CN103352216A - Copper or copper alloy surface coloring treatment method - Google Patents
Copper or copper alloy surface coloring treatment method Download PDFInfo
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- CN103352216A CN103352216A CN2013102853127A CN201310285312A CN103352216A CN 103352216 A CN103352216 A CN 103352216A CN 2013102853127 A CN2013102853127 A CN 2013102853127A CN 201310285312 A CN201310285312 A CN 201310285312A CN 103352216 A CN103352216 A CN 103352216A
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- alloy surface
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- coloring
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Abstract
The invention relates to a copper or copper alloy surface coloring treatment method, and belongs to the technical field of metal surface coloring treatment. The copper or copper alloy surface coloring treatment method comprises the following steps: grinding, deoiling and polishing the surface of copper or copper alloy to be colored; activating the surface of the copper or copper alloy to be colored to remove an oxide film from the surface of the copper or copper alloy; soaking the treated copper or copper alloy into coloring liquid, and coloring by controlling the temperature at 25-90 DEG C; cleaning, performing antioxidation treatment and painting the colored copper or copper alloy to obtain the copper or copper alloy with the colored surface. The copper or copper alloy surface coloring treatment method has the advantages of simple process, easy operation, good coloring density, high coloring stability and attractive appearance.
Description
Technical field
The present invention relates to copper or copper alloy surface and process, in particular, relate to the coloring treatment process of a kind of copper or copper alloy surface, belong to the painted processing technology field in metallic surface.
Background technology
Along with socioeconomic development, the purposes of copper decorations goods not only has been confined to door and window, but has extensively penetrated into building decoration etc.And copper or copper alloy have preferably corrosion resistance nature, and be very stable in the air of drying, can also carry out many surface treatments to its surface, can present different effects.Therefore, the copper decorations become the favorite in the fields such as top-grade building.According to different needs, copper or copper alloy surface can be processed into distinct colors, such as imitation copper, ancient green, bronze-colored or green etc.Such as Chinese patent application (publication number: CN102991264A) disclose a kind of making method of copper modelled after an antique, comprise oil removing, grinding and buffing processing are carried out in the copper surface, clean with clear water again, again to the painted processing of turning black of copper spare, be about to copper spare surface and the rear metallic compound rete that generates black of chemical stain liquid medicine reaction, etch processes is carried out on copper spare surface, obtain copper-colored copper spare after drying, the japanning.Such as Chinese patent application (publication number: CN102031509A) disclose the chemical pigmenting method of a kind of copper and alloy thereof, comprise copper alloy surface polishing, polishing and activation treatment, copper alloy surface being carried out the microetch processing makes copper alloy surface form the faint yellow zinc rete of one deck again, generate again the metallic compound rete of selenium with the chemical pigmenting liquid reaction, obtain the bronze copper alloy.Aforesaid method all has preferably coloring effect, but above-mentioned technological process all needs through etching processing, is equivalent to through twice painted processing, has increased the loaded down with trivial details property of technique, and has all needed usually to reach painted effect by selenium unit.
Summary of the invention
The present invention is directed to the defective that exists in the above prior art, the coloring treatment process of a kind of copper or copper alloy surface is provided, have advantages of that simple, the painted compactness of technique is good and stable high.
The objective of the invention is to be achieved by the following technical programs, the coloring treatment process of a kind of copper or copper alloy surface, the method may further comprise the steps:
A, with copper to be colored or copper alloy surface polish, oil removing and polished finish;
B, copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface;
C, treated copper or copper alloy are immersed in the coloring liquid, and the control temperature is carried out painted processing under 25 ℃～90 ℃ condition;
D, will clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, namely obtain copper or the copper alloy of surface colour.
In the coloring treatment process of above-mentioned copper or copper alloy surface, the copper of described surface colour or the color of copper alloy are ancient green, green, bronze-colored or burgundy.
In the coloring treatment process of above-mentioned copper or copper alloy surface, polishing described in the steps A can be adopted polishing machine, with the burr of copper or copper alloy surface, the removals such as stain, oxide compound of becoming rusty; Also can adopt sandpaper to polish, make the metallic surface light smooth, can improve the coloring effect of finished product.Described oil removing also can adopt weakly alkaline solution to carry out oil removing as adopting the wipe oils such as gasoline, alcohol, ketones solvent, such as yellow soda ash, and sodium phosphate etc.Adopt weakly alkaline solution can prevent oxidation on metal surface.Can also adopt the tensio-active agent oil removing, described tensio-active agent such as tetramethyl-ammonium acetate, tetrapropyl ammonium acetate etc.Described polished finish adopts conventional polished finish get final product, is that the nitration mixture led polishes etc. as adopting sulfuric acid, hydrochloric acid.
In the coloring treatment process of above-mentioned copper or copper alloy surface, surface activation process described in the step B, purpose be for remove the surface oxide film, make and expose copper or copper alloy matrix, can guarantee between pigmented layer and copper or the copper alloy in conjunction with stability.If copper or copper alloy surface only have slight oxidation, preferably copper or copper alloy are soaked in the dilute sulphuric acid of 5wt% and got final product in 10～15 seconds.If copper or copper alloy surface oxidation are serious, can be with the rare H of metal at 5wt%～8wt%
2SO
4, H
3PO
4And HNO
3Mixed acid solution in soak and got final product in 10～15 seconds.
In the coloring treatment process of above-mentioned copper or copper alloy surface, as preferably, the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
(NH
4)
2Ni(SO
4)
2：0.1～0.3mol/L；
Na
2S
2O
3：0.2～0.4mol/L；
CH
3COOH:25wt%～35wt%; And make after the described painted processing and form ancient green at copper or copper alloy surface.By adding Ni salt, can improve the speed of film forming and the compactness of raising pigmented layer; Can make the pH value of coloring liquid about 4 by adding acetic acid, the compactness of pigmented layer is strengthened, and have synergistic function between the Ni salt that adds, can also increase stability and the erosion resistance of bright property and raising pigmented layer, guarantee the aesthetic property on surface.Described Na
2S
2O
3Ionization S out
2O
3 2-And S
2-With metal ion Ni
2+Form the black sulfide particle and be attached to copper or copper alloy surface, become background color, along with the increase of painted time, color is green to Gu again from black to the bluish voilet.Therefore, as preferably, the temperature of described painted processing is 70 ℃～90 ℃, and the time of described painted processing is 3～10 minutes.As further preferred, the aqueous solution that described coloring liquid mainly consists of the following composition:
In the coloring treatment process of above-mentioned copper or copper alloy surface, as another embodiment, the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
CuSO
4·5H
2O：0.1～0.2mol/L；
MgCO
3：0.2～0.4mol/L；
NH
4Cl：0.1～0.2mol/L；
NH
4NO
3：0.1～0.2mol/L；
ZnCl
2：0.1～0.2mol/L；
CH
3COOH：15wt%～25wt%；
The pH value of described coloring liquid is 3.5～4.5; And make at copper or copper alloy surface after the described painted processing and form green.CuSO in the described coloring liquid
45H
2O is main painted salt, if concentration is too low, then color is not good; If excessive concentration, membranous layer binding force is poor, control CuSO
45H
2The concentration of O is key parameter.Described NH
4The adding of Cl can make CuO generate CuCl
2, aobvious green, and make rete become brighter; Described MgCO
3Can make the film even compact, also increase smooth finish; ZnCl
2Amount affect the depth of color and luster color, the too high levels of chlorion can cause rete partially green, color is undesirable, add in right amount.Nitrate has oxidisability, and the activity of metallic surface is increased, and the film of generation is firm wear-resisting; The pH value will strictly be controlled, and the pH value is too low, and loose phenomenon can appear in rete; The pH value is too high, and solution has precipitation and occurs.As preferably, the temperature of described painted processing is 35 ℃～45 ℃, and the time of described painted processing is 15～30 minutes.As further preferred, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.12mol/L；
MgCO
3：0.3mol/L；
NH
4Cl：0.1mol/L；
NH
4NO
3：0.1mol/L；
ZnCl
2：0.1mol/L；
CH
3COOH：20wt%；
The pH value of described coloring liquid is 4.0.
In the coloring treatment process of above-mentioned copper or copper alloy surface, as another embodiment, the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
Cu(Ac)
2：0.16～0.18mol/L；
NH
4(Ac)：0.3～0.6mol/L；
KNaC
4H
4O
6·4H
2O：0.2～0.4mol/L；
Na
2S
2O
3：0.2～0.4mol/L；
H
2O
2：2wt%～4wt%；
Making after the described painted processing forms bronze-colored at copper or copper alloy surface.Described Sulfothiorine can generate sulfurous gas and sulphur simple substance, and sulphur and copper can generate the cupric sulfide background color of brownish black.NH
4 +The copper base there is responsive corrosive nature, can forms corresponding alkali type nantokite, aobvious bronze-colored.But suitably the consumption of control ammonium salt prevents the unstable of rete, and is stable for making rete, by adding an amount of oxygenant H
2O
2, with NH
4 +The product synergistic function, the sticking power of raising rete, chromatograph is fine and close, and retention of color is good, and is corrosion-resistant, and bronze-colored effect is more desirable.As preferably, the temperature of described painted processing is 25 ℃～30 ℃, and the time of described painted processing is 2～5 minutes.As further preferred, the aqueous solution that described coloring liquid mainly consists of the following composition:
Cu(Ac)
2：0.165mol/L；
NH
4(Ac)：0.5mol/L；
KNaC
4H
4O
6·4H
2O：0.3mol/L；
Na
2S
2O
3：0.3mol/L；
H
2O
2：3wt%。
In the coloring treatment process of above-mentioned copper or copper alloy surface, as another embodiment, the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
CuSO
4·5H
2O：0.1～0.3mol/L；
KMnO
4：0.04～0.06mol/L；
(NH
4)
2Ni(SO
4)
2：0.1～0.3mol/L；
Make after the described painted processing at copper or copper alloy surface and form burgundy.KMnO in the described coloring liquid
4Adding, copper can be oxidized to cupric oxide, along with thickening of zone of oxidation, color is also deepened gradually, makes the coloring effect obfuscation, antique effect is good.But KMnO
4Can not be excessive, otherwise can produce mauve interference color.By adding (NH
4)
2Ni (SO
4)
2Can make retention of color good, chromatograph is fine and close, and anti-oxidant, corrosion-resistant, the surface is more attractive in appearance.As preferably, described painted number of times is twice, and secondary painted time is 1 minute.Each goes on foot coloring process, and temperature as requested, the time of immersion carry out, and the time can not be oversize, otherwise color is variable.Therefore, as further preferred, the temperature of described painted processing is 75 ℃～85 ℃, and the time of described painted processing is 10～15 minutes.As further preferred, the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
CuSO
4·5H
2O：0.2mol/L；
KMnO
4：0.05mol/L；
(NH
4)
2Ni(SO
4)
2：0.1mol/L。
In the coloring treatment process of above-mentioned copper or copper alloy surface, as preferably, antioxidation treatment described in the step D was soaked in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride 2～5 minutes for copper or the copper alloy with painted processing.Can improve the anti-oxidant and anti-corrosion capability of copper or copper alloy.
In the coloring treatment process of above-mentioned copper or copper alloy surface, as preferably, alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish etc. are adopted in japanning described in the step D, these japannings can and coloring film of the present invention between form preferably sticking power, and at room temperature quick solidifying can also play oxidation resistant effect through the japanning processing.
In sum, the present invention has the following advantages:
The coloring treatment process of copper of the present invention or copper alloy surface has advantages of that technological process is simple, easy handling, has advantages of that painted compactness is good, retention of color is high and attractive in appearance.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited to these embodiment.
Embodiment 1
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and control temperature and under 70 ℃～90 ℃ condition, carry out painted processing 3～10 minutes, preferably under 80 ℃ condition, carry out painted processing 5 minutes; Make after the painted processing at copper or copper alloy surface and form ancient green, the aqueous solution that described coloring liquid mainly consists of the following composition:
(NH
4)
2Ni(SO
4)
2：0.2mol/L；
Na
2S
2O
3：0.3mol/L；
CH
3COOH：30wt%；
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 2
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 3 minutes under 90 ℃ condition; Make after the painted processing at copper or copper alloy surface and form ancient green, the aqueous solution that described coloring liquid mainly consists of the following composition:
(NH
4)
2Ni(SO
4)
2：0.1mol/L；
Na
2S
2O
3：0.4mol/L；
CH
3COOH：25wt%；
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 3
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 10 minutes under 70 ℃ condition; Make after the painted processing at copper or copper alloy surface and form ancient green, the aqueous solution that described coloring liquid mainly consists of the following composition:
(NH
4)
2Ni(SO
4)
2：0.3mol/L；
Na
2S
2O
3：0.2mol/L；
CH
3COOH：35wt%；
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 4
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 30 minutes under 35 ℃ condition; Make at copper or copper alloy surface after the painted processing and form green, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.12mol/L；
MgCO
3：0.3mol/L；
NH
4Cl：0.1mol/L；
NH
4NO
3：0.1mol/L；
ZnCl
2：0.1mol/L；
CH
3COOH：20wt%；
The pH value of described coloring liquid is 4.0;
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 5
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 15 minutes under 45 ℃ condition; Make at copper or copper alloy surface after the painted processing and form green, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.1mol/L；
MgCO
3：0.4mol/L；
NH
4Cl：0.1mol/L；
NH
4NO
3：0.2mol/L；
ZnCl
2：0.15mol/L；
CH
3COOH：15wt%；
The pH value of described coloring liquid is 3.5;
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 6
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 20 minutes under 40 ℃ condition; Make at copper or copper alloy surface after the painted processing and form green, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.2mol/L；
MgCO
3：0.4mol/L；
NH
4Cl：0.2mol/L；
NH
4NO
3：0.1mol/L；
ZnCl
2：0.2mol/L；
CH
3COOH：25wt%；
The pH value of described coloring liquid is 4.5;
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 7
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 5 minutes under 25 ℃ condition; Make after the painted processing form at copper or copper alloy surface bronze-colored, the aqueous solution that described coloring liquid mainly consists of the following composition:
Cu(Ac)
2：0.165mol/L；
NH
4(Ac)：0.5mol/L；
KNaC
4H
4O
6·4H
2O：0.3mol/L；
Na
2S
2O
3：0.3mol/L；
H
2O
2：3wt%；
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 8
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 2 minutes under 30 ℃ condition; Make after the painted processing form at copper or copper alloy surface bronze-colored, the aqueous solution that described coloring liquid mainly consists of the following composition:
Cu(Ac)
2：0.16mol/L；
NH
4(Ac)：0.6mol/L；
KNaC
4H
4O
6·4H
2O：0.2mol/L；
Na
2S
2O
3：0.2mol/L；
H
2O
2：4wt%；
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 9
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 3 minutes under 28 ℃ condition; Make after the painted processing form at copper or copper alloy surface bronze-colored, the aqueous solution that described coloring liquid mainly consists of the following composition:
Cu(Ac)
2：0.18mol/L；
NH
4(Ac)：0.3mol/L；
KNaC
4H
4O
6·4H
2O：0.4mol/L；
Na
2S
2O
3：0.4mol/L；
H
2O
2：2wt%；
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 10
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 15 minutes under 75 ℃ condition; Make after the painted processing at copper or copper alloy surface and form burgundy, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.2mol/L；
KMnO
4：0.05mol/L；
(NH
4)
2Ni (SO
4)
2: 0.1mol/L; Preferably carry out twice painted, the painted time of the described second time is 1 minute;
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 11
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 10 minutes under 85 ℃ condition; Make after the painted processing at copper or copper alloy surface and form burgundy, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.1mol/L；
KMnO
4：0.06mol/L；
(NH
4)
2Ni (SO
4)
2: 0.3mol/L; Preferably carry out twice painted, the painted time of the described second time is 1 minute;
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour, alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Embodiment 12
Adopt polishing machine to polish copper to be colored or copper alloy surface, remove burr, rust stain and the oxide compound on surface, then adopt sodium carbonate solution to remove the greasy dirt on surface, carry out polished finish again, it is that main nitration mixture carries out polished finish that sulfuric acid, hydrochloric acid are preferably adopted in described polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface, and described activation treatment is about in the dilution heat of sulfuric acid that copper or copper alloy be immersed in 5wt% 10～15 seconds;
To be immersed in the coloring liquid through the copper after the activation treatment or copper alloy, and the control temperature is carried out painted processing 12 minutes under 80 ℃ condition; Make after the painted processing at copper or copper alloy surface and form burgundy, the aqueous solution that described coloring liquid mainly consists of the following composition:
CuSO
4·5H
2O：0.3mol/L；
KMnO
4：0.04mol/L；
(NH
4)
2Ni (SO
4)
2: 0.1mol/L; Preferably carry out twice painted, the painted time of the described second time is 1 minute;
To clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, described antioxidation treatment is preferably soaked the copper after the painted processing or copper alloy 2～5 minutes in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour.Alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish are preferably adopted in described japanning.
Copper or the copper alloy of choosing at random the surface colour that obtains in above-described embodiment detect, and before not carrying out antioxidation treatment, microscopically is observed, cover the medal polish face of coloring liquid, chromatograph is slightly inhomogeneous, and the surface also has some points not covered by chromatograph, these places, very easily oxidation stain.So the present invention will be dipped in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride through painted copper or copper alloy, time 2-3min can improve anti-oxidant and anti-corrosion capability.After the passivation fixation, film surface has sealing function, observes by microscopically, and the polished surface chromatograph is even, rete color stable, nondiscoloration.Carboxylic organic compound in the coloring liquid can make the compactness of film strengthen, and increase bright property, and rete is relatively better.The compactness of check rete can be carried out erosion resistance by brushing weak acid, weak base (or being immersed in weak acid, the weak caustic solution) and be detected after 2 weeks.Through check, rete compactness is good, and weak acid, weak base do not produce infection to its surface, illustrates that the membranous layer stability after painted is fine.
Specific embodiment described in the present invention only is to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or replenish or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made a detailed description and has quoted as proof some specific embodiments, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (10)
1. the coloring treatment process of a copper or copper alloy surface is characterized in that, the method may further comprise the steps:
A, with copper to be colored or copper alloy surface polish, oil removing and polished finish;
B, copper to be colored or copper alloy surface are carried out the oxide film that activation treatment is removed copper or copper alloy surface;
C, treated copper or copper alloy are immersed in the coloring liquid, and the control temperature is carried out painted processing under 25 ℃～90 ℃ condition;
D, will clean through the copper after the painted processing or copper alloy, antioxidation treatment and japanning, namely obtain copper or the copper alloy of surface colour.
2. the coloring treatment process of described copper or copper alloy surface according to claim 1 is characterized in that the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
(NH
4)
2Ni(SO
4)
2：0.1～0.3mol/L；
Na
2S
2O
3：0.2～0.4mol/L；
CH
3COOH：25wt%～35wt%；
And make after the described painted processing and form ancient green at copper or copper alloy surface.
3. the coloring treatment process of described copper or copper alloy surface according to claim 2 is characterized in that, the temperature of described painted processing is 70 ℃～90 ℃, and the time of described painted processing is 3～10 minutes.
4. the coloring treatment process of described copper or copper alloy surface according to claim 1 is characterized in that the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
CuSO
4·5H
2O：0.1～0.2mol/L；
MgCO
3：0.2～0.4mol/L；
NH
4Cl：0.1～0.2mol/L；
NH
4NO
3：0.1～0.2mol/L；
ZnCl
2：0.1～0.2mol/L；
CH
3COOH：15wt%～25wt%；
The pH value of described coloring liquid is 3.5～4.5; And make at copper or copper alloy surface after the described painted processing and form green.
5. the coloring treatment process of described copper or copper alloy surface according to claim 4 is characterized in that, the temperature of described painted processing is 35 ℃～45 ℃, and the time of described painted processing is 15～30 minutes.
6. the coloring treatment process of described copper or copper alloy surface according to claim 1 is characterized in that the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
Cu(Ac)
2：0.16～0.18mol/L；
NH
4(Ac)：0.3～0.6mol/L；
KNaC
4H
4O
6·4H
2O：0.2～0.4mol/L；
Na
2S
2O
3：0.2～0.4mol/L；
H
2O
2：2～4wt%；
Making after the described painted processing forms bronze-colored at copper or copper alloy surface.
7. the coloring treatment process of described copper or copper alloy surface according to claim 6 is characterized in that, the temperature of described painted processing is 25 ℃～30 ℃, and the time of described painted processing is 2～5 minutes.
8. the coloring treatment process of described copper or copper alloy surface according to claim 1 is characterized in that the aqueous solution that the coloring liquid described in the step C mainly consists of the following composition:
CuSO
4·5H
2O：0.1～0.3mol/L；
KMnO
4：0.04～0.06mol/L；
(NH
4)
2Ni(SO
4)
2：0.1～0.3mol/L；
Make after the described painted processing at copper or copper alloy surface and form burgundy.
9. the coloring treatment process of described copper or copper alloy surface according to claim 8 is characterized in that, the temperature of described painted processing is 75 ℃～85 ℃, and the time of described painted processing is 10～15 minutes.
10. the coloring treatment process of described copper or copper alloy surface according to claim 1, it is characterized in that, antioxidation treatment described in the step D was soaked in the passivator that contains Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride 2～5 minutes for copper or the copper alloy with painted processing.
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Cited By (9)
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| CN104088006A (en) * | 2014-06-30 | 2014-10-08 | 铜陵市青铜时代雕塑有限责任公司 | Formula of chemical agent for wearing out archaize bronze vessel |
| CN105887073A (en) * | 2016-04-29 | 2016-08-24 | 南京晨光艺术工程有限公司 | Coloring liquid for chemically coloring black on outer surface of copper product and coloring method thereof |
| CN105925973A (en) * | 2016-04-29 | 2016-09-07 | 南京晨光艺术工程有限公司 | Coloring liquid for chemically coloring copper green on outer surface of copper product and coloring method thereof |
| CN106222645A (en) * | 2016-08-17 | 2016-12-14 | 沈阳理工大学 | The method of brass surfaces chemically blackening |
| CN111674195A (en) * | 2020-06-08 | 2020-09-18 | 杭州朱炳仁文化艺术有限公司 | Method for processing mottled colored texture on copper surface |
| CN111748810A (en) * | 2020-06-30 | 2020-10-09 | 广东天承科技有限公司 | Blackening solution and preparation method and use method thereof |
| CN112442686A (en) * | 2020-11-30 | 2021-03-05 | 中国航空工业标准件制造有限责任公司 | Method for coloring copper alloy through constant-temperature oxidation and mauve |
| CN113118377A (en) * | 2021-04-20 | 2021-07-16 | 沈阳工业大学 | Production method of colored copper alloy casting |
| CN115674944A (en) * | 2022-10-25 | 2023-02-03 | 福建捷思金属科技发展有限公司 | Cold coloring process for stone-like black irregular stripes on surface of copper product |
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| CN104088006A (en) * | 2014-06-30 | 2014-10-08 | 铜陵市青铜时代雕塑有限责任公司 | Formula of chemical agent for wearing out archaize bronze vessel |
| CN105887073A (en) * | 2016-04-29 | 2016-08-24 | 南京晨光艺术工程有限公司 | Coloring liquid for chemically coloring black on outer surface of copper product and coloring method thereof |
| CN105925973A (en) * | 2016-04-29 | 2016-09-07 | 南京晨光艺术工程有限公司 | Coloring liquid for chemically coloring copper green on outer surface of copper product and coloring method thereof |
| CN106222645A (en) * | 2016-08-17 | 2016-12-14 | 沈阳理工大学 | The method of brass surfaces chemically blackening |
| CN111674195A (en) * | 2020-06-08 | 2020-09-18 | 杭州朱炳仁文化艺术有限公司 | Method for processing mottled colored texture on copper surface |
| CN111748810A (en) * | 2020-06-30 | 2020-10-09 | 广东天承科技有限公司 | Blackening solution and preparation method and use method thereof |
| CN112442686A (en) * | 2020-11-30 | 2021-03-05 | 中国航空工业标准件制造有限责任公司 | Method for coloring copper alloy through constant-temperature oxidation and mauve |
| CN113118377A (en) * | 2021-04-20 | 2021-07-16 | 沈阳工业大学 | Production method of colored copper alloy casting |
| CN115674944A (en) * | 2022-10-25 | 2023-02-03 | 福建捷思金属科技发展有限公司 | Cold coloring process for stone-like black irregular stripes on surface of copper product |
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