CN119900059A - A kind of electroplating solution and manufacturing method of rhodium alloy coating - Google Patents
A kind of electroplating solution and manufacturing method of rhodium alloy coating Download PDFInfo
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The application discloses an electroplating solution and a manufacturing method of a rhodium alloy plating layer, wherein each liter of the electroplating solution comprises rhodium salt, a PH regulator, alloy element salt, a phosphorus-containing additive, a low-stress agent, a wetting agent and the balance of water, and the alloy element salt comprises iridium sulfate and/or indium sulfate. The electroplating solution of the application introduces alloy elements and simultaneously adds additives and changes the current parameters of electroplating, so that the plating layer has lower stress and very high toughness, and meanwhile, the special advantage of high hardness of the rhodium plating layer is maintained.
Description
Technical Field
The application relates to the technical field of semiconductor coating, in particular to a manufacturing method of a high-toughness coating.
Background
The electroplating process is an excellent method for manufacturing the metal coating, has the characteristics of low cost, wide controllable range of process parameters, high purity of the coating, high deposition rate and the like, and is an indispensable process step in high and new technology industries such as micro-electromechanical systems and the like which need extremely fine structures, and is used for casting specific metal structures in micro-nano dimensions. Rhodium plating has a relatively high hardness, low contact resistance, and excellent corrosion resistance, and is commonly used for electrical or physical contact structures. However, high brittleness is accompanied with high hardness, so that the plastic is easy to break under external force, and the application scene and the service life of the plastic are greatly limited.
The current common electroplated rhodium alloy is mainly rhodium-ruthenium alloy, and the hardness of ruthenium is higher, so that more hardness cannot be lost after alloying, and the rhodium-ruthenium alloy has limited help for toughness improvement.
Disclosure of Invention
The application aims to solve the problems of high brittleness and easy fracture of a rhodium coating in the prior art. The application provides a plating solution and a method for manufacturing a rhodium alloy plating layer, which can manufacture the rhodium alloy plating layer with high toughness.
In order to achieve the above purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides a plating solution, wherein each liter of the plating solution comprises the following components in weight:
the balance of water and a PH regulator, wherein the alloy element salt contains iridium sulfate and/or indium sulfate, and the PH regulator ensures that the PH range of the electroplating solution is 0.2-3.
The electroplating solution is suitable for application in the fields of electronic products and semiconductors, the alloy element salt is iridium sulfate and/or indium sulfate which are matched with the crystal lattice of rhodium as much as possible, on one hand, the internal stress and grain refinement caused by lattice mismatch are reduced, on the other hand, the electrode potential of the alloy element is matched with the rhodium, the phenomenon that precipitation cannot be performed can be avoided, and finally, the alloy element salt content is moderate, the solid solution strengthening and the grain refinement are promoted due to the excessively low content, the improvement of the toughness of a coating is not facilitated, the crystallization second phase is easily generated due to the excessively high content, and the performance loss is serious. And the internal defects of the plating layer can be reduced by using the phosphorus-containing additive, and meanwhile, the rhodium alloy plating layer with higher toughness is comprehensively obtained by adding the low-stress agent and the wetting agent to relieve stress and hydrogen evolution. Therefore, the electroplating solution can better solve the problems of low toughness and easy fracture of the rhodium plating layer.
In one possible implementation manner, the rhodium salt is one or more than two of rhodium sulfate, rhodium phosphate, rhodium sulfate-rhodium phosphate, rhodium chloride, rhodium iodide, rhodium nitrate and chlororhodium salts.
In one possible implementation manner, the phosphorus-containing additive is one or more than two of sodium phosphite, monopotassium phosphite and diammonium phosphite.
In one possible implementation, the low stress agent is selected from one or both of magnesium sulfate and selenate.
In one possible implementation, the wetting agent is a surfactant.
In one possible implementation, the wetting agent is selected from one or both of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
The electroplating solution comprises the following components in mass-volume concentration:
The balance being water and a pH regulator.
In one possible implementation, the PH adjuster is sulfuric acid.
In a second aspect, the present application provides a method for producing a rhodium alloy plating layer, comprising the steps of:
immersing a substrate material into the electroplating solution by adopting the electroplating solution;
Electroplating the substrate material to be electroplated, wherein the electroplating is performed in constant current, the current density of the constant current is 0.5-6A/dm 2, and the temperature of the plating solution is kept at 30-70 ℃;
And taking out the substrate material with the coating from the electroplating solution, carrying out annealing treatment, wherein the heating rate of annealing is 1-10 ℃ per minute, the annealing temperature is 100-400 ℃, and the heat preservation time is 1-10h.
In one possible implementation, the substrate material to be electroplated is electroplated using a dc power source, which:
In one possible implementation, the equivalent current density ranges from 0.05 to 4.8A/dm 2;
And/or a duty cycle in the range of 10% -90%;
And/or the frequency range is 1-10000Hz.
In one possible implementation, the electroplating anode is made of platinum or titanium platinum material and/or the substrate material to be coated is at a distance in the range of 2-20cm from the electrode.
In one possible implementation, the substrate material is pretreated before coating, so that the surface of the substrate material is clean, good in conductivity and good in hydrophilicity.
In one possible implementation, the operating temperature of the plating solution during electroplating is in the range of 40-60 ℃.
In a third aspect, the present application also provides a method for testing fracture toughness of a plating layer, including the steps of:
S1, selecting a substrate material with a sacrificial layer, electroplating a layer of metal film to be tested on the sacrificial layer, wherein the thickness of the plating layer reaches the thickness of a calibrated film;
s2, corroding the sacrificial layer, releasing the plating layer and leveling to obtain a plating sample;
S3, fixing the release surface of the coating sample on a sample table in an upward direction;
S4, performing nano indentation test;
S5, testing the hardness H, the modulus E and the maximum load P of the test process of the obtained coating sample, and measuring the crack length of the residual indentation;
s6, calculating fracture toughness of the coating: Wherein K c is fracture toughness, alpha is 0.016, E is modulus, H is hardness, P is maximum load, and c is crack length.
In one possible implementation, the surface of the sacrificial layer is polished, and the surface is smooth and flat.
In one possible implementation manner, the material of the sacrificial layer is any one of copper, silver, zinc and nickel.
In one possible implementation, in step S1, the shape of the plating layer is determined using a mask.
In one possible implementation, the diameter of the plating sample is greater than 50 μm and the nominal film thickness is greater than 3 μm.
In one possible implementation manner, in step S1, a layer of high-hardness metal is further electroplated on the surface of the metal film to be tested as a supporting layer, where the area of the supporting layer is larger than that of the plating sample.
In one possible implementation, in step S4, the nanoindentation test is performed using a continuous stiffness method or a quasi-static method, with a maximum test depth of 8-15% of the thickness of the plating sample.
In one possible implementation, in step S4, the maximum test depth is 10% of the sample thickness.
Compared with the prior art, the method has the advantages that the plating solution of rhodium iridium alloy or rhodium indium alloy is prepared, the plating layer has lower stress and very high toughness by adding the additive and changing the current parameter of plating while introducing the alloy element, and meanwhile, the special high hardness advantage of the rhodium plating layer is maintained.
Drawings
Fig. 1 is an SEM image of residual indentation after nanoindentation testing of a rhodium coating in an embodiment of the application.
Detailed Description
For the purpose of illustrating in detail the technical content, constructional features, objects and effects of the application, the technical solutions of the application will be described below in connection with embodiments of the application, it being apparent that the described embodiments are only some, but not all, embodiments of the application. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a detailed description of various exemplary embodiments or implementations of the application. However, various exemplary embodiments may be practiced without these specific details or with one or more equivalent arrangements. Furthermore, the various exemplary embodiments may be different, but are not necessarily exclusive.
In the research of rhodium ruthenium alloy plating, the applicant found that the brittleness of rhodium plating is mainly derived from the aspects of internal stress, microcrack, hydrogen evolution, undersize of crystal grains and the like, and these problems can be improved to a certain extent by optimizing plating parameters, such as a pulse plating method and the like, and besides, the problems can be improved by adjusting the composition of the plating solution.
In the application, the alloy element salt is added into the electroplating solution, and the toughness of the plating layer is increased by an alloying method. The plating rhodium plating solution is usually rhodium sulfate, rhodium phosphate, a mixed system of sulfuric acid and rhodium phosphate, etc., and the salt added with the alloy element needs to be matched with the plating solution system, so that other anions are avoided being introduced. Because rhodium has high hardness, most of alloying elements can reduce the hardness and lose key performance, so the selection and the content of the alloying elements are very important.
In one embodiment of the application, an electroplating solution comprises rhodium salt, alloy element salt, acid, phosphorus-containing additive, low-stress agent, wetting agent and deionized water, wherein the alloy element salt comprises iridium sulfate and/or indium sulfate.
In the application, the inventor intentionally selects alloy elements which are matched with the lattice of rhodium as far as possible, such as iridium, indium and ruthenium, so as to reduce internal stress and grain refinement caused by lattice mismatch, in addition, in order to avoid the phenomenon that the alloy elements cannot be separated out, the alloy elements which are matched with the electrode potential of rhodium are selected, such as iridium, indium and ruthenium, finally, the alloy elements are moderate, the content of the alloy elements is too low, the solid solution strengthening and the grain refinement are promoted, the toughness is not promoted, the second phase is easy to generate in crystallization, and the performance loss is serious.
In some embodiments, the rhodium salt is one or more of rhodium sulfate, rhodium phosphate, rhodium sulfate-rhodium phosphate, rhodium chloride, rhodium iodide, rhodium nitrate and chlororhodium salt.
In some embodiments, the phosphorus-containing additive is selected from one or more of sodium phosphite, potassium dihydrogen phosphite and diammonium hydrogen phosphite. The phosphorus-containing additive has the functions of forming stable complex with metal ions, increasing the activation energy of metal ion reduction, thereby being beneficial to forming a finer and compact coating, reducing defects such as pinholes, pits and the like of the coating, reducing defects in the coating and improving compactness and corrosion resistance of the coating.
In some embodiments, the low stress agent is selected from magnesium sulfate and/or selenate. The low stress agent can reduce the internal stress of the coating, improve the ductility, prevent the coating from cracking, improve the adhesive capacity of the coating and improve the quality of the coating. Magnesium sulfate (MgSO 4) is added into the electroplating solution to increase the conductivity of the solution, and the reverse reaction of the complexation reaction can be reduced due to the existence of excessive sulfate ions (SO 4 2-) in the solution, SO that the cathode current efficiency is improved, the plating layer is thinned, and the internal stress is reduced.
In some embodiments, the wetting agent is a surfactant, and the surfactant acts to reduce the surface tension of the plating solution, so that the plating solution more easily and uniformly wets the surface of the plated workpiece, fills in narrow gaps, refines grains, helps hydrogen gas to separate out, reduces the generation of gas pinholes and pits, and improves the quality and uniformity of the plating layer.
In one embodiment, the wetting agent is selected from sodium dodecyl sulfate and/or sodium dodecyl benzene sulfonate. Sodium dodecyl sulfate is a common wetting agent, and can be used as a surfactant to obviously reduce the surface tension of electroplating liquid, so that small bubbles of hydrogen are not easy to stay on the surface of a workpiece, and gas pinholes and pitting defects of a plating layer are reduced and eliminated. In addition, the sodium dodecyl sulfate also has a certain cathode polarization function, which is helpful for refining the crystallization of the coating and improving the brightness of the coating.
In some embodiments, the plating solution contains the following components in mass-volume concentrations:
The balance of deionized water and a PH regulator, wherein the PH regulator is acid, preferably sulfuric acid, and the PH range of the electroplating solution can be regulated to be between 0.2 and 3.
In one embodiment of the present application, there is provided a method for manufacturing a rhodium alloy plating layer using the above-described plating solution, specifically including:
1. the substrate material is pretreated before coating, so that the surface of the substrate material is clean, good in conductivity and good in hydrophilicity;
2. immersing a base material in an electroplating solution;
3. Electroplating the substrate material to be electroplated by using a direct current power supply, wherein the electroplating process is carried out under constant current, the current density of the constant current is 0.5-6A/dm 2, and the temperature of the plating solution is kept at 30-70 ℃;
4. And taking out the substrate material with the coating from the electroplating solution, carrying out annealing treatment, wherein the heating rate of annealing is 1-10 ℃ per minute, the annealing temperature is 100-400 ℃, and the heat preservation time is 1-10h.
In one embodiment of the application, the current density of the electroplating process may be 0.6, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0. The peak current range of the direct current power supply is 0.5-6A/dm 2.
In one embodiment of the application, the equivalent current range of the direct current power supply is 0.05-4.8A/dm 2;
In one embodiment of the application, the DC power supply has a duty cycle in the range of 10% -90%;
In one embodiment of the application, the direct current power supply has a frequency range of 1-10000Hz.
In one embodiment of the application, the electroplating anode is made of platinum or titanium-platinum material.
In one embodiment of the application, the substrate material to be coated is at a distance in the range of 2-20cm from the electrode.
In a preferred embodiment of the application, the operating temperature of the plating solution during electroplating is in the range of 40-60 ℃, such as 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃, 50 ℃, 51 ℃, 52 ℃, 53 ℃, 54 ℃, 55 ℃, 56 ℃, 57 ℃, 58 ℃, 59 ℃ and 60 ℃.
In one embodiment, the rhodium coating is manufactured as follows:
1. bath for electroplating solution
① Rhodium sulfate is selected to prepare electroplating solution, and the concentration range of Rh 2+ ions is 1-4g/L;
② Adjusting the pH value of the electroplating solution by using sulfuric acid with the concentration range of 30-100g/L to ensure that the pH value of the electroplating solution is between 0.2 and 3;
③ Iridium sulfate and indium sulfate are selected as alloy element salts, and the concentration range of the iridium sulfate or the indium sulfate in the electroplating solution is 0.1-10g/L corresponding to the rhodium-iridium alloy and the rhodium-indium alloy;
④ Sodium phosphite is selected as a phosphorus-containing additive, and the concentration range in the electroplating solution is 1-10g/L;
⑤ Selecting magnesium sulfate as low stress agent, wherein the concentration of magnesium sulfate in the electroplating solution is 5-20g/L, or selecting selenate as low stress agent, wherein the concentration of selenate in the electroplating solution is 0.1-4g/L;
⑥ Sodium dodecyl sulfate is used as a wetting agent, and the concentration range in the electroplating solution is 0.01-1g/L.
2. Electroplating
① Platinum or titanium platinum anodes were used with an electrode distance in the range of 2-20cm.
② Pretreatment ensures that the surface of the substrate is clean, good in conductivity and good in hydrophilicity.
③ The working temperature of the plating solution is 30-70 ℃, the optimal working temperature is 40-60 ℃,
④ The electroplating parameter range is to use a direct current or pulse power supply, wherein the current density of the direct current power supply is in the range of 0.5-6A/dm 2, the optimal current density is in the range of 1-3A/dm 2, the peak current of the pulse power supply is in the range of 0.5-6A/dm 2, the equivalent current is in the range of 0.05-4.8A/dm 2, the duty ratio is in the range of 10% -90%, and the frequency is in the range of 1-10000Hz.
3. Annealing treatment
The coating and the substrate material may be annealed together after coating, or the coating may be released and annealed. The main purpose of the annealing treatment is stress release and recrystallization, and the annealing process can be reinforced by using a tool to maintain the shape of the plating layer during the stress release process.
The annealing parameter range is that the temperature rising speed is 1-10 ℃ per minute, the annealing temperature is 100-400 ℃ and the heat preservation time is 1-10 hours.
After the above-described plating, in order to further improve the properties of the plating, a series of tests, such as a test of fracture toughness of the plating, were also performed on the plating. In order to quantitatively characterize the toughness of a coating, a nano indentation method is a convenient and effective method for testing fracture toughness. However, the conventional method for testing the fracture toughness of the plating layer is limited by the plating layer, such as thickness, residual stress and the like, and the result has no absolute quantitative significance. In order to quantitatively analyze and compare the fracture toughness of the plating layers as much as possible, the application also provides a method for testing the fracture toughness of nano-indentation, which comprises the following steps:
S1, selecting a substrate material with a sacrificial layer, electroplating a layer of metal film to be tested on the sacrificial layer, wherein the thickness of the plating layer reaches the thickness of the calibrated film. Wherein, the sacrificial layer can be selected from copper, silver, zinc, nickel and other metals, and can be corroded by special corrosive liquid without corroding a substrate and a plating layer of subsequent electroplating. The sacrificial layer can be deposited on the surface of the substrate by electroplating or sputtering, and polishing can be properly performed to ensure smooth and flat surface. The shape of the coating can be determined using a mask, the diameter of the coating is greater than 50 μm, and the thickness of the coating is greater than 3 μm.
S2, corroding the sacrificial layer, releasing the plating layer and leveling to obtain a plating sample. Generally, if the size of the plating sample is enough, the sample preparation of the nano indentation sample can be directly transferred, the surface is only leveled after electroplating, and if the size of the plating sample is smaller, in the step S1, after the metal film to be tested is electroplated, a layer of high-hardness metal with larger area is electroplated as a supporting layer and leveled.
S3, fixing the release surface of the coating sample on the sample table in an upward direction. The sample can be fixed on the sample table by using a bonding mode such as hot melt adhesive, so that the sample is ensured to be completely flat and not inclined. The surface of one side of the plating sample, which is contacted with the sacrificial layer, is a release surface, and the release surface is selected as an indentation test surface.
S4, performing nano indentation test. The nano indentation test is carried out by adopting a continuous stiffness method or a quasi-static method, the maximum test depth is 8-15% of the thickness of the plating layer sample, and the maximum test depth is 10% of the thickness of the plating layer sample, so as to avoid surface and substrate effects.
S5, testing the hardness H, the modulus E and the maximum load P of the test process of the obtained coating sample, and measuring the crack length of the residual indentation.
S6, calculating fracture toughness of the coating: Wherein K c is fracture toughness, alpha is 0.016, E is modulus, H is hardness, P is maximum load, and c is crack length.
Comparative example:
Each liter of plating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in volume by using pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness is 0.5 MPa.m 1/2.
Example 1:
Each liter of electroplating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid, 0.5g of indium sulfate, 2g of sodium phosphite, 10g of magnesium sulfate and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness 1.5 MPa.m 1/2.
Example 2:
Each liter of electroplating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid, 1g of indium sulfate, 2g of sodium phosphite, 10g of magnesium sulfate and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in volume by using pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness 1.8MPa.m 1/2.
Example 3:
each liter of electroplating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid, 1.5g of indium sulfate, 2g of sodium phosphite, 10g of magnesium sulfate and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness is 2 MPa.m 1/2.
Example 4:
each liter of electroplating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid, 1g of iridium sulfate, 2g of sodium phosphite, 10g of magnesium sulfate and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in volume by using pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness 1.3 MPa.m 1/2.
Example 5:
Each liter of electroplating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid, 1.5g of iridium sulfate, 2g of sodium phosphite, 10g of magnesium sulfate and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness 1.6MPa.m 1/2.
Example 6:
each liter of electroplating solution comprises 10g of rhodium sulfate, 60g of sulfuric acid, 2g of iridium sulfate, 2g of sodium phosphite, 10g of magnesium sulfate and 0.5g of sodium dodecyl sulfate, and is dissolved and fixed in volume by using pure deionized water.
The electroplating was carried out using a DC power supply with a current density of 2A/dm 2 and a bath temperature of 50 ℃.
The electroplating time is 1h, and the thickness of the plating layer is 5 mu m.
The annealing parameters are that the temperature rising speed is 5 ℃ per minute, the annealing temperature is 250 ℃, and the heat preservation time is 2 hours.
Fracture toughness 1.9MPa.m 1/2.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the foregoing embodiments, which have been described in the foregoing embodiments and description merely illustrates the principles of the invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, the scope of which is defined in the appended claims, specification and their equivalents.
Claims (13)
1. The electroplating solution is characterized by comprising the following components in parts by weight per liter:
the balance of water and a PH regulator, wherein the alloy element salt contains iridium sulfate and/or indium sulfate, and the PH regulator ensures that the PH range of the electroplating solution is 0.2-3.
2. The plating solution according to claim 1, wherein the rhodium salt is one or more selected from the group consisting of rhodium sulfate, rhodium phosphate, rhodium sulfate-rhodium phosphate, rhodium chloride, rhodium iodide, rhodium nitrate and rhodium chloride.
3. The plating solution according to claim 1, wherein the phosphorus-containing additive is one or more selected from the group consisting of sodium phosphite, potassium dihydrogen phosphite and diammonium hydrogen phosphite.
4. The plating solution of claim 1, wherein said low stress agent is selected from one or both of magnesium sulfate and selenate.
5. The plating solution of claim 1, wherein said wetting agent is a surfactant.
6. The plating solution according to claim 5, wherein the wetting agent is one or both of sodium dodecyl sulfate and sodium dodecyl benzene sulfonate.
7. The plating solution of any of claims 1-6, wherein said plating solution comprises the following components in mass-to-volume concentrations:
Rhodium sulfate 2.4-9.6g/L;
0.1-10g/L of iridium sulfate or indium sulfate;
1-10g/L of sodium phosphite;
5-20g/L of magnesium sulfate;
0.01-1g/L of sodium dodecyl sulfate;
The balance being water and a pH regulator.
8. The plating solution of claim 7, wherein the pH adjustor is sulfuric acid.
9. A method for manufacturing a rhodium alloy plating layer, comprising the steps of:
Immersing a base material in the plating solution according to any one of claims 1 to 8;
Electroplating the substrate material to be electroplated, wherein the electroplating is performed in constant current, the current density of the constant current is 0.5-6A/dm 2, and the temperature of the plating solution is kept at 30-70 ℃;
And taking out the substrate material with the coating from the electroplating solution, carrying out annealing treatment, wherein the heating rate of annealing is 1-10 ℃ per minute, the annealing temperature is 100-400 ℃, and the heat preservation time is 1-10h.
10. The method of manufacturing according to claim 9, wherein the substrate material to be electroplated is subjected to electroplating treatment using a direct current power supply which:
the equivalent current density range is 0.05-4.8A/dm 2;
And/or a duty cycle in the range of 10% -90%;
And/or the frequency range is 1-10000Hz.
11. The method of claim 9, wherein the anode is made of platinum or titanium platinum material and/or the substrate material to be coated is at a distance ranging from 2 cm to 20cm from the electrode.
12. The method according to claim 9, wherein the substrate is subjected to pretreatment before coating, so that the substrate is clean in surface, good in conductivity and good in hydrophilicity.
13. The method of claim 9, wherein the plating solution is operated at a temperature in the range of 40-60 ℃ during the electroplating process.
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2025
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