CN106086958B - A kind of rare earth nickel cobalt tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite, electroplate liquid and preparation method thereof - Google Patents
A kind of rare earth nickel cobalt tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite, electroplate liquid and preparation method thereof Download PDFInfo
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- CN106086958B CN106086958B CN201610702616.2A CN201610702616A CN106086958B CN 106086958 B CN106086958 B CN 106086958B CN 201610702616 A CN201610702616 A CN 201610702616A CN 106086958 B CN106086958 B CN 106086958B
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 42
- 239000000956 alloy Substances 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 239000007788 liquid Substances 0.000 title claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 rare earth nickel cobalt tungsten disulfide Chemical class 0.000 title claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 50
- 239000011248 coating agent Substances 0.000 claims abstract description 48
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000007747 plating Methods 0.000 claims abstract description 36
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims abstract description 32
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 21
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229960001124 trientine Drugs 0.000 claims abstract description 14
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004327 boric acid Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000003643 water by type Substances 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052759 nickel Inorganic materials 0.000 abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 abstract description 11
- 239000010941 cobalt Substances 0.000 abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 238000000280 densification Methods 0.000 abstract description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 abstract 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 abstract 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 13
- 229910052796 boron Inorganic materials 0.000 description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 11
- 239000002253 acid Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 6
- 238000009713 electroplating Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002585 base Substances 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000002242 deionisation method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
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Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- 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)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a kind of rare earth nickel cobalt tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite, electroplate liquid and preparation method thereof, the coating is the grain structure that intermetallic compound and nano tungsten disulfide in disperse on nanocrystalline matrix；Coating plated state microhardness is HV700 HV1200；Content of the cobalt in coating is 1wt% 55wt%, and rare earth is 0.5wt% 12wt%, and tungsten disulfide is 0.1wt% 5wt%, and remaining is nickel.The electroplate liquid includes following component：The 400g/L of nickel sulfate 260, the 75g/L of cobaltous sulfate 10, the 50g/L of nickel chloride 30, the 55g/L of boric acid 35, the 28g/L of rare earth 0.1, the 35g/L of sodium borohydride 1, the 20g/L of triethylene tetramine 2, the 40g/L of citric acid 5, the 20g/L of malonic acid 5, the 4.9g/L of tungsten disulfide 0.01.Deposit appearance that the present invention is provided is bright, smooth, flawless, densification, while plated state hardness is high, internal stress is small, the thick ability of plating is strong, anticorrosion antiwear performance is good, with good comprehensive mechanical performance；Meanwhile, the preparation method of electroplate liquid and coating is simple, easily operation；The material of use is environmentally friendly, and production efficiency is high, energy-conserving and environment-protective.
Description
Technical field
The present invention relates to field of metal surface treatment technology, more particularly to a kind of polynary conjunction of rare earth-nickel-cobalt-tungsten disulfide
Golden anticorrosion antiwear composite deposite, electroplate liquid and preparation method thereof.
Background technology
At present, with the continuous enhancing of countries in the world environmental consciousness, traditional hexavalent chromium plating technique is due to existing to ring
The severe contamination in border, is seriously endangered to human body, at the same also high energy consumption, low production efficiency, plating offal treatment difficulty it is big, into
This high defect, is progressively limited or is forbidden by increasing country.The country such as the U.S., European Union strictly forbids Cr VI
The use of electroplating technology.The regulation of correlation has also been formulated in some areas of China, and hexavalent chromium plating is completely forbidden if Tianjin
Production technology.
In order to replace the hexavalent chromium plating technique of heavily contaminated, clean manufacturing is realized, the body preserved the ecological environment with the people
Health, people constantly explore new electroplating solution and technique.Some of which binary or multi-elements alloying coating are provided simultaneously with Cr VI
Hardness and wearability, also have light metal appearance, Cr VI can be replaced under some use conditions.But these coating
Also there is deficiency, being mainly manifested in plated state hardness not high, it is necessary to through can be only achieved required hardness at overheat；The internal stress of coating is high,
Fragility is big, and plating is easily cracked when thick, loses decay resistance, some can not even obtain thickness coating.
The content of the invention
An object of the present invention is to provide a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear Composite Coatings
Layer, electroplate liquid and preparation method thereof, low to solve the coating hardness that existing electroplating technology obtains, internal stress is high, and fragility is big, and plating is thick
Shi Rongyi is cracked, and loses decay resistance, the problem of some can not even obtain thickness coating.
The present invention solves prior art problem and realized by following technical proposals：
The invention provides a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite, the coating
For nanocrystalline structure；The coating plated state microhardness is HV700-HV1200；Content of the cobalt in coating is 1wt%--
55wt%, rare earth is 0.5wt%--12wt%, and remaining is nickel.
Further, the coating is the particle that intermetallic compound and nano tungsten disulfide in disperse on nanocrystalline matrix
Structure；The coating plated state microhardness is HV700-HV1200；Content of the cobalt in coating is 1wt%--55wt%, rare earth
For 0.5wt%--12wt%, tungsten disulfide is 0.1wt%--5wt%, and remaining is nickel.
Present invention also offers a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution, including
Following component：
Plus deionized water constant volume.
Further, a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution also includes：
Tungsten disulfide 0.01-4.9g/L.
Present invention also offers a kind of preparation of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution
Method, comprises the following steps：
Deionized water is heated to 50-60 DEG C, add 260-400g nickel sulfates, 10-75g cobaltous sulfates, 30-50g nickel chlorides,
35-55g boric acid, 0.1-28g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sodium borohydride 1-35g, triethylene tetramine 2-20g, citric acid 5- are added in the first solution obtained in previous step
40g, malonic acid 5-20g, are sufficiently stirred for that the second solution is made；
The pH value of second solution obtained in the previous step is adjusted to 4.5-5.0, plus deionized water to 1L, that is, is made a kind of dilute
Soil-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating electroplate liquid.
Further, the step：The pH value of second solution obtained in the previous step is adjusted to 4.5-5.0, plus deionization
Water is made in a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating electroplate liquid to 1L, in addition to following step
Suddenly：
The pH value of second solution obtained in the previous step is adjusted to 4.5-5.0,0.01-4.9g tungsten disulfides are added, plus
Deionized water is made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating electroplate liquid to 1L.
Further, the preparation method of a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution,
Specifically include following steps：
650ml deionized waters are heated to 50-60 DEG C, 380g nickel sulfates, 55g cobaltous sulfates, 45g nickel chlorides, 40g boron is added
Acid, 25g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sequentially added in the first solution obtained in the previous step sodium borohydride 35g, triethylene tetramine 20g, citric acid 25g,
Malonic acid 18g, is sufficiently stirred for that the second solution is made；
The pH value of the second solution obtained in the previous step is adjusted to 4.5-5.0 using ammoniacal liquor or dilute sulfuric acid, is being stirred continuously
Under conditions of add 4.5g tungsten disulfides, plus deionized water to 1L, that is, a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy is made
Anticorrosion antiwear coating electroplate liquid.
Further, the preparation method of a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution,
Specifically include following steps：
650ml deionized waters are heated to 50-60 DEG C, 260g nickel sulfates, 25g cobaltous sulfates, 35g nickel chlorides, 35g boron is added
Acid, 8g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sequentially added in the first solution obtained in the previous step sodium borohydride 10g, triethylene tetramine 10g, citric acid 15g,
Malonic acid 5g, is sufficiently stirred for that the second solution is made；
The pH value of the second solution obtained in the previous step is adjusted to 4.5-5.0 using ammoniacal liquor or dilute sulfuric acid, is being stirred continuously
Under conditions of add 2g tungsten disulfides, plus deionized water to 1L, that is, a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy is made and prevents
Rotten scuff-resistant coating electroplate liquid.
Further, the system of described a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution
Preparation Method, specifically includes following steps：
650ml deionized waters are heated to 50-60 DEG C, 300g nickel sulfates, 35g cobaltous sulfates, 35g nickel chlorides, 40g boron is added
Acid, 12g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sequentially added in the first solution obtained in the previous step sodium borohydride 18g, triethylene tetramine 15g, citric acid 15g,
Malonic acid 10g, is sufficiently stirred for that the second solution is made；
The pH value of the second solution obtained in the previous step is adjusted to 4.5-5.0 using ammoniacal liquor or dilute sulfuric acid, is being stirred continuously
Under conditions of add 3.5g tungsten disulfides, plus deionized water to 1L, that is, a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy is made
Anticorrosion antiwear coating electroplate liquid.
Further, the rare earth is the chloride of rare earth.
Beneficial effects of the present invention：The rare earth that the present invention is provided-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear is combined
Coating, shiny appearance, smooth, flawless, densification, while plated state hardness is high, internal stress is small, the thick ability of plating is strong, anticorrosion antiwear
Can be good, with good comprehensive mechanical performance；Meanwhile, the preparation method of electroplate liquid and coating is simple, easily operation；The material of use
Material is environmentally friendly, and production efficiency is high, energy-conserving and environment-protective.
Brief description of the drawings
Fig. 1 is the SEM of 1 middle rare earth of the embodiment of the present invention -3K times of nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating
Figure.
Fig. 2 used by 1 middle rare earth of the embodiment of the present invention-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating two
Vulcanize the distribution map of tungsten particle.
Fig. 3 used by 1 middle rare earth of the embodiment of the present invention-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating two
Vulcanize tungsten particle microscopic appearance figure.
Fig. 4 spreads out for the x- rays of 1 middle rare earth of the embodiment of the present invention-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating
Penetrate spectrum.
Embodiment
The present invention is described in detail below in conjunction with embodiment.It should be noted that described in following embodiments
The combination of technical characteristic or technical characteristic be not construed as it is isolated, they can be mutually combined so as to reach more preferably
Technique effect.
A kind of rare earth that the present invention is provided-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite is nanocrystalline base
The grain structure of intermetallic compound and nano tungsten disulfide in disperse on body；The coating plated state microhardness is HV700-
HV1200；Content of the cobalt in coating is 1wt%--55wt%, and rare earth is 0.5wt%--12wt%, and tungsten disulfide is
0.1wt%--5wt%, remaining is nickel.
Present invention also offers a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution, including
Following component：
Plus deionized water constant volume.
Further, a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution also includes two sulphur
Change tungsten 0.01-4.9g/L.
Present invention also offers a kind of preparation of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution
Method, comprises the following steps：
S1：Deionized water is heated to 50-60 DEG C, 260-400g nickel sulfates, 10-75g cobaltous sulfates, 30-50g chlorinations is added
Nickel, 35-55g boric acid, 0.1-28g rare earths are stirred well to be completely dissolved and obtain the first solution；
S2：Sodium borohydride 1-35g, triethylene tetramine 2-20g, citric acid are added in the first solution obtained in previous step
5-40g, malonic acid 5-20g, are sufficiently stirred for that the second solution is made；
S3：The pH value of second solution obtained in the previous step is adjusted to 4.5-5.0,0.01-4.9g tungsten disulfides are added,
Plus deionized water is made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating electroplate liquid to 1L.
Further, rare earth is the chloride of rare earth.
The preparation method for the electroplate liquid that the present invention is provided adds sodium borohydride as reducing agent, triethylene four in the plating solution
Amine, citric acid, malonic acid etc. are used as complexing agent so that rare earth element and nickel, cobalt formation rare earth compound, disperse nickel,
Cobalt is co-deposited on the nanocrystalline matrix to be formed.Common work of the tungsten disulfide particle of the nano-scale added in machinery and electric field
Under, absorption forms Composite Coatings in workpiece surface and with nickel and cobalt ions and rare earth compound co-deposition to workpiece surface
Layer.The rare earth compound of disperse can effectively improve the hardness of coating；Nano-crystal nickel, cobalt-based body and nano tungsten disulfide
Grain has extraordinary corrosion resistance；Arrangement magnetic property forms one layer of nanometer protection in metal surface in the cluster that tungsten disulfide has
Film, reduces coefficient of friction, improves antiwear and reducing friction performance；And tungsten disulfide particle has high decay resistance in itself.Solution
In the additive without poisonous salt and difficult degradation, it is environmentally friendly, it is harmless.And preparation method is simple, current efficiency
Height, is the clean manufacturing mode of energy-conserving and environment-protective.The Deposit appearance light that is obtained with the plating solution plating is smooth, good toughness, flawless,
Porosity is extremely low；Coefficient of friction only has 0.08-0.12, and plated state hardness HV700-HV1200, wearability improves 3-5 than Cr VI
Times；The adhesion of coating and base material is good, has fabulous corrosion resistance to media such as acid, alkali, sulfide.It can be widely applied to
The surface treatment of various machine components.
Embodiment 1
650ml deionized waters are heated to 50-60 DEG C, 260g nickel sulfates, 25g cobaltous sulfates, 35g nickel chlorides, 35g boron is added
Acid, 8g rare earth-iron-borons, is stirred well to and is completely dissolved, obtained solution (one)；Boron hydrogen is sequentially added in resulting solution (one)
Change sodium 10g, triethylene tetramine 10g, citric acid 15g, malonic acid 5g, be sufficiently stirred for obtained solution (two)；Use ammoniacal liquor or dilute sulphur
The pH value of resulting solution (two) is adjusted to 4.5-5.0 by acid, and 2g tungsten disulfides are added under conditions of being stirred continuously.Plus deionization
Water be made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite electroplate liquid to 1L.
Plating method：
(1) plating piece prepares：Cold-rolled carbon steel plate 50*50*1.5mm, pretreatment process：Manual sand paper derusting-washing-alkalescence
Oil removing-washing-acid activation-deionized water cleaning；
(2) electroplate liquid of above-mentioned preparation is imported in 1L electroplating baths, anode is using Canadian English Ke's sheet nickel 50*100*
Two pieces of 5mm, the coated terylene anode in outside, 55 DEG C are heated to by electroplate liquid；
(3) plating workpiece does negative electrode, is put into electroplating bath, and setting electric current density is 4A/dm2, plating time is 40 minutes.
After the completion of plating, first with 80 DEG C of hot water injections, then cold deionized water rinsing, hot blast drying are used.Thickness of coating is 25 microns, is calculated
Current efficiency is 91% when going out plating.
Testing result：
The sign of exterior appearance：Shiny appearance is smooth, no plating leakage, pin-free；
Use each element mass fraction of EDS energy spectrum analysis coating for：Cobalt 17.9wt%；Rare earth 2.5wt%；Tungsten disulfide
2.2wt%；Surplus is nickel；
The sign of microscopic appearance (SEM)：Flawless, it is extremely low in 3K times of SEM lower observation hole gap rate, as shown in Figure 1；Nanometer
The tungsten disulfide of grain is evenly distributed, as shown in Figure 2；The microscopic appearance of tungsten disulfide, as shown in figure 3, tungsten disulfide tufted is arranged,
Compressive property is good, and self-lubricating, coefficient of friction is small.
Tested using Shanghai material experiment-machine factory Vickers hardness instrument HV-30T, the case hardness of coating is HV786；
As shown in figure 4, it is 6.1nm to measure coating average grain size with XRD；
The adhesion of coating and base material：Tested through international method of scoring, thermal shock method and doubling, coating and base material adhesion
It is good, no obscission；
The corrosion resistance of coating：Through acid, alkali, sulfide corrosion test, the decay resistance of coating is fine；Mantoquita accelerates vinegar
Sour salt spray test (CASS) 96 hours, 10 grades of protection class；
Measuring friction coefficient average out to 0.08；
Wearability：Rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite is better than similar hardness after tested
Hard chromium.
Embodiment 2
650ml deionized waters are heated to 50-60 DEG C, 300g nickel sulfates, 35g cobaltous sulfates, 35g nickel chlorides, 40g boron is added
Acid, 12g rare earth-iron-borons, are stirred well to and are completely dissolved, obtained solution (one)；Boron hydrogen is sequentially added in resulting solution (one)
Change sodium 18g, triethylene tetramine 15g, citric acid 15g, malonic acid 10g, be sufficiently stirred for obtained solution (two)；With ammoniacal liquor or dilute sulfuric acid
The pH value of resulting solution (two) is adjusted to 4.5-5.0,3.5g tungsten disulfides are added under conditions of being stirred continuously.Plus deionization
Water be made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite electroplate liquid to 1L.
According to method plating same as Example 1, after testing, amount containing cobalt is 26wt%, rare earth 3.2wt% in coating,
Tungsten disulfide 2.8wt%；Surplus is nickel；Plated state hardness is HV840；Other testing results are substantially the same manner as Example 1.
Embodiment 3
650ml deionized waters are heated to 50-60 DEG C, 340g nickel sulfates, 45g cobaltous sulfates, 40g nickel chlorides, 40g boron is added
Acid, 16g rare earth-iron-borons, are stirred well to and are completely dissolved, obtained solution (one)；Boron hydrogen is sequentially added in resulting solution (one)
Change sodium 25g, triethylene tetramine 15g, citric acid 20g, malonic acid 15g, be sufficiently stirred for obtained solution (two)；With ammoniacal liquor or dilute sulfuric acid
The pH value of resulting solution (two) is adjusted to 4.5-5.0,4g tungsten disulfides, plus deionized water are added under conditions of being stirred continuously
To 1L, that is, a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite electroplate liquid is made.
According to method plating same as Example 1, after testing, amount containing cobalt is 35wt%, rare earth 5.8wt% in coating,
Tungsten disulfide 3.3wt%；Surplus is nickel；Plated state hardness is HV1030；Other testing results are substantially the same manner as Example 1.
Embodiment 4
650ml deionized waters are heated to 50-60 DEG C, 380g nickel sulfates, 55g cobaltous sulfates, 45g nickel chlorides, 40g boron is added
Acid, 25g rare earth-iron-borons, are stirred well to and are completely dissolved, obtained solution (one)；Boron hydrogen is sequentially added in resulting solution (one)
Change sodium 35g, triethylene tetramine 20g, citric acid 25g, malonic acid 18g, be sufficiently stirred for obtained solution (two)；With ammoniacal liquor or dilute sulfuric acid
The pH value of resulting solution (two) is adjusted to 4.5-5.0,4.5g tungsten disulfides, plus deionization are added under conditions of being stirred continuously
Water be made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite deposite electroplate liquid to 1L.
According to method plating same as Example 1, after testing, amount containing cobalt is 52wt%, rare earth 10.5wt% in coating,
Tungsten disulfide 4.1wt%；Surplus is nickel；Plated state hardness is HV1210；Other testing results are substantially the same manner as Example 1.
Embodiment 5
Rare earth-iron-boron in 1-embodiment of above-described embodiment 4 can have a variety of, and can be substituted for each other.
Although indeed, it will be appreciated that description above has been carried out by the example of the present invention, being done to the present invention
Go out will be apparent to those skilled in the science it is such and other improvement and change be deemed to fall such as set forth herein
Broad range of the present invention in.Therefore, although the present invention reference has been made to preferred embodiment be described, it is anticipated
It is not that the equipment for making tool novelty is restricted therefrom, on the contrary, it is intended to include meeting part disclosed above, claim
Broad range within various improvement and equivalent modifications.
Claims (6)
1. a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution, it is characterised in that including such as the following group
Point：
2. a kind of preparation method of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution, it is characterised in that
Comprise the following steps：
Deionized water is heated to 50-60 DEG C, 260-400g nickel sulfates, 10-75g cobaltous sulfates, 30-50g nickel chlorides, 35- is added
55g boric acid, 0.1-28g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Added in the first solution obtained in previous step sodium borohydride 1-35g, triethylene tetramine 2-20g, citric acid 5-40g,
Malonic acid 5-20g, is sufficiently stirred for that the second solution is made；
The pH value of second solution obtained in the previous step is adjusted to 4.5-5.0,0.01-4.9g tungsten disulfides are added, plus go from
Sub- water be made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear coating electroplate liquid to 1L.
3. a kind of system of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution as claimed in claim 2
Preparation Method, it is characterised in that specifically include following steps：
650ml deionized waters are heated to 50-60 DEG C, add 380g nickel sulfates, 55g cobaltous sulfates, 45g nickel chlorides, 40g boric acid,
25g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sodium borohydride 35g, triethylene tetramine 20g, citric acid 25g, the third two are sequentially added in the first solution obtained in the previous step
Sour 18g, is sufficiently stirred for that the second solution is made；
The pH value of the second solution obtained in the previous step is adjusted to 4.5-5.0 using ammoniacal liquor or dilute sulfuric acid, in the bar being stirred continuously
4.5g tungsten disulfides are added under part, plus deionized water is made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anti-corrosion to 1L
Scuff-resistant coating electroplate liquid.
4. a kind of system of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution as claimed in claim 2
Preparation Method, it is characterised in that specifically include following steps：
650ml deionized waters are heated to 50-60 DEG C, add 260g nickel sulfates, 25g cobaltous sulfates, 35g nickel chlorides, 35g boric acid,
8g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sodium borohydride 10g, triethylene tetramine 10g, citric acid 15g, the third two are sequentially added in the first solution obtained in the previous step
Sour 5g, is sufficiently stirred for that the second solution is made；
The pH value of the second solution obtained in the previous step is adjusted to 4.5-5.0 using ammoniacal liquor or dilute sulfuric acid, in the bar being stirred continuously
2g tungsten disulfides are added under part, plus deionized water is made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anti-corrosion resistance to 1L
Grind coating electroplate liquid.
5. a kind of system of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear composite plating solution as claimed in claim 2
Preparation Method, it is characterised in that specifically include following steps：
650ml deionized waters are heated to 50-60 DEG C, add 300g nickel sulfates, 35g cobaltous sulfates, 35g nickel chlorides, 40g boric acid,
12g rare earths, are stirred well to be completely dissolved and obtain the first solution；
Sodium borohydride 18g, triethylene tetramine 15g, citric acid 15g, the third two are sequentially added in the first solution obtained in the previous step
Sour 10g, is sufficiently stirred for that the second solution is made；
The pH value of the second solution obtained in the previous step is adjusted to 4.5-5.0 using ammoniacal liquor or dilute sulfuric acid, in the bar being stirred continuously
3.5g tungsten disulfides are added under part, plus deionized water is made a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anti-corrosion to 1L
Scuff-resistant coating electroplate liquid.
6. a kind of rare earth-nickel-cobalt-tungsten disulfide multicomponent alloy anticorrosion antiwear as any one of claim 2-5 is combined
The preparation method of electroplate liquid, it is characterised in that the rare earth is the chloride of rare earth.
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| CN109023451A (en) * | 2018-08-14 | 2018-12-18 | 苏州润纳斯纳米科技有限公司 | A kind of wear resistant friction reducing of component of machine is lengthened the life nano-deposit formula and processing method |
| CN109137014A (en) * | 2018-09-18 | 2019-01-04 | 广东工业大学 | A kind of tungsten disulfide/cobalt-based composite deposite and its preparation method and application |
| CN111041541B (en) * | 2019-12-30 | 2021-02-26 | 临沂鑫海新型材料有限公司 | High-performance nickel-based wear-resistant alloy |
| CN112267134B (en) * | 2020-11-24 | 2023-05-30 | 中山市康迪斯威科技有限公司 | Alloy electroplating solution |
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