CN100419125C

CN100419125C - Pickler of copper alloy materials

Info

Publication number: CN100419125C
Application number: CNB2004100876233A
Authority: CN
Inventors: 王振尧; 于国才; 韩薇; 孙立军; 刘禾
Original assignee: Institute of Metal Research of CAS
Current assignee: Institute of Metal Research of CAS
Priority date: 2004-11-19
Filing date: 2004-11-19
Publication date: 2008-09-17
Anticipated expiration: 2024-11-19
Also published as: CN1778996A

Abstract

The present invention relates to a pickler for copper alloy material, which belongs to the field of copper alloy surface treatment. Measured by weight percentage, the formula of the pickler comprises 6-10% of sulphuric acid, 6 to 10% of phosphonic acid, 0.3 to 0.4% of polyoxyethylene nonylphenol, 0.015 to 0.025% of benzortiazoel (BTA) and water as the rest. The present invention uses the formula for pickling copper alloy material according to certain technical conditions to enable the sample surface of a copper blank to present the obvious natural color of copper alloy, the copper alloy material is thoroughly washed, and the level of a German pickling formula CA is achieved. As for economic benefits, the input cost of the formula is only about 20% of that of the German pickling formula CA, and the formula has considerable efficiency. In a word, the formula has the advantages of good pickling quality and obvious economic benefit, and the formula can be used as a domestic substitute product of the German pickling formula CA.

Description

Pickler of copper alloy materials

Technical field

The invention belongs to the copper alloy surface process field, be specially a kind of pickler of copper alloy materials.

Background technology

Because the copper alloy matter coin of 5 edged surface values, under the base pie attitude before stamp, there are impurity such as oxide skin, greasy dirt in the surface, has a strong impact on the processing of surface-brightening degree and anticorrosion variable color of later stage.Under the situation of using German bright dipped finish prescription CA, though can obtain very surface of good effect, its cost is too high, has had a strong impact on the economic benefit of producer self at present.Although and lower by the bright dipped finish prescription cost of producer's independent development and development, the pickled surface effect is bigger with the weak effect distance of Germany prescription CA, be difficult to apply.

The metal cleaning is an important step during modern industry is produced.From raw metal warehouse-in and component processing and manufacturing (comprising hot and cold manufacturing procedure), product assembly and the decomposition of repairing trades, the maintenance of mechanical industry etc., all be unable to do without matting.

Acid cleaning process as one of important component part of cleaning; simple with its technology; the low and tangible many characteristics of cleaning quality of cost; in producing, modernization industry is widely used; and the quality of the selection of acid cleaning process and pickling quality; not only relate to significant problems such as the energy, technical security, environment protection, and directly have influence on the performance and the quality of product.So cleaning technique and even acid cleaning process have reflected the total quality control level of an enterprise to a certain extent.Metal cleans and pickling mainly comprises all exotics of removing the metallic surface, as greasy dirt, dirt, rust and high temperature oxide layer etc.

The object of the surface-brightening pickling of copper base cake mainly is the dirt that oxide skin, greasy dirt and the sedimentary spot of surface adsorption are constituted.

The composition of copper oxide and physical condition depend on its formation temperature, and when Heating temperature surpassed 80 ℃, the beginning deepening of copper surface generated the thin Red copper oxide of one deck; When Heating temperature surpassed more than 200 ℃, the oxidizing reaction of copper was proceeded, and the surface forms the oxide skin of being made up of cupric oxide and Red copper oxide.When temperature raises again, in fact only remaining cupric oxide.Because copper base cake is higher than 200 ℃ through the anneal temperature, so the surface scale of base cake mainly is a cupric oxide, can be with acid as etchant.

Copper is a kind of not too active metal, and it can not cement out the hydrogen ion in the acidic aqueous solution and produce hydrogen, and therefore under low temperature condition, copper is more stable in the non-oxidizable acid aqueous solution such as hydrochloric acid, phosphoric acid, acetate and dilute sulphuric acid.But under the coefficient situation of oxygen in these acid and the air, copper and alloy thereof can be corroded.Therefore, when using acid, should add an amount of effective corrosion inhibitors as etchant.

Industrial, the etchant that copper alloy products carries out bright dipped finish mainly contains two classes.One class is a chromic acid sulfuric acid type mixing acid washing lotion; Another kind of is sulfuric acid nitrate type mixing acid washing lotion.The former is because of having adopted deleterious chromic acid, and waste water must be handled with very high cost, stops using substantially.The latter has adopted the nitric acid of high density, also needs to add a large amount of urea, tensio-active agent and acid fog inhibitor etc. to reduce the pollution of the oxynitride that nitric acid was produced in the etchant.In addition, this acid washing method is finished in need be in several seconds, and need get express developed, also is not suitable for power operation.For a long time, in order to improve this deleterious operation, all done number of research projects both at home and abroad.In recent years, foreign study a kind of novel pickling etchant based on hydrogen peroxide.More domestic enterprises have carried out some improvement and have developed out several new acid cleaning process this emerging etchant acid washing method.But at present, this novel acid cleaning process only is applicable to the production of small sized product.Because the decomposing hydrogen dioxide solution problem is not solved so far, when the surface-area of goods big or output for a long time, this novel process since the production cost height will be restricted.

Common grease is divided into saponifiability oil and non-saponifiability oil substantially.Saponifiability oil is often referred to each vegetable oil, as soya-bean oil, sesame wet goods.And the grease of copper base cake surface adsorption mainly is non-saponifiability oil, be mineral oil, as various hydrocarbon polymers such as machine oil, diesel oil, Vaseline, paraffin, they can not play saponification reaction with alkali, be insoluble to alkaline solution, also water insoluble, therefore when the selection of water clean-out system, to add a large amount of acid solutions usually to reach good erosion effect.

Common deoiling method has Solvent degreasing, electrochemical deoiling, electrochemical degreasing, low oily oil removing, ultrasonic wave oil removing, wiping oil removing and cylinder oil removing.According to the original acid cleaning process appointed condition of Shenyang Mint Factory, and the characteristics of various deoiling methods and use range, select that equipment is simple, cost is low, the oil removing time is very not long for use, and be applicable to the electrochemical deoiling method of existing acid cleaning process condition.Because the grease on copper base cake surface mainly is non-saponifiability grease, so select the tensio-active agent oil removing usually for use.

Tensio-active agent is a class material that arrives commonly used in the washing, and they play an important role in washing process, are exactly a kind of tensio-active agent as soap.

The kind of tensio-active agent is a lot, and sorting technique also has multiple.A kind of method is in the purposes of different field they to be divided into emulsifying agent, solubilizing agent, whipping agent, froth suppressor, static inhibitor, wetting agent, permeate agent, dispersion agent, flocculation agent, emulsion splitter, mineral flotation agent, sterilant, fiber process auxiliary agent, dyeing auxiliary etc. according to tensio-active agent.The tensio-active agent that uses in cleaning is called washing composition or washing agent.

Adding tensio-active agent in water can make the surface tension of water or interfacial tension significantly reduce.In washing process, how many surface tension of washings that acts on the surface of object reduces, and is very important concerning tensio-active agent.Generally can reduce liquid greatly---the capillary tensio-active agent of gas meter face (as the separation surface of the aqueous solution and air), it is also big to reduce interface (as the separation surface of the aqueous solution and kerosene, the aqueous solution and metal, the aqueous solution and dirt) tensile ability simultaneously.Tensio-active agent is combined together to form by oleophylic agent and hydrophilizing agent two-part structure.Electron distributions is symmetrically in the hydrocarbon chain of oleophilic group part, generally is nonpolar therefore, so oleophilic group is called nonpolar group again; And hydrophilic group generally is that polar is arranged, the ionizable one-tenth ionic condition that has.The state that exists in water according to tensio-active agent is negatively charged ion, positively charged ion or two kinds of ions of yin, yang, and tensio-active agent is divided into anionic, cationic and amphoteric ion type.Show the character of tensio-active agent, not only in composition, will contain oleophilic group and hydrophilic group two-part structure, and will keep certain balance between oleophilic group and hydrophilic group two portions.

To sum up analyze describedly, selecting the tensio-active agent of diluted acid+inhibiter+have emulsifying effect for use is testing program.

Summary of the invention:

The object of the present invention is to provide the pickler of copper alloy materials that a kind of result of use is good, cost is low.

Technical scheme of the present invention is:

A kind of pickler of copper alloy materials, by weight percentage, its prescription is:

Sulfuric acid 6-10%

Phosphoric acid 6-10%

NONYL PHENOL POLYOXYETHYLENE 0.3-0.4%

Benzotriazole (BTA) 0.015-0.025%

All the other are water.

Cu alloy material is soaked in the pickle solution that obtains by above-mentioned prescription, under normal temperature, the continuous stirring, handled 30 minutes, can reach the purpose of pickling.

The present invention considers sulfuric acid (H ₂SO ₄) effect in Acidwash solution: with the raising of concentration and the increasing of viscosity, to the corresponding enhancing of the erosion action of metal, when concentration was higher than certain value, erosion action descended on the contrary.Phosphoric acid (H ₃PO ₄) be hyperbaric macromole group, in solution, be emulsifying agent on the one hand, also participate in reaction on the other hand indirectly, make the copper surface-brightening careful.In the finite concentration scope, select the composition of these two kinds acid mixing as pickle solution.

According to the surface and oil contaminant characteristics of copper base cake,, select the tensio-active agent of NONYL PHENOL POLYOXYETHYLENE as pickle solution in conjunction with the service condition and the documents and materials introduction of tensio-active agent in present China industrial production.Domestic and international many pertinent literatures report thinks that benzotriazole (BTA) and its derivative etc. are the most extensive, the effective corrosion inhibitors of copper alloy use, select its inhibiter as pickle solution.

Fs, utilizing the orthogonal test conceptual design, is test factor with sulfuric acid, phosphoric acid, NONYL PHENOL POLYOXYETHYLENE, benzotriazole, selects three concentration levels, promptly the orthogonal experimental design of four factors, three levels is carried out pickling by orthogonal test table to the copper base cake after annealing.After Total Test is finished, the copper base cake effect after each acid washing test is compared, analyzes and estimates, filter out respond well prescription.

Subordinate phase, the prescription that the fs is selected carries out the repeated authentication test, and it is stable to reach pickling performance, treats pilot plant test.

Phase III, selected prescription is carried out production inspection at Shenyang Mint Factory copper base cake pickling lines, pickling effect is obvious, under the macroscopic observation and microscopical microscopic observation of naked eyes, does not have significant difference with the pickling effect of German pickling prescription CA.After pickling, can make copper base cake surface manifest tangible copper true qualities, clean more thorough.

On economic benefit, the cost input of this prescription only is equivalent to about 20% of Germany prescription CA, and benefit is considerable.

In sum, the pickling quality of this prescription is good, economic benefit is obvious, so optional its production domesticization substitute products as German CA prescription.

Embodiment:

1, the key instrument of Shi Yonging: MP200-7 electronic balance, TS14-2 optical readings balance, electron microscope, beaker, graduated cylinder etc.

2, the test materials of Shi Yonging: copper alloy base cake.

3, the condition of Shi Yonging: laboratory pickling of copper alloy base cake or industrial acid-washed production line.

Table 1

	Sulfuric acid (wt.%)	Phosphoric acid (wt.%)	NONYL PHENOL POLYOXYETHYLENE (wt.%)	Benzotriazole (wt.%)	Tap water (wt.%)
	Sulfuric acid (wt.%)	Phosphoric acid (wt.%)	NONYL PHENOL POLYOXYETHYLENE (wt.%)	Benzotriazole (wt.%)	Tap water (wt.%)	1	6	6	0.4	0.02	Surplus
2	8	8	0.35	0.015	Surplus	1	6	6	0.4	0.02	Surplus
2	8	8	0.35	0.015	Surplus	3	10	10	0.3	0.025	Surplus

As shown in table 1, each component of above-mentioned prescription mixed obtain pickle solution, use this pickle solution that copper alloy base cake is carried out pickling by certain process conditions, Cu alloy material is soaked in the pickle solution that obtains by above-mentioned prescription, under normal temperature, the continuous stirring, handled 30 minutes, can reach the purpose of pickling, can make copper base cake specimen surface manifest tangible copper alloy true qualities, respond well, clean thoroughly, degree of cleaning reaches the level of German pickling prescription CA.This prescription can be used as the production domesticization substitute products of the German pickling prescription CA of copper alloy base cake, and economic benefit is obvious.

Claims

1. pickler of copper alloy materials, it is characterized in that: by weight percentage, its prescription is:

Sulfuric acid 6-10%;

Phosphoric acid 6-10%;

NONYL PHENOL POLYOXYETHYLENE 0.3-0.4%;

Benzotriazole 0.015-0.025%;

All the other are water.