CN111618316A - Surface-modified silver powder and coating preparation method thereof - Google Patents
Surface-modified silver powder and coating preparation method thereof Download PDFInfo
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- CN111618316A CN111618316A CN202010604717.2A CN202010604717A CN111618316A CN 111618316 A CN111618316 A CN 111618316A CN 202010604717 A CN202010604717 A CN 202010604717A CN 111618316 A CN111618316 A CN 111618316A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical class [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 silver ions Chemical class 0.000 claims abstract description 64
- 229910052709 silver Inorganic materials 0.000 claims abstract description 54
- 239000004332 silver Substances 0.000 claims abstract description 54
- 230000001590 oxidative effect Effects 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000003801 milling Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- 239000002270 dispersing agent Substances 0.000 claims description 28
- 239000003638 chemical reducing agent Substances 0.000 claims description 19
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 150000003868 ammonium compounds Chemical class 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- 235000010350 erythorbic acid Nutrition 0.000 claims description 8
- 239000008098 formaldehyde solution Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- 229940026239 isoascorbic acid Drugs 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 7
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 5
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 5
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 5
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 4
- 229920000084 Gum arabic Polymers 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 4
- 241000978776 Senegalia senegal Species 0.000 claims description 4
- 235000010489 acacia gum Nutrition 0.000 claims description 4
- 239000000205 acacia gum Substances 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 4
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 239000008273 gelatin Substances 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 235000011852 gelatine desserts Nutrition 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 15
- 239000000243 solution Substances 0.000 description 90
- 239000002245 particle Substances 0.000 description 12
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/102—Metallic powder coated with organic material
Abstract
The invention discloses a surface modified silver powder and a coating preparation method thereof, wherein the method comprises the following steps: step 1, preparing an oxidizing solution containing silver ions; step 2, preparing a reducing solution; step 3, preparing an auxiliary agent solution; step 4, adding the reducing solution into the assistant solution, and then adding the oxidizing solution containing silver ions into the assistant solution, or simultaneously adding the reducing solution and the oxidizing solution containing silver ions into the assistant solution and finishing adding the reducing solution and the oxidizing solution containing silver ions; and 5, adding one or more organic surface treating agents after the reaction is finished, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder. The invention also provides the surface modified silver powder prepared by the method. According to the invention, the roughness of the powder surface is effectively controlled by adjusting the pH of the assistant solution, so that the silver powder with different specific surface areas and different organic coating amounts and monodispersity is obtained.
Description
Technical Field
The invention relates to a preparation method for effectively controlling the dispersibility and the surface activity of silver powder in a silver powder treatment technology and excellent silver powder prepared by the preparation method, in particular to surface-modified silver powder and a coating preparation method thereof.
Background
Noble metal powder is generally used as a main raw material for functional phases of conductive paste, resistive paste, and electrode paste in noble silver paste, and is widely used. The functional phase is generally dispersed in the matrix in the form of spheres, flakes, fibers, or the like, constituting conductive paths. The method for producing silver powder which is widely applied at present is also a chemical method, and the liquid phase reduction method is the most main chemical method for preparing silver powder at present. Dissolving silver nitrate in water, adding a chemical reducing agent and a surfactant to protect the reduced silver particles, depositing silver powder, washing and drying to obtain powder. The powder performance of the conductive phase comprises the characteristics of the morphology, the surface structure, the specific surface area, the granularity and the distribution of the powder, the tap density of the powder, the organic coating on the surface of the particle, the dispersibility and the like. These properties directly determine the electrical properties of the paste and affect the physical and mechanical properties of the cured film. Thus, there is a need for a powder preparation method that optimizes the coating aids on the surface of the silver powder particles.
Disclosure of Invention
The invention aims to provide silver powder and a preparation method thereof, and the method can effectively control the dispersibility of the silver powder through the application of a surfactant and prepare the powder for optimizing the coating auxiliary agent on the surface of silver powder particles.
In order to achieve the above object, the present invention provides a method for coating and preparing a surface-modified silver powder, wherein the method comprises: step 1, preparing an oxidizing solution containing silver ions: dissolving silver salt solid in deionized water, fully stirring and dissolving uniformly, and keeping the temperature; step 2, preparing a reducing solution: adding isoascorbic acid or hydrazine hydrate solution or formaldehyde solution into deionized water, fully stirring and dissolving uniformly, and keeping the temperature; step 3, preparing an auxiliary agent solution: adding one or more dispersants and pH regulators into deionized water, fully stirring and dissolving uniformly, and keeping the temperature; step 4, adding the reducing solution into the assistant solution, and then adding the oxidizing solution containing silver ions into the assistant solution, or simultaneously adding the reducing solution and the oxidizing solution containing silver ions into the assistant solution and finishing adding the reducing solution and the oxidizing solution containing silver ions; and 5, adding one or more organic surface treating agents after the reaction is finished, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder.
In the coating preparation method of the surface modified silver powder, the holding temperature is a constant temperature state with the temperature controlled at 40-48 ℃.
In the step 1, the silver salt solid is dissolved in deionized water, or an ammonium compound capable of ionizing ammonium ions in water is additionally added, the mixture is fully stirred and dissolved uniformly, and the silver ions and the ammonium ions are complexed to generate a silver-ammonia solution.
In the method for coating and preparing the surface modified silver powder, the silver salt solid is any one or a combination of two of silver nitrate, silver carbonate and silver sulfate.
In the coating preparation method of the surface modified silver powder, the ammonium compound is selected from one or a combination of two of ammonia water, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium bicarbonate.
The coating preparation method of the surface modified silver powder is characterized in that the concentration of silver ions in the solution is 60-100 g/L.
In the coating preparation method of the surface modified silver powder, in the step 2, a reducing agent is added into deionized water, and the mixture is fully stirred and dissolved uniformly; the reducing agent is isoascorbic acid or hydrazine hydrate solution with the mass concentration of 54 percent or formaldehyde solution with the mass concentration of 40 percent, and the concentration of the reducing agent after the addition is 0.08-1.2 mol/L.
In the coating preparation method of the surface modified silver powder, in the step 3, one or more dispersants and pH regulators are added into deionized water, the concentration of the dispersant is 60-100 g/L, and the total mass of the added dispersants is 0.1-1.5 times of the mass of silver ions in an oxidizing solution containing the silver ions; and adding a pH regulator to regulate the pH range of the solution to 2.0-11.5.
In the coating preparation method of the surface modified silver powder, the dispersant is one or a combination of two of polyvinylpyrrolidone K30, rosin, gum arabic, gelatin, polyacrylamide and oleic acid.
The invention provides the surface modified silver powder prepared by the method.
The surface modified silver powder and the coating preparation method thereof provided by the invention have the following advantages:
according to the preparation method, the dispersibility of the silver powder can be effectively controlled through the application of the surfactant, and the powder for optimizing the coating auxiliary agent on the surface of the silver powder particles is prepared. Specifically, the roughness of the surface of the powder is effectively controlled by adjusting the pH value of the assistant solution, so that the silver powder with different specific surface areas and different organic coating amounts and monodispersity is obtained.
The silver powder prepared by the invention has the advantages of wide component sources, reduced production cost, high crystallinity of the obtained silver powder, high uniformity of morphology and particle size, small particle size compared with the existing silver powder, good dispersibility, stable performance, excellent quality, simple preparation method, low cost and high yield.
Drawings
FIGS. 1 to 3 are scanning electron micrographs of silver powders obtained by the present invention with different particle sizes.
Detailed Description
The following further describes embodiments of the present invention with reference to the drawings.
The invention provides a coating preparation method of surface modified silver powder, which comprises the following steps: step 1, preparing an oxidizing solution containing silver ions: dissolving silver salt solid in deionized water, fully stirring and dissolving uniformly, and keeping the temperature; step 2, preparing a reducing solution: adding isoascorbic acid or hydrazine hydrate solution or formaldehyde solution into deionized water, fully stirring and dissolving uniformly, and keeping the temperature; step 3, preparing an auxiliary agent solution: adding one or more dispersants and pH regulators into deionized water, fully stirring and dissolving uniformly, and keeping the temperature; step 4, adding the reducing solution into the assistant solution according to a certain flow rate, and then adding the oxidizing solution containing silver ions into the assistant solution according to a certain flow rate, wherein the flow rate range is 20-60 ml/min; or adding the rest part of the reducing solution and the oxidizing solution containing silver ions into the assistant solution at the same time; and 5, adding one or more organic surface treating agents after the reaction is finished, dissolving organic substances used as the surface treating agents into alcohol to prepare an alcohol solution, quickly pouring the alcohol solution into the reaction liquid, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder within the required particle size range.
The organic surface treating agent is any one or more of organic surface treating agents commonly used in the field, such as surfactants K12, FS-22, FS-10 and the like. K12 is also called AS, abbreviated AS SDS, namely sodium dodecyl sulfate. F-22 is a fluorosurfactant manufactured by DuPont (DuPont). FS-10 is a nonionic fluorosurfactant manufactured by DuPont (DuPont).
Preferably, the maintaining temperature is a constant temperature state with the temperature controlled between 40 ℃ and 48 ℃.
In the step 1, the silver salt solid is dissolved in deionized water, or an ammonium compound capable of ionizing ammonium ions in water is additionally added, the mixture is fully stirred and dissolved uniformly, and silver ions and ammonium ions are complexed to generate a silver-ammonia solution.
The silver salt solid is selected from any one or two of silver nitrate, silver carbonate and silver sulfate.
The ammonium compound is selected from one or two of ammonia water, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium bicarbonate.
The concentration of silver ions in the solution is 60-100 g/l. The concentration of the ammonium ions corresponds to that of the silver ions, and the silver ions can be completely complexed to generate a silver-ammonia solution.
In the step 2, adding a reducing agent into deionized water, and fully stirring and dissolving uniformly; the reducing agent is isoascorbic acid or hydrazine hydrate solution with the mass concentration of 54 percent or formaldehyde solution with the mass concentration of 40 percent, and the concentration of the reducing agent after the addition is 0.08-1.2 mol/L.
Step 3, adding one or more dispersants and pH regulators into deionized water, wherein the concentration of the dispersant is 60-100 g/L, and the total mass of the added dispersants is 0.1-1.5 times of the mass of silver ions in the oxidizing solution containing the silver ions; and adding a pH regulator to regulate the pH range of the solution to 2.0-11.5.
The dispersant is selected from one or two of polyvinylpyrrolidone K30, rosin, gum arabic, gelatin, polyacrylamide and oleic acid. The pH adjuster is an acidic or basic substance, and an acid-base adjuster commonly used in the art may be used.
Polyvinylpyrrolidone (PVP), a non-ionic polymer, is a common polymer. PVP is classified into four grades based on its average molecular weight, which is conventionally represented by the K value, with different K values representing the respective PVP average molecular weight ranges. The K value is actually a characteristic value related to the relative viscosity of the aqueous solution of PVP, which in turn is a physical quantity related to the molecular weight of the high polymer, and thus the K value can be used to characterize the average molecular weight of PVP. In general, the larger the K value, the higher the viscosity, and the stronger the adhesiveness.
After the pH regulator is added, the surface of the powder particles can be in a smooth or rough state, the powder particles are obviously gradually transited from the smooth surface state to the rough surface state along with the change of the pH value of the solution from strong acidity to strong basicity, and the dispersion effect is changed from excellent to poor.
The invention also provides the surface modified silver powder prepared by the method.
The surface-modified silver powder and the coating preparation method thereof according to the present invention will be further described with reference to the following examples.
Example 1
A method for cladding a surface-modified silver powder, comprising:
step 1, preparing an oxidizing solution containing silver ions: dissolving silver salt solid in deionized water, or additionally adding an ammonium compound capable of ionizing ammonium ions in water, fully stirring and dissolving uniformly, complexing the silver ions and the ammonium ions to generate a silver-ammonia solution, and keeping the temperature at a constant temperature of 40-48 ℃.
The silver salt solid is silver nitrate. The ammonium compound is ammonia water. The silver ion concentration in the solution was 80 g/l.
Step 2, preparing a reducing solution: adding isoascorbic acid into deionized water, fully stirring and dissolving uniformly, and keeping the temperature at a constant temperature of 40-48 ℃.
Namely, a reducing agent is added to deionized water, wherein the reducing agent is isoascorbic acid, and the concentration of the reducing agent after the addition is 0.5 mol/L.
Step 3, preparing an auxiliary agent solution: adding one or more dispersing agents and pH regulators into deionized water, fully stirring and dissolving uniformly, and keeping the temperature at a constant temperature of 40-48 ℃.
The concentration of the dispersing agent is 80 g/L, and the total mass of the added dispersing agent is 0.1-1.5 times of the mass of the silver ions in the oxidizing solution containing the silver ions; and adding a pH regulator to regulate the pH range of the solution to 2.0-11.5. The dispersant is polyvinylpyrrolidone K30 or rosin.
And 4, adding the reducing solution into the assistant solution, and then adding the oxidizing solution containing the silver ions into the assistant solution, or adding the reducing solution and the oxidizing solution containing the silver ions into the assistant solution at the same time and finishing adding the reducing solution and the oxidizing solution containing the silver ions at the same time.
And 5, adding one or more organic surface treating agents after the reaction is finished, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder.
The embodiment also provides the surface modified silver powder prepared by the method.
Example 2
A method for cladding a surface-modified silver powder, comprising:
step 1, preparing an oxidizing solution containing silver ions: dissolving silver salt solid in deionized water, or additionally adding an ammonium compound capable of ionizing ammonium ions in water, fully stirring and dissolving uniformly, complexing the silver ions and the ammonium ions to generate a silver-ammonia solution, and keeping the temperature at a constant temperature of 40-48 ℃.
The silver salt solid is silver carbonate and silver sulfate. The ammonium compound is ammonium nitrate or ammonium sulfate. The silver ion concentration in the solution was 60 g/l.
Step 2, preparing a reducing solution: adding hydrazine hydrate solution into deionized water, fully stirring and dissolving uniformly, and keeping the temperature at a constant temperature of 40-48 ℃.
Namely, a reducing agent is added into deionized water, wherein the reducing agent is hydrazine hydrate solution with the mass concentration of 54%, and the concentration of the reducing agent after the addition is 0.08 mol/L.
Step 3, preparing an auxiliary agent solution: adding one or more dispersing agents and pH regulators into deionized water, fully stirring and dissolving uniformly, and keeping the temperature at a constant temperature of 40-48 ℃.
The concentration of the dispersing agent is 100 g/L, and the total mass of the added dispersing agent is 0.1-1.5 times of the mass of the silver ions in the oxidizing solution containing the silver ions; and adding a pH regulator to regulate the pH range of the solution to 2.0-11.5. The dispersing agent is gum arabic and gelatin.
And 4, adding the reducing solution into the assistant solution, and then adding the oxidizing solution containing the silver ions into the assistant solution, or adding the reducing solution and the oxidizing solution containing the silver ions into the assistant solution at the same time and finishing adding the reducing solution and the oxidizing solution containing the silver ions at the same time.
And 5, adding one or more organic surface treating agents after the reaction is finished, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder.
The embodiment also provides the surface modified silver powder prepared by the method.
Example 3
A method for cladding a surface-modified silver powder, comprising:
step 1, preparing an oxidizing solution containing silver ions: dissolving silver salt solid in deionized water, or additionally adding an ammonium compound capable of ionizing ammonium ions in water, fully stirring and dissolving uniformly, complexing the silver ions and the ammonium ions to generate a silver-ammonia solution, and keeping the temperature at a constant temperature of 40-48 ℃.
The silver salt solid is selected from any one or two of silver nitrate, silver carbonate and silver sulfate. The ammonium compounds are ammonium carbonate and ammonium bicarbonate. The silver ion concentration in the solution was 100 g/l.
Step 2, preparing a reducing solution: adding a formaldehyde solution into deionized water, fully stirring and dissolving uniformly, and keeping the temperature at a constant temperature of 40-48 ℃.
Namely, a reducing agent is added into deionized water, wherein the reducing agent is a formaldehyde solution with the mass concentration of 40%, and the concentration of the reducing agent after the addition is 1.2 mol/L.
Step 3, preparing an auxiliary agent solution: adding one or more dispersing agents and pH regulators into deionized water, fully stirring and dissolving uniformly, and keeping the temperature at a constant temperature of 40-48 ℃.
The concentration of the dispersing agent is 60 g/L, and the total mass of the added dispersing agent is 0.1-1.5 times of the mass of the silver ions in the oxidizing solution containing the silver ions; and adding a pH regulator to regulate the pH range of the solution to 2.0-11.5. The dispersant is polyacrylamide and oleic acid.
And 4, adding the reducing solution into the assistant solution, and then adding the oxidizing solution containing the silver ions into the assistant solution, or adding the reducing solution and the oxidizing solution containing the silver ions into the assistant solution at the same time and finishing adding the reducing solution and the oxidizing solution containing the silver ions at the same time.
And 5, adding one or more organic surface treating agents after the reaction is finished, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder.
The embodiment also provides the surface modified silver powder prepared by the method.
The morphology and the particle size of the surface modified silver powder prepared by the embodiment of the invention are shown in figures 1-3.
The invention provides a surface modified silver powder and a coating preparation method thereof, which are a preparation method capable of effectively controlling the dispersibility of the silver powder by applying a surfactant, and specifically comprise the following steps: selecting one or more dispersants and one or more pH regulators to prepare an auxiliary solution, mixing all or part of the prepared reducing solution with the auxiliary solution, then simultaneously adding the reducing solution with the rest percentage and the oxidizing solution containing silver ions, controlling the temperature of all the solutions to be between 40 and 48 ℃, adding one or more organic surface treatment agents to organically wrap the powder after the reaction is finished, and then washing, filtering, drying and air-milling to obtain the silver powder with different requirements. According to the invention, the roughness of the powder surface can be effectively controlled by adjusting the PH of the assistant solution, so that the silver powder with different specific surface areas and different organic coating amounts and monodispersity can be obtained.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (10)
1. A coating preparation method of surface modified silver powder is characterized by comprising the following steps:
step 1, preparing an oxidizing solution containing silver ions: dissolving silver salt solid in deionized water, fully stirring and dissolving uniformly, and keeping the temperature;
step 2, preparing a reducing solution: adding isoascorbic acid or hydrazine hydrate solution or formaldehyde solution into deionized water, fully stirring and dissolving uniformly, and keeping the temperature;
step 3, preparing an auxiliary agent solution: adding one or more dispersants and pH regulators into deionized water, fully stirring and dissolving uniformly, and keeping the temperature;
step 4, adding the reducing solution into the assistant solution, and then adding the oxidizing solution containing silver ions into the assistant solution, or simultaneously adding the reducing solution and the oxidizing solution containing silver ions into the assistant solution and finishing adding the reducing solution and the oxidizing solution containing silver ions;
and 5, adding one or more organic surface treating agents after the reaction is finished, fully stirring, washing, filtering, drying and air-milling to obtain the required silver powder.
2. The coating preparation method of surface modified silver powder according to claim 1, wherein the holding temperature is a constant temperature state in which the temperature is controlled to 40 to 48 ℃.
3. The method for coating silver powder according to claim 1, wherein in step 1, the silver salt solid is dissolved in deionized water, or an ammonium compound capable of ionizing ammonium ions in water is further added, and the mixture is sufficiently stirred and dissolved uniformly, so that silver ions and ammonium ions are complexed to form a silver-ammonia solution.
4. The method for the coated production of surface modified silver powder according to claim 3, wherein the silver salt solid is selected from any one or a combination of two of silver nitrate, silver carbonate and silver sulfate.
5. The method for coating production of surface-modified silver powder according to claim 3, wherein the ammonium compound is selected from one or a combination of two of ammonia, ammonium nitrate, ammonium sulfate, ammonium carbonate and ammonium bicarbonate.
6. The method for coating production of surface-modified silver powder according to claim 3, wherein the concentration of silver ions in the solution is 60 to 100 g/l.
7. The coating preparation method of surface modified silver powder according to claim 1, wherein in step 2, a reducing agent is added into deionized water, and the mixture is fully stirred and dissolved uniformly; the reducing agent is isoascorbic acid or hydrazine hydrate solution with the mass concentration of 54 percent or formaldehyde solution with the mass concentration of 40 percent, and the concentration of the reducing agent after the addition is 0.08-1.2 mol/L.
8. The coating preparation method of surface modified silver powder according to claim 1, wherein in step 3, one or more dispersants and pH regulators are added to deionized water, the concentration of the dispersant is 60 to 100 g/l, and the total mass of the added dispersants is 0.1 to 1.5 times the mass of silver ions in the oxidizing solution containing silver ions; and adding a pH regulator to regulate the pH range of the solution to 2.0-11.5.
9. The method for coating silver powder according to claim 1, wherein the dispersant is one or a combination of two selected from the group consisting of polyvinylpyrrolidone K30, rosin, gum arabic, gelatin, polyacrylamide, and oleic acid.
10. A surface-modified silver powder prepared by the method of any one of claims 1 to 9.
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| CN114653962A (en) * | 2022-03-25 | 2022-06-24 | 电子科技大学 | Modification method of silver powder for conductive adhesive |
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| CN117300145A (en) * | 2023-09-21 | 2023-12-29 | 上海银波生物科技有限公司 | Preparation method of monocrystal-like silver powder with ultrahigh tap density |
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