CN115592125B - Preparation method of gold powder with coexistence of micron sheets and submicron particles - Google Patents
Preparation method of gold powder with coexistence of micron sheets and submicron particles Download PDFInfo
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- CN115592125B CN115592125B CN202211176400.9A CN202211176400A CN115592125B CN 115592125 B CN115592125 B CN 115592125B CN 202211176400 A CN202211176400 A CN 202211176400A CN 115592125 B CN115592125 B CN 115592125B
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000002245 particle Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 28
- 229910052737 gold Inorganic materials 0.000 claims abstract description 27
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 9
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 76
- 238000003756 stirring Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011550 stock solution Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- -1 alkyl ammonium halide Chemical group 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 6
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 5
- 239000011859 microparticle Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- YIFWXQBNRQNUON-UHFFFAOYSA-M dodecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCC[N+](C)(C)C YIFWXQBNRQNUON-UHFFFAOYSA-M 0.000 claims description 2
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 2
- LGPJVNLAZILZGQ-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCC[N+](C)(C)C LGPJVNLAZILZGQ-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- AXRFZYRPSHSKBF-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCC[N+](C)(C)C AXRFZYRPSHSKBF-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 4
- 238000010899 nucleation Methods 0.000 abstract description 4
- 239000002002 slurry Substances 0.000 abstract description 4
- 239000004020 conductor Substances 0.000 abstract description 3
- 230000012010 growth Effects 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 238000009826 distribution Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/068—Flake-like particles
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a preparation method of gold powder with coexistence of micron sheets and submicron particles, and aims to prepare gold powder with an adjustable structure in one step and solve the technical bottleneck of micron-sized gold powder in gold conductor slurry. The preparation method comprises the following steps: adding chloroauric acid solution into surfactant solution, and controlling nucleation and growth of micrometer tablet and submicron particle by temperature gradient change with ascorbic acid as reducer. The shape of the flaky gold powder prepared by the invention is hexagonal and triangular, the diameter range is 1-5 mu m, the thickness of the flaky gold powder is 100-800nm, and the flaking rate is 30-80%; the particle size of the spherical gold powder is 0.3-1.0 mu m. The preparation method has the advantages of simple and safe steps, short reaction time, easy mass production, controllable morphology, size and proportion of micron sheets and submicron particles in the gold powder, and important application value in printing type gold conductor slurry.
Description
Technical Field
The invention relates to a preparation method of gold powder, in particular to a preparation method of gold powder with coexistence of micron sheets and submicron particles for electronic paste.
Background
The electronic paste is an electronic functional material integrating metallurgy, chemical industry and electronic technology, is mainly composed of a functional phase, a bonding phase and an organic solvent phase, is formed into paste after uniform stirring and rolling, is printed and sintered on a substrate to form a film layer with a micron-sized thickness and plays a role in conducting electricity, and is mainly applied to manufacturing of integrated circuits, resistors, capacitors, solar cell electrodes, sensitive components and other electronic components, and has important strategic positions in the fields of aerospace and military industry.
The conductive functional phase components commonly used in electronic paste mainly comprise gold (Au), silver (Ag) and copper (Cu). Among them, au has characteristics of high ductility, high chemical inertness, oxidation resistance, and the like. It has little tendency to migrate as a conductor even under complex and severe operating conditions; the electronic paste prepared by the raw materials has the advantages of high resolution, strong adhesive force to a base material and a dielectric medium, low film forming surface porosity, high gold wire bonding property and the like, so that the electronic paste is widely applied to electronic technologies such as large-scale integrated circuits, semiconductor packaging, multilayer wiring circuits and the like, and plays a significant role in high-reliability military electronic technologies. In order to meet the performance requirements of high-performance military electronic equipment, the morphology and the size of the gold powder often have a strict application range, and the gold powder is generally composed of submicron spheroid-like gold powder and micron-level flake-like gold powder. Compared with spherical particles, the gold sheets are in line-surface contact, the contact area is far larger than the point contact between the spherical particles, and therefore the gold sheets have better conductivity. However, the size of the gold plate is not excessively large (> 5 μm), otherwise, the gold plate is not easy to pass through a screen plate during printing to cause mesh blocking, and finally, printed conductive lines are disconnected, so that the screen printing performance is reduced. Meanwhile, the gold sheet needs a certain thickness, so that the gold sheet is not easy to curl and deform during gold paste rolling, and the sintering is not compact, so that the conductivity is affected. In addition, the large number of sheet gold powder stacks can cause voids in the slurry during sintering, requiring some fine gold particles to fill. Therefore, the conductive gold paste prepared from gold powder with coexisting micron sheets and submicron particles has better comprehensive performance.
However, gold powder for electronic paste currently prepared domestically is mostly composed of particles of a single morphology, for example:
CN109622985a discloses a preparation method of high-dispersity submicron-sized gold powder, and the average particle size distribution of the prepared gold powder is 0.3-1.2 μm.
CN106825606a discloses a preparation method and application of multi-size monodisperse gold nanoparticle, the maximum size of the gold nanoparticle is 90-120 nm.
CN109108270a discloses a method for preparing gold nano-sheet by reducing antimony trichloride, and the size of the prepared gold sheet is 300-800 nm.
Moreover, the gold powder prepared by the method disclosed in the prior patent is often too wide in particle size distribution and small in size, and cannot well meet the actual use requirements of the electronic paste. Therefore, the gold powder synthesis method and the structure control technology which are jointly composed of submicron spherical and micron flaky gold powder are all the key technologies to be broken through in China.
Disclosure of Invention
The invention aims to provide a preparation method for directly synthesizing gold powder with coexistence of micron sheets and submicron particles by a one-step method, which can effectively solve the problem of accurate regulation and control of structures, sizes and shapes of the micron sheets and submicron particles, and has simple and convenient regulation and control means and easy control.
According to the invention, alkyl ammonium halide (with the carbon number more than or equal to 9) is used as a surfactant, ascorbic acid is used as a reducing agent, and gold powder with coexisting micron flakes and submicron particles is prepared in one pot at a relatively low temperature and in a short time through temperature gradient change. The gold powder prepared by the method can be widely applied to the fields of semiconductor packaging, multilayer wiring circuits, high-reliability military electronic materials and the like.
In order to achieve the above purpose, the invention provides a gold powder synthesis method with coexistence of micron sheets and submicron particles, which adopts the following technical scheme that the method comprises the following specific steps:
(1) Dissolving chloroauric acid in deionized water to prepare a solution a for later use;
(2) Dissolving a surfactant in deionized water to prepare a solution b for standby;
(3) Dissolving a reducing agent in deionized water to prepare a solution c for standby;
(4) Fully mixing the solution a and the solution b under the stirring condition to obtain a mixed solution d;
(5) Placing the solution c and the solution d at a specific temperature for a certain time, and then adding the solution c into the solution d for fully mixing to obtain a mixed solution e;
(6) Reacting the mixed solution e for a period of time under the temperature and stirring conditions in the step (5), then raising the reaction temperature, and continuing to react for a period of time to obtain gold powder stock solution;
(7) And (3) washing, separating and drying the gold powder stock solution obtained in the step (6) to obtain gold powder with coexistence of the micron sheets and submicron particles.
The mass concentration of chloroauric acid in the solution a is 50-200 g/L.
The surfactant in the solution b is alkyl ammonium halide (the carbon number is more than or equal to 9), and the mass concentration is 10-150 g/L.
Preferably:
the surfactant in the solution b is one of dodecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium iodide, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride and hexadecyl trimethyl ammonium iodide, and the mass concentration of the surfactant is 30-120 g/L;
the mass concentration of the ascorbic acid in the solution c is 25-150 g/L;
the stirring speed in the solution d is 0-300 rpm, and the stirring time is 1-30 min;
the first gradient temperature in the step (6) is 1-10 ℃, the reaction time is 1-60 min, the second gradient temperature is 60-90 ℃, and the reaction time is 20-60 min;
the vacuum drying temperature in the step (7) is 60-80 ℃ and the drying time is 60-720 min.
The gold powder prepared by the preparation method has the content of gold micron sheets of 30-80 percent and submicron particles of 70-20 percent; the shape of the micrometer sheet is hexagonal and triangular, and the size range is 1-5 mu m; the thickness range of the sheet is 100-800nm; the particle size of the submicron particles is in the range of 0.3-1.0 μm.
The technical principle of the invention is described as follows:
(1) The synthesis of gold powder generally goes through two processes, the nucleation stage and the growth stage, respectively. In the nucleation stage, gold ions are reduced under the combined action of a proper surfactant and a reducing agent to form gold seed crystals with specific morphology, and the forming proportion of the flaky gold seed crystals directly determines the ratio of the subsequent flaky gold powder in the product; during the growth phase, the rest of gold ions in the solution are gradually reduced and directionally deposited on the gold seed crystal, and finally the gold powder with a specific structure is grown. In general, the nucleation stage is very rapid and difficult to control, and if the reaction is carried out at a relatively high temperature at the beginning, the gold ions are more prone to be rapidly reduced to isotropic spherical or spheroidal particles than to two-dimensional sheet structures;
(2) The invention adopts a temperature gradient change method to effectively regulate and control the whole synthesis process. First, at a first gradient temperature, a lower reaction temperature is more favorable for the directional formation of the two-dimensional sheet Jin Jingchong in terms of kinetics theory; conversely, higher reaction temperatures increase the proportion of particles produced; then, at the second gradient temperature, a slightly higher temperature can promote the rapid growth of the flaky gold seeds formed in the first stage into micron-sized gold flakes with proper size. In addition, the fine regulation and control of the flaking rate, the size and the granularity distribution of the prepared gold powder can be realized through the specific reaction temperature and the reaction time under two temperature gradients.
The beneficial effects of the invention are as follows:
(1) The invention provides a preparation method of gold powder, which does not need to prepare gold nano seed crystal solution in advance, is different from common single-morphology gold powder, can prepare gold powder with coexisting micron sheets and submicron particles in one step, and is suitable for serving as a conductive functional phase of electronic slurry.
(2) The invention can realize the fine regulation and control of the flaking rate, the size and the granularity distribution of the prepared gold powder by regulating and controlling the reaction temperature, the reaction time and other means under the temperature gradient, has simple whole production process, low production cost, safety and environmental protection and is easy to realize industrialization.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a Scanning Electron Microscope (SEM) image of gold powder coexisting with micro-flakes and sub-micro particles prepared in example 1 of the present invention, with a scale of 20. Mu.m.
FIG. 3 is a Scanning Electron Microscope (SEM) image of a gold powder coexisting with a micro-sheet and sub-micro particles prepared in comparative example 1 according to the present invention, with a scale of 10. Mu.m.
FIG. 4 is a Scanning Electron Microscope (SEM) image of a gold powder coexisting with a micro-sheet and sub-micro particles prepared in comparative example 2 according to the present invention, with a scale of 20. Mu.m.
FIG. 5 is a Scanning Electron Microscope (SEM) image of a gold powder coexisting with a fine flake and a submicron particle prepared in comparative example 3 according to the present invention, with a scale of 5. Mu.m.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of gold powder with coexisting micron sheets and submicron particles, which comprises the following steps:
(1) Dissolving chloroauric acid in deionized water to prepare a solution a for later use;
(2) Dissolving a surfactant in deionized water to prepare a solution b for standby;
(3) Dissolving a reducing agent in deionized water to prepare a solution c for standby;
(4) Fully mixing the solution a and the solution b under the stirring condition to obtain a mixed solution d;
(5) Placing the solution c and the solution d at a specific temperature for a certain time, and then adding the solution c into the solution d for fully mixing to obtain a mixed solution e;
(6) Reacting the mixed solution e for a period of time at the temperature of the step (5) and the stirring speed, increasing the reaction temperature, and continuing to react for a period of time to obtain gold powder stock solution;
(7) And (3) washing, separating and drying the gold powder stock solution obtained in the step (6) to obtain gold powder with coexistence of the micron sheets and submicron particles.
The technical scheme and beneficial effects of the present invention are further described below in conjunction with specific embodiments.
Example 1, the preparation procedure is as follows:
(1) 32g of chloroauric acid is dissolved in 0.16L of deionized water to prepare a solution a for standby;
(2) 72g of dodecyl trimethyl ammonium chloride is dissolved in 1.6L of deionized water to prepare a solution b for later use;
(3) 13.6g of ascorbic acid is dissolved in 0.4L of deionized water to prepare a solution c for standby;
(4) Fully mixing the solution a and the solution b under the stirring condition, wherein the stirring speed is 250rpm, and the stirring time is 5min, so as to obtain a mixed solution d;
(5) Adjusting the temperature of the solution c and the solution d to 10 ℃, preserving the temperature for 10min, adding the solution c into the solution d, fully mixing, stirring at the speed of 250rpm for 1min, and obtaining a mixed solution e;
(6) Standing the mixed solution e at the temperature of the step (5) for reaction for 10min, increasing the reaction temperature to 90 ℃, and continuing the reaction for 30min to obtain a gold powder stock solution;
(7) And (3) carrying out centrifugal washing and separation treatment on the gold powder stock solution obtained in the step (6) by using absolute ethyl alcohol, and then placing the obtained precipitate in a vacuum drying oven at 60 ℃ for drying for 60min to obtain the gold powder with the coexistence of the micron flakes and submicron particles.
The gold powder prepared in this example consists of particles and flakes, the flake gold powder having a size range of 2 to 5 μm; the particle size range of the submicron particles is 0.8-1.0 mu m, and the use requirement of the electronic paste can be better met.
Comparative example 1, the preparation procedure is as follows:
(1) 32g of chloroauric acid is dissolved in 0.16L of deionized water to prepare a solution a for standby;
(2) 72g of dodecyl trimethyl ammonium chloride is dissolved in 1.6L of deionized water to prepare a solution b for later use;
(3) 13.6g of ascorbic acid is dissolved in 0.4L of deionized water to prepare a solution c for standby;
(4) Fully mixing the solution a and the solution b under the stirring condition, wherein the stirring speed is 250rpm, and the stirring time is 5min, so as to obtain a mixed solution d;
(5) Adjusting the temperature of the solution c and the solution d to 10 ℃, preserving the temperature for 10min, adding the solution c into the solution d, fully mixing, stirring at the speed of 250rpm for 1min, and obtaining a mixed solution e;
(6) Continuously standing the mixed solution e at the temperature of the step (5) for 60min to prepare gold powder stock solution;
(7) And (3) carrying out centrifugal washing and separation treatment on the gold powder stock solution obtained in the step (6) by using absolute ethyl alcohol, and then placing the obtained precipitate in a vacuum drying oven at 60 ℃ for drying for 60min to obtain the gold powder with the coexistence of the micron flakes and submicron particles.
This comparative example did not employ a temperature gradient change and reacted for the same period of time under the same first gradient temperature conditions as in example 1. The result shows that the gold powder consists of particles and flakes, but the particle size ranges of the flakes and the particles are less than 1.0 mu m, the whole reaction is incomplete, and the final yield of the gold powder is low.
Comparative example 2, the preparation procedure is as follows:
(1) 32g of chloroauric acid is dissolved in 0.16L of deionized water to prepare a solution a for standby;
(2) 72g of dodecyl trimethyl ammonium chloride is dissolved in 1.6L of deionized water to prepare a solution b for later use;
(3) 13.6g of ascorbic acid is dissolved in 0.4L of deionized water to prepare a solution c for standby;
(4) Fully mixing the solution a and the solution b under the stirring condition, wherein the stirring speed is 250rpm, and the stirring time is 5min, so as to obtain a mixed solution d;
(5) Heating the solution c and the solution d to 90 ℃, preserving heat at the temperature for 10min, adding the solution c into the solution d, fully mixing, stirring at the speed of 250rpm for 1min, and obtaining a mixed solution e;
(6) Continuously standing the mixed solution e at the temperature of the step (5) for reaction for 40min to obtain gold powder stock solution;
(7) And (3) carrying out centrifugal washing and separation treatment on the gold powder stock solution obtained in the step (6) by using absolute ethyl alcohol, and then placing the obtained precipitate in a vacuum drying oven at 60 ℃ for drying for 60min to obtain the gold powder with the coexistence of the micron flakes and submicron particles.
The comparative example did not employ a temperature gradient change and reacted for the same period of time at the same second gradient temperature as in example 1, and the results showed that the product consisted of a large amount of granular gold powder with a small proportion (< 30%) of flaky gold powder, and that the particle size distribution of the particles was wider and the particle size range was 0.5 to 1.8 μm.
Comparative example 3, the preparation procedure is as follows:
(1) 32g of chloroauric acid is dissolved in 0.16L of deionized water to prepare a solution a for standby;
(2) 30g of polyvinylpyrrolidone (K30) is dissolved in 1.6L of deionized water to prepare a solution b for later use;
(3) 13.6g of ascorbic acid is dissolved in 0.4L of deionized water to prepare a solution c for standby;
(4) Fully mixing the solution a and the solution b under the stirring condition, wherein the stirring speed is 250rpm, and the stirring time is 5min, so as to obtain a mixed solution d;
(5) Adjusting the temperature of the solution c and the solution d to 10 ℃, preserving the temperature for 10min, adding the solution c into the solution d, fully mixing, stirring at the speed of 250rpm for 1min, and obtaining a mixed solution e;
(6) Standing the mixed solution e at the temperature of the step (5) for reaction for 10min, increasing the reaction temperature to 90 ℃, and continuing the reaction for 30min to obtain a gold powder stock solution;
(7) And (3) carrying out centrifugal washing and separation treatment on the gold powder stock solution obtained in the step (6) by using absolute ethyl alcohol, and then placing the obtained precipitate in a vacuum drying oven at 60 ℃ for drying for 60min to obtain the gold powder with the coexistence of the micron flakes and submicron particles.
The gold powder prepared in the comparative example mainly consists of 100-300 nm ultrafine particles, and only a small amount of 200-500 nm flaky gold powder is generated, which indicates that under the reaction condition, the gold powder with coexisting micron flakes and submicron particles cannot be prepared by directly replacing alkyl ammonium halide surfactant with polyvinylpyrrolidone and other dispersing agents.
The above embodiments are only some embodiments of the present invention, and are not limited to the technical solutions of the present invention, and any technical solution that can be implemented on the basis of the above embodiments without inventive effort should be considered as falling within the scope of protection of the patent claims of the present invention.
Claims (4)
1. The preparation method of the gold powder with coexistence of the micron sheets and the submicron particles is characterized by comprising the following steps:
(1) Dissolving chloroauric acid in deionized water to prepare a solution a for standby, wherein the mass concentration of the chloroauric acid in the solution a is 50-200 g/L;
(2) Dissolving a surfactant in deionized water to prepare a solution b for standby; the surfactant in the solution b is alkyl ammonium halide, wherein the carbon number is more than or equal to 9, and the mass concentration of the surfactant is 30-120 g/L;
(3) Dissolving a reducing agent in deionized water to prepare a solution c for later use, wherein the reducing agent is ascorbic acid, and the mass concentration of the ascorbic acid is 25-150 g/L;
(4) Fully mixing the solution a and the solution b under the stirring condition to obtain a mixed solution d;
(5) Placing the solution c and the solution d at 1-10 ℃ and preserving heat for 5-60 min, and then adding the solution c into the solution d for fully mixing to obtain a mixed solution e;
(6) Reacting the mixed solution e for 1-60 min at the temperature of 1-10 ℃ and the stirring speed of 0-300 rpm for 1-30 min, then raising the reaction temperature to 60-90 ℃ and continuing the reaction for 20-60 min to obtain a gold powder stock solution;
(7) Washing, separating and drying the gold powder stock solution obtained in the step (6) to obtain gold powder with coexistence of the micron sheets and submicron particles, wherein the gold powder comprises the following components: the content of the gold micron sheet is 30-80%, and the content of submicron particles is 70-20%; the shape of the micrometer sheet is hexagonal and triangular, and the size range is 1-5 mu m; the thickness range of the sheet is 100-800nm; the particle size of the submicron particles is 0.3-1.0 μm.
2. The method for producing gold powder in which micro-flakes and sub-micro particles coexist according to claim 1, wherein the surfactant in the solution b is one of dodecyltrimethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium iodide, tetradecyltrimethylammonium bromide, tetradecyltrimethylammonium chloride, tetradecyltrimethylammonium iodide, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride and hexadecyltrimethylammonium iodide.
3. The method for producing gold powder with coexistence of micro-flakes and sub-micro-particles according to claim 1, wherein the stirring speed of the solution d is 50-300 rpm and the stirring time is 1-30 min.
4. The method for producing gold powder with coexistence of micro-sized pieces and sub-sized particles according to claim 1, wherein in step (7), the gold powder stock solution is subjected to washing and separation treatment, and the obtained precipitate is dried in a vacuum drying oven at 60-80 ℃ for 60-720 min, so as to produce gold powder with coexistence of micro-sized pieces and sub-sized particles.
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