CN109321861B - Corrosion-resistant and wear-resistant coating with lamellar and columnar composite structure and preparation method thereof - Google Patents

Corrosion-resistant and wear-resistant coating with lamellar and columnar composite structure and preparation method thereof Download PDF

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CN109321861B
CN109321861B CN201811386847.2A CN201811386847A CN109321861B CN 109321861 B CN109321861 B CN 109321861B CN 201811386847 A CN201811386847 A CN 201811386847A CN 109321861 B CN109321861 B CN 109321861B
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plasma
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spraying
alloy
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CN109321861A (en
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崔洪芝
王明亮
宋晓杰
王灿明
宋强
赵玉桥
赵永
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Shandong University of Science and Technology
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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
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic 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
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/027—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal matrix material comprising a mixture of at least two metals or metal phases or metal matrix composites, e.g. metal matrix with embedded inorganic hard particles, CERMET, MMC.
    • 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
    • C23C4/134—Plasma spraying

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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Abstract

The invention discloses a corrosion-resistant wear-resistant coating with a lamellar and columnar composite structure and a preparation method thereof, wherein alloy powder is sprayed on the surface of a pretreated substrate by a low-pressure plasma spraying method to obtain an alloy layer, then the alloy powder and ceramic powder mixed powder are sprayed on the surface of the alloy layer by preheating after plasma spraying to obtain a composite cladding layer with a columnar structure by a plasma spraying technology, and the composite cladding layer is circulated until a multilayer layer-column alternate gradient structure with continuously changed properties along the thickness direction is obtained. The invention not only improves the binding force between the coating and the substrate, but also improves the corrosion resistance and the wear resistance; and a multilayer layer and column alternate gradient structure with continuously changed performance in the thickness direction can be obtained, and the impact resistance of the coating material is improved.

Description

Corrosion-resistant and wear-resistant coating with lamellar and columnar composite structure and preparation method thereof
Technical Field
The invention relates to a wear-resistant and corrosion-resistant coating material structure and a preparation technology thereof, belonging to the field of metal material surface treatment. Specifically, the method for compounding plasma spraying and plasma melting is used for efficiently obtaining the coating material with a laminated and columnar composite structure, the surface corrosion resistance is ensured, the wear resistance is improved, a multi-layer gradient structure with continuously changed properties along the thickness direction can be obtained, and the impact resistance of the impact-resistant coating material is improved.
Background
The protective coating material and the performance of the surface of a workpiece are not satisfactory in complex and severe abrasion and corrosion environments when the gate valves in marine machinery, coal chemical industry and petroleum industry, various sand pumps, slurry pumps, water turbines, conveying pipelines and the like in mine and cement industry work, so that the service life is greatly shortened, potential safety hazards are brought, and the gate valves become wearing parts with the largest consumption. The currently common methods for improving surface properties mainly include: laser and plasma cladding, overlaying, bimetal composite casting or imbedding, spraying and the like can be used for preparing different coatings on different metal material base materials, so that the wear resistance or corrosion resistance is improved.
Chinese patent application No.: 201711298879.2 provides a thermal barrier coating ceramic layer with zigzag columnar structure and its preparation method, which comprises feeding powder into the thermal barrier coating ceramic layer by plasma spraying vapor deposition technique, and evaporating the powder to form vapor phase. The deposition growth direction of the ceramic layer columnar structure is adjusted through multiple changes of the angle between the deposition surface of the substrate and the plasma jet in the spraying process, and the thermal barrier coating ceramic layer with the zigzag columnar structure forming a certain angle with the normal direction of the surface of the substrate is obtained.
Chinese patent application No.: 201110280844.2, discloses a thermal barrier coating with a nano/columnar crystal-like mixed structure and a preparation method thereof, which comprises the steps of powder selection and pretreatment, matrix pretreatment, metal bonding layer preparation and 6-8% YSZ ceramic layer preparation. The coating disclosed by the invention has the advantages of high strain tolerance, excellent heat insulation performance, high bonding strength, high thermal cycle life and thermal shock life, so that the thermal barrier coating has better comprehensive performance.
Chinese patent application No.: 200480035764.9 discloses a vapor deposited coating of a layered structure covering a substrate for use in high shear and/or high impact applications.
Chinese patent application No.: 201810214053.1 discloses a thermal barrier coating with structural gradient and its preparation method, the thermal barrier coating comprises a base, a bonding layer and a ceramic surface layer arranged from bottom to top in sequence, wherein the microstructure of the ceramic surface layer is in gradient change, and comprises a quasi-columnar ceramic bottom layer, a layered and columnar mixed structure ceramic transition layer and a dense layered structure ceramic top layer arranged from bottom to top in sequence. The one-time continuous preparation of the thermal barrier coating can be realized by an ultra-low pressure plasma multiphase deposition method. The prepared thermal barrier coating has the advantages of high thermal insulation, long service life, stronger corrosion resistance, erosion resistance and the like.
By adopting the different coating designs and preparation methods, the service life of the workpiece can be prolonged. However, so far, the reports of ultra-thick and strong metallurgically bonded wear-resistant and corrosion-resistant coatings and preparation methods are not yet seen. Therefore, the development of a coating material which is an ultra-thick coating metallurgically bonded with a substrate and has gradient properties along the thickness direction and a high-efficiency preparation method, and meets the requirements of different industries on the wear-resistant material and the coating, is urgently needed.
Disclosure of Invention
The invention provides a corrosion-resistant wear-resistant coating with a laminar and columnar composite structure, which is metallurgically bonded with a substrate, and a preparation method thereof, aiming at solving the problems in the prior art. The invention adopts the method of combining plasma spraying and plasma melting and can efficiently obtain the coating material with a laminated and columnar composite structure. And a layered structure is formed after plasma spraying, so that the surface corrosion resistance is guaranteed. The subsequent plasma fusion injection fully utilizes the preheating after the plasma spraying, reduces the stress of the fusion injection coating, improves the binding force and improves the efficiency; meanwhile, the transfer arc type is adopted, the workpiece serves as an anode, the temperature is high, the melt-shot powder and the matrix reach a molten or molten state, a fine columnar structure is obtained after melt-shot, and the wear resistance is greatly improved. In addition, the alloy layer with a layered structure formed by plasma spray is reacted and diffused to form a stable phase, the porosity is reduced, and the binding force between the coating and the substrate and the corrosion resistance and the wear resistance are improved; and a multilayer layer and column alternate gradient structure with continuously changed performance in the thickness direction can be obtained, and the impact resistance of the coating material is improved. Compared with the traditional plasma spraying method, the preparation method can reduce the porosity, reduce the number of cracks, ensure that metastable phases in the ceramic coating are converted towards stable phases, and improve the surface hardness, the wear resistance, the thermal shock resistance and other properties of the coating.
In order to achieve the purpose, the invention adopts the technical scheme that:
a corrosion-resistant wear-resistant coating with a lamellar and columnar composite structure is characterized in that alloy powder is sprayed on the surface of a pretreated substrate by a low-pressure plasma spraying method to obtain an alloy layer, then the alloy powder and ceramic powder mixed powder are sprayed on the surface of the alloy layer by preheating after plasma spraying to obtain a composite cladding layer with a columnar structure by a plasma spraying technology, and the composite cladding layer is circulated and reciprocated until a multilayer layer-column alternate gradient structure with continuously changed properties along the thickness direction is obtained;
the alloy powder is selected from metal powder of Ni, Cr, Ti, Al, Co, Cu, Si, etc. with the granularity of 45-75 μm, and the ceramic powder is selected from WC and B4C、SiC、TiO2、ZrO2、Cr2O3、Al2O3Powder with the granularity of 35-45 μm.
Furthermore, the composite spray layer is formed by mixing 5-30wt% of alloy powder and the balance of ceramic powder;
further, the alloy powder in the alloy layer and the composite cladding layer consists of (0-90) wt% of Ni + Cr or/and (0-90) wt% of Ti + Al mixed powder and the balance of Co + Cu + Si mixed powder, and the proportion of three elements in the Co + Cu + Si mixed powder is equal to mole;
further, the ceramic powder in the composite cladding layer is composed of (45-95) wt% of WC and/or (2-25) wt% of B4C or/and (1-10) wt% SiC ceramic powder and the balance of TiO2+ZrO2+Cr2O3+Al2O3Mixed powder; requires TiO2+ZrO2+Cr2O3+Al2O3Four kinds of powder in the mixed powder are in equal molar ratio.
The method for preparing the corrosion-resistant and wear-resistant coating with the lamellar and columnar composite structure comprises the following steps:
the first step is as follows: powder preparation
Preparing alloy powder and ceramic powder according to requirements;
the second step is that: pretreatment of workpiece surfaces
The pretreatment comprises the working procedures of acid soaking, water washing, alkaline water soaking, warm water cleaning, drying and sand blasting coarsening treatment;
the third step: plasma spraying
Spraying alloy powder on the surface of the pretreated workpiece by adopting a low-pressure plasma spraying method to obtain an alloy layer with the thickness of 0.2-0.3 mm, wherein the plasma spraying process parameters are as follows: the voltage is 50V, the current is 150A, the spraying distance is 50-100mm, and the powder feeding rate is 30-50 g/min; the average hardness of the alloy layer is 330-440 HV0.3；
The fourth step: plasma meltblowing
On the alloy layer with the layered structure obtained after plasma spraying, preheating after plasma spraying is fully utilized, plasma spraying is carried out through a plasma generator, so that the stress of a spraying coating is reduced, the binding force is improved, a plasma torch for spraying and the plasma generator for spraying are required to move at the same speed and track, when plasma beams are sprayed, a workpiece is an anode, a transfer arc is formed, therefore, a melting layer can be formed on the surface of the workpiece due to high temperature, and the thickness of the melting layer is 0.8-1.2 mm after cooling; the plasma beam melt jet voltage is 50V, the current is 150A, the distance is 20mm, and the powder feeding rate is 50 g/min. Because of the directional heat dissipation, the solidified spray layer has a columnar structure, and the average hardness of the cladding layer reaches 670-0.3；
The fifth step: repeating plasma spraying and plasma meltallizing
And plasma spraying is performed again as required, then plasma melting is performed, and the steps are repeated, so that a multi-layer-column alternate gradient structure with continuously changed performance in the thickness direction is obtained, the impact resistance of the coating material is improved, and the total thickness of the coating can reach 2.5-3.0 mm.
The corrosion-resistant and wear-resistant coating with the lamellar and columnar composite structure can be used for strengthening the surfaces of gate valves, Q235 steel, Q255 steel and the like made of ZGMn13, 304 stainless steel and 316 stainless steel materials, and improves the corrosion resistance by 3-10 times and the wear resistance by 2-4 times.
The invention has the beneficial effects that:
1. because the invention adopts the method of plasma spraying and plasma melting composite treatment, firstly, an alloy layer with a lamellar organizational structure is obtained at the bottom of the coating by the plasma spraying process. And then plasma spray heating treatment is carried out, and preheating after plasma spraying is fully utilized, so that the stress of a spray coating is reduced, the binding force is improved, and the efficiency is improved. In the alloy layer with the laminated structure formed by plasma spraying, reaction diffusion occurs, and the formed main phases are as follows: NiAl, CrAl, NiTi, TiAl, CoAl, CuO or SiO2And intermetallic compounds and oxides improve the phase stability, reduce the porosity, reduce the residual stress of the coating and greatly improve the corrosion resistance of the coating. After the plasma molten layer is solidified, a fine columnar structure is obtained due to high cooling speed, and the phase composition of the fine columnar structure comprises WC and B4C、SiC、TiO2、ZrO2、Cr2O3、Al2O3Etc. and also Ti and B4C. TiB formed by reaction of SiC2、TiC、Ti2Various ceramic phases such as SiC provide hardness and wear resistance. Through multiple times of plasma spraying and meltallizing, a multilayer layer-column alternate gradient structure with continuously changed performance in the thickness direction can be obtained, and the impact resistance, thermal shock resistance and other performances of the coating material are improved.
2. Compared with the traditional plasma spraying method, the preparation method can reduce the porosity, reduce the number of cracks, ensure that metastable phases in the ceramic coating are converted towards stable phases, and improve the surface hardness, the wear resistance, the coating bonding force, the thermal shock resistance and other properties of the coating.
3. The invention adopts the method of combining plasma spraying and plasma melting and can efficiently obtain the coating material with a laminated and columnar composite structure. And a layered structure is formed after plasma spraying, so that the surface corrosion resistance is guaranteed. The subsequent plasma fusion injection fully utilizes the preheating after the plasma spraying, reduces the stress of the fusion injection coating, improves the binding force and improves the efficiency; meanwhile, the workpiece is used as an anode due to the adoption of the transfer arc form, the temperature is high, so that the melt-shot powder and the matrix reach a molten or semi-molten state, a fine columnar structure is obtained after melt-shot, and the wear resistance is greatly improved. In addition, the alloy layer with a layered structure formed by plasma spray is reacted and diffused to form a stable phase, the porosity is reduced, and the binding force between the coating and the substrate and the corrosion resistance and the wear resistance are improved; and a multilayer layer and column alternate gradient structure with continuously changed performance in the thickness direction can be obtained, and the impact resistance of the coating material is improved.
Drawings
FIG. 1 is a schematic view of plasma spraying + plasma meltdown according to the invention;
FIG. 2 is a cross-sectional microstructure of the corrosion and wear resistant coating of the layered sheet and columnar composite structure of the present invention;
in the figure: 1-workbench, 2-workpiece, 3-plasma spraying torch, 4-plasma generator, 5-alloy layer and 6-meltallizing layer.
Detailed description of the preferred embodiments
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, and the scope of the present invention will be more clearly and clearly defined.
Examples composites of the invention were prepared on pure 316L stainless steel substratesThe structure is taken as an example, and the self-corrosion current of a pure 316L stainless steel substrate selected in the example in a sodium chloride solution is detected to be 245nA cm-2The friction and wear test of 316 stainless steel adopts a reciprocating ball disk type, the test conditions are room temperature and dry friction, the alumina ceramic ball is used as a pair grinding pair, the wear time is 120min, and the wear volume loss is 7.5 × 107μ m3, for comparability, the self-corrosion current and the abrasion resistance test in the following examples were measured under the same test conditions as 316 stainless steel.
The first embodiment is as follows:
step 1: powder preparation
The raw materials of the wear-resistant and corrosion-resistant coating are alloy powder with the granularity of 45-75 mu m and ceramic powder with the granularity of 35-45 mu m, wherein the spray layer is formed by mixing 30wt% of alloy powder and 70 wt% of ceramic powder, and the ceramic powder in the spray layer is 45 wt% of WC and 25 wt% of B4C. 10 wt% of SiC, and the balance of mixed powder TiO2:ZrO2:Cr2O3:Al2O3Powder at a molar ratio of 1:1:1: 1; the alloy powder proportions in the spray layer and the alloy layer are as follows: 90 wt% of mixed powder Ni: Cr: 1:1, 5 wt% of mixed powder Ti: Al: 1:1, and the balance of mixed powder Co: Cu: Si: 1:1:1 (molar ratio);
step 2, pretreatment of the surface of the substrate
Firstly, the workpiece 2 is soaked in acid liquor, the soaking time is determined according to the dirt degree of the workpiece, and water is used for washing after acid soaking. Soaking with alkaline water to neutralize residual acid, and thoroughly washing with warm water for blow drying. And then, roughening the surface of the workpiece by adopting a conventional sand blasting roughening method.
And step 3: plasma spraying
As shown in fig. 1, in the implementation, firstly, a workpiece 2 is placed on a worktable 1, a plasma spraying torch 3 and a plasma generator 4 are arranged above the worktable 2, firstly, a low-pressure plasma spraying method of the plasma spraying torch 3 is adopted, and the process parameters are as follows: the voltage is 50V, the current is 150A, the spraying distance is 100mm, the powder feeding rate is 50g/min, the spraying powder is the alloy powder in the step 1, the alloy powder is sprayed on the workpiece to form an alloy layer 5 with a layered structure, and the thickness of the alloy layer 5 is 03mm, average microhardness 440HV0.3。
Step 4; plasma meltblowing
Starting a plasma generator 4 to perform plasma fusion on an alloy layer with a layered structure obtained after plasma spraying, fully utilizing preheating after plasma spraying, reducing stress of a fusion coating and improving binding force, wherein a plasma torch for spraying and a plasma generator for fusion are required to move at the same speed and track, and when plasma beams are fused, a workpiece is an anode and a transfer arc is formed, so that a fusion layer can be formed on the surface of the workpiece due to high temperature. The plasma beam melt jet voltage is 50V, the current is 150A, the distance is 20mm, and the powder feeding rate is 50 g/min. The spray powder is the mixed powder of the alloy powder and the ceramic powder in the step 1. Because of the heat radiation direction, the solidified spray layer 6 has a columnar structure, the thickness is 0.8mm, and the average hardness reaches 970HV0.3A spray coating layer with a layered structure having a columnar structure and a bottom as shown in FIG. 2;
and 5: repeating plasma spraying and plasma meltallizing
Plasma spraying is carried out again as required, and step 3 is carried out; and then performing plasma fusion, repeating the step 4 to obtain a multilayer layer-column alternating gradient structure with continuously changed performance in the thickness direction, improving the shock resistance of the coating material, wherein the total thickness of the coating can reach 2.5-3.0 mm, and the coating is used for surface reinforcement of a gate valve of ZGMn 13. The self-corrosion current of the material of the example is 49nA cm-2The volume loss after 120min of abrasion is 3.75 × 107μ m3, the smaller the self-etching current, the smaller the possibility of etching, the smaller the wear loss, and the better the wear resistance. It can be seen from the test data that the corrosion resistance and wear resistance of the present invention are greatly improved.
Example two:
step 1: powder preparation
Wherein the spray layer 6 is formed by mixing 5 wt% of alloy powder and 95 wt% of ceramic powder, and the ceramic powder in the spray layer 6 is composed of 90 wt% of WC and 2 wt% of B4C. 1 wt% of SiC, and the balance of mixed powder TiO2:ZrO2:Cr2O3:Al2O3Powder at a molar ratio of 1:1:1: 1; the alloy powder proportions in the spray layer 6 and the alloy layer 5 are as follows: 45 wt% of mixed powder Ni: Cr: 1:1, 45 wt% of mixed powder Ti: Al: 1:1, and the balance of mixed powder Co: Cu: Si: 1:1:1 (molar ratio);
and step 3: plasma spraying
The spraying distance is 50mm, the powder feeding rate is 30g/min, the thickness of the alloy layer is 0.2mm, and the average microhardness is 380HV0.3；
And 4, step 4: plasma meltblowing
The mixed powder of the alloy powder and the ceramic powder comprises the following components in percentage by weight: 5 percent of alloy powder and 95 percent of ceramic powder, the thickness is 1.2mm, and the average hardness reaches 1140HV0.3The alloy layer with the columnar structure and the layered structure at the bottom has a total thickness of about 1.4 mm.
Except for the differences, the other parts are the same as the first embodiment.
And 5: and repeating the plasma spraying and the plasma melting. Plasma spraying is carried out again as required, and step 3 is carried out; and then carrying out plasma fusion, and obtaining a multilayer layer-column alternate gradient structure with continuously changed performance in the thickness direction in step 4, so that the impact resistance of the coating material is improved, and the total thickness of the coating can reach 2.5-3.0 mm. The surface strengthening method is used for strengthening the surface of the gate valve made of 316 stainless steel materials. The self-corrosion current of the material of the second example is 81.7nA cm-2The volume loss after 120min of abrasion is 1.88 × 107μm3。
Example three:
step 1: powder preparation
Wherein the spray layer 6 is formed by mixing 20 wt% of alloy powder and 80 wt% of ceramic powder, and the ceramic powder in the spray layer 6 is 70% of WC and 15% of B4C. 5% of SiC, and the balance of mixed powder TiO2:ZrO2:Cr2O3:Al2O3Powder at a molar ratio of 1:1:1: 1; the alloy powder proportions in the spray layer 6 and the alloy layer 5 are as follows: 5 wt% of mixed powder Ni: Cr: 1:1, 90 wt% of mixed powder Ti: Al: 1:1, and the balance of mixed powder Co: Cu: Si: 1:1:1 (molar ratio);
and step 3: plasma spraying
The spraying distance is 70mm, the powder feeding rate is 40g/min, the thickness of the alloy layer is 0.25mm, and the average microhardness is 330HV0.3；
And 4, step 4: plasma meltblowing
The thickness of the meltallizing layer is 1.2mm, and the average hardness reaches 1070HV0.3The alloy layer with the columnar structure and the layered structure at the bottom has a total thickness of 1.45 mm.
Except for the differences, the other parts are the same as the first embodiment.
And 5: multiple plasma spraying and plasma meltallizing
Plasma spraying is carried out again as required, and step 3 is carried out; and then carrying out plasma fusion, and obtaining a multilayer layer-column alternate gradient structure with continuously changed performance in the thickness direction in step 4, so that the impact resistance of the coating material is improved, and the total thickness of the coating can reach 2.5-3.0 mm. The surface strengthening method is used for strengthening the surface of the gate valve made of 304 stainless steel. The self-corrosion current of the three materials of the example is 61.3 nA-cm-2The volume loss after 120min of abrasion is 2.5 × 107μm3。
Example four
Step 1: powder preparation
The raw materials of the wear-resistant and corrosion-resistant coating are alloy powder with the granularity of 45-75 mu m and ceramic powder with the granularity of 35-45 mu m, wherein the spray layer 6 is formed by mixing 10 wt% of alloy powder and 90 wt% of ceramic powder, and the proportion of the ceramic powder in the spray layer 6 is 80 wt% of WC and 10 wt% of B4C, the balance of mixed powder TiO2:ZrO2:Cr2O3:Al2O3Powder at a molar ratio of 1:1:1: 1; the alloy powder proportions in the spray layer 6 and the alloy layer 5 are as follows: the mixed powder Ni: Cr: 1:1 accounts for 90 wt%, and the balance is mixed powder Co: Cu: Si: 1:1:1 (molar ratio).
The average microhardness of the alloy layer in the step 3 is 410HV0.3. The average hardness of the molten injection layer in the step 4 reaches 1100HV0.3。
Example four the same as example one except for the difference from example one, finally a continuous variation in properties in the thickness direction was obtainedThe multi-layer alternating gradient structure of the layers and the columns improves the shock resistance of the coating material, and the total thickness of the coating can reach 2.5-3.0 mm. The surface strengthening agent is used for surface strengthening of Q235 steel. The self-corrosion current of the material in the example four is detected to be 24.5nA cm-2The volume loss after 120min of abrasion is 1.97 × 107μm3。

Claims (6)

1. A corrosion-resistant wear-resistant coating with a lamellar and columnar composite structure is characterized in that alloy powder is sprayed on the surface of a pretreated substrate by a low-pressure plasma spraying method to obtain an alloy layer, then mixed powder of the alloy powder and ceramic powder is sprayed on the surface of the alloy layer by preheating after plasma spraying to obtain a composite cladding layer with a columnar structure by a plasma spraying technology, the composite cladding layer is circularly reciprocated until a multilayer layer and column alternate gradient structure with continuously changed performances along the thickness direction is obtained, a plasma torch for spraying and a plasma generator for spraying are required to move at the same speed and track, and when plasma spraying is carried out, a workpiece is an anode, and a transfer arc is formed;
the alloy powder is selected from Ni, Cr, Ti, Al, Co, Cu and Si metal powder with the granularity of 45-75 mu m, and the ceramic powder is selected from WC and B4C、SiC、TiO2、ZrO2、Cr2O3、Al2O3Powder with the granularity of 35-45 μm.
2. The corrosion-resistant and wear-resistant coating with a laminated and columnar composite structure as claimed in claim 1, wherein the mixed powder is formed by mixing 5-30wt% of alloy powder and the balance of ceramic powder.
3. The corrosion-resistant and wear-resistant coating with a laminated and columnar composite structure as claimed in claim 1, wherein the alloy powder in the alloy layer and the composite cladding layer is composed of (0-90) wt% of Ni + Cr or/and (0-90) wt% of Ti + Al mixed powder, and the balance of Co + Cu + Si mixed powder, and the ratio of the three elements in the Co + Cu + Si mixed powder is required to be equimolar.
4. The corrosion-resistant and wear-resistant coating with a laminated and columnar composite structure as claimed in claim 1, wherein the ceramic powder in the composite cladding layer is composed of (45-95) wt% of WC and/or (2-25) wt% of B4C or/and (1-10) wt% of SiC ceramic powder and the balance of TiO2+ ZrO2+Cr2O3+ Al2O3Mixed powder; requires TiO2+ ZrO2+Cr2O3+ Al2O3Four kinds of powder in the mixed powder are in equal molar ratio.
5. A method for preparing a corrosion and wear resistant coating of a layered and columnar composite structure according to any of claims 1 to 4,
the first step is as follows: powder preparation
Preparing alloy powder and ceramic powder according to requirements;
the second step is that: pretreatment of workpiece surfaces
The pretreatment comprises the working procedures of acid soaking, water washing, alkaline water soaking, warm water cleaning, drying and sand blasting coarsening treatment;
the third step: plasma spraying
Spraying alloy powder on the surface of the pretreated workpiece by adopting a low-pressure plasma spraying method to obtain an alloy layer with the thickness of 0.2-0.3 mm, wherein the plasma spraying process parameters are as follows: the voltage is 50V, the current is 150A, the spraying distance is 50-100mm, and the powder feeding rate is 30-50 g/min; the average hardness of the alloy layer is 330-440 HV0.3；
The fourth step: plasma meltblowing
On the alloy layer with the laminated structure obtained after plasma spraying, plasma spraying is carried out by a plasma generator by utilizing preheating after plasma spraying, a plasma torch for spraying and the plasma generator for spraying are required to move at the same speed and track, when the plasma beam is sprayed, a workpiece is an anode, a transfer arc is formed, a cladding layer with the thickness of 0.8-1.2 mm is formed after cooling, and the average hardness reaches 670-1240HV 1240-0.3(ii) a The plasma beam melt jet voltage is 50V, the current is 150A, the distance is 20mm, and the powder feeding rate is 50 g/min;
the fifth step: repeating plasma spraying and plasma meltallizing
And plasma spraying is performed again as required, then plasma melting is performed, and the steps are repeated, so that a multi-layer-column alternate gradient structure with continuously changed performance in the thickness direction is obtained, the impact resistance of the coating material is improved, and the total thickness of the coating reaches 2.5-3.0 mm.
6. Use of a corrosion and wear resistant coating of a layered and columnar composite structure according to any of claims 1 to 4 for surface strengthening of a gate valve of ZGMn13 material, a gate valve of 304 stainless steel material, a gate valve of 316 stainless steel material, Q235 steel or Q255 steel.
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