CN102383150A - High-corrosion-resistance environmentally-friendly trivalent chromium electroplating solution and electroplating method thereof - Google Patents
High-corrosion-resistance environmentally-friendly trivalent chromium electroplating solution and electroplating method thereof Download PDFInfo
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- CN102383150A CN102383150A CN2011103526265A CN201110352626A CN102383150A CN 102383150 A CN102383150 A CN 102383150A CN 2011103526265 A CN2011103526265 A CN 2011103526265A CN 201110352626 A CN201110352626 A CN 201110352626A CN 102383150 A CN102383150 A CN 102383150A
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Abstract
The invention provides a high-corrosion-resistance environmentally-friendly trivalent chromium electroplating solution and an electroplating method thereof, belonging to the technical field of electroplating. The electroplating solution is composed of a main salt, a complexing agent, a stabilizing agent, a wetting agent, an additive, an electric conduction salt and water. The electroplating solution is environmentally-friendly and pollution-free in an electroplating process; the obtained plating layer has high corrosion resistance; and the chromium plating layer has good binding force with a base material, and can well resist the corrosion of a snow thawing agent to mechanical workpieces. By the electroplating method provided by the invention, the deposition speed in the electroplating process can be greatly increased. The electroplating solution and electroplating method can be widely applied in electroplating of surfaces of metal materials.
Description
Invention field
The present invention relates to a kind of electroplating technology, specifically, relate to a kind of high anti-corrosion trivalent chromium plating technology.
Background technology
In relatively colder low district such as Northern Europe and northern China, to avenge day accident rate winter and alleviate the urban traffic pressure in order to reduce, usually select for use Snow Agent to remove the snow.The chloride salt Snow Agent is obvious because of its low price, effect, thereby is widely used.But the muriate that wherein contains very easily produces corrosion to mechanical workpieces such as automobile chassis, road guards like materials such as sodium-chlor, calcium chloride.This just needs a kind of coating with high anti-corrosion, high-wearing feature, is used to resist the etching problem of Snow Agent to mechanical workpieces.
Solidity to corrosion chromium plating (hard chrome) owing to have higher hardness, bonding force and more low molecular frictional coefficient are widely used in machinery part surface preferably, can well improve the wear resistance and the corrosion resisting property of workpiece itself.
Though traditional functions property chrome-plated process has wear resistance and corrosion resisting property preferably, contains sexavalent chrome in waste water that technology relates to and the waste gas, can cause serious pollution to environment.At present, no matter be abroad or domestic, all carried out strict restriction to containing chromic electroplating technology.As the galvanized alternative techniques of sexavalent chrome, the trivalent chromium plating process quilt is thought the most a kind of.But; Trivalent chromium chrome plating is used for decoration chrome plating more; Its application on functional coating is also very limited; Reason mainly is that the binding force of cladding material of trivalent chromium chrome plating high current density region is poor, on corrosion resisting property, can not compare favourably with sexavalent chrome, says nothing of to solve Snow Agent to the quick corrosive problem of mechanical workpieces.So we need a kind of not only environmental protection but also corrosion resistant chromium coating technology.
Summary of the invention
To the problems referred to above, the present invention provides a kind of high anti-corrosion environmental protection trivalent chromium plating liquid and electro-plating method thereof.
First purpose of the present invention; Provide a kind of high anti-corrosion environmental protection trivalent chromium plating liquid, this electroplate liquid is environment friendly and pollution-free in electroplating process, and the coating that is obtained has high anti-corrosion; Chromium coating and base material also have good bonding force, can well resist the corrosion of Snow Agent to mechanical workpieces.
In order to realize first purpose of the present invention, the present invention provides a kind of high anti-corrosion environmental protection trivalent chromium plating liquid, mainly is made up of main salt, complexing agent, stablizer, wetting agent, additive, conducting salt and water; Said main salt is at least a in chromium sulphate, the potassium chromium sulfate; Said complexing agent is at least a in tertiarybutylhydroquinone, the o-hydroxy cinnamic acid ester; Said stablizer is sodium oxalate and boric acid; Said wetting agent is at least a in T 46155 Vestolen PP 7052 phenol ether, the cetyl trimethylammonium bromide; Said additive is nano silicon/aluminum oxide compound; Said conducting salt is at least a in vitriolate of tartar, sodium sulfate, the ammonium sulfate.
The present invention also can do following improvement:
Main salts contg is 10g/L～200g/L.
Complexing agent content is 1g/L～120g/L.
Stabiliser content is 1g/L～120g/L.
Humectant content is 0.01g/L～8g/L.
Additive level is 1g/L～10g/L.
Conducting salt content is 10g/L～120g/L.
Said main salts contg is 80g/L-140g/L; Said complexing agent content is 20g/L～80g/L; Said stabiliser content is 2g/L～10g/L; Said humectant content is 0.05g/L～2g/L; Said additive level is 2g/L～8g/L; Said conducting salt content is 200g/L～300g/L.
Second purpose of the present invention be, a kind of high anti-corrosion environmental protection trivalent chromium plating method is provided, and this method sedimentation velocity in electroplating process has significantly and improves.
In order to realize second purpose, the present invention provides a kind of method of electroplating the high anti-corrosion trivalent chromium coating of environmental protection, may further comprise the steps:
(1) workpiece pickling and washing;
(2) electroplate with the anti-corrosion environmental protection trivalent chromium bath of above-mentioned height; Galvanized condition is: temperature 20-60 ℃, cathode current density 5-30ASD (average current density), pH value 2-4; Electroplated 10-40 minute, employed anode is DSA (Dimensionally Stable Anode) iridium titanium coated anode in the electroplating process;
(3) electroplate the back water plating piece is cleaned up, dry up then.
The present invention also can do following improvement:
In the step (2), the plating condition is: temperature 45-55 ℃, cathode current density 10-20ASD, pH value 3-4, electroplated 25-35 minute.
Compared with prior art, the beneficial effect that has of the present invention is:
1) the high anti-corrosion trivalent chromium plating liquid of a kind of plating environmental protection of the present invention, cleanliness without any pollution, the coating outward appearance is light evenly, and solidity to corrosion is high.
2) the high anti-corrosion trivalent chromium plating liquid of a kind of plating environmental protection of the present invention is introduced potassium chromium sulfate, can effectively improve current efficiency to 30-40%, and rate of deposition is increased to 0.3-0.4 μ m/min, helps the increase of thickness of coating.
3) the high anti-corrosion trivalent chromium plating liquid of a kind of plating environmental protection of the present invention has been introduced nano silicon/aluminum oxide compound as additive; Improved the trivalent chromium corrosion resistance of coating greatly; Increased coating and between bonding force, the overall wear resistance of workpiece can be promoted.
High anti-corrosion trivalent chromium plating liquid of a kind of plating environmental protection provided by the invention and electro-plating method thereof make the promotion and application of trivalent chromium functional electroplating process become possibility.
Specific embodiment
Below in conjunction with specific embodiment the present invention is done further detailed description, but do not constitute to any restriction of the present invention.
Comparative Examples 1
Electroplating bath components:
Electro-plating method: get nickel plating sheet (9 microns of nickel layer thickness) after washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode uses DSA iridium titanium coated anode.Electroplate the back and clean up, dry up then with water.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 900HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 16 hours, and coating is high to be distinguished and low 3 microns of the thickness differences of distinguishing.Through CaCl
2/ NaCl (1: 1) salt-fog test is after 31 hours, and coating is high to be distinguished and low 7 microns of the thickness differences of distinguishing, and corrosion rate reaches 60%.Salt-fog test after 48 hours full sheet play rust, corrosion rate 100%.
Comparative Examples 2
Electroplating bath components:
Electro-plating method: get nickel plating sheet (9 microns of nickel layer thickness) after washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts graphite anode.Electroplate the back and clean up, dry up then with water.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 750HV, and 20 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 16 hours, and coating is high to be distinguished and low 7 microns of the thickness differences of distinguishing.Salt-fog test after 48 hours full sheet play rust, corrosion rate 100%.
Comparative Examples 3
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test condition and be: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.Electroplate the back and clean up, dry up then with water.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 760HV, and 22 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 16.5 hours, and coating is high to be distinguished and low 7 microns of the thickness differences of distinguishing.Salt-fog test after 48 hours full sheet play rust, corrosion rate 100%.
Embodiment 1
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.Electroplate the back and clean up, dry up then with water.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 1000HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of the thickness differences of distinguishing, and corrosion rate is 4%.
Embodiment 2
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.The plating back cleans up with water, dries up then.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 980HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of the thickness differences of distinguishing, and corrosion rate is 5%.
Embodiment 3
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.Electroplate the back and clean up, dry up then with water.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 990HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of the thickness differences of distinguishing, and corrosion rate is 4%.
Embodiment 4
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.The plating back cleans up with water, dries up then.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 985HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of the thickness differences of distinguishing, and corrosion rate is 4%.
Embodiment 5
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.The plating back cleans up with water, dries up then.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 975HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of the thickness differences of distinguishing, and corrosion rate is 5%.
Embodiment 6
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.The plating back cleans up with water, dries up then.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 995HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 4 microns of the thickness differences of distinguishing, and corrosion rate is 4%.
Embodiment 7
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.The plating back cleans up with water, dries up then.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 970HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of the thickness differences of distinguishing, and corrosion rate is 5%.
Embodiment 8
Electroplating bath components:
Electro-plating method: after getting nickel plating sheet (9 microns of nickel layer thickness) washing, in the groove of the Hull of 267ml, electroplate test, condition is: 45 ℃ of temperature, cathode current density 50ASD, electroplated 30 minutes, anode adopts DSA iridium titanium coated anode.The plating back cleans up with water, dries up then.
Electroplating effect is estimated: it is careful evenly to observe the chromium coating crystallization, measures surface hardness 990HV, and 30 millimeters of thickness are through CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and coating is high to be distinguished and low 4 microns of the thickness differences of distinguishing, and corrosion rate is 4%.
Visible by The above results, the comparative example table surface hardness is 750-900HV, and thickness is the 20-30 millimeter, and salt-fog test is after 16 hours, and 7 microns of high district of coating and low district thickness differences are proceeded CaCl
2/ NaCl (1: 1) salt-fog test is after 48 hours, and full sheet plays rust, corrosion rate 100%.And the embodiment surface hardness is 980-1000HV, and thickness is 30 millimeters, and salt-fog test is after 48 hours, and coating is high to be distinguished and low 5 microns of thickness differences, corrosion rate≤5% distinguished.Its hardness, thickness and erosion resistance are far above Comparative Examples.In sum, a kind of high anti-corrosion environmental protection trivalent chromium plating liquid provided by the invention and electro-plating method thereof have the hardness height, the advantage that erosion resistance is strong.
The above embodiments are merely the preferred embodiments of the present invention, can not limit interest field of the present invention with this, and therefore, the equivalent variations according to claim of the present invention is done still belongs to the scope that the present invention is contained.
Claims (10)
1. one kind high anti-corrosion environmental protection trivalent chromium plating liquid mainly is made up of main salt, complexing agent, stablizer, wetting agent, additive, conducting salt and water; It is characterized in that: said main salt is at least a in chromium sulphate, the potassium chromium sulfate; Said complexing agent is at least a in tertiarybutylhydroquinone, the o-hydroxy cinnamic acid ester; Said stablizer is sodium oxalate and boric acid; Said wetting agent is at least a in T 46155 Vestolen PP 7052 phenol ether, the cetyl trimethylammonium bromide; Said additive is nano silicon/aluminum oxide compound; Said conducting salt is at least a in vitriolate of tartar, sodium sulfate, the ammonium sulfate.
2. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: main salts contg is 10g/L～200g/L.
3. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: complexing agent content is 1g/L～120g/L.
4. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: stabiliser content is 1g/L～120g/L.
5. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: wetting agent content is 0.01g/L～8g/L.
6. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: additive level is 1g/L～10g/L.
7. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: conducting salt content is 10g/L～120g/L.
8. a kind of high anti-corrosion environmental protection trivalent chromium plating liquid according to claim 1, it is characterized in that: said main salts contg is 80g/L-140g/L; Said complexing agent content is 20g/L～80g/L; Said stabiliser content is 2g/L～10g/L; Said humectant content is 0.05g/L～2g/L; Said additive level is 2g/L～8g/L; Said conducting salt content is 200g/L～300g/L.
9. one kind high anti-corrosion environmental protection trivalent chromium plating method is characterized in that may further comprise the steps:
(1) workpiece pickling and washing;
(2) electroplate with the anti-corrosion environmental protection trivalent chromium bath of above-mentioned height; Galvanized condition is: temperature 20-60 ℃, cathode current density 5-30ASD, pH value 2-4; Electroplated 10-40 minute, employed anode is DSA (Dimensionally Stable Anode) iridium titanium coated anode in the electroplating process;
(3) electroplate the back water plating piece is cleaned up, dry up then.
10. a kind of high anti-corrosion environmental protection trivalent chromium plating method according to claim 9, it is characterized in that: in the step (2), the plating condition is: temperature 45-55 ℃, cathode current density 10-20ASD, pH value 3-4, electroplated 25-35 minute.
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| CN103255455A (en) * | 2013-05-31 | 2013-08-21 | 东北大学 | Method and device for pulse texturing treatment of surface of metal material |
| CN103898560A (en) * | 2013-06-03 | 2014-07-02 | 无锡市锡山区鹅湖镇荡口青荡金属制品厂 | Electroplating process for chrome plating on surface of magnesium alloy pressure casting |
| CN105506713A (en) * | 2014-09-25 | 2016-04-20 | 通用电气公司 | Method for formation of chromium based coating by electroplating, used electrolyte solution and formed coating |
| CN107119290A (en) * | 2017-03-06 | 2017-09-01 | 广东达志环保科技股份有限公司 | A kind of environmentally friendly hard chrome electroplate liquid and a kind of environmentally friendly hard chrome electroplating technology |
| CN109112581A (en) * | 2017-06-22 | 2019-01-01 | 江苏联动轴承股份有限公司 | A kind of Cr-plating Bath |
| US20200308723A1 (en) * | 2014-01-24 | 2020-10-01 | Coventya S.P.A. | Electroplating bath containing trivalent chromium and process for depositing chromium |
| CN112111776A (en) * | 2019-06-19 | 2020-12-22 | 广东禾木科技有限公司 | Cathode passivation protection solution for silver bonding wire |
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| CN103255455A (en) * | 2013-05-31 | 2013-08-21 | 东北大学 | Method and device for pulse texturing treatment of surface of metal material |
| CN103898560A (en) * | 2013-06-03 | 2014-07-02 | 无锡市锡山区鹅湖镇荡口青荡金属制品厂 | Electroplating process for chrome plating on surface of magnesium alloy pressure casting |
| CN103898560B (en) * | 2013-06-03 | 2016-12-28 | 顾玉奎 | A kind of at the chrome faced electroplating technology of magnesium alloy die casting |
| US20200308723A1 (en) * | 2014-01-24 | 2020-10-01 | Coventya S.P.A. | Electroplating bath containing trivalent chromium and process for depositing chromium |
| CN113818053A (en) * | 2014-01-24 | 2021-12-21 | 科文特亚共同股份公司 | Trivalent chromium-containing electroplating bath solution and method for depositing chromium |
| US11905613B2 (en) * | 2014-01-24 | 2024-02-20 | Coventya S.P.A. | Electroplating bath containing trivalent chromium and process for depositing chromium |
| CN105506713A (en) * | 2014-09-25 | 2016-04-20 | 通用电气公司 | Method for formation of chromium based coating by electroplating, used electrolyte solution and formed coating |
| CN105506713B (en) * | 2014-09-25 | 2018-05-08 | 通用电气公司 | Method, electrolyte used and the coating formed of chromium base coating are formed by plating |
| CN107119290A (en) * | 2017-03-06 | 2017-09-01 | 广东达志环保科技股份有限公司 | A kind of environmentally friendly hard chrome electroplate liquid and a kind of environmentally friendly hard chrome electroplating technology |
| CN109112581A (en) * | 2017-06-22 | 2019-01-01 | 江苏联动轴承股份有限公司 | A kind of Cr-plating Bath |
| CN112111776A (en) * | 2019-06-19 | 2020-12-22 | 广东禾木科技有限公司 | Cathode passivation protection solution for silver bonding wire |
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