CA2085430C - Method of adhering colored electroplating layer on a zinc-electroplated steel article - Google Patents
Method of adhering colored electroplating layer on a zinc-electroplated steel articleInfo
- Publication number
- CA2085430C CA2085430C CA002085430A CA2085430A CA2085430C CA 2085430 C CA2085430 C CA 2085430C CA 002085430 A CA002085430 A CA 002085430A CA 2085430 A CA2085430 A CA 2085430A CA 2085430 C CA2085430 C CA 2085430C
- Authority
- CA
- Canada
- Prior art keywords
- zinc
- salts
- layer
- colored
- electroplating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
Abstract
The present invention relates to a method of adhering a colored electroplating layer on zinc-electroplated steel articles. The method utilizes an alternating current power supply which supplies electricity of frequency of 10-120 Hz, and uses an aqueous electroplating solution which contains 150-200 g/l of silicate, 15-20 g/l of sodium hydroxide and 5-50 g/l of a metal salt. The electroplating liquid is kept at a constant temperature of 20°C - 30°C. In this method, two stages are utilized to perform the electroplating and adhere a colored electroplated layer so that the surface of the zinc-electroplated layer can adhere a blue electroplated layer. In the first stage, the electricity is applied at a constant voltage lying in the range 60-120 volts and in the second stage the electricity is applied at a constant current density in the range 20-80 Amps/dm2. Thus the aesthetics and the corrosion-resistant capability of the zinc-electroplated layer can be enhanced because of the colored electroplated layer adhered to the surface of the zinc-electroplated layer. In the method mentioned hereinabove the metal salt can be selected from cobalt salts at 5-50 g/l, manganese salts at 5-20 g/l, chromium salts at 5-15 g/l, iron salts at 2-15 g/l, and tin salts at 20-g/l so that the adhered color of the surface of the zinc-electroplated layer would be blue, brown, green, white, or grey color respectively.
Description
METHOD OF ADHERING COLORED ELECTROPLATING LAYER ON A ZINC-ELECTROPLATED STEEL ARTICLE
BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates to a method of adhering a colored electroplating layer on zinc-electroplated steel articles. The method utilizes an alternating current power supply which supplies electricity at a frequency of 10-120 Hz in an aqueous electroplating solution which contains 150-2300 g/I of silicate, 15~-20 g/I of sodium hydroxide and 5-50 g/I of a metal salt. The electroplating solution is kept at a constant temperature 20°C -30°C. In this method, two stages are utilized to perform the electroplating and adhere a colored electroplating layer so that the surface of the zinc-electroplated layer can adhere the electroplated layer.
In the first stage, the electricity is applied at a constant voltage lying in the range 60-120V and in the second stage the electricity is applied at a constant current density in the range 20-80 Amps/dm2. Thus the aesthetics and the corrosion-resistant capability of the zinc-electroplated layer can be enhanced because of the colored electroplated layer adhered to the surface of the zinc-electroplated layer. In the method mentioned hereinabove, preferably the metal salt is selected from the group consisting of cobalt salts at 5-50 l~/I, manganese salts at 5-20 g/I, chromium salts at 5-15 g/I, iron salts at 2-'15 gh, and tin salts at 20-40 g/I so that the adhered color of the surface oi' the zinc-electroplated layer would be blue, brown, green, white or grey respectively.
The main object of the preset invention is to apply a colored electroplated layer on the surface of a zinc-electroplated article so as to enhance corrosion-resistance. This is achieved by an alternating current electroplating method utilizing a voltage, a current, and a constant temperature of a limited range. In this method salts contained in the solution used in the electroplating process result in a colored electroplating layer being adhered to the surface of the zinc-electroplated layer of the zinc-electroplated steel arti~:le and the aesthetics and the corrosion resistance of the zinc-electroplated steel article is thereby enhanced by the colored electroplated layer.
Zinc is an amphoteric metal which is very active and which has the corrosion resistance capability. For this reason many commercially available products, which are made of iron or the like, such as home appliances, automobile; body, bridge structure, electric power transmission equipment utilize zinc as corrosion resistant layer. Since the surface coating of the zinc layer is soft and susceptible to wearing and corrosion, and the zinc layer becomes zinc oxide after being oxidized, the adherence between the zinc oxide and thE: iron material is deteriorated. This causes the zinc oxide to peel off the iron material. Further the surface of conventional zinc-plated steel articles is ;sliver white which lacks aesthetics and limits the field of usage. Conventionally, several methods are ~t~~54~d employed to improve l:he color of the surface of the zinc-plated layer and to inhibit the consumption of the zinc layer on the surface; e.g. (1 ) chemical conversion coating for metals; (2) coating treatment; (3) to product an interference coloring alloy by adding the elements such as titanium, magnesium or manganese during the process of hot-dip cialvanizing; and (4) electrochemical coloring treatment.
However, each of the above-mentioned methods has the following drawbacks:
(1 ) Chemical conversion coating for metals:
This method includes phosphates treatment method, chromates treatment method, and sulphurizing etc. Although the chemical conversion coating can be used for the corrosion resistant treatment for the zinc-plated steel articles, it has the drawbacks since the chromates and the sulphites are highly toxic and the phosphate is difficult to dissolve. This causes environmental pollution.
Furthermore, the corrosion resistant effect of this method is not ideal for the high corrosion areas such as the areas close to the sea.
(2) Coating treatment:
There are man~i kinds of resins which are being used in this method, e.g.
PVC resin, acrylic resin, epoxy resin, or the like. However, the coating on the zinc-plated steel articles which have been coated with these resins have the tendency to peel off after being exposed. In particular the adherence between a paint and the surface of a zinc-plated layer is not good if the paint is applied on a steel article which has just been zinc-electroplated.
BACKGROUND AND SUMMARY OF THE INVENTION
The present invention relates to a method of adhering a colored electroplating layer on zinc-electroplated steel articles. The method utilizes an alternating current power supply which supplies electricity at a frequency of 10-120 Hz in an aqueous electroplating solution which contains 150-2300 g/I of silicate, 15~-20 g/I of sodium hydroxide and 5-50 g/I of a metal salt. The electroplating solution is kept at a constant temperature 20°C -30°C. In this method, two stages are utilized to perform the electroplating and adhere a colored electroplating layer so that the surface of the zinc-electroplated layer can adhere the electroplated layer.
In the first stage, the electricity is applied at a constant voltage lying in the range 60-120V and in the second stage the electricity is applied at a constant current density in the range 20-80 Amps/dm2. Thus the aesthetics and the corrosion-resistant capability of the zinc-electroplated layer can be enhanced because of the colored electroplated layer adhered to the surface of the zinc-electroplated layer. In the method mentioned hereinabove, preferably the metal salt is selected from the group consisting of cobalt salts at 5-50 l~/I, manganese salts at 5-20 g/I, chromium salts at 5-15 g/I, iron salts at 2-'15 gh, and tin salts at 20-40 g/I so that the adhered color of the surface oi' the zinc-electroplated layer would be blue, brown, green, white or grey respectively.
The main object of the preset invention is to apply a colored electroplated layer on the surface of a zinc-electroplated article so as to enhance corrosion-resistance. This is achieved by an alternating current electroplating method utilizing a voltage, a current, and a constant temperature of a limited range. In this method salts contained in the solution used in the electroplating process result in a colored electroplating layer being adhered to the surface of the zinc-electroplated layer of the zinc-electroplated steel arti~:le and the aesthetics and the corrosion resistance of the zinc-electroplated steel article is thereby enhanced by the colored electroplated layer.
Zinc is an amphoteric metal which is very active and which has the corrosion resistance capability. For this reason many commercially available products, which are made of iron or the like, such as home appliances, automobile; body, bridge structure, electric power transmission equipment utilize zinc as corrosion resistant layer. Since the surface coating of the zinc layer is soft and susceptible to wearing and corrosion, and the zinc layer becomes zinc oxide after being oxidized, the adherence between the zinc oxide and thE: iron material is deteriorated. This causes the zinc oxide to peel off the iron material. Further the surface of conventional zinc-plated steel articles is ;sliver white which lacks aesthetics and limits the field of usage. Conventionally, several methods are ~t~~54~d employed to improve l:he color of the surface of the zinc-plated layer and to inhibit the consumption of the zinc layer on the surface; e.g. (1 ) chemical conversion coating for metals; (2) coating treatment; (3) to product an interference coloring alloy by adding the elements such as titanium, magnesium or manganese during the process of hot-dip cialvanizing; and (4) electrochemical coloring treatment.
However, each of the above-mentioned methods has the following drawbacks:
(1 ) Chemical conversion coating for metals:
This method includes phosphates treatment method, chromates treatment method, and sulphurizing etc. Although the chemical conversion coating can be used for the corrosion resistant treatment for the zinc-plated steel articles, it has the drawbacks since the chromates and the sulphites are highly toxic and the phosphate is difficult to dissolve. This causes environmental pollution.
Furthermore, the corrosion resistant effect of this method is not ideal for the high corrosion areas such as the areas close to the sea.
(2) Coating treatment:
There are man~i kinds of resins which are being used in this method, e.g.
PVC resin, acrylic resin, epoxy resin, or the like. However, the coating on the zinc-plated steel articles which have been coated with these resins have the tendency to peel off after being exposed. In particular the adherence between a paint and the surface of a zinc-plated layer is not good if the paint is applied on a steel article which has just been zinc-electroplated.
(3) To produce an interference coloring alloy by adding the elements such as titanium, magnesium, or manganese during the process of hot-dip galvanizing:
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This method produces alloy products in which the uniformity and the recurrence has to be overcome. Furthermore, the interference coloring alloy produced with this method is relatively thin and does riot have a good anti-wearing property.
(4) Electrochemical coloring treatment:
In 1962, a Canadian company named Convince developed APCF (zinc anodized treatment procedure) which is an anodized treatment which utilizes zinc chromate and zinc amrnonium phosphate electrolyte, with the voltage raised to V, to produce a green coating. In 1971, U.S. Navy set up standards for zinc and zinc alloy anodized treatment coating, in which there are tour kinds of colored coating treatment procedures, i.e., APCF (green coating), SSC (light grey coating), SSCV (dark grey coating), and SSMN (brown coating). These manufacturing procedures use solutions such as chromates, hydrofluoric acid, and permanganates, which are highly toxic and highly corrosive corrosion. Thus there is a tendency for causing environmental pollution.
The inventor of the present invention mitigates the problems such as coloring the zinc-plated layer and the thinness of the layer. The inventor conducted research in the technique relating to the zinc-plating of steel articles and the different clay coatings.
The present invention provides mainly a method for providing a colored layer adhered to zinc-plated layers which are zinc layers of pure zinc, hot-dip galvanized zinc, electroplated zinc, die casting zinc, and thermal sprayed zinc. In this method, the zinc-plated layer h~3s enhanced adherence, microhardness, and erosion-~Q~~43~
resistant property.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the voltage and the current density in each stage of the two-stage electroplating processing of the present invention; and Fig. 2 shows a picture, which has been enlarged with an electron microscope, a sample obtained by the method of the present invention.
DETAILED DI.SCRIPTION OF THE PREFERRED EMBODIMENTS
The method of the present invention utilizes an alternating current power supply. It employs a steel article to be zinc-electroplated as an electrode.
It uses a solution containing 15-20 g/I of sodium hydroxide, 150-200 g/I of silicate and 5 50 g/I of cobalt salt as the electroplating liquid. As shown in Fig. 1, an electricity of frequency of 1o-i2o Hz and a constant voltage of 60-1 20 V is utilized in the first stage for 3-7 minutes. This results in a uniform black layer on the surface of the zinc-plated steel article because of oxidation. In the second stage, the current density is raised to 20-80 Amp/dmz (so that the potential is raised beyond a spark potential) and the temperature is kept at a constant temperature of 20-30°C. The second stage takes 8-1 2 minutes. Since the potential is raised beyond a spark potential, the steel article being zinc-electroplated begins to generate sparks, this results in the ionization of the metal salts (cobalt salts) which adhered to the steel article and thus a blue colored electroplating layer is formed on the zinc-plated steel article. After this second stage, the steel article is rinsed with clean water and dried. A plated layer of a uniform thickness of about 20,um is obtained.
2~8~~~a Fig. 2 shows a picture of a sample of the steel article having been processed with the present invention. This picture has been enlarged 1500 times with electron microscope. The picture of figure 2 shows a steel article (1 ), zinc layer (2) adhered thereto, and a colored plated layer (3) on the top.
In the above-mentioned method, the metal salts in the mixed liquid is a variable factor for coloring, e.g., cobalt salts of 5-50 g/I can result in a blue layer, manganese salts of 5-20 g/I can result in a brown layer, chromium salts of 5-15 g/I
can result in a green layer, iron salts of 2-1 5 g/l can result in a white layer, and tin salts of 20-50 g/I can result in a grey layer. Different metal salts had different contents in the electroplating solution.
The zinc-plated steel article having a colored plated layer adhered thereto obtained with the method of the present invention has a colored plated layer which is not light-reflective and has an enhanced corrosion resistant capability.
The improvement of the adhered colored plated layer is demonstrated with the following experiment.
A pure zinc test sheet of 50 x 30 x 2 mm is put into a bath of 10% sodium hydroxide for two minutes, de-oiled, and rinsed with deionizing water. Then the test sheet is put into a bath of 10% hydrogen chloride for two minutes. The impurity on the surface of the test sheet is removed and then the test sheet is rinsed with deionizinc~ water. The test sheet is hung, as an electrode, in an electroplating bath of silicates of 150-200 g/I, sodium hydroxide of 15-20 g/I, and cobalt salts of 5-50 g/l. The bath is kept at a constant temperature of 20-30°C.
In the first stage, a constant voltage of 60-1 20 Volts is applied for 3-7 minutes to produce a black plated layer. In the second stage, the current density is kept at 20-80 Amp/dm2 for 8-12 minutes a blue uniform plated layer is gradually formed in the second stage because of the current therethrough. Thie test sheet is then removed from the bath and rinsed with water, put into a box which is kept at a temperature of 80°C for 10 minutes. Thus a uniform non-reflective blue plated layer having a thickness of 20 Nm is obtained.
The results of testing the test sheet which has been electroplated are as follows:
(1 ) Salt Spray Test:
A salt spray te~;t is conducted for 1000 hours on the color plated layer. The surface of the layer remains good after the test. No rust spots developed.
(Conventionally, a steE:l article having plated zinc of thickness of 100 Nm will show white spots after a sirnilar test of 50 hours and show yellow spots after a test of 150 hours).
(2) Corrosion Corrosion potential test in 3% salt water:
The corrosion potential of the test sheet having colored plated layer is 400 MV higher than that of ordinary test sheet of hot-dip galvanizing.
(3) Microhardness test:
The hardness of the test sheet having a colored plated layer is over 100 VHN, which is 20% higher than that of a pure zinc surface.
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(4) Cross hatch cut test (ASTM 3359-76):
The test sheet having a colored plated layer adhered thereto has a plated layer of better adherence and it's not easy for the layer to peel off.
Therefore, the ~:inc-plated steel article obtained by the method of the present invention improves the conventional zinc-plated steel article and has the following features:
1. Instead of the rnonotonous silver grey color of the prior art plated layer;
the plated layer of the present invention may be produced with several different colors, which enhances the aesthetics of the plated layer, 2. the present invention improves the corrosion resistant property of the zinc-plated layer and prevents white spots from forming on the layer, 3. the layer is non-reflective and the color thereof is uniform when viewed from different sides, 4. the electroplatE:d layer is of uniform thickness, ' 5. the thickness of the colored plated layer can be 20 ,um or more, and 6. zero pollution.
Therefore, the method of the present invention can accomplish a desirable result which not only provides a good coloring and plated layer on the surface of ~os~~-~~
the zinc-plated steel article (including pure zinc, hot-dip galvanizing, electroplated zinc, thermal spraying zinc, and die casting zinc), but also enhances the corrosion resistant property thereof. The drawbacks of the coriventional coloring technique of the zinc-plating and the inadequacy of the plated layer can be mitigated.
This makes the zinc-plated steel article more acceptable to the consumers.
(4) Electrochemical coloring treatment:
In 1962, a Canadian company named Convince developed APCF (zinc anodized treatment procedure) which is an anodized treatment which utilizes zinc chromate and zinc amrnonium phosphate electrolyte, with the voltage raised to V, to produce a green coating. In 1971, U.S. Navy set up standards for zinc and zinc alloy anodized treatment coating, in which there are tour kinds of colored coating treatment procedures, i.e., APCF (green coating), SSC (light grey coating), SSCV (dark grey coating), and SSMN (brown coating). These manufacturing procedures use solutions such as chromates, hydrofluoric acid, and permanganates, which are highly toxic and highly corrosive corrosion. Thus there is a tendency for causing environmental pollution.
The inventor of the present invention mitigates the problems such as coloring the zinc-plated layer and the thinness of the layer. The inventor conducted research in the technique relating to the zinc-plating of steel articles and the different clay coatings.
The present invention provides mainly a method for providing a colored layer adhered to zinc-plated layers which are zinc layers of pure zinc, hot-dip galvanized zinc, electroplated zinc, die casting zinc, and thermal sprayed zinc. In this method, the zinc-plated layer h~3s enhanced adherence, microhardness, and erosion-~Q~~43~
resistant property.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 shows the voltage and the current density in each stage of the two-stage electroplating processing of the present invention; and Fig. 2 shows a picture, which has been enlarged with an electron microscope, a sample obtained by the method of the present invention.
DETAILED DI.SCRIPTION OF THE PREFERRED EMBODIMENTS
The method of the present invention utilizes an alternating current power supply. It employs a steel article to be zinc-electroplated as an electrode.
It uses a solution containing 15-20 g/I of sodium hydroxide, 150-200 g/I of silicate and 5 50 g/I of cobalt salt as the electroplating liquid. As shown in Fig. 1, an electricity of frequency of 1o-i2o Hz and a constant voltage of 60-1 20 V is utilized in the first stage for 3-7 minutes. This results in a uniform black layer on the surface of the zinc-plated steel article because of oxidation. In the second stage, the current density is raised to 20-80 Amp/dmz (so that the potential is raised beyond a spark potential) and the temperature is kept at a constant temperature of 20-30°C. The second stage takes 8-1 2 minutes. Since the potential is raised beyond a spark potential, the steel article being zinc-electroplated begins to generate sparks, this results in the ionization of the metal salts (cobalt salts) which adhered to the steel article and thus a blue colored electroplating layer is formed on the zinc-plated steel article. After this second stage, the steel article is rinsed with clean water and dried. A plated layer of a uniform thickness of about 20,um is obtained.
2~8~~~a Fig. 2 shows a picture of a sample of the steel article having been processed with the present invention. This picture has been enlarged 1500 times with electron microscope. The picture of figure 2 shows a steel article (1 ), zinc layer (2) adhered thereto, and a colored plated layer (3) on the top.
In the above-mentioned method, the metal salts in the mixed liquid is a variable factor for coloring, e.g., cobalt salts of 5-50 g/I can result in a blue layer, manganese salts of 5-20 g/I can result in a brown layer, chromium salts of 5-15 g/I
can result in a green layer, iron salts of 2-1 5 g/l can result in a white layer, and tin salts of 20-50 g/I can result in a grey layer. Different metal salts had different contents in the electroplating solution.
The zinc-plated steel article having a colored plated layer adhered thereto obtained with the method of the present invention has a colored plated layer which is not light-reflective and has an enhanced corrosion resistant capability.
The improvement of the adhered colored plated layer is demonstrated with the following experiment.
A pure zinc test sheet of 50 x 30 x 2 mm is put into a bath of 10% sodium hydroxide for two minutes, de-oiled, and rinsed with deionizing water. Then the test sheet is put into a bath of 10% hydrogen chloride for two minutes. The impurity on the surface of the test sheet is removed and then the test sheet is rinsed with deionizinc~ water. The test sheet is hung, as an electrode, in an electroplating bath of silicates of 150-200 g/I, sodium hydroxide of 15-20 g/I, and cobalt salts of 5-50 g/l. The bath is kept at a constant temperature of 20-30°C.
In the first stage, a constant voltage of 60-1 20 Volts is applied for 3-7 minutes to produce a black plated layer. In the second stage, the current density is kept at 20-80 Amp/dm2 for 8-12 minutes a blue uniform plated layer is gradually formed in the second stage because of the current therethrough. Thie test sheet is then removed from the bath and rinsed with water, put into a box which is kept at a temperature of 80°C for 10 minutes. Thus a uniform non-reflective blue plated layer having a thickness of 20 Nm is obtained.
The results of testing the test sheet which has been electroplated are as follows:
(1 ) Salt Spray Test:
A salt spray te~;t is conducted for 1000 hours on the color plated layer. The surface of the layer remains good after the test. No rust spots developed.
(Conventionally, a steE:l article having plated zinc of thickness of 100 Nm will show white spots after a sirnilar test of 50 hours and show yellow spots after a test of 150 hours).
(2) Corrosion Corrosion potential test in 3% salt water:
The corrosion potential of the test sheet having colored plated layer is 400 MV higher than that of ordinary test sheet of hot-dip galvanizing.
(3) Microhardness test:
The hardness of the test sheet having a colored plated layer is over 100 VHN, which is 20% higher than that of a pure zinc surface.
2~85~.~~
(4) Cross hatch cut test (ASTM 3359-76):
The test sheet having a colored plated layer adhered thereto has a plated layer of better adherence and it's not easy for the layer to peel off.
Therefore, the ~:inc-plated steel article obtained by the method of the present invention improves the conventional zinc-plated steel article and has the following features:
1. Instead of the rnonotonous silver grey color of the prior art plated layer;
the plated layer of the present invention may be produced with several different colors, which enhances the aesthetics of the plated layer, 2. the present invention improves the corrosion resistant property of the zinc-plated layer and prevents white spots from forming on the layer, 3. the layer is non-reflective and the color thereof is uniform when viewed from different sides, 4. the electroplatE:d layer is of uniform thickness, ' 5. the thickness of the colored plated layer can be 20 ,um or more, and 6. zero pollution.
Therefore, the method of the present invention can accomplish a desirable result which not only provides a good coloring and plated layer on the surface of ~os~~-~~
the zinc-plated steel article (including pure zinc, hot-dip galvanizing, electroplated zinc, thermal spraying zinc, and die casting zinc), but also enhances the corrosion resistant property thereof. The drawbacks of the coriventional coloring technique of the zinc-plating and the inadequacy of the plated layer can be mitigated.
This makes the zinc-plated steel article more acceptable to the consumers.
Claims (5)
1. A method of adhering a colored electroplating layer on a zinc-electroplated steel article by utilizing an alternating current power supply of a frequency of 10-120 Hz comprising the steps of:
a) providing an electroplating liquid including 150-200 g/l silicates, 15-20 g/l sodium hydroxide and 5-50 g/l metal salts and maintained at a constant temperature of 20°C-30°C and;
b) conducting a two-stage electrolysis to perform an electroplating and to adhere a colored electroplating layer on the steel article by first applying a constant voltage of 60-120 volts; and thereafter applying a constant current density of 20-80 Amp/dm2.
a) providing an electroplating liquid including 150-200 g/l silicates, 15-20 g/l sodium hydroxide and 5-50 g/l metal salts and maintained at a constant temperature of 20°C-30°C and;
b) conducting a two-stage electrolysis to perform an electroplating and to adhere a colored electroplating layer on the steel article by first applying a constant voltage of 60-120 volts; and thereafter applying a constant current density of 20-80 Amp/dm2.
2. The method according to Claim 1, wherein the metal salts contents in the electroplating liquid is selected from the group consisting of 5-20 g/l manganese salts, 5-15 g/l chromium salts, 2-15 g/l iron salts, cobalt salts of 5-50 g/l, and tin salts at 20-40 g/l or mixtures thereof, for resulting in a specific colored layer, which is brown for manganese salts, green for chromium salts, white for iron salts, grey for tin salts and blue for cobalt salts.
3. The method according to Claim 1 or 2, wherein in the first stage of the two stages, the constant voltage of 60-120 volts is applied for a period of 3-7 minutes.
4. The method according to Claim 1 or 2, wherein in the second stage of the two stages, the constant current density of 20-80 Amp/dm2 is applied for a period of 8-12 minutes.
5. The method according to Claim 1 or 2, wherein the colored electroplated layer on the surface of the zinc-electroplated steel article is applied to a thickness of at least 20 µm.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9225323A GB2273108B (en) | 1992-12-03 | 1992-12-03 | The method of adhering colored electroplating layer on a zinc-electroplated steel article |
| HU9203840A HUT66679A (en) | 1992-12-03 | 1992-12-04 | The method of adhering colored electroplating layer on a zinc-electroplated steel article |
| DE4240903A DE4240903C2 (en) | 1992-12-03 | 1992-12-04 | Process for the electrolytic coloring of a steel object coated with zinc |
| AU30125/92A AU3012592A (en) | 1992-12-03 | 1992-12-11 | The method of adhering colored electroplating layer on a zinc-electroplated steel article |
| NL9202145A NL9202145A (en) | 1992-12-03 | 1992-12-11 | A method of applying a colored electroplating layer to a zinc electroplated steel object. |
| SE9203759A SE9203759L (en) | 1992-12-03 | 1992-12-14 | Method of applying a colored electrical metallization layer to a zinc electrical metallized steel article |
| US07/990,764 US5275703A (en) | 1992-12-03 | 1992-12-15 | Method of adhering a colored electroplating layer on a zinc-electroplated steel article |
| CA002085430A CA2085430C (en) | 1992-12-03 | 1992-12-15 | Method of adhering colored electroplating layer on a zinc-electroplated steel article |
| ES09202537A ES2055660B1 (en) | 1992-12-03 | 1992-12-15 | METHOD FOR THE ADHESION OF A COLORED ELECTROLYTIC LAYER ON ELECTROLYTICALLY ZINC PLATED STEEL ARTICLES. |
| JP5025956A JPH07122156B2 (en) | 1992-12-03 | 1993-01-22 | Method for depositing colored electroplated layer on zinc electroplated steel products |
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9225323A GB2273108B (en) | 1992-12-03 | 1992-12-03 | The method of adhering colored electroplating layer on a zinc-electroplated steel article |
| HU9203840A HUT66679A (en) | 1992-12-03 | 1992-12-04 | The method of adhering colored electroplating layer on a zinc-electroplated steel article |
| DE4240903A DE4240903C2 (en) | 1992-12-03 | 1992-12-04 | Process for the electrolytic coloring of a steel object coated with zinc |
| AU30125/92A AU3012592A (en) | 1992-12-03 | 1992-12-11 | The method of adhering colored electroplating layer on a zinc-electroplated steel article |
| NL9202145A NL9202145A (en) | 1992-12-03 | 1992-12-11 | A method of applying a colored electroplating layer to a zinc electroplated steel object. |
| SE9203759A SE9203759L (en) | 1992-12-03 | 1992-12-14 | Method of applying a colored electrical metallization layer to a zinc electrical metallized steel article |
| US07/990,764 US5275703A (en) | 1992-12-03 | 1992-12-15 | Method of adhering a colored electroplating layer on a zinc-electroplated steel article |
| CA002085430A CA2085430C (en) | 1992-12-03 | 1992-12-15 | Method of adhering colored electroplating layer on a zinc-electroplated steel article |
| ES09202537A ES2055660B1 (en) | 1992-12-03 | 1992-12-15 | METHOD FOR THE ADHESION OF A COLORED ELECTROLYTIC LAYER ON ELECTROLYTICALLY ZINC PLATED STEEL ARTICLES. |
| JP5025956A JPH07122156B2 (en) | 1992-12-03 | 1993-01-22 | Method for depositing colored electroplated layer on zinc electroplated steel products |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2085430A1 CA2085430A1 (en) | 1994-06-16 |
| CA2085430C true CA2085430C (en) | 1999-09-28 |
Family
ID=27578958
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002085430A Expired - Fee Related CA2085430C (en) | 1992-12-03 | 1992-12-15 | Method of adhering colored electroplating layer on a zinc-electroplated steel article |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5275703A (en) |
| JP (1) | JPH07122156B2 (en) |
| AU (1) | AU3012592A (en) |
| CA (1) | CA2085430C (en) |
| DE (1) | DE4240903C2 (en) |
| ES (1) | ES2055660B1 (en) |
| GB (1) | GB2273108B (en) |
| HU (1) | HUT66679A (en) |
| NL (1) | NL9202145A (en) |
| SE (1) | SE9203759L (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6124538A (en) * | 1996-06-21 | 2000-09-26 | Landell; Jonathon A. | Musical instrument |
| US6592738B2 (en) * | 1997-01-31 | 2003-07-15 | Elisha Holding Llc | Electrolytic process for treating a conductive surface and products formed thereby |
| US6599643B2 (en) | 1997-01-31 | 2003-07-29 | Elisha Holding Llc | Energy enhanced process for treating a conductive surface and products formed thereby |
| US6322687B1 (en) | 1997-01-31 | 2001-11-27 | Elisha Technologies Co Llc | Electrolytic process for forming a mineral |
| AU2003209010A1 (en) * | 2002-02-05 | 2003-09-02 | Elisha Holding Llc | Method for treating metallic surfaces and products formed thereby |
| US20040188262A1 (en) * | 2002-02-05 | 2004-09-30 | Heimann Robert L. | Method for treating metallic surfaces and products formed thereby |
| CN102677128B (en) * | 2011-03-07 | 2015-02-18 | 弘运钢铁工业股份有限公司 | Electrogalvanized steel sheet having zinc oxide film formed by electrolysis and preparation method thereof |
| CN105220187A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of pulse plating method plating bismuth electroplate liquid and bismuth thin film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL128525C (en) * | 1964-05-14 | |||
| JPS5591993A (en) * | 1978-12-28 | 1980-07-11 | Toyo Kohan Co Ltd | Production of colored galvanized product |
| JPS58151490A (en) * | 1982-03-01 | 1983-09-08 | Toyo Kohan Co Ltd | Production of colored metallic plate electroplated with zinc |
| JPS58151491A (en) * | 1982-03-01 | 1983-09-08 | Toyo Kohan Co Ltd | Production of colored zinc electroplated metallic plate |
| AU574609B2 (en) * | 1986-05-12 | 1988-07-07 | Nippon Steel Corporation | Chromate treatment of metal coated steel sheet |
| US4861441A (en) * | 1986-08-18 | 1989-08-29 | Nippon Steel Corporation | Method of making a black surface treated steel sheet |
| US4968391A (en) * | 1988-01-29 | 1990-11-06 | Nippon Steel Corporation | Process for the preparation of a black surface-treated steel sheet |
| EP0352399B1 (en) * | 1988-07-28 | 1992-05-13 | VOEST-ALPINE Stahl Linz GmbH | Process for the chemical after-treatment of steel-strip surfaces |
| ES2023557A6 (en) * | 1990-06-22 | 1992-01-16 | Pie Nicolas Jose | New hospital bedpan |
-
1992
- 1992-12-03 GB GB9225323A patent/GB2273108B/en not_active Expired - Fee Related
- 1992-12-04 DE DE4240903A patent/DE4240903C2/en not_active Expired - Fee Related
- 1992-12-04 HU HU9203840A patent/HUT66679A/en unknown
- 1992-12-11 AU AU30125/92A patent/AU3012592A/en not_active Abandoned
- 1992-12-11 NL NL9202145A patent/NL9202145A/en not_active Application Discontinuation
- 1992-12-14 SE SE9203759A patent/SE9203759L/en not_active Application Discontinuation
- 1992-12-15 US US07/990,764 patent/US5275703A/en not_active Expired - Fee Related
- 1992-12-15 CA CA002085430A patent/CA2085430C/en not_active Expired - Fee Related
- 1992-12-15 ES ES09202537A patent/ES2055660B1/en not_active Expired - Lifetime
-
1993
- 1993-01-22 JP JP5025956A patent/JPH07122156B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2085430A1 (en) | 1994-06-16 |
| GB2273108A (en) | 1994-06-08 |
| DE4240903C2 (en) | 1996-01-25 |
| HUT66679A (en) | 1994-12-28 |
| ES2055660B1 (en) | 1995-03-01 |
| GB2273108B (en) | 1997-06-04 |
| SE9203759L (en) | 1994-06-15 |
| SE9203759D0 (en) | 1992-12-14 |
| ES2055660A1 (en) | 1994-08-16 |
| US5275703A (en) | 1994-01-04 |
| GB9225323D0 (en) | 1993-01-27 |
| DE4240903A1 (en) | 1994-06-09 |
| JPH07122156B2 (en) | 1995-12-25 |
| AU3012592A (en) | 1994-06-23 |
| NL9202145A (en) | 1994-07-01 |
| JPH06240491A (en) | 1994-08-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |