CN112919542B - Preparation method of modified particles for composite electroplating - Google Patents
Preparation method of modified particles for composite electroplating Download PDFInfo
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- CN112919542B CN112919542B CN202110247426.7A CN202110247426A CN112919542B CN 112919542 B CN112919542 B CN 112919542B CN 202110247426 A CN202110247426 A CN 202110247426A CN 112919542 B CN112919542 B CN 112919542B
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- 239000002245 particle Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000009713 electroplating Methods 0.000 title claims abstract description 14
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 80
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 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
- 238000005406 washing Methods 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000007789 sealing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 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
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000007747 plating Methods 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 8
- 239000010703 silicon Substances 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 13
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000009467 reduction Effects 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
- 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
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 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
- 239000004519 grease Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 238000003760 magnetic stirring Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000005543 nano-size silicon particle Substances 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
- 230000020477 pH reduction 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
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged 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
- 238000005728 strengthening Methods 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 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
Classifications
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention provides a preparation method of modified particles for composite electroplating, which comprises the steps of introducing multifunctional functional groups through acidizing pretreatment on the surface of molybdenum sulfide, then grafting silicon-containing azo grafting agents on the functional groups, carrying out hydrothermal treatment, regulating the pH value, and oxidizing with pure oxygen to obtain silicon oxide-coated molybdenum sulfide nano particles, so that the modified particles are strong in hydrophilicity and low in contact angle, and the dispersity of the modified particles in composite electroplating is effectively improved.
Description
Technical Field
The invention belongs to the field of electroplating, relates to a modification method of 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. Frictional wear is one of the main reasons for failure of mechanical equipment, about 80% of parts fail due to various forms of wear, the wear not only consumes energy and materials, but also accelerates equipment rejection, causes frequent replacement of parts, causes great loss to economy, causes resource, energy waste and economic loss due to corrosion and rust, even endangers personal safety in severe cases, and statistics show that about 1/3 of energy is directly or indirectly consumed in wear and corrosion-induced loss in mechanical manufacturing. To improve the high temperature corrosion and abrasion resistance of metal surfaces, a number of methods have been developed to strengthen the surfaces. The electrodeposition technology has very important effects on improving the wear resistance, the lubricity and the like of the metal surface. At present, a better electrodeposition method for improving the high-temperature corrosion resistance and the abrasion resistance of the metal surface is to deposit metallic nickel or chromium and the like on the metal surface through electrodeposition to form a self-lubricating composite coating and a high-abrasion-resistance composite coating.
The self-lubricating composite coating is mechanically moved with friction and abrasion, and the loss caused by the annual reasons is huge. Both case hardening and reduction of the coefficient of friction are commonly employed to improve the wear resistance of the material. The self-lubricating composite coating is a composite coating with antifriction effect, and the added composite particles are so-called solid lubricating particles and have self-lubricating effect, such as: the composite plating layers formed by MoS 2, BN, graphite, polytetrafluoroethylene and the like and matrix metals such as nickel, cobalt, chromium and the like have higher hardness and excellent wear resistance.
High wear-resistant composite coating: high wear-resistant composite coatings are attracting more and more attention due to their excellent wear resistance. The high wear resistance of the composite coating results from the strength of the composite particles themselves, from the refinement of the matrix metal crystals, and from the dispersion strengthening of sufficiently small particles (typically of the nano-scale). The hard particles added in the high wear-resistant composite coating are the most widely applied and important composite coatings. The application of highly wear resistant composite coatings to internal combustion engine cylinders is the most successful example. The cylinder is the heart of the engine and its life determines to a large extent the life of the 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 have been made to find ways to improve the wear and corrosion resistance of cylinders and to extend their useful life.
For example, CN20091025571A electroplated nickel-graphite self-lubricating material and its coating treatment method, it discloses an electroplated nickel-graphite self-lubricating material and its coating treatment method, said material uses nickel sulfate as base material, and is formed from adding graphite, boric acid, sodium chloride, sodium sulfate, magnesium sulfate and sodium dodecyl sulfate, then it is directly electroplated on the surface of metal component by means of electroplating technology. The invention has the obvious advantages of simple process, convenient operation and low production cost, and can obviously improve the wear resistance of the surface of the metal part.
The invention discloses a nickel plating silicon carbide copper base alloy material and a preparation method thereof, such as CN201710481903A, wherein the nickel plating silicon carbide copper base alloy material comprises the following components by volume percent: the copper alloy ZCuAl Fe3Mn2 is 88-93.5%, the nickel-plated silicon carbide is 6.5-12%, and the performance of the nano silicon carbide, such as high hardness, high wear resistance, good self-lubrication and high temperature strength, is utilized to realize further improvement of the performance of the copper alloy material, so that the nickel-plated silicon carbide copper base alloy obtained by the method has higher strength, hardness, wear resistance and corrosion resistance, and the service lives of wear-resistant part products of aerospace high-strength pressure-resistant products, wear-resistant part products of petroleum engineering equipment and corrosion-resistant product accessories of marine engineering equipment are prolonged.
At present, the most critical limiting factor of composite plating is the hydrophilicity of doped particles, so that the particles such as molybdenum sulfide, tungsten sulfide, boron nitride and the like are known by the skilled in the art to have extremely poor hydrophilicity, and the dispersion of the particles in a liquid phase is realized, and the primary problem is that the particles can be wetted by the liquid so as to enter the liquid phase, so that the particles need to be subjected to surface modification 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 comprises the steps of introducing multifunctional functional groups through acidizing pretreatment on the surface of molybdenum sulfide, then grafting silicon-containing azo grafting agents on the functional groups, adjusting the pH value through hydrothermal treatment, and oxidizing with pure oxygen to obtain the molybdenum sulfide nano particles coated with silicon oxide.
A preparation method of modified particles for composite electroplating, wherein the modified particles are sulfide coated by silicon oxide, and the preparation method is as follows
(1) Placing 1.5-2.5 g molybdenum sulfide in a three-neck flask, adding 45-50 mL of 98% by mass of H 2SO4 and 65-67% by mass of 10-15 mL of HNO 3, sealing, magnetically stirring and stirring 15-20 min, heating in a water bath to perform reflux treatment on 4-6H at 100 o ℃, washing deionized water to neutrality, and drying in an air furnace at 60-70 o ℃ for 12-18H 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), adding 1-2ml of triethylamine into a three-mouth bottle, slowly and dropwise adding 50-75ml of azo grafting agent solution with the concentration of 5-15mmol/L, stirring for 18-24 hours at room temperature under the protection of N 2, washing for multiple times by using methanol, and 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);
(3) Placing the grafted molybdenum sulfide particle aqueous solution into a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, using pure oxygen for emptying, using pure oxygen for pressurizing to enable the pressure gauge 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 180-200 ℃, continuously reacting for 24-36h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting to obtain the molybdenum sulfide modified particles coated with silicon oxide.
Further, the particle size of the molybdenum sulfide is 50-150nm, and the purity is more than 99.8%.
Further, the structure of the azo grafting agent is as follows:
Further, the hydrothermal process is temperature programming, and the temperature is raised to 180-200 ℃ from normal temperature of 5-6 o C/min.
Further, the evacuation time is 3-5min.
Further, the silica-coated molybdenum sulfide modified particles are configured as a 1-7wt% suspension in water.
Further, the roasting temperature is 200-300 o ℃, and the atmosphere is air.
In regard to the invention, (1) 1.5-2.5 g molybdenum sulfide is placed in a three-neck flask, 45-50 mL of H 2SO4 with the mass fraction of 98% and HNO 3 with the mass fraction of 10-15 mL of 65% -67% are added, 15-20 min is stirred by sealed magnetic stirring, 4-6H is treated by water bath heating at 100 o C in a reflux way, deionized water is washed to be neutral, 60-70 o C in an air furnace is dried for 12-18H, and molybdenum sulfide particles subjected to mixed acid oxidation treatment are obtained;
The skilled in the art knows that the surface of molybdenum sulfide does not contain any water-soluble bond or functional group, so that the water solubility is extremely poor, the molybdenum sulfide is treated by mixing H 2SO4 and HNO 3 with acid and heating and refluxing, the aim of improving the solubility and the dispersibility of the molybdenum sulfide in the solution is achieved, and the following effects are achieved by the mixed acid treatment: (1) Can remove surface pollutants and impurities such as grease, dust, etc.; (2) increasing the roughness of the surface; (3) Hydrophilic functional groups are introduced, and infrared tests prove that the surface of the molybdenum sulfide at least contains strong active groups such as-COOH, -CHO, C=O and the like through acidification treatment.
(2) Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1), adding 1-2ml of triethylamine into a three-mouth bottle, slowly and dropwise adding 50-75ml of azo grafting agent solution with the concentration of 5-15mmol/L, stirring for 18-24 hours under the condition of room temperature under the protection of N 2, washing for many 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 condition of initiating catalysis of the triethylamine, the azo grafting agent solution containing silicon and the surface of molybdenum sulfide are subjected to chemical reaction, and are directly grafted onto the surface of sulfide to form Si-O-MoS 2.
(3) Placing the grafted molybdenum sulfide particle aqueous solution into a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, using pure oxygen to empty, using pure oxygen to pressurize, enabling a pressure gauge of the hydrothermal reaction kettle to be 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating to 180-200 o ℃ for continuous reaction for 24-36h under stirring, naturally cooling, and under the conditions of high temperature and high pressure, dissociating azo reagents, oxidizing silicon adsorbed on the surface of sulfide to form silicon sol or silicon oxide under the conditions of alkaline valence adjustment and pure oxygen valence adjustment, and finally drying to obtain the silicon oxide coated molybdenum sulfide nano particles, wherein the particles have extremely strong hydrophilicity.
Beneficial technical effects
(1) The preparation method comprises the steps of introducing a multifunctional functional group through acidizing pretreatment on the surface of molybdenum sulfide, then grafting a silicon-containing azo grafting agent on the functional group, adjusting the pH value through hydrothermal treatment, and obtaining the molybdenum sulfide nano particles coated with silicon oxide through pure oxygen oxidation, wherein the silicon oxide is a shell, the 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 sealing condition, the suspension solution with the concentration of 20wt.% is completely settled for 140 hours, obvious settlement is visible at the bottom of the solution for 80-90 hours, the suspension test with the concentration of 5wt.% is performed, the total settlement time is more than 160 hours, obvious settlement is visible at the bottom of the solution for 120-130 hours, 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 molybdenum sulfide particle high-dispersion particles coated with the silicon oxide are used for compound nickel plating and can be uniformly dispersed on the surface of a plating layer.
The drawings in the specification:
FIG. 1 is a TEM image of an acidified molybdenum sulfide of the present invention.
FIG. 2 is a TEM image of a silica coated molybdenum sulfide according to the present invention.
Fig. 3 is an SEM image (subjected to ultrasonic oscillation) of the silicon oxide-coated molybdenum sulfide according to the present invention.
FIG. 4 is a sedimentation test of the solution obtained after hydrothermal reaction in example 2 of the present invention.
The specific embodiment is as follows:
example 1
The preparation method of the modified particles for composite electroplating is as follows.
(1) Placing 1.5g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent into a three-neck flask, adding 45 mL mass percent of 98 percent of H 2SO4 and 10mL mass percent of 65-67 percent of HNO 3, sealing, magnetically stirring and stirring 15 min, heating in a water bath at 100 o C for reflux treatment of 4H, washing deionized water to be neutral, and drying 12H in a 60 o C air furnace to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1g of molybdenum sulfide particles treated in the step (1), adding 1ml of triethylamine into a three-necked flask, slowly and dropwise adding 50ml of an azo grafting agent solution with the concentration of 5mmol/L, protecting with N 2, stirring for 18 hours at room temperature, washing for multiple times by using methanol, and preparing a 2wt.% 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 into a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5, using pure oxygen to empty for 3min, using pure oxygen to pressurize, enabling the pressure gauge of the hydrothermal reaction kettle to be 1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, rising the speed to 180 o ℃ at the speed of 5 o C/min, continuously reacting for 24h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting with 200 o C air to obtain the molybdenum sulfide modified particles coated with silicon oxide.
The roasting temperature is that the atmosphere is air.
Example 2
The preparation method of the modified particles for composite electroplating is as follows.
(1) Placing 2g molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent into a three-neck flask, adding 47.5mL of 98 percent by mass of H 2SO4 and 65-67 percent by mass of 12.5 and mL percent of HNO 3, sealing, magnetically stirring and stirring for 17.5min, heating in a water bath at 100 o C for reflux treatment of 5H, washing deionized water to be neutral, and drying 65 o C in an air furnace for 15H to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of molybdenum sulfide particles treated in the step (1), adding 1.5ml of triethylamine into a three-necked flask, slowly and dropwise adding 62.5ml of an azo grafting agent solution with the concentration of 10mmol/L, protecting by N 2, stirring for 21 hours at room temperature, washing for multiple times by using methanol, and preparing a 3.5wt.% grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution into a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, using pure oxygen to empty for 4min, using pure oxygen to pressurize, enabling the pressure gauge of the hydrothermal reaction kettle to be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, rising the temperature to 190 o ℃ at the speed of 5.5 o C/min, continuously reacting for 30h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting with 250 o C air to obtain the molybdenum sulfide modified particles coated with silicon oxide.
The roasting temperature is that the atmosphere is air.
Example 3
The preparation method of the modified particles for composite electroplating is as follows.
(1) Placing 2.5 g molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent into a three-neck flask, adding 50mL of 98 percent by mass of H 2SO4 and 65-67 percent by mass of 15 mL percent of HNO 3, sealing, magnetically stirring and stirring 20 min, heating in a water bath at 100 o C for reflux treatment of 6H, washing deionized water to be neutral, and drying 18H in an air furnace at 70 o C 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), adding 2ml of triethylamine into a three-mouth bottle, slowly and dropwise adding 75ml of 15mmol/L azo grafting agent solution, protecting with N 2, stirring for 24 hours at room temperature, washing for many times by using methanol, and preparing 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 1:3.
(3) Placing the grafted molybdenum sulfide particle aqueous solution into a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 8, using pure oxygen to empty for 5min, using pure oxygen to pressurize, enabling the pressure gauge of the hydrothermal reaction kettle to be 1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, rising the speed of 6 o C/min to 200 o C, continuously reacting for 36h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting with 300 o ℃ air to obtain the molybdenum sulfide modified particles coated with silicon oxide.
The roasting temperature is that the atmosphere is air.
As shown in FIG. 1, by subjecting the molybdenum sulfide to a strong acid treatment, the particles are more dispersed, but optionally partially agglomerated.
As shown in figure 2, the silicon oxide film is coated on the surface of the molybdenum sulfide, so that the particle dispersity is effectively improved, and the molybdenum sulfide can be independently separated in the solution.
By ultrasonic oscillation of the molybdenum sulfide particles coated with silicon oxide, it is seen that the silicon oxide film is partially peeled off, and a remarkable core-shell structure exists as shown in the SEM of FIG. 3.
As shown in fig. 4, the molybdenum sulfide particles coated with silicon oxide obtained by the treatment method of example 2 were prepared as a suspension solution of 5-20wt.%, and were magnetically stirred at 500-800rpm for 5min, and a suspension time test was performed, and it was apparent from the test that fig. 4 is a suspension solution of 20wt.%, and it was apparent that the time for complete sedimentation was 140 hours, and that a clear sedimentation was visible at the bottom of the solution at 80-90 hours.
Through the suspension test for 5wt.%, the time to complete sedimentation was > 160h, and a clear precipitate was visible at the bottom of the solution at 120-130 h.
Comparative example 1
The commercial molybdenum sulphide particles pass the water solubility test for 5wt.% and the time to complete sedimentation is less than 3min.
Comparative example 2
The preparation method is as follows.
(1) And alternately washing the 2 g molybdenum sulfide deionized water with the particle size of 75nm and the purity of more than 99.8 percent with ethanol.
(2) Weighing 1.25g of molybdenum sulfide particles treated in the step (1), adding 1.5ml of triethylamine into a three-necked flask, slowly and dropwise adding 62.5ml of an azo grafting agent solution with the concentration of 10mmol/L, protecting by N 2, stirring for 21 hours at room temperature, washing for multiple times by using methanol, and preparing a 3.5wt.% grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution into a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, using pure oxygen to empty for 4min, using pure oxygen to pressurize, enabling the pressure gauge of the hydrothermal reaction kettle to be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, rising the temperature to 190 o ℃ at the speed of 5.5 o C/min, continuously reacting for 30h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting with 250 o C air.
Through a water solubility test of 5wt.% and less than 1h, the main reason is that no strong acid treatment introduces active groups on the surface of inert molybdenum sulfide, namely grafting effect cannot be exerted, the water solubility is improved by coating a part of hydrothermal ethyl orthosilicate, the coating is disordered, and silicon effectively self-aggregates due to the inert molybdenum sulfide surface, 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) Placing 2g molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent into a three-neck flask, adding 47.5mL of 98 percent by mass of H 2SO4 and 65-67 percent by mass of 12.5 and mL percent of HNO 3, sealing, magnetically stirring and stirring for 17.5min, heating in a water bath at 100 o C for reflux treatment of 5H, washing deionized water to be neutral, and drying 65 o C in an air furnace for 15H to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of molybdenum sulfide particles treated in the step (1), adding 1.5ml of triethylamine into a three-necked flask, slowly and dropwise adding 62.5ml of an azo grafting agent solution with the concentration of 10mmol/L, protecting by N 2, stirring for 21 hours at room temperature, washing for multiple times by using methanol, and preparing a 3.5wt.% grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution into a lining-free hydrothermal reaction kettle, pressurizing by using air to ensure that the pressure gauge of the hydrothermal reaction kettle is 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, raising the temperature to 190 o ℃ at the speed of 5.5 o C/min, continuously reacting for 30h under the stirring condition, and naturally cooling.
(4) Washing with deionized water, and roasting with 250 o C air to obtain the molybdenum sulfide modified particles coated with silicon oxide.
The roasting temperature is that the atmosphere is air.
The time for complete sedimentation is less than 3h by the water solubility test of 5wt.% mainly because the grafted silicon is directly oxidized in hydrothermal process without using ammonia water and pure oxygen under hydrothermal conditions, while the silicon oxide is fixed by means of subsequent calcination so that the silicon oxide is easily separated from molybdenum sulfide and from it, if the 5wt.% suspension obtained in comparative example 3 is subjected to ultrasonic vibration treatment, the time for complete sedimentation is less than 20min.
Further, contact angle tests were conducted on example 2 and comparative example 1, the silicon oxide-coated molybdenum sulfide of example 2 and the molybdenum sulfide particles of comparative example 1 were tabletted under a powder tableting machine of 40Mpa for 90s, a tableting thickness of about 1 to 2mm, and the contact angle of the tableting of example 2 was tested to be 9 to 12 o and the contact angle of comparative example 1 to 87 o using deionized water as a solution probe.
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.
Claims (2)
1. The preparation method of the modified particles for composite electroplating is characterized in that the modified particles are sulfide coated by silicon oxide, and the preparation method specifically comprises the following steps:
(1) Placing 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent into a three-neck flask, adding 47.5mL of H 2SO4 with the mass fraction of 98 percent and 12.5mL of HNO 3 with the mass fraction of 65-67 percent into the three-neck flask, sealing, magnetically stirring, stirring for 17.5min, heating in a water bath at 100 ℃ for reflux treatment for 5H, washing deionized water to be neutral, and drying at 65 ℃ in an air furnace for 15H to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
(2) 1.25g of the molybdenum sulfide particles treated in the step (1) are weighed and added into a three-necked flask, 1.5mL of triethylamine is added into the three-necked flask, 62.5mL of an azo grafting agent solution with the concentration of 10mmol/L is slowly and dropwise added, the mixture is protected by N 2, the mixture is stirred for 21 hours at room temperature, methanol is used for multiple washing, 3.5wt.% of grafted molybdenum sulfide particle aqueous solution is prepared by using deionized water-ethanol, and the volume ratio of the deionized water to the ethanol is 1:2.5;
the azo grafting agent has the following structure:
；
(3) Placing the grafted molybdenum sulfide particle aqueous solution into 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 enable the pressure gauge of the hydrothermal reaction kettle to be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating the hydrothermal process to a programmed temperature from normal temperature to 190 ℃ at a heating rate of 5.5 ℃/min, continuously reacting for 30h under stirring, naturally cooling,
(4) Washing with deionized water, and roasting in air at 250 ℃ to obtain molybdenum sulfide modified particles coated with silicon oxide;
The composite electroplating is composite electroplated nickel.
2. A method for producing modified particles for composite plating according to claim 1, wherein the silica-coated molybdenum sulfide modified particles are formulated as a suspension aqueous solution of 5 wt.%.
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| CA1261208A (en) * | 1985-07-29 | 1989-09-26 | Hiroshi Fukui | Modified powder or particulate material |
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| CA1261208A (en) * | 1985-07-29 | 1989-09-26 | Hiroshi Fukui | Modified powder or particulate material |
| JP2016190769A (en) * | 2015-03-31 | 2016-11-10 | 日揮触媒化成株式会社 | Method for producing silica particle |
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| 姜铸峰等."立方氮化硼表面Stober 法包覆硅氧纳米涂层及其表征".《中国表面工程》.2017,第30卷(第04期),第94-100页. * |
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