A method for preparing a high-strength fine-grained nickel-tungsten alloy coating

Abstract

The application provides a preparation method of a high-strength fine-grain nickel-tungsten alloy coating, comprising the following steps: a preparation process, in which a first metal salt containing a first metal, a metal salt containing a second metal, a complexing agent and an additive are mixed to obtain an electroplating solution, wherein the first metal is tungsten, the first metal and the second metal are different, and the additive comprises cobalt saccharinate and / or an organic metal salt containing an unsaturated bond; and an electroplating process, in which a workpiece to be electroplated and an anode are placed in the electroplating solution to perform electroplating treatment, so as to form a nickel-tungsten alloy coating on the surface of the workpiece to be electroplated. The preparation method 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 increasingly increasing development requirements.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of plating, in particular to a preparation method of high-strength fine-grain nickel-tungsten alloy plating. BACKGROUND

[0002] Nickel-tungsten alloy plating is favored due to its high hardness and high wear resistance, and is widely used in various mechanical parts. The tungsten content and grain size have a great influence on the structure and performance of the alloy. Generally, the higher the tungsten content and the smaller the grain size, the better the wear resistance and the higher the hardness of the plating.

[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 that the hardness and wear resistance cannot meet the increasing development needs. SUMMARY

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

[0005] The present application provides a preparation method of high-strength fine-grain nickel-tungsten alloy plating, which can not only increase the tungsten content in the nickel-tungsten alloy plating, but also reduce the size of the grains in the nickel-tungsten alloy plating, thereby meeting the increasing development needs.

[0006] The preparation method comprises the following steps:

[0007] The preparation method comprises the following steps:

[0008] According to any of the preceding embodiments of the present application, 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 preceding embodiments of the present application, the mass ratio of the cobalt saccharinate and the organic metal salt is (2-3):1.

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

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

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

[0013] According to any of the preceding embodiments of the present application, the first metal salt comprises sodium tungstate and / or ammonium tungstate.

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

[0015] According to any of the preceding embodiments of the present application, the second metal salt comprises at least one of nickel titanate, nickel sulfate, and nickel chloride.

[0016] According to any of the preceding embodiments of the present application, the current density of the electroplating process is 15-20 d / dm 2 2 .

[0017] The preparation method of the high-strength fine-grain nickel-tungsten alloy plating layer provided by the embodiments of the present application can reduce the size of the grains in the plating layer and reduce the impurity content in the plating layer by adding an additive, i.e., cobalt saccharinate and / or an organic metal salt containing an unsaturated bond, in the electroplating solution, so that the plating layer with a dense structure can be formed, and the tungsten content in the plating layer can be increased. Therefore, the preparation method provided by the embodiments of the present application can not only increase the tungsten content in the nickel-tungsten alloy plating layer, but also reduce the size of the grains in the nickel-tungsten alloy plating layer, thereby meeting the increasingly increasing development requirements.

[0018] The present application also provides a high-strength fine-grain nickel-tungsten alloy plating layer prepared according to the above preparation method.

[0019] The above description is only a summary of the technical solutions of the present application. In order to more clearly understand the technical means of the present application, the specific embodiments of the present application can be implemented according to the content of the present application, and in order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the following specific embodiments of the present application are described.

[0020] Drawings of the specification

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application, and therefore should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.

[0022] Figure 1 The flowchart of the preparation method of the high-strength fine-grain nickel-tungsten alloy plating layer provided by some embodiments of the present application is shown. Specific embodiments

[0023] ​The ranges disclosed herein are intended to be "open" ranges, meaning that the stated range includes the endpoints, unless otherwise specifically stated. Thus, for example, a range of 1 to 10 includes 1 and 10. The ranges disclosed herein can be combined with other ranges, even though the ranges are disclosed in the context of separate embodiments. For example, a range of 1 to 10 can be combined with a range of 4 to 8 to form a range of 1 to 8, 1 to 10, or 4 to 10.

[0024] Unless otherwise defined, all terms used in disclosing the application, including technical and scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which the application pertains.

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

[0026] Reference is made to Figure 1 As shown in the accompanying drawings, the embodiment of the application provides a preparation method of high-strength fine-grained nickel-tungsten alloy plating layer, comprising:

[0027] S100, 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, wherein the first metal is tungsten, the first metal and the second metal are not the same, and the additive includes cobalt saccharin and / or an organic metal salt containing an unsaturated bond;

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

[0029] In the embodiments provided by the application, the first metal salt and the second metal salt in the electroplating solution can improve the tungsten metal and other metals for the formation of the plating layer; the complexing agent can combine with impurity metals to form precipitates in the electroplating process, so as to reduce the deposition of impurity metals on the surface of the workpiece to be electroplated, i.e., into the nickel-tungsten alloy plating layer; the cobalt saccharin can limit the increase of the grain size in the plating layer, which can help to form a plating layer with a dense structure; the organic metal salt containing an unsaturated bond can decompose free radicals in the electroplating process, and the free radicals can quickly combine with active sites on the surfaces of the anode and the cathode, reducing the decomposition of the complexing agent, and thus reducing impurities in the plating layer.

[0030] The preparation method of the high-strength fine-grain nickel-tungsten alloy coating provided by the embodiment of the present application can reduce the size of the grains in the coating and reduce the impurity content in the coating by adding the additives, i.e., cobalt saccharinate and organic metal salt containing unsaturated bonds, in the electroplating solution, so that the tungsten content in the coating can be increased while the coating with a dense structure is formed. Therefore, the preparation method provided by the embodiment of the present application 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 requirements.

[0031] In some embodiments of the present application, the mass concentration of the additives in the electroplating solution is 0.05 g / L to 0.2 g / L. When the mass concentration of the additives is set within the above range, the tungsten content in the coating can be increased and the size of the grains can be reduced, so that the coating has higher hardness and wear resistance.

[0032] In addition, reasonable allocation of the mass of the cobalt saccharinate and the organic metal salt in the additives can further increase the tungsten content in the coating and reduce the size of the grains.

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

[0034] In the embodiments of the present application, the suitable organic metal salt can not only help to reduce the impurity content in the coating to increase the tungsten content in the coating, but also further help to reduce the size of the grains in the coating.

[0035] In some embodiments of the present application, the organic metal salt includes alkenyl cobalt. The alkenyl cobalt is decomposed to generate free radicals and cobalt ions in the electroplating process, wherein the free radicals can bind to 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 coating with a dense structure, so as to further improve the hardness and wear resistance of the coating.

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

[0037] In some embodiments of the present application, 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 application, the first metal salt includes sodium tungstate and / or ammonium tungstate.

[0039] In some embodiments of the present application, 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 application, the second metal salt comprises at least one of nickel titanate, nickel sulfate, and nickel chloride. By at least one of nickel titanate, nickel sulfate, and nickel chloride, a nickel tungsten alloy plating layer with better wear resistance can be formed.

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

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

[0043] The following embodiments describe the present application in more detail, which are only used for illustrative purposes, and various modifications and changes within the scope of the present application are obvious to those skilled in the art. 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 treatment, and the instruments used in the embodiments are commercially available.

[0044] Example 1

[0045] The present embodiment provides a preparation method of a high-hardness fine-grained nickel tungsten alloy plating layer, comprising:

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

[0047] A carbon steel sheet (a workpiece to be plated) is used as the cathode, and stainless steel is used as the anode, and electroplating is carried out at a temperature of 40°C, a cathode current density of 10 A / dm 2 for 15 min to obtain a nickel tungsten alloy plating layer sample.

[0048] Example 2

[0049] The present embodiment provides a preparation method of a high-hardness fine-grained nickel tungsten alloy plating layer, comprising:

[0050] A mixed solution containing nickel sulfate 20 g / L, citric acid 100 g / L, sodium tungstate 20 g / L, and cobalt saccharinate 0.2 g / L is prepared using deionized water, and then ammonia water is added to the mixed solution to adjust the pH to 6 to obtain an electroplating solution;

[0051] A carbon steel sheet (workpiece to be plated) is used as the cathode, and stainless steel is used as the anode, and electroplating is performed at a temperature of 40°C and a cathode current density of 10 A / dm 2 for 15 min under the conditions to obtain a nickel-tungsten alloy plating layer sample.

[0052] Example 3

[0053] The present example provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy plating layer, comprising:

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

[0055] A carbon steel sheet (workpiece to be plated) is used as the cathode, and stainless steel is used as the anode, and electroplating is performed at a temperature of 40°C and a cathode current density of 10 A / dm 2 for 15 min under the conditions to obtain a nickel-tungsten alloy plating layer sample.

[0056] Example 4

[0057] The present example provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy plating layer, comprising:

[0058] A mixed solution containing nickel sulfate 20 g / L, citric acid 100 g / L, sodium tungstate 20 g / L, cobalt saccharinate 0.15 g / L, and cyclopentadienyl cobalt 0.05 g / L (CAS No.: 1277-43-6) is prepared using deionized water, and ammonia water is added to the mixed solution to adjust the pH to 6 to obtain an electroplating solution;

[0059] A carbon steel sheet (workpiece to be plated) is used as the cathode, and stainless steel is used as the anode, and electroplating is performed at a temperature of 40°C and a cathode current density of 10 A / dm 2 for 15 min under the conditions to obtain a nickel-tungsten alloy plating layer sample.

[0060] Example 5

[0061] The present example provides a method for preparing a high-hardness fine-grained nickel-tungsten alloy plating layer, comprising:

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

[0063] The carbon steel sheet (workpiece to be plated) is used as the cathode, and the stainless steel is used as the anode, and the electroplating is carried out at a temperature of 40℃ and a cathode current density of 10 A / dm 2 The electroplating is carried out for 15 min under the conditions of a temperature of 40℃ and a cathode current density of 10 A / dm

[0064] Comparative Example 1

[0065] The comparative example provides a preparation method of a high-hardness fine-grained nickel-tungsten alloy plating layer, which comprises the following steps:

[0066] A mixed solution containing nickel sulfate with a concentration of 20 g / L, citric acid with a concentration of 100 g / L, and sodium tungstate with a concentration of 20 g / L is prepared using deionized water, and then ammonia water is added to the mixed solution to adjust the pH to 6, so as to obtain an electroplating solution;

[0067] The carbon steel sheet (workpiece to be plated) is used as the cathode, and the stainless steel is used as the anode, and the electroplating is carried out at a temperature of 40℃ and a cathode current density of 10 A / dm 2 The electroplating is carried out for 15 min under the conditions of a temperature of 40℃ and a cathode current density of 10 A / dm

[0068] Comparative Example 2

[0069] The comparative example provides a preparation method of a high-hardness fine-grained nickel-tungsten alloy plating layer, which comprises the following steps:

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

[0071] The carbon steel sheet (workpiece to be plated) is used as the cathode, and the stainless steel is used as the anode, and the electroplating is carried out at a temperature of 40℃ and a cathode current density of 10 A / dm 2 The electroplating is carried out for 15 min under the conditions of a temperature of 40℃ and a cathode current density of 10 A / dm

[0072] Comparative Example 3

[0073] The comparative example provides a preparation method of a high-hardness fine-grained nickel-tungsten alloy plating layer, which comprises the following steps:

[0074] A mixed solution containing nickel sulfate with a concentration of 20 g / L, citric acid with a concentration of 100 g / L, and sodium tungstate with a concentration of 20 g / L is prepared using deionized water, and then ammonia water is added to the mixed solution to adjust the pH to 6, so as to obtain an electroplating solution;

[0075] The carbon steel sheet (workpiece to be plated) is used as the cathode, and the stainless steel is used as the anode, and the electroplating is carried out at a temperature of 40℃ and a cathode current density of 10 A / dm 2 The electroplating is carried out for 15 min under the conditions of a temperature of 40℃ and a cathode current density of 10 A / dm

[0076] Test Part

[0077] 1) Grain size test

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

[0079] 2) Hardness test

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

[0081] 3) Wear resistance test

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

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

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

[0085] According to Table 1, it can be seen from the comparison of the test results of Examples 1-5 and Comparative Examples 1-3 that, by adding the additives, i.e. saccharin cobalt and organic metal salt containing unsaturated bond, in the electroplating solution, the size of the grains in the plating layer can be reduced and the impurity content in the plating layer can be reduced in the electroplating process, so that the plating layer with a dense structure can be formed, and the tungsten content in the plating layer can be improved. Therefore, the preparation method provided by the examples of the present application can not only improve the tungsten content in the nickel-tungsten alloy plating layer, but also reduce the size of the grains in the nickel-tungsten alloy plating layer, 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 application, but not to limit them; although the present application has been described in detail with reference to the foregoing experimental examples, those skilled in the art should understand that: they can still modify the technical solutions recorded in the foregoing experimental examples, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the experimental examples of the present application.

Claims

1. A method for producing a high-strength fine-grained nickel-tungsten alloy coating, characterized in that The preparation method comprises the following steps: A preparation process, in which a first metal salt containing a first metal, a metal salt containing a second metal, a complexing agent and an additive are mixed to obtain an electroplating solution, wherein the first metal is tungsten, the first metal and the second metal are different, and the additive is cobalt saccharinate and / or cyclopentadienyl cobalt; An electroplating process, in which a workpiece to be electroplated and an anode are placed in the electroplating solution to perform electroplating treatment, so as to form a nickel-tungsten alloy plating layer on the surface of the workpiece to be electroplated. The second metal salt comprises at least one of nickel titanate, nickel sulfate and nickel chloride. The mass concentration of the additive in the electroplating solution is 0.05 g / L-0.2 g / L, and the mass concentration of the first metal salt in the electroplating solution is 20 g / L-40 g / L.

2. The production method according to claim 1, characterized by, The mass ratio of the cobalt saccharinate to the cyclopentadienyl cobalt is (2-3):

1.

3. The preparation method according to claim 1, characterized in that, The complexing agent comprises at least one of lactic acid, citric acid, succinic acid, malic acid, glacial acetic acid and a salt thereof.

4. The method of claim 1, wherein, The first metal salt comprises sodium tungstate and / or ammonium tungstate. 5.A high-strength fine-grained nickel-tungsten alloy plating layer prepared by the preparation method according to any one of claims 1-4.

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