインダー粉末と塗布接着剤と溶剤との混合
物からなる銀ペーストが用いられてきたが、ＩＣの微細
化に伴う１０μｍ以下の巾のペーストのプリント塗布で
、ペーストの焼成後に途切れのない細線が形成されるた
めには、原料の銀粉もなるべく微細であり、好ましくは
３μｍ以下であることが必要である。現在、３μｍ以下
の粒径の銀粉が製造され使用されているが、銀は微粉化
すると粉末の表面積の増大に伴って化学的に活性となり
、その耐酸化性が劣化する。このため、銀微粉末からな
る導電ペーストはその比抵抗が経年的に増大するのを避
けることができなかった０例えば、その対策として銀微
粉末とパラジウム微粉末とを混合する方法が試みられて
いる。しかし、銀とパラジウムとが相互に合金化してい
ない粉末状態では、その混合物は工Ｃ性能の経年変化防
止に対して十分な効果を発揮しない。Silver powder paste is widely used for printed wiring in the electronics industry. In recent years, with the miniaturization, precision, and high integration of electronic components, the width of print application has become significantly narrower, and the silver powder in the silver powder paste is required to be finer. In particular, silver paste consisting of a mixture of silver powder, vitreous binder powder, coating adhesive, and solvent has traditionally been used as a conductive paste for ICs, but with the miniaturization of ICs, pastes with a width of 10 μm or less have been used. In print coating, in order to form an uninterrupted fine line after baking the paste, the raw material silver powder must be as fine as possible, preferably 3 μm or less. Currently, silver powder with a particle size of 3 μm or less is produced and used, but when silver is pulverized, it becomes chemically active as the surface area of the powder increases, and its oxidation resistance deteriorates. For this reason, conductive pastes made of fine silver powder cannot avoid increasing their resistivity over time. For example, as a countermeasure, a method of mixing fine silver powder and fine palladium powder has been attempted. There is. However, when silver and palladium are in a powder state in which they are not alloyed with each other, the mixture does not exhibit a sufficient effect in preventing aging of the C performance.
本発明者は、ＩＣの微細化の要求を満たすべく。The present inventor aimed to meet the demand for miniaturization of ICs.
導電ペースト用の導電粉末を３μｍ以下の微粉末とし、
かつ耐食性をあげるには単に銀微粉とパラジウム微粉と
をペースト加工時に混合するだけでなく、銀とパラジウ
ムとを合金化して、かつ微粉末を得る必要があると考え
た。The conductive powder for the conductive paste is a fine powder of 3 μm or less,
In addition, in order to improve corrosion resistance, it was thought that it was necessary not only to simply mix silver fine powder and palladium fine powder during paste processing, but also to alloy silver and palladium and obtain fine powder.
同様の用途に３μｍ以下の粒径の銅−銀合金粉末なども
十分使用できる可能性がある。少なくとも現在の１０μ
ｍ程度のプリント塗布配線用には、銅微粉末だけよりも
より酸化劣化しにくい銅−銀合金粉末のほうが望ましい
。しかし、一方で現在使用されている銀微粉末は３μｍ
を越える粒径であり、３μｍ以下の安価な銅微粉末を得
ることは戴しい。Copper-silver alloy powder having a particle size of 3 μm or less may also be used for similar purposes. At least the current 10μ
Copper-silver alloy powder, which is more resistant to oxidative deterioration, is more desirable than copper fine powder alone for printed coating wiring of about 500 yen. However, on the other hand, the silver fine powder currently used is 3 μm thick.
It is difficult to obtain inexpensive copper fine powder with a particle size of 3 μm or less.
このことはすなわち、従来の製法では３μｍ以下の銅−
銀合金粉末はさらに製造しがたいものであることを意味
している。This means that in conventional manufacturing methods, copper particles with a thickness of 3 μm or less
This means that silver alloy powders are even more difficult to manufacture.
また、ＩＣやＬＳＩの面実装化および基板のフレキシブ
ル化に伴って、印刷塗布〜焼付による配線が可能なはん
だペーストの使用が増大している。この方面でも電子部
品の小型化、精密化および高集積化に伴ってリード端子
の微細化が進行しており、より微細な印刷用はんだ粉末
の開発が望まれている。Further, as ICs and LSIs become surface-mounted and substrates become more flexible, the use of solder pastes that allow wiring by printing and baking is increasing. In this field as well, the miniaturization of lead terminals is progressing with the miniaturization, precision, and high integration of electronic components, and the development of finer printing solder powder is desired.
本発明者らは、安価で不純物及び酸化膜の少ない３μｍ
以下の微細粒状合金粉の製造技術の研究を重ねた結果、
−次粒子径が０．１μｍから３．０μｍの範囲の鉄粉を
、鉄イオンよりも電位が責である錫、鉛、銅、銀および
パラジウムの酸性塩の２種以上の混合溶液中に添加する
ことによって、−次粒子径が鉄粉とほぼ同じ０．１μｍ
から３．０μｍの範囲の錫−鉛、鋼−銀または銀−パラ
ジウム合金粉末を置換析出できる現象を見出し本発明を
完成した。The present inventors have developed a 3 μm film that is inexpensive and has few impurities and oxide films.
As a result of repeated research on the manufacturing technology of the following fine-grained alloy powder,
- Iron powder with a particle size in the range of 0.1 μm to 3.0 μm is added to a mixed solution of two or more acidic salts of tin, lead, copper, silver, and palladium whose electric potential is more important than iron ions. By doing so, the secondary particle size is 0.1 μm, which is almost the same as iron powder.
The present invention was completed by discovering a phenomenon in which tin-lead, steel-silver, or silver-palladium alloy powders having a diameter of 3.0 μm can be precipitated by displacement.
本発明は成分金属の酸性塩混合溶液に微細還元鉄粉を添
加することからなる鉄より責な金属の合金粉末の製造方
法を提供する。The present invention provides a method for producing an alloy powder of a metal stronger than iron, which comprises adding fine reduced iron powder to a mixed solution of acid salts of component metals.
具体的に言えば、本発明の方法は錫、鉛、銅。Specifically, the method of the present invention uses tin, lead, and copper.
銀およびパラジウムの２以上からなる粒径０．１〜３．
０μｍの範囲の合金粉末の製造方法であって、各成分金
属の酸性塩を目的とする合金の組成と同じ当量関係で含
む混合溶液を調整し、この溶液を溶液中に存在する成分
金属の全量を析出させるに足る量だけの０．１〜３．０
μｍ粒径の還元鉄粉と接触させることからなる方法を提
供する。A particle size of 0.1 to 3.0 consisting of two or more of silver and palladium.
A method for producing alloy powder in the range of 0 μm, comprising preparing a mixed solution containing acid salts of each component metal in the same equivalence relationship as the composition of the target alloy, and adding this solution to the total amount of the component metals present in the solution. 0.1 to 3.0 in an amount sufficient to precipitate
A method is provided comprising contacting with reduced iron powder of μm particle size.
即ち、本発明は従来の粉末製造法とは異なり、機械的粉
砕を一切行なわないで、単に金属のイオン化傾向を利用
した湿式反応のみで、−次粒子径が０．１μｍから３μ
ｍの各種合金粉末を得ることができる。That is, unlike conventional powder manufacturing methods, the present invention does not perform any mechanical pulverization, but merely uses a wet reaction that utilizes the ionization tendency of metals, and the primary particle size can be reduced from 0.1 μm to 3 μm.
Various alloy powders of m can be obtained.
本発明において使用する鉄粉の形態、純度および粒径は
、生成する微細合金粉の形態、純度および粒径に大きく
影響することから、酸化鉄粉、硫酸第一鉄粉または塩化
第一鉄粉を水素ガスや一酸化炭素などで還元した一次粒
子径が０．１μｍから３μｍの微細な還元鉄粉が、価格
や純度の点から最も好ましい。The form, purity, and particle size of the iron powder used in the present invention greatly affect the form, purity, and particle size of the fine alloy powder produced, so iron oxide powder, ferrous sulfate powder, or ferrous chloride powder Fine reduced iron powder having a primary particle size of 0.1 μm to 3 μm, which is obtained by reducing iron powder with hydrogen gas, carbon monoxide, etc., is most preferable in terms of cost and purity.
錫、鉛、銅、銀およびパラジウムの酸性塩としては、こ
れらの金属の塩化物、硫酸塩、硝酸塩が一般的であるが
、塩化物が最も好ましい。これらの酸性塩水溶液の作成
にあたっては、「市販の塩化物をそのまま水に溶解する
方法」、「酸化物を塩酸などと反応させて溶解する方法
」および「塩酸などの水溶液中で陽極電解して溶解する
方法」などが可能である。これらの酸性塩混合水溶液中
に、上記の還元鉄粉を、例えば水を溶媒としてアトライ
ターやサンドミルでスラリー状に分散して添加した場合
、微細粒状合金粉が生成沈殿すると共に溶液は第一鉄水
溶液となる。As acidic salts of tin, lead, copper, silver and palladium, chlorides, sulfates and nitrates of these metals are common, with chlorides being most preferred. When creating these acidic salt aqueous solutions, there are three methods: ``dissolving commercially available chloride in water as it is'', ``reacting the oxide with hydrochloric acid etc. and dissolving it'', and ``anodic electrolysis in an aqueous solution such as hydrochloric acid''. Possible methods include ``dissolving method.'' When the above-mentioned reduced iron powder is dispersed into a slurry using an attritor or a sand mill using water as a solvent and added to an aqueous solution of these acid salt mixtures, fine grained alloy powder is formed and precipitated, and the solution becomes ferrous iron. It becomes an aqueous solution.
当量の鉄の溶解によって溶液中に存在する鉄より責な成
分金属は全量が析出するから、始め溶液中に存在したと
同じ割合の合金粉末ができる。By dissolving an equivalent amount of iron, all of the component metals present in the solution that are more important than the iron precipitate out, so an alloy powder is formed in the same proportion as was initially present in the solution.
生成する合金は実質的に微視的状態で成分が混合したも
のである。The resulting alloy is a mixture of components in a substantially microscopic state.
３μｍ以下の鉄粉が当量以下の量で存在する場合は鉄粉
は生成合金粉のなかに核として残ることはない。When iron powder of 3 μm or less is present in an amount less than the equivalent amount, the iron powder will not remain as a nucleus in the produced alloy powder.
成分金属の析出速度制御のために錯化剤を加えてもよい
。A complexing agent may be added to control the precipitation rate of component metals.
各種微細粒状〆合金粉の置換析出反応においては浴温か
高いほど、酸性塩の濃度がうすいほど、鉄粉の添加速度
が早いほどおよび攪拌が強いほど、より微細な金属粉が
置換析出する傾向がある。ただし使用する鉄粉の一次粒
子径が大きいほど置換析出する合金粉の粒径が大きくな
り、置換析出する速度も遅くなる。この理由としては、
原理的に溶解する鉄イオンと同等のモル数の責な金属が
析出して合金を生成すること、鉄粉の表面に錫、鉛、銅
、銀およびパラジウムなどが析出すればするほど逆に鉄
の溶解速度が低下しやすいことなどが考えられる。また
、還元鉄粉としてはロータリーキルンなどを用いて水素
ガス中で３８０℃から７００℃で還元した還元率が８０
〜９９％のものを用いるうえ、空気中で取扱うことから
表面は通常うすい酸化膜でおおわれており、溶解反応の
開始時期の遅速に対しては、残留Ｃｆ１．ＳＯ４などの
酸性基の影響が大きい。このため、塩酸などの微量添加
は、鉄粉の溶解反応を早める点で効果がある。析出する
合金粉は基本的に還元鉄粉の形態に左右される。還元鉄
粉が一粒づつに単分散していれば生成する合金粉も単分
散粒子となり、鉄粉がクラスター状に焼結していれば合
金粉もクラスター状となる６本法による微細粒状合金粉
の製造はきわめて簡単なプロセスからなり１例えばボー
ルミル粉砕などのような工程が不要であるから、不純物
の混入などは極めて少なく、生産コストも安い。In the displacement precipitation reaction of various fine-grained final alloy powders, the higher the bath temperature, the weaker the acid salt concentration, the faster the addition rate of iron powder, and the stronger the stirring, the more fine metal powder tends to precipitate by displacement. be. However, the larger the primary particle size of the iron powder used, the larger the particle size of the alloy powder that precipitates by displacement, and the slower the rate of displacement precipitation. The reason for this is
In principle, the same number of moles of metals as dissolved iron ions precipitate to form an alloy. This may be due to the fact that the dissolution rate is likely to decrease. In addition, reduced iron powder has a reduction rate of 80% when reduced at 380°C to 700°C in hydrogen gas using a rotary kiln etc.
~99% of Cf is used, and since it is handled in air, the surface is usually covered with a thin oxide film, and due to the slow start of the dissolution reaction, residual Cf1. The influence of acidic groups such as SO4 is large. Therefore, adding a small amount of hydrochloric acid or the like is effective in accelerating the dissolution reaction of iron powder. The alloy powder that precipitates basically depends on the form of the reduced iron powder. If the reduced iron powder is monodispersed one by one, the alloy powder produced will also be monodisperse particles, and if the iron powder is sintered in clusters, the alloy powder will also be clusters. Fine granular alloy using the six-prong method. The production of powder is an extremely simple process and does not require steps such as ball milling, so there is very little contamination with impurities and the production cost is low.
以下に本発明の実施例を示す。 Examples of the present invention are shown below.
実施例１
日新農鋼株式会社堺製造所の塩酸回収装置より得られた
高純度酸化鉄粉（Ｆｅ、 ０３分として９９．９％以上
、粒径０．１〜１．０μｍ）を、電気抵抗加熱方式のロ
ータリーキルンを用いて５００℃で５時間、水素ガス還
元を行い、還元率９９％、粒径０．５〜２．０μ履の微
細な還元鉄粉を得た。この還元鉄粉５６ｇと水１００ｃ
ｃとを三井三池化工機（株）製のアトライターで３００
ｒｐｍで２時間分散処理を行ってスラリー化した。この
スラリーを８０〜９０℃に昇温保持し、プロペラ攪拌機
で強力に攪拌しつつ、硫酸第一錫（ＳｎＳＯ４・２Ｈ，
Ｏ） １３２ｇ／ Ｑと硝酸鉛（Ｐｂ（ＮＯ３）ｚ）１
４０ｇ／ ｎとの混合水溶液（この溶液中のＳｎ ：
Ｐｂ＝６０ ： ４０（重量））中に添加し、添加後３
０分間加熱、攪拌保持した。その後、攪拌をやめ、静置
して生成した錫−船台金粉を沈殿させ、上澄み液を除去
した。次いで、水洗〜静置〜分離の作業を５回くり返し
行い、その後濾過し、乾燥して錫−鉛合金微粉末１５４
ｇを得た。ＩＣＰによる分析によれば、この粉末の組成
はＳｎ ： Ｐｂ ＝６０ ： ４０（重量）であり、
不純物は１％未満であった。またマイクロトラック分析
による測定ではこの粉末の粒径は０．５〜２．５μｍで
あった。Example 1 High-purity iron oxide powder (Fe, 99.9% or more, particle size 0.1 to 1.0 μm) obtained from the hydrochloric acid recovery equipment of Nisshin Noh Steel Co., Ltd.'s Sakai Works was heated using electricity. Hydrogen gas reduction was performed at 500° C. for 5 hours using a resistance heating type rotary kiln to obtain fine reduced iron powder with a reduction rate of 99% and a particle size of 0.5 to 2.0 μm. 56g of this reduced iron powder and 100c of water
c and 300 with an attritor manufactured by Mitsui Miike Kakoki Co., Ltd.
A dispersion treatment was performed at rpm for 2 hours to form a slurry. This slurry was heated to 80 to 90°C and stirred vigorously using a propeller stirrer, while adding stannous sulfate (SnSO4.2H,
O) 132g/Q and lead nitrate (Pb(NO3)z) 1
Mixed aqueous solution with 40g/n (Sn in this solution:
Pb = 60: 40 (weight)), and after addition 3
The mixture was heated and stirred for 0 minutes. Thereafter, stirring was stopped and the mixture was allowed to stand still to precipitate the produced tin-ship gold powder, and the supernatant liquid was removed. Next, the operations of washing with water, standing still, and separating are repeated five times, followed by filtration and drying to obtain tin-lead alloy fine powder 154.
I got g. According to analysis by ICP, the composition of this powder is Sn: Pb = 60: 40 (weight),
Impurities were less than 1%. Furthermore, the particle size of this powder was determined to be 0.5 to 2.5 μm as measured by microtrack analysis.
実施例２
実施例１で使用したのと同じ還元鉄粉３３ｇと水１００
ｃｃとをアトライターでスラリー化した。次に、塩化ア
ンモニウム（ＮＨ４ＣＱ）２００ｇ／ Ｑと塩化銀（Ａ
ｇＣＱ）１２０ｇ／Ｑおよび塩化パラジウム（ＰｄＣｎ
、 ）３５．５ｇ／ Ｑの混合液（この溶液中のＡｇ
： Ｐｄ＝８０ ： ２０（重量））ＩＱを８０〜９０
℃に昇温保持し、プロペラ攪拌機で強力に攪拌しつつ、
前記のスラリーを添加した。なお塩化アンモニウムは銀
の錯体形成のために加えた。Example 2 33 g of reduced iron powder and 100 g of water, the same as used in Example 1
cc was made into a slurry using an attritor. Next, ammonium chloride (NH4CQ) 200g/Q and silver chloride (A
gCQ) 120g/Q and palladium chloride (PdCn
, ) 35.5g/Q mixed solution (Ag in this solution
: Pd=80 : 20 (weight)) IQ 80-90
While maintaining the temperature at ℃ and stirring strongly with a propeller stirrer,
The slurry from above was added. Note that ammonium chloride was added to form a silver complex.
添加後、３０分間加熱、攪拌保持して、十分置換反応を
進めた。その後、攪拌をやめ、静置して生成した銀〜パ
ラン９４合金粉を沈殿させ、上澄み液を除去した０次い
で、水洗〜静置〜分離の作業を５回くり返し、その後濾
過、乾燥して、銀−パラジウム合金微粉末１０７ｇを得
た。実施例１と同じ分析により、Ａｇ： Ｐｄ＝ｆｌＯ
： ２０、不純物１％未満、粒径０．５〜２．５μｍで
あった。After the addition, the mixture was heated and stirred for 30 minutes to sufficiently advance the substitution reaction. After that, stirring was stopped, and the produced silver-Paran 94 alloy powder was allowed to settle, and the supernatant liquid was removed.Then, the steps of washing with water, standing, and separation were repeated 5 times, and then filtered and dried. 107 g of silver-palladium alloy fine powder was obtained. By the same analysis as in Example 1, Ag: Pd=flO
: 20, impurities less than 1%, particle size 0.5-2.5 μm.
実施例３
実施例１と同じ還元鉄粉５０ｇと水１００ｃｃとをアト
ライターでスラリー化した。次に、チオ硫酸ナトリウム
（Ｎａ２ＳｚＯａ）１００ｇ／＋２と塩化第二銅（Ｃｕ
ＣＱ、 ・２Ｈ，Ｏ）１４４ｇおよび塩化銀（Ａｇ（、
Ｑ）３０ｇの混合液（この溶液中のＣｕ ： Ａｇ＝８
０ ： ２０（重量））ＩＱを８０〜９０℃に昇温保持
し、プロペラ攪拌機にて強力に攪拌しつつ、前記のスラ
リーを添加した。なおチオ硫酸ナトリウムは銀の錯体形
成のために加えた。添加熱、加熱。Example 3 50 g of the same reduced iron powder as in Example 1 and 100 cc of water were made into a slurry using an attritor. Next, 100g/+2 of sodium thiosulfate (Na2SzOa) and cupric chloride (Cu
CQ, 2H,O) 144g and silver chloride (Ag(,
Q) 30g of mixed solution (Cu:Ag=8 in this solution)
0:20 (weight)) IQ was heated and maintained at 80 to 90°C, and the slurry was added while stirring strongly with a propeller stirrer. Note that sodium thiosulfate was added to form a silver complex. Added heat, heating.
攪拌保持して十分置換反応を進めた。その後攪拌をやめ
、静置して生成した銅−銀金金粉を沈殿させ、上澄み液
を除去した０次いで、水洗〜静置〜分離の作業を５回く
り返し、その後、濾過、乾燥して銅−銀合金微粉末７２
ｇを得た。実施例１と同じ分析によりＣｕ ： Ａｇ＝
８０ ： ２０（重量）、不純物１７％未満、粒径０．
５〜２．５μｍであった。While stirring, the substitution reaction proceeded sufficiently. After that, stirring was stopped and the copper-silver-gold powder was allowed to settle, and the supernatant liquid was removed.Next, the process of washing with water, standing still, and separating was repeated 5 times, followed by filtration, drying, and copper-silver gold powder. Silver alloy fine powder 72
I got g. According to the same analysis as in Example 1, Cu:Ag=
80: 20 (weight), impurities less than 17%, particle size 0.
It was 5 to 2.5 μm.
以上、詳細に説明したように本発明の製造方法によれば
、粒径が０．１μｍから３．０μｍで、はぼ球形をした
各種合金微粉末をボールミルなどの粉砕機を用いないで
も、比較的簡単な装置で安価に製造できる。なお１本法
は高温での作業を伴わないことから、比較的酸化膜も少
なく、かつ粉砕機からの不純物の混入も少ないという利
点を有する。As explained in detail above, according to the manufacturing method of the present invention, various alloy fine powders with a particle size of 0.1 μm to 3.0 μm and a spherical shape can be produced in a comparative manner without using a crusher such as a ball mill. It can be manufactured at low cost using simple equipment. Note that this method does not involve work at high temperatures, so it has the advantage of having a relatively small amount of oxide film and less contamination of impurities from the crusher.
したがって、酸化膜の少ないことが要求される導電ペー
スト、導電接着剤およびはんだペースト用の材料として
使用可能である。Therefore, it can be used as a material for conductive pastes, conductive adhesives, and solder pastes that require a small oxide film.
Claims (1)
粒径０．１〜３．０μｍの範囲の合金粉末の製造方法で
あって、各成分金属の酸性塩を目的とする合金の組成と
同じ当量関係で含む混合溶液を調整し、この溶液を溶液
中に存在する成分金属の全量を析出させるに足る量だけ
の０．１〜３．０μｍ粒径の還元鉄粉と接触させること
からなる方法。1. A method for producing an alloy powder consisting of two or more of tin, lead, copper, silver, and palladium and having a particle size in the range of 0.1 to 3.0 μm, the composition of the alloy aiming at acid salts of each component metal. By preparing a mixed solution containing in the same equivalence relationship as and bringing this solution into contact with reduced iron powder with a particle size of 0.1 to 3.0 μm in an amount sufficient to precipitate the entire amount of component metals present in the solution. How to become.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29770187A JPH01139710A (en) | 1987-11-27 | 1987-11-27 | Manufacture of fine granular alloy powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29770187A JPH01139710A (en) | 1987-11-27 | 1987-11-27 | Manufacture of fine granular alloy powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01139710A true JPH01139710A (en) | 1989-06-01 |
Family
ID=17850041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29770187A Pending JPH01139710A (en) | 1987-11-27 | 1987-11-27 | Manufacture of fine granular alloy powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01139710A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03126805A (en) * | 1989-10-12 | 1991-05-30 | Kojundo Chem Lab Co Ltd | Manufacture of ag-pd alloy powder for thick film paste |
| JP2009202032A (en) * | 2003-04-24 | 2009-09-10 | Asics Corp | Sports shoes having upper with improved fitting property |
| JP2011088198A (en) * | 2009-09-01 | 2011-05-06 | Dowa Holdings Co Ltd | Solder powder and method for producing the solder powder |
| US8272148B2 (en) | 2006-10-19 | 2012-09-25 | Asics Corporation | Sports shoes having upper part with improved fitting property |
| US8555525B2 (en) | 2011-01-18 | 2013-10-15 | Saucony Ip Holdings Llc | Footwear |
| US8732982B2 (en) | 2011-01-18 | 2014-05-27 | Saucony IP Holdings, LLC | Footwear |
| US8839531B2 (en) | 2011-07-19 | 2014-09-23 | Saucony Ip Holdings Llc | Footwear |
| US9132514B2 (en) | 2010-11-18 | 2015-09-15 | Dowa Holdings Co., Ltd. | Solder powder and method of producing solder powder |
| CN107498063A (en) * | 2017-08-03 | 2017-12-22 | 昆明贵金属研究所 | A kind of preparation method of the spherical silver powder of high dispersive micron order |
| WO2020129117A1 (en) | 2018-12-17 | 2020-06-25 | 株式会社アシックス | Lacing structure for shoe upper and shoe |
-
1987
- 1987-11-27 JP JP29770187A patent/JPH01139710A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03126805A (en) * | 1989-10-12 | 1991-05-30 | Kojundo Chem Lab Co Ltd | Manufacture of ag-pd alloy powder for thick film paste |
| JP2009202032A (en) * | 2003-04-24 | 2009-09-10 | Asics Corp | Sports shoes having upper with improved fitting property |
| US7823298B2 (en) | 2003-04-24 | 2010-11-02 | Asics Corporation | Athletic shoes having an upper whose fitting property is improved |
| US8713821B2 (en) | 2003-04-24 | 2014-05-06 | Asics Corporation | Athletic shoes having an upper whose fitting property is improved |
| US8272148B2 (en) | 2006-10-19 | 2012-09-25 | Asics Corporation | Sports shoes having upper part with improved fitting property |
| JP2011088198A (en) * | 2009-09-01 | 2011-05-06 | Dowa Holdings Co Ltd | Solder powder and method for producing the solder powder |
| US9132514B2 (en) | 2010-11-18 | 2015-09-15 | Dowa Holdings Co., Ltd. | Solder powder and method of producing solder powder |
| US8555525B2 (en) | 2011-01-18 | 2013-10-15 | Saucony Ip Holdings Llc | Footwear |
| US8732982B2 (en) | 2011-01-18 | 2014-05-27 | Saucony IP Holdings, LLC | Footwear |
| US8839531B2 (en) | 2011-07-19 | 2014-09-23 | Saucony Ip Holdings Llc | Footwear |
| CN107498063A (en) * | 2017-08-03 | 2017-12-22 | 昆明贵金属研究所 | A kind of preparation method of the spherical silver powder of high dispersive micron order |
| WO2020129117A1 (en) | 2018-12-17 | 2020-06-25 | 株式会社アシックス | Lacing structure for shoe upper and shoe |
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