CN115074729A - High-hot-hardness Ni-W-based high-hardness ceramic phase composite coating and preparation method thereof - Google Patents
High-hot-hardness Ni-W-based high-hardness ceramic phase composite coating and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 238000005238 degreasing Methods 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 238000004506 ultrasonic cleaning Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000007781 pre-processing Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 31
- 229910001369 Brass Inorganic materials 0.000 claims description 24
- 239000010951 brass Substances 0.000 claims description 24
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 9
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
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- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims 1
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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
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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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
- 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
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
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- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a preparation method of a Ni-W-based high-hardness ceramic phase composite coating with high hot hardness, which comprises the following steps: step S1, mechanically preprocessing the substrate to make the surface smooth; then degreasing and ultrasonic cleaning are carried out, activation treatment is carried out, and an oxide layer is removed. And step S2, depositing a Ni-W coating in a nickel ion-tungstate-citrate system electroplating solution by using direct current with graphite as an anode. Step S3, in the process of electrodepositing the Ni-W coating by S2, adding urea solution containing high-hardness ceramic phase particles into the plating solution and stirring at a high speed of 300 r/min to prepare the deposited Ni-W based high-hardness ceramic phase composite coating. And step S4, carrying out vacuum heat treatment on the coating obtained by the deposition of the S3 to obtain the final annealed Ni-W based high-hardness ceramic phase composite coating. The invention has simple operation, easy control of conditions and good repeatability, and the composite coating has good high-temperature hardness and wear resistance.
Description
Technical Field
The invention belongs to the field of alloy coating preparation and application, and relates to a Ni-W-based high-hardness ceramic phase composite coating with high hot hardness and a preparation method thereof, in particular to preparation of a Ni-W-based composite coating which takes Ni and W as main elements and contains one or more high-hardness ceramic phases.
Background
With the progress of industrialization, in the past, Cr plating is mainly used in the traditional industry, and the traditional Cr plating technology is gradually eliminated due to the defects of toxicity, high waste liquid treatment cost and the like. At present, the Ni-W-based plating layer enters the visual field of people with the advantages of high comprehensive performance, convenient and fast operation and the like. And the composite plating layer made of Ni and other alloys can be made into plating layers with different functionalities through a plating solution formula, so that the research on the relevant preparation process and performance of the Ni-W-based plating layer has great application development space and prospect. Although Ni-based plating has certain advantages over Cr-based plating, with the development of modernization, binary Ni-W-based alloys have not been able to meet certain requirements of scientific production, so we often use composite electrodeposition to surface-modify parts. Composite electrodeposition is a surface protection technique for obtaining functional coatings. The nickel-based composite coating which is stable in the atmospheric environment can be prepared by the composite electrodeposition method, and compared with a film prepared by a single-phase electrodeposition method, the film has stronger passivation capability, higher hardness and brighter surface, so that the surface performance of the material is effectively improved, and certain economic benefits can be generated in the aspects of decorative coating and the like. One or more high-hardness ceramic phases are used as dispersed particles to prepare the Ni-W-based composite coating, so that the wear resistance of the coating can be further improved to achieve the purpose of repairing the surface of a part.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a preparation method of a Ni-W-based high-hardness ceramic phase composite coating with high hot hardness, the process is simple to operate, the conditions are easy to control, the repeatability is good, the prepared deposition coating is well combined with a matrix, the film forming quality is good, and the hardness and the wear resistance are good at high temperature.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a Ni-W-based high-hardness ceramic phase composite coating with high hot hardness comprises the following steps:
step S1, mechanically preprocessing the substrate to make the surface smooth; then, degreasing and ultrasonic cleaning are carried out on the surface of the substrate by using a commercial degreasing agent, and the surface of the substrate is activated to remove an oxide layer.
And step S2, depositing a Ni-W coating by using direct current in a nickel ion-tungstate-citrate system electroplating solution by taking graphite as an anode.
And S3, adding urea solution containing high-hardness ceramic phase particles into the plating solution in the process of electrodepositing the Ni-W coating at S2, and stirring at a high speed of 200-400 r/min to prepare the deposited Ni-W-based high-hardness ceramic phase composite coating.
And S4, carrying out vacuum heat treatment on the coating obtained by the deposition in the S3 to obtain the final annealed Ni-W-based high-hardness ceramic phase composite coating.
Preferably, the substrate is one of brass sheet, stainless steel or low carbon steel; the ultrasonic cleaning time is 10-30 min, and the activating solution is dilute hydrochloric acid or dilute sulfuric acid with volume fraction of 5-15%.
Preferably, the nickel ion-tungstate-citrate system electroplating solution of step S2Comprises 20-120 g/L nickel sulfate, 5-80 g/L sodium tungstate, 5-40 g/L ammonium chloride, 5-60 g/L sodium carbonate, 30-150 g/L sodium citrate, 0.02-0.25 g/L sodium dodecyl sulfate and 0.5-3 g/L saccharin sodium. The DC deposition current density is 0.5-5.0A/dm 2 The deposition time is 10-30 min.
Preferably, the urea solution in step S3 is a mixed solution containing urea and high-hardness ceramic phase particles, the pH of the mixed solution is 3 to 8 after the mixed solution is mixed with the plating solution in step S2, the deposition time is 5 to 30 min, and the high-hardness ceramic phase particles are one or more of SiC ceramic phase particles, TiC ceramic phase particles and WC ceramic phase particles. The concentration of each component in the urea solution is respectively as follows: 0-20 g/L of urea and not 0; 0-30 g/L, TiC g/L of SiC ceramic phase particles and 0-30 g/L of WC ceramic phase particles, and not 0 at the same time.
Preferably, the vacuum heat treatment of the deposited coating in step S4 is specifically: heating the mixture from room temperature to 300-700 ℃, preserving the heat for 30-300 min, and naturally cooling the mixture; the temperature rise time is 60min, and the preferred maximum temperature is 500-700 ℃.
Preferably, the high-hardness ceramic phase is preferably contained in the composite coating layer in an amount in the range of 10% or less.
The invention provides a preparation method of a Ni-W-based high-hardness ceramic phase composite coating with high hot hardness, wherein the high-hardness ceramic phase is mainly a mixed solution of one or more high-hardness ceramic phases of SiC ceramic, TiC ceramic particles and WC ceramic. The Ni-W-based high-hardness ceramic phase composite coating prepared by the electro-deposition method has the advantages of uniform and compact surface, no obvious crack and pore defects and good combination of a film layer and a matrix. The high-hardness ceramic phase nano particles are uniformly dispersed in the Ni-W alloy coating, but with the increase of the addition amount of the high-hardness ceramic phase in the coating solution, the deposition amount of the high-hardness ceramic phase on the surface of the substrate is increased firstly and then decreased. The addition of the high-hardness ceramic phase particles can play a certain role in grain refinement of the coating, and the refinement effect is more obvious compared with that of the Ni-W film after the annealing at 700 ℃. The strengthening of the film layer at 700 ℃ is caused by the combined action of grain refinement and other precipitated phases after mutual diffusion. The high-hardness ceramic phase nano particles can improve the wear resistance of the Ni-W based composite coating by improving the hardness of the film. Meanwhile, a certain antifriction effect is achieved through the self-lubricating property of part of high-hardness ceramic phase particles. Particularly, with the increase of the annealing temperature, when the temperature reaches 700 ℃, the friction mechanism is changed from adhesive wear to abrasive wear, and the wear resistance and the friction and wear resistance are obviously improved.
From the aspects of raw materials, preparation process and product structure, the invention has the following advantages:
1. the process has the advantages of simple operation, easily controlled conditions and good repeatability.
2. The prepared deposition coating has good combination with the matrix and good film forming quality.
3. The obtained coating has good hardness and wear resistance at high temperature.
4. The coating uses Ni-W as a main element, and the heat stability of the Ni-W based coating structure is improved by adding a mixed solution of one or more high-hardness ceramic phases of SiC ceramic, TiC ceramic particles and WC ceramic, and the heat resistance of the coating is good.
Drawings
FIG. 1 is a parameter diagram of a coating heat treatment process;
FIG. 2 SEM pictures of the micro-morphology of Ni-W coating at different temperatures: (a) no annealing treatment, (b) example 1, (c) example 2, (d) example 3.
Detailed Description
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure.
The present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the invention. The examples, where specific techniques and reaction conditions are not indicated, can be carried out according to the techniques or conditions or product specifications described in the literature in the field. Reagents, instruments or equipment of any manufacturer not indicated are commercially available.
Example 1
Mechanically pretreating the brass sheet to make the brass sheet have a smooth surface; then degreasing and ultrasonic cleaning the surface of the steel plate by using a commercial degreasing agent for 10 min, and using 10 volume percent of dilute sulfurAnd (4) carrying out activation treatment on the surface of the brass sheet by acid to remove an oxidation layer. Graphite is used as an anode, and a current density of 2A/cm is adopted in an electroplating solution containing 60 g/L of nickel sulfate, 10 g/L of sodium tungstate, 10 g/L of ammonium chloride, 10 g/L of sodium carbonate, 80g/L of sodium citrate, 0.1 g/L of sodium dodecyl sulfate and 1.5 g/L of saccharin sodium 2 Depositing a Ni-W coating by direct current, adding 10 g/L urea and 10 g/L SiC ceramic particle phase into the plating solution after 5 min of deposition, stirring at a high speed of 300 r/min, and depositing to obtain the Ni-W based high-hardness ceramic phase composite coating. And drying the coating obtained by deposition to remove moisture, and performing heat treatment at 500 ℃ for 1h to obtain the Ni-W-SiC composite coating with the SiC content of 3.1 wt.%.
Example 2
Mechanically pretreating the brass sheet to make the surface of the brass sheet smooth; then, degreasing and ultrasonic cleaning are carried out on the surface of the brass sheet for 10 min by using a commercial degreasing agent, and activation treatment is carried out on the surface of the brass sheet by using dilute sulfuric acid with the volume fraction of 10% to remove an oxidation layer. Graphite is used as an anode, and a current density of 2A/cm is adopted in an electroplating solution containing 60 g/L of nickel sulfate, 10 g/L of sodium tungstate, 10 g/L of ammonium chloride, 10 g/L of sodium carbonate, 80g/L of sodium citrate, 0.1 g/L of sodium dodecyl sulfate and 1.5 g/L of saccharin sodium 2 Depositing the Ni-W coating by direct current, adding 10 g/L urea and 10 g/L SiC ceramic particle phase into the plating solution after 5 min of deposition, stirring at a high speed of 300 r/min, and depositing to obtain the Ni-W-SiC composite coating. And drying the coating obtained by deposition to remove moisture, and performing heat treatment at 600 ℃ for 1h to obtain the Ni-W-SiC composite coating with the SiC content of 5.7 wt.%.
Example 3
Mechanically pretreating the brass sheet to make the surface of the brass sheet smooth; and then degreasing and ultrasonically cleaning the surface of the brass sheet for 10 min by using a commercial degreasing agent, and activating the surface of the brass sheet by using dilute sulfuric acid with the volume fraction of 10% to remove an oxide layer. Graphite is used as an anode, and a current density of 2A/cm is adopted in an electroplating solution containing 60 g/L of nickel sulfate, 10 g/L of sodium tungstate, 10 g/L of ammonium chloride, 10 g/L of sodium carbonate, 80g/L of sodium citrate, 0.1 g/L of sodium dodecyl sulfate and 1.5 g/L of saccharin sodium 2 Depositing Ni-W coating by direct current, adding urea into the plating solution after beginning deposition for 5 min10 g/L and 10 g/L of SiC ceramic particle phase, and stirring at a high speed of 300 r/min, and depositing to obtain the Ni-W-SiC composite coating. And drying the coating obtained by deposition to remove moisture, and performing heat treatment at 700 ℃ for 1h to obtain the Ni-W-SiC composite coating with the SiC content of 6.2 wt.%.
Example 4
Mechanically pretreating the brass sheet to make the surface of the brass sheet smooth; then, degreasing and ultrasonic cleaning are carried out on the surface of the brass sheet for 10 min by using a commercial degreasing agent, and activation treatment is carried out on the surface of the brass sheet by using dilute sulfuric acid with the volume fraction of 10% to remove an oxidation layer. Graphite is used as an anode, and a current density of 2A/cm is adopted in an electroplating solution containing 60 g/L of nickel sulfate, 10 g/L of sodium tungstate, 10 g/L of ammonium chloride, 10 g/L of sodium carbonate, 80g/L of sodium citrate, 0.1 g/L of sodium dodecyl sulfate and 1.5 g/L of saccharin sodium 2 Depositing the Ni-W coating by direct current, adding 10 g/L urea and 10 g/L WC ceramic particle phase into the plating solution after beginning to deposit for 5 min, and stirring at a high speed of 300 r/min to deposit and obtain the Ni-W-WC composite coating. And drying the coating obtained by deposition to remove moisture, and performing heat treatment at 500 ℃ for 1h to obtain the Ni-W-WC composite coating with the WC content of 6.1 wt.%.
Example 5
Mechanically pretreating the brass sheet to make the surface of the brass sheet smooth; and then degreasing and ultrasonically cleaning the surface of the brass sheet for 10 min by using a commercial degreasing agent, and activating the surface of the brass sheet by using dilute sulfuric acid with the volume fraction of 10% to remove an oxide layer. Graphite is used as an anode, and a current density of 2A/cm is adopted in an electroplating solution containing 60 g/L of nickel sulfate, 10 g/L of sodium tungstate, 10 g/L of ammonium chloride, 10 g/L of sodium carbonate, 80g/L of sodium citrate, 0.1 g/L of sodium dodecyl sulfate and 1.5 g/L of saccharin sodium 2 Depositing the Ni-W coating by direct current, adding 10 g/L urea and 10 g/L WC ceramic particle phase into the plating solution after beginning to deposit for 5 min, and stirring at a high speed of 300 r/min to deposit and obtain the Ni-W-WC composite coating. And drying the coating obtained by deposition to remove moisture, and performing heat treatment at 600 ℃ for 1h to obtain the Ni-W-WC composite coating with the WC content of 8.5 wt.%.
Example 6
Mechanically pretreating the brass sheet to make the surface of the brass sheet smooth; then treated with commercial degreasing agentDegreasing and ultrasonically cleaning the surface for 10 min, and activating the surface of the brass sheet by using dilute sulfuric acid with the volume fraction of 10% to remove an oxide layer. Graphite is used as an anode, and a current density of 2A/cm is adopted in an electroplating solution containing 60 g/L of nickel sulfate, 10 g/L of sodium tungstate, 10 g/L of ammonium chloride, 10 g/L of sodium carbonate, 80g/L of sodium citrate, 0.1 g/L of sodium dodecyl sulfate and 1.5 g/L of saccharin sodium 2 Depositing the Ni-W coating by direct current, adding 10 g/L urea and 10 g/L WC ceramic particle phase into the plating solution after beginning to deposit for 5 min, and stirring at a high speed of 300 r/min to deposit and obtain the Ni-W-WC composite coating. And drying the coating obtained by deposition to remove moisture, and performing heat treatment at 700 ℃ for 1h to obtain the Ni-W-WC composite coating with the WC content of 9.5 wt.%.
See table 1 for details.
From the above table, it can be seen that the Ni — W based SiC high-hardness ceramic phase composite coatings obtained in examples 1, 2, and 3 have monotonically increasing hardness with increasing annealing temperature, and the coatings also exhibit good hot hardness. The friction coefficient and the abrasion loss of the coating are reduced, and the high-temperature wear resistance of the coating is improved. The Ni-W based WC high-hardness ceramic phase composite coatings obtained in the examples 4, 5 and 6 have monotonous hardness increase along with the increase of the environment temperature, and the coatings also have good hot hardness. The friction coefficient and the abrasion loss of the coating are reduced, and the high-temperature wear resistance of the coating is also improved.
As can be seen from fig. 2(a-d), the SiC content in the composite coating varied at different annealing temperatures, and the roughness of the coating surface increased with increasing annealing temperature.
Examples 1-3 show that as the annealing temperature increases, the SiC content of the coating surface increases, indicating that annealing the composite coating aids in the attachment of SiC particles to the coating. This contributes to the increase in coating hardness and wear resistance, as shown in table 1.
Other embodiments of the invention will be apparent to those skilled in the art from consideration of the specification and practice of the invention disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
It is to be understood that the present invention is not limited to what has been described above, and that various modifications and changes may be made without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (9)
1. A preparation method of a high-hot-hardness Ni-W-based high-hardness ceramic phase composite coating is characterized by comprising the following steps:
step S1, mechanically preprocessing the substrate to make the surface smooth; then degreasing and ultrasonic cleaning the surface of the substrate by using a degreasing agent, and activating the surface of the substrate to remove an oxide layer;
s2, depositing a Ni-W coating in a nickel ion-tungstate-citrate system electroplating solution by using direct current with graphite as an anode;
step S3, in the process of electrodepositing the Ni-W coating in the step S2, adding urea solution containing high-hardness ceramic phase particles into the plating solution, and stirring at a high speed of 200-400 r/min to prepare a deposition state Ni-W based high-hardness ceramic phase composite coating;
and step S4, carrying out vacuum heat treatment on the coating deposited in the step S3 to obtain the final annealed Ni-W-based high-hardness ceramic phase composite coating, namely the high-hot-hardness Ni-W-based high-hardness ceramic phase composite coating.
2. The method according to claim 1, wherein the substrate of step S1 is one of brass sheet, stainless steel or low carbon steel; the ultrasonic cleaning time is 10-30 min, and the activating solution is dilute hydrochloric acid or dilute sulfuric acid with the volume fraction of 10-25%.
3. The method according to claim 1, wherein the nickel ion-tungstate-citrate system electroplating solution in step S2 is an aqueous solution containing nickel sulfate, sodium tungstate, nickel chloride, sodium citrate, sodium lauryl sulfate, and sodium saccharin.
4. The method according to claim 3, wherein the concentrations of the components in the nickel ion-tungstate-citrate system plating solution are as follows: 10-120 g/L of nickel sulfate, 3-80 g/L of sodium tungstate, 3-40 g/L of ammonium chloride, 3-60 g/L of sodium carbonate, 20-150 g/L of sodium citrate, 0.01-0.30 g/L of sodium dodecyl sulfate and 0.2-3 g/L of saccharin sodium.
5. The method according to claim 1, wherein the galvanic deposition in step S2 has a current density of 0.5 to 5.0A/dm 2 The deposition time is 10-40 min.
6. The method according to claim 1, wherein the urea solution in step S3 is a mixed solution containing urea and high-hardness ceramic phase particles, the pH value of the mixed solution is 3-8 after the mixed solution is mixed with the plating solution in step S2, the deposition time is 5-30 min, and the high-hardness ceramic phase particles are one or more of SiC ceramic phase particles, TiC ceramic phase particles and WC ceramic phase particles.
7. The process according to claim 6, characterized in that the concentrations of the constituents of the urea solution are: 0-20 g/L of urea and not 0; 0-30 g/L, TiC g/L of SiC ceramic phase particles and 0-30 g/L of WC ceramic phase particles, and not 0 at the same time.
8. The method according to claim 1, wherein the vacuum heat treatment of step S4 is specifically: heating the mixture from room temperature to 300-700 ℃, preserving the heat for 30-300 min, and naturally cooling the mixture; the temperature rise time was 60 min.
9. A high hot hardness Ni-W based high hard ceramic phase composite coating produced by the production method according to any one of claims 1 to 8.
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