CN112919542A - Preparation method of modified particles for composite electroplating - Google Patents
Preparation method of modified particles for composite electroplating Download PDFInfo
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- CN112919542A CN112919542A CN202110247426.7A CN202110247426A CN112919542A CN 112919542 A CN112919542 A CN 112919542A CN 202110247426 A CN202110247426 A CN 202110247426A CN 112919542 A CN112919542 A CN 112919542A
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- molybdenum sulfide
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- 239000002245 particle Substances 0.000 title claims abstract description 91
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000009713 electroplating Methods 0.000 title claims description 13
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 89
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 30
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 5
- 150000004763 sulfides Chemical class 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 230000020477 pH reduction Effects 0.000 abstract description 5
- 238000007747 plating Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 14
- 239000000725 suspension Substances 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 2
- 241001584785 Anavitrinella pampinaria Species 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910001060 Gray iron Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Condensed Matter Physics & Semiconductors (AREA)
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- Electrochemistry (AREA)
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Abstract
The invention provides a preparation method of modified particles for composite plating, which is characterized in that a multifunctional functional group is introduced by carrying out acidification pretreatment on the surface of molybdenum sulfide, then a silicon-containing azo grafting agent is grafted on the functional group, and the molybdenum sulfide nano particles coated by silicon oxide are obtained by hydrothermal treatment, pH value adjustment and pure oxygen oxidation.
Description
Technical Field
The invention belongs to the field of electroplating, relates to a method for modifying insoluble particles in composite electroplating, and particularly relates to a preparation method of hydrophilic silicon oxide coated molybdenum sulfide particles.
Background
Wear and corrosion are the primary forms of material failure. The friction wear is one of the main reasons of the failure of mechanical equipment, about 80 percent of the failure of parts is caused by various types of wear, the wear not only consumes energy and materials, but also accelerates the scrapping of the equipment, causes frequent part replacement, causes great loss to economy, causes resource, energy waste and economic loss due to corrosion and rusting, and even endangers the personal safety in severe cases, statistics show that about 1/3 of energy in the mechanical manufacturing is directly or indirectly consumed by the loss caused by the wear and the corrosion. To improve the high temperature corrosion resistance and wear resistance of metal surfaces, many methods for strengthening the surfaces have been developed. The electrodeposition technology is very important in improving the wear resistance, lubricity and the like of the metal surface. At present, a better electrodeposition method for improving the high-temperature corrosion resistance and wear resistance of a metal surface is to deposit metallic nickel or chromium and the like on the metal surface by electrodeposition to form a self-lubricating resistant composite coating and a highly wear-resistant composite coating.
The self-lubricating composite coating is accompanied with friction and abrasion in mechanical motion, and the loss caused by the mechanical motion is huge every year. Two methods of case hardening and reducing the coefficient of friction are commonly used to improve the wear resistance of materials. The self-lubricating composite coating is a composite coating with an antifriction effect, and the added composite particles are so-called solid lubricating particles with a self-lubricating effect, such as: MoS2BN, graphite, polytetrafluoroethylene and other matrix metals form various composite coatings with higher hardness and excellent wear resistance.
High wear-resistant composite coating: the high wear-resistant composite coating has attracted more and more attention due to its good wear resistance. The high wear resistance of the composite coating comes from the strength of the composite particles themselves, the refinement of the matrix metal crystals, and also the dispersion strengthening of sufficiently small particles (usually of the order of nanometers). The hard particles added in the high-wear-resistance composite coating are the most widely applied and important composite coatings. The application of highly wear resistant composite coatings to internal combustion engine blocks is the most successful example. The cylinder block is the heart of the internal combustion engine and its life determines to a large extent the life of the internal combustion engine. The sliding surface of the cylinder body of the internal combustion engine is required to have the performances of wear resistance, heat resistance, mechanical scratch resistance, corrosion resistance and the like, and the common gray cast iron cylinder is difficult to meet the requirements. Efforts are constantly being made to find ways to improve the wear and corrosion resistance and extend the service life of the cylinder.
For example, CN20091025571A discloses an electroplated nickel-based-graphite self-lubricating material and a coating treatment method thereof, wherein the material is prepared by using nickel sulfate as a base material, adding graphite, boric acid, sodium chloride, sodium sulfate, magnesium sulfate and sodium dodecyl sulfate, and then directly electroplating the surface of a metal part by an electroplating technology. The invention can obviously improve the wear-resisting strength of the surface of the metal part and has the obvious advantages of simple process, convenient operation and low production cost.
For example, CN201710481903A discloses a nickel-plated silicon carbide copper-based alloy material and a preparation method thereof, and the material comprises the following components by volume percent: 88-93.5% of copper alloy ZCuAl10Fe3Mn2 and 6.5-12% of nickel-plated silicon carbide, and further improvement of the performance of the copper alloy material is realized by utilizing the high hardness, high wear resistance, good self-lubrication and high-temperature strength of the nano-scale silicon carbide, so that the nickel-plated silicon carbide copper-based alloy obtained according to the invention has higher strength, hardness, wear resistance and corrosion resistance, thereby prolonging the service life of aerospace high-strength pressure-resistant products, petroleum engineering wear-resistant part products and ocean engineering equipment corrosion-resistant product accessories.
At present, the most critical limiting factor of composite plating is the hydrophilicity of the doped particles, and those skilled in the art know that the hydrophilicity of particles such as molybdenum sulfide, tungsten sulfide, boron nitride and the like is very poor, so that the particles are dispersed in a liquid phase, and the primary problem is that the particles can be wetted by liquid and can enter the liquid phase, so that the surface modification of the particles is needed to realize uniform composite plating of the particles.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a preparation method of modified particles for composite electroplating, which is characterized in that a multifunctional functional group is introduced by carrying out acidification pretreatment on the surface of molybdenum sulfide, then a silicon-containing azo grafting agent is grafted on the functional group, and the silicon oxide-coated molybdenum sulfide nano particles are obtained by hydrothermal treatment, pH value adjustment and pure oxygen oxidation.
A preparation method of modified particles for composite electroplating, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method comprises the following steps
(1) Putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15 mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, adding in water bathHeat is in 100oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoC, drying for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
(2) weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2Protecting, stirring for 18-24h at room temperature, washing with methanol for multiple times, and preparing 2-5wt.% aqueous solution of grafted molybdenum sulfide particles by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1- (2-3);
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to enable the pressure of the hydrothermal reaction kettle to be 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating and placing at 180 ℃ and 200 ℃, continuously reacting for 24-36h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting to obtain the silicon oxide coated molybdenum sulfide modified particles.
Furthermore, the particle size of the molybdenum sulfide is 50-150nm, and the purity is more than 99.8%.
Further, the azo grafting agent has the following structure:
further, the hydrothermal process is temperature programming, and the temperature is 5-6 ℃ from the normal temperatureoThe C/min is increased to 180-200 ℃.
Further, the emptying time is 3-5 min.
Further, the silicon oxide coated molybdenum sulfide modified particles are prepared into 1-7wt% of suspension water solution.
Further, the temperature of the roasting is 200-300-oAnd C, the atmosphere is air.
For the present invention, (1) 1.5-2.5 g of molybdenum sulfide was placed in a three-necked flask, and 45-50 mL of a mass was addedFraction of H98%2SO4And 10-15 mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoC, drying for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
as known to those skilled in the art, the molybdenum sulfide surface does not contain any water-soluble bonds or functional groups, making it extremely poorly water-soluble, via H2SO4And HNO3Mixed acid, heating and refluxing the molybdenum sulfide, aiming at improving the solubility and the dispersibility of the molybdenum sulfide in the solution, and the mixed acid treatment has the following effects: (1) can remove the pollutants and impurities on the surface, such as grease, dust and the like; (2) the roughness of the surface is improved; (3) hydrophilic functional groups are introduced, and infrared tests show that the molybdenum sulfide is acidified and at least contains strong active groups such as-COOH, -CHO, C = O and the like on the surface.
(2) Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2Protecting, stirring for 18-24h at room temperature, washing for multiple times by using methanol, preparing 2-5wt.% of grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1- (2-3), and under the initiated catalysis condition of triethylamine, performing chemical reaction on the silicon-containing azo grafting agent solution and the molybdenum sulfide surface to directly graft the molybdenum sulfide surface to form Si-O-MoS2。
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating and placing in a 180-phase 200-phase reactoroC, continuously reacting for 24-36h under the stirring condition, naturally cooling, performing hydrothermal reaction, dissociating the azo reagent under the conditions of high temperature and high pressure, and adjusting the valence of silicon adsorbed on the sulfide surface under the conditions of alkalinity and pure oxygenAnd finally drying to obtain the molybdenum sulfide nano particles coated by the silicon oxide, wherein the particles have extremely strong hydrophilicity.
Advantageous technical effects
(1) The preparation method comprises the steps of introducing a multifunctional functional group through acidification pretreatment on the surface of molybdenum sulfide, then grafting a silicon-containing azo grafting agent on the functional group, regulating the pH value through hydrothermal treatment, and oxidizing with pure oxygen to obtain silicon oxide-coated molybdenum sulfide nanoparticles, wherein silicon oxide is a shell, molybdenum sulfide is a core, and the coating rate is 100%.
(2) The molybdenum sulfide particles coated with the silicon oxide have extremely high dispersibility in water, under a sealed condition, the complete settling time of 20wt.% of the suspension solution is 140h, obvious precipitation can be seen at the bottom of the solution within 80-90h, the complete settling time is more than 160h under a 5wt.% suspension test, obvious precipitation can be seen at the bottom of the solution within 120-130h, and the suspension time is increased along with the reduction of the concentration of the molybdenum sulfide particles coated with the silicon oxide.
(3) The silicon oxide-coated molybdenum sulfide particle high-dispersion particles are used for composite nickel plating and can be uniformly dispersed on the surface of a plating layer.
The attached drawings of the specification:
FIG. 1 is a TEM image of molybdenum sulfide of the present invention after acidification treatment.
FIG. 2 is a TEM image of molybdenum sulfide coated with silicon oxide according to the present invention.
FIG. 3 is an SEM image (with ultrasonic oscillation) of a molybdenum sulfide coated with silicon oxide according to the present invention.
FIG. 4 is a test of a sedimentation experiment of a solution obtained after hydrothermal reaction in example 2 of the present invention.
The specific implementation mode is as follows:
example 1
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) Has a particle diameter of75nm of molybdenum sulfide with the purity of more than 99.8 percent in 1.5g is placed in a three-neck flask, and 45 mL of H with the mass fraction of 98 percent is added2SO4And 10 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 15 min, heating in water bath to 100%oC refluxing for 4h, washing to neutrality with deionized water, 60 in an air furnaceoAnd C, drying for 12 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1g of molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50ml of 5mmol/L azo grafting agent solution, and N2Protection, stirring for 18h at room temperature, washing with methanol for multiple times, and preparing a 2wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5, evacuating with pure oxygen for 3min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5MpaoThe rate of C/min is increased to 180oAnd C, continuously reacting for 24 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 200oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
Example 2
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 2 g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oC, drying for 15 h to obtain mixed acid oxidation treatmentOf molybdenum sulphide particles.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, evacuating with pure oxygen for 4min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5.5 MpaoThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
Example 3
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 2.5 g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 50mL of H with the mass fraction of 98 percent is added2SO4And 15 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 20min, heating in water bath to 100%oC refluxing for 6h, washing to neutrality with deionized water, and air-oven drying for 70%oAnd C, drying for 18h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 75ml of 15mmol/L azo grafting agent solution, and N2Protecting, stirring at room temperature for 24h, washing with methanol for several times, and usingPreparing a 5wt.% aqueous solution of grafted molybdenum sulfide particles by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: 3.
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 8, evacuating with pure oxygen for 5min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 6 MPaoThe rate of C/min is increased to 200oAnd C, continuously reacting for 36 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 300oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
As shown in fig. 1, by subjecting molybdenum sulfide to a strong acid acidification treatment, the particles are relatively dispersed, but are left to partially agglomerate.
As shown in fig. 2, the surface of the molybdenum sulfide is coated with a silicon oxide film, so that the particle dispersity is effectively improved, and the molybdenum sulfide can be separated and exist in the solution.
Ultrasonic oscillation is carried out on the molybdenum sulfide particles coated with the silicon oxide, so that a part of the silicon oxide film is stripped, and an obvious core-shell structure exists as shown in SEM of attached figure 3.
As shown in fig. 4, the molybdenum sulfide particles coated with silicon oxide obtained by the treatment method of example 2 were prepared into 5-20wt.% suspension solution, and the suspension solution was magnetically stirred at 500-800rpm for 5min, and the suspension time test was performed, so that it is obvious that the suspension solution of fig. 4 was 20wt.% suspension solution, the complete settling time was 140h, and obvious precipitation was observed at the bottom of the solution in 80-90 h.
The time to complete settling was > 160h, with a significant precipitation at the bottom of the solution seen at 120-130h, by testing for 5wt.% suspension.
Comparative example 1
Commercial molybdenum sulphide particles, passing the water solubility test at 5wt.%, have a time to complete sedimentation of less than 3 min.
Comparative example 2
The preparation method is as follows.
(1) 2 g of molybdenum sulfide deionized water with the particle size of 75nm and the purity of more than 99.8 percent and ethanol are alternately washed.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, evacuating with pure oxygen for 4min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5.5 MpaoThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, air roasting.
The complete settling time is less than 1h through a water solubility test of 5wt.%, the main reason is that no strong acid treatment is used for introducing active groups on the surface of the inert molybdenum sulfide, namely, the grafting effect cannot be exerted, the water solubility is improved through partial coating of hydrothermal ethyl orthosilicate, the coating is disordered coating, silicon effectively performs self-aggregation due to the fact that the surface of the molybdenum sulfide is inert, and a small amount of partially physically coated molybdenum sulfide can be formed under the stirring condition.
Comparative example 3
The preparation method is as follows.
(1) 2 g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oC dryingAnd 15 h, obtaining molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, pressurizing by using air to ensure that the pressure of the hydrothermal reaction kettle is 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle by 5.5oThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
The time for complete settling was less than 3h by testing the water solubility of 5wt.%, mainly because the grafted silicon was directly oxidized in a hydrothermal process under hydrothermal conditions without using ammonia and pure oxygen, and the silicon oxide was fixed by means of subsequent calcination, so that the silicon oxide was easily separated from the molybdenum sulfide and it was easy to separate, and if the 5wt.% suspension obtained in comparative example 3 was subjected to ultrasonic vibration treatment, the time for complete settling was less than 20 min.
In addition, the contact angle test was performed on example 2 and comparative example 1, and the silicon oxide-coated molybdenum sulfide of example 2 and the molybdenum sulfide particles of comparative example 1 were tabletted for 90s under a powder tabletting machine of 40MPa with a thickness of about 1-2mm, and the contact angle of the tabletted sheets of example 2 was tested to be 9-12 using deionized water as a solution probeoContact angles 83-87 of comparative example 1o。
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (7)
1. A preparation method of modified particles for composite electroplating is characterized in that the modified particles are sulfides coated by silicon oxide, and the preparation method comprises the following steps
(1) Putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15 mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoC, drying for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
(2) weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2And (2) protecting, stirring for 18-24h at room temperature, washing with methanol for multiple times, and preparing 2-5wt.% of a grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3);
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating to 180-oC, continuously reacting for 24-36h under the stirring condition, naturally cooling,
(4) washing with deionized water, and roasting to obtain the silicon oxide coated molybdenum sulfide modified particles.
2. The method according to claim 1, wherein the molybdenum sulfide has a particle size of 50 to 150nm and a purity of more than 99.8%.
3. The method according to claim 1, wherein the azo grafting agent has the following structure:
4. the method according to claim 1, wherein the hydrothermal process is temperature programming and is performed from room temperature 5-6oC/min is raised to 180-oC。
5. The method according to claim 1, wherein the evacuation time is 3 to 5 min.
6. The method according to claim 1, wherein the silica-coated molybdenum sulfide modified particle is prepared as a 1-7wt% aqueous suspension solution.
7. The method for preparing modified particles for composite electroplating as claimed in claim 1, wherein the calcination temperature is 200-300-oAnd C, the atmosphere is air.
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| CA1261208A (en) * | 1985-07-29 | 1989-09-26 | Hiroshi Fukui | Modified powder or particulate material |
| US20160304346A1 (en) * | 2014-08-11 | 2016-10-20 | Hohai University | Method for preparing high-density hexagonal boron nitride ceramic material |
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| CN112981501B (en) * | 2021-03-05 | 2024-03-01 | 惠州市荣安达化工有限公司 | Composite bright nickel plating solution |
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Effective date of registration: 20240717 Address after: Plot E-4-2-1, Hon Hai Fine Chemical Industry Base, Yonghu Town, Huiyang District, Huizhou City, Guangdong Province, 516200 Patentee after: Taihe fine chemicals (Huizhou) Co.,Ltd. Country or region after: China Address before: College of chemistry and chemical engineering, Nanjing University, 22 Hankou Road, Gulou District, Nanjing City, Jiangsu Province, 210000 Patentee before: Zhao Linlin Country or region before: China |