CN117620164A - Silver-plated nickel powder and industrial preparation method and application thereof - Google Patents
Silver-plated nickel powder and industrial preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 165
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 75
- 229910052709 silver Inorganic materials 0.000 claims abstract description 68
- 239000004332 silver Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000007747 plating Methods 0.000 claims abstract description 26
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004381 surface treatment Methods 0.000 claims abstract description 15
- 238000009776 industrial production Methods 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 21
- 239000003945 anionic surfactant Substances 0.000 claims description 13
- 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 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000003064 anti-oxidating effect Effects 0.000 claims description 3
- -1 fatty alcohol sulfate Chemical class 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 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 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000003929 acidic solution Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 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 2
- 239000008103 glucose Substances 0.000 claims description 2
- 229960001031 glucose Drugs 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 235000019263 trisodium citrate Nutrition 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- 235000019256 formaldehyde Nutrition 0.000 claims 1
- 229960004279 formaldehyde Drugs 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 10
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001994 activation Methods 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000010953 base metal Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
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- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 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
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses silver-plated nickel powder and an industrialized preparation method and application thereof, and relates to the technical field of surface treatment of metal powder and preparation of composite powder, wherein the industrialized preparation method of the silver-plated nickel powder comprises the following steps: s1, nickel powder surface treatment; s2, active center formation: uniformly dispersing silver nano particles with negative charges and a surfactant in a solvent, then adding nickel powder subjected to surface treatment and a reducing agent, and adjusting the pH value of a system to be more than 11 to obtain a nickel powder reducing solution; s3, silver plating: and (3) dripping the silver ammine complex solution into a nickel powder reducing solution to react, so as to obtain silver-plated nickel powder. The silver layer on the surface of the silver-plated nickel powder is compact, low in volume resistivity, good in oxidation resistance and excellent in comprehensive performance, and the preparation method is simple in process, low in cost and easy for industrial production.
Description
Technical field:
the invention relates to the technical field of metal powder surface treatment and composite powder preparation, in particular to silver-plated nickel powder and an industrial preparation method and application thereof.
The background technology is as follows:
in electronics, electrical appliances, communications, modern electronic warfare, warships, nuclear submarines, effective shielding measures are required in order to prevent external electromagnetic interference and to prevent electromagnetic waves of the device from radiating outwards. At present, conductive paste or conductive rubber is mostly used for solving the problems of electromagnetic wave interference and shielding of electronic products, and the conductive paste is also an important component of electronic ceramic elements and solar photovoltaic panels.
The base metal is used for replacing noble metals such as silver, gold, palladium and the like, and the preparation of conductive slurry, conductive coating and conductive rubber is a pursuit target, and becomes an important trend and a necessary trend of the electronic industry materials in the future. The base metal is used for replacing noble metal, so that the defects of the noble metal electronic paste can be overcome, and the metal powder of the base metal nickel is mainly used for replacing the filler of the conductive paste at present. However, the following problems exist in use: firstly, pure nickel powder is easy to oxidize at high temperature, so that the pure nickel powder cannot be sintered in high-temperature air or oxidizing atmosphere for a long time, otherwise, the pure nickel powder is oxidized to lose conductivity, and the usability is affected; sintering must therefore be carried out under a protective or reducing atmosphere, but sintering equipment is expensive and unsuitable for use in an oxidizing atmosphere.
Base metal powder having excellent oxidation resistance is necessary as a conductive phase, and therefore, oxidation-resistant treatment must be performed to the base metal powder as a conductive medium. The silver-plated nickel powder is prepared by combining base metal nickel and silver, so that the antioxidation capability of the nickel powder can be greatly improved, the temperature application range of the nickel powder is widened, the defect of base metal is overcome to a great extent, and the cost of the silver powder is reduced. At present, scientific researchers also perform certain researches on silver-plated nickel powder.
The patent CN1188544C, CN108284224B, CN105880633B adopts the processes of surface cleaning, sensitization, activation and re-silvering to prepare the silver-plated nickel powder, the process is complex and difficult to control, and a large amount of waste liquid is generated in the production process, so that the industrial production is not facilitated; patent CN102218533A adopts a physical vapor deposition process to prepare silver-plated nickel powder, but has high equipment requirement, high cost and difficult industrial production; patent CN112643026A adopts surface pickling and then a direct chemical silver plating process, the process is simple, but the surface of nickel powder has no activation point, which is unfavorable for silver deposition on the surface of nickel powder, and leads to non-compact silver layer on the surface of silver plating nickel powder; the patent CN112935245A adopts a method of plating copper on the surface of nickel powder and then plating silver, and the product contains a copper plating layer in the middle, so that the oxidation resistance is reduced.
Therefore, it is very necessary to provide a silver plating method which is simple, environment-friendly, low in cost and compact in plating and is suitable for industrialization.
The invention comprises the following steps:
the invention aims to solve the problems of complicated preparation process, high cost, non-compact coating and the like in the prior art, which are unfavorable for industrial production, and provides a preparation method of silver-plated nickel powder with simple process and compact coating, which can realize industrial production.
In order to achieve the above object, one of the objects of the present invention is to provide an industrialized preparation method of silver-plated nickel powder, comprising the following steps:
s1, nickel powder surface treatment;
s2, active center formation: uniformly dispersing silver nano particles with negative charges and a surfactant in a solvent, then adding nickel powder subjected to surface treatment and a reducing agent, and adjusting the pH value of a system to be more than 11 to obtain a nickel powder reducing solution;
s3, silver plating: and (3) dripping the silver ammine complex solution into a nickel powder reducing solution to react, so as to obtain silver-plated nickel powder.
The second object of the present invention is to provide silver-plated nickel powder obtained by the aforementioned production method.
The invention further aims to provide an application of the silver-plated nickel powder in electromagnetic shielding.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the silver activation points are introduced into the surface of the nickel powder by a physical method, the uniform distribution of the silver activation points on the surface of the nickel powder is realized by the conventional process control, and the size of the activation points is equivalent because the particle size distribution of the nano silver particles is single, so that a uniform and compact silver layer is formed on the surface of the nickel powder in the subsequent silver plating process.
2. The invention adopts a one-step physical activation process to replace the conventional sensitization activation process at present, so that the process flow can be shortened, the product quality can be improved, the preparation method is environment-friendly, the cost is low, and the method is particularly suitable for industrially preparing silver-plated nickel powder.
Description of the drawings:
FIG. 1 is an SEM image of silver-plated nickel powder obtained in example 1;
fig. 2 is an SEM image of the silver-plated nickel powder obtained in comparative example 1;
FIG. 3 is an SEM image of silver-plated nickel powder obtained in example 5;
FIG. 4 is an SEM image of silver-plated nickel powder obtained in example 6;
FIG. 5 is an SEM image of silver-plated nickel powder obtained in comparative example 4;
FIG. 6 is a thermogravimetric analysis of the silver-plated nickel powder obtained in example 1;
FIG. 7 is a thermogravimetric analysis of the silver-plated nickel powder obtained in example 5.
The specific embodiment is as follows:
the invention is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the invention easy to understand.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides an industrialized preparation method of silver-plated nickel powder, which comprises the following steps:
s1, nickel powder surface treatment;
s2, active center formation: uniformly dispersing silver nano particles with negative charges and a surfactant in a solvent, then adding nickel powder subjected to surface treatment and a reducing agent, and adjusting the pH value of a system to be more than 11 to obtain a nickel powder reducing solution;
s3, silver plating: and (3) dripping the silver ammine complex solution into a nickel powder reducing solution to react, so as to obtain silver-plated nickel powder.
According to the present invention, in step S1, the method for surface treatment of nickel powder includes: the nickel powder is pickled in an acidic solution. Specifically, the nickel powder surface treatment method comprises the following steps: and (3) putting the nickel powder into dilute acid for stirring, removing an oxide layer on the surface of the nickel powder, and finally washing the nickel powder with deionized water.
The method provided by the invention is suitable for silver plating on the surfaces of nickel powder with different particle sizes, but the particle size of the nickel powder is not smaller than 1 mu m, and because the nickel powder is difficult to disperse when the particle size of the nickel powder is too small, the nickel powder can be agglomerated during silver plating, so that a complete and compact silver plating layer cannot be formed, and the performance of the silver-plated nickel powder is poor. The size of the nickel powder may be selected by those skilled in the art according to actual needs, and the median particle diameter of the nickel powder is illustratively greater than 1 μm, such as 1 μm, 2 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, or any value in the range of any two values described above.
In the present invention, if the particle size of the silver nanoparticle having negative charges is too large, it may cause a decrease in adsorption stability on the surface of nickel powder, resulting in uneven silver layer in which pure silver particles appear. Preferably, the median particle diameter of the negatively charged silver nanoparticle is 1 to 30nm, and may be, for example, 1nm, 2nm, 5nm, 8nm, 10nm, 15nm, 20nm, 25nm, 30nm or any value in the range of any two values. The negatively charged silver nanoparticles may be self-made or commercially available.
In the invention, active centers can be formed on the surface of nickel powder by only adding a trace amount of silver nano particles with negative charges, thereby realizing silver plating on the surface of the nickel powder. Preferably, the mass ratio of the silver nano particles with negative charges to the nickel powder is (2×10) -6 -1×10 -5 ):100。
In the invention, in an alkaline environment, the surface of the nickel powder has positive charges, and an electric double layer can be formed by adding the anionic surfactant, so that the dispersion effect can be improved. Preferably, the surfactant is an anionic surfactant; preferably, the anionic surfactant is sodium linear alkylbenzenesulfonate and/or fatty alcohol sulfate. In some preferred embodiments of the present invention, the anionic surfactant is added in an amount of 0.5 to 3% by mass of the nickel powder, and may be, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3 or any value in the range of any two values mentioned above.
According to the invention, in step S2, the dispersion means is preferably ultrasonic dispersion, and the silver nanoparticles having negative charges and the surfactant are uniformly dispersed in the solvent.
The inventors of the present invention have found that it is necessary to control the pH of the nickel powder reducing solution to 11 or more, and for example, it may be 12, 13, 14 or any value in the range of any two values. If the pH value is too low, the reduction rate of silver in the silver plating process is low, the silver content of the surface of the silver-plated nickel powder is low, and the volume resistivity of the silver-plated nickel powder is increased and the oxidation resistance is reduced.
In the present invention, in order to enhance the dissolution and dispersion effects of the surfactant, the solvent is preferably a mixed solvent of deionized water and ethanol. Further, the mass ratio of the deionized water to the ethanol is 8:2-9:1.
In the present invention, the reducing agent includes, but is not limited to, at least one of trisodium citrate, potassium sodium tartrate, glucose, formaldehyde, and ascorbic acid.
In the present invention, the preparation method of the silver ammine complex solution may be known to those skilled in the art, and the preparation method of the silver ammine complex solution may include: dissolving silver nitrate with deionized water, and then adding a complexing agent to prepare a silver ammonia complex solution; wherein the complexing agent can be one of ammonia water, ethylenediamine, diethylenetriamine and triethylenetetramine.
The invention also provides silver-plated nickel powder prepared by the preparation method.
Under the preferable condition, the median particle diameter of the silver-plated nickel powder is 1-50 mu m, and the surface silver content is 15-50%; further preferably, the volume resistivity of the silver-plated nickel powder is < 1×10 -4 Omega cm; more preferably, the silver-plated nickel powder has an oxidation resistance temperature of > 500 ℃.
Theoretically, the lower the volume resistivity of the silver-plated nickel powder is, the better the product performance is. The combination experiment shows that the volume resistivity of the silver-plated nickel powder is between (0.85 and 0.95) multiplied by 10 -4 Between Ω·cm, when the volume resistivity is more than 1×10 -4 Omega cm, the use requirement is not met; in addition, the denser the silver coating in the silver-plated nickel powder, the more beneficial to reducing the volume resistivity of the silver-plated nickel powder and improving the oxidation resistance of the silver-plated nickel powder. The combination experiment shows that the antioxidation temperature of the qualified product is more than 500 ℃.
The invention also provides application of the silver-plated nickel powder in electromagnetic shielding.
The present invention will be described in detail with reference to examples.
Example 1
S1, surface treatment of nickel powder: weighing 960g of deionized water in a reaction kettle, slowly adding 24g of concentrated sulfuric acid, then adding 480g of nickel powder (with the median particle diameter of 30 mu m), stirring for 30min at the rotation speed of 500r/min, removing an oxide layer on the surface of the nickel powder, and then washing with deionized water to obtain the surface-treated nickel powder.
S2, active center formation: accurately weighing 0.05mg of nano silver particles (purchased from Jiangsu Xianfeng nano materials science and technology Co., ltd., median particle diameter of 5 nm), 6g of sodium dodecyl benzene sulfonate, 3000g of deionized water and 300g of ethanol, carrying out ultrasonic and mechanical stirring composite dispersion for 30min, and then adding 480g of surface treatment nickel powder obtained in the step S1 to form stable and uniform nickel powder dispersion; 160g of potassium sodium tartrate was added thereto, and the pH was adjusted to 13.2 with sodium hydroxide to obtain a reduced solution of nickel powder.
S3, silver plating: dissolving 190g of silver nitrate with 3000g of deionized water, and adding 101g of diethylenetriamine to prepare a silver ammonia complex solution; and then, dropwise adding the silver ammonia complex solution into the nickel powder reduction solution obtained in the step S2, reacting for 2 hours, washing with deionized water, and drying at 80 ℃ for 2 hours to obtain 595g of silver-plated nickel powder.
Fig. 1 is an SEM image of the silver-plated nickel powder obtained in example 1. As can be seen from fig. 1, the silver coating on the surface of the silver-plated nickel powder obtained in example 1 has high density and no silver particles on the surface of the silver coating, which indicates that the silver coating with high density and uniformity can be prepared on the surface of the nickel powder by the method in example 1.
FIG. 6 is a thermogravimetric analysis of the silver-plated nickel powder obtained in example 1. As can be seen from FIG. 6, the silver-plated nickel powder product has good oxidation resistance (> 500 ℃).
Comparative example 1
The procedure of example 1 was followed, except that: silver nanoparticles with negative charges are not added.
Example 2 and comparative example 2
The procedure of example 1 was followed, except that: the particle size of the silver nanoparticles was adjusted, as shown in table 1.
The performance test results of the silver-plated nickel powder obtained in examples 1-2 and comparative examples 1-2 are shown in Table 1.
TABLE 1
Fig. 2 is an SEM image of the silver-plated nickel powder obtained in comparative example 1. As can be seen from table 1 in combination with fig. 1 and 2: the addition of silver nanoparticles provides an activation center that can effectively improve the overall performance of silver-plated nickel powder, but the size of the silver nanoparticles needs to be controlled. The surface activation point of the nickel powder is few without adding nano silver particles, and the reduction speed of silver is high, so that the product contains pure silver particles, and the silver layer on the surface of the nickel powder is not compact; meanwhile, as the particle size of the silver nano particles increases, the adsorption stability of the silver nano particles on the surface of nickel powder is reduced, so that the solution contains nano silver particles, and pure silver particles also appear after silver plating.
Examples 3 to 4
The procedure of example 2 was followed, except that: the amount of silver nanoparticles was adjusted and is shown in table 2.
The performance test results of the silver-plated nickel powder obtained in examples 3 to 4 are shown in Table 2.
TABLE 2
As is clear from table 2, since the addition amount of the negatively charged silver nanoparticles does not significantly affect the performance of the silver-plated nickel powder, a dense silver coating can be obtained by adding a trace amount of nano silver ions. And the comprehensive consideration of the production cost is combined, and the addition amount of the nano silver particles is reduced as much as possible on the basis of stable product performance.
Examples 5 to 6 and comparative example 3
The procedure of example 1 was followed, except that: the particle size of the nickel powder was adjusted and is shown in Table 3.
The performance test results of the silver-plated nickel powder obtained in examples 5 to 6 and comparative example 3 are shown in Table 3.
TABLE 3 Table 3
FIG. 3 is an SEM image of silver-plated nickel powder obtained in example 5; fig. 4 is an SEM image of the silver-plated nickel powder obtained in example 6. As can be seen from fig. 3 and 4, the silver coating on the surface of the product silver-plated nickel powder has high density and no silver particles on the surface of the silver coating.
FIG. 7 is a thermogravimetric analysis of the silver-plated nickel powder obtained in example 5. As can be seen from FIG. 7, the silver-plated nickel powder product has good oxidation resistance (> 500 ℃).
As is clear from Table 3, the silver content required for the surface of the silver-plated nickel powder was also different by using nickel powders with different particle diameters, and as the particle diameter of the nickel powder was decreased, the specific surface area was increased accordingly, and the silver content required for the surface of the silver-plated nickel powder was higher. When the particle size of the nickel powder is smaller than 1 mu m, the nickel powder is difficult to disperse, the agglomeration is serious during silver plating, and a complete and compact silver plating layer cannot be formed, so that the performance deviation of the silver-plated nickel powder is caused.
Comparative example 4
The procedure of example 1 was followed, except that: in the step S2, the silver nano particles and the sodium dodecyl benzene sulfonate are not subjected to ultrasonic treatment in the mixing process, but are mechanically stirred and dispersed for 30min.
The performance test results of the silver-plated nickel powder obtained in comparative example 4 are shown in table 4.
TABLE 4 Table 4
Fig. 5 is an SEM image of the silver-plated nickel powder obtained in comparative example 4. As can be seen from table 4 in combination with fig. 1 and 5: the uniformity and the density of the silver layer on the surface of the silver-plated nickel powder obtained by ultrasonic dispersion are high, and the possible reason is that the ultrasonic can effectively improve the dispersion of silver nano particles in the solution, so that the dispersion uniformity of the silver nano particles on the surface of the nickel powder is improved.
Example 7 and comparative examples 5 to 6
The procedure of example 1 was followed, except that: the amount of the anionic surfactant Sodium Dodecyl Benzene Sulfonate (SDBS) added was adjusted, and is specifically shown in Table 5.
The performance test results of the silver-plated nickel powder obtained in example 7 and comparative examples 5 to 6 are shown in Table 5.
TABLE 5
As can be seen from table 5: the addition of the anionic surfactant is beneficial to subsequent silver plating and improves the comprehensive performance of silver-plated nickel powder, and the possible reason is that the anionic surfactant can obviously improve the distribution uniformity of silver nano particles on the surface of the nickel powder and the dispersibility of the nickel powder; however, as the addition amount of the anionic surfactant is continuously increased, the coating layer on the surface of the nickel powder is too thick, which is unfavorable for subsequent silver plating, and the product is mixed with partial pure silver particles.
Example 8 and comparative example 7
The procedure of example 1 was followed, except that: the pH of the nickel powder reduction solution in step S2 was adjusted, as shown in table 6.
The performance test results of the silver-plated nickel powder obtained in example 8 and comparative example 7 are shown in table 6.
TABLE 6
As can be seen from table 6: when the pH value of the nickel reduction solution is 11, the reduction rate of a silver source in the silver plating process is low, the silver content on the surface of the silver-plated nickel powder is low, the volume resistivity is increased, and the oxidation resistance is reduced; when the pH value reaches more than 12, the silver content on the surface of the nickel powder is increased, and the silver-plated nickel powder has excellent comprehensive performance.
Comparative examples 8 to 9
The procedure of example 1 was followed, except that: the types of the surfactants were adjusted, and the specific examples are shown in Table 7.
The results of performance test of the silver-plated nickel powder obtained in example 1 and comparative examples 8 to 9 are shown in Table 7.
TABLE 7
As can be seen from table 7: the addition of anionic surfactant is beneficial to subsequent silver plating, while the addition of cationic and nonionic surfactant deviates the silver plating effect; the analysis reasons may be that the surface of the nickel powder is positively charged, and the anionic surfactant is favorable for forming an electric double layer on the surface of the nickel powder, so that the dispersion of the nickel powder and the uniform adsorption of the nano silver particles on the surface of the nickel powder are facilitated; while the nonionic surfactant and the cation have no influence on the silver content of the nickel powder surface, the silver layer on the nickel powder surface is not dense due to uneven dispersion of the nickel powder, and free pure silver particles are formed.
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The industrial preparation method of the silver-plated nickel powder is characterized by comprising the following steps of:
s1, nickel powder surface treatment;
s2, active center formation: uniformly dispersing silver nano particles with negative charges and a surfactant in a solvent, then adding nickel powder subjected to surface treatment and a reducing agent, and adjusting the pH value of a system to be more than 11 to obtain a nickel powder reducing solution;
s3, silver plating: and (3) dripping the silver ammine complex solution into a nickel powder reducing solution to react, so as to obtain silver-plated nickel powder.
2. The industrial production method according to claim 1, wherein: the nickel powder surface treatment method comprises the following steps: the nickel powder is pickled in an acidic solution.
3. The industrial production method according to claim 1 or 2, characterized in that: the median particle diameter of the nickel powder is larger than 1 mu m.
4. The industrial production method according to any one of claims 1 to 3, characterized in that: the median particle diameter of the silver nano particles with negative charges is 1-30nm.
5. The industrial production method according to any one of claims 1 to 4, wherein: the mass ratio of the silver nano particles with negative charges to the nickel powder is (2 multiplied by 10) -6 -1×10 -5 ):100。
6. The industrial production method according to any one of claims 1 to 5, characterized in that: the surfactant is an anionic surfactant;
preferably, the anionic surfactant is sodium linear alkylbenzenesulfonate and/or fatty alcohol sulfate;
preferably, the addition amount of the anionic surfactant is 0.5-3% of the mass of the nickel powder.
7. The industrial production method according to any one of claims 1 to 6, characterized in that: the reducing agent is at least one selected from trisodium citrate, potassium sodium tartrate, glucose, formaldehyde and ascorbic acid.
8. Silver-plated nickel powder produced by the production method according to any one of claims 1 to 7.
9. Silver-plated nickel powder according to claim 8, characterized in that: the surface silver content of the silver-plated nickel powder is 15-50%;
preferably, the volume resistivity of the silver-plated nickel powder is less than 1 multiplied by 10 -4 Ω·cm；
Preferably, the antioxidation temperature of the silver-plated nickel powder is more than 500 ℃.
10. Use of silver-plated nickel powder according to claim 8 or 9 in electromagnetic shielding.
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