CN115491674A - Preparation method of anti-corrosion and anti-pollution copper-nickel-silver cladding layer - Google Patents
Preparation method of anti-corrosion and anti-pollution copper-nickel-silver cladding layer Download PDFInfo
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- CN115491674A CN115491674A CN202211232383.6A CN202211232383A CN115491674A CN 115491674 A CN115491674 A CN 115491674A CN 202211232383 A CN202211232383 A CN 202211232383A CN 115491674 A CN115491674 A CN 115491674A
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
A preparation method of an anticorrosion antifouling copper-nickel-silver cladding layer comprises the following raw material powder in percentage by mass: 57.0-86.7 parts of copper, 10.0-35.0 parts of nickel, 0.1-8.0 parts of silver, 1.0-2.0 parts of iron and 0.5-1.8 parts of manganese; the preparation method is a laser cladding technology and comprises the following steps: the method comprises the following steps of (1) uniformly mixing powder, (2) polishing the surface of a substrate to be smooth and clean, and (3) laser cladding. The cladding layer obtained by the invention contains 2-4% of silver, has good seawater corrosion resistance and marine organism pollution damage resistance, can be applied to protective coatings of metal parts in the fields of ocean engineering and ships, and prolongs the service life of the parts.
Description
Technical Field
The invention belongs to the technical field of laser surface modification, relates to a preparation method for preparing an alloy cladding layer on the surface of a material, and particularly relates to a preparation method for a corrosion-resistant and antifouling copper-nickel-silver laser cladding layer.
Background
For metal parts in marine engineering, the parts are generally damaged by seawater corrosion and marine organism fouling, wherein the marine fouling is more serious. Therefore, metal components in ocean engineering need to be subjected to surface protection treatment. Among the most effective methods of protection is the application of protective coatings to the metal surface.
The metal protective coating which can be applied to ocean engineering comprises copper-based, nickel-based, cobalt-based, iron-based and metal-based composite coatings and the like, and the coating method mainly comprises thermal spraying and electroplating. Generally speaking, coatings related to processes such as thermal spraying, electroplating and the like have the problem of weak adhesion of the coatings to different degrees, so that the coatings are difficult to meet the requirements of marine engineering, particularly the service working conditions of ship propellers serving as power systems. Moreover, the above-mentioned coating is difficult to be applied as a corrosion-resistant antifouling coating because the antifouling property is limited or not sufficient, in addition to the copper-based coating.
From the viewpoint of antifouling effect, the metal ions having the best antifouling and antibacterial properties are ions such as silver, copper, and nickel, which are the reasons for the excellent antifouling properties of copper-nickel alloys and silver alloys, and silver and copper are often added to metals and coatings to exhibit excellent antibacterial properties. Copper-nickel alloys such as cupronickel (B30 and B10) have excellent seawater corrosion resistance in view of corrosion resistance, and are widely used in seawater piping systems such as ship cooling water piping, fire water piping of offshore oil platforms, heat exchangers of coastal power plants, and brine heaters of seawater desalination multistage flash evaporation apparatuses. Silver is also commonly used as an alloying element to improve pitting corrosion resistance of structural materials such as steel. However, silver has very low solubility in both copper and nickel, and the solubility at room temperature is close to 0. Therefore, silver forms only a two-phase alloy with them, and in seawater, such an alloy causes severe galvanic corrosion, resulting in poor corrosion resistance, and thus cannot be practically used as a corrosion-resistant coating.
Laser cladding is an advanced technology for preparing high-performance wear-resistant and corrosion-resistant metal coatings, and is widely used for preparing surface protective coatings of metal components in the fields of metallurgy, petrifaction, electric power, aviation, aerospace and the like. Compared with the fusion welding technology, the laser cladding coating is a fast solidification structure, has high solid solubility of alloy elements, and has the outstanding advantages of fine structure, small component segregation, small heat affected zone, metallurgical bonding with a matrix interface and the like. For extreme stressThe advantages of the laser cladding coating are particularly obvious in the wear-resistant and corrosion-resistant application under the working condition of the etching. Rapid cooling of the laser melt pool (up to 10) despite the very low solubility of silver in copper, nickel 6 K/s) results in a substantial increase in the solubility of silver and a copper-nickel-silver solid solution is obtained which cannot be formed in equilibrium. The invention discloses a preparation method of a copper-nickel-silver alloy coating by a laser cladding method, and research results show that the corrosion resistance and the antifouling performance of the copper-nickel-silver coating are obviously superior to those of an aluminum bronze matrix and B10 and B30 alloys in simulated seawater inoculated with marine microorganisms, and the copper-nickel-silver coating has a good application prospect. So far, reports about laser cladding antifouling coatings are very rare, and laser cladding copper-nickel-silver coatings are not seen yet and are applied to the field of corrosion resistance and antifouling.
Disclosure of Invention
The invention aims to provide a preparation method of an anti-corrosion and anti-fouling copper-nickel-silver cladding layer. The coating prepared by the method is a rapid solidification structure, the silver content in the coating reaches 2-4%, the silver content is obviously higher than that of an equilibrium structure component, and the coating has enhanced corrosion resistance and antifouling property.
The preparation method of the corrosion-resistant and pollution-resistant copper-nickel-silver cladding layer is characterized by comprising the following steps of:
1. raw material powder of an anti-corrosion and anti-fouling copper-nickel-silver cladding layer comprises the following components in percentage by mass: 57.0 to 86.7 parts of copper, 10.0 to 35.0 parts of nickel, 0.1 to 8.0 parts of silver, 1.0 to 2.0 parts of iron and 0.5 to 1.8 parts of manganese. Putting the raw material powder into a sealed container, and putting the sealed container into a mixer to mix for 5~8 hours;
2. laser cladding takes an aluminum bronze plate as a substrate, the surface of the substrate is polished to be flat, smooth and clean by No. 200 abrasive paper, and the substrate is dried after being deoiled by acetone and absolute ethyl alcohol; then, uniformly pre-coating the raw material powder obtained in the step 1 on a substrate for 1.0 to 2.0 millimeters; and then, preparing the copper-nickel-silver cladding layer by adopting a laser cladding process. The laser used for laser cladding is a 3 kilowatt semiconductor laser (the central wavelength is 980 nm), and the cladding process parameters are as follows: the power is 1.8 to 2.6 kilowatts, the diameter of a light spot is 2~4 mm, the scanning speed is 600 to 1200 mm per minute, the lap joint rate is 20 to 50 percent, and the protective atmosphere is argon. In the laser cladding process, the substrate is preferably cooled by circulating cooling water. Thus obtaining the anti-corrosion and anti-fouling copper-nickel-silver cladding layer.
According to the preparation method of the anticorrosive antifouling copper-nickel-silver cladding layer, the raw material powder is inert gas atomized powder, the shape of the powder is nearly spherical, and the granularity is 60-150 micrometers.
The preparation method of the anticorrosion antifouling copper-nickel-silver cladding layer comprises the following steps of adding silver powder in the form of copper-silver alloy powder, wherein the silver powder comprises the following components in percentage by mass: 71.0 to 73.0 percent of silver, less than or equal to 0.05 percent of oxygen and the balance of copper.
The preparation method of the corrosion-resistant and pollution-resistant copper-nickel-silver cladding layer is characterized in that the purity of the copper, nickel, iron and manganese powder is 99.5%.
The invention has the advantages and effects that:
the invention provides a preparation method of a corrosion-resistant antifouling copper-nickel-silver cladding layer, which is prepared by adopting a laser cladding process. The prepared corrosion-resistant and antifouling copper-nickel-silver cladding layer is a copper-nickel-silver solid solution or a copper-nickel-silver solid solution with a small amount of dispersed fine silver particles, and has the defects of fine tissue, no crack, no air hole and the like. Because the laser cladding layer is a rapid solidification structure, the content of silver dissolved in the coating can reach 2-4 percent and is far higher than the content (approximate to 0) in a copper-silver alloy and nickel-silver alloy equilibrium phase diagram. Through corrosion resistance and antifouling property detection, compared with corrosion-resistant antifouling copper-nickel alloys (B30 and B10) and aluminum bronze matrixes widely applied in the field of ocean engineering, the prepared cladding layer has higher seawater corrosion resistance and marine microorganism fouling resistance, and can be applied as a corrosion-resistant antifouling coating of metal parts in the field of ocean engineering. The prepared cladding layer has good corrosion resistance and the synergistic antifouling effect of copper ions, nickel ions and silver ions, so that the service life of the matrix can be greatly prolonged, and the antifouling effect is broad-spectrum, efficient, safe and lasting.
Detailed Description
Example 1
A preparation method of an anti-corrosion and anti-fouling copper-nickel-silver cladding layer comprises the following steps:
1. raw material powder of an anticorrosion antifouling copper-nickel-silver cladding layer comprises the following components in percentage by mass: 65.0 parts of copper, 32.0 parts of nickel, 1.5 parts of silver, 1.0 part of iron and 0.5 part of manganese. The above raw material powders were put in a sealed container and mixed in a blender for 5 hours. The raw material powder is inert gas atomized powder, the shape of the raw material powder is nearly spherical, and the granularity is 60 to 150 micrometers. The silver powder is added in the form of copper-silver alloy powder, and the mass percentage of the silver powder is as follows: 72.1 parts of silver, less than or equal to 0.05 part of oxygen and the balance of copper. The purity of the copper, nickel, iron and manganese powder is 99.5 percent;
2. the laser cladding takes a manganese-aluminum bronze plate as a substrate, the surface of the substrate is polished to be flat, smooth and clean by No. 200 abrasive paper, and the substrate is dried after being deoiled by acetone and absolute ethyl alcohol; then, uniformly pre-coating the raw material powder obtained in the step 1 on a substrate by 1.5 mm; and then preparing the copper-nickel-silver cladding layer by adopting a laser cladding process. LaserFusion furnaceThe laser used for cladding is a 3 kilowatt semiconductor laser (the central wavelength is 980 nm), and the cladding process parameters are as follows: the power is 2.0 kilowatt, the diameter of a light spot is 3 millimeters, the scanning speed is 700 millimeters per minute, the lap joint rate is 30 percent, and the protective atmosphere is argon. In the laser cladding process, the substrate is preferably cooled by circulating cooling water. Thus obtaining the anti-corrosion and anti-fouling copper-nickel-silver cladding layer.
Example 2
A preparation method of an anti-corrosion and anti-fouling copper-nickel-silver cladding layer comprises the following steps:
1. raw material powder of an anticorrosion antifouling copper-nickel-silver cladding layer comprises the following components in percentage by mass: 77.5 parts of copper, 15.0 parts of nickel, 5.0 parts of silver, 1.5 parts of iron and 1.0 part of manganese. The above raw material powders were put in a sealed container and mixed in a blender for 6 hours. The raw material powder is inert gas atomized powder, the shape of the raw material powder is nearly spherical, and the granularity is 60 to 150 micrometers. The silver powder is added in the form of copper-silver alloy powder, and the mass percentage of the silver powder is as follows: 72.1 parts of silver, less than or equal to 0.05 part of oxygen and the balance of copper. The purity of the copper, nickel, iron and manganese powder is 99.5 percent;
2. laser cladding takes a high manganese aluminum bronze plate as a substrate, firstly, 200 # abrasive paper is used for polishing the surface of the substrate to be flat, smooth and clean, and after acetone and absolute ethyl alcohol are used for removing oil, the substrate is dried; then, uniformly pre-coating the raw material powder obtained in the step 1 on a substrate by 2.0 mm; and then preparing the copper-nickel-silver cladding layer by adopting a laser cladding process. LaserFusion furnaceThe laser used is a 3 kilowatt semiconductor laser (central wavelength)980 nm), cladding technological parameters are as follows: the power is 2.2 kilowatts, the diameter of a light spot is 3 millimeters, the scanning speed is 800 millimeters per minute, the lap joint rate is 35 percent, and the protective atmosphere is argon. In the laser cladding process, the substrate is preferably cooled by circulating cooling water. Thus obtaining the anti-corrosion and anti-fouling copper-nickel-silver cladding layer.
Example 3
A preparation method of an anti-corrosion and anti-fouling copper-nickel-silver cladding layer comprises the following steps:
1. raw material powder of an anticorrosion antifouling copper-nickel-silver cladding layer comprises the following components in percentage by mass: 80.0 parts of copper, 11.0 parts of nickel, 6.0 parts of silver, 1.8 parts of iron and 1.2 parts of manganese. The above raw material powders were put in a sealed container and mixed in a blender for 8 hours. The raw material powder is inert gas atomized powder, the shape of the raw material powder is nearly spherical, and the granularity is 60 to 150 micrometers. The silver powder is added in the form of copper-silver alloy powder, and the mass percentage of the silver powder is as follows: 72.1 parts of silver, less than or equal to 0.05 part of oxygen and the balance of copper. The purity of the copper, nickel, iron and manganese powder is 99.5 percent;
2. laser cladding takes a nickel-aluminum bronze plate as a substrate, firstly, 200 # abrasive paper is used for polishing the surface of the substrate to be flat, smooth and clean, oil is removed through acetone and absolute ethyl alcohol, and then drying is carried out; then, uniformly pre-coating the raw material powder obtained in the step 1 on a substrate by 2.0 mm; and then preparing the copper-nickel-silver cladding layer by adopting a laser cladding process. Laser beamFusion furnaceThe laser used for cladding is a 3 kilowatt semiconductor laser (the central wavelength is 980 nm), and the cladding process parameters are as follows: the power is 2.4 kilowatts, the diameter of a light spot is 3 millimeters, the scanning speed is 1000 millimeters per minute, the lap joint rate is 35 percent, and the protective atmosphere is argon. In the laser cladding process, the substrate is preferably cooled by circulating cooling water. Thus obtaining the anti-corrosion and anti-fouling copper-nickel-silver cladding layer.
Claims (4)
1. A preparation method of an anticorrosion antifouling copper-nickel-silver cladding layer is characterized by comprising the following steps:
(1) Raw material powder of an anticorrosion antifouling copper-nickel-silver cladding layer comprises the following components in percentage by mass: 57.0 to 86.7 parts of copper, 10.0 to 35.0 parts of nickel, 0.1 to 8.0 parts of silver, 1.0 to 2.0 parts of iron and 0.5 to 1.8 parts of manganese, putting the raw material powder into a sealed container, and mixing the raw material powder in a mixer for 5~8 hours;
(2) The laser cladding takes an aluminum bronze plate as a substrate, the surface of the substrate is polished to be flat, smooth and clean by No. 200 abrasive paper, and the substrate is dried after being degreased by acetone and absolute ethyl alcohol; then, uniformly pre-coating the raw material powder obtained in the step (1) on a substrate for 1.0 to 2.0 millimeters; then, a laser cladding process is adopted to prepare a copper-nickel-silver cladding layer, a laser used for laser cladding is a 3 kilowatt semiconductor laser (the central wavelength is 980 nanometers), and the cladding process parameters are as follows: the power is 1.8 to 2.6 kilowatts, the diameter of a light spot is 2~4 mm, the scanning speed is 600 to 1200 mm per minute, the lap joint rate is 20 to 50 percent, the protective atmosphere is argon, and the substrate is cooled by circulating cooling water in the laser cladding process, so that the anticorrosion and antifouling copper-nickel-silver cladding layer is obtained.
2. The method for preparing the corrosion-resistant and pollution-resistant copper-nickel-silver cladding layer according to claim 1, wherein the raw material powder is inert gas atomized powder, the shape of the inert gas atomized powder is nearly spherical, and the particle size of the inert gas atomized powder is 60 to 150 micrometers.
3. The preparation method of the corrosion-resistant and pollution-resistant copper-nickel-silver cladding layer according to claim 1, wherein the silver powder is added in the form of copper-silver alloy powder, and the mass percentage of the silver powder is as follows: 71.0 to 73.0 percent of silver, less than or equal to 0.05 percent of oxygen and the balance of copper.
4. The method for preparing an anti-corrosion and anti-fouling copper-nickel-silver cladding layer according to claim 1, wherein the purity of the copper, nickel, iron and manganese powder is 99.5%.
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Citations (3)
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| JP2016117194A (en) * | 2014-12-19 | 2016-06-30 | 三菱エンジニアリングプラスチックス株式会社 | Resin metal composite and manufacturing method therefor |
| CN112176337A (en) * | 2020-09-30 | 2021-01-05 | 万事泰集团(广东)技术研究有限公司 | Laser cladding biological metal ceramic pot and preparation method thereof |
| CN113953712A (en) * | 2021-10-11 | 2022-01-21 | 西安理工大学 | Material for butt welding of TA1-Q235 composite plates and welding method |
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- 2022-10-10 CN CN202211232383.6A patent/CN115491674A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016117194A (en) * | 2014-12-19 | 2016-06-30 | 三菱エンジニアリングプラスチックス株式会社 | Resin metal composite and manufacturing method therefor |
| CN112176337A (en) * | 2020-09-30 | 2021-01-05 | 万事泰集团(广东)技术研究有限公司 | Laser cladding biological metal ceramic pot and preparation method thereof |
| CN113953712A (en) * | 2021-10-11 | 2022-01-21 | 西安理工大学 | Material for butt welding of TA1-Q235 composite plates and welding method |
Non-Patent Citations (1)
| Title |
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| 贺春林等: "高锰铝青铜表面激光熔覆铜基合金的耐蚀性能", 沈阳大学学报(自然科学版), pages 5 - 9 * |
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