CN1313647C - Electroplating liquid and technology used in electrodeposition of trngsten series noncrystalline alloy cladding material or nanometer alloy cladding material - Google Patents
Electroplating liquid and technology used in electrodeposition of trngsten series noncrystalline alloy cladding material or nanometer alloy cladding material Download PDFInfo
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- CN1313647C CN1313647C CNB03124792XA CN03124792A CN1313647C CN 1313647 C CN1313647 C CN 1313647C CN B03124792X A CNB03124792X A CN B03124792XA CN 03124792 A CN03124792 A CN 03124792A CN 1313647 C CN1313647 C CN 1313647C
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Abstract
The present invention relates to an electrodeposition tungsten-base series non-crystalline alloy plating layer or a nanostalline alloy plating layer, an electroplating liquid and a technique used by the electrodeposition tungsten-base series non-crystalline alloy plating layer or the nanocrystalline alloy plating layer, particularly a technique using electrodeposition tungsten-base series non-crystalline alloy or nanocrystalline alloy to replace electroplating hard chromium. Ferrous sulfate heptahydrate, nickel sulphate, cobalt sulfate and sodium tungstate are used as main raw materials; the tungsten-base series non-crystalline alloy plating layer or the nanocrystalline alloy plating layer is electrodeposited; in the alloy plating layers, the tungsten content is from 40 to 50%, and the microhardness of the plating layers is from 600 to 1300 Hv. The plating layers can resist corrosion of acid, alkali and salt fog; the friction coefficients are superior to or equal to that of the electroplating hard chromium, so the plating layers can completely replace hard chromium.
Description
Technical field
The invention belongs to electrochemistry and field of metal surface treatment technology, relate to particularly that aqueous solution electrodeposition goes out tungsten base system row non-crystaline amorphous metal or nanometer crystal alloy coating and in order to replace chromed hardened technology.
Background technology
Hard chrome plating is a traditional technology, and applicating history reaches more than 70 year, and chromed hardened two purposes the most basic are: the first, a wear-resistant surface is provided, and increase the service life, the second, be to repair damage component, wherein be used for the patching machine abrasion piece in a large number.
Chromed hardened characteristics are: bath stability, and easy handling, quality of coating is higher, has light, advantage such as wear-resisting, stable.But this technology has a fatal shortcoming: be chromic pollution.Sexavalent chrome is the major cause that causes rhinocarcinoma and lung cancer, and the environmental administration of countries in the world forbids this technology or limits.Because it is very wide that chromium plating is used, therefore, domestic and international many investigators are devoted to for the chromium plating Study on Technology always, and the technology that relates to has: plating, thermospray, built-up welding etc.With regard to electroplating technology, the alloy of electroplating the replacement decorative chromium mainly contains tin-cobalt, tin-nickel, nickel-tungsten, cobalt-tungstenalloy, and the chromed hardened alloy of replacement of research then mainly contains nickel-base alloy, i.e. nickel-tungsten, nickel-phosphorus, nickel-boron, nickel-molybdenum alloy.Concerning nickel-tungsten, when the tungstenic amount was 30%-32% in the alloy layer, microhardness was 450-500Hv, and after 350-400 ℃ of thermal treatment, hardness can reach 1000-1200Hv.At this moment, the tungstenic amount surpasses 25% in coating, and coating fragility increases, and the bonding force of coating and iron is bad.Concerning nickel-tungsten-phosphorus alloy, in electroplating nickel-tungsten solution, add a certain amount of sodium hypophosphite, can obtain nickel-tungsten-phosphorus alloy, after 300 ℃ of thermal treatment, hardness can reach 1200Hv, but fragility is still very big, bonding force does not improve, and plates thick yet existing problems.If in the nickel-tungsten plating bath, add a certain amount of boride, then can obtain the ternary alloy of nickel-tungsten-boron, this alloy outward appearance is bright to be non-crystalline state like the chromium layer, and hardness is 600Hv, through 315 ℃ of thermal treatments, hardness can reach 950-1050Hv, wear-resisting and good corrosion resistance, but poor stability, cost height, the application on producing also need further research.The another kind of technology of having used on producing is a chemical plating nickel-phosphorus, and its great advantage is to try plating on various complex geometry profiles, and the hardness height, and phosphorous 1-4% can reach 700Hv, and after 400 ℃ of thermal treatment in 1 hour, coating hardness can reach 1100-1200Hv.But chemical plating nickel-phosphorus plates thick ability, is generally less than 175 μ m, seldom can plate the coating greater than 175 μ m, thus limited in many application, and the cost height.
Summary of the invention
The purpose of this invention is to provide a kind of tungsten base system row amorphous alloy coating or nanometer crystal alloy coating and can be used for generation chromed hardened technology and employed electroplate liquid, avoid chromic environmental pollution, improve current efficiency and utilization of materials, satisfy pressing for of mechanical industry and environmental administration.
The objective of the invention is to realize by following manner
This coating can be the alloy of W-Ni-X alloy or W-Ni-X-Y, and wherein X is Co, Fe, and Y is P, B or the two mixing, coating is typical non-crystal structure or nanocrystalline structure, and the content of tungsten is 40-50%, and the content of Ni is 10-20%, in wt%, coating microhardness is 600-1300Hv.
Electroplate liquid used in the present invention comprises sodium wolframate 0.01-0.25mol/l, ferrous sulfate 0.01-0.1mol/l, single nickel salt 0.01-0.1mol/l, boric acid 0.05-0.3mol/l, Citrate trianion 0.05-0.5mol/l.
Technological process of the present invention is
1. the preparation of electroplate liquid
Add clear water earlier, add sodium wolframate, ferrous sulfate, single nickel salt, boric acid, Citrate trianion again, stir, and add the compound of pure carboxylic or pure carboxylic and inorganics and their mixture 0-20ml/l, with the ammoniacal liquor adjust pH to 7.0-8.5, add clear water to use range, sodium wolframate 0.01-0.25Mol/l in the electroplate liquid wherein, ferrous sulfate 0.01-0.1mol/l, single nickel salt 0.01-0.05mol/l, boric acid 0.05-0.3mol/l, Citrate trianion 0.05-0.5mol/l makes and can try plating;
2. the pre-treatment of plating piece, electrochemical deoiling and electrolytic degreasing;
3. plating
Plating piece is put into the plating tank of the electroplate liquid of 1. preparing through step and is electroplated after treatment, and pH is 6-9, and current density is 1-10A/dm
2, temperature is 30-90 ℃, stirs, anode, washes after having plated with inert anode (graphite, Ti-Pt alloy, stainless steel), dries up.
4. dehydrogenation
Product after having plated can 200 ℃ of dehydrogenase 12 h.
More excellent operational condition is 60-80 ℃ in the above-mentioned technological process plating, and current density is 5-10A/dm
2, pH=8.0.
The present invention plates to such an extent that component is the alloy of W-Ni-X or W-Ni-X-Y in the aqueous solution on steel, iron, copper and alloy substrate, and wherein: X is cobalt or iron, and Y is P, B or the mixing of the two.
Utilize plating tungsten based amorphous alloy or nanometer crystal alloy to replace hard chrome plating all not appear in the newspapers, the present invention goes out tungsten base system row non-crystaline amorphous metal by the electroplate liquid galvanic deposit or nanocrystalline coating replaces chromed hardened technology, the content of tungsten accounts for more than 40% in this coating, contain the above component of ternary or ternary, this coating and base material bonding force are good, and wear resistance is equivalent to or is better than hard chrome plating, the energy acid-and base-resisting, the energy plating is thick, and current efficiency and utilization of materials all are higher than chromium plating, bath stability.
This class material directly is raw material with vitriol, electroplate from the ammonium medium of the aqueous solution, current efficiency (30-50%) and utilization of materials (greater than 70%) be all greater than hard chrome plating, plating bath to this corrodibility that is equipped with less than hard chrome plating, and the pollution of non-hexavalent chromium, compliance with environmental protection requirements.Utilize the vitriol of sodium wolframate and iron, cobalt, nickel, add the complexing agent Citrate trianion again, can make this alloy layer have acidproof, alkaline-resisting and resisting salt fog corrosion, the microhardness height, characteristics such as wear resistance is good can replace hard chrome plating and are used widely.
Embodiment
Embodiment 1
1. the preparation of solution
Main raw material(s): sodium wolframate, ferrous sulfate, single nickel salt, boric acid, Citrate trianion, process for preparation: after adding half groove clear water, add each main salt component of plating bath of calculated amount again, stir, and add each additive, use the ammoniacal liquor adjust pH, add clear water to use range, make and to try plating.
2. the pre-treatment of plating piece
Electrochemical deoiling and electrolytic degreasing are arranged.
3. plating
Plating piece is put into plating tank after treatment,
The electroplate liquid component is:
Na
2WO
4(0.12mol/l)+FeSO
4(0.056mol/l)+NiSO
4(0.024mol/l)+H
3cit(0.19mol/l)+H
3BO
3(0.16mol/l)
In current density is 5-10A/dm
2, pH=8, temperature is electroplated down for 60 ℃, and after having plated, flushing dries up.
4. dehydrogenation
Product after having plated can 200 ℃ of dehydrogenase 12 h.
5. check
With visual method check coating whether densification, free of pinholes, come off, peeling, phenomenon such as burn, use its hardness of microhardness instrumentation again, immerse soda acid to check its corrosion resisting property, carry out wear resistance again and check.
Embodiment 2
1. the preparation of solution
Main raw material(s): sodium wolframate, rose vitriol, single nickel salt, boric acid, Citrate trianion, pure carboxylic class and the compound of pure carboxylic and inorganics and their mixture.
Process for preparation: after adding half groove clear water, add each main salt component of plating bath of calculated amount again, stir, and add each additive, use the ammoniacal liquor adjust pH, add clear water, just can try plating to use range.
2. the pre-treatment of plating piece
Pretreatment process by existing electroplating technology can.
3. plating
Plating piece is put into plating tank after treatment,
The electroplate liquid component is:
Na
2WO
4(0.20mol/l)+CoSO
4(0.048mol/l)+NiSO
4(0.032mol/l)+H
3cit(0.3mol/l)+H
3BO
3(0.16mol/l
In current density is 5-10A/dm
3, pH=8, temperature is electroplated down for 80 ℃, and after having plated, flushing dries up.
4. dehydrogenation
Product after having plated can 200 ℃ of dehydrogenase 12 h.
5. check
With visual method check coating whether densification, free of pinholes, come off, peeling, phenomenon such as burn, use its hardness of microhardness instrumentation again, immerse soda acid to check its corrosion resisting property, carry out wear resistance again and check.
Embodiment 1,2 results
The component of tungsten based amorphous alloy or nanometer crystal alloy and structure
We will carry out quantitative assay by the WFeNi of operational path gained and the alloy of WCoNi, XRD structural analysis and SEM morphology analysis, and the component result of gained is: (wt%)
Tungstenic is 40-50% in the WFeNi coating, iron content 30-40%, nickeliferous 10-20%, boracic 0.5-2%.
Tungstenic is 40-50% in the WCoNi coating, contains cobalt 30-40%, nickeliferous 10-20%, boracic 0.5-2%.
Tungsten based amorphous alloy or nanometer crystal alloy performance:
Microhardness: the tungsten-bast alloy that we plate out as stated above, its microhardness are 600-750Hv.After the thermal treatment dehydrogenation, microhardness can reach 1000-1300Hv.
Solidity to corrosion: coating energy acid-alkali-corrosive-resisting, WCoNi coating is through neutral salt spray test 72h nondiscoloration.
Plate thick ability: plating thick ability, can to reach 1.0mm thick.
Coating and base material bonding force: by testing by GB scribble method or doubling, coating and base material bonding force are good.
Base material shape: can on various different shapes base materials, obtain qualified coating.
Wear resistance: with SST-ST pin disc type friction wear testing machine (West Germany), dry friction coefficient and abrasion loss all are better than the chromium plating sample.
Claims (9)
1, tungsten electrodeposition base system row non-crystaline amorphous metal or nanometer crystal alloy coating, it is the alloy of W-Ni-X alloy or W-Ni-X-Y, wherein X is Co, Fe, Y is P, B or the two mixing, coating is typical non-crystal structure or nanocrystalline structure, the content of tungsten is 40-50%, and the content of Ni is 10-20%, is 600-1300Hv in the wt% coating microhardness.
2, tungsten electrodeposition base system row non-crystaline amorphous metal according to claim 1 or be nano-alloy plating layer, tungstenic is more than 40% in the WFeNi coating, iron content 30-40%, nickeliferous 10-20% is in wt%.
3, tungsten electrodeposition base system row non-crystaline amorphous metal according to claim 1 or nano-alloy plating layer, tungstenic is more than 40% in the WCoNi coating, contains cobalt 30-40%, nickeliferous 10-20% is in wt%.
4, employed electroplate liquid in tungsten electrodeposition base system row non-crystaline amorphous metal or the nanometer crystal alloy plating process, comprise sodium wolframate 0.01-0.25mol/l, ferrous sulfate 0.01-0.1mol/l, single nickel salt 0.01-0.1mol/l, boric acid 0.05-0.3mol/l, Citrate trianion 0.05-0.5mol/l.
5, employed electroplate liquid in tungsten electrodeposition base system row non-crystaline amorphous metal according to claim 4 or the nanometer crystal alloy plating process comprises Na
2WO
40.12mol/l, FeSO
40.056mol/l, NiSO
40.024mol/l, H
3Cit0.19mol/l, H
3BO
30.16mol/l.
6, employed electroplate liquid in tungsten electrodeposition base system row non-crystaline amorphous metal or the nanometer crystal alloy plating process comprises Na
2WO
40.20mol/l, CoSO
40.048mol/l, NiSO
40.032mol/l, H
3Cit0.3mol/l, H
3BO
30.16mol/l.
7, the technological process of tungsten electrodeposition base system row amorphous alloy coating or nanometer crystal alloy coating is
1. the preparation of electroplate liquid
Add clear water earlier, add sodium wolframate, ferrous sulfate, single nickel salt, boric acid, Citrate trianion again, stir, and add the compound of pure carboxylic and inorganics and their mixture 0-20ml/l, use the ammoniacal liquor adjust pH, add clear water to use range, sodium wolframate 0.01-0.25mol/l in the electroplate liquid wherein, ferrous sulfate 0.01-0.1mol/l, single nickel salt 0.01-0.05mol/l, boric acid 0.05-0.3mol/l, Citrate trianion 0.05-0.5mol/l makes and can try plating;
2. the pre-treatment of plating piece, electrochemical deoiling and electrolytic degreasing;
3. plating
Plating piece is put into the plating tank of the electroplate liquid of 1. preparing through step and is electroplated after treatment, and pH is 6-9, and current density is 3-10A/dm
2, temperature is 45-90 ℃, stirs, and the anode inert anode, after having plated, flushing dries up.
4. dehydrogenation
Product after having plated can 200 ℃ of dehydrogenase 12 h.
8, the tungsten electrodeposition base system row non-crystaline amorphous metal according to claim 7 or the technological process of expecting peritectic alloy coating of receiving, anode uses graphite or Ti-Pt alloy in the plating, or stainless steel anode.
9, the technological process of tungsten electrodeposition base system row amorphous alloy coating according to claim 7, the temperature in the plating is controlled at 45-80 ℃, and current density is 3-10A/dm
2, pH=7-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03124792XA CN1313647C (en) | 2003-09-04 | 2003-09-04 | Electroplating liquid and technology used in electrodeposition of trngsten series noncrystalline alloy cladding material or nanometer alloy cladding material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03124792XA CN1313647C (en) | 2003-09-04 | 2003-09-04 | Electroplating liquid and technology used in electrodeposition of trngsten series noncrystalline alloy cladding material or nanometer alloy cladding material |
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| CN1590595A CN1590595A (en) | 2005-03-09 |
| CN1313647C true CN1313647C (en) | 2007-05-02 |
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| CN101042044B (en) * | 2007-01-16 | 2011-01-05 | 湖南纳菲尔新材料科技股份有限公司 | Pumping rod or oil sucking pipe electroplating iron-nickel/tungsten alloy double-layer coating and surface processing technology |
| CN101311322B (en) * | 2008-02-02 | 2010-12-15 | 湖南纳菲尔新材料科技股份有限公司 | Surface treatment process for electroplating iron-nickel alloy and electroplating solution thereof |
| US8652649B2 (en) * | 2009-07-10 | 2014-02-18 | Xtalic Corporation | Coated articles and methods |
| CN101928967B (en) * | 2010-08-30 | 2011-08-24 | 赵汝山 | Cobalt-tungsten-nickel-phosphorus alloy electroplating liquid |
| CN101928968B (en) * | 2010-08-30 | 2011-08-24 | 赵汝山 | Boron-tungsten-iron-nickel alloy electroplating liquid |
| CN102337569B (en) * | 2011-09-19 | 2014-06-11 | 华南理工大学 | Cobalt-tungsten nanometer alloy plating layer and preparation method thereof |
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| CN104372389A (en) * | 2014-11-14 | 2015-02-25 | 无锡信大气象传感网科技有限公司 | Cobalt-tungsten-nickel alloy electroplating solution and preparation method thereof |
| CN105350036B (en) * | 2015-10-31 | 2018-03-13 | 北京工业大学 | A kind of method of tungsten electrodeposition alloy |
| CN108560017B (en) * | 2017-12-07 | 2020-05-19 | 华东理工大学 | Amorphous cobalt-tungsten modified foamed nickel catalytic electrode, preparation method and application thereof |
| CN108145150A (en) * | 2017-12-29 | 2018-06-12 | 刘志红 | One kind is based on amorphous nickel plating-phosphor powder production technology |
| CN110359067A (en) * | 2019-08-29 | 2019-10-22 | 营口奥捷专用汽车制造有限公司 | A kind of alloy electrolyte instead of chromium |
| CN113388870B (en) * | 2021-06-11 | 2022-03-11 | 东莞天正新材料有限公司 | Composite plating solution and preparation method thereof, electroplating method and plating layer formed by electroplating method |
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2003
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Patent Citations (6)
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|---|---|---|---|---|
| JPS5357138A (en) * | 1976-11-04 | 1978-05-24 | Hitachi Chemical Co Ltd | Electrolyte for tungsten type alloy plating |
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| JP2000218346A (en) * | 1999-02-01 | 2000-08-08 | Satosen Co Ltd | Continuous casting mold for steel and its manufacturing method |
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| CN1590595A (en) | 2005-03-09 |
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