CN116652204B - Spherical gold powder and preparation method thereof - Google Patents
Spherical gold powder and preparation method thereof Download PDFInfo
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- CN116652204B CN116652204B CN202310934512.4A CN202310934512A CN116652204B CN 116652204 B CN116652204 B CN 116652204B CN 202310934512 A CN202310934512 A CN 202310934512A CN 116652204 B CN116652204 B CN 116652204B
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 68
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010931 gold Substances 0.000 claims abstract description 34
- 229910052737 gold Inorganic materials 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 238000010306 acid treatment Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- CABDFQZZWFMZOD-UHFFFAOYSA-N hydrogen peroxide;hydrochloride Chemical compound Cl.OO CABDFQZZWFMZOD-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- -1 hydrochloric acid-hydrogen peroxide gold Chemical compound 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920000084 Gum arabic Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 235000010489 acacia gum Nutrition 0.000 claims description 3
- 239000000205 acacia gum Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 235000001727 glucose Nutrition 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 6
- 239000000843 powder Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 72
- 230000000052 comparative effect Effects 0.000 description 20
- 239000000919 ceramic Substances 0.000 description 12
- 230000006872 improvement Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 244000215068 Acacia senegal Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant 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
- B22F1/065—Spherical particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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 discloses spherical gold powder and a preparation method thereof, and relates to the technical field of metal powder. The gold is dissolved by using hydrochloric acid and hydrogen peroxide to obtain chloroauric acid solution, the concentration of the chloroauric acid solution is controlled within a preset range, alkali treatment and acid treatment are respectively carried out on the chloroauric acid solution, and then dispersing agent and reducing agent are added to prepare the spherical gold powder. In the preparation process of spherical gold powder, the pH of the gold-containing complex is reduced to below 1.8 by using hydrochloric acid, and the gold powder prepared by the method can be in a spherical shape with regular shape and smooth surface, has the particle size of 1.0-3.0 mu m, has uniform particle size, small specific surface area and good dispersibility, can be directly mixed with various resins without post treatment, has no agglomeration phenomenon, and has excellent compatibility by combining a one-time quick dumping mode of a reducing agent and the concentration control of chloroauric acid.
Description
Technical Field
The invention relates to the technical field of metal powder, in particular to spherical gold powder and a preparation method thereof.
Background
Porcelain is one of the most widely used vessels in daily life, and with the improvement of the material and culture level of people, the requirements on the ornamental value and the functionality of ceramic products are higher and higher, and the requirements of people cannot be met by the traditional ceramic products. Gold is a noble metal that has been favored by people and has begun to be used in various porcelain applications due to its excellent decorative properties.
At present, the micron-sized gold powder prepared at home and abroad is generally applied to the fields of electronic gold paste and conductive paste, and almost no application relates to the ceramic field, and the use of the gold powder in the ceramic gold paste field not only requires good dispersibility, but also requires that the gold powder does not contain toxic and harmful substances. So far, researchers have developed many experimental methods to prepare gold powder, however, the prepared gold powder cannot meet the application requirements in the ceramic field.
In the prior art, the patent with publication number CN1772422A discloses a preparation method of micron-sized spherical gold powder for decoration, which is prepared by FeSO 4 And (3) preparing gold powder by reducing chloroauric acid by the solution. However, during the preparation, fe is generated after the reaction 3+ Incomplete cleaning, fe 3+ The salt exists in the gold powder, and impurities are introduced, so that the gold powder is insufficient in purity, and the use effect is affected; in addition, the electron microscope result shows that the gold powder prepared by the method has serious agglomeration and large particle size distribution range, and is not suitable for being used in ceramic gold paste. The patent with publication number CN 115026300A discloses a preparation method of spherical gold powder for conductive paste, which needs to remove nitrate when preparing chloroauric acid solution, and yellow smoke is emitted from the solution during the nitrate removal, thus severely polluting the environment; meanwhile, the nitrate removal temperature is generally between 90 ℃ and 130 ℃, the requirement on the temperature in the experimental process is high, and dangers exist; in addition, halogen salt is added in the preparation process, and impurity ions can be possibly introduced.
In view of the above, there is a need to design a spherical gold powder and a preparation method thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide spherical gold powder which has uniform granularity, small specific surface area, good dispersibility, no toxic or harmful substances, regular shape and smooth surface and a preparation method thereof.
In order to achieve the above object, the present invention provides a method for preparing spherical gold powder, comprising the steps of:
s1, adding a predetermined amount of gold particles into a hydrochloric acid-hydrogen peroxide gold-dissolving solution, heating and stirring, adding hydrogen peroxide in the reaction process, and filtering to obtain a chloroauric acid solution;
s2, pretreating the chloroauric acid solution prepared in the step S1, performing alkali treatment on the chloroauric acid solution by using alkali liquor to form a gold-containing complex, uniformly mixing, and adding acid liquor for acid treatment to obtain a first solution;
s3, pouring a predetermined amount of dispersant solution into the first solution prepared in the step S2 to obtain a second solution; then pouring a predetermined amount of reducing agent into the second solution at one time, stirring and performing ultrasonic treatment to obtain a third solution;
s4, taking the reaction precipitate in the third solution prepared in the step S3, washing and drying to obtain spherical gold powder.
As a further improvement of the present invention, in step S2, the specific operation of the alkali treatment is as follows: adjusting the pH value of chloroauric acid solution to 7-8 by using alkali liquor, wherein the alkali liquor is ammonia water with the concentration of 10-15 wt%; the specific operation of the acid treatment is as follows: the pH value of chloroauric acid solution is adjusted to be below 1.8 by using acid liquor, wherein the acid liquor is hydrochloric acid with the concentration of 10-20wt%.
As a further improvement of the present invention, in step S2, the pretreatment is to dilute the chloroauric acid solution so that the concentration of chloroauric acid in the chloroauric acid solution is 0.01-0.04g/mL.
As a further improvement of the invention, in the step S1, the mass volume ratio of the gold particles to the hydrochloric acid and the hydrogen peroxide in the hydrochloric acid-hydrogen peroxide gold-dissolving solution is 1 (3.5-4.0): 0.5-1; the mass volume ratio of the gold particles to the added hydrogen peroxide is 1 (0.5-1).
As a further improvement of the invention, the concentration of hydrochloric acid in the hydrochloric acid-hydrogen peroxide gold dissolving solution is 6mol/L, and the concentration of hydrogen peroxide is 30wt%.
As a further improvement of the invention, in the step S1, the heating temperature of the heating and stirring is 60-80 ℃.
As a further improvement of the invention, the mass ratio of chloroauric acid in the chloroauric acid solution to the dispersing agent is 1 (0.1-0.25); the dispersing agent comprises any one of polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecyl sulfonate, citric acid, ethylenediamine tetraacetic acid, polyethylene glycol, polyvinyl alcohol and gum arabic.
As a further improvement of the invention, the mass ratio of chloroauric acid in the chloroauric acid solution to the reducing agent is 1 (1.1-1.5); the reducing agent comprises any one of ascorbic acid, oxalic acid, sodium sulfite and glucose.
As a further improvement of the present invention, in step S3, the stirring and the ultrasonic treatment specifically include: stirring at 200-300r/min under water bath condition of 25-30deg.C for 30-60min, and simultaneously performing ultrasonic treatment.
The invention also provides spherical gold powder, which is prepared according to the preparation method of the spherical gold powder in the technical scheme, wherein the spherical gold powder has a smooth surface and a particle size of 1.0-3.0 mu m.
The beneficial effects of the invention are as follows:
according to the invention, the pH of the gold-containing complex is reduced to below 1.8 by using hydrochloric acid, and the gold powder can be formed into a spherical shape with a regular shape and a smooth surface by combining a one-time quick dumping mode of the reducing agent, so that the dispersibility of the gold powder is effectively improved, burrs are prevented from being generated on the surface of the gold powder due to overhigh pH value or too slow speed of pouring the reducing agent into the second solution, the gold powder cannot form a spherical shape with a smooth surface, and the powder is easy to agglomerate due to large specific surface area caused by the generation of the burrs.
According to the invention, gold is preliminarily dissolved by using the hydrochloric acid and the hydrogen peroxide with specific dosage, and the gold can be fully dissolved by combining the additional treatment of the hydrogen peroxide in the heating and stirring process, so that chloroauric acid with a certain concentration is prepared. Compared with the existing nitrate removal treatment, the preparation process is simple, does not generate toxic and harmful substances, and meets the environmental protection requirement. Meanwhile, the use concentration of chloroauric acid is controlled within a certain range, so that the phenomenon that gold powder cannot form a spherical shape due to the fact that the chloroauric acid concentration is too high and burrs are formed on the surface of the gold powder to enable the gold powder to agglomerate can be avoided, meanwhile, the problem that the size of the gold powder is too large due to the fact that the chloroauric acid concentration is too low is avoided, and therefore the spherical gold powder with good dispersivity and the average particle size of 1.0-3.0 mu m is prepared.
The preparation method of the spherical gold powder has the advantages of safe reaction conditions, simple and easily controlled preparation process, short production period, uniform granularity, small specific surface area, good dispersibility, no agglomeration phenomenon, good wettability with an organic carrier, no toxic and harmful elements and substances, no need of aftertreatment, direct mixing with various resins, excellent compatibility, uniform adhesion on the surface of ceramics after sintering, difficult falling off, and wide application in ceramics including ceramic vases, ceramic sculptures, ceramic wares, ceramic tableware, tea sets and the like.
Drawings
FIG. 1 shows the result of a scanning electron microscope of the spherical gold powder prepared in example 1.
FIG. 2 is a scanning electron microscope result of the spherical gold powder prepared in comparative example 1.
FIG. 3 is a scanning electron microscope result of the spherical gold powder prepared in comparative example 2.
FIG. 4 is a scanning electron microscope result of the spherical gold powder prepared in comparative example 3.
FIG. 5 is a scanning electron microscope result of the spherical gold powder prepared in comparative example 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in detail with reference to the accompanying drawings and specific embodiments.
It should be noted that, in order to avoid obscuring the present invention due to unnecessary details, only structures and/or processing steps closely related to aspects of the present invention are shown in the drawings, and other details not greatly related to the present invention are omitted.
In addition, it should be further noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a preparation method of spherical gold powder, which comprises the following steps:
s1, adding a predetermined amount of gold particles into a hydrochloric acid-hydrogen peroxide gold-dissolving solution, heating and stirring, adding a certain amount of hydrogen peroxide in the reaction process until the gold particles are completely dissolved, and filtering by a solvent filter to obtain a chloroauric acid solution;
s2, diluting the chloroauric acid solution prepared in the step S1 to a concentration of 0.01-0.04g/mL, adjusting the pH value of the chloroauric acid solution to 7-8 by using ammonia water with a concentration of 10-15wt% to form a gold-containing complex, and adjusting the pH value of the chloroauric acid solution to below 1.8 by using hydrochloric acid with a concentration of 10-20wt% to obtain a first solution;
s3, pouring a predetermined amount of dispersant solution into the first solution prepared in the step S2 to obtain a second solution; then pouring a predetermined amount of reducing agent into the second solution at one time, stirring and performing ultrasonic treatment to obtain a third solution;
s4, taking the reaction precipitate in the third solution prepared in the step S3, washing and drying to obtain spherical gold powder.
Specifically, in the step S1, the mass volume ratio of gold particles to hydrochloric acid and hydrogen peroxide in the hydrochloric acid-hydrogen peroxide gold-dissolving solution is 1 (3.5-4.0): 0.5-1; the concentration of hydrochloric acid in the hydrochloric acid-hydrogen peroxide gold dissolving solution is 6mol/L, and the concentration of hydrogen peroxide is 30wt%; the mass volume ratio of the gold particles to the added hydrogen peroxide is 1 (0.5-1); heating and stirring until gold particles are completely dissolved, wherein the heating temperature is 60-80 ℃.
Specifically, in step S3, the stirring and the ultrasonic treatment specifically include: under the water bath condition of 25-30 ℃, stirring continuously for 30-60min at the rotating speed of 200-300r/min until the reaction is complete, inserting the probe of the ultrasonic cell grinder below the liquid level, and carrying out ultrasonic treatment at the energy output of 20Hz until the reaction is completely stopped. The spherical gold powder is further dispersed by utilizing the dispersion effect of ultrasonic waves in the liquid.
Specifically, in step S4, the dispersing agent includes any one of polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecyl sulfonate, citric acid, ethylenediamine tetraacetic acid, polyethylene glycol, polyvinyl alcohol and gum arabic, water is used as a solvent, the concentration of the dispersing agent is 0.05-0.1g/mL, and preferably, the dispersing agent is polyvinylpyrrolidone; the mass ratio of chloroauric acid to the dispersing agent in the chloroauric acid solution is 1 (0.1-0.25).
Specifically, in step S4, the reducing agent includes any one of ascorbic acid, oxalic acid, sodium sulfite, and glucose, water is used as a solvent, the concentration of the reducing agent is 0.16-0.32 g/mL, and preferably, the reducing agent is ascorbic acid; the mass ratio of chloroauric acid to the reducing agent in the chloroauric acid solution is 1 (1.1-1.5).
Specifically, in step S4, the drying temperature is 60 ℃ and the time is 20-30min.
The invention also provides spherical gold powder, which is prepared according to the preparation method of the spherical gold powder in the scheme, wherein the spherical gold powder has a smooth surface and a particle size of 1.0-3.0 mu m.
The preparation method of the spherical gold powder provided by the invention is described below with reference to specific examples.
Example 1
The embodiment provides a preparation method of spherical gold powder, which comprises the following steps:
s1, putting 10g of gold particles into a round-bottom flask, adding into a hydrochloric acid-hydrogen peroxide gold dissolving solution formed by mixing 35mL hydrochloric acid and 10mL of hydrogen peroxide, heating and stirring at 80 ℃, adding 10mL of hydrogen peroxide into the round-bottom flask in a heating and stirring process for two times, filtering to obtain HAuCl after gold is completely dissolved 4 A solution; the HAuCl 4 In the solution, the concentration of chloroauric acid is 0.2g/mL.
S2, taking 10mL of HAuCl prepared in the step S1 4 The solution was added to 40mL of deionized water to obtain a diluted chloroauric acid solution (the concentration of chloroauric acid in the chloroauric acid solution was 0.04 g/mL), the pH of the diluted chloroauric acid solution was adjusted to 7.5 using aqueous ammonia having a concentration of 12wt% to form a gold-containing complex, and the pH of the diluted chloroauric acid solution was adjusted to 1.8 using hydrochloric acid having a concentration of 15wt% to obtain a first solution.
S3, weighing 2.2g of ascorbic acid to be dissolved in 10mL of deionized water according to the chloroauric acid content in the chloroauric acid solution diluted in the step S2 to obtain a reducer solution, and weighing 0.5g of polyvinylpyrrolidone to be dissolved in 10mL of water to obtain a dispersant solution; pouring the dispersant solution into the first solution prepared in the step S2 to obtain a second solution; and pouring the reducing agent solution into the second solution at one time, continuously stirring for 30 at a rotating speed of 280r/min under the water bath condition of 30 ℃, inserting the probe of the ultrasonic cell grinder below the liquid level, and performing ultrasonic treatment for 30min at an energy output of 20Hz to obtain a third solution.
S4, standing the third solution prepared in the step S3, standing for solid-liquid delamination, pouring out supernatant, washing reaction precipitate with deionized water and ethanol, and then placing in a 60 ℃ oven for drying to obtain spherical gold powder with the average particle size of 1.2 mu m, wherein the gold powder is spherical, uniform in particle size, good in dispersibility and free of agglomeration phenomenon, as shown in figure 1.
In other embodiments of the present invention, the reaction parameters in the above steps may be appropriately adjusted as needed. For example, in step S1, the mass-to-volume ratio of gold particles to hydrochloric acid and hydrogen peroxide in the hydrochloric acid-hydrogen peroxide gold-dissolving solution may be adjusted within the range of 1 (3.5-4.0): 0.5-1, the mass-to-volume ratio of gold particles to additional hydrogen peroxide may be adjusted within the range of 1 (0.5-1), and the heating temperature of the heating and stirring may be adjusted within the range of 60-80 ℃; in step S2, the chloroauric acid concentration in the diluted chloroauric acid solution can be adjusted in the range of 0.01-0.04g/mL; in the step S3, the dosages of the dispersing agent and the reducing agent can be adjusted, the mass ratio of the chloroauric acid in the diluted chloroauric acid solution to the dispersing agent is 1 (0.1-0.25), the mass ratio of the chloroauric acid in the diluted chloroauric acid solution to the reducing agent is 1 (1.1-1.5), the water bath condition temperature during stirring can be adjusted within the range of 25-30 ℃, the rotating speed during stirring is adjusted to be within the range of 200-300r/min, and the stirring time is adjusted to be within the range of 30-60 min. After the reaction parameters are adjusted within the above ranges, the prepared spherical gold powder is spherical particles with smooth surfaces, similar to that of example 1, and has a particle size ranging from 1.0 to 3.0 μm and good dispersibility.
Comparative examples 1 to 5
Comparative examples 1 to 5 respectively provide a method for preparing gold powder, in which the pH of the diluted chloroauric acid solution is adjusted to 3 in step S2 of comparative example 1, as compared with example 1; comparative example 2 the reducing agent in step S3 was added at a rate of 3 mL/min; in step S2 of comparative example 3, the diluted chloroauric acid solution was pH-adjusted without using ammonia water; comparative example 4 HAuCl in step S2 4 Adding 10mL of water into the solution for dilution; in step S1 of comparative example 5, 10g of gold particles were put inAdding the mixture into a hydrochloric acid-hydrogen peroxide gold-dissolving solution formed by mixing 35mL of hydrochloric acid and 20mL of hydrogen peroxide in a round bottom flask at one time, and not adding hydrogen peroxide; the remaining steps of each comparative example are identical to those of example 1 and will not be described again.
In comparative example 5, hydrogen peroxide is added at one time without being added, and the high temperature process decomposes hydrogen peroxide, so that gold particles in step S1 are not completely dissolved, the yield of gold powder is seriously affected, and the subsequent steps are inconvenient to implement. The methods provided by the other comparative examples can ensure that gold particles are completely dissolved to obtain corresponding gold powder products, but the morphology of the gold powder prepared by each comparative example is obviously different.
The content and composition of the gold powder of example 1 were measured, and the measurement results are shown in table 1. The morphology of the gold powders of example 1 and comparative examples 1 to 4 was examined, and the examination results are shown in FIGS. 1 to 5.
TABLE 1 Table of the content and other Components of gold powder prepared in EXAMPLE 1
| Component analysis | Au | Ni | Cd |
| Content (%) | 99.989 | ＜0.0002 | ＜0.0002 |
| Component analysis | Ag | Cu | Fe |
| Content (%) | ＜0.0002 | ＜0.0002 | ＜0.0002 |
| Component analysis | Cr | Mn | Pb |
| Content (%) | ＜0.0002 | ＜0.0002 | ＜0.0002 |
As can be seen from Table 1, the gold powder prepared in example 1 has a high gold content and hardly contains toxic and harmful elements and substances. As can be seen from fig. 1, the gold powder prepared by the method of the present invention has smooth and regular spherical surface, uniform granularity and good dispersibility. When the pH of the acid treatment was adjusted to 3 in comparative example 1, the surface smoothness of the prepared gold powder was lowered, and burr-like substances were grown on the powder surface, and a spherical shape with a smooth surface could not be formed; in addition, the prepared gold powder has smaller particle size and is easy to agglomerate (figure 2); when the addition rate of the reducing agent in comparative example 2 is too slow, burrs are formed on the surface of the prepared gold powder, and the particle size of the gold powder is small (fig. 3); in comparative example 3, no pH adjustment treatment with ammonia water was performed during the preparation of gold powder, no spherical gold powder was obtained, and the prepared gold powder had irregular morphology and no dispersion of particles (fig. 4); when the concentration of chloroauric acid solution used in comparative example 4 was too high, the prepared gold powder had a particle size of 100-200nm, was serious in agglomeration and poor in dispersibility (fig. 5), and in addition, the prepared gold powder was black brown after being dried.
In summary, according to the spherical gold powder and the preparation method thereof disclosed by the invention, the pH of the gold-containing complex is reduced to below 1.8 by using hydrochloric acid, and the gold powder can be formed into a spherical shape with regular shape and smooth surface by combining a one-time rapid dumping mode of a reducing agent, so that the dispersibility of the gold powder is effectively improved; the phenomenon that the surface of the gold powder is not smooth and burrs are generated due to overhigh pH value of the reaction solution or too slow pouring speed of the reducing agent into the second solution, so that the powder is easy to agglomerate due to large specific surface area of the gold powder is avoided. Meanwhile, the use concentration of the chloroauric acid is controlled within a certain range, so that the phenomenon of agglomeration of gold powder caused by too small particle size of the gold powder due to too high concentration of the chloroauric acid can be avoided, and meanwhile, the phenomenon of too large size of the gold powder caused by too low concentration of the chloroauric acid is avoided, so that the spherical gold powder with high sphericity and good dispersity, wherein the average particle size of the spherical gold powder is 1.0-3.0 mu m, is prepared.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present invention.
Claims (5)
1. The preparation method of the spherical gold powder is characterized by comprising the following steps:
s1, adding a predetermined amount of gold particles into a hydrochloric acid-hydrogen peroxide gold-dissolving solution, heating and stirring, adding hydrogen peroxide in the reaction process, and filtering to obtain a chloroauric acid solution; the mass volume ratio of the gold particles to the hydrochloric acid and the hydrogen peroxide in the hydrochloric acid-hydrogen peroxide gold-dissolving solution is 1 (3.5-4.0): 0.5-1; the mass volume ratio of the gold particles to the added hydrogen peroxide is 1 (0.5-1);
s2, pretreating the chloroauric acid solution prepared in the step S1, performing alkali treatment on the chloroauric acid solution by using alkali liquor to form a gold-containing complex, uniformly mixing, and adding acid liquor for acid treatment to obtain a first solution; the pretreatment is to dilute the chloroauric acid solution so that the concentration of chloroauric acid in the chloroauric acid solution is 0.01-0.04g/mL; the specific operation of the alkali treatment is as follows: adjusting the pH value of chloroauric acid solution to 7-8 by using alkali liquor, wherein the alkali liquor is ammonia water with the concentration of 10-15 wt%; the specific operation of the acid treatment is as follows: adjusting the pH value of chloroauric acid solution to be below 1.8 by using acid liquor, wherein the acid liquor is hydrochloric acid with the concentration of 10-20wt%;
s3, pouring a predetermined amount of dispersant solution into the first solution prepared in the step S2 to obtain a second solution; then pouring a predetermined amount of reducing agent into the second solution at one time, stirring and performing ultrasonic treatment to obtain a third solution; the mass ratio of chloroauric acid in the chloroauric acid solution to the dispersing agent is 1 (0.1-0.25); the dispersing agent comprises any one of polyvinylpyrrolidone, cetyltrimethylammonium bromide, sodium dodecyl sulfonate, citric acid, ethylenediamine tetraacetic acid, polyethylene glycol, polyvinyl alcohol and gum arabic; the mass ratio of chloroauric acid in the chloroauric acid solution to the reducing agent is 1 (1.1-1.5); the reducing agent comprises any one of ascorbic acid, oxalic acid, sodium sulfite and glucose;
s4, taking the reaction precipitate in the third solution prepared in the step S3, washing and drying to obtain spherical gold powder.
2. The method for preparing spherical gold powder according to claim 1, characterized in that: the concentration of hydrochloric acid in the hydrochloric acid-hydrogen peroxide gold dissolving solution is 6mol/L, and the concentration of hydrogen peroxide is 30wt%.
3. The method for preparing spherical gold powder according to claim 1, characterized in that: in the step S1, the heating temperature of the heating and stirring is 60-80 ℃.
4. The method for preparing spherical gold powder according to claim 1, characterized in that: in step S3, the stirring and ultrasonic treatment specifically includes: stirring at 200-300r/min under water bath condition of 25-30deg.C for 30-60min, and simultaneously performing ultrasonic treatment.
5. A spherical gold powder, characterized in that the spherical gold powder is prepared according to the preparation method of the spherical gold powder of any one of claims 1 to 4, the spherical gold powder has a smooth surface and a particle diameter of 1.0 to 3.0 μm.
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