CN110629153B - Preparation method of graphene nanosheet/amorphous iron-based composite coating - Google Patents

Preparation method of graphene nanosheet/amorphous iron-based composite coating Download PDF

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CN110629153B
CN110629153B CN201910991191.5A CN201910991191A CN110629153B CN 110629153 B CN110629153 B CN 110629153B CN 201910991191 A CN201910991191 A CN 201910991191A CN 110629153 B CN110629153 B CN 110629153B
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amorphous iron
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CN110629153A (en
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赵晓兵
唐万源
姚李帆
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/02—Amorphous alloys with iron as the major constituent
    • 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
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • 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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Abstract

The invention belongs to the technical field of material surface modification, and particularly relates to a preparation method of a graphene nanosheet/amorphous iron-based composite coating. Firstly, preparing composite powder used for plasma spraying by a planetary ball mill and PVA solution granulation, wherein the granularity of the composite powder is between 60 and 120 mu m. And then the preparation of the wear-resistant anticorrosive coating is realized under the plasma spraying effect. The graphene/amorphous iron-based composite coating prepared by the method has low porosity, high hardness, excellent wear-resistant and corrosion-resistant properties and excellent mechanical properties, plays an important role in wear resistance and corrosion resistance of materials, and greatly improves market competitiveness.

Description

Preparation method of graphene nanosheet/amorphous iron-based composite coating
Technical Field
The invention belongs to the field of material surface modification, and particularly relates to a preparation method of a graphene nanosheet/amorphous iron-based composite coating.
Background
The amorphous material has short-range order and long-range disorder, and various local nonuniformities such as common crystal boundaries and defects in the crystalline material are avoided, so that the corrosive liquid can drill seamlessly; meanwhile, the catalyst has higher activity per se and can quickly form a passive film on the surface, so that the catalyst has better corrosion resistance than the traditional crystalline substance. On the other hand, the atoms of the amorphous material are irregularly arranged, and the atoms are not regularly arranged on a crystal plane but are staggered with canines, so that the material needs higher strength and hardness for fracture, and the corresponding mechanical property is better.
Plasma spraying has high energy density, high heat flux density, and high quenching rate. However, the plasma spraying flame temperature is high, oxidation and over-melting phenomena are easily generated in the spraying process, the density of the prepared coating is slightly poor (generally more than 95 percent), and the deposition efficiency is low. In addition, the amorphous coating prepared by adopting the plasma spraying technology has low amorphous content. And although the amorphous iron-based coating has better corrosion resistance, the wear resistance of the amorphous iron-based coating is slightly poor, so that the use of the amorphous iron-based coating under severe working conditions is limited.
Disclosure of Invention
In order to solve the technical problems in the prior art, the iron-based amorphous powder is added with graphene nano sheets in different proportions to form composite spraying powder, and a layer of composite coating is sprayed on the surface of metal through plasma spraying, so that the wear-resistant and corrosion-resistant performance of the composite coating is improved, and the composite coating can better play a better role in wear-resistant and corrosion-resistant occasions of mechanical parts.
According to the invention, graphene nanosheets with different proportions are added into traditional iron-based amorphous powder to form a composite coating, the coating has higher wear resistance and corrosion resistance compared with a single iron-based amorphous coating, and meanwhile, the addition of the graphene nanosheets can improve the hardness of the coating, so that the coating is more compact in structure, has lower porosity, and can be better applied to wear resistance and corrosion resistance of petroleum pipelines.
The invention provides a simple and feasible method for plasma spraying by doping graphene nanosheets in iron-based amorphous powder. The formed composite amorphous coating has no heterogeneous phase and segregation, the coating can form passivation to improve corrosion resistance, and the mechanical property of the material is improved and the wear resistance of the material is improved due to the addition of the graphene nanosheets. The invention is expected to form a novel and efficient method for improving the corrosion resistance and the wear resistance of the surface of the material, greatly prolongs the service life of the petroleum pipeline and reduces the economic cost.
The invention is realized by the following technical scheme through 3 steps:
(1) preparing composite powder for plasma spraying;
(2) pretreating a substrate before spraying, including oil removal and decontamination, ultrasonic cleaning, drying and surface sand blasting before spraying;
(3) and (3) preparing the composite coating, namely melting the composite powder prepared in the step (1) by using a plasma spray gun with the model of 9MB, depositing the melted composite powder on the surface of the substrate pretreated in the step (2) and installed on a rotary worktable, and finally obtaining the graphene nanosheet/amorphous iron-based composite coating.
The particle size of the composite powder in the step (1) is 60-120 microns, and the composite powder comprises the following components in percentage by mass: 3.0-10.0 wt% of Graphene Nanosheets (GNS), 16.0-16.4 wt% of Cr, 9.7-14.0 wt% of Co, 0.1-0.6 wt% of Cu, 25.9-26.1 wt% of Mo, and the balance of Fe.
In the step (1), graphene nanosheets (GNS, sixth-element material science and technology Co., Ltd.) and iron-based amorphous powder (Beijing Sangs Purui new material Co., Ltd.) are fully mixed to achieve the purpose of uniformity, and then a planetary ball mill is used for fully ball-milling. The ball milling beads are zirconium dioxide with three specifications: the diameter of the large ball is 10mm, the diameter of the medium ball is 5mm, the diameter of the small ball is 3mm, and the material-ball ratio is selected (spraying composite powder: zirconium dioxide ball milling beads are 1: 1.5). Adjusting parameters of the planetary ball mill: the rotating speed is 380 r/min, the mode is a normal mode, and the ball milling time is 4 h.
And (2) putting the composite powder milled by the planetary ball mill in the step (1) into a drying oven at 60 ℃ for drying for 8h, pouring the composite powder into a mortar, grinding by using a grinding rod, sieving the ground powder by using an 80-mesh sieve, pouring the powder which cannot be removed into the mortar for secondary grinding, and repeating the steps until all the powder can be sieved.
Granulating the sieved powder by PVA (polyvinyl alcohol solution), pouring the composite powder which is sieved by 80-mesh sieve into a mortar, and only paving the bottom of the mortar all the time; sucking a proper amount of PVA solution (100g of composite powder corresponds to 150ml of PVA solution with the concentration of 5 wt.%) by using a rubber head dropper, and dropping the PVA solution on the composite powder; the PVA solution and the composite powder were mixed together with a grinding rod, and it was standard that the composite powder and the PVA solution were brought into sufficient contact so as to improve its fluidity.
The substrate in step (2) of the present invention includes, but is not limited to, stainless steel, titanium alloy, carbon steel, aluminum alloy, and copper alloy.
In the step (2), the matrix is pretreated in advance, acetone solution is used for oil removal and dirt removal, the medium for ultrasonic cleaning is absolute ethyl alcohol, and the base material is subjected to sand blasting before plasma spraying, so that an oxide layer on the surface is removed, the surface roughness of the base material is improved, the surface adhesive force of the coating is increased, the coating is not easy to fall off, and a compact coating is formed. The material used for sand blasting is brown corundum, the base material tool is placed in a sand blasting tank on a plate, sand grains obtain a pressure by utilizing compressed air (the pressure is 0.6MPa), a valve is opened by utilizing the pressure to mix the compressed air and the sand grains, the mixture is sprayed out through a rubber hose, a sand blasting nozzle forms an angle of 45 degrees with the base material in the sand blasting process, and each part needs to be blasted slowly at a constant speed in the moving process of the sand blasting nozzle. And then, the metal matrix tool after the pretreatment is arranged on the spraying used barrel, so that the pretreatment before the spraying of the base material is finished.
The preferred technique is the technique of the step (3) of the present inventionThe technical scheme is as follows: plasma spray H2The flow is 4-16 slpm, the Ar flow is 20-60 slpm, the spraying power range is 15-50 Kw, the spraying distance is 80-150 mm, the powder feeding rate is 20-40 g/min, the preheating times are 1-10 times, and the moving speed of the spraying gun nozzle relative to the rotary spraying surface is 5-120 mm/s.
The step (3) of the invention is preferably implemented as follows: the thickness range of the coating finally obtained by plasma spraying is 20-400 mu m.
The diameter of the rotary worktable in the step (3) is 50-300 mm, and the rotating speed is 120-300 rpm.
In the experimental process of step (3) of the present invention, it may occur that some powder is not melted and remains on the surface of the substrate or is oxidized at high temperature to form impurities to be attached to the surface of the substrate, which cause errors in the subsequent characterization process, so that the surface must be cleaned. And (3) putting the sprayed coating into a beaker, putting the beaker into an ultrasonic cleaning machine for cleaning, wherein the cleaning medium is absolute ethyl alcohol, and finally cleaning the beaker with deionized water for the last time, and then naturally drying the beaker.
Step (3) of the present invention in the course of the experiment, H2As the torch combustion gas, Ar is used as the plasma gas and the shielding gas.
In the step (3), in the experimental process, the hardness of the coating and the base material is measured by using a Vickers hardness tester; cross-sectional structure was observed under a microscope and coating thickness was measured; the wear resistance is measured by the load loaded on the surface of the coating by a friction wear meter; the microstructure of the iron-based powder and the coating is characterized by an X-ray diffractometer (XRD), an X-ray energy dispersion spectrometer (EDX) and a Field Emission Scanning Electron Microscope (FESEM); measuring the corrosion resistance of the coating by using an electrochemical workstation; the roughness of the coating surface was measured with a roughness tester.
The composite coating is simple to prepare and operate, the thickness and the spraying area are easy to control, the adaptability is relatively wide, and the production efficiency is high.
Compared with the prior art, the invention has the advantages that:
(1) according to the invention, a proper amount of graphene nanosheets are added into the amorphous iron-based coating, so that the quality of the coating can be improved, the coating is not easy to fall off in use, and the anti-wear and wear-resistant effects are achieved; and the price is low, and the cost performance is good.
(2) In the process of manufacturing the spraying powder, the planet ball mill is used for remixing, and then the more uniform components are changed into submicron-sized components from micron-sized components.
(3) Compared with the existing common spraying method, the plasma spraying coating adopted by the invention has higher density, can improve the wear-resisting and corrosion-resisting properties of the surface of the material, and has good economical efficiency.
The invention is further described in detail below with reference to the figures and the detailed description.
Description of the figures
FIG. 1 is an XRD (X-ray diffraction) spectrum of a graphene nanosheet/amorphous iron-based composite coating in examples 1-3;
FIG. 2 is a friction coefficient diagram of the graphene nanoplate/amorphous iron-based composite coating in examples 1-3;
fig. 3 is a surface SEM image of the graphene nanoplate/amorphous iron-based composite coating in example 1;
fig. 4 is a cross-sectional SEM image of the graphene nanoplate/amorphous iron-based composite coating in example 2;
FIG. 5 is a metallographic diagram of a cross section of a graphene nanosheet/amorphous iron-based composite coating in example 3;
FIG. 6 shows H at 0.5mol/L for the graphene nanosheet/amorphous iron-based composite coating in examples 1-32SO4Polarization curve of the solution;
FIG. 7 is a polarization curve of the graphene nanosheet/amorphous iron-based composite coating in 1mol/L NaOH solution in examples 1 to 3
Fig. 8 is a polarization curve of the graphene nanosheet/amorphous iron-based composite coating in the NaCl solution with the mass fraction of 3% in examples 1-3.
Detailed Description
The composite powder used before plasma spraying is obtained by mixing iron-based amorphous powder and Graphene Nano Sheets (GNS), and the following embodiment is that the two powders are mixed in different proportions.
Example 1
The first step is as follows: preparing graphene nanosheet/amorphous iron-based composite powder used for plasma spraying;
97g of iron-based amorphous powder (Cr 16.3 wt.%, Co 9.7 wt.%, Cu 0.2 wt.%, Mo 26.2 wt.%, Fe 47.6 wt.%) and 3g of Graphene Nanoplatelets (GNS) were weighed with a balance.
A clean nylon ball milling tank is selected, zirconium dioxide ball milling beads are selected during ball milling, the mass of the ball milling beads is calculated to be 150g according to the material-to-ball ratio (spraying composite powder: zirconium dioxide ball milling beads are 1:1.5), and 21.428g of large balls, 42.857g of medium balls and 85.714g of small balls are selected for full ball milling of the composite powder (the mass ratio of the large balls to the medium balls to the small balls is 1:2: 4). And (2) putting 100g of the weighed composite powder and zirconium dioxide ball-milling beads into a nylon ball-milling tank, then adding a proper amount of absolute ethyl alcohol, and fully stirring by using a glass rod to mix the ball-milling beads, the composite powder and the absolute ethyl alcohol together. Putting the ball milling tank on a planetary ball mill for full ball milling, and adjusting the parameters of the planetary ball mill: the rotating speed is 380 r/min, the mode is a normal mode, and the ball milling time is 4 h.
After ball milling of the composite powder on a planetary ball mill for 4 hours is finished, separating the composite powder mixed in the ethanol and the ball milling beads from a nylon ball milling tank, taking care not to pollute the composite powder and also not to damage in the whole process, then placing the composite powder into a tray, and after the ethanol is completely volatilized, placing the tray into a drying oven at 60 ℃ to dry for 8 hours. And pouring the composite powder into a mortar, grinding by using a grinding rod, sieving the powder after grinding by using an 80-mesh sieve, pouring the powder which cannot be removed into the mortar for secondary grinding, and repeatedly waiting until all the powder can be sieved.
The composite powder milled in the above steps has poor fluidity, and agglomeration is easily formed between the powders, so that the experiment cannot be continued due to the fact that a gun nozzle is easily blocked in the plasma spraying process, and the composite powder needs to be granulated to improve the fluidity of the composite powder. Preparing a PVA solution (specifically, 25g of a polyvinyl alcohol reagent is slowly added into 500 ml of deionized water at 100 ℃ and is naturally cooled to form the PVA solution after being completely dissolved). Pouring the composite powder which is sieved by the 80-mesh sieve into a mortar, and only fully paving the bottom of the mortar every time; sucking a proper amount of PVA solution by a rubber head dropper and dropping the PVA solution on the composite powder; the PVA solution and the composite powder were mixed together with a grinding rod, and it was standard that the composite powder and the PVA solution were brought into sufficient contact so as to improve its fluidity. Finally, all the powders are mixed according to the previous steps to complete the granulation of the composite powder. Similarly, we dried the granulated composite powder in a drying oven at 60 ℃ for 8 h. The previous milling step was repeated.
The second step is that: pretreating a substrate before spraying, including oil removal and decontamination, ultrasonic cleaning, drying and surface sand blasting before spraying;
the substrate sprayed this time was 45# steel (substrates described herein include, but are not limited to, stainless steel, titanium alloys, carbon steel, aluminum alloys, and copper alloys.) in the size of 20mm by 1mm small square pieces. Before spraying, a base body is pretreated, firstly, a base material is subjected to rust removal and oil stain removal, then, an ultrasonic cleaning machine is used for cleaning, a medium used in ultrasonic cleaning is absolute ethyl alcohol, and then, the base material is dried to obtain a clean 45# steel small square piece. Before plasma spraying, the base material is subjected to sand blasting treatment, so that an oxide layer on the surface is removed, the surface roughness of the base material is improved, the surface adhesion of the coating is increased, the coating is not easy to fall off, and a compact coating is formed. The material used for sand blasting is 60-mesh brown corundum, the base material tool is placed in a sand blasting tank on a plate, sand grains are enabled to obtain a pressure by utilizing compressed air (the pressure is 0.6MPa), a valve is opened by utilizing the pressure, the compressed air and the sand grains are mixed and are sprayed out through a rubber hose, a sand blasting nozzle forms an angle of 45 degrees with the base material in the sand blasting process, and each part needs to be blasted slowly at a constant speed in the moving process of the sand blasting nozzle. And then, the 45# steel base material after the pretreatment is finished is arranged on a spraying used barrel, so that the pretreatment before the base material spraying is finished.
The third step: preparation of composite coatings
The plasma spraying has high temperature of the composite coating just melted from the spray gun, so that the composite coating is not directly combined with a normal-temperature substrate, preheating treatment is needed to improve the adhesive force of the coating and the substrate, the preheating times are 5 times, and the temperature after preheating is about 60 ℃.
Spray gas H2Flow rate (slpm): spray gas Ar flow (slpm): 40, power (kW): 22.5, spray distance (mm): 90, powder feed rate (g/min): 30, spraying times are 20.
After the spraying, some powder may remain on the surface of the substrate without melting or be oxidized at high temperature to form impurities to be attached to the surface of the substrate, which cause errors in the subsequent characterization process, so that the surface must be cleaned. And (3) putting the sprayed coating into a beaker, putting the beaker into an ultrasonic cleaning machine for cleaning, wherein the cleaning medium is absolute ethyl alcohol, cleaning with deionized water for the last time, and naturally drying. The coatings were characterized after obtaining clean coated pieces. The average porosity of the coating was 2.79% and the average thickness of the coating was 221.3. mu.m
Example 2
The first step, the second step and the third step are all the same as the example 1, only the weighing proportion of the composite powder in the first step is adjusted, and 93g of iron-based amorphous powder and 7g of graphene nano-sheets (GNS) are weighed by using a balance.
The average porosity of the coating was 2.93% and the average thickness of the coating was 196.4 μm.
Example 3
Step one, step two and step three are all the same as example 1, only the weighing proportion of the composite powder in step one is adjusted, and 90g of iron-based amorphous powder and 10g of Graphene Nanoplatelets (GNS) are weighed by using a balance.
The average porosity of the coating was 3.01% and the average thickness of the coating was 185.7. mu.m
Comparative example 1
Comparative example 1 differs from example 1 in that:
and (3) only adjusting the weighing proportion of the composite powder in the step one, and weighing 99g of iron-based amorphous powder and 1g of Graphene Nano Sheets (GNS) by using balance.
A series of performance tests were performed on this comparative example in the same manner as in example 1, and the test results are shown in table 1: the friction coefficient is 0.516, the abrasion loss is 0.725g and is more than 3 groupsAny one set of the examples, illustrating that the abrasion resistance of the examples is better than that of the comparative example; likewise, at 0.5mol/L H2SO4The self-corrosion potential (mV) of the 3 groups of examples was higher than that of the comparative example in each of 1mol/L NaOH and 3% NaCl, indicating that the corrosion resistance of the examples was also better than that of the comparative example. The average porosity of the coating is 2.68%, and the average thickness of the coating is 247.6 μm, which indicates that the density and thickness of the coating are not greatly influenced by the small addition amount of graphene.
Comparative example 2
Comparative example 2 differs from example 1 in that:
and (3) only adjusting the weighing proportion of the composite powder in the step one, and weighing 85g of iron-based amorphous powder and 15g of Graphene Nano Sheets (GNS) by using balance.
A series of performance tests were performed on this comparative example in the same manner as in example 1, and the test results are shown in table 1: the coefficient of friction was 0.511 and the wear loss was 0.718g, greater than either of the 3 examples, indicating that the wear resistance of the examples is superior to that of the comparative example; likewise, at 0.5mol/L H2SO4The self-corrosion potential (mV) of the 3 groups of examples was higher than that of the comparative example in each of 1mol/L NaOH and 3% NaCl, indicating that the corrosion resistance of the examples was also better than that of the comparative example. The average porosity of the coating is 5.02%, and the average thickness of the coating is 156.6 μm, which indicates that the density and thickness of the coating are reduced when the graphene nano-sheets are added in too large amount.
Comparative example 3
Comparative example 3 differs from example 1 in that:
adjusting only the spraying gas H in step three2The flow rate (slpm) was adjusted from 12 in example 1 to 18.
A series of performance tests were performed on this comparative example in the same manner as in example 1, and the test results are shown in table 1: the coefficient of friction was 0.728, the wear loss was 1.023g, greater than any of the 3 examples, indicating that the wear performance of the example is better than the comparative example; likewise, at 0.5mol/L H2SO4The self-corrosion potential (mV) of the 3 groups of examples in 1mol/L NaOH and 3% NaCl are respectively higher than that of the comparative example, which shows the corrosion resistance of the examplesThe etching performance was also superior to that of the present comparative example. The average porosity of the coating was 6.79% and the average thickness of the coating was 134.4 μm, indicating that the higher the hydrogen flow, the higher the flame temperature, leaving pores, resulting in a reduction in the density and thickness of the coating.
Comparative example 4
Comparative example 4 differs from example 1 in that:
only the spraying distance (mm) in step three was adjusted from 90 to 160 in example 1.
This comparative example was characterized in the same manner as example 1, and the test results are shown in table 1: the coefficient of friction was 0.826 and the wear loss was 1.161g, greater than any of the 3 examples, indicating that the wear resistance of the examples is better than that of the comparative example; likewise, at 0.5mol/L H2SO4The self-corrosion potential (mV) of the 3 groups of examples was higher than that of the comparative example in each of 1mol/L NaOH and 3% NaCl, indicating that the corrosion resistance of the examples was also better than that of the comparative example. The average porosity of the coating was 6.47% and the average thickness of the coating was 188.9 μm, indicating that too large a spray distance would increase the residence time of the droplets in the flame and would also result in a reduction in the density and thickness of the coating.
Characterization of composite coatings
The hardness of the coating and the substrate was measured using a vickers hardness tester for the coatings prepared in examples 1 to 3; cross-sectional structure was observed under a microscope and coating thickness was measured; the wear resistance is measured by the load loaded on the surface of the coating by a friction wear meter; the microstructure of the iron-based powder and the coating is characterized by an X-ray diffractometer (XRD), an X-ray energy dispersion spectrometer (EDX) and a Field Emission Scanning Electron Microscope (FESEM); measuring the corrosion resistance of the coating by using an electrochemical workstation; the roughness of the coating surface was measured with a roughness tester.
The diffraction pattern obtained by carrying out X-ray diffraction detection on the composite coatings prepared in the embodiments 1-3 is shown in figure 1, and it can be seen from the figure that three groups of cases all have obvious diffuse scattering peaks with amorphous structures, and crystal phases are mainly alpha-Fe and C.
H of 0.5mol/L for the composite coating prepared in examples 1-32SO4Solution, 1mol/L NaOThe corrosion resistance test is carried out on the H solution and the NaCl solution with the mass fraction of 3%, and the obtained result is shown in figure 6, and the corrosion resistance of the composite coating is better than that of the matrix in the three solutions.
The composite coatings prepared in examples 1 to 3 were subjected to a frictional wear test, and the coating pieces were weighed before the measurement to obtain a starting mass M1, and after the wear test, the coating pieces were similarly weighed to obtain an ending mass M2. In the friction and wear test, the frequency of a small steel ball motor serving as a counter grinding pair is 3.6, the friction radius is 4mm, the test time is 10min, data are obtained, and the data are subjected to drawing analysis to obtain a graph 2.
The performance indexes of examples 1 to 3 and comparative examples 1 to 4 are shown in Table 1.
TABLE 1
Figure BDA0002238346250000111
The smaller the friction coefficient of the coating, the less wear, and the better the wear resistance of the coating. The more positive the self-corrosion potential, the better the corrosion resistance of the coating.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, and all modifications, equivalents, improvements, etc. that are made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (5)

1. A preparation method of a graphene nanosheet/amorphous iron-based composite coating is characterized by comprising the following specific steps:
(1) preparing graphene nanosheet/amorphous iron-based alloy composite powder for plasma spraying;
the preparation method of the composite powder comprises the steps of ball-milling and mixing the graphene nanosheets and the amorphous iron-based alloy, and granulating by using a PVA solution to obtain spraying powder with good fluidity;
the particle size of the composite powder is 60-120 mu m, and the composite powder comprises the following components in percentage by mass: 3.0-10.0 wt% of graphene nanosheets, 16.0-16.4 wt% of Cr, 9.7-14.0 wt% of Co, 0.1-0.6 wt% of Cu, 25.9-26.1 wt% of Mo, and the balance of Fe;
(2) before spraying, carrying out oil and stain removal, ultrasonic cleaning, drying and surface sand blasting pretreatment before spraying on the matrix;
(3) preparing a composite coating, namely melting the composite powder prepared in the step (1) by using a plasma spray gun with the model of 9MB, depositing the melted composite powder on the surface of a substrate pretreated in the step (2) and installed on a rotary worktable, and finally obtaining the graphene nanosheet/amorphous iron-based composite coating;
the plasma spraying conditions are as follows: h2The flow is 4-16 slpm, the Ar flow is 20-60 slpm, the spraying power is 15-50 kW, the spraying distance is 80-150 mm, the powder feeding rate is 20-40 g/min, the preheating frequency is 1-10 times, and the moving speed of a spraying gun nozzle relative to a rotary spraying surface is 5-120 mm/s.
2. The preparation method of the graphene nanosheet/amorphous iron-based composite coating according to claim 1, wherein: the substrate in the step (2) includes but is not limited to stainless steel, titanium alloy, carbon steel, aluminum alloy or copper alloy.
3. The preparation method of the graphene nanosheet/amorphous iron-based composite coating according to claim 1, wherein: the oil removal and decontamination in the step (2) are carried out by soaking in acetone solution, the medium for ultrasonic cleaning is absolute ethyl alcohol, the material for sand blasting is brown corundum with the particle size of 40-80 meshes, and the pressure for sand blasting is 0.4-0.7 Mpa.
4. The preparation method of the graphene nanosheet/amorphous iron-based composite coating according to claim 1, wherein: the diameter of the rotary worktable in the step (3) is 50-300 mm, and the rotating speed is 120-300 rpm.
5. The preparation method of the graphene nanosheet/amorphous iron-based composite coating according to claim 1, wherein: the thickness of the composite coating in the step (3) is 20-400 mu m.
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