CN103352216B - The coloring treatment process of a kind of copper or copper alloy surface - Google Patents
The coloring treatment process of a kind of copper or copper alloy surface Download PDFInfo
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- CN103352216B CN103352216B CN201310285312.7A CN201310285312A CN103352216B CN 103352216 B CN103352216 B CN 103352216B CN 201310285312 A CN201310285312 A CN 201310285312A CN 103352216 B CN103352216 B CN 103352216B
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Abstract
The present invention relates to the coloring treatment process of a kind of copper or copper alloy surface, belong to metallic surface coloring treatment technical field.The coloring treatment process of a kind of copper or copper alloy surface is provided, the method comprise copper to be colored or copper alloy surface carried out polish, oil removing and polished finish; Copper to be colored or copper alloy surface are carried out the oxide film of activation treatment removing copper or copper alloy surface; Treated copper or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment under the condition of 25 DEG C ~ 90 DEG C; Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, namely obtain copper or the copper alloy of surface colour.Have that technological process is simple, the advantage of easy handling, there is the advantage that painted compactness is good, retention of color is high and attractive in appearance.
Description
Technical field
The present invention relates to copper or copper alloy surface process, in particular, relate to the coloring treatment process of a kind of copper or copper alloy surface, belong to metallic surface coloring treatment technical field.
Background technology
Along with socioeconomic development, the purposes of copper decorations goods, is not only confined to door and window, but extensively penetrates into building decoration etc.And copper or copper alloy have good corrosion resistance nature, very stable in the air of drying, many surface treatments can also be carried out to its surface, different effects can be presented.Therefore, copper decorations become the favorite in the fields such as top-grade building.According to different needs, copper or copper alloy surface can be carried out being processed into distinct colors, as imitation copper, ancient green, bronze-colored or green etc.As Chinese patent application (publication number: CN102991264A) discloses a kind of making method of antique copper, comprise and oil removing, grinding and buffing process are carried out in copper surface, use clean water again, again blackout coloring treatment is carried out to copper piece, the metallic compound rete of black is generated after reacting with chemical stain liquid medicine by copper piece surface, etch processes is carried out to copper piece surface, after drying, japanning, obtains copper-colored copper piece.As Chinese patent application (publication number: CN102031509A) discloses 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 microetch process makes copper alloy surface form the faint yellow zinc rete of one deck again, react the metallic compound rete generating selenium again with chemical pigmenting liquid, obtain bronze copper alloy.Aforesaid method all has good coloring effect, but above-mentioned technological process all needs through etching processing, is equivalent to, through twice coloring treatment, add the triviality of technique, and all needs usually to reach painted effect by selenium unit.
Summary of the invention
The present invention is directed to the defect existed in above prior art, the coloring treatment process of a kind of copper or copper alloy surface is provided, there is the advantage that simple, the painted compactness of technique is good and stability is high.
The object 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 comprises the following steps:
A, copper to be colored or copper alloy surface carried out polish, oil removing and polished finish;
B, copper to be colored or copper alloy surface carried out the oxide film of activation treatment removing copper or copper alloy surface;
C, treated copper or copper alloy to be immersed in coloring liquid, and control temperature carries out coloring treatment under the condition of 25 DEG C ~ 90 DEG C;
D, the copper after coloring treatment or copper alloy carried out clean, 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 steps A can adopt polishing machine, by the burr of copper or copper alloy surface, removal such as rust stain, oxide compound etc.; Also sandpaper can be adopted to polish, make metallic surface light smooth, the coloring effect of finished product can be improved.Described oil removing, as adopted the wipe oils such as gasoline, alcohol, ketones solvent, also can adopt weakly alkaline solution to carry out oil removing, as sodium carbonate, and sodium phosphate etc.Weakly alkaline solution is adopted to prevent oxidation on metal surface.Can also adopt tensio-active agent oil removing, described tensio-active agent is as tetramethyl-ammonium acetate, tetrapropyl ammonium acetate etc.Described polished finish adopts conventional polished finish, if employing sulfuric acid, hydrochloric acid are that main nitration mixture carries out polishing etc.
In the coloring treatment process of above-mentioned copper or copper alloy surface, surface activation process described in step B, object is the oxide film in order to remove surface, makes to expose copper or copper alloy matrix, can ensure between pigmented layer and copper or copper alloy in conjunction with stability.If copper or copper alloy surface only have slight oxidation, preferably copper or copper alloy are soaked 10 ~ 15 seconds in the dilute sulphuric acid of 5wt%.If copper or copper alloy surface oxidation are seriously, can by the rare H of metal at 5wt% ~ 8wt%
2sO
4, H
3pO
4and HNO
3mixed acid solution in soak 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 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 described coloring treatment to form ancient green at copper or copper alloy surface.By adding Ni salt, the speed of film forming can be improved and improve the compactness of pigmented layer; The pH value of coloring liquid can be made about 4 by adding acetic acid, the compactness of pigmented layer can be made to strengthen, and between the Ni salt added, there is synergistic function, stability and the erosion resistance of bright property and raising pigmented layer can also be increased, ensure the aesthetic property on surface.Described Na
2s
2o
3ionization S out
2o
3 2-and S
2-with metal ion Ni
2+form black sulfide particle and be attached to copper or copper alloy surface, become background color, along with the increase of coloration time, color is green to Gu again from black to bluish voilet.Therefore, as preferably, the temperature of described coloring treatment is 70 DEG C ~ 90 DEG C, and the time of described coloring treatment 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 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 after described coloring treatment to form green at copper or copper alloy surface.CuSO in 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
4cl adds, and CuO can be made to generate CuCl
2, aobvious green, and make rete become brighter; Described MgCO
3film even compact can be made, also increase smooth finish; ZnCl
2amount affect the depth of color and luster color, the too high levels of chlorion, rete can be caused partially green, and color is undesirable, add in right amount.Nitrate is oxidizing, and the activity of metallic surface can be made to increase, and the film of generation is firm wear-resisting; PH value will strictly control, and pH value is too low, and rete there will be loose phenomenon; PH value is too high, and solution has precipitation and occurs.As preferably, the temperature of described coloring treatment is 35 DEG C ~ 45 DEG C, and the time of described coloring treatment 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 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%；
Make after described coloring treatment to be formed 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 +there is responsive corrosive nature to copper base, corresponding alkali type nantokite can be formed, aobvious bronze-colored.But suitably must controlling the consumption of ammonium salt, prevent the instability of rete, stablizing, by adding appropriate oxygenant H for making rete
2o
2, with NH
4 +product synergistic function, improves the sticking power of rete, and chromatograph is fine and close, and retention of color is good, corrosion-resistant, and bronze-colored effect is more desirable.As preferably, the temperature of described coloring treatment is 25 DEG C ~ 30 DEG C, and the time of described coloring treatment 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 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 described coloring treatment to form burgundy at copper or copper alloy surface.KMnO in described coloring liquid
4add, copper can be oxidized to cupric oxide, along with thickening of zone of oxidation, color is also deepened gradually, and coloring effect is shaded, and antique effect is good.But KMnO
4can not be excessive, otherwise mauve interference color can be produced.By adding (NH
4)
2ni (SO
4)
2retention of color can be made good, and chromatograph is fine and close, and anti-oxidant, corrosion-resistant, surface is more attractive in appearance.As preferably, described painted number of times is twice, and secondary coloration time is 1 minute.Each walks 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 coloring treatment is 75 DEG C ~ 85 DEG C, and the time of described coloring treatment is 10 ~ 15 minutes.As further preferred, the aqueous solution that the coloring liquid described in 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 step D is the copper of coloring treatment or copper alloy are soaked 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride.Anti-oxidant and the anti-corrosion capability of copper or copper alloy can be improved.
In the coloring treatment process of above-mentioned copper or copper alloy surface, as preferably, japanning described in step D adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish etc., these japannings can and coloring film of the present invention between form good sticking power, and at room temperature quick solidifying, can also play oxidation resistant effect through japanning process.
In sum, the present invention has the following advantages:
The coloring treatment process of copper of the present invention or copper alloy surface, has that technological process is simple, the advantage of easy handling, has the advantage 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 embodiments.
Embodiment 1
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 3 ~ 10 minutes under the condition of 70 DEG C ~ 90 DEG C, preferably under the condition of 80 DEG C, carry out coloring treatment 5 minutes; Make after coloring treatment to form ancient green, the aqueous solution that described coloring liquid mainly consists of the following composition at copper or copper alloy surface:
(NH
4)
2Ni(SO
4)
2：0.2mol/L；
Na
2S
2O
3：0.3mol/L；
CH
3COOH：30wt%；
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 2
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 3 minutes under the condition of 90 DEG C; Make after coloring treatment to form ancient green, the aqueous solution that described coloring liquid mainly consists of the following composition at copper or copper alloy surface:
(NH
4)
2Ni(SO
4)
2：0.1mol/L；
Na
2S
2O
3：0.4mol/L；
CH
3COOH：25wt%；
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 3
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 10 minutes under the condition of 70 DEG C; Make after coloring treatment to form ancient green, the aqueous solution that described coloring liquid mainly consists of the following composition at copper or copper alloy surface:
(NH
4)
2Ni(SO
4)
2：0.3mol/L；
Na
2S
2O
3：0.2mol/L；
CH
3COOH：35wt%；
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 4
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 30 minutes under the condition of 35 DEG C; Make after coloring treatment to form green at copper or copper alloy surface, 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;
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 5
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 15 minutes under the condition of 45 DEG C; Make after coloring treatment to form green at copper or copper alloy surface, 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;
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 6
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 20 minutes under the condition of 40 DEG C; Make after coloring treatment to form green at copper or copper alloy surface, 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;
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 7
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 5 minutes under the condition of 25 DEG C; Make after coloring treatment to be formed bronze-colored at copper or copper alloy surface, 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%；
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 8
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 2 minutes under the condition of 30 DEG C; Make after coloring treatment to be formed bronze-colored at copper or copper alloy surface, 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%；
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 9
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 3 minutes under the condition of 28 DEG C; Make after coloring treatment to be formed bronze-colored at copper or copper alloy surface, 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%；
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 10
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 15 minutes under the condition of 75 DEG C; Make after coloring treatment to form burgundy, the aqueous solution that described coloring liquid mainly consists of the following composition at copper or copper alloy surface:
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, described second time painted time is 1 minute;
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 11
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 10 minutes under the condition of 85 DEG C; Make after coloring treatment to form burgundy, the aqueous solution that described coloring liquid mainly consists of the following composition at copper or copper alloy surface:
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, described second time painted time is 1 minute;
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtain copper or the copper alloy of surface colour, described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Embodiment 12
Polishing machine is adopted to polish copper to be colored or copper alloy surface, the burr on removing surface, stain of becoming rusty and oxide compound, then adopt sodium carbonate solution to remove the greasy dirt on surface, then carry out polished finish, described polished finish preferably adopts sulfuric acid, hydrochloric acid to be that main nitration mixture carries out polished finish;
Above-mentioned pretreated copper to be colored or copper alloy surface are carried out activation treatment removing copper or the oxide film of copper alloy surface, described activation treatment to be immersed in the dilution heat of sulfuric acid of 5wt% 10 ~ 15 seconds by copper or copper alloy;
Copper after activation treatment or copper alloy are immersed in coloring liquid, and control temperature carries out coloring treatment 12 minutes under the condition of 80 DEG C; Make after coloring treatment to form burgundy, the aqueous solution that described coloring liquid mainly consists of the following composition at copper or copper alloy surface:
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, described second time painted time is 1 minute;
Copper after coloring treatment or copper alloy are carried out clean, antioxidation treatment and japanning, described antioxidation treatment is preferably soaks the copper after coloring treatment or copper alloy 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride, namely obtains copper or the copper alloy of surface colour.Described japanning preferably adopts alkyd varnish, phenolic varnish, zapon varnish or acrylic varnish.
Copper or the copper alloy of the surface colour obtained in random selecting above-described embodiment detect, before not carrying out antioxidation treatment, and basis of microscopic observation, cover the medal polish face of coloring liquid, chromatograph is slightly uneven, and surface also has some points not covered by chromatograph, these are local, very easily oxidation stain.So the present invention is by the passivator that is dipped in containing Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride through painted copper or copper alloy, and time 2-3min, can improve anti-oxidant and anti-corrosion capability.After passivation fixation, film surface has sealing function, and by basis of microscopic observation, polished surface chromatograph is even, rete color stable, nondiscoloration.Carboxylic organic compound in coloring liquid, the compactness of film can be made to strengthen, and increase bright property, rete is relatively better.The compactness of inspection rete, can pass through brushing weak acid after 2 weeks, weak base (or being immersed in weak acid, weak caustic solution) carries out erosion resistance detection.Through inspection, rete compactness is good, and weak acid, weak base do not produce infection to its surface, illustrate painted after membranous layer stability fine.
Specific embodiment described in the present invention is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.
Although made a detailed description the present invention and quoted some specific embodiments as proof, to those skilled in the art, only otherwise it is obvious for leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (1)
1. a coloring treatment process for copper or copper alloy surface, is characterized in that, the method comprises the following steps:
A, copper to be colored or copper alloy surface carried out polish, oil removing and polished finish;
B, copper to be colored or copper alloy surface carried out the oxide film of activation treatment removing copper or copper alloy surface;
C, treated copper or copper alloy to be immersed in coloring liquid, and control temperature carries out coloring treatment under the condition of 25 DEG C ~ 90 DEG C;
D, the copper after coloring treatment or copper alloy carried out clean, antioxidation treatment and japanning, namely obtain copper or the copper alloy of surface colour; The aqueous solution that coloring liquid described in 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 it is green to make to form Gu at copper or copper alloy surface after described coloring treatment; The temperature of described coloring treatment is 70 DEG C ~ 90 DEG C, and the time of described coloring treatment is 3 ~ 10 minutes;
Or the aqueous solution that the coloring liquid described in 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 after described coloring treatment to form green at copper or copper alloy surface; The temperature of described coloring treatment is 35 DEG C ~ 45 DEG C, and the time of described coloring treatment is 15 ~ 30 minutes;
Or the aqueous solution that the coloring liquid described in 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％；
Make after described coloring treatment to be formed bronze-colored at copper or copper alloy surface; The temperature of described coloring treatment is 25 DEG C ~ 30 DEG C, and the time of described coloring treatment is 2 ~ 5 minutes;
Or the aqueous solution that the coloring liquid described in 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 described coloring treatment to form burgundy at copper or copper alloy surface; The temperature of described coloring treatment is 75 DEG C ~ 85 DEG C, and the time of described coloring treatment is 10 ~ 15 minutes; Antioxidation treatment described in step D is the copper of coloring treatment or copper alloy are soaked 2 ~ 5 minutes in containing the passivator of Sodium orthomolybdate, potassium bichromate, 124 Triazole and tin protochloride.
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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 |
| 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 |
| 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 |
| CN106222645B (en) * | 2016-08-17 | 2018-11-13 | 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 |
| CN111748810B (en) * | 2020-06-30 | 2021-03-26 | 广东天承科技股份有限公司 | 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 |
| CN113118377B (en) * | 2021-04-20 | 2022-09-20 | 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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| CN101130869A (en) * | 2007-09-20 | 2008-02-27 | 吴江市天地人真空炉业有限公司 | Chemical tinting method for bronze color of copper |
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| CN101130869A (en) * | 2007-09-20 | 2008-02-27 | 吴江市天地人真空炉业有限公司 | Chemical tinting method for bronze color of copper |
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