CN115041698B - Preparation method of silver-palladium alloy powder - Google Patents
Preparation method of silver-palladium alloy powder Download PDFInfo
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- CN115041698B CN115041698B CN202210767800.0A CN202210767800A CN115041698B CN 115041698 B CN115041698 B CN 115041698B CN 202210767800 A CN202210767800 A CN 202210767800A CN 115041698 B CN115041698 B CN 115041698B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
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Abstract
The invention discloses a method for preparing silver-palladium alloy powder by reverse microemulsion, which comprises the steps of preparing a metal salt solution and a reducing agent solution according to concentration requirements respectively, keeping the solutions at a specified temperature, uniformly mixing an oil phase medium, the metal salt solution and a surfactant according to a certain proportion, adding a certain amount of cosurfactant into a mixed system, and stirring for a period of time to form the microemulsion; then slowly dripping the reducing agent solution, stirring and reacting for a period of time, and then increasing the temperature to demulsify and age; after the reaction is finished, centrifugal solid-liquid separation is carried out, washing is carried out by adding into the detergent, centrifugal washing is repeated for a plurality of times, and the mixture is placed in an oven for drying, thus obtaining the silver-palladium alloy powder product. The silver-palladium alloy powder prepared by the method has the advantages of adjustable Ag/Pd, controllable particle size, uniform distribution, high alloying degree and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of noble metal powder materials, and relates to a method for preparing silver-palladium alloy powder by reverse microemulsion.
Background
The silver-palladium alloy powder has the advantages of good conductivity and stable chemical property, silver ion migration resistance, soldering tin etching resistance and the like, so that the reliability of a microelectronic device is greatly improved, and the silver-palladium alloy powder becomes an electronic paste conductive phase material with wide prospects.
Because of the difference of the electric potentials of the oxidation-reduction electrodes of the two metal elements, the preparation of silver-palladium alloy powder with good dispersion performance and high alloying degree is difficult at present. The surface morphology, particle size and distribution of the silver-palladium alloy powder determine performance indexes such as film forming compactness, conductivity and the like of the electronic paste, and the silver-palladium alloy powder which mainly meets the requirements of the electronic paste and adopts submicron approximately spherical particles has high dispersibility and smooth surface is commercially adopted.
At present, a chemical reduction method is mainly adopted for preparing silver-palladium alloy powder, han Weiru et al research on a silver-palladium alloying mechanism, and the fact that the pH is regulated to 2 under a palladium-silver-ammonia reaction system so that redox electrodes of two elements are similar can be directly used for preparing the silver-palladium alloy powder, and the alloying degree is high is pointed out (China non-ferrous metals journal, 1998, volume 8, journal 2,406-408). However, in the reaction process of the chemical reduction method, many influencing factors, such as reaction temperature, time, pH, types and dosage of dispersing agents and reducing agents, and the like, are often difficult to achieve the indexes of the dispersibility, the alloying degree and the like of the silver-palladium alloy powder. Patent CN 106270544a discloses a preparation method of silver-palladium co-deposited powder with high dispersibility and high tap density, the reaction steps are simple and easy to control, and the preparation method is suitable for large-scale batch production, but the silver-palladium co-deposited powder has a defect in alloying degree.
Disclosure of Invention
The invention aims to provide a method for preparing silver-palladium alloy powder by reverse microemulsion, which takes the dispersibility and the alloying degree of the silver-palladium alloy powder into consideration.
The technical scheme adopted for solving the technical problems is as follows: a preparation method of silver palladium alloy powder comprises the following steps:
(1) Preparing a metal salt solution: 50.37g to 66.11g of AgNO 3 And 17.36 to 39.06g of Pd (NO) 3 ) 2 Dissolving in 100-300 mL deionized water, adding 100mL dispersing agent after dissolving completely, mixing thoroughly and preservingMaintaining the solution temperature at 20-40 ℃ to obtain a metal salt solution with the concentration of total metal ions of 20-60 g/L; agNO 3 、Pd(NO 3 ) 2 The concentration of (2) is determined according to Ag/Pd of silver-palladium alloy powder;
(2) Preparation of a reducing agent solution: dissolving 79.70-132.45 g of reducing agent in 200-400 mL of deionized water, wherein the mass of the reducing agent is 2 times of the stoichiometric number required by the reaction with the total metal ions in the metal salt solution in the step (1), and keeping the temperature of the solution at 20-40 ℃ after the reducing agent is fully dissolved to obtain a reducing agent solution;
(3) Preparing reverse microemulsion: under the stirring condition of 600-1200 rpm, uniformly mixing a metal salt solution, 460-780 mL of silicone oil and 10-20 mL of surfactant according to a certain proportion, then adding 10-20 mL of cosurfactant into a mixed system, stirring for 30min to form reverse microemulsion, wherein the total volume of the microemulsion is 100%, the metal salt solution accounts for 20-40%, the surfactant accounts for 0.5-2%, the cosurfactant accounts for 0.5-2%, and the balance is an oil phase medium;
(4) Dropwise adding a reducing agent solution into the reverse microemulsion within 20-40 min, continuously stirring and reacting for 30min, and demulsifying and aging for 60min at an elevated temperature; the complete addition time of the reducing agent is 20-40 min, and the demulsification and aging temperature is 80-110 ℃;
(5) After the reaction is finished, centrifugal solid-liquid separation is carried out, washing is carried out by adding into the detergent, repeating is carried out for 5 times, and the mixture is placed in an oven for drying, thus obtaining the silver-palladium alloy powder product.
The dispersing agent in the step (1) is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and gum arabic.
The preparation method of the silver-palladium alloy powder comprises the following steps of: 1.
the reducing agent in the step (2) is one or more of ascorbic acid, glucose and sodium citrate.
The surfactant in the step (3) is one or more of TX-100, span and fatty alcohol polyoxyethylene ether.
The cosurfactant in the step (3) is one or more of ethanol, propanol and isopropanol.
The detergent in the step (5) is higher fatty acid potassium salt or higher fatty acid sodium salt or a combination of the higher fatty acid potassium salt and the higher fatty acid sodium salt.
The invention has the following advantages and positive effects:
1, the micro-emulsion is used as a micro-reactor, and the size of the micro-reactor is controlled by regulating and controlling the proportion of an oil phase medium of the inverse micro-emulsion and a noble metal salt solution, the addition of a surfactant and a cosurfactant and other influencing factors, so that the surface morphology, the particle size and the distribution of silver-palladium alloy powder are controlled uniformly.
2, the demulsification and ageing process is carried out by increasing the temperature, and meanwhile, the increasing temperature has positive effect on the alloying degree of the silver-palladium alloy powder.
The method has the advantages of taking the dispersibility and the alloying degree of the silver-palladium alloy powder into consideration, continuous reaction process, simple steps and large-scale production and application prospect.
Drawings
FIG. 1 is an SEM image of silver-palladium alloy powder of example 1 of the present invention;
FIG. 2 is an XRD pattern of silver-palladium alloy powder of example 1 of the present invention;
FIG. 3 is an SEM image of silver-palladium alloy powder of example 2 of the present invention;
fig. 4 is an XRD pattern of silver-palladium alloy powder of example 2 of the present invention.
Detailed Description
The invention will be further illustrated by the following examples, which are given solely for the purpose of illustration and are not intended to limit the invention.
Example 1
The preparation method of the silver-palladium alloy powder comprises the following steps.
(1) Preparing a metal salt solution: 50.37g of AgNO 3 And 17.36g of Pd (NO 3 ) 2 After dissolution in 100mL of deionized water, 100mL of an aqueous solution containing 4g of polyvinylpyrrolidone was added, and after thorough mixing, the solution temperature was maintained at 20 ℃.
(2) Preparation of a reducing agent solution: 79.70g of ascorbic acid was dissolved in 200mL of deionized water, and after sufficient dissolution, the solution temperature was maintained at 20 ℃.
(3) Preparing reverse microemulsion: under the stirring condition of 1200rpm, uniformly mixing the metal salt solution, 780mL of silicone oil and 10mL of TX-100, then adding 10mL of ethanol into the mixed system, and stirring for 30min to form the microemulsion.
(4) And (3) dropwise adding the reducing agent solution for 20min, continuously stirring and reacting for 30min, and increasing the temperature to 80 ℃ to demulsify and age for 60min.
(5) After the reaction is finished, centrifugal solid-liquid separation is carried out, higher fatty acid sodium is added for washing, and after repeating for 5 times, the mixture is placed in an oven for drying, and a silver-palladium alloy powder product is obtained. The Ag/Pd of the silver-palladium alloy powder is 8:2, carrying out characterization analysis by SEM, wherein the size of the silver-palladium alloy powder is 200-300nm, and the distribution is uniform as shown in figure 1; the alloying degree analysis by XRD, as shown in fig. 2, was offset by about 0.2 ° compared to PDF cards of pure Ag.
Example 2
The preparation method of the silver-palladium alloy powder comprises the following steps.
(1) Preparing a metal salt solution: 66.11g of AgNO 3 And 39.06g of Pd (NO 3 ) 2 After dissolution in 300mL of deionized water, 100mL of an aqueous solution containing 2g of polyvinyl alcohol was added, and after thorough mixing, the solution temperature was maintained at 40 ℃.
(2) Preparation of a reducing agent solution: 132.45g of glucose was dissolved in 400mL of deionized water, and after sufficient dissolution, the solution temperature was maintained at 40 ℃.
(3) Preparing reverse microemulsion: under the stirring condition of 600rpm, uniformly mixing the metal salt solution, 460mL of silicone oil and 20mL of span 80, then adding 20mL of isopropanol into the mixed system, and stirring for 30min to form the microemulsion.
(4) And (3) dropwise adding the reducing agent solution for 40min, continuously stirring and reacting for 30min, and increasing the temperature to 110 ℃ to demulsify and age for 60min.
(5) After the reaction is finished, centrifugal solid-liquid separation is carried out, higher fatty acid potassium is added for washing, the mixture is repeatedly placed in an oven for drying after 5 times, and a silver-palladium alloy powder product is obtained. The Ag/Pd of the silver-palladium alloy powder is 7:3, carrying out characterization analysis by SEM, wherein the size of the silver-palladium alloy powder is 400-500nm, and the distribution is uniform as shown in figure 3; the alloying degree analysis by XRD, as shown in fig. 4, was offset by about 0.4 ° compared to the PDF card of pure Ag.
Example 3
This embodiment differs from embodiment 3 in that: the dispersing agent in the step (1) is polyethylene glycol or gum arabic or a combination of the two; the reducing agent in the step (2) is sodium citrate; the surfactant in the step (3) is fatty alcohol polyoxyethylene ether, and the cosurfactant is propanol.
The foregoing embodiments are merely illustrative and explanatory of the invention, and various modifications, additions and substitutions are possible, for those skilled in the art, of the described embodiments without departing from the scope of the invention as disclosed in the accompanying claims.
Claims (7)
1. A preparation method of silver palladium alloy powder is characterized in that: the method comprises the following steps:
(1) AgNO is to be carried out 3 And Pd (NO) 3 ) 2 Dissolving in deionized water, adding a dispersing agent after complete dissolution, and keeping the temperature of the solution at 20-40 ℃ after full mixing to obtain a metal salt solution with the concentration of total metal ions at 20-60 g/L;
(2) Dissolving a reducing agent in deionized water, wherein the concentration of the reducing agent is 40-120 g/L, and keeping the temperature of the solution at 20-40 ℃ after the reducing agent is fully dissolved to obtain a reducing agent solution;
(3) Under the stirring condition of 600-1200 rpm, uniformly mixing the metal salt solution, the silicone oil and the surfactant, then adding the cosurfactant, stirring for 30min to form reverse microemulsion, wherein the volume of the metal salt solution in the reverse microemulsion is 20-40%, the volume of the surfactant is 0.5-2%, the volume of the cosurfactant is 0.5-2%, and the balance is oil phase medium;
(4) Dropwise adding a reducing agent solution into the reverse microemulsion within 20-40 min, stirring and reacting for 30min, and demulsifying and aging for 60min at an elevated temperature; the addition time of the reducing agent is 20-40 min, and the demulsification and aging temperature is 80-110 ℃;
(5) After the reaction is finished, centrifugal solid-liquid separation is carried out, washing is carried out by adding into the detergent, repeating is carried out for 5 times, and the mixture is placed in an oven for drying, thus obtaining silver-palladium alloy powder.
2. The method for preparing silver-palladium alloy powder according to claim 1, wherein the dispersing agent in the step (1) is one or more of polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and gum arabic.
3. The method for preparing silver-palladium alloy powder according to claim 2, wherein the mass ratio of the dispersant to the total metal ions in the metal salt solution is 0.05-0.1: 1.
4. the method for preparing silver-palladium alloy powder according to claim 1, wherein the reducing agent in the step (2) is one or more of ascorbic acid, glucose and sodium citrate.
5. The method for preparing silver-palladium alloy powder according to claim 1, wherein the surfactant in the step (3) is one or more of TX-100, span and fatty alcohol-polyoxyethylene ether.
6. The method for preparing silver-palladium alloy powder according to claim 1, wherein the cosurfactant in the step (3) is one or more of ethanol, propanol and isopropanol.
7. The method for producing a silver-palladium alloy powder according to claim 1, wherein the detergent in the step (5) is a potassium salt of a higher fatty acid or a sodium salt of a higher fatty acid or a combination of both.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147841A (en) * | 1990-11-23 | 1992-09-15 | The United States Of America As Represented By The United States Department Of Energy | Method for the preparation of metal colloids in inverse micelles and product preferred by the method |
| KR20030043453A (en) * | 2001-11-28 | 2003-06-02 | (주)케미피아 | A method for preparing sphere and/or plate type micrometal using liquid phase reduction method and micrometal prepared from this method |
| US6660058B1 (en) * | 2000-08-22 | 2003-12-09 | Nanopros, Inc. | Preparation of silver and silver alloyed nanoparticles in surfactant solutions |
| KR20070101091A (en) * | 2006-04-11 | 2007-10-16 | 삼성전기주식회사 | Method for manufacturing nickel nano particle |
| US7608461B1 (en) * | 2005-09-16 | 2009-10-27 | Sandia Corporation | Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same |
| CN104415752A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C3-fraction liquid phase selective hydrogenation catalyst as well as preparation method and application thereof |
| CN104415751A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C2 fraction gas-phase selective hydrogenation catalyst and preparation method and application thereof |
| CN106270544A (en) * | 2015-06-12 | 2017-01-04 | 中国振华集团云科电子有限公司 | A kind of preparation method of the silver coprecipitated accumulated powder of palladium |
| CN108714700A (en) * | 2018-06-07 | 2018-10-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of the highly crystalline type silver powder of monodisperse and its silver powder obtained |
| CN114160804A (en) * | 2021-11-17 | 2022-03-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of submicron monodisperse silver-palladium powder |
-
2022
- 2022-07-01 CN CN202210767800.0A patent/CN115041698B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5147841A (en) * | 1990-11-23 | 1992-09-15 | The United States Of America As Represented By The United States Department Of Energy | Method for the preparation of metal colloids in inverse micelles and product preferred by the method |
| US6660058B1 (en) * | 2000-08-22 | 2003-12-09 | Nanopros, Inc. | Preparation of silver and silver alloyed nanoparticles in surfactant solutions |
| KR20030043453A (en) * | 2001-11-28 | 2003-06-02 | (주)케미피아 | A method for preparing sphere and/or plate type micrometal using liquid phase reduction method and micrometal prepared from this method |
| US7608461B1 (en) * | 2005-09-16 | 2009-10-27 | Sandia Corporation | Surface engineered nanoparticles for improved surface enhanced Raman scattering applications and method for preparing same |
| KR20070101091A (en) * | 2006-04-11 | 2007-10-16 | 삼성전기주식회사 | Method for manufacturing nickel nano particle |
| JP2011122248A (en) * | 2006-04-11 | 2011-06-23 | Samsung Electro-Mechanics Co Ltd | Method for manufacturing nickel nanoparticle |
| CN104415752A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C3-fraction liquid phase selective hydrogenation catalyst as well as preparation method and application thereof |
| CN104415751A (en) * | 2013-08-27 | 2015-03-18 | 中国石油化工股份有限公司 | C2 fraction gas-phase selective hydrogenation catalyst and preparation method and application thereof |
| CN106270544A (en) * | 2015-06-12 | 2017-01-04 | 中国振华集团云科电子有限公司 | A kind of preparation method of the silver coprecipitated accumulated powder of palladium |
| CN108714700A (en) * | 2018-06-07 | 2018-10-30 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七二研究所） | A kind of preparation method of the highly crystalline type silver powder of monodisperse and its silver powder obtained |
| CN114160804A (en) * | 2021-11-17 | 2022-03-11 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method of submicron monodisperse silver-palladium powder |
Non-Patent Citations (3)
| Title |
|---|
| Pd-Ag/Al_2O_3催化剂的制备及性能;卫国宾;穆玮;赵晓玮;;石油化工(08);第17-23页 * |
| 冯年平.中药经皮给药与功效性化妆品.中国医药科技出版社,2019,第173-174页. * |
| 微乳液法制备Pd负载型催化剂及其催化性能;卫国宾;杨思源;张敬畅;曹维良;戴伟;;石油化工;第41卷(11);第1239-1244页 * |
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