CN109208046B - Method for in-situ electrodeposition of tungsten carbide/tungsten composite coating by molten salt - Google Patents
Method for in-situ electrodeposition of tungsten carbide/tungsten composite coating by molten salt Download PDFInfo
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Abstract
The invention discloses a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt, which comprises the steps of taking a tungstate system as a molten salt electrolyte, taking tungsten carbide or tungsten carbide-cobalt hard alloy as an auxiliary electrode, taking a conductive plated part subjected to polishing treatment as a working electrode, heating, melting, preserving heat, and carrying out in-situ electrodeposition to obtain the tungsten carbide/tungsten composite coating. The tungsten carbide/tungsten composite coating is prepared by a fused salt in-situ electrodeposition method, has the characteristics of high efficiency and short preparation flow, simultaneously takes a tungstate system as a fused salt electrolyte, has low volatility, can accelerate the electrochemical dissolution speed of an auxiliary electrode, is favorable for improving the recovery rate of the tungsten carbide/tungsten composite coating, can treat workpieces with curved surfaces, inner holes and other complex shapes, and has the advantages of simple process equipment, convenient operation, low cost and low pollution.
Description
Technical Field
The invention belongs to the technical field of molten salt electroplating, relates to a preparation method of a composite coating, and particularly relates to a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt.
Background
Tungsten-cobalt hard alloy has extremely high hardness and strength, has extremely wide application in industry, and is known as 'industrial teeth'; along with the large-scale application of the alloy in industry, the alloy faces a large amount of scrap, and if the scrap hard alloy can be recycled fully, the alloy has important significance for developing recycling economy.
Although the pure tungsten coating has certain hardness, strength and wear resistance, under complex working conditions, the composite tungsten coating taking tungsten carbide as a reinforcement has more advantages, and compared with the pure tungsten coating, the composite tungsten coating has higher hardness and strength, the wear resistance is further improved, and the application range is wider.
Because the potential of the tungsten is more negative than that of the hydrogen, the tungsten composite coating can only be prepared by a molten salt system, namely, the tungsten composite coating is prepared by in-situ electrodeposition of the molten salt system. Compared with non-in-situ electrodeposition, the in-situ electrodeposition coating has better contact with the substrate, and the coating and the substrate have good wettability and interface bonding performance, thereby being beneficial to reducing the crack tendency in the deposition process; moreover, the dispersion distribution of the reinforcing phase in the tungsten-based coating is beneficial to strengthening the coating and improving the wear resistance of the coating. Refractory metal carbides represented by tungsten carbide have the advantages of high hardness, good wear resistance and the like, so that in-situ electrodeposition of tungsten carbide hard phase and tungsten on a substrate is a good way for preparing a tungsten enhanced coating.
At present, from the viewpoints of high deposition speed, high product quality and the like, the processes for preparing the tungsten carbide/tungsten composite coating by a Chemical Vapor Deposition (CVD) method and a Plasma Spraying (PS) method are nearly mature, but the prepared tungsten carbide/tungsten composite coating still has some defects, such as weak crystallinity, matrix bonding force and high oxygen content; in the molten salt electroplating process, the coating and the surface of the plated part are fully diffused, the binding capacity is improved, and the cathode continuously generates electro-deoxidation reaction (reduction reaction), so that the oxygen content is lower.
So far, no relevant report about fused salt in-situ electrodeposition of tungsten carbide/tungsten composite coating is seen.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt.
The invention adopts the following technical scheme:
under the protection of inert gas, taking a tungstate system as a molten salt electrolyte, taking tungsten carbide or tungsten carbide-cobalt hard alloy as an auxiliary electrode and a conductive plating part as a working electrode, heating the molten salt electrolyte, preserving heat, and carrying out in-situ electrodeposition to obtain the tungsten carbide/tungsten composite coating.
In the technical scheme, the tungstate system is a mixture of tungstate and a molten salt active substance with a molar ratio of 1 (0.001-0.5).
Further, in the above technical scheme, the tungstate is Na2WO4、K2WO4、CaWO4Preferably Na2WO4。
Further, in the above technical solution, the molten salt active substance is NaPO3、NaF、KF、WO3、ZnO、B2O3One or more of (a).
In the technical scheme, the content of cobalt in the tungsten carbide-cobalt hard alloy is less than or equal to 6 wt%.
In the technical scheme, the surface roughness of the conductive plated part after grinding and polishing treatment is not more than Ra 1.6, and the conductivity is not less than 250S-cm-1The metal plated part of (1).
Still further, in the above technical solution, the electrodeposition is constant potential step in-situ electrodeposition or constant current step in-situ electrodeposition.
Still further, in the above technical solution, the process conditions of the constant potential step method in-situ electrodeposition are as follows: the potential is 0.2-2V, and the reference electrode is a metal platinum wire.
Still further, in the above technical solution, the process conditions of the constant current step method in-situ electrodeposition are as follows: the current density is 10-150mA/cm2。
In the above technical solution, the inert gas is selected from one of helium, neon and argon.
In the technical scheme, the temperature for heating, melting and heat preservation is 750-950 ℃.
Still further, in the above technical solution, the method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by using molten salt comprises the following steps:
s1, placing the tungsten carbide or the tungsten carbide-cobalt hard alloy subjected to mechanical cutting and polishing treatment in deionized water, acetone and alcohol in sequence for ultrasonic cleaning, and drying for later use;
s2, soaking the metal plated part after mechanical grinding and surface polishing in alkali liquor, then sequentially placing the metal plated part in deionized water, acetone and alcohol for ultrasonic cleaning, and drying for later use;
s3, heating the molten salt electrolyte after vacuum drying and dehydration for 12-24h at the temperature of 350 ℃ below zero to 900 ℃ at a constant heating rate under the protection of argon, and preserving heat for 2.5-4h to uniformly melt the molten salt;
s4, placing the auxiliary electrode and the working electrode in molten salt and adopting a constant potential step method for in-situ electrodeposition, or placing the auxiliary electrode, the working electrode and the reference electrode in molten salt and adopting a constant current step method for in-situ electrodeposition, cooling, taking out the metal plated part, soaking in alkali liquor, and drying to obtain the metal plated part.
Compared with the prior art, the invention has the following beneficial effects:
(1) the tungsten carbide/tungsten composite coating is prepared by a fused salt in-situ electrodeposition method, so that the tungsten carbide/tungsten composite coating has the characteristics of high efficiency and short preparation flow, meanwhile, a tungstate system is taken as a fused salt electrolyte, so that the tungsten carbide/tungsten composite coating has low volatility, and the waste hard alloy has high electrochemical activity due to the existence of tungstate, so that the electrochemical dissolution speed of the hard alloy is accelerated, and the recovery rate of the waste hard alloy is improved;
(2) the method selects the fused salt in-situ electrodeposition method to prepare the tungsten carbide/tungsten composite coating, can treat workpieces with curved surfaces, inner holes and other complex shapes, and has the advantages of simple process equipment, convenient operation, low cost and low pollution;
(3) the tungsten carbide/tungsten composite coating prepared by the fused salt in-situ electrodeposition method has the advantages of compact structure, complete crystal grains, high bonding strength, smooth surface, high hardness and good wear resistance, realizes the improvement of the performance of the tungsten coating, and can greatly reduce the pressure on the environment by selecting waste tungsten carbide-cobalt hard alloy as an auxiliary electrode.
Drawings
FIG. 1 is an XRD spectrum of a tungsten carbide/tungsten composite coating prepared by a molten salt in-situ electrodeposition method in example 1 of the present invention;
FIG. 2 is a low-magnification SEM photograph of a tungsten carbide/tungsten composite coating prepared by a molten salt in-situ electrodeposition method in example 1 of the present invention;
FIG. 3 is a high-power SEM photograph of a tungsten carbide/tungsten composite coating prepared by a molten salt in-situ electrodeposition method in example 1 of the present invention.
Detailed Description
In order to facilitate understanding of the present invention, the method for fused salt in-situ electrodeposition of a tungsten carbide/tungsten composite coating according to the present invention will be described in more detail with reference to the accompanying drawings and examples.
The preferred embodiment of the present invention is shown in the drawings; this invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The raw materials and the related experimental equipment used in the examples and comparative examples of the present invention are all commercially available products.
Example 1
The embodiment of the invention provides a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt, which is prepared by taking waste tungsten carbide as an auxiliary electrode and a molybdenum plate as a working electrode and adopting a constant-current step method in-situ electrodeposition process.
Specifically, the method comprises the following steps:
s1, simply and mechanically cutting the waste tungsten carbide to obtain a proper size, mechanically polishing, soaking in alkali liquor for 20 minutes, cleaning with deionized water, ultrasonically cleaning in acetone and alcohol, and drying for later use;
s2, mechanically grinding and polishing the molybdenum plate until the surface is smooth, soaking the molybdenum plate in alkali liquor for 20 minutes, then cleaning the molybdenum plate with deionized water, ultrasonically cleaning the molybdenum plate in acetone and alcohol, and drying the molybdenum plate for later use;
s3, mixing Na2WO4Drying in a vacuum drying oven at 300 deg.C for 12 hr, dewatering, and weighing a certain amount of Na2WO4Molten salt is put into an electrolytic cell, the temperature is raised to 900 ℃ at a stable temperature rise rate, and the temperature is kept for 3 hours to ensure that the molten salt is uniformly melted;
s4, placing the auxiliary electrode and the working electrode in molten salt, connecting an electrochemical workstation, adopting a constant current step method in-situ electrodeposition process, and setting the cathode current density at 50mA/cm2And performing electrodeposition for 5 hours, then taking out the working electrode, soaking the working electrode in alkali liquor, and cleaning salt in the coating to obtain the electrode.
Fig. 1 is an XRD spectrogram of the tungsten carbide/tungsten composite coating prepared by the molten salt in-situ electrodeposition method in example 1 of the present invention, and it can be seen from the XRD spectrogram that the prepared composite coating mainly comprises 3 phases, including both the matrix tungsten phase and two enhancement phases of tungsten carbide and ditungsten carbide, wherein the crystal form of the tungsten phase is body-centered cubic, the diffraction angles at 40.26 °, 58.27 °, 73.19 ° and 87.02 ° respectively correspond to the plane indices (110), (200), (211) and (220), and the tungsten carbide and the ditungsten carbide phases are both hexagonal crystal forms.
Fig. 2 is a low-magnification SEM photograph of the tungsten carbide/tungsten composite coating prepared by the molten salt in-situ electrodeposition method in example 1 of the present invention, and it can be seen from the figure that the prepared composite coating has a clear profile, a flat surface, no obvious protrusions and pits, a very low porosity, and a clean and smooth surface.
Fig. 3 is a high-power SEM photograph of the tungsten carbide/tungsten composite coating prepared by the molten salt in-situ electrodeposition method in example 1 of the present invention, and it can be seen from the figure that the grains of the prepared composite coating are obvious and complete, and have irregular shapes, compact arrangement between grains, few gaps, and high microcosmic density.
Example 2
The embodiment of the invention provides a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt, which is prepared by taking waste WC-6Co hard alloy (tungsten carbide-cobalt hard alloy with the cobalt content of 6 wt%) as an auxiliary electrode, a copper plate as a working electrode and a platinum wire as a reference electrode and adopting a constant potential step method in-situ electrodeposition process.
Specifically, the method comprises the following steps:
s1, simply and mechanically cutting the waste WC-6Co hard alloy to obtain a proper size, mechanically polishing, soaking in alkali liquor for 20 minutes, cleaning with deionized water, ultrasonically cleaning in acetone and alcohol, and drying for later use;
s2, mechanically grinding and polishing the copper plate until the surface is smooth, soaking the copper plate in alkali liquor for 20 minutes, then cleaning the copper plate with deionized water, ultrasonically cleaning the copper plate in acetone and alcohol, and drying the copper plate for later use, meanwhile, grinding the platinum wire with abrasive paper, cleaning the platinum wire with alcohol, and drying the platinum wire for later use;
s3, mixing Na2WO4And NaPO3Drying in a vacuum drying oven at 300 deg.C for 12 hr, and dehydrating with Na as molar percentage2WO4：NaPO31: 0.15 separately weighing Na2WO4And NaPO3Putting the uniformly mixed molten salt into an electrolytic cell, raising the temperature to 850 ℃ at a stable heating rate, and keeping the temperature for 3 hours to uniformly melt the molten salt;
s4, placing the auxiliary electrode, the working electrode and the reference electrode in molten salt, connecting an electrochemical workstation, adopting a constant potential step method in-situ electrodeposition process, setting the voltage to be 1.5V, performing electrodeposition for 10 hours, then taking out the working electrode, soaking in alkali liquor, and cleaning salt in the coating to obtain the electrode.
Example 3
The embodiment of the invention provides a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt, which takes waste tungsten carbide as an auxiliary electrode and a stainless steel plate as a working electrode and adopts a constant-current step method in-situ electrodeposition process for preparation.
Specifically, the method comprises the following steps:
s1, simply and mechanically cutting the waste tungsten carbide to obtain a proper size, mechanically polishing, soaking in alkali liquor for 20 minutes, cleaning with deionized water, ultrasonically cleaning in acetone and alcohol, and drying for later use;
s2, mechanically grinding and polishing the stainless steel plate until the surface is smooth, soaking the stainless steel plate in alkali liquor for 20 minutes, then cleaning the stainless steel plate with deionized water, ultrasonically cleaning the stainless steel plate in acetone and alcohol, and drying the stainless steel plate for later use;
s3, mixing K2WO4And KF is dried in a vacuum drying oven at 300 ℃ for 24 hours in advance, and is dehydrated, wherein the molar percentage is K2WO4: KF ═ 1: 0.2 separately weigh K2WO4And KF, putting the uniformly mixed molten salt into an electrolytic cell, raising the temperature to 850 ℃ at a stable heating rate, and keeping the temperature for 3 hours to uniformly melt the molten salt;
s4, placing the auxiliary electrode and the working electrode in molten salt, connecting an electrochemical workstation, adopting a constant current step method in-situ electrodeposition process, and setting the cathode current density at 80mA/cm2And performing electrodeposition for 15 hours, then taking out the working electrode, soaking the working electrode in alkali liquor, and cleaning salt in the coating to obtain the electrode.
Comparative example 1
The invention provides a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt, which takes waste WC-9.5Co hard alloy (tungsten carbide-cobalt hard alloy with 9.5 wt% of cobalt) as an auxiliary electrode, takes a stainless steel plate as a working electrode and adopts a constant current step method in-situ electrodeposition process for preparation.
Specifically, the method comprises the following steps:
s1, simply and mechanically cutting the waste WC-9.5Co hard alloy to obtain a proper size, mechanically polishing, soaking in alkali liquor for 20 minutes, cleaning with deionized water, ultrasonically cleaning in acetone and alcohol, and drying for later use;
s2, mechanically grinding and polishing the stainless steel plate until the surface is smooth, soaking the stainless steel plate in alkali liquor for 20 minutes, then cleaning the stainless steel plate with deionized water, ultrasonically cleaning the stainless steel plate in acetone and alcohol, and drying the stainless steel plate for later use;
s3, mixing K2WO4And ZnO is dried in a vacuum drying oven at 300 ℃ for 24 hours in advance, and dehydration treatment is carried out according to the molar percentage of K2WO4: 1-ZnO: 0.12 each independentlyWeighing K2WO4And ZnO, putting the uniformly mixed molten salt into an electrolytic cell, raising the temperature to 850 ℃ at a stable temperature rise rate, and keeping the temperature for 3 hours to uniformly melt the molten salt;
s4, placing the auxiliary electrode and the working electrode in molten salt, connecting an electrochemical workstation, adopting a constant current step method in-situ electrodeposition process, and setting the cathode current density to 65mA/cm2And performing electrodeposition for 9 hours, then taking out the working electrode, soaking the working electrode in alkali liquor, and cleaning salt in the coating to obtain the electrode.
Comparative example 1 the coating prepared has a complex phase, not only contains a matrix tungsten phase, a tungsten carbide reinforcing phase and a ditungsten carbide reinforcing phase, but also contains a cobalt phase, and the coating prepared has poor comprehensive mechanical properties.
Comparative example 2
The invention provides a method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt, which is prepared by taking waste tungsten carbide as an auxiliary electrode, a molybdenum plate as a working electrode and Ag/AgCl as a reference electrode and adopting a constant potential step method in-situ electrodeposition process.
Specifically, the method comprises the following steps:
s1, simply and mechanically cutting the waste tungsten carbide to obtain a proper size, mechanically polishing, soaking in alkali liquor for 20 minutes, cleaning with deionized water, ultrasonically cleaning in acetone and alcohol, and drying for later use;
s2, mechanically grinding and polishing the molybdenum plate until the surface is smooth, soaking the molybdenum plate in alkali liquor for 20 minutes, then cleaning the molybdenum plate with deionized water, ultrasonically cleaning the molybdenum plate in acetone and alcohol, and drying the molybdenum plate for later use, meanwhile, grinding the silver wires with abrasive paper, cleaning the silver wires with alcohol, and drying the silver wires for later use;
s3, mixing Na2WO4And NaPO3Drying in a vacuum drying oven at 300 deg.C for 12 hr, and dehydrating with Na as molar percentage2WO4：NaPO31: 0.09 separately weighing Na2WO4And NaPO3Putting the uniformly mixed molten salt into an electrolytic cell, raising the temperature to 850 ℃ at a stable heating rate, and keeping the temperature for 3 hours to uniformly melt the molten salt;
s4, placing the auxiliary electrode, the working electrode and the reference electrode in molten salt, connecting an electrochemical workstation, adopting a constant potential step method in-situ electrodeposition process, setting the voltage to be 3.2V, performing electrodeposition for 10 hours, then taking out the working electrode, soaking in alkali liquor, and cleaning salt in the coating to obtain the electrode.
Comparative example 2 could not produce a coating with a dense structure and a smooth surface, a large amount of nodules and a few powder deposits appeared on the surface of the coating, and the combination property was poor.
The coatings prepared in the embodiments and the comparative examples of the invention are detected, and the adhesive force is tested by a grid method; the wear resistance of the abrasion meter at room temperature (CS-10 grinding wheel, 500g load force, 500 times of circulation) is adopted, and the mass loss of the abrasion meter is used for representing the abrasion resistance; the hardness was measured using a vickers hardness tester, and the specific results are shown in table 1 below.
TABLE 1 comparison table of mechanical properties of coatings prepared in each experimental example and comparative example of the present invention
The results in table 1 show that the embodiment of the invention selects a fused salt in-situ electrodeposition method to prepare the tungsten carbide/tungsten composite coating, has the characteristics of high efficiency and short preparation flow, and simultaneously takes a tungstate system as a fused salt electrolyte, so that the tungstate system has lower volatility, and the existence of tungstate enables waste hard alloy to have very high electrochemical activity, thereby accelerating the electrochemical dissolution speed of hard alloy, being beneficial to improving the recovery and utilization rate of the waste hard alloy; the tungsten carbide/tungsten composite coating prepared by the fused salt in-situ electrodeposition method in the embodiment of the invention has the advantages of compact structure, complete crystal grains, high bonding strength, smooth surface, high hardness and good wear resistance, realizes the improvement of the performance of the tungsten coating, and can greatly reduce the pressure on the environment by selecting the waste tungsten carbide-cobalt hard alloy as the auxiliary electrode.
Finally, the above is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating by molten salt is characterized in that under the protection of inert gas, a tungstate system is taken as a molten salt electrolyte, tungsten carbide or tungsten carbide-cobalt hard alloy is taken as an auxiliary electrode, a conductive plated part is taken as a working electrode, the molten salt electrolyte is heated and melted, then heat preservation is carried out, and in-situ electrodeposition is carried out, so as to obtain the tungsten carbide/tungsten composite coating;
wherein the tungstate system is a mixture of tungstate and a molten salt active substance with a molar ratio of 1 (0.001-0.5), and the tungstate is Na2WO4、K2WO4、CaWO4The molten salt active substance is NaPO3、NaF、KF、WO3、ZnO 、B2O3One or more of (a); the content of cobalt in the tungsten carbide-cobalt hard alloy is less than or equal to 6 wt%; the electrodeposition is constant potential step method in-situ electrodeposition or constant current step method in-situ electrodeposition, and the process conditions of the constant potential step method in-situ electrodeposition are as follows: the potential is 0.2-2V, the reference electrode is a metal platinum wire, and the process conditions of the constant current step method in-situ electrodeposition are as follows: the current density is 10-150mA/cm2(ii) a The temperature for heating, melting and heat preservation is 750-950 ℃.
2. The method of fused salt in-situ electrodeposition of tungsten carbide/tungsten composite coating according to claim 1, wherein the tungstate is preferably Na2WO4。
3. The method for in-situ electrodeposition of a tungsten carbide/tungsten composite coating through molten salt according to claim 1, wherein the conductive plated part is polished to have a surface roughness of not more than Ra 1.6 and an electrical conductivity of not less than 250S-cm-1The metal plated part of (1).
4. The method of fused salt in-situ electrodeposition of a tungsten carbide/tungsten composite coating according to claim 1, wherein the inert gas is selected from one of helium, neon and argon.
5. The molten salt in-situ electrodeposition method of tungsten carbide/tungsten composite coating according to any one of claims 1 to 4, characterized by comprising the steps of:
s1, placing the tungsten carbide or the tungsten carbide-cobalt hard alloy subjected to mechanical cutting and polishing treatment in deionized water, acetone and alcohol in sequence for ultrasonic cleaning, and drying for later use;
s2, soaking the metal plated part after mechanical grinding and surface polishing in alkali liquor, then sequentially placing the metal plated part in deionized water, acetone and alcohol for ultrasonic cleaning, and drying for later use;
s3, heating the molten salt electrolyte after vacuum drying and dehydration for 12-24h at the temperature of 350 ℃ below zero to 900 ℃ at a constant heating rate under the protection of argon, and preserving heat for 2.5-4h to uniformly melt the molten salt;
s4, placing the auxiliary electrode and the working electrode in molten salt and adopting a constant potential step method for in-situ electrodeposition, or placing the auxiliary electrode, the working electrode and the reference electrode in molten salt and adopting a constant current step method for in-situ electrodeposition, cooling, taking out the metal plated part, soaking in alkali liquor, and drying to obtain the metal plated part.
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