Preparation method of high-strength fine-grain nickel-tungsten alloy coating

Abstract

The invention provides a preparation method of a high-strength fine-grain nickel-tungsten alloy coating, which comprises the following steps: a preparation process: mixing a first metal salt containing a first metal, a metal salt containing a second metal, a complexing agent and an additive to obtain an electroplating solution, the first metal being tungsten, the first metal being different from the second metal, and the metal salt containing the second metal being different from the complexing agent; the additive comprises saccharin cobalt and / or an organic metal salt containing unsaturated bonds; and an electroplating procedure: placing a to-be-electroplated workpiece and an anode in the electroplating solution for electroplating treatment so as to form a nickel-tungsten alloy coating on the surface of the to-be-electroplated workpiece. According to the preparation method, the tungsten content in the nickel-tungsten alloy coating can be increased, the size of crystal grains in the nickel-tungsten alloy coating can be reduced, and therefore the increasing development requirement is met.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to a method for preparing a high-strength fine-grained nickel-tungsten alloy coating. Background Art

[0002] Nickel-tungsten alloy coatings are favored due to their excellent properties such as high hardness and high wear resistance, and are widely used in various mechanical parts. Among them, the tungsten content and its grain size have a greater impact on the alloy structure and properties. Generally, the higher the tungsten content and the smaller the grain size, the better the wear resistance and the higher the hardness of the coating.

[0003] However, in the related art, the high content and small grain size of nickel-tungsten alloy cannot be met at the same time, resulting in its hardness and wear resistance failing to meet the increasing development needs. Summary of the invention

[0004] The present invention provides a method for preparing a high-strength fine-grained nickel-tungsten alloy coating, which can not only increase the tungsten content in the nickel-tungsten alloy coating, but also reduce the size of the grains in the nickel-tungsten alloy coating, thereby meeting the increasing development needs.

[0005] The embodiment of the present invention provides a method for preparing a high-strength fine-grained nickel-tungsten alloy coating, comprising:

[0006] a preparation step of mixing a first metal salt containing a first metal, a metal salt containing a second metal, a complexing agent and an additive to obtain an electroplating solution, wherein the first metal is tungsten, the first metal and the second metal are different, and the additive comprises saccharinate cobalt and / or an organic metal salt containing an unsaturated bond;

[0007] The electroplating process is to place the workpiece to be electroplated and the anode in the electroplating solution for electroplating to form a nickel-tungsten alloy coating on the surface of the workpiece to be electroplated.

[0008] According to any of the aforementioned embodiments of the present invention, the mass concentration of the additive in the electroplating solution is 0.05 g / L to 0.2 g / L.

[0009] According to any of the aforementioned embodiments of the present invention, the mass ratio of the saccharin cobalt to the organic metal salt is (2-3):1.

[0010] According to any of the foregoing embodiments of the present invention, the organic metal salt comprises alkenyl cobalt.

[0011] According to any of the foregoing embodiments of the present invention, the alkenyl cobalt comprises cyclopentadienyl cobalt.

[0012] According to any of the aforementioned embodiments of the present invention, the complexing agent includes at least one of lactic acid, citric acid, succinic acid, malic acid, glacial acetic acid and salts thereof.

[0013] According to any of the aforementioned embodiments of the present invention, the first metal salt includes sodium tungstate and / or ammonium tungstate.

[0014] According to any of the aforementioned embodiments of the present invention, the mass concentration of the first metal salt in the electroplating solution is 20 g / L to 40 g / L.

[0015] According to any of the aforementioned embodiments of the present invention, the second metal salt includes at least one of nickel titanate, nickel sulfate, and nickel chloride.

[0016] According to any of the foregoing embodiments of the present invention, the current density of the electroplating process is 15 d / dm 2 ~20d / dm 2 .

[0017] The method for preparing a high-strength fine-grained nickel-tungsten alloy coating provided by the embodiment of the present invention can reduce the size of the grains in the coating and reduce the impurity content in the coating during the electroplating process through the additives in the electroplating solution, namely, saccharin cobalt and / or an organic metal salt containing an unsaturated bond, so that the coating can be formed into a dense structure while increasing the tungsten content in the coating. Therefore, the preparation method provided by the embodiment of the present invention can not only increase the tungsten content in the nickel-tungsten alloy coating, but also reduce the size of the grains in the nickel-tungsten alloy coating, thereby meeting the increasing development needs.

[0018] The present invention also provides a high-strength fine-grained nickel-tungsten alloy coating prepared according to the above preparation method.

[0019] The above description is only an overview of the technical solution of this specification. In order to more clearly understand the technical means of this specification, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of this specification more obvious and easy to understand, the specific implementation methods of this specification are listed below.

[0020] Instruction Manual

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments are briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without creative work.

[0022] Figure 1 A schematic flow chart of a method for preparing a high-strength fine-grained nickel-tungsten alloy coating provided in some embodiments of the present invention is shown. DETAILED DESCRIPTION

[0023] The "range" disclosed in the present invention is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of the particular range. The range defined in this way can be inclusive or exclusive of the end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range.

[0024] Unless otherwise specified, the terms used in the present invention have the commonly understood meanings that are generally understood by those skilled in the art.

[0025] Unless otherwise specified, the values ​​of the parameters mentioned in the present invention can be measured by various test methods commonly used in the art, for example, they can be measured according to the test methods given in the embodiments of the present invention.

[0026] See also Figure 1 As shown, an embodiment of the present invention provides a method for preparing a high-strength fine-grained nickel-tungsten alloy coating, comprising:

[0027] S100, a preparation step of mixing a first metal salt containing a first metal, a metal salt containing a second metal, a complexing agent, and an additive to obtain an electroplating solution, wherein the first metal is tungsten, the first metal and the second metal are different, and the additive includes saccharinate cobalt and / or an organic metal salt containing an unsaturated bond;

[0028] S200, electroplating process, placing the workpiece to be electroplated and the anode in the electroplating solution for electroplating treatment to form a nickel-tungsten alloy coating on the surface of the workpiece to be electroplated.

[0029] In the embodiments provided by the present invention, the first metal salt and the second metal salt in the electroplating solution can increase the concentration of tungsten metal and other metals for the formation of the coating; the complexing agent can combine with the impurity metal to form a precipitate during the electroplating process to reduce the deposition of the impurity metal on the surface of the workpiece to be electroplated, that is, entering the nickel-tungsten alloy coating; saccharinate cobalt can limit the increase of the grain size in the coating, which can help form a dense structure of the coating; the organic metal salt containing unsaturated bonds can decompose free radicals during the electroplating process, and the free radicals can quickly combine with the active sites on the surfaces of the anode and cathode, reduce the decomposition of the complexing agent, and thus reduce the impurities in the coating.

[0030] The method for preparing a high-strength fine-grained nickel-tungsten alloy coating provided by the embodiment of the present invention can reduce the size of the grains in the coating and reduce the impurity content in the coating during the electroplating process through the additives in the electroplating solution, namely, saccharin cobalt and an organic metal salt containing an unsaturated bond, so that the coating can be formed into a dense structure while increasing the tungsten content in the coating. Therefore, the preparation method provided by the embodiment of the present invention can not only increase the tungsten content in the nickel-tungsten alloy coating, but also reduce the size of the grains in the nickel-tungsten alloy coating, thereby meeting the increasing development needs.

[0031] In some embodiments of the present invention, the mass concentration of the additive in the electroplating solution is 0.05 g / L to 0.2 g / L. When the mass concentration of the additive is set within the above range, it can help to increase the tungsten content in the coating and reduce the size of the grains, so that the coating has higher hardness and wear resistance.

[0032] In addition, the reasonable distribution of the mass of saccharinate cobalt and organic metal salt in the additive can help to further increase the tungsten content in the coating and reduce the grain size.

[0033] In some embodiments of the present invention, the mass ratio of saccharin cobalt to the organic metal salt is (2-3):1.

[0034] In the embodiment of the present invention, a suitable organic metal salt can help reduce the impurity content in the coating to increase the tungsten content in the coating, and can also further help reduce the size of grains in the coating.

[0035] In some embodiments of the present invention, the organic metal salt includes alkenyl cobalt. The alkenyl cobalt decomposes in the electroplating process to generate free radicals and cobalt ions, wherein the free radicals can combine with the active sites on the anode and the cathode to reduce the decomposition of the complexing agent, thereby reducing the impurity content in the coating. The cobalt ions can refine the size of the tungsten grains in the coating, thereby helping to form a dense structure coating, thereby further improving the hardness and wear resistance of the coating.

[0036] In some specific embodiments of the present invention, the alkenyl cobalt includes cyclopentadienyl cobalt.

[0037] In some embodiments of the present invention, the complexing agent includes at least one of lactic acid, citric acid, succinic acid, malic acid, glacial acetic acid and salts thereof.

[0038] In some embodiments of the present invention, the first metal salt includes sodium tungstate and / or ammonium tungstate.

[0039] In some embodiments of the present invention, the mass concentration of the first metal salt in the electroplating solution is 20 g / L to 40 g / L.

[0040] In some embodiments of the present invention, the second metal salt includes at least one of nickel titanate, nickel sulfate, and nickel chloride. By using at least one of nickel titanate, nickel sulfate, and nickel chloride, a nickel-tungsten alloy coating with better wear resistance can be formed.

[0041] In some embodiments of the present invention, the current density of the electroplating process is 15 d / dm 2 ~20d / dm 2 .

[0042] Furthermore, in some embodiments of the present invention, the pH of the electroplating solution is set in the range of 5 to 7, the temperature of the electroplating treatment is in the range of 50° C. to 70° C., and the electroplating time is 10 min to 60 min.

[0043] The following embodiments describe the disclosure of the present invention in more detail, and these embodiments are only for illustrative purposes, because it is obvious to those skilled in the art that various modifications and variations are made within the scope of the disclosure of the present invention. Unless otherwise stated, all parts, percentages and ratios reported in the following embodiments are based on mass, and all reagents used in the embodiments are commercially available or synthesized according to conventional methods, and can be used directly without further processing, and the instruments used in the embodiments are commercially available.

[0044] Example 1

[0045] This embodiment provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0046] A mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, 20 g / L sodium tungstate, and 0.2 g / L saccharin cobalt is prepared using deionized water, and then ammonia water is added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0047] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0048] Example 2

[0049] This embodiment provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0050] A mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, 20 g / L sodium tungstate, and 0.2 g / L cyclopentadienyl cobalt (CAS No.: 1277-43-6) is prepared using deionized water, and then ammonia water is added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0051] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0052] Example 3

[0053] This embodiment provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0054] A mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, 20 g / L sodium tungstate, 0.15 g / L saccharinate cobalt and 0.05 g / L cyclopentadienyl cobalt (CAS No.: 1277-43-6) was prepared using deionized water, and ammonia water was added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0055] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0056] Example 4

[0057] This embodiment provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0058] A mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, 20 g / L sodium tungstate, 0.1 g / L saccharinate cobalt and 0.05 g / L cyclopentadienyl cobalt (CAS No.: 1277-43-6) was prepared using deionized water, and ammonia water was added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0059] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0060] Example 5

[0061] This embodiment provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0062] A mixed solution containing 20 g / L nickel titanate, 100 g / L citric acid, 20 g / L sodium tungstate, 0.15 g / L saccharinate cobalt and 0.05 g / L cyclopentadienyl cobalt (CAS No.: 1277-43-6) was prepared using deionized water, and ammonia water was added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0063] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0064] Comparative Example 1

[0065] This comparative example provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0066] Deionized water is used to prepare a mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, and 20 g / L sodium tungstate, and then ammonia water is added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0067] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0068] Comparative Example 2

[0069] This comparative example provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0070] A mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, 20 g / L sodium tungstate, and 0.1 g / L saccharin is prepared using deionized water, and then ammonia water is added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0071] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0072] Comparative Example 3

[0073] This comparative example provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy coating, comprising:

[0074] A mixed solution containing 20 g / L nickel sulfate, 100 g / L citric acid, 20 g / L sodium tungstate, and 0.1 g / L pentene is prepared using deionized water, and ammonia water is added to the mixed solution to adjust its pH to 6 to obtain an electroplating solution;

[0075] Use carbon steel sheet (workpiece to be plated) as cathode and stainless steel as anode, at a temperature of 40°C and a cathode current density of 10A / dm 2 Electroplating was carried out under the conditions of 15 min to obtain a nickel-tungsten alloy coating sample.

[0076] Test Section

[0077] 1) Grain size test

[0078] The nickel-tungsten alloy coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were characterized by transmission electron microscopy. TEM samples (5 μm×10 μm×0.08 μm) were prepared using a focused ion beam (FIB) and tested using a Thermo Fisher Talos F200X scanning transmission electron microscope with an acceleration voltage of 100 kV-200 kV. The test results are shown in Table 1.

[0079] 2) Hardness test

[0080] The test was carried out according to the method of national standard GB / T4340-1990. The test results are shown in Table 1.

[0081] 3) Wear resistance test

[0082] The nickel-tungsten alloy coatings prepared in Examples 1 to 5 and Comparative Examples 1 to 3 were placed on a vertical universal wear tester to test their wear. The rotation speed during the test was 300 rpm, the load was 9 N, the grinding wheel was GCr15, the test time was 1 h, and the test results are shown in Table 1.

[0083] Table 1 Test results of Examples 1 to 5 and Comparative Examples 1 to 3

[0084] Serial number Grain size Hardness (HV) Wear resistance Example 1 3.8nm 1435 10.2mg Example 2 4.0nm 1354 11.5mg Example 3 3.3nm 1652 9.0mg Example 4 3.5nm 1581 9.3mg Example 5 3.0nm 1857 8.5mg Comparative Example 1 7.4nm 521 19.9mg Comparative Example 2 5.7nm 845 15.3mg Comparative Example 3 7.0nm 576 18.7mg

[0085] According to Table 1, by comparing the test results of Examples 1 to 5 and Comparative Examples 1 to 3, it can be seen that the embodiment of the present invention can reduce the size of the grains in the coating and reduce the impurity content in the coating during the electroplating process through the additives in the electroplating solution, namely, saccharin cobalt and the organic metal salt containing unsaturated bonds, so that the coating can be formed into a dense structure while increasing the tungsten content in the coating. Therefore, the preparation method provided by the embodiment of the present invention can not only increase the tungsten content in the nickel-tungsten alloy coating, but also reduce the size of the grains in the nickel-tungsten alloy coating, thereby meeting the increasing development needs.

[0086] Finally, it should be noted that the above experimental examples are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned experimental examples, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned experimental examples, or replace some or all of the technical features therein with equivalents. These modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the experimental examples of the present invention.

Claims

1. A method for preparing a high-strength fine-grained nickel-tungsten alloy coating, characterized in that: include: a preparation step of mixing a first metal salt containing a first metal, a metal salt containing a second metal, a complexing agent and an additive to obtain an electroplating solution, wherein the first metal is tungsten, the first metal and the second metal are different, and the additive comprises saccharinate cobalt and / or an organic metal salt containing an unsaturated bond; The electroplating step is to place the workpiece to be electroplated and the anode in the electroplating solution for electroplating to form a nickel-tungsten alloy coating on the surface of the workpiece to be electroplated; The second metal salt includes at least one of nickel titanate, nickel sulfate and nickel chloride.

2. The preparation method according to claim 1, characterized in that: The mass concentration of the additive in the electroplating solution is 0.05 g / L to 0.2 g / L.

3. The preparation method according to claim 2, characterized in that: The mass ratio of the saccharin cobalt to the organic metal salt is (2-3):

1.

4. The preparation method according to any one of claims 1 to 3, characterized in that The organometallic salt includes alkenylcobalt.

5. The preparation method according to claim 4, characterized in that: The alkenyl cobalt includes cyclopentadienyl cobalt.

6. The preparation method according to claim 1, characterized in that: The complexing agent includes at least one of lactic acid, citric acid, succinic acid, malic acid, glacial acetic acid and salts thereof.

7. The preparation method according to claim 1, characterized in that: The first metal salt includes sodium tungstate and / or ammonium tungstate.

8. The preparation method according to claim 1, characterized in that: The mass concentration of the first metal salt in the electroplating solution is 20 g / L to 40 g / L.

9. The preparation method according to claim 1, characterized in that: The current density of the electroplating process is 15d / dm 2 ~20d / dm 2 .

10. A high-strength fine-grained nickel-tungsten alloy coating prepared according to the preparation method according to any one of claims 1 to 9.

Images