CN104805484B - Production method for Cu-Ni/Ni-Ag double-composite coating extra-thin steel strip - Google Patents

Production method for Cu-Ni/Ni-Ag double-composite coating extra-thin steel strip Download PDF

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Publication number
CN104805484B
CN104805484B CN201510231636.1A CN201510231636A CN104805484B CN 104805484 B CN104805484 B CN 104805484B CN 201510231636 A CN201510231636 A CN 201510231636A CN 104805484 B CN104805484 B CN 104805484B
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controlled
cold rolling
carry
production
annealing
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CN104805484A (en
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黄菲
匡伟
白会平
张兆丽
涂元强
李青丽
刘占增
余晓静
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Wuhan Iron and Steel Group Corp
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Wuhan Iron and Steel Group Corp
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Abstract

The invention discloses a production method for a Cu-Ni/Ni-Ag double-composite coating extra-thin steel strip. The production method comprises the following steps of performing primary cold rolling on an SPHC hot rolled coil subjected to acid pickling; after conventional degreasing is finished, performing primary annealing; performing secondary cold rolling; performing conventional degreasing and coiling; preparing a strip; uncoiling, striping and removing burrs; electroplating Cu-Ni; performing primary conventional washing and drying; performing thermal spraying on Ni-Ag; performing secondary conventional washing and drying; performing secondary annealing; naturally cooling to room temperature and then coiling. According to the product disclosed by the production method disclosed by the invention, the tensile strength is 330 to 380MPa, and the elongation is 34 to 38 percent; a layer of Cu-Ni/Ni-Ag double-composite coating with uniformity, compactness and high adhesive force is generated on the surface of the product; the surface hardness of the coating is 90 to 100HV, the roughness of the coating is 0.15 to 0.30 mu m, the mirror reflectivity is 88 to 95 percent, the resistivity is 6.5 to 8.7 mu omega cm, and the thermal conductivity is 6 to 10W/cm DEG C. The problems of high cost, great waste, serious pollution and low efficiency caused by a traditional process are solved.

Description

A kind of production method of the Cu-Ni/Ni-Ag very thin steel bands of double composite deposites
Technical field
The present invention relates to a kind of production method of steel band, specifically belongs to a kind of double composite deposites of Cu-Ni/Ni-Ag very thin The production method of steel band.
Background technology
Very thin plating Ag steel bands have relatively thin thickness, excellent surface property, electric conductivity and heat conductivility due to which, extensively General to be applied to opto-electronic industry, to produce precise electronic components and parts and optical instrument parts, market demand is very big.
At present, production plating Ag steel bands mainly electroplate Cu, Ni, Ag monometallic in Cold-strip Steel Surface contiguous segmentation, are formed Traditional Cu-Ni-Ag composite deposites.Although the process history is long, its there are problems that it is several insoluble, i.e.,:One is this Coating is susceptible to oxidation, causes the stability of coating to decline with Cu as substrate.Additionally, once corrosive medium is by Ag layers Crackle and pin hole, the hole through Ni and Cu reach Fe matrixes, as Fe matrixes are the anodes of corrosion galvanic couple, will soon corrode There is rust spot;Two is, if adopting continuous electroplating, during plating Ag, to need to cook electroplate liquid using the cyanide of severe toxicity, Cause serious environment pollution;Three be steel band after continuous electroplating, surface is easily passivated, the combination property of gained composite deposite compared with Difficult control;Four is that continuous electroplating process causes energy consumption larger, and waste liquid is more.Need using substantial amounts of expensive in particularly producing Heavy metal Ni and Ag, production cost are quite high.
The Chinese patent of Publication No. CN104195607A, discloses a kind of manufacture method of stannum copper double-layer electroplating steel plate. Its technical scheme mainly comprises the steps:By cold-reduced sheet rust cleaning, clean, then in steel strip surface chemistry after being activated with diluted acid Leaching nickel, then electro-coppering, electrotinning successively subsequently carry out soft heat, hardening, soda cleaning, chromate negative electrode and are passivated, clean, blow Finished product is obtained after dry, gained stannum copper double-layer electroplating steel plate has excellent welding performance and corrosion resisting property.But, clad steel sheet master It is used to produce food cans and beverage can, due to the composite deposite for not containing Ag in steel band, causes surface property, the conduction of product Performance and heat conductivility can not meet the requirement of opto-electronic industry.
The Chinese patent of Publication No. CN101619474B, discloses a kind of manufacture method of zinc-nickel double-layer electroplating steel plate. Its technical scheme mainly comprises the steps:Cold-rolled steel sheet is carried out into processing of rust removing or hot rolled steel plate is carried out into de-scaling process, used Water is cleaned, then is activated with diluted acid, then carries out electronickelling in surface of steel plate.Subsequently to steel plate under hydrogen or nitrogen protection atmosphere Made annealing treatment, dilval layer is formed in surface of steel plate, then in dilval layer surface electrogalvanizing.After zinc-plated end, Steel plate is washed, finished product is obtained, the corrosion resisting property of gained zinc-nickel double-layer electroplating steel plate is greatly improved, while solving plating The adhesion problem of layer and matrix.But, the clad steel sheet mainly for the manufacture of automobile and household electrical appliance outside plate, due in steel band The composite deposite containing Ag, does not cause surface property, electric conductivity and the heat conductivility of product meet opto-electronic industry Require.
The Chinese patent of Publication No. CN102206842B, discloses a kind of manufacture method of zinc/tin double-layer electroplated steel plate. Its technical scheme mainly comprises the steps:Low-carbon cold rolling steel plate is carried out into pickling, rust cleaning, defat, clean process, and uses diluted acid Activation.Electrogalvanizing is carried out to the steel plate after activation, after the completion of be washed with water it is net.Subsequently carry out electrotinning, after the completion of use water again Clean.Then tin plate is carried out with resistance reflow stove soft heat, hardening, soda clean, the passivation of chromate negative electrode, after the completion of by zinc Stannum double-layer electroplating steel plate is washed, is dried up, and obtains finished product.But, the clad steel sheet is mainly for the production of food cans and beverage can.By Do not contain the composite deposite of Ag in steel band, cause surface property, electric conductivity and the heat conductivility of product meet photoelectricity The requirement of sub-industry.
The Chinese patent of Publication No. CN101922031B, discloses a kind of manufacture method of double-plating steel belt, mainly After cleaning steel is clean, re-plating nickel after first ferro-nickel alloy electroplating.Solve Poor problem, the double clad steel sheets of gained are mainly for the manufacture of electrode.But, due to the composite deposite for not containing Ag in steel band, lead Cause the surface property of product, electric conductivity and heat conductivility meet the requirement of opto-electronic industry.
The content of the invention
The present invention is in view of the shortcomings of the prior art, there is provided a kind of with excellent surface property, electric conductivity and to lead Hot property, fully meets the double very thin steel bands of composite deposite of Cu-Ni/Ni-Ag and production method of opto-electronic industry requirement.
Realize the measure of above-mentioned purpose:
A kind of production method of Cu-Ni/Ni-Ag very thin steel bands of double composite deposites, its step:
1) for the first time cold rolling, 8 passes are carried out to the SPHC hot rolled coils after pickling, cold rolling total reduction is controlled to 80 ~ 88%;
2) after conventional defat, first time annealing is carried out under perhydro protective atmosphere, annealing temperature is controlled to 690 ~ 730 ° C, temperature retention time are controlled to 20 ~ 30 min;
3) carry out cold rolling for the second time and be rolled to product thickness, 4 passes, cold rolling total reduction are controlled to 40 ~ 67%;
4) carry out conventional defat and batch;
5) carry out band processed:
A, uncoiling, slitting simultaneously remove flash removed;
B, plating Cu-Ni, electroplate liquid is CuSO4+NiSO4Acidic aqueous solution, electroplating temperature are controlled to 20 ~ 30 °C;
C, carry out first time conventional water wash and dry to steel strip surface no moisture;
D, thermal spraying Ni-Ag, particle diameter are controlled to 0.3 ~ 0.5 for Ni the and Ag concentration ratios of 0.5 ~ 0.8 m:1, spraying speed Degree is controlled to 500 ~ 700 m/s, and deposition is controlled to 0.4 ~ 0.6 kg/h;
E, carry out second conventional water wash and dry to steel strip surface no moisture;
F, second annealing is carried out under perhydro protective atmosphere, annealing temperature is controlled to 450 ~ 500 °C, temperature retention time control It is made as 25 ~ 35 min;
G, natural air cooling are batched to room temperature.
Which is:CuSO4And NiSO4Concentration ratio be 3:0.95 ~ 1.05, electric current density is 4.5 ~ 6.5 A/dm2
Which is:Particle diameter wants mix homogeneously for Ni the and Ag powder of 0.5 ~ 0.8 m.
For the problem that existing process is present, the present invention passes through lot of experiments and research, proposes a kind of new thinking, that is, adopt Rolled up as raw material base with common SPHC hot rolling acid-cleanings, using secondary cold-rolling+once anneal+electroplate Cu-Ni+ thermal spraying Ni-Ag+ The technique of double annealing is produced.Its feature:One is, using common carbon steel SPHC as raw material steel grade, both to have can ensure that product The mechanical property of product, can reduce cost of material again;Two is by secondary cold-rolling+once anneal, it is ensured that cold rolling feedses Thickness and mechanical property;Three is the effect for giving full play to Ni, by the Ni coating designs in the middle of traditional Cu-Ni-Ag composite deposites point Into two parts, i.e., on the one hand first electroplate one layer of Cu-Ni alloy to replace Cu metal single layers on base steel, substrate can be remarkably reinforced Corrosion resisting property and stability;On the other hand, Ag is electroplated come replacing electroplating Ni+ with thermal spraying Ni-Ag, without using the cyanogen of severe toxicity Compound, protects environment, and reduces technological process, improve work efficiency.Compared with continuous electroplating, thermal spray process speed Degree is fast, wastage of material is few, and production cost is relatively low, thickness of coating controllable precise.In addition, relative to Ag metal single layers, Ni-Ag alloys Both the electric conductivity and heat conductivity of coating had been enhanced, the glossiness of coating had been improve again;Four is, after the completion of thermal spraying, to carry out second Secondary annealing, which can both adjust the mechanical property of product, reduce the internal stress of coating, again can be by the oxygen of coating surface remaining Compound is removed, it is ensured that the surface smoothness of coating, moreover it is possible to promote the alloying process of coating, improves the surface property of coating.
Compared with existing ordinary steel belts, the present invention production product, its thickness be 0.2 ~ 0.3 mm, tensile strength be 330 ~ 380 MPa, elongation percentage are 34 ~ 38%;Surface Creation one layer of even compact, adhesive force are strong, thickness for 7 ~ 10 m Cu-Ni/ The double composite deposites of Ni-Ag, coating surface hardness is 90 ~ 100 HV, and roughness is 0.15 ~ 0.30 m, specular reflectivity is 88 ~ 95%, resistivity is 6.5 ~ 8.7 Ω cm, and thermal conductivity is 6 ~ 10 W/cm °C.The surface property of product, electric conductivity and heat conduction It is functional, fully meet the requirement of opto-electronic industry.After especially with plating Cu-Ni+ thermal spraying Ni-Ag techniques, solve Conventionally produced brought high cost, waste the low problem of big, pollution weight, efficiency.
Specific embodiment
Below the present invention is described in detail:
Table 1 is the cold-rolling process parameter list of various embodiments of the present invention and comparative example;
Table 2 is the belt making process parameter list of various embodiments of the present invention and comparative example;
Table 3 is the properties of product list of various embodiments of the present invention and comparative example.
Various embodiments of the present invention are produced in accordance with the following steps:
1) for the first time cold rolling, 8 passes are carried out to the SPHC hot rolled coils after pickling, cold rolling total reduction is controlled to 80 ~ 88%;
2) after conventional defat, first time annealing is carried out under perhydro protective atmosphere, annealing temperature is controlled to 690 ~ 730 ° C, temperature retention time are controlled to 20 ~ 30 min;
3) carry out cold rolling for the second time and be rolled to product thickness, 4 passes, cold rolling total reduction are controlled to 40 ~ 67%;
4) carry out conventional defat and batch;
5) carry out band processed:
A, uncoiling, slitting simultaneously remove flash removed;
B, plating Cu-Ni, electroplate liquid is CuSO4+NiSO4Acidic aqueous solution, electroplating temperature are controlled to 20 ~ 30 °C;
C, carry out first time conventional water wash and dry to steel strip surface no moisture;
D, thermal spraying Ni-Ag, particle diameter are controlled to 0.3 ~ 0.5 for Ni the and Ag concentration ratios of 0.5 ~ 0.8 m:1, spraying speed Degree is controlled to 500 ~ 700 m/s, and deposition is controlled to 0.4 ~ 0.6 kg/h;
E, carry out second conventional water wash and dry to steel strip surface no moisture;
F, second annealing is carried out under perhydro protective atmosphere, annealing temperature is controlled to 450 ~ 500 °C, temperature retention time control It is made as 25 ~ 35 min;
G, natural air cooling are batched to room temperature.
Which is:CuSO4And NiSO4Concentration ratio be 3:0.95 ~ 1.05, electric current density is 4.5 ~ 6.5 A/dm2
Which is:Particle diameter wants mix homogeneously for Ni the and Ag powder of 0.5 ~ 0.8 m.
The product thickness of following embodiment production is in the range of 0.20 ~ 0.30 mm.
The cold-rolling process parameter list of 1 various embodiments of the present invention of table and comparative example
The belt making process parameter list of 2 various embodiments of the present invention of table and comparative example
The properties of product list of 3 various embodiments of the present invention of table and comparative example
From table 3 it can be seen that the steel band of the present patent application, its thickness is 0.2 ~ 0.3 mm;Tensile strength is 330 ~ 380 MPa;Elongation percentage is 34 ~ 38%;Surface Creation one layer of even compact, adhesive force are strong, thickness for 7 ~ 10 m Cu-Ni/Ni-Ag Double composite deposites;Coating surface hardness is 90 ~ 100 HV;Roughness is 0.15 ~ 0.30 m;Specular reflectivity is 88 ~ 95%;Electricity Resistance rate is 6.5 ~ 8.7 Ω cm;Thermal conductivity is 6 ~ 10 W/cm °C.The surface property of product, electric conductivity and heat conductivility are good It is good, fully meet the requirement of opto-electronic industry.
Above-described embodiment is only most preferably enumerated, and is not the restriction to embodiments of the present invention.

Claims (1)

1. the production method of the double very thin steel bands of composite deposite of a kind of Cu-Ni/Ni-Ag, its step:
1) the SPHC hot rolled coils after pickling are carried out for the first time cold rolling, 8 passes, cold rolling total reduction are controlled to 80 ~ 88%;
2) after conventional defat, first time annealing is carried out under perhydro protective atmosphere, annealing temperature is controlled to 690 ~ 730 °C, protects Warm time control is 20 ~ 30 min;
3) carry out cold rolling for the second time and be rolled to product thickness, 4 passes, cold rolling total reduction are controlled to 40 ~ 67%;
4) carry out conventional defat and batch;
5) carry out band processed:
A, uncoiling, slitting simultaneously remove flash removed;
B, plating Cu-Ni, electroplate liquid is CuSO4+NiSO4Acidic aqueous solution, electroplating temperature are controlled to 20 ~ 30 °C;CuSO4With NiSO4Concentration ratio be 3:0.95 ~ 1.05, electric current density is 4.5 ~ 6.5 A/dm2
C, carry out first time conventional water wash and dry to steel strip surface no moisture;
D, thermal spraying Ni-Ag, particle diameter are controlled to 0.3 ~ 0.5, and mix homogeneously for Ni the and Ag concentration ratios of 0.5 ~ 0.8 m:1, Spraying rate is controlled to 500 ~ 700 m/s, and deposition is controlled to 0.4 ~ 0.6 kg/h;
E, carry out second conventional water wash and dry to steel strip surface no moisture;
F, second annealing is carried out under perhydro protective atmosphere, annealing temperature is controlled to 450 ~ 500 °C, and temperature retention time is controlled to 25~35 min;
G, natural air cooling are batched to room temperature.
CN201510231636.1A 2015-05-08 2015-05-08 Production method for Cu-Ni/Ni-Ag double-composite coating extra-thin steel strip Expired - Fee Related CN104805484B (en)

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CN105063620B (en) * 2015-08-07 2017-12-29 武汉钢铁有限公司 A kind of production method of photoelectric material Zn/Cu Ag/Cu Au composite deposite steel bands
CN105154933A (en) * 2015-08-21 2015-12-16 无锡桥阳机械制造有限公司 Nickel silver alloy electroplate liquid and electroplating method thereof
CN105887085B (en) * 2016-04-22 2018-03-16 武汉钢铁有限公司 A kind of production method for plating the very thin steel band of noble metal
CN105887146B (en) * 2016-04-22 2018-01-23 武汉钢铁有限公司 A kind of production method of domestic gas ware coated steel strips
CN105887145B (en) * 2016-04-22 2018-03-16 武汉钢铁有限公司 A kind of production method of gearing parts composite deposite steel band
CN105925775B (en) * 2016-07-08 2017-10-27 武汉钢铁有限公司 A kind of production method of the corrosion resistance decoration composite deposite steel band of thickness≤0.1mm
CN108198762B (en) * 2017-12-29 2020-04-21 广东禾木科技有限公司 Preparation method of double-plating bonding copper wire

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442181A (en) * 1981-04-23 1984-04-10 Nippon Steel Corporation Steel strip having differentiated multilayer coatings and being useful for manufacturing of cans
CN86102549A (en) * 1986-10-29 1988-05-11 上海工业大学 A kind of technology for plating thick silver on high nickel-base alloy-steel
CN101591725A (en) * 2009-06-25 2009-12-02 昆山龙鹰金属制品有限公司 The production technique of band steel
CN101597780A (en) * 2009-07-03 2009-12-09 湖南利德材料科技股份有限公司 A kind of method for preparing the nickel-silver alloy steel strip that battery case uses
CN103540977A (en) * 2013-10-12 2014-01-29 北京工业大学 Method for preparing high-gas tightness nickel-copper alloy for travelling wave tube
CN104018084A (en) * 2014-06-23 2014-09-03 武汉钢铁(集团)公司 Decorative bundling belt with tensile strength of more than or equal to 950MPa and production method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442181A (en) * 1981-04-23 1984-04-10 Nippon Steel Corporation Steel strip having differentiated multilayer coatings and being useful for manufacturing of cans
CN86102549A (en) * 1986-10-29 1988-05-11 上海工业大学 A kind of technology for plating thick silver on high nickel-base alloy-steel
CN101591725A (en) * 2009-06-25 2009-12-02 昆山龙鹰金属制品有限公司 The production technique of band steel
CN101597780A (en) * 2009-07-03 2009-12-09 湖南利德材料科技股份有限公司 A kind of method for preparing the nickel-silver alloy steel strip that battery case uses
CN103540977A (en) * 2013-10-12 2014-01-29 北京工业大学 Method for preparing high-gas tightness nickel-copper alloy for travelling wave tube
CN104018084A (en) * 2014-06-23 2014-09-03 武汉钢铁(集团)公司 Decorative bundling belt with tensile strength of more than or equal to 950MPa and production method thereof

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