CN112719264A - Preparation method of polystyrene/silver composite microspheres - Google Patents
Preparation method of polystyrene/silver composite microspheres Download PDFInfo
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- CN112719264A CN112719264A CN202011488043.0A CN202011488043A CN112719264A CN 112719264 A CN112719264 A CN 112719264A CN 202011488043 A CN202011488043 A CN 202011488043A CN 112719264 A CN112719264 A CN 112719264A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 103
- 239000004793 Polystyrene Substances 0.000 title claims abstract description 101
- 229920002223 polystyrene Polymers 0.000 title claims abstract description 82
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 43
- 239000004332 silver Substances 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 42
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 21
- 238000007788 roughening Methods 0.000 claims abstract description 14
- 206010070834 Sensitisation Diseases 0.000 claims abstract description 12
- 230000008313 sensitization Effects 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 3
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 64
- 239000000243 solution Substances 0.000 claims description 37
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 32
- 230000001235 sensitizing effect Effects 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 13
- 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 12
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 229940117975 chromium trioxide Drugs 0.000 claims description 10
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 10
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 2
- 239000011246 composite particle Substances 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- 239000002998 adhesive polymer Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Images
Classifications
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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
- B22F1/17—Metallic particles coated with metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
The invention discloses a preparation method of polystyrene/silver composite microspheres, and belongs to the technical field of material preparation. The method comprises the steps of firstly roughening the surface of a PS (polystyrene) microsphere, then carrying out multiple sensitization and silver plating on the roughened PS microsphere, adding the treated PS microsphere into a silver ammonia solution under the ultrasonic condition, and adding a quantitative reducing agent to complete chemical silver plating on the surface of the PS microsphere; filtering, washing, centrifuging and drying to obtain the PS/Ag composite particles. The PS silver plating method has the advantages of relatively high preparation process, simple raw material composition, easiness in large-scale production, high silver coverage rate on the surface of the prepared composite microsphere and relatively high dispersibility.
Description
Technical Field
The invention relates to a preparation method of polystyrene/silver composite microspheres, belonging to the technical field of chemical silver plating.
Background
Conventional anisotropic conductive films are made by using metal particles or organic-inorganic composite particles as fillers in a matrix of an adhesive polymer and forming them into a solid film. Organic-inorganic composite particles having a diameter of several micrometers are generally coated with a highly conductive metal such as gold or silver. At the same time, the elastic core has a similar coefficient of thermal expansion compared to the adhesive polymer matrix and provides a larger contact area between the two electrode interconnects after hot pressing. In the polymer core, the Polystyrene (PS) microspheres have the advantages of controllable size, controllable shape, good monodispersity, various functional groups, easy high-temperature calcination or solvent dissolution and the like.
When the PS microspheres are used as the core of the composite material, the composite microspheres with various particle sizes and shapes can be prepared by controlling the size of the microspheres, but in the traditional chemical plating process, due to the self property of the PS microspheres, the surface of the microspheres is difficult to coat, so that the coverage rate is low and the dispersibility is poor.
Disclosure of Invention
The invention aims to provide a preparation method of polystyrene/silver composite microspheres, which specifically comprises the following steps:
(1) adding PS microspheres into a roughening solution mixed by chromium trioxide and concentrated sulfuric acid for roughening treatment;
(2) sequentially adding the PS microspheres obtained in the step (1) into a sensitizing solution and a silver ammonia solution for sensitization and silver plating, wherein the sensitizing solution is a mixed solution of stannous chloride dihydrate and concentrated hydrochloric acid;
(3) repeatedly treating the PS microspheres obtained in the step (2) for 4-6 times under the condition of the step (2);
(4) and (4) adding the PS microspheres obtained in the step (3) into a silver-ammonia solution, dropwise adding a reducing agent hydrazine hydrate under the ultrasonic dispersion condition, and filtering, washing and drying to obtain the PS/Ag composite filler.
Preferably, in the roughening solution in the step (1) of the present invention, the mass fraction of chromium trioxide is 2-8%, the mass fraction of concentrated sulfuric acid is 30-50%, the concentrated sulfuric acid is 98% by mass, and the addition ratio of the roughening solution is 50-80 ml per gram of PS microspheres.
Preferably, the reaction conditions of the coarsening process in the step (1) of the present invention are constant temperature at 20 ℃, and the magnetic stirring speed is 100 r/min.
Preferably, SnCl is contained in the sensitizing solution in the step (2) of the invention2·2H2The mass fraction of O is 2-10%, the mass fraction of concentrated hydrochloric acid is 2-6%, and the usage amount of the sensitizing solution is 50-80 mL per gram of PS microspheres.
Preferably, the conditions of the sensitization process in step (2) of the present invention are: stirring the mixture magnetically at a constant temperature of 20 ℃ for 400 r/min.
Preferably, the mass-to-volume ratio of the silver nitrate to the ammonia water in the silver-ammonia solution in the step (2) is 1: 2-6, the addition amount of the silver-ammonia solution is 20-40 ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 1-2.
Preferably, the reaction conditions for silver plating in step (2) of the present invention are constant temperature of 20 ℃ and magnetic stirring speed of 200 r/min.
Preferably, in the step (4), the mass-to-volume ratio of silver nitrate to ammonia water in the silver-ammonia solution is 1: 4-10, the addition amount of the silver-ammonia solution is 40-60 ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 1-4; 2-4 ml of hydrazine hydrate with the mass percentage concentration of 50% is required for each gram of silver nitrate.
Preferably, the reaction condition in the silver plating in the step (4) of the invention is that hydrazine hydrate is dropwise added at a constant speed for 4min/mL under 40Hz ultrasound; the drying condition of the composite microspheres is constant temperature of 60 ℃.
The invention has the beneficial effects that:
(1) the method has safe, simple and effective process, and the prepared composite particles have high coating rate and good dispersibility; the composite particle prepared by taking the Polystyrene (PS) microsphere as the core is widely applied by owners; for example, conductive particles that can be anisotropic conductive paste; can be used as a carrier for silver catalytic reaction, and the catalytic capability is improved by adjusting the specific surface area.
(2) The invention utilizes the strong oxidation of the acid aqueous solution to coarsen the surface of the PS microsphere, so that the specific surface area of the PS microsphere is increased, and the Sn is beneficial to the sensitization process2+The attachment of ions improves the sensitization efficiency; in addition, in the coarsening process, the compound oxidation liquid prepared by the invention can implant sulfonic acid groups (SO) into the surface of the PS microspheres3 2-) (ii) a The group is negatively charged and is a hydrophilic group, so that the adhesion capability of the surface of the PS microsphere can be improved; after sensitization, silver ammonia, Ag is added+Is covered with Sn2+Reducing to the surface of the PS microspheres; in the silver plating process, Ag+Reducing by taking metal Ag as an in-situ reduction center, and attaching the reduced Ag simple substance to the surface of the PS microspheres to gradually form a compact silver layer. The principle schematic diagram of PS microsphere chemical silvering is shown in figure (1)
(3) Compared with the prior art, the PS/Ag composite particles obtained by the PS microsphere chemical silvering method have high coating rate and good dispersibility; because the sulfonic acid groups are uniformly distributed in the coarsening process, uniform silver growing points can be reduced on the PS microspheres through multiple sensitization and silver plating processes and are used as a growing core for the in-situ reduction of the surfaces of the subsequent microspheres; the ultrasonic-assisted chemical plating improves the coverage rate of the plating layer and the dispersibility of the composite microspheres due to the cavitation effect of the ultrasonic.
Drawings
FIG. 1 is a scanning electron micrograph of PS/Ag composite particles according to three embodiments of the present invention;
FIG. 2 is a schematic diagram of the PS/Ag composite particle according to the present invention;
FIG. 3 is a scanning electron microscope image of the PS/Ag composite particles prepared by the present invention.
Detailed Description
The present invention is further described in detail with reference to the following specific examples, but the scope of the present invention is not limited to the above description.
Example 1
A preparation method of polystyrene/silver composite microspheres specifically comprises the following steps:
(1) adding PS microspheres into a coarsening solution mixed by chromium trioxide and concentrated sulfuric acid, and coarsening for 4 hours at the constant temperature of 20 ℃ and the magnetic stirring speed of 100 r/min; the mass fraction of chromium trioxide in the roughening solution is 2%, the mass fraction of concentrated sulfuric acid is 40%, the concentrated sulfuric acid is 98% in mass percentage, and the adding proportion of the roughening solution is 50ml per gram of PS microspheres.
(2) Adding the PS microspheres obtained in the step (1) into a sensitizing solution, and sensitizing for 20min under the conditions of constant temperature of 20 ℃ and magnetic stirring of 400r/min, wherein the sensitizing solution is a mixed solution of stannous chloride dihydrate and concentrated hydrochloric acid, and SnCl is contained in the sensitizing solution2·2H2The mass fraction of O is 2%, the mass fraction of concentrated hydrochloric acid is 4%, and the usage amount of the sensitizing solution is 50mL per gram of PS microspheres; and then adding the silver nitrate solution into silver ammonia solution, carrying out silver plating under the conditions of constant temperature of 20 ℃ and magnetic stirring speed of 200r/min, wherein the mass-to-volume ratio of silver nitrate to ammonia water in the silver ammonia solution is 1:4, the addition amount of the silver ammonia solution is 20ml per gram of PS microspheres, the mass ratio of the PS microspheres to the silver nitrate is 1:1, and repeating the treatment for 4 times.
(3) Adding the PS microspheres obtained in the step (2) into a silver-ammonia solution, dropwise adding a reducing agent hydrazine hydrate at a dropping speed of 4min/mL under the ultrasonic dispersion condition of 40Hz, filtering, washing, and drying at a constant temperature of 60 ℃ to obtain a PS/Ag composite filler; the mass volume ratio of silver nitrate to ammonia water in the silver-ammonia solution is 1:8, the addition amount of the silver-ammonia solution is 40ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 1; the required mass percent concentration of 50 percent hydrazine hydrate per gram of silver nitrate is 2 ml.
Example 2
A preparation method of polystyrene/silver composite microspheres specifically comprises the following steps:
(1) adding PS microspheres into a coarsening solution mixed by chromium trioxide and concentrated sulfuric acid, and coarsening for 4 hours at the constant temperature of 20 ℃ and the magnetic stirring speed of 100 r/min; the mass fraction of the chromium trioxide in the coarsening liquid is 8%, the mass fraction of the concentrated sulfuric acid is 50%, the concentrated sulfuric acid is 98% in mass percentage, and the adding proportion of the coarsening liquid is 80ml per gram of PS microspheres.
(2) Adding the PS microspheres obtained in the step (1) into a sensitizing solution, and sensitizing for 20min under the conditions of constant temperature of 20 ℃ and magnetic stirring of 400r/min, wherein the sensitizing solution is a mixed solution of stannous chloride dihydrate and concentrated hydrochloric acid, and SnCl is contained in the sensitizing solution2·2H2The mass fraction of O is 10%, the mass fraction of concentrated hydrochloric acid is 6%, and the usage amount of the sensitizing solution is 80mL per gram of PS microspheres; and then adding the silver nitrate solution into silver ammonia solution, carrying out silver plating under the conditions of constant temperature of 20 ℃ and magnetic stirring speed of 200r/min, wherein the mass-to-volume ratio of silver nitrate to ammonia water in the silver ammonia solution is 1:6, the addition amount of the silver ammonia solution is 40ml per gram of PS microspheres, the mass ratio of the PS microspheres to the silver nitrate is 1:2, and repeating the treatment for 5 times.
(3) Adding the PS microspheres obtained in the step (2) into a silver-ammonia solution, dropwise adding a reducing agent hydrazine hydrate at a dropping speed of 4min/mL under the ultrasonic dispersion condition of 40Hz, filtering, washing, and drying at a constant temperature of 60 ℃ to obtain a PS/Ag composite filler; the mass volume ratio of silver nitrate to ammonia water in the silver-ammonia solution is 1:10, the addition amount of the silver-ammonia solution is 60ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 4; the required mass percentage concentration of 50 percent hydrazine hydrate per gram of silver nitrate is 4 ml.
Example 3
A preparation method of polystyrene/silver composite microspheres specifically comprises the following steps:
(1) adding PS microspheres into a coarsening solution mixed by chromium trioxide and concentrated sulfuric acid, and coarsening for 4 hours at the constant temperature of 20 ℃ and the magnetic stirring speed of 100 r/min; the mass fraction of the chromium trioxide in the coarsening liquid is 6%, the mass fraction of the concentrated sulfuric acid is 30%, the concentrated sulfuric acid is 98% in mass percentage, and the adding proportion of the coarsening liquid is 60ml per gram of PS microspheres.
(2) Adding the PS microspheres obtained in the step (1) into a sensitizing solution, and sensitizing for 20min under the conditions of constant temperature of 20 ℃ and magnetic stirring of 400r/min, wherein the sensitizing solution is a mixed solution of stannous chloride dihydrate and concentrated hydrochloric acid, and SnCl is contained in the sensitizing solution2·2H2The mass fraction of O is 6%, the mass fraction of concentrated hydrochloric acid is 2%, and the usage amount of the sensitizing solution is 60mL per gram of PS microspheres; and then adding the silver nitrate solution into silver ammonia solution, carrying out silver plating under the conditions of constant temperature of 20 ℃ and magnetic stirring speed of 200r/min, wherein the mass-to-volume ratio of silver nitrate to ammonia water in the silver ammonia solution is 1:2, the addition amount of the silver ammonia solution is 30ml per gram of PS microspheres, the mass ratio of the PS microspheres to the silver nitrate is 1:1, and repeating the treatment for 6 times.
(3) Adding the PS microspheres obtained in the step (2) into a silver-ammonia solution, dropwise adding a reducing agent hydrazine hydrate at a dropping speed of 4min/mL under the ultrasonic dispersion condition of 40Hz, filtering, washing, and drying at a constant temperature of 60 ℃ to obtain a PS/Ag composite filler; the mass volume ratio of silver nitrate to ammonia water in the silver-ammonia solution is 1:4, the addition amount of the silver-ammonia solution is 50ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 1; 3ml of hydrazine hydrate with the mass percent concentration of 50 percent is needed for each gram of silver nitrate.
FIG. 1 is SEM images of examples 1-3, wherein in the SEM images of example 1, the surface coating rate of PS microspheres is low under the conditions of low-concentration roughening solution, less sensitization and silver plating times and low mass ratio of PS microspheres to silver nitrate; example 2 shows that the surface coating rate of the PS microspheres is high and the dispersibility of the microspheres is good under the conditions of higher concentration of the roughening solution, increased primary sensitization and silver plating times and proper mass ratio of the PS microspheres to silver nitrate. Example 3 shows that the low concentration roughening solution has reduced microsphere surface modification effect, and even if the sensitization and silver plating times are increased and the mass ratio of the PS microspheres to silver nitrate is increased, the coating rate of the silver on the microsphere surface is not high, and the microspheres are agglomerated due to excessive silver nitrate.
As shown in fig. 3, the Ag/PS composite microspheres are prepared under the above conditions by ultrasound assistance, and it can be seen from SEM that the PS microspheres are covered with uniform silver shells, and the coating effect is good; from the overall distribution of the microspheres, the dispersibility of the microspheres is also good, i.e. the polystyrene/silver composite microspheres with good dispersibility and complete coating can be prepared by the method.
Claims (9)
1. The preparation method of the polystyrene/silver composite microsphere is characterized by comprising the following steps:
(1) adding PS microspheres into a roughening solution mixed by chromium trioxide and concentrated sulfuric acid for roughening treatment;
(2) sequentially adding the PS microspheres obtained in the step (1) into a sensitizing solution and a silver ammonia solution for sensitization and silver plating, wherein the sensitizing solution is a mixed solution of stannous chloride dihydrate and concentrated hydrochloric acid;
(3) repeatedly treating the PS microspheres obtained in the step (2) for 4-6 times under the condition of the step (2);
(4) and (4) adding the PS microspheres obtained in the step (3) into a silver-ammonia solution, dropwise adding a reducing agent hydrazine hydrate under the ultrasonic dispersion condition, and filtering, washing and drying to obtain the PS/Ag composite filler.
2. The method for preparing polystyrene/silver composite microspheres according to claim 1, wherein the method comprises the following steps: the mass fraction of chromium trioxide in the roughening solution in the step (1) is 2-8%, the mass fraction of concentrated sulfuric acid is 30-50%, the concentrated sulfuric acid is 98% by mass, and the adding proportion of the roughening solution is 50-80 ml per gram of PS microspheres.
3. The method for preparing polystyrene/silver composite microspheres according to claim 2, wherein the method comprises the following steps: the reaction condition of the coarsening process in the step (1) is that the magnetic stirring speed is 100r/min at the constant temperature of 20 ℃.
4. The method for preparing polystyrene/silver composite microspheres according to claim 1, wherein the method comprises the following steps: SnCl in the sensitizing solution in the step (2)2·2H2The mass fraction of O is 2-10%, the mass fraction of concentrated hydrochloric acid is 2-6%, and the usage amount of the sensitizing solution is 50-80 mL per gram of PS microspheres.
5. The method for preparing polystyrene/silver composite microspheres according to claim 4, wherein the method comprises the following steps: the conditions of the sensitization process in the step (2) are as follows: stirring the mixture magnetically at a constant temperature of 20 ℃ for 400 r/min.
6. The method for preparing polystyrene/silver composite microspheres according to claim 1, wherein the method comprises the following steps: the mass volume ratio of the silver nitrate to the ammonia water in the silver-ammonia solution in the step (2) is 1: 2-6, the addition amount of the silver-ammonia solution is 20-40 ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 1-2.
7. The method for preparing polystyrene/silver composite microspheres according to claim 1, wherein the method comprises the following steps: the reaction condition of silver plating in the step (2) is that the temperature is kept constant at 20 ℃, and the magnetic stirring speed is 200 r/min.
8. The method for preparing polystyrene/silver composite microspheres according to claim 1, wherein the method comprises the following steps: in the step (4), the mass-to-volume ratio of silver nitrate to ammonia water in the silver-ammonia solution is 1: 4-10, the addition amount of the silver-ammonia solution is 40-60 ml per gram of PS microspheres, and the mass ratio of the PS microspheres to the silver nitrate is 1: 1-4; 2-4 ml of hydrazine hydrate with the mass percentage concentration of 50% is required for each gram of silver nitrate.
9. The method for preparing polystyrene/silver composite microspheres according to claim 1, wherein the method comprises the following steps: the reaction condition during silver plating in the step (4) is that hydrazine hydrate is dropwise added at a constant speed for 4min/mL under 40Hz ultrasonic; the drying condition of the composite microspheres is constant temperature of 60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202011488043.0A CN112719264A (en) | 2020-12-16 | 2020-12-16 | Preparation method of polystyrene/silver composite microspheres |
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| CN114535570A (en) * | 2022-02-13 | 2022-05-27 | 西南大学 | Preparation method of hollow bimetallic microspheres and electromagnetic protection composite material |
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