CN1029094C - Super fine copper powder and its preparation technology - Google Patents
Super fine copper powder and its preparation technology Download PDFInfo
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- CN1029094C CN1029094C CN 93106588 CN93106588A CN1029094C CN 1029094 C CN1029094 C CN 1029094C CN 93106588 CN93106588 CN 93106588 CN 93106588 A CN93106588 A CN 93106588A CN 1029094 C CN1029094 C CN 1029094C
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- China
- Prior art keywords
- copper powder
- sodium
- glycerine
- liquid phase
- superfine
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- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title abstract description 13
- 238000005516 engineering process Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 hydrogen compound Chemical class 0.000 claims abstract description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 17
- 239000011734 sodium Substances 0.000 claims description 15
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- 235000011187 glycerol Nutrition 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229940116318 copper carbonate Drugs 0.000 claims description 6
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 6
- 239000003599 detergent Substances 0.000 claims description 6
- 239000003966 growth inhibitor Substances 0.000 claims description 6
- 239000003223 protective agent Substances 0.000 claims description 6
- 239000000344 soap Substances 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- 150000001298 alcohols Chemical group 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- 229960004643 cupric oxide Drugs 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 229940112669 cuprous oxide Drugs 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229940077388 benzenesulfonate Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002483 hydrogen compounds Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract 2
- 238000004377 microelectronic Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000220317 Rosa Species 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention relates to a ceramic pulp element sheet capacitor prepared by superfine copper powder. The copper powder is directly sintered in air at 500 to 700 DEG C and is not oxidized. The electric conduction of the copper powder can achieve 10<-3> to 10<-5> omega /Vm2, the grain size of the copper powder can be optionally controlled between 0.1 mu and 30 mu, and grain size distribution is narrow. Liquid phase method technology with alcohol as a solvent and an active hydrogen compound as a reducing agent is adopted for producing the superfine copper powder. Reaction temperature is from zero to 250 DEG C, and pressure is from 0.1 to 1.0MPa. The superfine copper powder is cleaned twice by water with a surface acting agent and alcohol and is dried in a vacuum mode so as to obtain the product. The product is widely used for industries of astronavigation, microelectronics, etc. and for preparing the element sheet capacitor, a ceramic based printed circuit board (PCB), etc.
Description
The present invention belongs to liquid phase reduction superfine cupper powder preparation method.
The superfine cupper powder technology of preparing has electrolysis, atomization, mechanical efflorescence method, solid gas phase reduction process, liquid phase reduction etc., and is advanced with liquid phase reduction at present.Described liquid phase reduction main technique such as the open EP 0417757A1 of European patent are to adopt water as reaction medium, and 1. the shortcoming of this process route is. mantoquita must be converted into copper formate, can not directly reduce; 2.. formic acid, methyl alcohol toxicity are big, and equipment corrosion is serious, operating condition is abominable; 3.. the copper powder of production easily condenses, and copper powder is of poor quality; 4.. conversion ratio is low, only about 50%, production control difficulty, three-waste pollution be serious.
Purpose of the present invention is exactly in order to overcome above-mentioned shortcoming, provides a cover can prepare non-oxidizing superfine cupper powder technology of preparing.
The present invention belongs to liquid phase reduction superfine cupper powder preparation method.
1. a liquid phase reduction superfine cupper powder technology of preparing is an initiation material with mantoquita such as copper carbonate, basic copper carbonate, cupric oxide and compound thereof, it is characterized in that:
1. be initiation material with mantoquitas such as copper sulphate, copper nitrate, cuprous oxide;
2. solvent is an alcohols, as is monohydric alcohol, is preferably ethanol; Polyalcohol is preferably ethylene glycol, glycerine, a condensed ethandiol, tirethylene glycol, 1, the 4-butanediol;
3. reducing agent is an active hydrogen compounds, as glycerine, hydrogen, hydrazine and hydrazine compound, is preferably glycerine;
4. surfactant protective agent, as sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium soap, AES, MES, peregal etc., its addition is 0.1～0.8%;
5. phosphoric acid salt compound diffusant is as sodium pyrophosphate, pyrophosphorous acid sodium, sodium phosphate;
6. sylvite compounds nucleus growth inhibitor is as KBr, KI;
7. reaction temperature is 0 ℃～250 ℃, and reaction pressure is 0.1～1.0MPa, and product is prepared not oxidation superfine cupper powder through washing, vacuum drying under 60～100 ℃/680～760mmHg.
2. liquid phase reduction superfine cupper powder preparation method according to claim 1 is characterized in that the preparation feedback product need be with the solution washing that is dissolved with surfactants such as White Cat detergent, sodium soap, and then with the alcohols washing that is dissolved with above-mentioned detergent.
The particle diameter of superfine cupper powder can be by saturation degree and reaction temperature or raw material type control.The not oxidation superfine cupper powder particle diameter that obtains is 0.1～30 μ m, narrow diameter distribution, and yield 〉=95%, purity 〉=99.9%, outward appearance is the sphere of golden light under micro-border, or the almost spherical particle.Adopt the not oxidation superfine cupper powder of this explained hereafter, be used to prepare the pottery slurry element capacitor, not oxidation of direct sintering in 500～700 ℃ of air, electric conductivity reaches 10
-3～10
-5Ω/cm
2
A kind of liquid phase reduction superfine cupper powder preparation method adds the fatty alcohol solvent in the reactor of belt stirrer, as monohydric alcohol, be preferably ethanol; Polyalcohol is preferably ethylene glycol, glycerine, a condensed ethandiol, tirethylene glycol, 1, the 4-butanediol; Nucleus growth inhibitor sylvite compounds is as KBr, KI; The surfactant protective agent, as sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium soap, AES, MES, peregal etc., its addition is 0.1～0.8%; Diffusant phosphoric acid salt compound is as sodium pyrophosphate, pyrophosphorous acid sodium, sodium phosphate.Start stirring, after stirring, add mantoquita and compound thereof such as copper carbonate, basic copper carbonate, cupric oxide, copper sulphate, copper nitrate, cuprous oxide initiation material, needn't be converted into copper formate; Progressively be warmed up to (as 150 ℃) under the uniform temperature, slowly add active hydrogen compounds reducing agent glycerine, hydrogen, hydrazine and hydrazine compound, be preferably glycerine; Reaction temperature is 0 ℃～250 ℃, is preferably 150～220 ℃; Reaction pressure is 0.1～1.0MPa.The preparation feedback product need be with the solution washing that is dissolved with surfactants such as White Cat detergent, sodium soap, and then washs with alcohols that is dissolved with above-mentioned detergent such as ethanol.Product after the washing, vacuum drying under 60～100 ℃/680～760mmHg.The particle diameter of superfine cupper powder can be by saturation degree and reaction temperature or raw material type control.The not oxidation superfine cupper powder particle diameter that obtains is 0.1～30 μ m, narrow diameter distribution, and yield 〉=95%, purity 〉=99.9%, outward appearance is the sphere of golden light under micro-border, or the almost spherical particle.Adopt the not oxidation superfine cupper powder of this explained hereafter, be used to prepare the pottery slurry element capacitor, not oxidation of direct sintering in 500～700 ℃ of air, electric conductivity reaches 10
-3～10
-5Ω/cm
2
Example 1
Cold pouring pipe is being housed; thermometer; in the 1000ml there-necked flask that breather pipe and band stir; add the 500ml solvent glycerin; ethylene glycol; nucleus growth inhibitor KBr is a small amount of; 4g surfactant protective agent peregal; 3g diffusant sodium phosphate; after stirring, add Kocide SD 200g again, under agitation progressively heating up also slowly feeds hydrogen in 150 ℃; the control temperature is no more than 250 ℃; reaction pressure 0.1～1.0MPa, after reaction is reached home, the cooling cooling; turn off hydrogen; isolated by filtration is with the water washing that is dissolved with low quantity of surfactant, again with the ethanolic solution washing that is dissolved with peregal.The product of receiving after the filtration, under the condition of 60～100 ℃/680～760mmHg, drying obtains the about 125g of rose copper powder, and yield is about 96%, particle diameter 0.2～1.2 μ m.
Example 2
Cold pouring pipe is being housed; thermometer; in the 1000ml there-necked flask that breather pipe and band stir; add the 400ml solvent glycerin; 100ml ethylene glycol; nucleus growth inhibitor KI is a small amount of; 4g surfactant protective agent peregal; 3g diffusant sodium phosphate; cupric oxide 100g; under stirring, brute force progressively heats up; and slowly feeding hydrogen, the control temperature is no more than 250 ℃, reaction pressure 0.1～1.0MPa; reaction is in case reach home; cooling cooling rapidly, isolated by filtration is with the aqueous solution that is dissolved with low quantity of surfactant; alcoholic solution washs successively; washing the back filters; then that product is dry under the condition of 60～100 ℃/680～760mmHg, can obtain the about 77g of rose copper powder, particle diameter 3～5 μ m.
Example 3
Cold pouring pipe is being housed; thermometer; in the 1000ml there-necked flask that breather pipe and band stir; add the 400ml solvent glycerin; 100ml ethylene glycol; nucleus growth inhibitor KI is a small amount of; 4g surfactant protective agent peregal; 3g diffusant sodium phosphate; cuprous oxide 250g; progressively be warming up to 150 ℃ and slowly feed hydrogen under brute force stirs, the control temperature is no more than 190 ℃, reaction pressure 0.1～1.0MPa; when reaction will be reached home; slowly cooling reduces logical hydrogen amount, when reaching home, turns off hydrogen; cold filtration separates; with the aqueous solution that is dissolved with surfactant; alcoholic solution washs successively, washes the back and filters, and is then that product is dry under the condition of 60～100 ℃/680～760mmHg; can obtain the about 210g of rose copper powder, particle diameter is about 0.1～0.8 μ m.
Claims (2)
1, a kind of liquid phase reduction superfine cupper powder preparation method is an initiation material with mantoquita such as copper carbonate, basic copper carbonate, cupric oxide and compound thereof, it is characterized in that:
1. be initiation material with copper sulphate, copper nitrate, cuprous oxide;
2. solvent is an alcohols, as is monohydric alcohol, is preferably ethanol; Polyalcohol is preferably ethylene glycol, glycerine, a condensed ethandiol, tirethylene glycol, 1, the 4-butanediol;
3. reducing agent is an active hydrogen compounds, as glycerine, hydrogen, hydrazine and hydrazine compound, is preferably glycerine;
4. surfactant protective agent, as sodium alkyl benzene sulfonate, sodium alkyl sulfate, sodium soap, AES, MES, peregal, its addition is 0.1～0.8%;
5. phosphoric acid salt compound diffusant is as sodium pyrophosphate, pyrophosphorous acid sodium, sodium phosphate;
6. sylvite compounds nucleus growth inhibitor is as KBr, KI;
7. reaction temperature is 0 ℃～250 ℃, and reaction pressure is 0.1～1.0MPa, and product is prepared not oxidation superfine cupper powder through washing vacuum drying under 60～100 ℃/680～760mmHg.
2, liquid phase reduction superfine cupper powder preparation method according to claim 1 is characterized in that the preparation feedback product need be with the solution washing that is dissolved with surfactants such as White Cat detergent, sodium soap, and then with the alcohols washing that is dissolved with above-mentioned detergent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93106588 CN1029094C (en) | 1993-06-05 | 1993-06-05 | Super fine copper powder and its preparation technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93106588 CN1029094C (en) | 1993-06-05 | 1993-06-05 | Super fine copper powder and its preparation technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1082468A CN1082468A (en) | 1994-02-23 |
| CN1029094C true CN1029094C (en) | 1995-06-28 |
Family
ID=4986306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93106588 Expired - Fee Related CN1029094C (en) | 1993-06-05 | 1993-06-05 | Super fine copper powder and its preparation technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1029094C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060108C (en) * | 1997-01-21 | 2001-01-03 | 北京化工大学 | Method for preparing superfine copper powder |
| JP3915387B2 (en) * | 2000-08-29 | 2007-05-16 | 昭栄化学工業株式会社 | Conductor paste |
| KR101533860B1 (en) * | 2007-11-05 | 2015-07-03 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Copper fine particle, method for producing the same, and copper fine particle dispersion |
| CN102205422A (en) * | 2011-01-17 | 2011-10-05 | 深圳市圣龙特电子有限公司 | Nano copper powder for electronic paste and preparation process |
| CN105462365A (en) * | 2014-09-11 | 2016-04-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Electric conduction nanometer copper ink preparation method |
| CN105710383A (en) * | 2016-04-30 | 2016-06-29 | 安徽农业大学 | Method for preparing Cu powder by reducing CuO by adopting glycerinum |
| CN116275025B (en) * | 2022-12-29 | 2025-03-04 | 宁波维柔电子科技有限公司 | Preparation method of silver-plated copper powder of conductive paste for heterojunction solar cell |
| CN116441556B (en) * | 2023-06-15 | 2023-08-22 | 华北电力大学 | A hydrogen-assisted ultra-pure copper powder hygrothermal synthesis method and ultra-pure copper powder material |
-
1993
- 1993-06-05 CN CN 93106588 patent/CN1029094C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1082468A (en) | 1994-02-23 |
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