CN100580151C - Sn crystal flower induced electrodeposition plaque-imitating copper crystal flower surface finishing process - Google Patents

Sn crystal flower induced electrodeposition plaque-imitating copper crystal flower surface finishing process Download PDF

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CN100580151C
CN100580151C CN200710066460A CN200710066460A CN100580151C CN 100580151 C CN100580151 C CN 100580151C CN 200710066460 A CN200710066460 A CN 200710066460A CN 200710066460 A CN200710066460 A CN 200710066460A CN 100580151 C CN100580151 C CN 100580151C
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tin
copper
crystal
flower
crystal flower
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CN101255583A (en
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苏永庆
钟云
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Yunnan Normal University
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Yunnan Normal University
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Abstract

The invention relates to a finishing process, which electro-deposits surface of fake porphyritic crystal copper crystal flower induced by tin crystal flower, and belongs to the field of metal material surface processing and craftwork producing, comprising the following steps of undergoing heat treatment to melt clad layer after electro-depositing tin on metal surface, so as to transform three types of allotropes of tin metal, and undergo re-crystallization for coexistence of the three types of allotropes of tin metal; using H2SO4 solution for erosion and activation, then undergoing re-tinning in a same coating bath, to produce tine crystal flower on surface of clad layer; the surface having tin crystal flower electro-deposits copper or copper alloy in alkalescent pyrophosphate bath, so as to interpenetrate copper or copper alloy with different crystal forms of tin crystal flower, in order to obtain surface layer of copper alloy crystal flower with the same foundation tin crystal flower form but different component or color, that is the surface layer of fake porphyritic crystal copper crystal flower. The invention has the following advantage of low production cost, simple operation and handsome product modeling.

Description

The brilliant flower of the brilliant flower of tin induced electrodeposition plaque-imitating copper surface finishing process
Technical field:
The present invention relates to the brilliant flower of the brilliant flower of a kind of tin induced electrodeposition plaque-imitating copper surface finishing 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.The spot ore deposit is rare to get, 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:
[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
Summary of the invention:
The object of the present invention is to provide the brilliant flower of a kind of production cost tin low, easy and simple to handle brilliant flower induced electrodeposition plaque-imitating copper surface finishing process.
The present invention utilizes the brilliant flower process of traditional eleetrotinplate, behind metallic surface galvanic deposit tin, by certain thermal treatment, under the temperature that is higher than the tin fusing point, with the coating fusion,, adopt the different types of cooling (water-cooled, air-cooled or naturally cooling fast) according to the not requirement of isomorphous floral pattern, (α-Sn also claims gray tin, is the diamond shape isometric system to make three kinds of allotropic substances of simple substance tin; β-Sn also claims tin, is tetragonal system; γ-Sn also claims crisp tin, is rhombic system) transform mutually, make it that recrystallization take place, make three kinds of allotropic substances coexistences of metallic tin, because their color difference to some extent, in crystallisation process, can grow the crystalline substance flower of different crystal shape.H with 10%wt 2SO 4Solution corrosion activation, it is zinc-plated to carry out secondary then in same coating bath, and coating surface promptly can produce the brilliant flower of beautiful tin (Fig. 1).
Surface acid copper or copper alloy in weakly alkaline pyrophosphate plating solution with the brilliant flower of tin, the brilliant flower of the tin coating generation of copper or copper alloy and different crystal forms is oozed mutually, under the inducing action of the brilliant flower of tin, obtain to have identical with the brilliant flower of substrate tin shape, but composition, the different brilliant upper layer of spending of copper alloy of color, promptly imitative spot copper upper layer (Fig. 2).
The concrete operation of present method is as follows:
A. plate pre-treatment: metal sample surface burr 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. eleetrotinplate: electroplate liquid is formed and operational condition is: stannous sulfate (SnSO 4) 20-30g/L; Sulfuric acid (H 2SO 4(ρ=1.84)) 40-60ml/L; Phenol 20-30mg/L; Gelatin 1-2g/L; Cathode current density (D K) 1-2A/dm 2Ratio of cathodic to anodic area is 1: 1-2; Anode purity (Sn%) 〉=99.9,15-30 ℃, electroplating time 25-30min;
C. the heat-transmission of brilliant flower is handled: make coating fusion 2-10min in 250-350 ℃ holding furnace, the back of coming out of the stove is according to the not requirement of isomorphous floral pattern, adopts quick water-cooled, air-cooled or naturally cooling mode to cool off;
D. acid-wash activation: at the H of 10%wt 2SO 4Solution corrosion activation 5-10sec;
E. second time electroplating tin: carry out second time electroplating tin in the plating molten tin bath of b step, cathode current density is 0.5-1A/dm 2, electroplating time 3-10min;
F. acid copper: electroplate liquid is formed and operational condition is: cupric pyrophosphate (Cu 2P 2O 7) 70-100g/L, potassium pyrophosphate (K 4P 2O 7) 300～400g/L, Triammonium citrate ((NH 4) 3C 6H 5O 7) 20-25g/L, pH8.0-8.8; Temperature 20-30 ℃, solution stirring or negative electrode move (25～30 times/min), cathode current density (D K) 0.8～1.5A/dm 2, electroplating time 40-60min;
G. Passivation Treatment: passivating solution is formed and operational condition is: potassium bichromate (K 2Cr 2O 7) 5-12g/L, with Glacial acetic acid adjust pH 3-4, temperature 30-40 ℃, time 6-12min;
H. seal at coating surface figure varnishing.
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 the brilliant flower of a tin upper layer.
Fig. 2 is imitative spot copper upper layer.
Embodiment:
Embodiment 1:
The steel disc of present method sample 45# steel.Technology comprises plating pre-treatment, eleetrotinplate, brilliant flower heat-transmission processing, acid-wash activation, second time electroplating tin, acid copper, Passivation Treatment and a coating closing step; Concrete operation is as follows:
A. plate pre-treatment: metal sample surface burr is manually removed; Soak with gasoline, in containing the water of washing composition, clean and remove surperficial grease; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;
B. eleetrotinplate: electroplate liquid is formed and operational condition is: stannous sulfate (SnSO 4) 20g/L; Sulfuric acid (H 2SO 4(ρ=1.84)) 40ml/L; Phenol 20mg/L; Gelatin 1g/L; Cathode current density 1A/dm 2Ratio of cathodic to anodic area is 1: 1; Anode purity (Sn%) 〉=99.9,15 ℃ of temperature, electroplating time 25min;
C. the heat-transmission of brilliant flower is handled: heat treated 2min in 250 ℃ holding furnace, naturally cooling in air subsequently;
D. acid-wash activation: at the H of 10%wt 2SO 4Solution corrosion activation 5sec;
E. second time electroplating tin: carry out second time electroplating tin in the plating molten tin bath of b step, cathode current density is 0.5A/dm 2, electroplating time 3min;
F. acid copper: electroplate liquid is formed and operational condition is: cupric pyrophosphate (Cu 2P 2O 7) 70g/L, potassium pyrophosphate (K 4P 2O 7) 300g/L, Triammonium citrate ((NH 4) 3C 6H 5O 7) 20g/L, pH8.0; 20 ℃ of temperature, solution stirring, cathode current density (D K) 0.8A/dm 2, electroplating time 40min;
G. Passivation Treatment: passivating solution is formed and operational condition is: potassium bichromate (K 2Cr 2O 7) 5g/L, with Glacial acetic acid adjust pH 3,30 ℃ of temperature, time 6min;
H. at coating surface figure varnishing coating is sealed.
Embodiment 2:
Present method sample is the fine copper copper sheet.Technology comprises plating piece plating pre-treatment, eleetrotinplate, brilliant flower heat-transmission processing, acid-wash activation, second time electroplating tin, acid copper, Passivation Treatment and a coating closing step; Concrete operation is as follows:
A. plate pre-treatment: metal sample surface burr is manually removed; Remove surperficial grease with the acetone immersion; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;
B. eleetrotinplate: electroplate liquid is formed and operational condition is: stannous sulfate (SnSO 4) 25g/L; Sulfuric acid (H 2SO 4(ρ=1.84)) 50ml/L; Phenol 25mg/L; Gelatin 1.5g/L; Cathode current density (D K) 1.5A/dm 2Ratio of cathodic to anodic area is 1: 1.5; Anode purity (Sn%) 〉=99.9,20 ℃ of temperature, electroplating time 28min;
C. the heat-transmission of brilliant flower is handled: the holding furnace heat treated 6min at 300 ℃, carry out quick water-cooled after coming out of the stove;
D. acid-wash activation: at the H of 10%wt 2SO 4Solution corrosion activation 6sec;
E. second time electroplating tin: carry out second time electroplating tin in the plating molten tin bath of b step, cathode current density is 0.7A/dm 2, electroplating time 7min;
F. acid copper: electroplate liquid is formed and operational condition is: cupric pyrophosphate (Cu 2P 2O 7) 85g/L, potassium pyrophosphate (K 4P 2O 7) 350g/L, Triammonium citrate ((NH 4) 3C 6H 5O 7) 22g/L, pH8.5; 25 ℃ of temperature, solution stirring, cathode current density (D K) 1A/dm 2, electroplating time 50min;
G. Passivation Treatment: passivating solution is formed and operational condition is: potassium bichromate (K 2Cr 2O 7) 8g/L, with Glacial acetic acid adjust pH 3.5,35 ℃ of temperature, time 8min;
H. at coating surface figure varnishing coating is sealed.
Embodiment 3:
Present method sample is commercial galvanized sheet iron.Technology comprises plating piece plating pre-treatment, eleetrotinplate, brilliant flower heat-transmission processing, acid-wash activation, second time electroplating tin, acid copper, Passivation Treatment and a coating closing step; Concrete operation is as follows:
A. plate pre-treatment: metal sample surface burr is manually removed; Soak with gasoline, in containing the water of washing composition, clean and remove surperficial grease; Use the hydrochloric acid soln of 10%wt to soak the removal surface scale;
B. eleetrotinplate: electroplate liquid is formed and operational condition is: stannous sulfate (SnSO 4) 30g/L; Sulfuric acid (H 2SO 4(ρ=1.84)) 60ml/L; Phenol 30mg/L; Gelatin 2g/L; Cathode current density (D K) 2A/dm 2Ratio of cathodic to anodic area is 1: 2; Anode purity (Sn%) 〉=99.9,30 ℃, electroplating time 30min;
C. the heat-transmission of brilliant flower is handled: heat treated 10min in 350 ℃ holding furnace, and the laggard sector-style of coming out of the stove is cold;
D. acid-wash activation: at the H of 10%wt 2SO 4Solution corrosion activation 10sec;
E. second time electroplating tin: carry out second time electroplating tin in the plating molten tin bath of b step, cathode current density is 0.5-1A/dm 2, electroplating time 3-10min;
F. acid copper: electroplate liquid is formed and operational condition is: cupric pyrophosphate (Cu 2P 2O 7) 70-100g/L, potassium pyrophosphate (K 4P 2O 7) 300～400g/L, Triammonium citrate ((NH 4) 3C 6H 5O 7) 20-25g/L, pH8.0-8.8; Temperature 20-30 ℃, negative electrode moves 30 times/min, cathode current density (D K) 0.8～1.5A/dm 2, electroplating time 40-60min;
G. Passivation Treatment: passivating solution is formed and operational condition is: potassium bichromate (K 2Cr 2O 7) 5-12g/L, with Glacial acetic acid adjust pH 3-4, temperature 30-40 ℃, time 6-12min;
H. at coating surface figure varnishing coating is sealed.

Claims (1)

1, the brilliant flower of the brilliant flower of a kind of tin induced electrodeposition plaque-imitating copper surface finishing 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 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. eleetrotinplate: electroplate liquid is formed and operational condition is: stannous sulfate 20-30g/L; Sulfuric acid 40-60ml/L; Phenol 20-30mg/L; Gelatin 1-2g/L; Cathode current density 1-2A/dm 2Ratio of cathodic to anodic area is 1: 1-2; Tin anode purity 〉=99.9,15-30 ℃, electroplating time 25-30min;
C. the heat-transmission of brilliant flower is handled: heating makes coating fusion 2-10min in 250-350 ℃ holding furnace, and the back of coming out of the stove adopt quick water-cooled or air-cooled, or the naturally cooling mode is cooled off according to the not requirement of isomorphous floral pattern;
D. acid-wash activation: at the H of 10%wt 2SO 4Solution corrosion activation 5-10sec;
E. second time electroplating tin: carry out second time electroplating tin in the plating molten tin bath of b step, cathode current density is 0.5-1A/dm 2, electroplating time 3-10min;
F. acid copper: electroplate liquid is: cupric pyrophosphate 70-100g/L, potassium pyrophosphate 300～400g/L, Triammonium citrate 20-25g/L; PH8.0-8.8; Temperature 20-30 ℃, solution stirring or move cathode current density 0.8～1.5A/dm with 25～30 times/min negative electrode 2, electroplating time 40-60min;
G. Passivation Treatment: passivating solution is: potassium bichromate 5-12g/L, with Glacial acetic acid adjust pH 3-4, temperature 30-40 ℃, time 6-12min;
H. at coating surface figure varnishing coating is sealed.
CN200710066460A 2007-12-14 2007-12-14 Sn crystal flower induced electrodeposition plaque-imitating copper crystal flower surface finishing process Expired - Fee Related CN100580151C (en)

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Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
电镀工艺手册. 张允诚等，281-284、286-287、307，国防工业出版社. 1997 *
电镀铜锡合金工艺研究进展. 钟云等.电镀与环保，第27卷第4期. 2007
电镀铜锡合金工艺研究进展. 钟云等.电镀与环保，第27卷第4期. 2007 *
电镀锡及晶花化工艺的研究. 钟云等.电镀与环保，第26卷第6期. 2006
电镀锡及晶花化工艺的研究. 钟云等.电镀与环保，第26卷第6期. 2006 *
表面处理工实用技术手册. 樊新民，111-112、384-385，江苏科学技术出版社. 2003 电镀工艺手册. 张允诚等，281-284、286-287、307，国防工业出版社. 1997
表面处理工实用技术手册. 樊新民，111-112、384-385，江苏科学技术出版社. 2003 *

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