CN112981501A - Composite bright nickel plating solution - Google Patents
Composite bright nickel plating solution Download PDFInfo
- Publication number
- CN112981501A CN112981501A CN202110247427.1A CN202110247427A CN112981501A CN 112981501 A CN112981501 A CN 112981501A CN 202110247427 A CN202110247427 A CN 202110247427A CN 112981501 A CN112981501 A CN 112981501A
- Authority
- CN
- China
- Prior art keywords
- molybdenum sulfide
- plating solution
- particles
- nickel plating
- bright nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 24
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000002245 particle Substances 0.000 claims abstract description 88
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 16
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 34
- 238000005282 brightening Methods 0.000 claims description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 28
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 25
- 229910021641 deionized water Inorganic materials 0.000 claims description 25
- 239000010954 inorganic particle Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000725 suspension Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 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 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 13
- 239000004327 boric acid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000080 wetting agent Substances 0.000 claims description 12
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical group ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000009713 electroplating 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 3
- LCRMGUFGEDUSOG-UHFFFAOYSA-N naphthalen-1-ylsulfonyloxymethyl naphthalene-1-sulfonate;sodium Chemical group [Na].C1=CC=C2C(S(=O)(OCOS(=O)(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 LCRMGUFGEDUSOG-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- 239000002105 nanoparticle Substances 0.000 abstract description 5
- 238000000576 coating method Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000011734 sodium Substances 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
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical group [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 7
- XEGMDUOAESTQCC-UHFFFAOYSA-N 1-(naphthalen-1-ylmethyl)naphthalene;sodium Chemical compound [Na].C1=CC=C2C(CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 XEGMDUOAESTQCC-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 229910010271 silicon carbide Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 2
- 241001584785 Anavitrinella pampinaria Species 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229910001060 Gray iron Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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 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
- 238000005299 abrasion Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000000643 oven drying Methods 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000377 silicon dioxide 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
- 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
Images
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
-
- 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
Landscapes
- 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, and 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.
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. The friction wear is one of the main reasons of the failure of mechanical equipment, about 80 percent of the failure of parts is caused by various types of wear, the wear not only consumes energy and materials, but also accelerates the scrapping of the equipment, causes frequent part replacement, causes great loss to economy, causes resource, energy waste and economic loss due to corrosion and rusting, and even endangers the personal safety in severe cases, statistics show that about 1/3 of energy in the mechanical manufacturing is directly or indirectly consumed by the loss caused by the wear and the corrosion. To improve the high temperature corrosion resistance and wear resistance of metal surfaces, many methods for strengthening the surfaces have been developed. The electrodeposition technology is very important in improving the wear resistance, lubricity and the like of the metal surface. At present, a better electrodeposition method for improving the high-temperature corrosion resistance and wear resistance of a metal surface is to deposit metallic nickel or chromium and the like on the metal surface by electrodeposition to form a self-lubricating resistant composite coating and a highly wear-resistant composite coating.
The self-lubricating composite coating is accompanied with friction and abrasion in mechanical motion, and the loss caused by the mechanical motion is huge every year. Two methods of case hardening and reducing the coefficient of friction are commonly used to improve the wear resistance of materials. The self-lubricating composite coating is a composite coating with an antifriction effect, and the added composite particles are so-called solid lubricating particles with a self-lubricating effect, such as: MoS2BN, graphite, polytetrafluoroethylene and other matrix metals form various composite coatings with higher hardness and excellent wear resistance.
High wear-resistant composite coating: the high wear-resistant composite coating has attracted more and more attention due to its good wear resistance. The high wear resistance of the composite coating comes from the strength of the composite particles themselves, the refinement of the matrix metal crystals, and also the dispersion strengthening of sufficiently small particles (usually of the order of nanometers). The hard particles added in the high-wear-resistance composite coating are the most widely applied and important composite coatings. The application of highly wear resistant composite coatings to internal combustion engine blocks is the most successful example. The cylinder block is the heart of the internal combustion engine and its life determines to a large extent the life of the internal combustion engine. The sliding surface of the cylinder body of the internal combustion engine is required to have the performances of wear resistance, heat resistance, mechanical scratch resistance, corrosion resistance and the like, and the common gray cast iron cylinder is difficult to meet the requirements. Efforts are constantly being made to find ways to improve the wear and corrosion resistance and extend the service life of the cylinder.
For example, CN20091025571A discloses an electroplated nickel-based-graphite self-lubricating material and a coating treatment method thereof, wherein the material is prepared by using nickel sulfate as a base material, adding graphite, boric acid, sodium chloride, sodium sulfate, magnesium sulfate and sodium dodecyl sulfate, and then directly electroplating the surface of a metal part by an electroplating technology. The invention can obviously improve the wear-resisting strength of the surface of the metal part and has the obvious advantages of simple process, convenient operation and low production cost.
For example, CN201710481903A discloses a nickel-plated silicon carbide copper-based alloy material and a preparation method thereof, and the material comprises the following components by volume percent: 88-93.5% of copper alloy ZCuAl10Fe3Mn2 and 6.5-12% of nickel-plated silicon carbide, and further improvement of the performance of the copper alloy material is realized by utilizing the high hardness, high wear resistance, good self-lubrication and high-temperature strength of the nano-scale silicon carbide, so that the nickel-plated silicon carbide copper-based alloy obtained according to the invention has higher strength, hardness, wear resistance and corrosion resistance, thereby prolonging the service life of aerospace high-strength pressure-resistant products, petroleum engineering wear-resistant part products and ocean engineering equipment corrosion-resistant product accessories.
At present, the most critical limiting factor of composite plating is the hydrophilicity of the doped particles, and those skilled in the art know that the hydrophilicity of particles such as molybdenum sulfide, tungsten sulfide, boron nitride and the like is very poor, so that the particles are dispersed in a liquid phase, and the primary problem is that the particles can be wetted by liquid and can enter the liquid phase, so that the surface modification of the particles is needed to realize uniform composite plating of the particles.
Disclosure of Invention
Based on the defects of the prior art, the plating solution provided by the invention comprises high-dispersion inorganic nano particles, the particles are molybdenum sulfide coated with silicon oxide, the molybdenum sulfide 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 the plating layer is effectively improved and the friction coefficient is reduced by adding the lubricating inorganic particles, and the brightness of the plating layer is effectively maintained by using the composite brightener.
The high-wear-resistance lubricating composite electroplating bright nickel 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 dinaphthalene 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 agent grafting treatment, hydrothermal treatment and roasting treatment in sequence.
Further, 240g/L of nickel sulfate 230-40 g/L, 30-35g/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 brightener, 0.2-0.4g/L of secondary brightener, 0.15-0.25g/L of auxiliary brightener and 1-20wt.% of inorganic particle suspension solvent.
Further, the pH value of the plating solution is 4-6, and the plating parameters are as follows: cathode current density of 2.5-3A/dm2Stirring at 5-15rpm for 30-50min at 40-50 deg.CoC。
Further, the strong mixed acid treatment process comprises the following steps: putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15 mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoAnd C, drying for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
Further, the azo grafting agent is grafted: weighing 1-1.5g of molybdenum sulfide particles pretreated by strong mixed acid, adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2And (2) protecting, stirring for 18-24h at room temperature, washing with methanol for multiple times, and preparing 2-5wt.% of a grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3).
Further, the hydrothermal treatment comprises the following steps: placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa,closing the pure oxygen inlet valve, sealing the hydrothermal reaction kettle, and heating to 180-oAnd C, continuously reacting for 24-36h under the stirring condition, and naturally cooling.
Further, the temperature of the roasting is 200-300-oAnd C, the atmosphere is air.
Furthermore, the particle size of the molybdenum sulfide is 50-150nm, and the purity is more than 99.8%.
Further, the azo grafting agent has the following structure:
furthermore, the hydrothermal process is temperature programming, and the temperature is 5-6 ℃ from the normal temperatureoC/min is raised to 180-oC。
With respect to the present invention:
(1) the brightness nickel liquid of the invention is composed of 240g/L of nickel sulfate 230-,
wherein, the nickel sulfate and the nickel chloride are main salts, the dosage of the nickel sulfate is almost 6 to 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.
The boric acid is used as a buffering agent, so that the stability of the pH value of 4-6 is effectively maintained, and the phenomena that a pinhole is generated due to too low pH value and hydroxide precipitation is generated due to too low pH value are avoided.
The wetting agent is sodium dodecyl benzene sulfonate which can be used as a brightening agent and a surface wetting agent simultaneously, can effectively reduce the consumption of the primary brightening agent, and can be used as a surfactant to further improve the wettability of the inorganic particles and improve the dispersibility of the inorganic composite plating particles in a plating layer.
Primary brightening agent: sodium dodecyl diphenyl oxide disulfonate, an unsaturated organic compound, can be used alone to obtain a semi-bright coating.
Secondary brightener: the secondary brightener is o-chlorobenzaldehyde, and can obviously improve the brightness and leveling property of the plating layer.
Auxiliary brightening agent: the auxiliary brightener is sodium methylene dinaphthalene sulfonate, so that the brightness and the evenness of the plating layer are further improved, the plating layer contains inorganic particles, the inorganic particles have great influence on the evenness of the surface of the plating layer in the composite plating process, and if the auxiliary brightener is not added, the brightness and the evenness of the plating layer are required to be improved.
Inorganic particle suspension solvent: sulfide particles coated with silicon oxide, wherein the silicon oxide is used for improving the water solubility of the sulfide, the sulfide is molybdenum sulfide, and the sulfide is conventional lubricating particles for composite plating and is mainly used for reducing the friction coefficient of a plating layer.
(2) Preparing inorganic composite plating particles: putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15 mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoC, drying for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment;
as known to those skilled in the art, the molybdenum sulfide surface does not contain any water-soluble bonds or functional groups, making it extremely poorly water-soluble, via H2SO4And HNO3Mixed acid, heating and refluxing the molybdenum sulfide, aiming at improving the solubility and the dispersibility of the molybdenum sulfide in the solution, and the mixed acid treatment has the following effects: (1) can remove the pollutants and impurities on the surface, such as grease, dust and the like; (2) the roughness of the surface is improved; (3) hydrophilic functional groups are introduced, and infrared tests show that the molybdenum sulfide is acidified and at least contains strong active groups such as-COOH, -CHO, C = O and the like on the surface.
Weighing 1-1.5g of the molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, and slowly dropwise adding the triethylamineThen 50-75ml of 5-15mmol/L azo grafting agent solution is measured, N2Protecting, stirring for 18-24h at room temperature, washing for multiple times by using methanol, preparing 2-5wt.% of grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1- (2-3), and under the initiated catalysis condition of triethylamine, performing chemical reaction on the silicon-containing azo grafting agent solution and the molybdenum sulfide surface to directly graft the molybdenum sulfide surface to form Si-O-MoS2。
Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating and placing in a 180-phase 200-phase reactoroAnd C, continuously reacting for 24-36h under the stirring condition, naturally cooling, performing hydrothermal reaction, performing dissociation on an azo reagent under the conditions of high temperature and high pressure, oxidizing silicon adsorbed on the surface of the sulfide under the conditions of alkaline price adjustment and pure oxygen price adjustment to form silicon sol or silicon oxide, and finally drying to obtain silicon oxide-coated molybdenum sulfide nanoparticles, wherein the particles have extremely high hydrophilicity.
Advantageous technical effects
(1) The preparation method comprises the steps of introducing a multifunctional functional group through acidification pretreatment on the surface of molybdenum sulfide, then grafting a silicon-containing azo grafting agent on the functional group, regulating the pH value through hydrothermal treatment, and oxidizing with pure oxygen to obtain silicon oxide-coated molybdenum sulfide nanoparticles, wherein silicon oxide is a shell, molybdenum sulfide is a core, and the coating rate is 100%.
(2) The molybdenum sulfide particles coated with the silicon oxide have extremely high dispersibility in water, under a sealed condition, the complete settling time of 20wt.% of the suspension solution is 140h, obvious precipitation can be seen at the bottom of the solution within 80-90h, the complete settling time is more than 160h under a 5wt.% suspension test, obvious precipitation can be seen at the bottom of the solution within 120-130h, and the suspension time is increased along with the reduction of the concentration of the molybdenum sulfide particles coated with the silicon oxide.
(3) The silicon oxide-coated molybdenum sulfide particle high-dispersion particles are used for composite nickel plating and can be uniformly dispersed on the surface of a plating layer.
(4) The obtained nickel coating effectively ensures the brightness and the flatness of the coating under the synergistic action of the primary brightener, the secondary brightener and the auxiliary brightener.
(5) In the composite plating process, the 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.
The attached drawings of the specification:
FIG. 1 is a TEM image of molybdenum sulfide of the present invention after acidification treatment.
FIG. 2 is a TEM image of molybdenum sulfide coated with silicon oxide according to the present invention.
FIG. 3 is an SEM image (with ultrasonic oscillation) of a molybdenum sulfide coated with silicon oxide according to the present invention.
FIG. 4 is a sedimentation test of the modified inorganic particles of the present invention.
FIG. 5 is a SEM image of a cross-sectional view of a composite coating of the present invention.
FIG. 6 is an SEM image of the surface of the composite coating of the present invention.
The specific implementation mode 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 solutions, and the inorganic particle suspension solvents used in examples 4 to 6 were prepared by the method of example 2.
Example 1
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 1.5g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 45 mL of H with the mass fraction of 98 percent is added2SO4And 10 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 15 min, heating in water bath to 100%oC refluxing for 4h, washing to neutrality with deionized water, 60 in an air furnaceoC, drying for 12 h to obtain mixed acid oxidation treatmentOf molybdenum sulphide particles.
(2) Weighing 1g of molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, weighing 50ml of 5mmol/L azo grafting agent solution, and N2Protection, stirring for 18h at room temperature, washing with methanol for multiple times, and preparing a 2wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5, evacuating with pure oxygen for 3min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5MpaoThe rate of C/min is increased to 180oAnd C, continuously reacting for 24 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 200oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
Example 2
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oAnd C, drying for 15 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protection, stirring for 21h at room temperature, washing with methanol for several times, and deionizationPreparing 3.5wt.% aqueous solution of grafted molybdenum sulfide particles by using water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, evacuating with pure oxygen for 4min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5.5 MpaoThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
Example 3
A preparation method of modified particles for composite electroplating is provided, wherein the modified particles are sulfides coated by silicon oxide, and the preparation method is as follows.
(1) 2.5g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 50mL of H with the mass fraction of 98 percent is added2SO4And 15 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 20min, heating in water bath to 100%oC refluxing for 6h, washing to neutrality with deionized water, and air-oven drying for 70%oAnd C, drying for 18h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1-1.5g of molybdenum sulfide particles treated in the step (1) and adding the molybdenum sulfide particles into a three-necked bottle, adding 2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 75ml of 15mmol/L azo grafting agent solution, and N2Protection, stirring for 24 hours at room temperature, washing with methanol for multiple times, and preparing a 5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: 3.
(3) placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 8, evacuating with pure oxygen for 5min, and pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettleMeasured as 1.1Mpa, closing the pure oxygen inlet valve, sealing the hydrothermal reaction kettle by 6oThe rate of C/min is increased to 200oAnd C, continuously reacting for 36 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 300oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
As shown in fig. 1, by subjecting molybdenum sulfide to a strong acid acidification treatment, the particles are relatively dispersed, but are left to partially agglomerate.
As shown in fig. 2, the surface of the molybdenum sulfide is coated with a silicon oxide film, so that the particle dispersity is effectively improved, and the molybdenum sulfide can be separated and exist in the solution.
Ultrasonic oscillation is carried out on the molybdenum sulfide particles coated with the silicon oxide, so that a part of the silicon oxide film is stripped, and an obvious core-shell structure exists as shown in SEM of attached figure 3.
As shown in fig. 4, the molybdenum sulfide particles coated with silicon oxide obtained by the treatment method of example 2 were prepared into 5-20wt.% suspension solution, and the suspension solution was magnetically stirred at 500-800rpm for 5min, and the suspension time test was performed, so that it is obvious that the suspension solution of fig. 4 was 20wt.% suspension solution, the complete settling time was 140h, and obvious precipitation was observed at the bottom of the solution in 80-90 h.
The time to complete settling was > 160h, with a significant precipitation at the bottom of the solution seen at 120-130h, by testing for 5wt.% suspension.
Comparative example 1
Commercial molybdenum sulphide particles, passing the water solubility test at 5wt.%, have a time to complete sedimentation of less than 3 min.
Comparative example 2
The preparation method is as follows.
(1) 2g of molybdenum sulfide deionized water with the particle size of 75nm and the purity of more than 99.8 percent and ethanol are alternately washed.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked flask, adding 1.5ml of triethylamine into the three-necked flask, and slowly dropwise adding the triethylamineThen 62.5ml of 10mmol/L azo grafting agent solution is measured in, N2Protection, stirring for 21 hours at room temperature, washing with methanol for multiple times, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles with deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.75, evacuating with pure oxygen for 4min, pressurizing with pure oxygen to make the pressure of the hydrothermal reaction kettle be 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle to 5.5 MpaoThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, air roasting.
The complete settling time is less than 1h through a water solubility test of 5wt.%, the main reason is that no strong acid treatment is used for introducing active groups on the surface of the inert molybdenum sulfide, namely, the grafting effect cannot be exerted, the water solubility is improved through partial coating of hydrothermal ethyl orthosilicate, the coating is disordered coating, silicon effectively performs self-aggregation due to the fact that the surface of the molybdenum sulfide is inert, and a small amount of partially physically coated molybdenum sulfide can be formed under the stirring condition.
Comparative example 3
The preparation method is as follows.
(1) 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oAnd C, drying for 15 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
(2) Weighing 1.25g of the molybdenum sulfide particles treated in the step (1), adding the molybdenum sulfide particles into a three-necked bottle, adding 1.5ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 62.5ml of 10mmol/L azo grafting agent solution, and measuring N2Protecting, stirring at room temperature for 21h, and adding methanolAnd performing secondary washing, and preparing a 3.5wt.% aqueous solution of grafted molybdenum sulfide particles by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2.5).
(3) Placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, pressurizing by using air to ensure that the pressure of the hydrothermal reaction kettle is 1.05Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle by 5.5oThe rate of C/min is increased to 190oAnd C, continuously reacting for 30 hours under the stirring condition, and naturally cooling.
(4) Deionized Water Wash, 250oAnd C, roasting in air to obtain the silicon oxide coated molybdenum sulfide modified particles.
The roasting temperature is that the atmosphere is air.
The time for complete settling was less than 3h by testing the water solubility of 5wt.%, mainly because the grafted silicon was directly oxidized in a hydrothermal process under hydrothermal conditions without using ammonia and pure oxygen, and the silicon oxide was fixed by means of subsequent calcination, so that the silicon oxide was easily separated from the molybdenum sulfide and it was easy to separate, and if the 5wt.% suspension obtained in comparative example 3 was subjected to ultrasonic vibration treatment, the time for complete settling was less than 20 min.
In addition, the contact angle test was performed on example 2 and comparative example 1, and the silicon oxide-coated molybdenum sulfide of example 2 and the molybdenum sulfide particles of comparative example 1 were tabletted for 90s under a powder tabletting machine of 40MPa with a thickness of about 1-2mm, and the contact angle of the tabletted sheets of example 2 was tested to be 9-12 using deionized water as a solution probeoContact angles 83-87 of comparative example 1o。
Example 4
2300g/L of nickel sulfate;
30g/L of nickel chloride;
30g/L of boric acid;
0.02g/L sodium dodecyl benzene sulfonate wetting agent;
0.6g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.2g/L of o-chlorobenzaldehyde secondary brightener;
0.15g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.5A/dm2Stirring at 5rpm for 30min at 40 deg.CoC。
Example 5
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Example 6
240g/L of nickel sulfate;
40g/L of nickel chloride;
35g/L of boric acid;
0.05g/L of sodium dodecyl benzene sulfonate wetting agent;
0.8g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.4g/L of o-chlorobenzaldehyde secondary brightener;
0.25g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 3A/dm2Stirring at 15rpm for 50min at 50 deg.CoC。
Comparative example 4
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% aqueous molybdenum sulfide;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Is named D-4.
Comparative example 5
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Is named D-5.
Comparative example 6
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
5wt.% inorganic particle suspending solvent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
The preparation process of the inorganic particles is as follows:
(1) 2g of molybdenum sulfide with the particle size of 75nm and the purity of more than 99.8 percent is placed in a three-neck flask, and 47.5mL of H with the mass fraction of 98 percent is added2SO4And 12.5 mL of HNO with the mass fraction of 65-67 percent3Sealing, magnetically stirring for 17.5min, heating in water bath to 100%oC refluxing for 5 h, washing to neutrality with deionized water, and air-drying in an air furnace 65oAnd C, drying for 15 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
Is named D-6.
Comparative example 7
235g/L of nickel sulfate;
35g/L of nickel chloride;
32.5g/L of boric acid;
0.035g/L sodium dodecyl benzene sulfonate wetting agent;
0.7g/L of dodecyl diphenyl ether sodium disulfonate primary brightening agent;
0.3g/L of o-chlorobenzaldehyde secondary brightener;
0.2g/L of methylene dinaphthalene sodium sulfonate auxiliary brightening agent;
cathode current density 2.75A/dm2Stirring at 10rpm for 40min at 45 deg.CoC。
Was designated as D-7.
As is apparent from the above table and fig. 5 and fig. 6, the surface smoothness, brightness and hardness of the plating layer can be effectively improved by the composite plating of the inorganic modified particles and the brightener with synergistic effect, and the friction coefficient is extremely low, wherein the brightness GU value is 249, the hardness is 923HV, and the friction coefficient is 0.27-0.32, compared with D-7, the hardness and the friction coefficient of the plating layer are both significantly improved, but the brightness is lost, the main reason is that the introduction of the inorganic particles usually generates an obvious plating layer unevenness phenomenon, as shown in D-4, when the pure molybdenum sulfide without modification is added into the plating solution, the surface brightness of the plating layer is only 117 due to the unevenness of the plating layer surface.
It should be noted here that the bath settling time of example 5 is significantly reduced compared to examples 1-3, mainly because the bath is acidic and can significantly corrode the silica coating on the sulfide surface, resulting in a reduction in the suspension settling time of the bath.
Furthermore, it is further demonstrated by comparative examples 5 and D-5 that only a semi-bright nickel coating can be obtained using the primary brightener alone, and further that the brightness is inferior to D-6 due to the influence of the inorganic particles, and further that the flatness of the coating is affected due to the absence of the secondary and secondary brighteners in the bath, resulting in no significant difference in the coefficient of friction from D-7.
In conclusion, the composite plating inorganic modified particles and the synergistic brightener can effectively improve the surface smoothness, brightness and hardness of the nickel plating layer and reduce the friction coefficient of the nickel plating layer.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (10)
1. The 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 dinaphthalene sulfonate, the inorganic particle suspension solvent is composed 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 with a grafting agent, hydrothermal treatment and roasting treatment in sequence.
2. The composite bright nickel plating solution as set forth in claim 1, wherein the nickel sulfate is 230-240g/L, the nickel chloride is 30-40g/L, the boric acid is 30-35g/L, the wetting agent is 0.02-0.05g/L, the primary brightener is 0.6-0.8g/L, the secondary brightener is 0.2-0.4g/L, the auxiliary brightener is 0.15-0.25g/L, and the inorganic particle suspension solvent is 1-20 wt.%.
3. The composite bright nickel plating solution according to claim 2, wherein the pH value of the plating solution is 4-6, and the plating parameters are as follows: cathode current density of 2.5-3A/dm2Stirring at 5-15rpm for 30-50min at 40-50 deg.CoC。
4. A process as claimed in claim 1The composite bright nickel plating solution is characterized in that the strong mixed acid treatment process comprises the following steps: putting 1.5-2.5 g of molybdenum sulfide into a three-neck flask, and adding 45-50 mL of 98% H by mass fraction2SO4And 10-15 mL of HNO with the mass fraction of 65% -67%3Sealing, magnetically stirring for 15-20 min, heating in water bath to 100%oC refluxing for 4-6 h, washing with deionized water to neutrality, and air-drying in an air furnace for 60-70 hoAnd C, drying for 12-18 h to obtain molybdenum sulfide particles subjected to mixed acid oxidation treatment.
5. The composite bright nickel plating solution according to claim 1, wherein the azo grafting agent is grafted: weighing 1-1.5g of molybdenum sulfide particles pretreated by strong mixed acid, adding the molybdenum sulfide particles into a three-necked bottle, adding 1-2ml of triethylamine into the three-necked bottle, slowly dropwise adding the triethylamine, measuring 50-75ml of 5-15mmol/L azo grafting agent solution, and adding N2And (2) protecting, stirring for 18-24h at room temperature, washing with methanol for multiple times, and preparing 2-5wt.% of a grafted molybdenum sulfide particle aqueous solution by using deionized water-ethanol, wherein the volume ratio of the deionized water to the ethanol is 1: (2-3).
6. The composite bright nickel plating solution according to claim 1, wherein the hydrothermal treatment comprises: placing the grafted molybdenum sulfide particle aqueous solution in a lining-free hydrothermal reaction kettle, adding a proper amount of ammonia water to adjust the pH value to 7.5-8, evacuating by using pure oxygen, pressurizing by using pure oxygen to ensure that the pressure of the hydrothermal reaction kettle is 1-1.1Mpa, closing a pure oxygen inlet valve, sealing the hydrothermal reaction kettle, heating to 180-oAnd C, continuously reacting for 24-36h under the stirring condition, and naturally cooling.
7. The composite bright nickel plating solution as claimed in claim 1, wherein the baking temperature is 200-300-oAnd C, the atmosphere is air.
8. The composite bright nickel plating solution according to claim 1, wherein the molybdenum sulfide has a particle size of 50 to 150nm and a purity of more than 99.8%.
9. The composite bright nickel plating solution according to claim 5, wherein the azo grafting agent has the following structure:
10. the composite bright nickel plating solution according to claim 6, wherein the hydrothermal process is temperature programming from 5 to 6 times at room temperatureoC/min is raised to 180-oC。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110247427.1A CN112981501B (en) | 2021-03-05 | 2021-03-05 | Composite bright nickel plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110247427.1A CN112981501B (en) | 2021-03-05 | 2021-03-05 | Composite bright nickel plating solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112981501A true CN112981501A (en) | 2021-06-18 |
| CN112981501B CN112981501B (en) | 2024-03-01 |
Family
ID=76353189
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110247427.1A Active CN112981501B (en) | 2021-03-05 | 2021-03-05 | Composite bright nickel plating solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112981501B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660154A (en) * | 2012-04-28 | 2012-09-12 | 常州大学 | Surface modification method for nanometer titanium dioxide |
| CN105502421A (en) * | 2016-01-08 | 2016-04-20 | 中山大学 | Preparation method of zinc silicate hollow micron ball |
| CN106977762A (en) * | 2017-03-31 | 2017-07-25 | 济南大学 | A kind of method of production of low-density and high-strength phenol formaldehyde foam |
| CN108321371A (en) * | 2018-01-17 | 2018-07-24 | 电子科技大学 | A kind of preparation method of silica and molybdenum trioxide composite positive pole |
| CN108404854A (en) * | 2018-01-19 | 2018-08-17 | 江苏大学 | A kind of preparation method and applications of mackle mark porous silicon film |
| CN112919542A (en) * | 2021-03-05 | 2021-06-08 | 赵琳琳 | Preparation method of modified particles for composite electroplating |
| CN113354960A (en) * | 2021-05-24 | 2021-09-07 | 广东海浦倍尔新材料有限公司 | Modified inorganic nano particle and preparation method thereof |
| CN112981500B (en) * | 2021-03-05 | 2022-05-20 | 深圳市康恒电子有限公司 | High-brightness composite nickel-plated layer |
| CN113584542B (en) * | 2021-07-27 | 2022-07-26 | 东莞普瑞得五金塑胶制品有限公司 | Method for plating nickel on surface of aluminum alloy |
-
2021
- 2021-03-05 CN CN202110247427.1A patent/CN112981501B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660154A (en) * | 2012-04-28 | 2012-09-12 | 常州大学 | Surface modification method for nanometer titanium dioxide |
| CN105502421A (en) * | 2016-01-08 | 2016-04-20 | 中山大学 | Preparation method of zinc silicate hollow micron ball |
| CN106977762A (en) * | 2017-03-31 | 2017-07-25 | 济南大学 | A kind of method of production of low-density and high-strength phenol formaldehyde foam |
| CN108321371A (en) * | 2018-01-17 | 2018-07-24 | 电子科技大学 | A kind of preparation method of silica and molybdenum trioxide composite positive pole |
| CN108404854A (en) * | 2018-01-19 | 2018-08-17 | 江苏大学 | A kind of preparation method and applications of mackle mark porous silicon film |
| CN112919542A (en) * | 2021-03-05 | 2021-06-08 | 赵琳琳 | Preparation method of modified particles for composite electroplating |
| CN112981500B (en) * | 2021-03-05 | 2022-05-20 | 深圳市康恒电子有限公司 | High-brightness composite nickel-plated layer |
| CN113354960A (en) * | 2021-05-24 | 2021-09-07 | 广东海浦倍尔新材料有限公司 | Modified inorganic nano particle and preparation method thereof |
| CN113584542B (en) * | 2021-07-27 | 2022-07-26 | 东莞普瑞得五金塑胶制品有限公司 | Method for plating nickel on surface of aluminum alloy |
Non-Patent Citations (1)
| Title |
|---|
| 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, no. 04, pages 94 - 100 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112981501B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112981500B (en) | High-brightness composite nickel-plated layer | |
| Sadeghzadeh-Attar et al. | Improvement in tribological behavior of novel sol-enhanced electroless Ni-P-SiO2 nanocomposite coatings | |
| CN101545104B (en) | Nanometer chemical composite plating method | |
| CN101665937B (en) | Method for producing nanometer composite phosphated film based on current carrier control technology | |
| WO2019119487A1 (en) | Hydroxyl graphene modified clad layer sealant and preparation method therefor | |
| CN109056006B (en) | A kind of electro-plating method and electroplate liquid of anticorrosion antiwear workpiece | |
| CN108914172A (en) | A kind of amorphous nickel tungsten cobalt-tungsten-nickel-phosphorus alloy electroplating and processing technology applied to oil pump sleeve plating | |
| CN111547752A (en) | Alumina-coated nano flaky hexagonal boron nitride composite powder and preparation method and application thereof | |
| CN107586989B (en) | A kind of copper base high temperature self lubricating composite material | |
| CN112919542B (en) | Preparation method of modified particles for composite electroplating | |
| CN109023488B (en) | Micro-crack hard chromium composite coating and preparation method thereof | |
| CN112981501B (en) | Composite bright nickel plating solution | |
| CN112981502B (en) | Suspending agent for high-dispersion composite electroplating | |
| CN109183132B (en) | Preparation process of Sn-Ni-graphene/fluorinated graphene composite coating | |
| CN113584542B (en) | Method for plating nickel on surface of aluminum alloy | |
| CN113502518B (en) | Wear-resistant aluminum alloy composite material | |
| WO2023015602A1 (en) | In-situ synthesis method for ni-w-wc composite plating | |
| RU2437967C1 (en) | Procedure for sedimentation of composite coating nickel-vanadium-phosphorus-boron nitride | |
| CN2581703Y (en) | Full aluminium alloy cylinder of engine | |
| CN111962112B (en) | High-wear-resistance and corrosion-resistance Ni-Mo/diamond composite coating based on phase change and preparation method thereof | |
| CN106087003A (en) | A kind of improve the method for Cr nano-particle content in Ni Cr nano-composite plate | |
| Jothi et al. | Electroless Composite Coatings | |
| CN113584535B (en) | Nickel plating solution for aluminum alloy | |
| CN101122043A (en) | Nano tungsten carbide-nickel composite coat and its preparation method and application | |
| CN114107881B (en) | High-speed fan blade processing technology |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240109 Address after: 516000 C-9, Honghai fine chemical base, Yonghu Town, Huiyang District, Huizhou City, Guangdong Province Applicant after: HUIZHOU RONG AN DA CHEMICAL Co.,Ltd. Address before: College of chemistry and chemical engineering, Nanjing University, 22 Hankou Road, Gulou District, Nanjing City, Jiangsu Province, 210000 Applicant before: Zhao Linlin |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |