CN108754388B - Metal/polymer composite powder core wire, metal/polymer composite coating and preparation method thereof - Google Patents

Metal/polymer composite powder core wire, metal/polymer composite coating and preparation method thereof Download PDF

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CN108754388B
CN108754388B CN201810549939.1A CN201810549939A CN108754388B CN 108754388 B CN108754388 B CN 108754388B CN 201810549939 A CN201810549939 A CN 201810549939A CN 108754388 B CN108754388 B CN 108754388B
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metal
polymer composite
coating
polymer
powder core
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CN108754388A (en
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所新坤
王晓霞
黄晶
龚永锋
周平
陈秀勇
李华
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/129—Flame spraying
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying

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  • Coating By Spraying Or Casting (AREA)
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Abstract

The invention discloses a metal/polymer composite cored wire, a metal/polymer composite coating and a preparation method thereof; the metal/polymer composite powder core wire sequentially comprises a metal belt, a middle layer and a powder core; the metal belt and the middle layer coated on the surface of the metal belt form a sheath and wrap the powder core; the filling rate of the powder core is 5-45%; the metal/polymer composite coating comprises metal and polymer, wherein the volume fraction of the metal is 50-95%, and the volume fraction of the polymer is 5-50%; the metal/polymer composite coating is formed by spraying and depositing a metal/polymer composite powder core wire on the surface of a substrate. The metal/polymer composite coating provided by the invention can be well combined with a substrate, and the polymer is uniformly distributed in the whole coating, has excellent corrosion resistance, and can be applied to the outer surfaces of various marine industrial parts and other occasions requiring corrosion resistance.

Description

Metal/polymer composite powder core wire, metal/polymer composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of metal and polymer coatings, in particular to a metal/polymer composite cored wire, a metal/polymer composite coating and a preparation method thereof.
Background
In recent years, with the continuous development of the marine industry, the corrosion problem of marine engineering materials has become a focus of world attention, and particularly, China has abundant marine resources, and the loss caused by marine corrosion is reduced as much as possible while the marine resources are developed and utilized. The corrosion problem of ocean engineering materials is widely researched at home and abroad, and good effects are achieved by selecting corrosion-resistant materials, surface plating layers, cathode protection, coating anticorrosive coatings and other methods. The ocean corrosion has great damage to ocean engineering materials, reduces the service life of the materials and causes serious economic loss. According to statistics, at least 900 million yuan of economic loss of China is caused by corrosion every year, and the proportion of marine corrosion accounts for more than 30%. Therefore, research on a novel anticorrosive coating technology is a scientific problem to be solved urgently, and development of a corrosion-resistant composite coating and a preparation technology thereof are very necessary.
The Chinese patent publication No. CN106591768A discloses a cored wire for preparing Al-Ni-Nb-Co amorphous coating by high-speed electric arc spraying technology, which is characterized in that the outer skin of the cored wire is a pure aluminum strip; the mass percentage of the powder core in the wire is 34-38%; the powder core comprises the following components in percentage by mass: 12-16% of Ni, 12-16% of Nb and 6-10% of Co. The powder core wire has strong amorphous forming capability, the coating prepared by adopting the high-speed electric arc spraying technology has high amorphous content, has dual functions of corrosion resistance and wear resistance, and can provide solid material guarantee for the surface protection of steel and light alloy parts.
The service life of the electric arc spraying coating in thermal spraying is the longest, the electric arc spraying material comprises solid wires and powder core wires, the powder core wires have the advantages of the solid wires and powder, wire drawing is easy, the non-conductive powder material can be applied to electric arc spraying, and further research and application of the electric arc spraying technology in the field of wear resistance and corrosion resistance are promoted. The powder core wire is composed of a metal sheath and a powder core, wherein the metal sheath can be a low-carbon steel strip and can also be other strips suitable for rolling and drawing, such as Ni, Al, Zn, Cu, stainless steel strips and the like; the powder core part can be used as a filler after powders of various metal alloys, oxides, carbides, ceramics, polymers and the like are mixed in proportion according to design requirements. The manufacturing of the wire is similar to that of a flux-cored wire used for welding, and comprises the working procedures of powder preparation, powder mixing, wire rolling, wire drawing, wire winding, packaging and the like. Compared with solid wire and powder, the electric arc spraying powder core wire can conveniently adjust the wire components according to the coating component requirements, and has the advantages of convenient processing, low cost, simple use equipment, convenient operation and huge development potential.
However, the electric arc spraying coating has the inevitable defects of cracks, pores and the like, and the corrosion medium enters the coating to rapidly cause the failure of the coating. The existing method for solving the problems is to coat a high-molecular barrier layer on the surface of the electric arc spraying coating, and the method can effectively prevent corrosive media from permeating into the coating. However, the polymer layer coated on the surface has low mechanical properties and is easily damaged by mechanical external force, and the barrier effect is lost. Therefore, a new arc spraying coating is continuously invented to meet the requirements of low cost and large area corrosion protection.
Disclosure of Invention
The invention aims to provide a metal/polymer composite cored wire, a metal/polymer composite coating and a preparation method thereof. The metal/polymer composite coating prepared by the metal/polymer composite cored wire provided by the invention has a compact coating, is well combined with a substrate, has excellent anti-corrosion performance and anti-biofouling performance, can meet the requirements of a coating in a severe corrosion environment, and is beneficial to the application of the coating in the field of marine corrosion prevention.
The invention provides the following technical scheme:
a metal/polymer composite powder core wire comprises a metal belt, a middle layer and a powder core in sequence; the metal belt and the middle layer coated on the surface of the metal belt form a sheath and wrap the powder core; the filling rate of the powder core is 5-45%.
Preferably, the filling rate of the powder core is 39-41%. Too high a filling rate of the powder core can cause agglomeration, and too low a filling rate cannot meet the requirements of compactness and corrosion resistance of the coating.
The metal band is made of one or a combination of at least two of low-carbon steel band, stainless steel band, Ni band, Al band, Zn band or Cu band; the materials of the middle layer and the powder core are selected from one or the combination of at least two of polyethylene, polymethyl methacrylate, polyimide, polyperfluoroethylpropylene or polytetrafluoroethylene.
Preferably, the metal band is selected from one of a stainless steel band or Al, and the material of the intermediate layer and the powder core is selected from one of polyethylene, polymethyl methacrylate, polyimide or polytetrafluoroethylene. The metal/polymer coating obtained by spraying the metal/polymer composite cored wire prepared from the material has better compactness and corrosion resistance.
Preferably, the material of the powder core is selected from one of PE powder or PMMA solution (20%) or the combination of the PE powder and the PMMA solution. The PE powder has excellent fluidity, is not easy to agglomerate and is beneficial to thermal spraying.
The metal/polymer composite coating comprises a metal and a polymer, wherein the volume fraction of the metal is 50-95%, and the volume fraction of the polymer is 5-50%. Preferably, the volume fraction of the metal is 60-70% and the volume fraction of the polymer is 30-40%. The metal/polymer composite coating prepared in the range has a more compact layered structure, the polymer is uniformly distributed more uniformly, and the coating is well combined with the matrix; the corrosion defects of the surface micro-morphology after the salt spray test are less.
The metal/polymer composite coating is formed by spraying and depositing metal/polymer composite powder core wires on the surface of a substrate;
the thickness of the metal/polymer composite coating is 50 mu m-3 mm.
Preferably, the thickness of the metal/polymer composite coating is 500-1000 μm, and the thickness of the substrate is 2-5 mm.
The invention also provides a method for preparing the metal/polymer composite coating, which comprises the following steps:
(1) preparing a metal/polymer composite strip;
(2) preparing a metal/polymer composite powder core wire;
(3) carrying out surface oil removal and coarsening treatment on the matrix;
(4) and (3) taking the metal/polymer composite cored wire prepared in the step (2) as a spraying raw material, and preparing the metal/polymer composite coating on the surface of the substrate treated in the step (3) by a thermal spraying method.
The preparation method of the metal/polymer composite strip in the step (1) comprises the steps of flame spraying a layer of polymer material on the surface of the metal strip or brushing a layer of polymer material on the surface of the metal strip by using a brush.
The diameter of the metal/polymer composite powder core wire is 1.8-3mm, the width of the metal belt is 6-16mm, and the thickness of the metal belt is 0.3-0.8 mm; the thickness of the middle layer is 3 μm-1 mm. Preferably, the diameter of the metal/polymer composite powder core wire is 1.8-2mm, the width of the metal belt is 7-10mm, the thickness of the metal belt is 0.4-0.6mm, and the thickness of the middle layer is 3-50 μm.
The diameter of the metal/polymer composite powder core wire, the width and the thickness of the metal belt and the thickness of the intermediate layer are related to the volume fractions of metal and polymer in the metal/polymer composite coating generated after spraying and the distribution of the polymer in the metal, thereby influencing the compactness and the corrosion resistance of the coating.
The flame spraying parameters in the step (1) are as follows: the combustion-supporting gas is O2The pressure is 0.2-1.0 MPa; the fuel gas is acetylene, and the pressure is 0.05-0.4 MPa; the auxiliary gas is compressed air with the pressure of 0.3-6.0 MPa; the powder feeding speed is 10-100 g/min; the spraying distance is 100-300 mm; the moving speed of the flame spray gun is 50-400 mm/s; the spraying times are 1-10 times.
Brushing a layer of polymer material on the surface of a metal strip by using a brush, wherein the brushing method of the polymer material comprises the following steps: and (3) after dissolving the polymer powder into a solvent, brushing the polymer powder onto the surface of the material.
The preparation method of the metal/polymer composite powder core wire in the step (2) comprises the following steps: and (2) feeding the metal/polymer composite strip obtained in the step (1) into a roller, rolling the metal/polymer composite strip into a groove shape, feeding the powder core material into the groove, closing the metal/polymer composite strip through the roller, rolling the metal/polymer composite strip into a circular shape, and gradually reducing the diameter through a wire drawing die to obtain the metal/polymer composite powder core wire.
The substrate in the step (3) is selected from one or a combination of at least two of Q235 steel, Q345 steel, 45 steel, 304 stainless steel, 316 stainless steel or cast iron.
The coarsening treatment method in the step (3) is to use white corundum for sand blasting.
The thickness of the substrate is 1-10 mm.
The thermal spraying method in the step (4) is selected from electric arc spraying or flame spraying.
The process parameters of the electric arc spraying are as follows: the electric arc spraying current is 80-200A, the voltage is 20-40V, the spraying distance is 100-300mm, compressed air with 0.4-0.8MPa is adopted, and the thickness of the electric arc spraying coating is 50 mu m-3 mm.
The flame spraying parameters are as follows: the combustion-supporting gas is O2The pressure is 0.5-0.6 MPa; the fuel gas is acetylene, and the pressure is 0.07-0.08 MPa; the auxiliary gas is compressed air with the pressure of 0.75-0.85 MPa; the powder feeding rate is 55-65 g/min; the spraying distance is 240 mm and 260 mm; the moving speed of the flame spray gun is 190-210 mm/s; the spraying times are 1-3 times.
Preferably, the process parameters of the electric arc spraying are as follows: the electric arc spraying current is 100-120A, the voltage is 32-36V, the spraying distance is 150-200mm, compressed air with the pressure of 0.6-0.7MPa is adopted, and the thickness of the electric arc spraying coating is 500 mu m.
The metal/polymer composite powder core wire is also called as a metal/polymer composite wire.
Compared with the prior art, the invention has the beneficial effects that:
the metal surface of the metal/polymer composite coating provided by the invention is easy to passivate to form a layer of oxide film, so that the metal matrix can be protected from further corrosion.
The metal/polymer composite powder core wire is used as a raw material, the outer skin of the metal/polymer composite powder core wire comprises a metal belt and an intermediate layer, and the polymer in the powder core is uniformly coated in the metal; by introducing the intermediate layer, the phenomenon of polymer agglomeration in the powder core in the traditional method is avoided; the invention effectively avoids the defect of insufficient powder core filling rate caused by powder leakage, and further obtains the metal/polymer composite anticorrosive coating with excellent barrier property.
For a metal/polymer composite coating, factors such as compactness of the coating, bonding degree with a matrix, shape, size and distribution state of a polymer and the like are closely related to the corrosion resistance of the coating; by introducing the intermediate layer, the polymer is obviously flat strip-shaped or sheet-shaped and is uniformly distributed in the coating, so that the coating has good barrier property, is compact and well combined with the substrate, can meet the requirement of the coating in a severe corrosion environment, is beneficial to the application of the coating in the field of marine corrosion resistance, and is expected to generate great social and economic benefits.
The polymer in the middle layer and the powder core which play a role in separation is uniformly dispersed in cracks and pores of the thermal spraying, so that the metal/polymer composite coating provided by the invention has excellent anti-corrosion performance and anti-biofouling performance; the polymer dispersed in the coating has good chemical stability and strong acid and alkali resistance, and the polymer is uniformly distributed in the composite coating, so that the corrosion effect of a corrosive medium on a base material can be effectively isolated; the corrosion inhibitor is not influenced by external mechanical force, and has better corrosion effect.
The preparation method of the metal/polymer coating provided by the invention has the advantages of low cost, good repeatability, easiness in manual control, suitability for industrial production and the like, and has good application prospect and economic benefit.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a metal/polymer composite coating according to the present invention;
FIG. 2 is a graph comparing the structure of the metal/polymer composite coating provided in example 1 with that of a pure Al coating;
fig. 3 is a graph comparing the salt spray corrosion of the metal/polymer composite coating provided in example 2 with a pure Al coating.
Detailed Description
The present invention is described in further detail below with reference to the drawings and examples, and it should be noted that the following examples are intended to facilitate understanding of the present invention and are not intended to limit the present invention in any way.
As shown in fig. 1, the preparation method of the metal/polymer composite coating provided by the invention comprises the following steps:
(1) preparing a metal/polymer composite strip;
(2) preparing a metal/polymer composite powder core wire;
(3) carrying out surface oil removal and coarsening treatment on the matrix;
(4) and (3) taking the metal/polymer composite cored wire prepared in the step (2) as a spraying raw material, and preparing the metal/polymer composite coating on the surface of the substrate treated in the step (3) by a thermal spraying method.
Example 1
In this example, the thickness of the substrate is 2mm of Q235 steel sheet, and the thickness of the Al/PE composite coating on the surface of the substrate is 500 μm, and the specific preparation method is as follows:
1. firstly, 5052 aluminum alloy strip with the width of 7mm and the thickness of 0.4mm is flame-sprayed with a PE layer with the thickness of 10 microns, and the flame spraying parameters are as follows: the combustion-supporting gas is O2The pressure is 0.55 MPa; the fuel gas is acetylene, and the pressure is 0.075 MPa; the auxiliary gas is compressed air, the pressure is 0.8MPa, the powder feeding speed is 60g/min, the spraying distance is 250mm, the moving speed of a flame spray gun is 200mm/s, and the spraying times are 1 time, so that the Al/PE composite strip is obtained;
2. and (2) feeding the Al/PE composite strip into a roller, rolling the Al/PE composite strip into a groove shape, then feeding PE powder into the groove, setting the filling rate to be 41%, closing the metal strip through the roller, rolling the metal strip into a circular shape, and gradually reducing the diameter of the metal strip to 1.97mm through drawing dies of 2.65mm, 2.45mm, 2.20mm and 1.97mm in sequence to obtain the Al/PE composite powder core wire.
3. Sand blasting the substrate with white corundum;
4. the parameters of the electric arc spraying process are as follows: current 100A, voltage 32V, spraying distance 150mm, using 0.6MPa compressed air, thickness of the arc sprayed coating 500 μm, resulting in a metal/polymer composite coating, wherein the volume fraction of metal is 70 vol.%, and the volume fraction of the polymer is 30 vol.%.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: FIG. 2 is a schematic diagram showing the qualitative detection and analysis of the elemental composition distribution in the Al/PE composite coating and the pure Al coating by using the backscattering mode of a Field Emission Scanning Electron Microscope (FESEM), wherein a is the pure Al coating and b is the composite coating; from fig. 2, it can be seen that the Al/PE composite coating is typically layered and dense, and the black part is polymer, flat strip or plate, and is uniformly distributed, wherein the coating is well combined with the substrate, and the thickness of the coating is 500 μm.
(2) And (3) testing the corrosion resistance of the coating: a JK/60A precision type salt water spray testing machine is used for carrying out neutral salt spray testing, and the experimental conditions are as follows: the test temperature was 35 ℃, the solution concentration was 50g/L, the solution pH was 6.9, and the spray pressure was 1Kgf/cm2(ii) a And (3) detecting the micro-morphology of the surface of the coating after the test, wherein the micro-morphology of the surface has fewer corrosion defects, and the Al/PE composite coating is proved to have good corrosion prevention effect.
Example 2
In this example, the substrate was a 45 steel sheet having a thickness of 2mm, and the substrate surface was stainless steel
The thickness of the PMMA composite coating is 500 mu m, and the specific preparation method is as follows:
1. brushing a layer of PMMA solution (20%) with the thickness of 10 mu m on a stainless steel belt with the width of 7mm and the thickness of 0.4mm to obtain a stainless steel/PMMA composite belt material;
2. feeding the stainless steel/PMMA composite strip into a roller, rolling the stainless steel/PMMA composite strip into a groove shape, feeding PMMA powder into the groove, setting the filling rate to be 41%, closing a metal strip through the roller, rolling the metal strip into a circular shape, and gradually reducing the diameter of the metal strip to 1.97mm through wire drawing dies of 2.65mm, 2.45mm, 2.20mm and 1.97mm in sequence to obtain a stainless steel/PMMA composite powder core wire;
3. sand blasting the substrate with white corundum;
4. the parameters of the electric arc spraying process are as follows: the current is 100A, the voltage is 32V, the spraying distance is 150mm, 0.6MPa compressed air is adopted, the thickness of the electric arc spraying coating is 500 mu m, and the metal/polymer composite coating is obtained, wherein the metal volume fraction is 68 percent, and the polymer volume fraction is 32 percent.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), so that the stainless steel/PE composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, the coating is well combined with the matrix, and the thickness of the coating is 500 mu m;
(2) and (3) testing the corrosion resistance of the coating: JK/60A precision salt water spray testerAnd (3) carrying out a neutral salt spray test, wherein the experimental conditions are as follows: the test temperature was 35 ℃, the solution concentration was 50g/L, the solution pH was 6.9, and the spray pressure was 1Kgf/cm2. FIG. 3 shows the macroscopic corrosion morphology of the pure Al coating and the Al/PMMA composite coating after 10 days of salt spray, which confirms that the stainless steel/PMMA composite coating has good corrosion prevention effect. In FIG. 3, a is the surface morphology of the coating before etching, and b is the surface morphology of the coating after etching; in a and b, the left sample is an Al coating, and the right sample is a stainless steel/PMMA composite coating.
Example 3
In this example, a substrate is a 304 stainless steel sheet with a thickness of 2mm, and an Al/PTFE composite coating on the surface of the substrate has a thickness of 500 μm, and the specific preparation method is as follows:
1. firstly, 5052 aluminum alloy strip with the width of 7mm and the thickness of 0.4mm is flame-sprayed with PTFE with the thickness of 10 mu m, and the flame spraying parameters are as follows: the combustion-supporting gas is O2The pressure is 0.55 MPa; the fuel gas is acetylene, and the pressure is 0.075 MPa; the auxiliary gas is compressed air, the pressure is 0.8MPa, the powder feeding rate is 60g/min, the spraying distance is 250mm, the moving speed of a flame spray gun is 200mm/s, and the spraying times are 1 time, so that the Al/PTFE composite strip is obtained;
2. feeding the Al/PTFE composite strip into a roller, rolling the Al/PTFE composite strip into a groove, then feeding PTFE powder into the groove, setting the filling rate to be 41%, closing a metal strip through the roller, rolling the metal strip into a circular shape, and gradually reducing the diameter of the metal strip to 1.97mm through drawing dies of 2.65mm, 2.45mm, 2.20mm and 1.97mm in sequence to obtain an Al/PTFE composite powder core wire;
3. sand blasting the substrate with white corundum;
4. the parameters of the electric arc spraying process are as follows: the current is 100A, the voltage is 32V, the spraying distance is 150mm, 0.6MPa compressed air is adopted, the thickness of the coating sprayed by electric arc is 500 mu m, and the metal/polymer composite coating is obtained, wherein the metal volume fraction is 67 percent, and the polymer volume fraction is 33 percent.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), and the Al/PTFE composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, wherein the coating is well combined with the matrix, and the thickness of the coating is 500 mu m.
(2) And (3) testing the corrosion resistance of the coating: a JK/60A precision type salt water spray testing machine is used for carrying out neutral salt spray testing, and the experimental conditions are as follows: the test temperature was 35 ℃, the solution concentration was 50g/L, the solution pH was 6.9, and the spray pressure was 1Kgf/cm2. And (3) detecting the micro-morphology of the surface of the coating after the test, and confirming that the Al/PTFE composite coating has good corrosion prevention effect because fewer corrosion defects appear in the micro-morphology of the surface.
Example 4
In this example, the thickness of the substrate is 2mm of Q235 steel sheet, and the thickness of the stainless steel/PI composite coating on the surface of the substrate is 500 μm, and the specific preparation method is as follows:
1. brushing a layer of PI solution with the thickness of 10 mu m on a stainless steel belt with the width of 7mm and the thickness of 0.4mm to obtain an Al/PI composite belt material;
2. feeding the stainless steel/PI composite strip into a roller, rolling the stainless steel/PI composite strip into a groove shape, then feeding PI powder into the groove, setting the filling rate to be 41%, closing a metal strip through the roller, rolling the metal strip into a circular shape, and gradually reducing the diameter of the metal strip to 1.97mm through wire drawing dies of 2.65mm, 2.45mm, 2.20mm and 1.97mm in sequence to obtain a stainless steel/PI composite powder core wire material;
3. sand blasting the substrate with white corundum;
4. the parameters of the electric arc spraying process are as follows: the current is 100A, the voltage is 32V, the spraying distance is 150mm, 0.6MPa compressed air is adopted, the thickness of the electric arc spraying coating is 500 mu m, and the metal/polymer composite coating is obtained, wherein the metal volume fraction is 70%, and the polymer volume fraction is 30%.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), and the stainless steel/PI composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, wherein the coating is well combined with the matrix, and the thickness of the coating is 500 mu m.
(2) And (3) testing the corrosion resistance of the coating: by usingThe JK/60A precision type salt water spray testing machine is used for carrying out neutral salt spray testing, and the experimental conditions are as follows: the test temperature was 35 ℃, the solution concentration was 50g/L, the solution pH was 6.9, and the spray pressure was 1Kgf/cm2. And (3) detecting the micro-morphology of the surface of the coating after the test, wherein the micro-morphology of the surface has fewer corrosion defects, and the corrosion prevention effect of the stainless steel/PI composite coating is proved to be good.
Example 5
In this example, the thickness of the substrate is 45 steel sheets with a thickness of 2mm, and the thickness of the Al/PMMA composite coating on the surface of the substrate is about 500 μm, and the specific preparation method is as follows:
1. brushing a 5052 aluminum alloy strip with the width of 7mm and the thickness of 0.4mm with a PMMA solution (20%) with the thickness of 10 microns to obtain an Al/PMMA composite strip;
2. and (2) feeding the Al/PMMA composite strip into a roller, rolling the Al/PMMA composite strip into a groove shape, then feeding PMMA powder into the groove, setting the filling rate to be 41%, closing a metal strip through the roller, rolling the metal strip into a circular shape, and gradually reducing the diameter of the metal strip to 1.97mm through wire drawing dies of 2.65mm, 2.45mm, 2.20mm and 1.97mm in sequence to obtain the Al/PMMA composite powder core wire.
3. Sand blasting the substrate with white corundum;
4. the parameters of the electric arc spraying process are as follows: the current is 100A, the voltage is 32V, the spraying distance is 150mm, 0.6MPa compressed air is adopted, the thickness of the electric arc spraying coating is 500 mu m, and the metal/polymer composite coating is obtained, wherein the metal volume fraction is 65 percent, and the polymer volume fraction is 35 percent.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), and the Al/PMMA composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, wherein the coating is well combined with the matrix, and the thickness of the coating is 500 mu m.
(2) And (3) testing the corrosion resistance of the coating: a JK/60A precision type salt water spray testing machine is used for carrying out neutral salt spray testing, and the experimental conditions are as follows: the test temperature was 35 ℃, the solution concentration was 50g/L, the solution pH was 6.9, and the spray pressure was 1Kgf/cm2. After the detection testThe microscopic appearance of the surface of the coating shows less corrosion defects in the microscopic appearance of the surface, and the Al/PMMA composite coating is proved to have good corrosion prevention effect.
Example 6
In this example, a substrate is a 304 stainless steel sheet with a thickness of 2mm, and a stainless steel/PE composite coating on the substrate has a thickness of 500 μm, and the specific preparation method is as follows:
1. firstly, a layer of PE with the thickness of 10 mu m is flame-sprayed on a stainless steel belt with the width of 7mm and the thickness of 0.4mm, and the flame spraying parameters are as follows: the combustion-supporting gas is O2The pressure is 0.55 MPa; the fuel gas is acetylene, and the pressure is 0.075 MPa; the auxiliary gas is compressed air, the pressure is 0.8MPa, the powder feeding speed is 60g/min, the spraying distance is 250mm, the moving speed of a flame spray gun is 200mm/s, and the spraying times are 1. Obtaining a stainless steel/PE composite strip;
2. feeding the stainless steel/PE composite strip into a roller, rolling the stainless steel/PE composite strip into a groove shape, feeding PE powder into the groove, setting the filling rate to be 41%, closing a metal strip through the roller, rolling the metal strip into a circular shape, and gradually reducing the diameter of the metal strip to 1.97mm through wire drawing dies of 2.65mm, 2.45mm, 2.20mm and 1.97mm in sequence to obtain a stainless steel/PE composite powder core wire;
3. sand blasting the substrate with white corundum;
4. the parameters of the electric arc spraying process are as follows: the current is 100A, the voltage is 32V, the spraying distance is 150mm, 0.6MPa compressed air is adopted, the thickness of the electric arc spraying coating is 500 mu m, and the metal/polymer composite coating is obtained, wherein the metal volume fraction is 62 percent, and the polymer volume fraction is 38 percent.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), and the stainless steel/PE composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, wherein the coating is well combined with the matrix, and the thickness of the coating is 500 mu m.
(2) And (3) testing the corrosion resistance of the coating: a JK/60A precision type salt water spray testing machine is used for carrying out neutral salt spray testing, and the experimental conditions are as follows: the test temperature is 35 ℃ and the solution is dissolvedThe solution concentration was 50g/L, the solution pH was 6.9, and the spray pressure was 1Kgf/cm2. And (3) detecting the micro-morphology of the surface of the coating after the test, wherein the micro-morphology of the surface has fewer corrosion defects, and the corrosion prevention effect of the stainless steel/PE composite coating is proved to be good.
Example 7
As in the metal/polymer composite coating provided in example 1, a layer of PE with a thickness of 10 μm was flame-sprayed on an aluminum alloy strip, the filling ratio was set to 45%, and the thickness of the arc-sprayed coating was set to 50 μm; wherein the metal volume fraction is 65% and the polymer volume fraction is 35%.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), and the stainless steel/PE composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, wherein the coating is well combined with the matrix, and the thickness of the coating is 50 mu m.
(2) And (3) testing the corrosion resistance of the coating: and (3) detecting the micro-morphology of the surface of the coating after the test, and confirming that the corrosion prevention effect of the aluminum alloy/PE composite coating is good because fewer corrosion defects appear in the micro-morphology of the surface.
The uniformity and corrosion prevention effect of the metal/polymer composite coating were slightly reduced compared to example 1.
Example 8
As in the metal/polymer composite coating provided in example 1, a layer of PE with a thickness of 10 μm was flame-sprayed on an aluminum alloy strip, the filling ratio was set to 40%, and the thickness of the arc-sprayed coating was 1 mm; wherein the metal volume fraction is 68% and the polymer volume fraction is 32%.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the distribution of element components in the coating is qualitatively detected and analyzed by utilizing the backscattering of a Field Emission Scanning Electron Microscope (FESEM), so that the stainless steel/PE composite coating is a typical laminated structure and is compact, the polymer is in a flat strip shape or a plate shape and is uniformly distributed, the coating is well combined with the matrix, and the thickness of the coating is 1 mm.
(2) And (3) testing the corrosion resistance of the coating: and (3) detecting the micro-morphology of the surface of the coating after the test, and confirming that the corrosion prevention effect of the aluminum alloy/PE composite coating is good because fewer corrosion defects appear in the micro-morphology of the surface.
The uniformity and corrosion prevention effect of the metal/polymer composite coating were slightly reduced compared to example 1.
Example 9
The metal/polymer composite coating as provided in example 1, wherein the thickness of the substrate is 10mm, and the thickness of the Al/PE composite coating on the surface of the substrate is 3mm, in the preparation method: the width of the 5052 aluminum alloy strip is 6mm, and the thickness of the aluminum alloy strip is 0.3 mm; setting the filling rate to be 45%; the diameter of the wire drawing die is gradually reduced to 1.80 mm; the thickness of the electric arc spraying coating is 3 mm; the volume fraction of metal in the resulting metal/polymer composite coating was 50 vol.%, and the volume fraction of polymer was 50 vol.%.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the metal/polymer composite coating is a typical layered structure and is compact, the black part is a polymer and is in a flat strip shape or a plate shape and is uniformly distributed, and the coating is well combined with the substrate.
(2) And (3) testing the corrosion resistance of the coating: and (3) detecting the micro-morphology of the surface of the coating after the test, wherein the micro-morphology of the surface has fewer corrosion defects, and the Al/PE composite coating is proved to have good corrosion prevention effect.
The uniformity and corrosion prevention effect of the metal/polymer composite coating were slightly reduced compared to example 1.
Example 10
The metal/polymer composite coating as provided in example 1, wherein the thickness of the substrate is 1mm, and the thickness of the Al/PE composite coating on the surface of the substrate is 500 μm, in the preparation method: the width of the 5052 aluminum alloy strip is 16mm, and the thickness of the aluminum alloy strip is 0.8 mm; setting the filling rate to be 5%; the diameter of the wire drawing die is gradually reduced to 3 mm; the thickness of the electric arc spraying coating is 500 mu m; the volume fraction of metal in the resulting metal/polymer composite coating was 95 vol.%, and the integral number of polymerized bodies was 5 vol.%.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the metal/polymer composite coating is a typical layered structure and is compact, the black part is a polymer and is in a flat strip shape or a plate shape and is uniformly distributed, and the coating is well combined with the substrate.
(2) And (3) testing the corrosion resistance of the coating: and (3) detecting the micro-morphology of the surface of the coating after the test, wherein the micro-morphology of the surface has fewer corrosion defects, and the Al/PE composite coating is proved to have good corrosion prevention effect.
The uniformity and corrosion prevention effect of the metal/polymer composite coating were slightly reduced compared to example 1.
Example 11
The metal/polymer composite coating as provided in example 1, wherein the thickness of the substrate is 10mm, and the thickness of the Al/PE composite coating on the surface of the substrate is 1mm, in the preparation method: the width of the 5052 aluminum alloy strip is 10mm, and the thickness of the aluminum alloy strip is 0.6 mm; setting the filling rate to 39%; the diameter of the wire drawing die is gradually reduced to 1.80 mm; the thickness of the electric arc spraying coating is 1 mm; the volume fraction of metal in the resulting metal/polymer composite coating was 60 vol.%, and the integral number of polymerized bodies was 40 vol.%.
The process parameters of the electric arc spraying are as follows: the electric arc spraying current is 120A, the voltage is 36V, the spraying distance is 200mm, and compressed air of 0.7MPa is adopted.
The coating prepared above was tested for the following properties:
(1) the section morphology of the coating is as follows: the metal/polymer composite coating is a typical layered structure and is compact, the black part is a polymer and is in a flat strip shape or a plate shape and is uniformly distributed, and the coating is well combined with the substrate.
(2) And (3) testing the corrosion resistance of the coating: and (3) detecting the micro-morphology of the surface of the coating after the test, wherein the micro-morphology of the surface has fewer corrosion defects, and the Al/PE composite coating is proved to have good corrosion prevention effect.

Claims (8)

1. A metal/polymer composite powder core wire is characterized by comprising a metal belt, a middle layer and a powder core in sequence; the metal belt and the middle layer coated on the surface of the metal belt form a sheath and wrap the powder core; the middle layer and the powder core are the same polymer, and the filling rate of the powder core is 5-45%;
the metal band is made of one or a combination of at least two of low-carbon steel band, stainless steel band, Ni band, Al band, Zn band or Cu band; the materials of the middle layer and the powder core are selected from one or the combination of at least two of polyethylene, polymethyl methacrylate, polyimide, polyperfluoroethylpropylene or polytetrafluoroethylene;
the width of the metal belt is 6-16mm, and the thickness of the metal belt is 0.3-0.8 mm; the thickness of the middle layer is 3 mu m-1 mm; the diameter of the metal/polymer composite powder core wire is 1.8-3 mm.
2. A metal/polymer composite coating prepared from the metal/polymer composite cored wire of claim 1, wherein the metal/polymer composite coating comprises a metal and a polymer, the volume fraction of the metal is 50-95%, and the volume fraction of the polymer is 5-50%.
3. The metal/polymer composite coating according to claim 2, wherein the thickness of the metal/polymer composite coating is 50 μ ι η -3 mm.
4. A method of making the metal/polymer composite coating of claim 2, comprising the steps of:
(1) preparing a metal/polymer composite strip;
(2) preparing a metal/polymer composite powder core wire;
(3) carrying out surface oil removal and coarsening treatment on the matrix;
(4) and (3) taking the metal/polymer composite cored wire prepared in the step (2) as a spraying raw material, and preparing the metal/polymer composite coating on the surface of the substrate treated in the step (3) by a thermal spraying method.
5. The method for preparing a metal/polymer composite coating according to claim 4, wherein the metal/polymer composite strip in the step (1) is prepared by flame spraying a layer of polymer material on the surface of the metal strip or brushing a layer of polymer material on the surface of the metal strip with a brush.
6. The method for preparing a metal/polymer composite coating layer according to claim 4, wherein the method for preparing the metal/polymer composite cored wire in the step (2) comprises the following steps: and (2) feeding the metal/polymer composite strip obtained in the step (1) into a roller, rolling the metal/polymer composite strip into a groove shape, feeding the powder core material into the groove, closing the metal/polymer composite strip through the roller, rolling the metal/polymer composite strip into a circular shape, and gradually reducing the diameter through a wire drawing die to obtain the metal/polymer composite powder core wire.
7. The method for preparing a metal/polymer composite coating according to claim 4, wherein the substrate in the step (3) is selected from one or a combination of at least two of Q235 steel, Q345 steel, 45 steel, 304 stainless steel, 316 stainless steel or cast iron.
8. The method for preparing a metal/polymer composite coating according to claim 4, wherein the thermal spraying method in the step (4) is selected from arc spraying or flame spraying.
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US4076883A (en) * 1975-07-30 1978-02-28 Metco, Inc. Flame-sprayable flexible wires
CN102869814A (en) * 2010-05-11 2013-01-09 苏舍美特科（美国）公司 Metal matrix ceramic wire manufacturing technology and usage
CN203765186U (en) * 2014-02-19 2014-08-13 常州运河新瑞焊材有限公司 Novel double-layered flux-cored wire
CN204914768U (en) * 2015-07-10 2015-12-30 中国科学院理化技术研究所 A combined material wire rod for 3D prints
CN106676451A (en) * 2016-12-22 2017-05-17 中国科学院宁波材料技术与工程研究所 Cored wire with super-hydrophobic function and application of cored wire with super-hydrophobic function to preparation of coating with super-hydrophobic function

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4076883A (en) * 1975-07-30 1978-02-28 Metco, Inc. Flame-sprayable flexible wires
CN102869814A (en) * 2010-05-11 2013-01-09 苏舍美特科（美国）公司 Metal matrix ceramic wire manufacturing technology and usage
CN203765186U (en) * 2014-02-19 2014-08-13 常州运河新瑞焊材有限公司 Novel double-layered flux-cored wire
CN204914768U (en) * 2015-07-10 2015-12-30 中国科学院理化技术研究所 A combined material wire rod for 3D prints
CN106676451A (en) * 2016-12-22 2017-05-17 中国科学院宁波材料技术与工程研究所 Cored wire with super-hydrophobic function and application of cored wire with super-hydrophobic function to preparation of coating with super-hydrophobic function

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