CN111394695B - Method for plating palladium on surface of steel strip - Google Patents
Method for plating palladium on surface of steel strip Download PDFInfo
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- CN111394695B CN111394695B CN202010278447.0A CN202010278447A CN111394695B CN 111394695 B CN111394695 B CN 111394695B CN 202010278447 A CN202010278447 A CN 202010278447A CN 111394695 B CN111394695 B CN 111394695B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000007747 plating Methods 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 43
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 32
- 239000010959 steel Substances 0.000 title claims abstract description 32
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 15
- 229910017944 Ag—Cu Inorganic materials 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 239000010960 cold rolled steel Substances 0.000 claims abstract description 8
- 238000005238 degreasing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000005240 physical vapour deposition Methods 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 27
- 239000000956 alloy Substances 0.000 claims description 27
- 238000000151 deposition Methods 0.000 claims description 25
- 230000008021 deposition Effects 0.000 claims description 24
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 238000002513 implantation Methods 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 238000005468 ion implantation Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 abstract description 47
- 239000011248 coating agent Substances 0.000 abstract description 44
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000002310 reflectometry Methods 0.000 abstract description 8
- 238000010301 surface-oxidation reaction Methods 0.000 abstract description 8
- 238000004891 communication Methods 0.000 abstract description 5
- 230000003746 surface roughness Effects 0.000 abstract description 5
- 230000005693 optoelectronics Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 239000010949 copper Substances 0.000 description 18
- 238000009713 electroplating Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 229910052737 gold Inorganic materials 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 4
- 229910001316 Ag alloy Inorganic materials 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000010953 base metal 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
- 239000010931 gold Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- 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
- C23C14/22—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
-
- 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
- C23C14/54—Controlling or regulating the coating process
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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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G3/00—Apparatus for cleaning or pickling metallic material
- C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Physical Vapour Deposition (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
一种钢带表面镀钯方法：以普通低碳冷轧钢带为原料并脱脂除油；水洗并烘干；在全氢保护气氛下退火；镀覆；自然空冷。本发明在钢带表面生成厚度1~2µm的Ni/Ag‑Cu/Au/Pd复合镀层，其硬度62~68 HV，表面粗糙度0.015~0.030µm，孔隙率不超过2个/cm2，镜面反射率99.90~99.99%；电阻率0.03~0.06µΩ∙cm，热导率390~400 W/m∙K；在常温下连续放置5000 d后，表面氧化面积不超过0.03%，失光率不超过0.05%；在350~400℃下连续放置5000 h后，表面氧化面积不超过0.06%，失光率不超过0.08%；在100 KHz超声波下连续放置5000 h后，镀层厚度无变化，也未出现脱落和裂纹，完全满足光电、通信等行业的需要。A method for palladium plating on the surface of a steel strip: taking ordinary low-carbon cold-rolled steel strips as raw materials, degreasing and degreasing; washing with water and drying; annealing in a full hydrogen protective atmosphere; plating; and natural air cooling. In the invention, a Ni/Ag-Cu/Au/Pd composite coating with a thickness of 1-2 µm is formed on the surface of the steel strip, the hardness is 62-68 HV, the surface roughness is 0.015-0.030 µm, the porosity is not more than 2/cm 2 , and the mirror surface is Reflectivity 99.90~99.99%; resistivity 0.03~0.06µΩ∙cm, thermal conductivity 390~400 W/m∙K; after being placed at room temperature for 5000 d continuously, the surface oxidation area does not exceed 0.03%, and the loss rate does not exceed 0.03% 0.05%; after being continuously placed at 350~400 ℃ for 5000 h, the surface oxidation area does not exceed 0.06%, and the loss of light does not exceed 0.08%; after 5000 h of continuous placement under 100 KHz ultrasonic wave, the coating thickness does not change, nor does it appear Falling off and cracks, fully meet the needs of optoelectronics, communications and other industries.
Description
Technical Field
The invention relates to a material surface treatment method, in particular to a method for plating palladium on the surface of a steel strip, which is widely applied to the industries of photoelectricity, communication, clocks, jewelry, precise instruments, medical appliances and the like.
Background
Palladium (Pd) is an important noble metal, has good ductility, surface property, conductivity, heat conductivity, oxidation resistance and the like, and is widely used in the industries of photoelectricity, communication, clocks and watches, jewelry, precision instruments, medical appliances and the like. However, since Pd is a rare element in the earth crust and is expensive, the application of Pd 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 Pd with a Pd-plated steel strip and realize certain service performance through a Pd plating layer.
In the traditional palladium plating process for the steel strip, single metals such as Cu, Ni, Ag, Pd and the like are continuously and sectionally plated on the surface of the cold-rolled steel strip to form a Cu/Ni/Ag/Pd composite plating layer. It has the following disadvantages:
first, since the plating layer uses Cu as an inner plating layer, it is easily oxidized, resulting in a decrease in stability of the plating layer. In addition, once the corrosion medium passes through the pores of Ag, Ni and Cu through the cracks and pinholes of the Pd coating and reaches the Fe matrix, the Fe matrix is an anode of a corrosion couple, and the Fe matrix is quickly corroded to generate rusty spots, so that the stability of the whole composite coating is greatly reduced.
Second, H is easily precipitated in the process of plating 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 Pd plating process cannot follow up in time, more defects are generated on the surface of the Ag plating layer, the stability of the Pd 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 Pd plating is more unfavorable.
Fourthly, in the process of plating Pd, the main problems are that: firstly, H is easy to be separated out in the electroplating process2And Pd is right for H2Has strong absorption capacity, is easy to permeate into the whole plating layer to generate hydrogen embrittlement phenomenon, and leads the plating layer to generateAnd (5) cracking. And Pd is one of the most rare noble metals in the world, the content of Pd in the crust is only one billion, the total yield per year is less than 5 per thousand of Au, and the Pd is much less than Au and Pt. Therefore, Pd is extremely expensive, far exceeding Au and Pt. The latest data provided by london exchange in 2020 shows that: the price per ounce of Pd is about 2-3 times that of Pt or 1.5 times that of Au. The electroplating process is adopted to plate Pd, and because the current efficiency is difficult to reach 100 percent, the thickness of a plating layer cannot be accurately controlled, more waste liquid can be generated, and a great amount of Pd is wasted. 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 the energy consumption is high, but also the surface of the plating layer is easy to generate passivation effect, so that the surface quality of the Pd plating layer is often poor, the pores are large, the stress is large, and the glossiness is low.
Therefore, the traditional process for forming the Pd 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:
chinese patent publication No. CN105887085A discloses "a method for producing an extremely thin steel strip plated with noble metal". The steel strip is produced by taking a common DC01 cold-rolled steel plate as a substrate and adopting the processes of electroplating Zn-Fe alloy, physical vapor deposition Ni-Au alloy (or Ni-Ag alloy) and physical vapor deposition Ni-Pd alloy, wherein a Zn-Fe/Ni-Au (or Ni-Ag)/Ni-Pd composite coating with the thickness of 4.7-5.3 mu m is generated on the surface of the steel strip, the surface roughness is 0.05-0.10 mu m, the specular reflectivity is 99-99.9%, after the steel strip is placed for 1800 days under the indoor normal atmospheric condition, the specular reflectivity of the coating is 98.7-99.7%, the light loss rate is not more than 0.5%, and the corrosion area is not more than 0.05%; in the presence of 30ppm H2After the coating is exposed in the air for 1200 days, the specular reflectivity of the coating is 98.5-99.5%, the light loss rate is not more than 0.6%, and the corrosion area is not more than 0.08%. The plating layer has high stability, good surface performance and corrosion resistance, and completely meets the requirements of jewelry and instrument industries.
However, the Pd plating process proposed in this document still has several significant problemsTitle: first, the Zn-Fe alloy as the inner plating layer has high hardness, poor ductility, and poor workability. When a workpiece is punched, the deformation between the plating layer and the substrate is inconsistent, the workpiece is easy to pulverize and fall off, and the stability is not high. In addition, in the Zn-Fe alloy, both Zn and Fe are active metals, and the alloy also belongs to a primary battery, and the corrosion resistance of the alloy is insufficient. In an acidic environment, the coating is easily corroded, and the inner plating layer is unstable. Second, Ni-Au or Ni-Ag alloys as the intermediate plating layer are not miscible with each other due to poor affinity between Ni and Au or Ag. Both Ni-Au and Ni-Ag alloys are difficult to form continuous solid solutions at normal temperature and do not have the property of single-phase alloys, for example, the Ni-Au alloy can be decomposed into Au-rich and Ni-rich two-phase solid solutions at normal temperature. As a result, the entire alloy exhibits loose, isolated structural or interfacial features and lacks uniformity in the metallurgical properties. This results in poor stability of the intermediate plating layer and difficulty in connecting and stabilizing the inner and outer plating layers. Thirdly, the Ni-Pd alloy used as the outer coating is used for replacing pure Pd, although the use amount of Pd can be reduced to save the cost, the Ni belongs to base metal, and the Pd belongs to noble metal, the great difference of the physicochemical properties of the Ni and the Pd can cause that the comprehensive use performance of the Ni-Pd alloy can not be comparable with that of the pure Pd, the color of the coating is insufficient, and the possibility that the product performance can not reach the standard still exists in the industry with strict requirements. Furthermore, in this document, the main purpose is to produce Au-or Ag-plated steel strips, the main purpose of Pd-plating being merely to prevent the Au or Ag layer from being H-plated as a simple subsequent surface protection measure2The corrosion of sulfide such as S is not due to the unique precious property of Pd, and the attention is limited. Therefore, the stability of the composite coatings constructed in this way as described in the literature is still insufficient and the product performance is still 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/Ag-Cu/Au/Pd composite coating with the thickness of 1-2 mu m on the surface of a steel strip, wherein the hardness is 62-68 HV, the surface roughness is 0.015-0.030 mu m, the porosity is not more than2 pieces/cm2The mirror surface reflectivity is 99.90-99.99%; the resistivity is 0.03-0.06 mu omega-cm, and the thermal conductivity is 390-400W/m-K; after being continuously placed for 5000 days at normal temperature, namely 25-35 ℃, the surface oxidation area is not more than 0.03 percent, and the light loss rate is not more than 0.05 percent. After being continuously placed for 5000 hours at the high temperature of 350-400 ℃, the surface oxidation area is not more than 0.06 percent, and the light loss rate is not more than 0.08 percent; after the steel strip is continuously placed for 5000 hours in a 100KHz ultrasonic environment, the thickness of a plating layer is not obviously changed, and the steel strip does not fall off or crack, so that the plating layer stability is high.
The measures for realizing the aim are as follows:
a method for plating palladium 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 540-560 ℃, and preserving heat for 8-12 min at the temperature;
4) and (3) plating:
A. carrying out physical vapor deposition on Ni, wherein the deposition rate is controlled to be 0.03-0.05 mu m/min, and the deposition time is controlled to be 5-8 min;
B. carrying out physical vapor deposition on the Ag-Cu alloy, wherein the mass percent of Ag is controlled to be 78-87%, the mass percent of Cu is controlled to be 22-13%, the deposition rate is controlled to be 0.04-0.07 mu m/min, and the deposition time is 4-6 min;
C. performing physical vapor deposition of Au, wherein the deposition rate is controlled to be 0.07-0.10 mu m/min, and the deposition time is controlled to be 7-9 min;
D. ion implantation of Pd, wherein the implantation energy is controlled to be 170-180 KeV, and the implantation dose of Pd is (4-6) x 1019/cm2；
E. Naturally cooling to room temperature.
Preferably: in the process of physical vapor deposition of Ni, the deposition rate is 0.033-0.047 mu m/min.
Preferably: in the process of physical vapor deposition of the Ag-Cu alloy, the mass percent of Ag is 78-83%, the mass percent of Cu is 22-17%, and the deposition rate is 0.045-0.067 mu m/min.
Preferably: in the process of physical vapor deposition of Au, the deposition rate is 0.075-0.095 μm/min.
Preferably: in the process of ion implantation of Pd, the implantation energy is 173-178 KeV, and the implantation dose of Pd is (4.3-5.5) × 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, total hydrogen annealing, physical vapor deposition of Ni, physical vapor deposition of Ag-Cu alloy, physical vapor deposition of Au and ion implantation of Pd for surface treatment, because:
first, the surface of the cold-rolled steel strip must be kept clean before the coating process, and appropriate pretreatment is performed. Wherein, the alkali degreasing is mainly used for removing 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 metal Ni is physically deposited on the surface of the steel strip in a vapor phase mode to be used as an inner plating layer. Since Ni has a much stronger corrosion resistance than Cu, it is used as an inner plating layer and the stability is greatly improved. Compared with the Cu/Ni double plating layer formed by 'electroplating Cu → electroplating Ni' segmented electroplating in the traditional process, the pure Ni plating layer overcomes the defects of two-phase separation and uneven metallurgical performance of the interface of the double plating layer, and the stability of the plating layer is naturally increased. Moreover, the two electroplating processes are combined into one physical vapor deposition process, so that the process flow is shortened, and the waste liquid discharge is reduced. Here, the inner plating layer is formed using a physical vapor deposition Ni process because it can prevent a hydrogen embrittlement phenomenon generated during the Ni electroplating. Meanwhile, 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.
Thirdly, after the physical vapor deposition of Ni is finished, continuing to perform the physical vapor deposition of a layer of Ag-Cu alloy as an intermediate coating. Physical vapor deposition of Ag-Cu alloys is used here instead of electroplating Ag for four reasons: 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 Cu is added as an alloy element to form the Ag-Cu alloy, the normal-temperature oxidation resistance and sulfide corrosion resistance of the Ag-Cu 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 Cu belong to the copper group elements, have strong affinity with each other, can be dissolved in each other infinitely, so that a continuous solid solution, namely an Ag-Cu single-phase alloy is formed, has excellent electric conductivity, heat conductivity and extensibility, is small in brittleness, moderate in hardness and low in price, can replace pure Ag, and greatly improves the stability of the whole plating layer. And fourthly, after Cu is added as an alloy element, as Cu and Ni can be dissolved in each other infinitely to form a continuous solid solution, in the process of depositing the Ag-Cu alloy on the surface of the Ni coating, Cu atoms and Ni atoms of a two-phase interface can generate an alloying reaction, 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-Cu alloy is finished, a layer of metal Au is continuously deposited in a physical vapor deposition mode to be used as a pre-plating layer of Pd. There are two reasons for this: firstly, although the normal temperature oxidation resistance and sulfide corrosion resistance of the Ag-Cu alloy are strong, the high temperature oxidation resistance is still insufficient, and the phenomenon of plating layer discoloration can still occur, but Au does not. Therefore, a layer of Au is deposited on the Ag-Cu alloy to completely cover the Ag-Cu alloy coating, so that the Ag-Cu coating is protected, and the defects caused by oxidation on the surface of the coating are avoided. Cu, Ag and Au belong to the copper group elements, have high affinity with each other, and the Au plating layer can completely stabilize the Ag-Cu plating layer. And secondly, Au is a noble metal, the performance of the Au is similar to that of Pd, and the addition of Au can not only improve the color of the whole composite plating layer, but also play the role of part of Pd. And because the electric conduction and the heat conduction of the Cu, the Ag and the Au are all very excellent, a layer of Au is deposited on the Ag-Cu plating layer, the comprehensive performance of the whole plating layer is only enhanced, and the stability is improved. Here, physical vapor deposition of Au is adopted instead of plating Au, mainly because the latter requires the use of highly toxic cyanide as plating solution, which causes serious environmental pollution. Meanwhile, 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 Au is finished, ion implantation of Pd is continued to form a final Pd plating layer (outer plating layer). As mentioned above, Pd is extremely rare and expensive, far exceeding Au and Pt, and since the Au plating layer is already deposited on the surface of the steel strip, if the plating or the physical vapor deposition of a thicker Pd layer is continued, the cost will be greatly increased, and therefore, only the proper plating method can be selected. Ion implantation of Pd is adopted, a large number of Pd atoms are doped and permeated to the outer boundary of the Au plating layer in vacuum, and finally the extremely thin Pd plating layer with good uniformity and qualified performance is formed on the surface of the Au plating layer. Because Pd and Au have good affinity and can be dissolved in each other infinitely to form a continuous solid solution, and the alloying reaction of Au atoms and Pd atoms can occur between interfaces, the Pd plating layer can be completely and firmly attached on the Au plating layer.
In general, the Ni/Ag-Cu/Au/Pd composite plating layer constructed by the invention has the following advantages:
firstly, except a small amount of Cu contained in the inner plating layer Ni and the middle plating layer, the other elements of Ag, Au and Pd are noble metals, the excellent physical and chemical properties of the noble metals are integrally reserved, the color is sufficient, and the alloy can be used as a proper Pd plating layer.
And secondly, the adopted Ni, Ag-Cu alloy, Au and Pd are soft metals or soft alloys, the formed plating layer has moderate hardness, strong adhesive force and good ductility and plasticity, the dropping and the cracking can not occur when a workpiece is punched, and the stability of the whole composite plating layer 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/Ag-Cu/Au/Pd composite coating with the thickness of 1-2 mu m is generated on the surface of the steel strip, the hardness of the coating is 62-68 HV, the surface roughness is 0.015-0.030 mu m, and the porosity is not more than 2/cm2The specular reflectivity is 99.90-99.99%, and the surface quality of the coating is good. The electrical resistivity is 0.03-0.06 mu omega-cm, the thermal conductivity is 390-400W/m-K, and the electric conduction and heat conduction performance of the coating is good. After being continuously placed for 5000 days at the normal temperature of 25-35 ℃, the surface oxidation area is not more than 0.03 percent, and the light loss rate is not more than 0.05 percent. After the coating is continuously placed for 5000 hours at the high temperature of 350-400 ℃, the surface oxidation area is not more than 0.06%, the light loss rate is not more than 0.08%, and the oxidation resistance of the coating is good. In addition, 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 photoelectricity, communication, clocks, jewelry, precise instruments, medical appliances 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 540-560 ℃, and preserving heat for 8-12 min at the temperature;
4) and (3) plating:
A. carrying out physical vapor deposition on Ni, wherein the deposition rate is controlled to be 0.03-0.05 mu m/min, and the deposition time is controlled to be 5-8 min;
B. carrying out physical vapor deposition on the Ag-Cu alloy, wherein the mass percent of Ag is controlled to be 78-87%, the mass percent of Cu is controlled to be 22-13%, the deposition rate is controlled to be 0.04-0.07 mu m/min, and the deposition time is 4-6 min;
C. performing physical vapor deposition of Au, wherein the deposition rate is controlled to be 0.07-0.10 mu m/min, and the deposition time is controlled to be 7-9 min;
D. ion implantation of Pd, wherein the implantation energy is controlled to be 170-180 KeV, and the implantation dose of Pd is (4-6) x 1019/cm2；
E. Naturally cooling to room temperature.
TABLE 1 Process parameters for 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, the Pd plating is carried out according to the process provided by the invention, the Ni/Ag-Cu/Au/Pd composite plating layer with the thickness of 1-2 μm is generated on the surface of the steel strip, the hardness is 62-68 HV, the surface roughness is 0.015-0.030 μm, and the porosity is not more than 2/cm2The specular reflectivity is 99.90-99.99%, and the surface quality of the coating is good. The electrical resistivity is 0.03-0.06 mu omega-cm, the thermal conductivity is 390-400W/m-K, and the electric conduction and heat conduction performance of the coating is good. After being continuously placed for 5000 days at the normal temperature of 25-35 ℃, the surface oxidation area is not more than 0.03 percent, and the light loss rate is not more than 0.05 percent. After being continuously placed for 5000 hours at the high temperature of 350-400 ℃, the surface oxidation area is not more than 0.06 percent, and the light loss rate is not more than 008 percent, and the oxidation resistance of the plating layer is good. In addition, 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 photoelectricity, communication, clocks, jewelry, precise instruments, medical appliances and the like.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention.
Claims (4)
1. A method for plating palladium 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 540-560 ℃, and preserving heat for 8-12 min at the temperature;
4) and (3) plating:
A. carrying out physical vapor deposition on Ni, controlling the deposition rate to be 0.03-0.05 mu m/min, and controlling the deposition time to be 5-7.5 min;
B. carrying out physical vapor deposition on an Ag-Cu alloy, controlling the mass percent of Ag to be 78-87%, the mass percent of Cu to be 22-13%, controlling the deposition rate to be 0.04-0.07 mu m/min, and controlling the deposition time to be 4-6 min;
C. performing physical vapor deposition of Au, wherein the deposition rate is controlled to be 0.07-0.095 mu m/min, and the deposition time is 7-9 min;
D. ion implantation of Pd, wherein the implantation energy is controlled to be 170-180 KeV, and the implantation dose of Pd is (4-6) x 1019/cm2；
E. Naturally cooling to room temperature.
2. The method of claim 1, wherein the palladium plating is performed on the surface of the steel strip by: in the process of physical vapor deposition of Ni, the deposition rate is 0.033-0.047 mu m/min.
3. The method of claim 1, wherein the palladium plating is performed on the surface of the steel strip by: in the process of physical vapor deposition of the Ag-Cu alloy, the mass percent of Ag is 78-83%, the mass percent of Cu is 22-17%, and the deposition rate is 0.045-0.067 mu m/min.
4. The method of claim 1, wherein the palladium plating is performed on the surface of the steel strip by: in the process of ion implantation of Pd, the implantation energy is 173-178 KeV, and the implantation dose of Pd is (4.3-5.5) × 1019/cm2。
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| CN105887146A (en) * | 2016-04-22 | 2016-08-24 | 武汉钢铁股份有限公司 | Production method of plating steel belt for household gas wares |
| CN105887085A (en) * | 2016-04-22 | 2016-08-24 | 武汉钢铁股份有限公司 | Production method of ultra-thin steel belt plated with precious metal |
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