CN112981501B - Composite bright nickel plating solution - Google Patents
Composite bright nickel plating solution Download PDFInfo
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- CN112981501B CN112981501B CN202110247427.1A CN202110247427A CN112981501B CN 112981501 B CN112981501 B CN 112981501B CN 202110247427 A CN202110247427 A CN 202110247427A CN 112981501 B CN112981501 B CN 112981501B
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- molybdenum sulfide
- brightening agent
- agent
- particles
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- 238000007747 plating Methods 0.000 title claims abstract description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 19
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 90
- 239000002245 particle Substances 0.000 claims abstract description 83
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 75
- 238000005282 brightening Methods 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 238000003756 stirring Methods 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 27
- 239000010954 inorganic particle Substances 0.000 claims description 25
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 24
- 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
- 239000000725 suspension Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 16
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000004327 boric acid Substances 0.000 claims description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000000080 wetting agent Substances 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- -1 methylene dinaphthyl Chemical group 0.000 claims description 11
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical group ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000009713 electroplating Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- ZIWRUEGECALFST-UHFFFAOYSA-M sodium 4-(4-dodecoxysulfonylphenoxy)benzenesulfonate Chemical group [Na+].CCCCCCCCCCCCOS(=O)(=O)c1ccc(Oc2ccc(cc2)S([O-])(=O)=O)cc1 ZIWRUEGECALFST-UHFFFAOYSA-M 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 description 28
- 239000011248 coating agent Substances 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 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
- 238000002360 preparation method Methods 0.000 description 8
- LGNQGTFARHLQFB-UHFFFAOYSA-N 1-dodecyl-2-phenoxybenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OC1=CC=CC=C1 LGNQGTFARHLQFB-UHFFFAOYSA-N 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004062 sedimentation Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 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
- 238000010306 acid treatment Methods 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 125000000524 functional group Chemical group 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion 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
- 238000005461 lubrication Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 230000002195 synergetic effect Effects 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000006172 buffering agent Substances 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
- 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
- 239000008187 granular material Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 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
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 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
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 239000004094 surface-active agent 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
Classifications
-
- 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
-
- 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
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a composite bright nickel plating solution, which comprises highly dispersed inorganic nano particles, wherein the particles are molybdenum sulfide coated with silicon oxide, the composite bright nickel plating solution is obtained by sequentially carrying out strong mixed acid pretreatment, azo grafting agent grafting treatment, hydrothermal treatment and roasting treatment on the molybdenum sulfide, the hardness of a plating layer is effectively improved, the friction coefficient is reduced, and the brightness of the plating layer is effectively maintained by the composite brightening agent.
Description
Technical Field
The invention belongs to the field of electroplating, and relates to an inorganic modified particle composite bright nickel plating solution.
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. Self-lubricatingThe composite coating is a composite coating with antifriction effect, and the added composite particles are so-called solid lubrication particles and have self-lubrication effect, such as: moS (MoS) 2 Various composite plating layers formed by 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, disclosed is an electroplated nickel-graphite self-lubricating material and its coating treatment method, the material uses nickel sulfate as base material, and is formed by adding graphite, boric acid, sodium chloride, sodium sulfate, magnesium sulfate and sodium dodecyl sulfate, then directly electroplating on the surface of metal component by 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 in percentage by volume: the copper alloy ZCuAl10Fe3Mn2 is 88-93.5%, the nickel-plated silicon carbide is 6.5-12%, and the properties of high hardness, high wear resistance, good self-lubrication and high-temperature strength of the nanoscale silicon carbide are utilized to further improve the properties 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 in the prior art, the plating solution provided by the invention comprises the highly dispersed inorganic nano particles, wherein the particles are molybdenum sulfide coated with silicon oxide, the plating solution is obtained by sequentially carrying out strong mixed acid pretreatment, azo grafting agent grafting treatment, hydrothermal treatment and roasting treatment on the molybdenum sulfide, the hardness of a plating layer is effectively improved, the friction coefficient is reduced, and the brightness of the plating layer is effectively maintained by the composite brightening agent.
The plating solution consists of nickel sulfate, nickel chloride, boric acid, a wetting agent, a primary brightening agent, a secondary brightening agent, an auxiliary brightening agent and an inorganic particle suspension solvent, wherein the primary brightening agent is sodium dodecyl diphenyl ether disulfonate, the secondary brightening agent is o-chlorobenzaldehyde, the auxiliary brightening agent is sodium methylene dinaphthyl sulfonate, the inorganic particle suspension solvent consists of 1-20wt.% of inorganic particles and deionized water, the inorganic particles are of a core-shell structure with silicon oxide as a shell and molybdenum sulfide as a core, and the molybdenum sulfide is subjected to strong mixed acid pretreatment, azo grafting treatment, hydrothermal treatment and roasting treatment in sequence.
Further, 230-240g/L of nickel sulfate, 30-40g/L of nickel chloride, 30-35g/L of boric acid, 0.02-0.05g/L of wetting agent, 0.6-0.8g/L of primary brightening agent, 0.2-0.4g/L of secondary brightening agent, 0.15-0.25g/L of auxiliary brightening agent and 1-20wt.% of inorganic particle suspending solvent.
Further, the pH value of the plating solution is 4-6, and the electroplating parameters are as follows: cathode current density of 2.5-3A/dm 2 Stirring at 5-15rpm for 30-50min at 40-50 o C。
Further, the strong mixed acid treatment process is as follows: putting 1.5-2.5. 2.5g molybdenum sulfide into a three-neck flask, adding 45-50 mL of 98% H by mass 2 SO 4 And from 10 to 15 and mL mass percent of HNO of 65 to 67 percent 3 Sealing, magnetically stirring for 15-20 min, and heating in water bath at 100 o C reflux treating 4-6 h, washing with deionized water to neutrality, and air heating in air furnace 60-70 o C, drying 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
Further, the azo grafting agent is subjected to grafting treatment: 1-1.5g of molybdenum sulfide particles pretreated by strong mixed acid are weighed and added into a three-mouth bottle, 1-2ml of triethylamine is added into the three-mouth bottle, then 50-75ml of azo grafting agent solution with the concentration of 5-15mmol/L is slowly and dropwise added, and N is measured 2 Stirring at room temperature for 18-24h, 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).
Further, the hydrothermal treatment: 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, and heating to 180-200 MPa o And C, continuously reacting for 24-36h under the stirring condition, and naturally cooling.
Further, the roasting temperature is 200-300 DEG C o And C, the atmosphere is air.
Further, 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 ℃ at normal temperature o C/min up to 180-200 o C。
Regarding the present invention:
(1) The bright nickel solution of the invention consists of 230-240g/L of nickel sulfate, 30-40g/L of nickel chloride, 30-35g/L of boric acid, 0.02-0.05g/L of wetting agent, 0.6-0.8g/L of primary brightening agent, 0.2-0.4g/L of secondary brightening agent, 0.15-0.25g/L of auxiliary brightening agent and 1-20wt.% of inorganic particle suspension solvent, wherein the primary brightening agent is sodium dodecyl diphenyl ether disulfonate, the secondary brightening agent is o-chlorobenzaldehyde, the auxiliary brightening agent is sodium methylene dinaphthyl sulfonate,
wherein, nickel sulfate and nickel chloride are main salts, the dosage of the nickel sulfate is almost 6-8 times of that of the nickel chloride, and the nickel sulfate is mainly used for maintaining the conductivity of the plating solution and simultaneously effectively reducing the internal stress of the plating layer.
Wherein boric acid is a buffering agent, so that the stability of pH 4-6 is effectively maintained, pinholes are avoided from being generated too low, and hydroxide precipitation is avoided from being generated too low.
The wetting agent is sodium dodecyl benzene sulfonate, and the sodium dodecyl benzene sulfonate can be used as a brightening agent, and can be used as a surface wetting agent, so that the consumption of the primary brightening agent can be effectively reduced, and the surfactant can be used for further improving the water wettability of inorganic particles and the dispersibility of inorganic composite plating particles in a plating layer.
Primary brightening agent: the sodium dodecyl diphenyl ether disulfonate is an unsaturated organic compound, and can be singly used to obtain a semi-bright coating.
Secondary brightening agent: the secondary brightening agent is o-chlorobenzaldehyde, and can obviously improve the brightness and leveling property of the coating.
Auxiliary brightening agent: the auxiliary brightening agent is methylene dinaphthyl sodium sulfonate, so that the brightness and the flatness of the coating are further improved, and the inorganic particles are contained in the coating, so that the influence on the surface flatness of the coating is great in the composite coating process of the inorganic particles, and the brightness and the flatness of the coating need to be improved if the auxiliary brightening agent is not added.
Inorganic particle suspension solvent: the sulfide particles coated with silicon oxide are used for improving the water solubility of sulfide, the sulfide is molybdenum sulfide, and the sulfide particles are lubricating particles used for composite plating and are mainly used for reducing the friction coefficient of a plating layer.
(2) Preparing inorganic composite plating particles: putting 1.5-2.5. 2.5g molybdenum sulfide into a three-neck flask, adding 45-50 mL of 98% H by mass 2 SO 4 And from 10 to 15 and mL mass percent of HNO of 65 to 67 percent 3 Sealing, magnetically stirring for 15-20 min, and heating in water bath at 100 o C reflux treating 4-6 h, washing with deionized water to neutrality, and air heating in air furnace 60-70 o C, drying 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
as known to those skilled in the art, molybdenum sulfide has a surface that does not contain any water-soluble bonds or functional groups, making it extremely poorly water-soluble by H 2 SO 4 And HNO 3 The mixed acid is used for heating and refluxing the molybdenum sulfide, so as to improve the solubility and the dispersibility of the molybdenum sulfide in the solution, and the mixed acid treatment has the following effects: (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.
Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked flask, adding 1-2ml of triethylamine into the three-necked flask, slowly and dropwise adding the solution, and then weighing 50-75ml of the solution of the azo grafting agent with the concentration of 5-15mmol/L, and N 2 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 initiation catalysis condition of triethylamine, the silicon-containing azo grafting agent solution and the molybdenum sulfide surface are subjected to chemical reaction and are directly grafted to the sulfide surface to form Si-O-MoS 2 。
The grafted molybdenum sulfide particles are subjected toPlacing the granule water solution into lining-free hydrothermal reaction kettle, adding appropriate amount of ammonia water to adjust pH to 7.5-8, evacuating with pure oxygen, pressurizing with pure oxygen to make the pressure gauge of hydrothermal reaction kettle be 1-1.1Mpa, closing pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating and placing in 180-200 o And C, continuously reacting for 24-36h under the stirring condition, naturally cooling, dissociating azo reagents under the conditions of hydrothermal treatment and high temperature and high pressure, oxidizing silicon adsorbed on the surface of sulfide under the conditions of alkaline valence adjustment and pure oxygen valence adjustment to form silicon sol or silicon oxide, 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.
(4) The obtained nickel coating has synergistic effect among the primary brightening agent, the secondary brightening agent and the auxiliary brightening agent, and effectively ensures the brightness and the flatness of the coating.
(5) In the composite plating process, inorganic modified nano particles are added into the plating solution, so that the hardness of the plating layer is effectively improved, and the friction coefficient of the plating layer is reduced.
Description of the drawings:
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 modified inorganic particles of the present invention.
Fig. 5 is a cross-sectional SEM image of the composite plating layer of the invention.
Fig. 6 is an SEM image of the surface of the composite plating layer of the invention.
The specific embodiment is as follows:
examples 1 to 3 and comparative examples 1 to 3 are methods for preparing inorganic modified particles, examples 4 to 6 and comparative examples 4 to 7 are composite bright nickel plating baths, and inorganic particle suspension solvents used in examples 4 to 6 were prepared by the method of example 2.
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, and adding 45 mL mass percent of 98 percent of H 2 SO 4 And 10-67% HNO by mass of 10 mL 3 Sealing, magnetically stirring for 15 min, and heating in water bath at 100 o C reflux treating 4h, washing with deionized water to neutrality, and heating in an air furnace 60 o C, drying 12 and 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 1ml of triethylamine into a three-necked flask, slowly and dropwise adding the solution, and weighing 50ml of 5mmol/L azo grafting agent solution, N 2 The mixture was stirred at room temperature for 18h, washed with methanol multiple times, and a 2wt.% aqueous solution of grafted molybdenum sulfide particles was prepared using deionized water-ethanol in a volume ratio of 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, evacuating with pure oxygen for 3min, pressurizing with pure oxygen to enable the pressure gauge of the hydrothermal reaction kettle to be 1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, and controlling the pH value to be 5 o The rate of C/min rises to 180 o And C, continuously reacting for 24 hours under the stirring condition, and naturally cooling.
(4) Deionized water wash, 200 o And C, roasting in air to obtain the molybdenum sulfide modified particles coated with the 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, and adding 47.5mL of H with the mass fraction of 98 percent 2 SO 4 And HNO with the mass fraction of between 65 and 67 percent of 12.5 and 12.5 mL 3 Sealing, magnetically stirring for 17.5min, and heating in water bath at 100 o C reflux treating 5 h, washing with deionized water to neutrality, and air-heating in a furnace 65 o And C, drying 15 and h 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 the molybdenum sulfide particles into a three-necked flask, adding 1.5ml of triethylamine into the three-necked flask, slowly and dropwise adding the solution, and then weighing 62.5ml of an azo grafting agent solution with the concentration of 10mmol/L, and N 2 Protection, stirring at room temperature for 21h, washing with methanol multiple times, and preparing 3.5wt.% of grafted molybdenum sulfide particle aqueous solution with deionized water-ethanol, wherein the volume ratio of deionized water to 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, 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, and controlling the pressure of the hydrothermal reaction kettle to be 5.5 o The rate of C/min rises to 190 o C, in stirring barThe reaction is continued for 30 hours under the piece and naturally cooled.
(4) Deionized water wash, 250 o And C, roasting in air to obtain the molybdenum sulfide modified particles coated with the 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. 2.5g molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent into a three-neck flask, and adding 50mL of H with the mass fraction of 98 percent 2 SO 4 And 15-67% HNO by mass fraction of 15 mL 3 Sealing, magnetically stirring for 20min, and heating in water bath at 100 o C reflux treatment 6h, deionized water washing to neutrality, and air furnace 70 o And C, drying 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), adding the molybdenum sulfide particles into a three-port bottle, adding 2ml of triethylamine into the three-port bottle, slowly and dropwise adding the solution, then weighing 75ml of 15mmol/L of azo grafting agent solution, and N 2 Protection, stirring for 24h at room temperature, washing with methanol for several times, and preparing 5wt.% of grafted molybdenum sulfide particle aqueous solution with deionized water-ethanol, wherein the volume ratio of deionized water to 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, evacuating with pure oxygen for 5min, pressurizing with pure oxygen to enable the pressure gauge of the hydrothermal reaction kettle to be 1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, and controlling the pH value to be 6 o The rate of C/min rises to 200 o And C, continuously reacting for 36h under the stirring condition, and naturally cooling.
(4) Deionized water wash, 300 o And C, roasting in air to obtain the molybdenum sulfide modified particles coated with the 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 2g 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 the molybdenum sulfide particles into a three-necked flask, adding 1.5ml of triethylamine into the three-necked flask, slowly and dropwise adding the solution, and then weighing 62.5ml of an azo grafting agent solution with the concentration of 10mmol/L, and N 2 Protection, stirring at room temperature for 21h, washing with methanol multiple times, and preparing 3.5wt.% of grafted molybdenum sulfide particle aqueous solution with deionized water-ethanol, wherein the volume ratio of deionized water to 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, evacuating with pure oxygen for 4min, and pressurizing with pure oxygenThe pressure gauge of the hydrothermal reaction kettle is 1.05Mpa, the pure oxygen inlet valve is closed, and the hydrothermal reaction kettle is sealed to 5.5 o The rate of C/min rises to 190 o And C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized water wash, 250 o And C, roasting in 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, and adding 47.5mL of H with the mass fraction of 98 percent 2 SO 4 And HNO with the mass fraction of between 65 and 67 percent of 12.5 and 12.5 mL 3 Sealing, magnetically stirring for 17.5min, and heating in water bath at 100 o C reflux treating 5 h, washing with deionized water to neutrality, and air-heating in a furnace 65 o And C, drying 15 and h 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 the molybdenum sulfide particles into a three-necked flask, adding 1.5ml of triethylamine into the three-necked flask, slowly and dropwise adding the solution, and then weighing 62.5ml of an azo grafting agent solution with the concentration of 10mmol/L, and N 2 Protection, stirring at room temperature for 21h, washing with methanol multiple times, and preparing 3.5wt.% of grafted molybdenum sulfide particle aqueous solution with deionized water-ethanol, wherein the volume ratio of deionized water to 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, and sealing the hydrothermal reaction kettle to 5.5 o The rate of C/min rises to 190 o C, continuously reacting for 30h under the stirring condition, and self-reactingAnd then cooling.
(4) Deionized water wash, 250 o And C, roasting in air to obtain the molybdenum sulfide modified particles coated with the 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.
In addition, contact angle test was 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 with a tableting thickness of about 1 to 2mm, deionized water was used as a solution probe, and contact angle of the tableting of example 2 was tested to be 9 to 12 o Contact angles 83-87 for comparative example 1 o 。
Example 4
2300g/L nickel sulfate;
30g/L of nickel chloride;
boric acid 30g/L;
0.02g/L sodium dodecyl benzene sulfonate wetting agent;
0.6g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
0.2g/L o-chlorobenzaldehyde secondary brightening agent;
0.15g/L of sodium methylene dinaphthyl sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspension solvent;
cathode current density 2.5A/dm 2 Stirring at 5rpm for 30min at 40 o C。
Example 5
235g/L nickel sulfate;
35g/L of nickel chloride;
boric acid 32.5g/L;
0.035g/L of sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
0.3g/L o-chlorobenzaldehyde secondary brightening agent;
0.2g/L of sodium methylene dinaphthyl sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspension solvent;
cathode current density 2.75A/dm 2 Stirring at 10rpm for 40min at 45 o C。
Example 6
240g/L nickel sulfate;
nickel chloride 40g/L;
boric acid 35g/L;
0.05g/L sodium dodecyl benzene sulfonate wetting agent;
0.8g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
0.4g/L o-chlorobenzaldehyde secondary brightening agent;
0.25g/L of sodium methylene dinaphthyl sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspension solvent;
cathode current density 3A/dm 2 Stirring at 15rpm for 50min at 50 o C。
Comparative example 4
235g/L nickel sulfate;
35g/L of nickel chloride;
boric acid 32.5g/L;
0.035g/L of sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
0.3g/L o-chlorobenzaldehyde secondary brightening agent;
0.2g/L of sodium methylene dinaphthyl sulfonate auxiliary brightening agent;
5wt.% molybdenum sulfide aqueous solution;
cathode current density 2.75A/dm 2 Stirring at 10rpm for 40min at 45 o C。
Designated as D-4.
Comparative example 5
235g/L nickel sulfate;
35g/L of nickel chloride;
boric acid 32.5g/L;
0.7g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
5wt.% inorganic particle suspension solvent;
cathode current density 2.75A/dm 2 Stirring at 10rpm for 40min at 45 o C。
Designated as D-5.
Comparative example 6
235g/L nickel sulfate;
35g/L of nickel chloride;
boric acid 32.5g/L;
0.035g/L of sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
0.3g/L o-chlorobenzaldehyde secondary brightening agent;
0.2g/L of sodium methylene dinaphthyl sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspension solvent;
cathode current density 2.75A/dm 2 Stirring at 10rpm for 40min at 45 o C。
The preparation process of the inorganic particles comprises the following steps:
(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, and adding 47.5mL of H with the mass fraction of 98 percent 2 SO 4 And HNO with the mass fraction of between 65 and 67 percent of 12.5 and 12.5 mL 3 Sealing, magnetically stirring for 17.5min, and heating in water bath at 100 o C reflux treating 5 h, washing with deionized water to neutrality, and air-heating in a furnace 65 o And C, drying 15 and h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
Designated as D-6.
Comparative example 7
235g/L nickel sulfate;
35g/L of nickel chloride;
boric acid 32.5g/L;
0.035g/L of sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether disulfonate primary brightening agent;
0.3g/L o-chlorobenzaldehyde secondary brightening agent;
0.2g/L of sodium methylene dinaphthyl sulfonate auxiliary brightening agent;
cathode current density 2.75A/dm 2 Stirring at 10rpm for 40min at 45 o C。
Designated as D-7.
As is apparent from the above table and fig. 5 and fig. 6, the surface flatness, brightness and hardness of the plating layer can be effectively improved by the composite plating inorganic modified particles and the synergistic brightening agent, and the friction coefficient is extremely low, wherein the brightness GU value is 249, the hardness is 923HV, the friction coefficient is 0.27-0.32, compared with D-7, the hardness and friction coefficient of the plating layer are obviously improved, but the brightness is lost, mainly because the introduction of the inorganic particles can generate obvious plating unevenness phenomenon, as shown in D-4, when the unmodified pure molybdenum sulfide is added into the plating solution, the surface brightness of the plating layer is only 117 due to the uneven surface of the plating layer.
Furthermore, it should be noted herein that the plating bath settling time of example 5 is significantly reduced compared to examples 1-3, mainly because the bath is acidic and significantly corrodes the silica coating on the sulfide surface, resulting in a reduced suspension settling time of the bath.
Furthermore, it was further demonstrated by comparative examples 5 and D-5 that the main brightener alone only gave a semi-bright nickel coating, and further that the brightness was inferior to D-6 due to the influence of inorganic particles, and further that the flatness of the coating was affected by the absence of secondary and auxiliary brighteners, resulting in no significant difference in coefficient of friction from D-7.
In sum, the composite plating inorganic modified particles and the synergistic brightening agent can effectively improve the surface flatness, the brightness and the hardness of the nickel plating layer and reduce the friction coefficient of the nickel plating layer.
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 (4)
1. A composite electroplating bright nickel plating solution is characterized by comprising nickel sulfate, nickel chloride, boric acid, a wetting agent, a primary brightening agent, a secondary brightening agent, an auxiliary brightening agent and an inorganic particle suspension solvent, wherein the primary brightening agent is sodium dodecyl diphenyl ether disulfonate; the secondary brightening agent is o-chlorobenzaldehyde; the auxiliary brightening agent is sodium methylene dinaphthyl sulfonate, the wetting agent is sodium dodecyl benzene sulfonate, wherein the inorganic particle suspension solvent consists of 1-20wt.% of inorganic particles and deionized water, the inorganic particles are of a core-shell structure with silicon oxide as a shell and molybdenum sulfide as a core, and the molybdenum sulfide is subjected to strong mixed acid pretreatment, azo grafting agent grafting treatment, hydrothermal treatment and roasting treatment in sequence;
the pretreatment process of the strong mixed acid comprises the following steps: putting 1.5-2.5. 2.5g molybdenum sulfide into a three-neck flask, adding 45-50 mL of 98% H by mass 2 SO 4 And from 10 to 15 and mL mass percent of HNO of 65 to 67 percent 3 Sealing, magnetically stirring, stirring for 15-20 min, heating in water bath at 100deg.C, reflux treating for 4-6 h, washing with deionized water to neutrality, and drying at 60-70deg.C in air furnace for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
grafting treatment of azo grafting agent: weighing 1-1.5g of molybdenum sulfide particles pretreated by strong mixed acid, adding the molybdenum sulfide particles into a three-mouth bottle, adding 1-2ml of triethylamine into the three-mouth bottle, slowly and dropwise adding 50-75ml of azo grafting agent solution with the concentration of 5-15mmol/L, and N 2 Stirring at room temperature for 18-24h, 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;
the azo grafting agent has the following structure:
；
the hydrothermal treatment: 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 to 180-200 ℃, continuously reacting for 24-36h under the stirring condition, and naturally cooling;
the temperature of the roasting treatment is 200-300 ℃, and the atmosphere is air.
2. A composite bright nickel plating solution according to claim 1, characterized in that said solution consists of 230-240g/L of nickel sulfate, 30-40g/L of nickel chloride, 30-35g/L of boric acid, 0.02-0.05g/L of wetting agent, 0.6-0.8g/L of primary brightening agent, 0.2-0.4g/L of secondary brightening agent, 0.15-0.25g/L of auxiliary brightening agent and 1-20wt.% of inorganic particle suspension solvent.
3. A composite electroplated bright nickel plating solution according to claim 1, wherein the pH of the plating solution is 4-6, electroplating parameters: cathode current density of 2.5-3A/dm 2 Stirring at 5-15rpm for 30-50min at 40-50deg.C.
4. The composite bright nickel plating solution according to claim 1, wherein the hydrothermal treatment is a programmed temperature rise from normal temperature to 180-200 ℃ at a temperature rise rate of 5-6 ℃/min.
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