CN102601383A - Method for preparing ultrafine copper powder at room temperature - Google Patents
Method for preparing ultrafine copper powder at room temperature Download PDFInfo
- Publication number
- CN102601383A CN102601383A CN2012100906905A CN201210090690A CN102601383A CN 102601383 A CN102601383 A CN 102601383A CN 2012100906905 A CN2012100906905 A CN 2012100906905A CN 201210090690 A CN201210090690 A CN 201210090690A CN 102601383 A CN102601383 A CN 102601383A
- Authority
- CN
- China
- Prior art keywords
- ascorbic acid
- room temperature
- copper
- copper acetate
- solution
- 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
Images
Abstract
A method for preparing ultrafine copper powder at room temperature belongs to the technical field of materials. Copper acetate and ascorbic acid are used as main reactants, ethylene glycol is used as a reaction medium, polyvinylpyrrolidone is used as a protective agent, glycol nantokite solution of the copper acetate and reducing protection solution dissolved with the ascorbic acid and the polyvinylpyrrolidone are mixed at the room temperature according to the molar ratio of the copper acetate to the ascorbic acid to perform liquid phase reaction, and solids are collected, washed and dried during reaction to obtain the ultrafine copper powder, wherein the molar ratio of the copper acetate to the ascorbic acid is 1:(2-10). The method for preparing the ultrafine copper powder at the room temperature can be directly implemented at normal temperature and under normal pressure, an external heating source is omitted, the method is convenient to implement and low in cost, the green and environment-friendly ascorbic acid without toxic or side effects on a human body is used as a reducing agent and is beneficial to recycling, the prepared ultrafine copper powder is uniform in size distribution, free of agglomeration and fine in dispersibility, and the method is simple in technological process, short in reaction time and convenient in industrial production.
Description
Technical field
The invention belongs to the material technology field, relate to functional material, especially the preparation method of superfine cupper powder under the room temperature condition.
Background technology
The skin effect of ultra-fine metallic particles, small-size effect, quantum effect and macroscopical tunnel-effect make it have extremely important using value in fields such as integrated circuit, catalysis, lubricated, antibiotic, electromagnetic shieldings.At present the ultrafine dust of some noble metals has all obtained extensive studies like gold, platinum, silver, and the metallic copper particulate is easy oxidized, particle is dispersed relatively poor and pattern is wayward, so correlative study is less.Than fine particle of noble metal, the relative low price of metallic copper, and have good electrical conductivity, this is with a wide range of applications it.
The method for preparing at present superfine cupper powder mainly contains ball-milling method, gas evaporation method, microemulsion method, electrolysis, gamma-ray irradiation method, sol-gel process, supercritical fluid drying, liquid phase reduction etc.Wherein liquid phase reduction, equipment low owing to its preparation cost be simple and easy to, reaction easily advantage such as control have research value.Yet usually liquid phase reduction prepares the committed step of superfine cupper powder, and promptly copper ion is reduced agent and is reduced into this reactions step of metallic copper and usually higher reaction temperature need be provided.Higher reaction temperature has caused the increase of cost, the link of intensification to consume the time, and this has limited the development that liquid phase reduction prepares superfine cupper powder.
Kyoohee Woo [list of references Kyoohee Woo; Kongjo Kim, Jang Sub Kim, Soonkwon Lim; Jooho Moon.Ink-Jet Printing of Cu-Ag-Based Highly Conductive Tracks on a Transparent Substrate [J] .Langmuir; 2009, Vol25 (1): 429～433.] etc. the people be dispersant with the polyvinylpyrrolidone, be that reducing agent reduces copper sulphate with the inferior sodium phosphate in the diglycol system; Made superfine cupper powder, but the reaction temperature of 140 ℃ of this reaction needed.
Publication number is that the one Chinese patent application of CN 1188700A provides a kind of method that in liquid phase, prepares superfine cupper powder with hydrosulfurous acid sodium reduction bivalent cupric ion, but this method needs 40～100 ℃ reaction temperature in copper ion is reduced into the step of metallic copper particulate.
Publication number is that the one Chinese patent application of CN 101195170A provides a kind of employing two to go on foot the method that bivalent cupric ion is reduced to superfine cupper powder of reducing, but this method all need provide 60～80 ℃ environment temperature when the first step and second goes on foot reduction.
The superfine cupper powder that above method obtains all need provide higher reaction temperature in copper ion is reduced into this step of metallic copper, and liquid phase reduction prepares the reducing agent that uses in the superfine cupper powder process and mostly is toxic reagents such as formaldehyde, hydrazine hydrate.This has restricted commercial production and practical application that liquid phase reduction prepares superfine cupper powder to a great extent.
Summary of the invention
The present invention aims to provide the method for preparing superfine cupper powder under a kind of room temperature; To solve reaction temperature prepares superfine cupper powder to liquid phase reduction restriction; The superfine cupper powder purity that this method equipment simply, does not need thermal source, technological process is short, cost is low, prepare is high, good dispersion; And the raw material that adopts in the preparation process is harmless, and is environmentally friendly.
Detailed technology scheme of the present invention is:
Prepare the method for superfine cupper powder under a kind of room temperature, as shown in Figure 1, may further comprise the steps:
Step 1: preparation copper salt solution.With the copper acetate is solute, and ethylene glycol is solvent, and the ethylene glycol solution of preparation copper acetate is as copper salt solution, and wherein the mass concentration of copper acetate is controlled between 2.9g/L～20g/L.
Step 2: preparation restitutive protection solution.With the ascorbic acid is reducing agent, and polyvinylpyrrolidone is a protective agent, and said reducing agent and protective agent are dissolved in the ethylene glycol, obtains restitutive protection's solution; The mass concentration of wherein said reducing agent is controlled between 11g/L～50g/L, and said protectant mass concentration is controlled between 2.5g/L～100g/L.
Step 3: liquid-phase reduction reaction.Restitutive protection's solution of at ambient temperature copper salt solution of step 1 preparation and step 2 being prepared is according to copper acetate: ascorbic acid=1: the mol ratio of (2～10) is mixed, and stirs simultaneously.
Step 4: collect step 3 liquid-phase reduction reaction gained solids,, obtain final superfine cupper powder through absolute ethanol washing, vacuum drying.
Essence of the present invention is that to adopt copper acetate and ascorbic acid be reactant, is that the anhydrous system of solvent reacts the generation metallic copper down at ethylene glycol, and reaction equation is C
6H
8O
6+ Cu (CH
3COO)
2→ Cu+C
6H
6O
6+ 2CH
3COOH.Aspect raw material chooses, adopt human non-toxic side effect and environmentally friendly, free of contamination ascorbic acid (being vitamin C) and faintly acid mantoquita copper acetate.In ethylene glycol medium, ascorbic acid can be sloughed two hydrogen and copper ions on the hydroxyl and at room temperature react, and restore metallic copper, and the oxidation product hydroascorbic acid of ascorbic acid is prone to be reduced back ascorbic acid, is convenient to recycling.If use highly acid copper salts such as copper sulphate, copper nitrate or copper chloride instead, then at room temperature can not obtain metallic copper with the ascorbic acid reaction.With ethylene glycol as reaction medium; Be the modest viscosity that should be ethylene glycol, the copper powder that helps restoring disperses, and also copper powder is shielded simultaneously; If use other polyalcohol instead as reaction medium, thereby the dispersion that can be unfavorable for reactant can't obtain superfine cupper powder.Polyvinylpyrrolidone is a kind of surfactant commonly used in the Fine Chemical Industry, and is very little to the human injury, in this reaction, is protective agent, also is surfactant, also plays simultaneously and accelerates the effect that the metallic copper nucleus forms.
Need to prove: 1, the superfine cupper powder of the present invention's preparation, its average grain diameter need to adopt excessive reducing agent (mole dosage of actual reducing agent is 2 to 10 times of mantoquita) in the course of reaction about 200 nanometers; Amount like reducing agent is less; The metallic copper that then generates in the course of reaction can generate univalent copper ion with the bivalent cupric ion reaction in the solution, is unfavorable for the generation of metallic copper, and is too much like the amount of reducing agent; Then reaction generates the speed increase of copper powder; The nucleus nucleation rate that is metallic copper is accelerated, and causes nucleus to be assembled, and makes the particle diameter of reaction gained copper powder become big; 2, the concrete mode of step 4 collection liquid-phase reduction reaction gained solids can be the mode of centrifugation; 3, vacuum drying vacuum described in the step 4 is 2～5Pa, and baking temperature is 50～70 ℃; 4:, the concrete liquid phase reactor and the solids collection process of step 3 and step 4, carry out solids again after not only can the question response total overall reaction accomplishing and collect, can also the limit border ring collect, thereby the purpose that reaches continuous production, enhances productivity.
To sum up, the invention has the beneficial effects as follows:
The method of a kind of room temperature preparation superfine cupper powder according to the invention can directly be carried out at normal temperatures and pressures, does not need external heat source, and it is lower to be convenient to enforcement and cost; Employing as reducing agent, is beneficial to recycling to the ascorbic acid of human non-toxic side effect, environmentally safe, environmental protection; The superfine cupper powder even size distribution of preparation does not have and reunites, favorable dispersibility; This method technological process is simple, and the reaction required time is shorter, is convenient to carry out commercial production.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
Fig. 2 is the scanning electron microscope image of the prepared superfine cupper powder of the present invention.
Fig. 3 is the energy spectrum composition analysis figure of the prepared superfine cupper powder of the present invention.
Fig. 4 is the X-ray diffractogram of the prepared superfine cupper powder of the present invention.
The specific embodiment
Prepare the method for superfine cupper powder under a kind of room temperature, may further comprise the steps:
Step 1: preparation copper salt solution; With the copper acetate is solute, and ethylene glycol is solvent, and the ethylene glycol solution of preparation copper acetate is as copper salt solution, and wherein the mass concentration of copper acetate is controlled between 2.9g/L～20g/L;
Step 2: preparation restitutive protection solution; With the ascorbic acid is reducing agent, and polyvinylpyrrolidone is a protective agent, and said reducing agent and protective agent are dissolved in the ethylene glycol, obtains restitutive protection's solution; The mass concentration of wherein said reducing agent is controlled between 11g/L～50g/L, and said protectant mass concentration is controlled between 2.5g/L～100g/L;
Step 3: liquid-phase reduction reaction; Restitutive protection's solution of at ambient temperature copper salt solution of step 1 preparation and step 2 being prepared is according to copper acetate: ascorbic acid=1: the mol ratio of (2～10) is mixed, and stirs simultaneously;
Step 4: step 3 liquid-phase reduction reaction gained solids is centrifugalized, and, obtain final superfine cupper powder through absolute ethanol washing, vacuum drying.Wherein vacuum drying vacuum is 2～5Pa, and baking temperature is 50～70 ℃.
Prepare multiple superfine cupper powder sample according to such scheme and the said different Cu concentration of salt solution of according to the form below, different ascorbic acid restitutive protection solution concentration and different mantoquitas and ascorbic acid mol ratio.Wherein the sem test result of sample 1 is as shown in Figure 2, and its energy spectrum composition analysis and X-ray diffraction analysis result are respectively like Fig. 3 and shown in Figure 4.Energy spectrum composition analysis and X-ray diffraction analysis result show that the sample that makes is a metallic copper, and the sem test result shows that gained copper powder average grain diameter is 200nm.All the other sample analysis method of testings and sample are 1 identical, test result is similar.
Claims (3)
1. prepare the method for superfine cupper powder under the room temperature, may further comprise the steps:
Step 1: preparation copper salt solution; With the copper acetate is solute, and ethylene glycol is solvent, and the ethylene glycol solution of preparation copper acetate is as copper salt solution, and wherein the mass concentration of copper acetate is controlled between 3.0g/L～10g/L;
Step 2: preparation restitutive protection solution; With the ascorbic acid is reducing agent, and polyvinylpyrrolidone is a protective agent, and said reducing agent and protective agent are dissolved in the ethylene glycol, obtains restitutive protection's solution; The mass concentration of wherein said reducing agent is controlled between 4.0g/L～50g/L, and said protectant mass concentration is controlled between 2.5g/L～100g/L;
Step 3: liquid-phase reduction reaction; Restitutive protection's solution of at ambient temperature copper salt solution of step 1 preparation and step 2 being prepared is according to copper acetate: ascorbic acid=1: the mol ratio of (2～10) is mixed, and stirs simultaneously;
Step 4: collect step 3 liquid-phase reduction reaction gained solids,, obtain final superfine cupper powder through absolute ethanol washing, vacuum drying.
2. prepare the method for superfine cupper powder under the room temperature according to claim 1, it is characterized in that, the concrete mode that step 4 is collected liquid-phase reduction reaction gained solids is the mode of centrifugation.
3. prepare the method for superfine cupper powder under the room temperature according to claim 1, it is characterized in that, vacuum drying vacuum described in the step 4 is 2～5Pa, and baking temperature is 50～70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100906905A CN102601383A (en) | 2012-03-30 | 2012-03-30 | Method for preparing ultrafine copper powder at room temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100906905A CN102601383A (en) | 2012-03-30 | 2012-03-30 | Method for preparing ultrafine copper powder at room temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102601383A true CN102601383A (en) | 2012-07-25 |
Family
ID=46519364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100906905A Pending CN102601383A (en) | 2012-03-30 | 2012-03-30 | Method for preparing ultrafine copper powder at room temperature |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102601383A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104227015A (en) * | 2014-09-19 | 2014-12-24 | 洛阳理工学院 | Method for preparing antimony powder |
| CN104227012A (en) * | 2013-06-14 | 2014-12-24 | 中国振华集团云科电子有限公司 | Preparation method for ultra-fine copper powder |
| CN110039069A (en) * | 2019-05-30 | 2019-07-23 | 江西省科学院能源研究所 | A kind of spongy Micron Copper Powder and preparation method thereof |
| CN110153443A (en) * | 2019-07-11 | 2019-08-23 | 中国科学院深圳先进技术研究院 | A kind of copper nanometer sheet and its preparation method and application |
| CN110560702A (en) * | 2019-09-16 | 2019-12-13 | 上海交通大学 | method for preparing micron-sized single crystal copper powder at room temperature |
| CN111906329A (en) * | 2020-09-01 | 2020-11-10 | 中国科学院深圳先进技术研究院 | Preparation method of copper nano material structure |
| CN111922360A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
| CN114749677A (en) * | 2022-04-26 | 2022-07-15 | 苏州星翰新材料科技有限公司 | Preparation method and application of micron copper powder |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63186803A (en) * | 1987-01-27 | 1988-08-02 | Tanaka Kikinzoku Kogyo Kk | Production of fine copper particles |
| US4863510A (en) * | 1988-07-27 | 1989-09-05 | Tanaka Kikinzoku Kogyo K.K. | Reduction process for preparing copper, silver, and admixed silver-palladium metal particles |
| US20080087137A1 (en) * | 2006-07-06 | 2008-04-17 | Samsung Electro-Mecanics Co., Ltd. | Method for manufacturing metal nanoparticles |
| CN101693297A (en) * | 2009-10-16 | 2010-04-14 | 厦门大学 | Preparation method of copper nanoparticles with different particle diameters |
| CN101890504A (en) * | 2010-07-07 | 2010-11-24 | 江苏技术师范学院 | Method for preparing flaky nano copper powder |
| CN102240813A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院过程工程研究所 | Preparing method for cubic crystallized copper micro powder |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
-
2012
- 2012-03-30 CN CN2012100906905A patent/CN102601383A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63186803A (en) * | 1987-01-27 | 1988-08-02 | Tanaka Kikinzoku Kogyo Kk | Production of fine copper particles |
| US4863510A (en) * | 1988-07-27 | 1989-09-05 | Tanaka Kikinzoku Kogyo K.K. | Reduction process for preparing copper, silver, and admixed silver-palladium metal particles |
| US20080087137A1 (en) * | 2006-07-06 | 2008-04-17 | Samsung Electro-Mecanics Co., Ltd. | Method for manufacturing metal nanoparticles |
| CN101693297A (en) * | 2009-10-16 | 2010-04-14 | 厦门大学 | Preparation method of copper nanoparticles with different particle diameters |
| CN102240813A (en) * | 2010-05-10 | 2011-11-16 | 中国科学院过程工程研究所 | Preparing method for cubic crystallized copper micro powder |
| CN101890504A (en) * | 2010-07-07 | 2010-11-24 | 江苏技术师范学院 | Method for preparing flaky nano copper powder |
| CN102371358A (en) * | 2011-11-18 | 2012-03-14 | 复旦大学 | Aqueous-phase preparation method for re-dispersible nano-copper particles |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104227012A (en) * | 2013-06-14 | 2014-12-24 | 中国振华集团云科电子有限公司 | Preparation method for ultra-fine copper powder |
| CN104227015A (en) * | 2014-09-19 | 2014-12-24 | 洛阳理工学院 | Method for preparing antimony powder |
| CN110039069A (en) * | 2019-05-30 | 2019-07-23 | 江西省科学院能源研究所 | A kind of spongy Micron Copper Powder and preparation method thereof |
| CN110039069B (en) * | 2019-05-30 | 2021-05-14 | 江西省科学院能源研究所 | Spongy micron copper powder and preparation method thereof |
| CN110153443A (en) * | 2019-07-11 | 2019-08-23 | 中国科学院深圳先进技术研究院 | A kind of copper nanometer sheet and its preparation method and application |
| CN110560702A (en) * | 2019-09-16 | 2019-12-13 | 上海交通大学 | method for preparing micron-sized single crystal copper powder at room temperature |
| CN111906329A (en) * | 2020-09-01 | 2020-11-10 | 中国科学院深圳先进技术研究院 | Preparation method of copper nano material structure |
| CN111922360A (en) * | 2020-10-19 | 2020-11-13 | 西安宏星电子浆料科技股份有限公司 | Preparation method of nano copper powder |
| CN114749677A (en) * | 2022-04-26 | 2022-07-15 | 苏州星翰新材料科技有限公司 | Preparation method and application of micron copper powder |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102601383A (en) | Method for preparing ultrafine copper powder at room temperature | |
| CN103157803B (en) | A kind of solid state reaction prepares the method for Nanoalloy | |
| Songping et al. | Preparation of micron size copper powder with chemical reduction method | |
| CN106583712B (en) | A kind of preparation method of wicker copper nano particle | |
| CN101716685B (en) | Method for preparing spherical superfine silver powder by using chemical reduction method | |
| CN101693297B (en) | Preparation method of copper nanoparticles with different particle diameters | |
| CN103204525B (en) | Application of the lactams as solvent in nano material preparation | |
| CN103708560B (en) | Preparation method of nano tungsten trioxide powder | |
| CN102205421A (en) | Method for preparing gold and silver nanoparticles with hydro-thermal method | |
| CN108213456B (en) | Preparation method of cubic nanometer copper powder | |
| CN100448570C (en) | Preparation method of nanometer copper-silver bimetallic composite powder | |
| CN103170636A (en) | Method for preparing nano metal simple substance through solid-state chemical reaction | |
| CN107876795B (en) | Preparation method of single crystal copper powder | |
| Li et al. | Synthesis and characterization of silver–copper colloidal ink and its performance against electrical migration | |
| CN100496819C (en) | Reduced preparation method for metal nanometer particle using hydroxy ion liquid | |
| Khanna et al. | Synthesis of hydrophilic copper nanoparticles: effect of reaction temperature | |
| Li et al. | Synthesis of octahedral and cubic Cu 2 O microcrystals in sub-and super-critical methanol and their photocatalytic performance | |
| CN101664810B (en) | Method for synthetizing nano-copper in microemulsion system | |
| Trinh et al. | Synthesis of Cu core Ag shell nanoparticles using chemical reduction method | |
| CN102205420A (en) | Preparation method of water-phase noble metal nano particles | |
| Huang et al. | Synthesis of nanocrystalline and monodispersed copper particles of uniform spherical shape | |
| CN104625082B (en) | Nanometer nickel powder preparation method | |
| CN106876000B (en) | A kind of mixed metal powder, preparation method, conductive silver paste and purposes | |
| Khanna et al. | Effect of reducing agent on the synthesis of nickel nanoparticles | |
| CN111906329A (en) | Preparation method of copper nano material structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120725 |