CN100585021C - Plaque copper electroplating process - Google Patents

Abstract

The present invention relates to a kind of plaque copper electroplating process, belong to metal material surface Finish ﹠ Workmanship product making field.The present invention utilizes traditional pyrophosphate method of electro-plating to hang down tin gunmetal technology, and adds zinc in electroplate liquid, and silver, nickel, phosphorus doping element carry out the copper tin-based alloy and electroplates.The amount of mixing up zinc, silver, nickel, phosphoric is 0.5-1g/L, and the mode of mixing up element is for wherein a kind of, or several use simultaneously.After obtaining copper tin-based alloy coating, under 360-400 ℃ of temperature, sample carried out 30-90 minute thermal treatment, allow the copper tin-based alloy carry out the generation of different crystal and grow up, make and contain macroscopic heterogeneity in the coating, present the glass mark or the crystallized of different color, i.e. spot copper upper layer.The present invention has advantages such as production cost is low, easy and simple to handle, product-forming is attractive in appearance.

Description

Plaque copper electroplating process

Technical field:

The present invention relates to a kind of plaque copper electroplating process, belong to metal material surface Finish ﹠ Workmanship product making field.

Background technology:

The main component of spot copper is a copper, and wherein also assorted other metals such as gold and silver that metallic tin, zinc and trace are arranged do not merge and the brightness spot that forms completely ^[1]The spot brass work is solely put extraordinary splendor, and dark blue, Zijin, crimson isochrome are arranged, and the most dazzling is golden yellow, manually also can refine afterwards, and it is made daily necessities or artwork, after the surface finish on copper-colored bottom the spot coloured silk sparking, more beautiful things than one can take in.The rib spot of all kinds of spot copper is natural formation, and none is identical for the speckle of all implements, and it is beautiful as bright cherry-red both can to have made it surface color after the polishing, and the verdigris point point of the history of can dieing again shows the years vicissitudes.It is the distinctive folk tradition artwork in Yunnan.

The spot brass work is exquisite artwork, has very high using value in decoration, and its singularity is the moulding and the surperficial glass mark of spot brass work.Spot brass work branch " is given birth to spot ", " ripe spot " two kinds.Give birth to spot and promptly take copper content to reach natural bornite ore 90% or more, manually founding, forge dozen, grind and process.Purple copper is rare to be got, and raw material is difficult for, and product is very few.Ripe spot is then by unique smelting founding, and complicated aftertreatment technology makes and process, though technology is complicated, and the raw material of not worrying, product is than horn of plenty.But no matter present spot brass work is " giving birth to spot ", " ripe spot " goods, all is to adopt casting, makes whole spot brass work be become by the spot copper entirely, and cost is higher.Simultaneously because the limitation of casting technique is difficult to widespread use in surface finishing.

By literature search, do not see the open report identical with the present invention.

Reference:

Reference:

[1] Xu Ruidong. the research and the application of plaque copper skill. outer scientific and technological works contest [J] .2001.10. of the first " challenge cup " Kunming University of Science and Technology research course

[2] " electroplating technology handbook editorial committee compiles. electroplating technology handbook [M]. and Shanghai: Shanghai science tech publishing house, 1989:214,215.199-202.

[3] Zhang Yuncheng, Hu Runan is to honor. electroplate handbook [M]. and Beijing: National Defense Industry Press, 2002:80-82,281-308,490-513

Summary of the invention:

The object of the present invention is to provide a kind of production cost plaque copper electroplating process low, easy and simple to handle.

The present invention utilizes traditional pyrophosphate method of electro-plating to hang down tin gunmetal technology ^[2,3], and in electroplate liquid, adding zinc, silver, nickel, phosphorus doping element carry out the copper tin-based alloy and electroplate.After obtaining copper tin-based alloy coating, under 360-400 ℃ of temperature, sample carried out 30-90 minute thermal treatment, allow the copper tin-based alloy carry out the generation of different crystal and grow up, make and contain macroscopic heterogeneity in the coating, the glass mark or the crystallized that present different color, i.e. spot copper upper layer (Fig. 1).

The concrete operation of present method is as follows:

A. plate pre-treatment: the sample surfaces burr of selecting is carried out machinery or artificial the removing; Soak or hot alkaline solution or washing composition soak wiping and remove surperficial grease with gasoline or acetone; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;

B. electro-coppering tin-based alloy: on the low tin gunmetal technology basis of traditional pyrophosphate method of electro-plating, add zinc, silver, nickel, phosphorus and mix up element and carry out the copper tin-based alloy and electroplate; Plating solution formula and operational condition are: potassium pyrophosphate (K ₄P ₂O ₇) 240～280g/L, Cu ²⁺(adding) 20～25g/L, Sn with the cupric pyrophosphate form ²⁺(adding) 20～25g/L, Sodium phosphate dibasic (Na with the stannous pyrophosphate form ₂HPO ₄) 30～50g/L, two hydration trisodium citrate (Na ₃C ₆H ₅O ₇2H ₂O) 5～10g/L, nitrilotriacetic acid(NTA) (N (CH ₂COOH) ₃) 30～40g/L, mix up element (zinc, silver, nickel, phosphorus) 0.5-1g/L, mix up element for wherein a kind of, or severally use simultaneously; PH value 8.3～8.8; Temperature is a room temperature; Cathode current density 0.5～1.0A/dm ²The negative and positive area is than 1: 2～3; Negative electrode moves 20～25 times/min; Anode is the electrolysis copper coin; Electroplating time 150min;

C. the heat-transmission of brilliant flower is handled: under temperature 360-400 ℃, the heat preservation hot of carrying out 30-90 minute is handled, and is cooled to room temperature subsequently;

D. acid-wash activation: at the H of 10%wt ₂SO ₄Corrosion activation in the solution treats that atropurpureus coating decorporates, and stops activation when exposing peach alloy layer;

E. Passivation Treatment: at potassium bichromate (K ₂Cr ₂O ₇) 5-12g/L, with handling 6-12min in Glacial acetic acid adjust pH 3-4, temperature 30-40 ℃ the passivating solution;

F. at coating surface figure varnishing protective organic film.

E in the above-mentioned operation and f treatment process can not implemented yet.

The present invention has advantages such as production cost is low, easy and simple to handle, product-forming is attractive in appearance.

Description of drawings:

Fig. 1 is for electroplating spot copper upper layer.

Embodiment:

Embodiment 1:

This process implementing sample is the steel disc sample of 45# steel.Technology comprises plating pre-treatment, electro-coppering tin-based alloy, brilliant flower heat-transmission processing, acid-wash activation, Passivation Treatment, and concrete operation is as follows:

A. plate pre-treatment: steel disc sample surfaces burr is manually removed; After the gasoline immersion, in containing the water of washing composition, clean to remove surperficial grease; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;

B. electro-coppering tin-based alloy: plating solution formula and working conditions are: potassium pyrophosphate (K ₄P ₂O ₇) 240g/L, Cu ²⁺(adding) 20g/L, Sn with the cupric pyrophosphate form ²⁺(adding) 20g/L, Sodium phosphate dibasic (Na with the stannous pyrophosphate form ₂HPO ₄) 30g/L, two hydration trisodium citrate (Na ₃C ₆H ₅O ₇2H ₂O) 5g/L, nitrilotriacetic acid(NTA) (N (CH ₂COOH) ₃) 30g/L, zinc+silver (adding with the pyrophosphate salt form) 0.5g/L; PH value 8.3; Temperature is a room temperature; Cathode current density 0.5A/dm ²The negative and positive area was than 1: 2; Negative electrode moves 20 times/min; Anode is the electrolysis copper coin; Electroplating time 150min;

C. the heat-transmission of brilliant flower is handled: under 360 ℃ of temperature, the heat preservation hot of carrying out 30 minutes is handled, subsequently naturally cooling in air;

D. acid-wash activation: at the H of 10%wt ₂SO ₄Corrosion activation in the solution treats that atropurpureus coating decorporates, and stops activation when exposing peach alloy layer;

E. Passivation Treatment: at potassium bichromate (K ₂Cr ₂O ₇) handle 6min among the 5g/L, passivating solution with 30 ℃ of Glacial acetic acid adjust pHs 3, temperature;

Embodiment 2:

This process implementing sample fine copper sheet.Technology comprises plating pre-treatment, electro-coppering tin-based alloy, brilliant flower heat-transmission processing, acid-wash activation, Passivation Treatment and coating closing step, and concrete operation is as follows:

A. plate pre-treatment: copper sheet sample surfaces burr is manually removed; In containing the water of washing composition, clean to remove surperficial grease; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;

B. electro-coppering tin-based alloy: plating solution formula and working conditions are: potassium pyrophosphate (K ₄P ₂O ₇) 260g/L, Cu ²⁺(adding) 22g/L, Sn with the cupric pyrophosphate form ²⁺(adding) 22g/L, Sodium phosphate dibasic (Na with the stannous pyrophosphate form ₂HPO ₄) 40g/L, two hydration trisodium citrate (Na ₃C ₆H ₅O ₇2H ₂O) 8g/L, nitrilotriacetic acid(NTA) (N (CH ₂COOH) ₃) 35g/L, zinc+nickel+phosphorus (zinc and nickel add with the pyrophosphate salt form, and phosphorus adds with the simple substance form of powder) 0.8g/L; PH value 8.6; Temperature is a room temperature; Cathode current density 0.7A/dm ²The negative and positive area was than 1: 2.5; Negative electrode moves 22 times/min; Anode is the electrolysis copper coin; Electroplating time 150min;

C. the heat-transmission of brilliant flower is handled: under 380 ℃ of temperature, the heat preservation hot of carrying out 60 minutes is handled, and carries out water cooling subsequently in water;

D. acid-wash activation: at the H of 10%wt ₂SO ₄Corrosion activation in the solution treats that atropurpureus coating decorporates, and stops activation when exposing peach alloy layer;

E. Passivation Treatment: at potassium bichromate (K ₂Cr ₂O ₇) handle 8min among the 9g/L, passivating solution with 35 ℃ of Glacial acetic acid adjust pHs 3.5, temperature;

F. be coated with the varnishing protective organic film at coating surface.

Embodiment 3:

This process implementing sample nickel plating steel disc.Technology comprises plating pre-treatment, electro-coppering tin-based alloy, brilliant flower heat-transmission processing, acid-wash activation, coating closing step, and concrete operation is as follows:

A. plate pre-treatment: soak with acetone and remove surperficial grease; Use the hydrochloric acid soln of 10%wt to soak activation nickel plating surface;

B. electro-coppering tin-based alloy: plating solution formula and working conditions are: potassium pyrophosphate (K ₄P ₂O ₇) 280g/L, Cu ²⁺(adding) 25g/L, Sn with the cupric pyrophosphate form ²⁺(adding) 25g/L, Sodium phosphate dibasic (Na with the stannous pyrophosphate form ₂HPO ₄) 50g/L, two hydration trisodium citrate (Na ₃C ₆H ₅O ₇2H ₂O) 10g/L, nitrilotriacetic acid(NTA) (N (CH ₂COOH) ₃) 40g/L, zinc+silver+nickel+phosphorus (zinc, silver and nickel add with the pyrophosphate salt form, and phosphorus adds with the simple substance form of powder) 1g/L, pH value 8.8; Temperature is room temperature, cathode current density 1.0A/dm ², the negative and positive area than 1: 3, negative electrode move 25 times/min, anode is electrolysis copper coin, electroplating time 150min;

C. the heat-transmission of brilliant flower is handled: under 400 ℃ of temperature, the heat preservation hot of carrying out 90 minutes is handled, and uses the cold wind blast-cold subsequently.

This example is not for carrying out e and f treatment process

Claims (1)

1, a kind of plaque copper electroplating process is characterized in that the concrete operation of this technology is as follows:

A. plate pre-treatment: the metal sample surface burr of selecting is removed with the mechanical removal method; Soak or hot alkaline solution or washing composition soak wiping and remove surperficial grease with gasoline or acetone; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;

B. electro-coppering tin-based alloy: the zinc that mixes in traditional low tin gunmetal technology of pyrophosphate salt plating, silver, nickel, phosphoric carry out the copper tin-based alloy and electroplate; Low tin gunmetal solution formula of pyrophosphate salt plating and working conditions are: potassium pyrophosphate 240～280g/L, Cu ²⁺20～25g/L, Sn ²⁺20～25g/L, Sodium phosphate dibasic 30～50g/L, two hydration trisodium citrates, 5～10g/L, nitrilotriacetic acid(NTA) 30～40g/L mixes up zinc, silver, nickel, the phosphoric of 0.5-1g/L, and the mode of mixing up element is for wherein a kind of, or severally uses Cu simultaneously ²⁺Add Sn with the cupric pyrophosphate form ²⁺Add with the stannous pyrophosphate form, zinc, silver and nickel add with the pyrophosphate salt form, and phosphorus adds with the simple substance form of powder; PH value 8.3～8.8; Temperature is room temperature, cathode current density 0.5～1.0A/dm ², the negative and positive area than 1: 2～3, negative electrode moves 20～25 times/min, anode is electrolysis copper coin, electroplating time 150min;

C. the heat-transmission of brilliant flower is handled: under temperature 360-400 ℃, the heat preservation hot of carrying out 30-90 minute is handled, and carries out quick water-cooled, air-cooled or naturally cooling subsequently;

D. acid-wash activation: at the H of 10%wt ₂SO ₄Corrosion activation in the solution treats that atropurpureus coating decorporates, and stops activation when exposing peach alloy layer;

E. Passivation Treatment or non-Passivation Treatment:. Passivation Treatment is at potassium bichromate (K ₂Cr ₂O ₇) 5-12g/L, with handling 6-12min in Glacial acetic acid adjust pH 3-4, temperature 30-40 ℃ the passivating solution;

F. be coated with varnishing protective organic film or varnishing protective organic film not at coating surface.