CN111334753B - Method for plating rhodium on surface of steel strip - Google Patents
Method for plating rhodium on surface of steel strip Download PDFInfo
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- CN111334753B CN111334753B CN202010278449.XA CN202010278449A CN111334753B CN 111334753 B CN111334753 B CN 111334753B CN 202010278449 A CN202010278449 A CN 202010278449A CN 111334753 B CN111334753 B CN 111334753B
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- 238000007747 plating Methods 0.000 title claims abstract description 83
- 239000010948 rhodium Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 54
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 28
- 239000010959 steel Substances 0.000 title claims abstract description 28
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 21
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910018054 Ni-Cu Inorganic materials 0.000 claims abstract description 18
- 229910018481 Ni—Cu Inorganic materials 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 38
- 238000000151 deposition Methods 0.000 claims description 31
- 238000005240 physical vapour deposition Methods 0.000 claims description 29
- 230000008021 deposition Effects 0.000 claims description 26
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002513 implantation Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000005468 ion implantation Methods 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 238000005238 degreasing Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 abstract description 61
- 239000011248 coating agent Substances 0.000 abstract description 59
- 239000002131 composite material Substances 0.000 abstract description 12
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 8
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- 230000003746 surface roughness Effects 0.000 abstract description 4
- 239000011521 glass Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 41
- 239000010944 silver (metal) Substances 0.000 description 20
- 238000009713 electroplating Methods 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
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- 230000007797 corrosion Effects 0.000 description 7
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- 239000010931 gold Substances 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010437 gem Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
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- 230000005501 phase interface Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
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- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/48—Ion implantation
Abstract
A method for plating rhodium on the surface of a steel strip: common low-carbon cold-rolled steel strips are used as raw materials and degreased to remove oil; washing and drying; annealing under the protective atmosphere of full hydrogen; plating; naturally cooling to room temperature. According to the invention, a Ni-Cu/Ag-Pd/Pt/Rh composite coating with the hardness of 70-75 HV, the surface roughness of 0.020-0.030 mu m and the porosity of not more than 2/cm is generated on the surface of a steel strip2The mirror surface reflectivity is 99.92-99.99%; the resistivity is 0.05-0.09 mu omega ∙ cm, and the thermal conductivity is 380-390W/m ∙ K; after being continuously placed for 5000 days at normal temperature, the surface oxidation area is not more than 0.05 percent, and the light loss rate is not more than 0.07 percent; after the glass is continuously placed for 5000 hours at the temperature of 350-400 ℃, the surface oxidation area is not more than 0.07 percent, and the light loss rate is not more than 0.09 percent; after the coating is continuously placed for 5000 hours under 100KHz ultrasonic waves, the thickness of the coating has no obvious change, and the coating does not fall off or crack, thereby completely meeting the industrial requirements of clocks, jewelries, precision instruments and the like.
Description
Technical Field
The invention relates to a material surface treatment method, in particular to a method for plating rhodium on the surface of a steel strip, which is widely applied to the industries of clocks, jewelries, precision instruments and the like.
Background
Rhodium (Rh) is an important precious metal, has good ductility, surface property, conductivity, heat conductivity, oxidation resistance and the like, and is widely used in the industries of clocks, jewels, precision instruments and the like. However, since Rh is a rare element in the earth crust and is expensive, its application is greatly limited. In order to reduce the cost and save the use amount, the current practice in the industry is to replace pure metal Rh with a Rh-plated steel strip and realize certain service performance through an Rh plating layer.
In the conventional rhodium plating process for a steel strip, single metals such as Cu, Ni, Ag, Rh and the like are continuously and sectionally plated on the surface of the cold-rolled steel strip to form a Cu/Ni/Ag/Rh composite plating layer, and the following defects exist:
first, since the plating layer uses Cu as an inner plating layer, oxidation easily occurs, thereby causing a decrease in stability of the plating layer. In addition, once the corrosion medium passes through cracks and pinholes of the Rh plating layer and reaches the Fe matrix through pores of Ag, Ni, and Cu, the Fe matrix is an anode of a corrosion couple, and is quickly corroded to cause rust spots, thereby causing a great decrease in the stability of the entire composite plating layer.
Second, H is easily precipitated during the process of electroplating Ni2And Ni is just a kind of H-absorption2Of metal of (A), H2The hydrogen embrittlement is easily caused by penetration into the plating layer, resulting in cracking of the plating layer.
Thirdly, in the process of electroplating Ag, a highly toxic cyanide is used as an electroplating solution, which can seriously pollute the environment. In addition, the Ag plating layer as the intermediate layer is highly susceptible to oxidation in air and corrosion by sulfides. If the subsequent Rh plating process cannot follow up in time, more defects are generated on the surface of the Ag plating layer, the stability of the Rh plating layer is greatly influenced, the specular reflectivity and the glossiness of the whole composite plating layer are greatly reduced, and the service performance is seriously influenced. Although there is a report in the literature that Ag can be plated by means of thermal spraying, on one hand, the thickness of the obtained Ag plating layer is often large, generally reaching tens of micrometers, or even higher, the raw material waste is too large, and the cost performance is too low. On the other hand, in the thermal spraying process, the heating temperature is not lower than the melting point of Ag, so that the Ag coating with a glowing surface is easier to oxidize in the air, the surface defects are more, and the subsequent Rh plating is not facilitated.
Fourth, in the process of plating Rh, the main problems are: firstly, H is easy to be separated out in the electroplating process2And Rh happens to H2The coating has strong absorption capacity, and is easy to permeate into the whole coating to generate hydrogen embrittlement, so that the coating is cracked. And the other is that Rh is one of the most rare precious metals in the world, the content of Rh in the earth crust is only one billionth, which is about 2 percent of the Pt storage or 10 percent of the Pd storage, and is much less than the precious metals such as Au, Ag, Pt, Pd, etc. Therefore, Rh is extremely expensive, with a price per ounce of Rh of about 2 times that of Au. The electroplating process is adopted to plate Rh, because the current efficiency is difficult to reach 100%, the thickness of a plating layer cannot be accurately controlled, more waste liquid can be generated, and a great amount of Rh waste is caused.Generally, the waste is recovered through a complicated subsequent process, which increases additional production costs. Thirdly, because of long-time continuous sectional electroplating, not only energy consumption is high, but also passivation effect is easily generated on the surface of the plating layer, so that the surface quality of the Rh plating layer is often poor, the pores are more, and the glossiness is low. Fourth, the Rh plating layer generally has high hardness, large stress, and strong brittleness, and cracks are easily generated when the thickness exceeds 3 μm. When a workpiece is punched, the deformation between the plating layer and the substrate is inconsistent, the plating layer is easy to fall off, and the stability is poor.
Therefore, the traditional process for forming the Rh coating by continuous sectional electroplating has more problems, the traditional process does not meet the requirements of national energy-saving and environment-friendly policies, and the coating performance cannot meet increasingly severe use standards of the industry.
After retrieval:
a Chinese journal article, stainless steel rhodium plating technology (Yang Fuguo, surface technology, 2000, 29 (6): 48-49), discloses a technology for plating Rh on a stainless steel piece. The main process is as follows: the method comprises the steps of hanging a stainless steel watchband (or watchcase) on a hanger → washing with trichloroethylene → washing with paraffin removal water → washing with water → soaking in 5% KCN → washing with water → electrolytic degreasing → washing with water → peracid → washing with pure water → activation → washing with pure water → preplating with trivalent gold → washing → electrolysis → washing → peracid → washing with pure water → rhodium → recovery → electrolysis → washing → peracid → washing → drying → inspection. In addition to the problems generally associated with Rh electroplating processes, which have been mentioned above, the proposed process, in particular in this document, has the following disadvantages: firstly, trichloroethylene and KCN which are carcinogens and explosives are used in the pretreatment process, obviously, the trichloroethylene and the KCN can cause serious damage to human bodies and the environment, and the requirements of national environmental protection policies are not met completely. Secondly, in the electroplating process, in order to maintain the current efficiency, rhodium sulfate solution needs to be supplemented to the bath night according to ampere minute, so that the maintenance is quite troublesome and the cost is high. Thirdly, the whole electroplating process is complicated and long and is not easy to operate. For example, the normal water washing is repeated many times, and the work efficiency is too low. Further, it is described that after the sample is plated with Rh and subjected to an artificial sweat test, the color of the sample is not changed after sealing at 40 ± 2 ℃ for 24 hours, but a small amount of plating is rusted, which indicates that the corrosion resistance of the plating is not good and the surface quality is to be improved.
Disclosure of Invention
The invention aims to overcome the defects of heavy environmental pollution, large raw material waste, poor coating quality, poor stability and the like in the prior art, and provides a method for generating a Ni-Cu/Ag-Pd/Pt/Rh composite coating with the thickness of 2.5-3.5 mu m on the surface of a steel strip, wherein the hardness is 70-75 HV, the surface roughness is 0.020-0.030 mu m, and the porosity is not more than 2/cm2The specular reflectivity is 99.92-99.99%, and the surface quality of the coating is good. The resistivity is 0.05-0.09 mu omega cm, and the thermal conductivity is 380-390W/m.K; after being continuously placed for 5000 days at the normal temperature of 25-35 ℃, the surface oxidation area is not more than 0.05 percent, and the light loss rate is not more than 0.07 percent. After being continuously placed for 5000 hours at the high temperature of 350-400 ℃, the surface oxidation area is not more than 0.07 percent, and the light loss rate is not more than 0.09 percent; in addition, after the rhodium plating solution is continuously placed for 5000 hours in a 100KHz ultrasonic environment, the thickness of a plating layer is not obviously changed, and the rhodium plating solution does not fall off or crack, so that the surface of a steel strip with high plating layer stability is plated with rhodium.
The measures for realizing the aim are as follows:
a method for plating rhodium on the surface of a steel strip comprises the following steps:
1) taking a common low-carbon cold-rolled steel strip as a raw material, and carrying out conventional alkali liquor degreasing and deoiling;
2) washing with water and drying until the surface of the steel strip is free of moisture;
3) annealing in a full hydrogen protective atmosphere, controlling the annealing temperature to be 520-540 ℃, and preserving heat for 10-15 min at the temperature;
4) and (3) plating:
A. carrying out physical vapor deposition on a Ni-Cu alloy, wherein the mass percent of Ni is controlled to be 85-90%, the mass percent of Cu is 15-10%, the deposition rate is controlled to be 0.06-0.07 mu m/min, and the deposition time is 10-12 min;
B. carrying out physical vapor deposition on the Ag-Pd alloy, wherein the mass percent of Ag is controlled to be 88-93%, the mass percent of Pd is controlled to be 12-7%, the deposition rate is controlled to be 0.05-0.09 mu m/min, and the deposition time is 9-11 min;
C. carrying out physical vapor deposition on Pt, wherein the deposition rate is controlled to be 0.04-0.06 mu m/min, and the deposition time is controlled to be 3-5 min;
D. ion implantation of Rh with implantation energy of 190-200 KeV and implantation dosage of Rh of (3-5) x 1019/cm2；
E. Naturally cooling to room temperature.
Preferably: in the process of physical vapor deposition of Ni-Cu alloy, the deposition rate is 0.063-0.068 μm/min.
Preferably: in the process of physical vapor deposition of the Ag-Pd alloy, the deposition rate is 0.054 to 0.085 mu m/min.
Preferably: in the process of physical vapor deposition of Pt, the deposition rate is 0.045-0.055 mu m/min.
Preferably: in the process of ion implantation of Rh, the implantation energy is 193-198 KeV, and the implantation dosage of Rh is (3.3-4.5) × 1019/cm2。
The main process mechanism and action of the invention are as follows:
the invention adopts the processes of degreasing and degreasing by alkali liquor, annealing by total hydrogen, depositing Ni-Cu alloy by physical vapor deposition, depositing Ag-Pd alloy by physical vapor deposition, depositing Pt by physical vapor deposition and injecting Rh to carry out surface treatment, because:
firstly, before the cold-rolled steel strip is subjected to a plating treatment, the surface of the cold-rolled steel strip must be ensured to be clean, and the cold-rolled steel strip is degreased by alkali liquor to remove oil stains on the surface of the steel strip; and the hydrogen annealing has three functions: firstly, volatilizing a very small amount of grease remained on the surface of the steel strip at high temperature; secondly, under the atmosphere of reducing hydrogen, removing a small amount of oxides on the surface of the steel strip; thirdly, the steel belt is properly softened, the internal stress of the steel belt is reduced, the probability of generating cracks is reduced, and the stability of the composite coating is improved.
Secondly, after the pretreatment of the cold-rolled steel strip is finished, a layer of Ni-Cu alloy is physically deposited on the surface of the steel strip in a vapor phase mode to be used as an inner coating. Compared with a Cu/Ni double-plating layer formed by 'electroplated Cu → electroplated Ni' section electroplating in the traditional process, Ni and Cu in the alloy have strong affinity and can be infinitely solid-dissolved with each other to form a continuous solid solution, namely a single-phase alloy. In terms of stability, the Ni-Cu alloy plating layer is obviously superior to the Cu/Ni double plating layer in two phases. In addition, compared with a pure Cu plating layer, the Ni-Cu alloy plating layer has the advantages that the corrosion resistance is greatly improved due to the existence of Ni elements, and the stability of the inner plating layer is greatly enhanced. Compared with a pure Ni plating layer, the Ni-Cu alloy plating layer can enhance the electric conductivity and the heat conductivity of the inner plating layer due to the existence of Cu element. Therefore, the Ni — Cu alloy plating layer combines the advantages of both the Cu plating layer and the Ni plating layer, and is an ideal inner plating layer. The physical vapor deposition process is adopted, because the alloy deposition is carried out under the vacuum condition, no air, water or other impurities exist, and the purity of the alloy is ensured. Moreover, the two electroplating processes are combined into one physical vapor deposition process, which is beneficial to shortening the process flow and reducing the discharge of waste liquid.
Thirdly, after the physical vapor deposition of the Ni-Cu alloy is finished, the physical vapor deposition of a layer of Ag-Pd alloy is continued to be used as an intermediate coating. There are four reasons why physical vapor deposition of Ag — Pd alloys is used instead of electroplating Ag: one is that the physical vapor deposition does not need to use highly toxic cyanide, thereby greatly protecting the environment. The thickness of the coating can be accurately controlled, waste is reduced, and the stability and compactness of the coating are greatly improved. And secondly, because the alloy deposition is carried out under the vacuum condition, no air, water or other impurities exist, and the purity of the alloy is ensured. Meanwhile, a proper amount of Pd is added as an alloy element to form the Ag-Pd alloy, the normal-temperature oxidation resistance and sulfide corrosion resistance of the Ag-Pd alloy are greatly better than those of a pure Ag coating, surface defects are reduced, and the stability of the whole coating is improved. And the Ag and the Pd have strong affinity, can be dissolved in each other infinitely to form a continuous solid solution, namely the Ag-Pd single-phase alloy, has excellent conductivity, heat conductivity and extensibility, has small brittleness and proper hardness, can replace pure metal Ag, and greatly improves the stability of the whole plating layer. And fourthly, Ag and Pd in the middle coating have strong affinity with Cu and Ni in the inner coating respectively, so that a continuous solid solution can be formed, and Ag and Pd atoms at two-phase interfaces respectively have alloying reaction with Cu and Ni atoms in the process of depositing an Ag-Pd alloy on the surface of the Ni-Cu coating, so that the binding force between the coatings is enhanced, and the stability of the whole coating is greatly improved.
Fourthly, after the physical vapor deposition of the Ag-Pd alloy is finished,and continuously carrying out physical vapor deposition on a layer of metal Pt as a precoating layer of Rh. There are three reasons for this: firstly, although the normal temperature oxidation resistance and sulfide corrosion resistance of the Ag-Pd alloy are strong, the high temperature oxidation resistance is still insufficient, and the phenomenon of coating discoloration can still occur, but Pt does not. Therefore, a layer of Pt is deposited on the Ag-Pd alloy to completely cover the Ag-Pd alloy coating, so that the Ag-Pd coating is protected, and the defects caused by high-temperature oxidation on the surface of the coating are avoided. In addition, Pd and Pt in the Ag-Pd alloy belong to the same platinum group elements and have high affinity with each other, and in the process of depositing Pt, the alloying reaction of Pd atoms and Pt atoms can occur between two phase interfaces, so that the binding force between the plating layers is enhanced, and the stability of the plating layers is improved. And secondly, Pt and Rh belong to the same platinum group elements, the affinity between the Pt and the Rh is strong, and the Pt coating is used as a pre-coating of the Rh, so that the stability of the whole composite coating is improved. In addition, because of the similarity of certain chemistries of Pt and Rh, Pt plating can also serve as part of the Rh plating where Rh is extremely expensive. And the ductility of Pt is better, and the Rh plating layer with relatively higher hardness is fixed on the Pt plating layer, so that the possibility of falling off during the process of stamping the product can be reduced. Here, physical vapor deposition of Pt is used instead of electroplating Pt, mainly because the main component of the electroplating solution is still P salt (Pt (NH)3)2(NO2)2) When electroplating, a large amount of carcinogenic nitrite is easily generated in the solution, which can seriously pollute the environment. And the electroplating is carried out at about 100 ℃, and the pollution is further aggravated by high-temperature electroplating. In addition, H is easily generated in the electroplating process2And Pt is exactly for H2Has strong absorption capacity, and is easy to permeate into the whole plating layer, thereby causing the plating layer to generate cracks. In addition, because the metal deposition is carried out under the vacuum condition, no air, water or other impurities exist, and the purity of the metal is ensured.
Fifthly, after the physical vapor deposition of Pt is completed, ion implantation of Rh is continued to form a final Rh plating layer (outer plating layer). As mentioned previously, Rh is extremely scarce and quite expensive, far exceeding Au and Pt. Since the cost of the steel strip is increased considerably if the plating or physical vapor deposition of Rh is continued to form a relatively thick layer, since a Pt plating layer is already deposited on the surface of the steel strip, only an appropriate plating method can be selected. Ion implantation of Rh is adopted, a large amount of Rh atoms are doped and permeated to the outer boundary of the Pt coating in vacuum, and finally the extremely thin Pt coating with good uniformity and qualified performance is formed on the surface of the Pt coating. Because Pt and Rh are the same as platinum group elements, have good affinity and can be infinitely mutually dissolved to form a continuous solid solution, and the alloying reaction of Pt atoms and Rh atoms can occur between two phase interfaces, the Rh plating layer can be completely and firmly attached on the Pt plating layer. In addition, by adopting the ion implantation mode, a very thin Rh coating can be formed, and the cracking phenomenon caused by thick coating and large internal stress due to other coating modes is avoided.
In general, the Ni-Cu/Ag-Pd/Pt/Rh composite coating constructed by the invention has the following advantages:
firstly, except Ni and Cu in the inner plating alloy, the other elements of Ag, Pd, Pt and Rh are all noble metals, the excellent physical and chemical properties of the noble metals are kept on the whole, the color is sufficient, and the alloy can be used as a proper Rh plating.
And secondly, the adopted Ni-Cu, Ag-Pd alloy and Pt are soft metals or soft alloys, so that the ductility and plasticity are strong, the processing performance is good, the Rh coating with higher hardness and thinner thickness is fixed on the coatings, the Rh coating can not fall off and crack when a workpiece is stamped, and the stability of the whole composite coating is extremely high.
And thirdly, the alloy elements in each plating layer are infinitely mutually dissolved to form a continuous solid solution, the property of single-phase alloy is presented, and the performance uniformity is good. And the metal elements among the plating layers have strong affinity with each other, so that alloying reaction is easy to occur at the interface. This shows that the construction of the whole composite coating is based on strong internal force of metal atoms, not weak external environment, thereby ensuring high stability of the whole coating.
Compared with the prior art, the invention has the advantages that: a Ni-Cu/Ag-Pd/Pt/Rh composite coating with the thickness of 2.5-3.5 mu m is generated on the surface of the steel strip, the hardness is 70-75 HV, and the surface roughness is 0.020-0.030 μm, porosity not more than 2/cm2The specular reflectivity is 99.92-99.99%, and the surface quality of the coating is good. The specific resistance is 0.05-0.09 mu omega cm, the thermal conductivity is 380-390W/m.K, and the electric conduction and heat conduction performance of the plating layer is good. After being continuously placed for 5000 days at the normal temperature of 25-35 ℃, the surface oxidation area is not more than 0.05 percent, and the light loss rate is not more than 0.07 percent. After the coating is continuously placed at the high temperature of 350-400 ℃ for 5000 hours, the surface oxidation area is not more than 0.07%, the light loss rate is not more than 0.09%, and the oxidation resistance of the coating is good. After the coating is continuously placed for 5000 hours in a 100KHz ultrasonic environment, the thickness of the coating is not obviously changed, and the coating does not fall off or crack, has high stability, and completely meets the requirements of industries such as clocks, jewels, precise instruments and the like.
Detailed Description
The present invention is described in detail below:
table 1 shows the process parameters of the examples of the present invention and the comparative examples;
table 2 shows the properties of the plating layers of the examples of the present invention and the comparative examples.
The following embodiments of the invention are implemented as follows:
1) taking a common low-carbon cold-rolled steel strip as a raw material, and carrying out conventional alkali liquor degreasing and deoiling;
2) washing with water and drying until the surface of the steel strip is free of moisture;
3) annealing in a full hydrogen protective atmosphere, controlling the annealing temperature to be 520-540 ℃, and preserving heat for 10-15 min at the temperature;
4) and (3) plating:
A. carrying out physical vapor deposition on a Ni-Cu alloy, wherein the mass percent of Ni is controlled to be 85-90%, the mass percent of Cu is 15-10%, the deposition rate is controlled to be 0.06-0.07 mu m/min, and the deposition time is 10-12 min;
B. carrying out physical vapor deposition on the Ag-Pd alloy, wherein the mass percent of Ag is controlled to be 88-93%, the mass percent of Pd is controlled to be 12-7%, the deposition rate is controlled to be 0.05-0.09 mu m/min, and the deposition time is 9-11 min;
C. carrying out physical vapor deposition on Pt, wherein the deposition rate is controlled to be 0.04-0.06 mu m/min, and the deposition time is controlled to be 3-5 min;
D. ion implantation of Rh with implantation energy of 190-200 KeV and implantation dosage of Rh of (3-5) x 1019/cm2；
E. Naturally cooling to room temperature.
TABLE 1 Process parameters for examples of the invention and comparative examples
TABLE 1 Process parameters of examples of the invention and comparative examples
TABLE 2 coating Properties of examples of the present invention and comparative examples
As can be seen from Table 2, when Rh is plated according to the process provided by the invention, a Ni-Cu/Ag-Pd/Pt/Rh composite coating with the thickness of 2.5-3.5 microns is formed on the surface of the steel strip, the hardness is 70-75 HV, the surface roughness is 0.020-0.030 microns, the porosity is not more than 2/cm2The specular reflectivity is 99.92-99.99%, and the surface quality of the coating is good. The specific resistance is 0.05-0.09 mu omega cm, the thermal conductivity is 380-390W/m.K, and the electric conduction and heat conduction performance of the plating layer is good. After being continuously placed for 5000 days at the normal temperature of 25-35 ℃, the surface oxidation area is not more than 0.05 percent, and the light loss rate is not more than 0.07 percent. After the coating is continuously placed at the high temperature of 350-400 ℃ for 5000 hours, the surface oxidation area is not more than 0.07%, the light loss rate is not more than 0.09%, and the oxidation resistance of the coating is good. In addition, after the coating is continuously placed for 5000 hours in the 100KHz ultrasonic environment, the thickness of the coating is not obviously changed, and the coating is not subjected to any obvious changeThe coating has high stability and can completely meet the requirements of the industries of clocks, jewels, precise instruments and the like.
The foregoing examples are merely illustrative and are not to be construed as limiting the embodiments of the present invention.
Claims (5)
1. A method for plating rhodium on the surface of a steel strip comprises the following steps:
1) taking a common low-carbon cold-rolled steel strip as a raw material, and carrying out conventional alkali liquor degreasing and deoiling;
2) washing with water and drying until the surface of the steel strip is free of moisture;
3) annealing in a full hydrogen protective atmosphere, controlling the annealing temperature to be 520-540 ℃, and preserving heat for 10-15 min at the temperature;
4) and (3) plating:
A. carrying out physical vapor deposition on a Ni-Cu alloy, controlling the mass percent of Ni to be 85-90%, controlling the mass percent of Cu to be 15-10%, controlling the deposition rate to be 0.06-0.07 mu m/min, and controlling the deposition time to be 10-12 min;
B. carrying out physical vapor deposition on an Ag-Pd alloy, wherein the mass percent of Ag is controlled to be 88-93%, the mass percent of Pd is controlled to be 12-7%, the deposition rate is controlled to be 0.05-0.09 mu m/min, and the deposition time is 9-11 min;
C. carrying out physical vapor deposition on Pt, controlling the deposition rate to be 0.04-0.06 mu m/min, and controlling the deposition time to be 3-5 min;
D. ion implantation of Rh with implantation energy of 190-200 KeV and implantation dosage of Rh of (3-5) x 1019/cm2；
E. Naturally cooling to room temperature.
2. A method of rhodium plating a surface of a steel strip as claimed in claim 1 wherein: in the process of physical vapor deposition of the Ni-Cu alloy, the deposition rate is 0.063-0.068 mu m/min.
3. A method of rhodium plating a surface of a steel strip as claimed in claim 1 wherein: in the process of physical vapor deposition of the Ag-Pd alloy, the deposition rate is 0.054-0.085 mu m/min.
4. A method of rhodium plating a surface of a steel strip as claimed in claim 1 wherein: in the physical vapor deposition Pt process, the deposition rate is 0.045-0.055μm/min.
5. A method of rhodium plating a surface of a steel strip as claimed in claim 1 wherein: in the process of ion implantation of Rh, the implantation energy is 193-198 KeV, and the implantation dosage of Rh is (3.3-4.5) × 1019/cm2。
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| CN105063620A (en) * | 2015-08-07 | 2015-11-18 | 武汉钢铁(集团)公司 | Production method of Zn/Cu-Ag/Cu-Au composite coating steel band for photoelectric material |
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| 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 |
| 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 |
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