CN115613087A - High-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution and application thereof - Google Patents
High-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution and application thereof Download PDFInfo
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- 238000009713 electroplating Methods 0.000 title claims abstract description 64
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 55
- 239000000956 alloy Substances 0.000 title claims abstract description 55
- 229910020674 Co—B Inorganic materials 0.000 title claims abstract description 51
- 238000007747 plating Methods 0.000 claims abstract description 60
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000080 wetting agent Substances 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000012190 activator Substances 0.000 claims abstract description 10
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000006174 pH buffer Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical group [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 claims description 6
- 239000006179 pH buffering agent Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000001488 sodium phosphate Substances 0.000 claims description 6
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 6
- IKCWFYCMZBNCKA-UHFFFAOYSA-N 2-(ethylamino)-4-methyl-1,3-thiazole-5-carboxylic acid Chemical compound CCNC1=NC(C)=C(C(O)=O)S1 IKCWFYCMZBNCKA-UHFFFAOYSA-N 0.000 claims description 5
- YOMSJEATGXXYPX-UHFFFAOYSA-N 2-methoxy-4-vinylphenol Chemical compound COC1=CC(C=C)=CC=C1O YOMSJEATGXXYPX-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- VIQXICKUKPVFRK-UHFFFAOYSA-N (S)-3-Methylthiohexyl acetate Chemical compound CCCC(SC)CCOC(C)=O VIQXICKUKPVFRK-UHFFFAOYSA-N 0.000 claims description 3
- NBYNIEZPFNQVQK-UHFFFAOYSA-N 1,3-dicyclohexyl-1,2-dihydroimidazol-1-ium;chloride Chemical group [Cl-].C1N(C2CCCCC2)C=C[NH+]1C1CCCCC1 NBYNIEZPFNQVQK-UHFFFAOYSA-N 0.000 claims description 3
- SJRQTHAMRUOPBJ-UHFFFAOYSA-N 2-Propenyl 2-furancarboxylate Chemical compound C=CCOC(=O)C1=CC=CO1 SJRQTHAMRUOPBJ-UHFFFAOYSA-N 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 3
- 239000010960 cold rolled steel Substances 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229930187593 rose bengal Natural products 0.000 claims description 3
- AZJPTIGZZTZIDR-UHFFFAOYSA-L rose bengal Chemical compound [K+].[K+].[O-]C(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 AZJPTIGZZTZIDR-UHFFFAOYSA-L 0.000 claims description 3
- 229940081623 rose bengal Drugs 0.000 claims description 3
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 230000001276 controlling effect Effects 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005238 degreasing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 229910052804 chromium Inorganic materials 0.000 abstract description 14
- 239000011651 chromium Substances 0.000 abstract description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 7
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 6
- 241000080590 Niso Species 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 150000001844 chromium Chemical class 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002103 nanocoating Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
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- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
A high-hardness nano Ni-Co-B alloy chromium-replacing electroplating solution and application thereof belong to the field of electroplating, and particularly relate to a high-hardness nano Ni-Co-B alloy chromium-replacing electroplating solution and application thereof. The invention aims to solve the problems that the conventional trivalent chromium electroplating can not meet the requirement of replacing hard chromium, the composite plating process is complex, the plating thickness is not uniform due to uneven current distribution, the large-scale application of the plating is still greatly limited, and the nickel-based alloy has large internal stress, low hardness and low plating speed. A high-hardness nano Ni-Co-B alloy chromium-substituting electroplating liquid is prepared from main salt, boron source, anode activator, pH buffer, grain refiner, stress relieving agent, wetting agent and distilled water. The Ni-Co-B alloy chromium-substituted plating layer prepared by adopting the high-hardness nano Ni-Co-B alloy chromium-substituted electroplating solution has the hardness of 1100-1300 HV-50.
Description
Technical Field
The invention belongs to the field of electroplating, and particularly relates to high-hardness nano Ni-Co-B alloy chromium-replacing electroplating solution and application thereof.
Background
As one of indispensable processes in the electroplating industry, the hexavalent chromium electroplating technology is widely applied. When used as a protective-decorative coating, the coating has the advantages of bright and beautiful color and strong anti-tarnishing capability; in addition, the chromium coating has the advantages of high hardness, good wear resistance, corrosion resistance and the like, and is widely applied to cylinders and piston rings of engines, roll surfaces of impression rollers, inner cavities of guns and the like. However, hexavalent chromium electroplating techniques also have several disadvantages that limit their application. Such as serious cathodic hydrogen evolution, low current efficiency, high current and high voltage deposition, high toxicity of hexavalent chromium, difficult wastewater treatment and the like. It is necessary to find a green environment-friendly chromium-substituted plating layer and a process method which meet or even exceed the performance of a chromium (VI) plating layer.
The nano-coating has unique physical and chemical properties, such as high corrosion resistance, high hardness, high wear resistance and the like, due to the great reduction of the grain size and the existence of a large number of grain boundaries between adjacent grains. In the electroplating process, it is usually necessary to add suitable additives to increase the cathode polarization, so that the nucleation rate of the crystal nuclei is increased and the crystal grains are finer, thereby obtaining a nano-coating. Therefore, the first problem in preparing the nano-plating layer lies in developing a proper non-toxic additive, obviously increasing the cathode polarization under the inhibition of the blocking effect or the penetration effect, and greatly improving the performance of the plating layer by adding a small amount of additive into the plating solution. According to different types of additives, the effects of grain refinement, leveling, wetting, stress relief and the like are achieved.
The current chromium-substituting technology mainly comprises a trivalent chromium electroplating process, a composite electroplating process, an alloy electroplating/chemical plating process and the like. Among them, trivalent chromium plating is increasingly used in the field of replacing decorative chromium due to its low toxicity, high dispersing ability and covering ability. However, this technique does not satisfy the demand for hard chromium. By using the composite electroplating technology, the hardness of the plating layer can be obviously improved by adding insoluble hard phase particles into the plating solution, for example, the hardness of the Ni-diamond and Ni-Co-diamond composite plating layers can reach 700HV. However, the composite plating process is complicated, and the thickness of the plating layer is not uniform due to the non-uniform current distribution, so that the large-scale application of the composite plating process is still greatly limited. The nickel-based alloy has the advantages of bright appearance, high hardness, high wear resistance, high corrosion resistance and the like, and is the most promising plating layer for replacing hard chromium, but the currently researched nickel-tungsten alloy, nickel-cobalt alloy, nickel-boron alloy, nickel-molybdenum alloy and the like also have the problems of large internal stress, low hardness, slow plating speed and the like.
Disclosure of Invention
The invention aims to solve the problems that the conventional trivalent chromium electroplating can not meet the requirement of replacing hard chromium, the composite plating process is complex, the plating thickness is not uniform due to uneven current distribution, the large-scale application of the plating is still greatly limited, and the nickel-based alloy has large internal stress, low hardness and slow plating speed, and provides a high-hardness nano Ni-Co-B alloy chromium-replacing electroplating solution and application thereof.
A high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is prepared from main salt, a boron source, an anode activator, a pH buffer, a grain refiner, a stress relieving agent, a wetting agent and distilled water;
the main salt is nickel salt and cobalt salt;
the grain refiner is one or a mixture of more of 2-ethylamino-4-methylthiazole-5-carboxylic acid, polyethyleneimine, myrcene, allyl furoate and 3- (methylthio) hexanol acetate;
the stress relieving agent is 1,3-dicyclohexyl imidazole chloride, 2-methoxy-4-vinylphenol or rose bengal;
the wetting agent is polyethylene glycol, OP emulsifier or lauryl sodium sulfate.
A high-hardness nano-Ni-Co-B alloy chromium-substituting electroplating solution is used for preparing a Ni-Co-B alloy chromium-substituting plating layer.
The principle of the invention is as follows:
the grain refiner forms a very thin adsorption layer on the surface of the cathode through adsorption, so that the discharge of metal ions is blocked, and the polarization of the cathode is improved; the grain refiner adsorbed on the surface of the cathode can block or even completely inhibit the growth of crystals, so that new crystals are generated at other positions; the above steps are repeated to obtain a high-quality plating layer with fine and bright crystal grains;
the stress relieving agent can enable the coating to generate certain compressive stress, thereby counteracting the tensile stress in the coating, improving the ductility of the coating, preventing the generation of micro cracks on the surface of the coating and improving the brightness of the coating;
the addition of the wetting agent can reduce the surface tension of an electrode/solution interface, improve the wetting performance of the electrolyte on the electrode surface and enable metal ions to be more easily deposited on a cathode; meanwhile, the hydrogen bubbles are separated from the surface of the electrode when the size is smaller, so that the hydrogen bubbles are prevented from being retained on the surface of the cathode to generate a shielding effect, a pinhole eliminating effect is achieved, and the hardness and the brightness of the plating layer are improved.
The addition of the grain refiner, the stress relieving agent and the wetting agent can enable the coating of the invention to reach the requirements of appearance and hardness of the hexavalent chromium coating, and avoid the use of toxic hexavalent chromium.
The invention has the advantages that:
1. the average grain size of the Ni-Co-B alloy chromium-substituted plating layer prepared by the high-hardness nano Ni-Co-B alloy chromium-substituted electroplating solution prepared by the method is about 10nm, the Ni-Co-B alloy chromium-substituted plating layer is a nanocrystalline plating layer, the stress of the plating layer is lower, and microcracks do not exist in long-time electroplating;
2. the hardness of the plating layer after heat treatment can reach 1100-1300 HV-50, the corrosion resistance is good, the bonding strength of the plating layer and a substrate is high, and the plating layer has no cracks;
3. the cathode current efficiency of the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution prepared by the invention reaches 95%, and the deposition speed is 70-80 mu m/h.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern in which 1 is an X-ray diffraction curve of a plated article prepared in step three of example 1 before heat treatment, 2 is an X-ray diffraction curve of a Ni-Co-B alloy substituted chromium plating layer obtained in step four of example 1 after heat treatment at 200 ℃, and 3 is an X-ray diffraction curve of a Ni-Co-B alloy substituted chromium plating layer obtained in step four of example 2 after heat treatment at 300 ℃;
FIG. 2 is an SEM photograph of a Ni-Co-B alloy chrome-substituted plating layer obtained after a heat treatment at 200 ℃ in the fourth step of example 1;
FIG. 3 is an optical microscopic photograph of the Ni-Co-B alloy chrome-substituted plating layer obtained by the heat treatment at 200 ℃ in the fourth step of example 1;
FIG. 4 is an optical microscope photograph of the Ni-Co-B alloy chrome-substituted plating layer obtained by the heat treatment at 200 ℃ in the fourth step of example 1 after being corroded by 3.5% sodium chloride solution.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment provides a high-hardness nano Ni-Co-B alloy chromium-substituted electroplating solution which is prepared from main salt, a boron source, an anode activator, a pH buffering agent, a grain refiner, a stress relieving agent, a wetting agent and distilled water;
the main salt is nickel salt and cobalt salt;
the grain refiner is one or a mixture of more of 2-ethylamino-4-methylthiazole-5-carboxylic acid, polyethyleneimine, myrcene, allyl furoate and 3- (methylthio) hexanol acetate;
the stress relieving agent is 1,3-dicyclohexyl imidazole chloride, 2-methoxy-4-vinylphenol or rose bengal;
the wetting agent is polyethylene glycol, OP emulsifier or lauryl sodium sulfate.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the nickel salt is nickel sulfate; the cobalt salt is cobalt sulfate. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the boron source is dimethylamino borane; the anode activator is nickel chloride; the pH buffering agent is boric acid. The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode is as follows: the difference between this embodiment and one of the first to third embodiments is as follows: the concentration of nickel salt in the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is 100-150 g/L, the concentration of cobalt salt is 10-15 g/L, the concentration of a boron source is 1-5 g/L, the concentration of an anode activator is 20-50 g/L, the concentration of a pH buffer agent is 30-50 g/L, the concentration of a grain refiner is 0.1-5 g/L, the concentration of a stress eliminator is 0.5-1.5 g/L, and the concentration of a wetting agent is 0.05-1 g/L. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode is as follows: the difference between this embodiment and one of the first to fourth embodiments is: a high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is used for preparing a Ni-Co-B alloy chromium-substituting plating layer. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: the preparation of the Ni-Co-B alloy chromium-substituted plating layer by using the high-hardness nano Ni-Co-B alloy chromium-substituted electroplating solution is completed according to the following steps:
1. preparing a chromium-substituted electroplating solution:
dissolving main salt, a boron source, an anode activator, a pH buffering agent, a grain refiner, a stress relieving agent and a wetting agent into distilled water to obtain a chromium-substituted electroplating solution;
2. pretreating the substrate to obtain a pretreated substrate;
soaking the matrix into deoiling liquid at 80-90 ℃, taking out and washing with distilled water; then using hydrochloric acid for pickling and washing by distilled water to obtain a pretreated matrix;
3. regulating the pH value of the chromium-substituting electroplating solution to 3.5-4.0, immersing the pretreated substrate into the chromium-substituting electroplating solution, and then controlling the temperature to be 40-50 ℃ and the current density to be 2-7A/dm 2 Electroplating under the condition of (1) to obtain a plated part;
4. high-temperature heat treatment:
and (3) placing the plated part in a tube furnace, heating the plated part to 200-300 ℃ under the protection of argon atmosphere, preserving heat at 200-300 ℃, and naturally cooling to room temperature to obtain the Ni-Co-B alloy chromium-substituted plating layer on the surface of the base material. The other steps are the same as those in the first to fifth embodiments.
The seventh concrete implementation mode: the difference between this embodiment and the first to sixth embodiments is: the deoiling liquid in the step two is formed by mixing sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate and distilled water, wherein the concentration of the sodium hydroxide is 60-80 g/L, the concentration of the sodium carbonate is 20-60 g/L, the concentration of the sodium phosphate is 15-30 g/L, and the concentration of the sodium silicate is 5-10 g/L; the mass fraction of the hydrochloric acid in the second step is 10-20%; and the substrate in the second step is cold-rolled steel. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: and step two, immersing the matrix into deoiling liquid for 5-10 min, taking out, washing with distilled water for 3-5 times, washing with hydrochloric acid for 3-5 times, and washing with distilled water for 3-5 times to obtain the pretreated matrix. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the electroplating time in the third step is 30-180 min. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: the heat preservation time in the fourth step is 1-2 h; the heating rate in the fourth step is 5-10 ℃/min. The other steps are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: the preparation of the Ni-Co-B alloy chromium-substituted plating layer by using the high-hardness nano Ni-Co-B alloy chromium-substituted electroplating solution is completed according to the following steps:
1. preparing a chromium-substituted electroplating solution:
mixing NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、NiCl 2 ·6H 2 O、Dissolving boric acid, dimethylamino borane, 2-ethylamino-4-methylthiazole-5-carboxylic acid, 2-methoxy-4-vinylphenol and sodium dodecyl sulfate in distilled water to obtain a chromium-substituted electroplating solution;
NiSO in the chromium-substituting electroplating solution in the step one 4 ·6H 2 The concentration of O is 120g/L, coSO 4 ·7H 2 O concentration of 12g/L, niCl 2 ·6H 2 The concentration of O is 40g/L, the concentration of boric acid is 35g/L, the concentration of dimethylamino borane is 3g/L, the concentration of 2-ethylamino-4-methylthiazole-5-carboxylic acid is 3g/L, the concentration of 2-methoxy-4-vinylphenol is 1g/L, and the concentration of sodium dodecyl sulfate is 0.1g/L;
2. pretreating the substrate to obtain a pretreated substrate;
step two, immersing the matrix into 90 ℃ deoiling liquid for soaking for 5min, taking out the matrix, washing the matrix with distilled water for 5 times, then washing the matrix with 15% hydrochloric acid for 3 times by using the mass fraction, and washing the matrix with the distilled water for 5 times to obtain a pretreated matrix;
the deoiling liquid in the step two is formed by mixing sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate and distilled water, wherein the concentration of the sodium hydroxide is 60g/L, the concentration of the sodium carbonate is 30g/L, the concentration of the sodium phosphate is 20g/L, and the concentration of the sodium silicate is 8g/L;
the substrate in the second step is cold-rolled steel;
3. adjusting the pH value of the chromium-substituting electroplating solution to 3.5-4.0, immersing the pretreated substrate into the chromium-substituting electroplating solution, and then performing electroplating at the temperature of 50 ℃ and the current density of 7A/dm 2 Electroplating for 30min under the condition to obtain a plated piece;
4. high-temperature heat treatment:
and (3) placing the plated part in a tube furnace, heating the plated part to 200 ℃ at the heating rate of 10 ℃/min under the protection of argon atmosphere, then preserving the heat at 200 ℃ for 1h, and finally naturally cooling to room temperature to obtain the Ni-Co-B alloy chrome-substituted plating layer on the surface of the base material.
The XRD patterns of the plated part obtained in the embodiment before and after heat treatment are shown in FIG. 1; indicating that the grains grow preferentially along the (111) crystal plane. As a result of comparison, it was found that the half-value width of the diffraction peak of the plating layer corresponding to Ni (111) after the heat treatment was small and the peak intensity was gradually increased, and it was found that the hardness was rapidly increased due to coarsening of crystal grains and precipitation of fine intermetallic compounds during the heat treatment.
FIG. 1 is an X-ray diffraction (XRD) pattern in which 1 is an X-ray diffraction curve of a plated article prepared in step three of example 1 before heat treatment, 2 is an X-ray diffraction curve of a Ni-Co-B alloy substituted chromium plating layer obtained in step four of example 1 after heat treatment at 200 ℃, and 3 is an X-ray diffraction curve of a Ni-Co-B alloy substituted chromium plating layer obtained in step four of example 2 after heat treatment at 300 ℃;
further, when the grain size is between 1 nm and 100nm, the average size of the grains can be calculated by the scherrer equation, which is shown as follows:
wherein d is the average size of crystal grains (nm);
λ — X-ray wavelength (λ =0.154 nm);
k — scherrer constant (K = 0.89);
b-diffraction peak full width at half maximum;
theta-Bragg diffraction angle;
the average size of crystal grains is 10.26nm through calculation, and the coating is proved to be a nano coating. The hardness value is 1210HV-50.
FIG. 2 is an SEM photograph of a Ni-Co-B alloy chrome-substituted plating layer obtained by heat treatment at 200 ℃ in step four of example 1;
FIG. 3 is an optical microscope photograph of the Ni-Co-B alloy chrome-substituted plating layer obtained after the heat treatment at 200 ℃ in step four of example 1;
FIGS. 2 and 3 show that the surface is compact and flat, and the hard phase is uniformly distributed.
Example 2: the present embodiment is different from embodiment 1 in that: and step four, placing the plated part in a tubular furnace, heating the plated part to 300 ℃ at the heating rate of 10 ℃/min under the protection of argon atmosphere, then preserving the heat at 300 ℃ for 1h, and finally naturally cooling to room temperature to obtain the Ni-Co-B alloy chrome-substituted plating layer on the surface of the base material. The other steps and parameters were the same as in example 1.
XRD of the plating obtained in example 2 is shown in FIG. 1;
from fig. 2 it can be found that: at the moment, the plating layer also has a crystalline state, so that the hardness of the plating layer is improved.
Further, the average size of crystal grains was calculated by the scherrer equation, and in example 2, the average size of crystal grains was 9.38nm, which confirmed that the plating layer was a nano-plating layer. Hardness values of 1290HV-50.
Comparative example: the present embodiment is different from embodiment 1 in that: in the first step: preparing a chromium-substituted electroplating solution:
mixing NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O、NiCl 2 ·6H 2 Dissolving O, boric acid and dimethylamino borane in distilled water to obtain a chromium-substituted electroplating solution; niSO in the chromium-substituting electroplating solution in the step one 4 ·6H 2 The concentration of O is 120g/L, coSO 4 ·7H 2 O concentration of 12g/L, niCl 2 ·6H 2 The concentration of O is 40g/L, the concentration of boric acid is 35g/L, and the concentration of dimethylaminoborane is 3g/L. The other steps and parameters were the same as in example 1.
Comparative examples the coating prepared had a grain size of 100.4nm and hardness values of 698HV-50. Further, the grain refiner, the stress relieving agent and the wetting agent play a significant role in reducing the crystal size and improving the hardness of a plating layer.
Claims (10)
1. A high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is characterized in that the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is prepared from main salt, a boron source, an anode activator, a pH buffering agent, a grain refiner, a stress relieving agent, a wetting agent and distilled water;
the main salt is nickel salt and cobalt salt;
the grain refiner is one or a mixture of more of 2-ethylamino-4-methylthiazole-5-carboxylic acid, polyethyleneimine, myrcene, allyl furoate and 3- (methylthio) hexanol acetate;
the stress relieving agent is 1,3-dicyclohexyl imidazole chloride, 2-methoxy-4-vinylphenol or rose bengal;
the wetting agent is polyethylene glycol, OP emulsifier or lauryl sodium sulfate.
2. The plating solution of high hardness nano Ni-Co-B alloy as recited in claim 1, wherein the nickel salt is nickel sulfate; the cobalt salt is cobalt sulfate.
3. The plating solution of high hardness nano Ni-Co-B alloy as recited in claim 1, wherein the boron source is dimethyl amino borane; the anode activator is nickel chloride; the pH buffering agent is boric acid.
4. The electroplating solution as claimed in any one of claims 1 to 3, wherein the concentration of the nickel salt, the cobalt salt, the boron source, the anode activator, the pH buffer and the grain refiner is 100 to 150g/L, 10 to 15g/L, 1 to 5g/L, 20 to 50g/L, 30 to 50g/L, 0.1 to 5g/L, 0.5 to 1.5g/L, and 0.05 to 1g/L, respectively.
5. The use of the high hardness nano Ni-Co-B alloy chromium-substituting electroplating solution according to claim 1, wherein a high hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is used for preparing the Ni-Co-B alloy chromium-substituting plating layer.
6. The use of the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution as claimed in claim 5, wherein the preparation of the Ni-Co-B alloy chromium-substituting electroplating solution by using the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution is carried out by the following steps:
1. preparing a chromium-substituted electroplating solution:
dissolving main salt, a boron source, an anode activator, a pH buffering agent, a grain refiner, a stress relieving agent and a wetting agent into distilled water to obtain a chromium-substituted electroplating solution;
2. pretreating the substrate to obtain a pretreated substrate;
soaking the matrix into deoiling liquid at 80-90 ℃, taking out and washing with distilled water; then using hydrochloric acid for pickling and washing by distilled water to obtain a pretreated matrix;
3. regulating the pH value of the chromium-substituting electroplating solution to 3.5-4.0, immersing the pretreated substrate into the chromium-substituting electroplating solution, and then controlling the temperature to be 40-50 ℃ and the current density to be 2-7A/dm 2 Electroplating under the condition of (1) to obtain a plated part;
4. high-temperature heat treatment:
and (3) placing the plated part in a tube furnace, heating the plated part to 200-300 ℃ under the protection of argon atmosphere, preserving heat at 200-300 ℃, and naturally cooling to room temperature to obtain the Ni-Co-B alloy chromium-substituted plating layer on the surface of the base material.
7. The use of the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution according to claim 5, wherein the degreasing liquid in the step two is formed by mixing sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate and distilled water, wherein the concentration of the sodium hydroxide is 60-80 g/L, the concentration of the sodium carbonate is 20-60 g/L, the concentration of the sodium phosphate is 15-30 g/L, and the concentration of the sodium silicate is 5-10 g/L; the mass fraction of the hydrochloric acid in the second step is 10-20%; and the substrate in the second step is cold-rolled steel.
8. The application of the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution according to claim 5 is characterized in that in the second step, the substrate is immersed in deoiling liquid for 5min to 10min, the substrate is taken out and washed by distilled water for 3 times to 5 times, then washed by hydrochloric acid for 3 times to 5 times, and washed by distilled water for 3 times to 5 times, so that the pretreated substrate is obtained.
9. The use of the electroplating solution of high hardness nano Ni-Co-B alloy as claimed in claim 5, wherein the electroplating time in step three is 30-180 min.
10. The application of the high-hardness nano Ni-Co-B alloy chromium-substituting electroplating solution as claimed in claim 5, wherein the heat preservation time in the fourth step is 1-2 h; the heating rate in the fourth step is 5-10 ℃/min.
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|---|---|---|---|---|
| KR20080101342A (en) * | 2007-05-17 | 2008-11-21 | 주식회사 엘막 | Using high frequence pluse of electrolytic plating method of ni-co-b for heat resistance hardness and high conductivity |
| CN102352522A (en) * | 2011-10-31 | 2012-02-15 | 哈尔滨工业大学 | Electric deposition preparation method of Ni-Co-B alloy substituted hard chromium plating |
| CN112779573A (en) * | 2019-11-04 | 2021-05-11 | 天津科技大学 | Preparation method of Ni-Co-B alloy coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20080101342A (en) * | 2007-05-17 | 2008-11-21 | 주식회사 엘막 | Using high frequence pluse of electrolytic plating method of ni-co-b for heat resistance hardness and high conductivity |
| CN102352522A (en) * | 2011-10-31 | 2012-02-15 | 哈尔滨工业大学 | Electric deposition preparation method of Ni-Co-B alloy substituted hard chromium plating |
| CN112779573A (en) * | 2019-11-04 | 2021-05-11 | 天津科技大学 | Preparation method of Ni-Co-B alloy coating |
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