CN115415519A - Chemical nickel plating solution of graphite micropowder and method for judging nickel plating reaction end point - Google Patents
Chemical nickel plating solution of graphite micropowder and method for judging nickel plating reaction end point Download PDFInfo
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- CN115415519A CN115415519A CN202211238613.XA CN202211238613A CN115415519A CN 115415519 A CN115415519 A CN 115415519A CN 202211238613 A CN202211238613 A CN 202211238613A CN 115415519 A CN115415519 A CN 115415519A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/18—Non-metallic particles coated with metal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
Abstract
The invention discloses a chemical nickel plating solution of graphite micropowder and a method for judging a nickel plating reaction end point, wherein the chemical nickel plating solution comprises the following components: the main salt is one or more of nickel sulfamate, nickel chloride, nickel acetate or nickel sulfate; the reducing agent is one or more of sodium hypophosphite, sodium borohydride, methyl ammonia borane, nickel powder and zinc powder; the complexing agent is one or more of ammonia water and citric acid; the buffer is one or more of boric acid, ammonium chloride and sodium acetate; and a combination additive; wherein the mass ratio of the main salt, the reducing agent, the complexing agent, the buffering agent and the combined additive is (1.8) - (2.2). The formula of the chemical nickel plating solution is precisely designed, and after the coating is completed, the concentration of nickel in the waste solution can reach the milligram level, so that the chemical nickel plating solution is very environment-friendly. The method for judging the end point of the nickel plating reaction can accurately judge the reaction end point, has small error, realizes accurate control of the end point and realizes complete coating of the graphite micro powder.
Description
Technical Field
The invention relates to the technical field of chemical nickel plating, in particular to a chemical nickel plating solution of graphite micro powder and a method for judging a nickel plating reaction end point.
Background
The nickel-coated graphite powder is a coated composite powder material formed by coating a layer of metallic nickel on the surface of graphite core powder by adopting a chemical reduction method. The nickel-coated graphite powder composite material has excellent lubricating property of graphite, good electrical conductivity and thermal conductivity of metal, and is widely applied to the fields of electromagnetic shielding, wave absorption and thermal spraying.
The chemical nickel plating solution of graphite micropowder is a thermodynamically unstable system, the formula of the chemical nickel plating solution needs to be precisely designed, the stability of the nickel plating solution is adversely affected due to improper selection, insufficient concentration or overhigh concentration of each formula in the nickel plating solution, a large amount of waste liquid is easily generated, and the treatment difficulty is high.
Disclosure of Invention
Based on the above, the invention provides a chemical nickel plating solution of graphite micropowder and a method for judging the nickel plating reaction end point, the formula of the chemical nickel plating solution is precisely designed, when the coating is completed, the nickel concentration in the waste liquid can reach the milligram level, the difficulty of waste liquid treatment is greatly reduced, and the waste liquid generated in the nickel plating process only contains ammonia salt, sulfate, phosphite and trace carbohydrate; meanwhile, the method for judging the end point of the nickel plating reaction of the chemical nickel plating solution is provided, the reaction end point can be accurately judged, and the error is small, so that the end point can be accurately controlled, and the complete coating of the graphite micro powder can be realized.
The technical scheme adopted by the invention is as follows:
the chemical nickel plating solution of graphite micropowder comprises:
the main salt is one or more of nickel sulfamate, nickel chloride, nickel acetate or nickel sulfate;
the reducing agent is one or more of sodium hypophosphite, sodium borohydride, methyl ammonia borane, nickel powder and zinc powder;
the complexing agent is one or more of ammonia water and citric acid;
the buffer is one or more of boric acid, ammonium chloride and sodium acetate;
and a combination additive;
wherein the mass ratio of the main salt to the reducing agent to the complexing agent to the buffering agent to the combined additive is 2 to 1.8 to 2.2.
In the chemical nickel plating solution of graphite micropowder disclosed in the present application, the combined additive comprises:
distilled water;
the wetting agent is one or more of 2-ethylhexyl sulfate sodium salt, dioctyl sodium sulfosuccinate and sodium dodecyl sulfate;
the stabilizer is one or more of pyridine compounds, butynes compounds, propynes compounds and propylene compounds;
the accelerator is one or more of thiourea, ATPN and UPS.
In the electroless nickel plating solution for graphite fine powder disclosed in the present application, in the combined additive, the mass ratio of distilled water, wetting agent, stabilizer and accelerator in the combined additive is 96.
In the chemical nickel plating solution of graphite micropowder disclosed in the application, the main salt is nickel sulfate, the reducing agent is sodium hypophosphite, the complexing agent is ammonia water, and the buffering agent is ammonium chloride.
Based on the same inventive concept, the invention also discloses a method for judging the nickel plating reaction end point of the chemical nickel plating solution of the graphite micropowder, namely
The method for judging the nickel plating reaction end point comprises the following steps:
step S1, stirring and mixing graphite micro powder and chemical nickel plating solution without adding a reducing agent to obtain graphite powder mixed solution;
s2, stopping stirring after the graphite is fully wetted, adding the coated nickel-carbon powder, and then adding part of the reducing agent solution at one time to obtain a nickel plating reaction solution;
and S3, when a large amount of bubbles appear in the nickel plating reaction solution, slowly dripping the residual reducing agent solution, continuously stirring, reaching the end point of the nickel plating reaction when the nickel plating reaction solution is clear and the color of the solution is changed from light blue to colorless, and dripping excessive reducing agent solution to obtain a product mixed solution.
In the method for judging the nickel plating reaction end point, in the step S1, the concentration of a main salt in a graphite powder mixed solution is 200 to 600g/L, and the loading capacity of graphite micropowder is 45 to 90g/L.
In the method for judging the nickel plating reaction end point, in the step S2, the adding amount of the coated nickel-carbon powder is 0.5 to 2g.
In the method for judging the nickel plating reaction end point, the concentration of the reducing agent solution is 1000g/L.
In the method for judging the nickel plating reaction end point, in the step S2, the addition amount of the reducing agent solution is 10-20mL in each liter of graphite powder mixed solution.
In the method for determining the end point of the nickel plating reaction disclosed in the present application, in step S3, the excess addition amount of the reducing agent solution is 10 to 20ml.
The invention has the beneficial effects that:
the invention provides a chemical nickel plating solution of graphite micropowder and a method for judging a nickel plating reaction end point, the chemical nickel plating solution is safe and environment-friendly, the nickel plating reaction is carried out under the conditions of normal pressure and medium and low temperature, the formula is precisely designed, the nickel concentration in the waste liquid can reach the milligram level after the coating is complete, the difficulty of waste liquid treatment is greatly reduced, and the waste liquid generated in the nickel plating process only contains ammonia salt, sulfate, phosphite and trace carbohydrate. The method for judging the nickel plating reaction end point can accurately judge the reaction end point, has small error, realizes accurate control of the end point and realizes complete coating of the graphite micro powder.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is a microscopic view of an electroless nickel plating layer obtained by the electroless nickel plating solution of the present application.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein may be combined with other embodiments.
The following provides a detailed description of embodiments of the invention.
The application provides a chemical nickel plating solution of graphite micropowder and a method for judging a nickel plating reaction end point, and mainly aims to solve the problems of poor stability of the chemical nickel plating solution, a large amount of waste liquid generated by a nickel plating reaction and poor judgment of the nickel plating reaction end point.
The application discloses a chemical nickel plating solution of graphite miropowder includes:
the main salt is one or more of nickel sulfamate, nickel chloride, nickel acetate or nickel sulfate;
the reducing agent is one or more of sodium hypophosphite, sodium borohydride, methyl ammonia borane, nickel powder and zinc powder;
the complexing agent is one or more of ammonia water and citric acid;
the buffer is one or more of boric acid, ammonium chloride and sodium acetate;
and a combination additive;
wherein the mass ratio of the main salt to the reducing agent to the complexing agent to the buffering agent to the combined additive is 2 to 1.8 to 2.2.
The main salt, reducing agent, complexing agent and buffering agent of the chemical nickel plating solution are prepared into bath according to a certain proportion, and under the condition of the proportion, the nickel ions in the plating solution are almost completely reacted. Wherein the additive is combined to keep a stable state during the particle micro powder coating process.
The chemical nickel plating solution is safe and environment-friendly, the nickel plating reaction is carried out under the conditions of normal pressure and medium and low temperature, the formula is precisely designed, the concentration of nickel in the waste liquid can reach milligram level (1-10ppm) after the coating is completed, the difficulty of waste liquid treatment is greatly reduced, and the waste liquid generated in the nickel plating process only contains ammonia salt, sulfate, phosphite and trace carbohydrate. Fig. 1 shows a microscopic image (enlarged 10000 times) of an electroless nickel plating layer obtained by using the electroless nickel plating solution of the present invention, wherein the surface of the graphite micro powder is completely coated with nickel, and the graphite micro powder has a good binding force and a uniform plating layer.
In one particular embodiment, the combination additive comprises:
distilled water;
the wetting agent is one or more of 2-ethylhexyl sulfate sodium salt, dioctyl sodium sulfosuccinate and sodium dodecyl sulfate;
the stabilizer is one or more of pyridines (for example, pyridinium hydroxypropanesulfonate), butynes (for example, 1' 4-butynediol), propynes (for example, 2- (2-propynyloxy) ethanol) and propylene compounds (for example, sodium allylsulfonate).
The accelerant is one or more of thiourea, ATPN (S-carboxyethyl isothiouronium salt) and UPS (3-sulfur-isothiouronium propanesulfonic acid compound);
in a specific embodiment, in the combined additive, the mass ratio of distilled water, wetting agent, stabilizer and accelerator is 96. Wetting agents, promoters and stabilizers maintain the particulate fines in a stable state during the plating process.
In a particular embodiment, the primary salt is preferably nickel sulfate, the reducing agent is preferably sodium hypophosphite, the complexing agent is preferably ammonia, and the buffering agent is preferably ammonium chloride.
The application also discloses a method for judging the nickel plating reaction end point of the chemical nickel plating solution, which comprises the following steps:
and S1, stirring and mixing the graphite micro powder and the chemical nickel plating solution without adding a reducing agent to obtain a graphite powder mixed solution.
And S2, stopping stirring after the graphite is fully wetted, adding the coated nickel-carbon powder, and then adding part of the reducing agent solution at one time to obtain the nickel plating reaction solution. The coated nickel-carbon powder is added, which can provide a small amount of active center for chemical nickel plating reaction and is used as a catalyst to slowly reduce nickel ions adsorbed on the surface of graphite. Adding partial reducing agent as initiator to make graphite micropowder contact with its surface to initiate graphite micropowder autocatalysis to produce chemical nickel-plating reaction, and decomposing the plating solution into nickel particles by using said reducing agent.
And S3, when a large amount of bubbles appear in the nickel plating reaction solution, slowly dripping the residual reducing agent solution, continuously stirring, reaching the end point of the nickel plating reaction when the nickel plating reaction solution is clear and the color of the solution is changed from light blue to colorless, and dripping excessive reducing agent solution to obtain a product mixed solution. Nickel reduction equation:
as can be seen from the reaction formula, hydrogen is generated along with the nickel plating reaction, when the nickel ion reaction is completed, the solution becomes clear, the color is changed from light blue to colorless, and the end point of the nickel plating reaction is reached. The slow dropping of the residual reducing agent solution can slow down the reaction and obtain a more compact plating layer.
The method for judging the nickel plating reaction end point can accurately judge the reaction end point, has small error, realizes accurate control of the end point and realizes complete coating of the graphite micro powder.
In a specific embodiment, in the step S2, the concentration of the main salt in the graphite powder mixed solution is 200 to 600g/L, and the loading capacity of the graphite powder is 45 to 90g/L. Specifically, the concentration of the main salt may be 200g/L, 300g/L, 400g/L, 500 g/L, 600 g/L; the loading of the graphite fine powder may be 45g/L, 50g/L, 60g/L, 70g/L, 80g/L, or 90g/L.
In a specific embodiment, in the step S2, the addition amount of the coated nickel-carbon powder is 0.5 to 2g.
In a specific embodiment, the concentration of the reducing agent solution is 1000g/L. The reducing agent is preferably sodium hypophosphite, and the obtained coating is a low phosphorus nickel coating which has good weather resistance.
Specifically, in step S2, the amount of the reducing agent solution is 10 to 20ml per liter of the graphite powder mixed solution, so as to provide the initiator. And (3) adding 10-20mL of reducing agent solution as an initiator to avoid excessive addition amount so as to ensure that the plating layer is not compact enough.
Specifically, in step S3, the excessive addition amount of the reducing agent solution is 10 to 20ml.
Example 1
Stirring and mixing graphite micro powder and chemical nickel plating solution without adding sodium hypophosphite, stopping stirring after the graphite is fully wetted, adding 0.5-2g of coated nickel-carbon powder, and then adding 10-20mL of sodium hypophosphite solution with the concentration of 1000g/L to obtain nickel plating reaction solution, wherein the loading amount of the graphite is 45g/L, the concentration of nickel sulfate is 300g/L, and the concentration of ammonium chloride is 150g/L; when a large amount of bubbles appear in the graphite powder mixed solution, slowly dropping the residual reducing agent solution, continuously stirring, and when the nickel plating reaction solution is clear and the color of the solution is changed from light blue to colorless, reaching the end point of the nickel plating reaction, and then dropping 10-20mL of reducing agent solution to obtain a product mixed solution.
Example 2
Stirring and mixing graphite micro powder and chemical nickel plating solution without sodium hypophosphite, stopping stirring after the graphite is fully wetted, adding 0.5-2g of coated nickel-carbon powder, and then adding 10-20mL of sodium hypophosphite solution with the concentration of 1000g/L to obtain nickel plating reaction solution, wherein the loading capacity of the graphite is 60g/L, the concentration of nickel sulfate is 400g/L, and the concentration of ammonium chloride is 200g/L; when a large amount of bubbles appear in the graphite powder mixed solution, slowly dropping the residual reducing agent solution, continuously stirring, and when the nickel plating reaction solution is clear and the color of the solution is changed from light blue to colorless, reaching the end point of the nickel plating reaction, and then dropping 10-20mL of reducing agent solution to obtain a product mixed solution.
Example 3
Stirring and mixing graphite micro powder and chemical nickel plating solution without sodium hypophosphite, stopping stirring after the graphite is fully wetted, adding 0.5-2g of coated nickel-carbon powder, and then adding 10-20mL of sodium hypophosphite solution with the concentration of 1000g/L to obtain nickel plating reaction solution, wherein the loading capacity of the graphite is 90g/L, the concentration of nickel sulfate is 600g/L, and the concentration of ammonium chloride is 300g/L; when a large amount of bubbles appear in the graphite powder mixed solution, slowly dropping the residual reducing agent solution, continuously stirring, and when the nickel plating reaction solution is clear and the color of the solution is changed from light blue to colorless, reaching the end point of the nickel plating reaction, and then dropping 10-20mL of reducing agent solution to obtain a product mixed solution.
Example 4
Stirring and mixing graphite micro powder and chemical nickel plating solution without sodium hypophosphite, stopping stirring after the graphite is fully wetted, adding 0.5-2g of coated nickel-carbon powder, and then adding 10-20mL of sodium hypophosphite solution with the concentration of 1000g/L to obtain nickel plating reaction solution, wherein the loading capacity of the graphite is 45g/L, the concentration of nickel sulfate is 600g/L, and the concentration of ammonium chloride is 300g/L; when a large amount of bubbles appear in the graphite powder mixed solution, slowly dripping the residual reducing agent solution, continuously stirring, clarifying the nickel plating reaction solution, and when the color of the solution is changed from light blue to colorless, reaching the end point of the nickel plating reaction, and then dripping 10 to 20mL of reducing agent solution to obtain a product mixed solution.
Example 5
Stirring and mixing graphite micro powder and chemical nickel plating solution without sodium hypophosphite, stopping stirring after the graphite is fully wetted, adding 0.5-2g of coated nickel-carbon powder, and then adding 10-20mL of sodium hypophosphite solution with the concentration of 1000g/L to obtain nickel plating reaction solution, wherein the loading capacity of the graphite is 45g/L, the concentration of nickel sulfate is 200g/L, and the concentration of ammonium chloride is 200g/L; when a large amount of bubbles appear in the graphite powder mixed solution, slowly dripping the residual reducing agent solution, continuously stirring, clarifying the nickel plating reaction solution, and when the color of the solution is changed from light blue to colorless, reaching the end point of the nickel plating reaction, and then dripping 10 to 20mL of reducing agent solution to obtain a product mixed solution.
The application provides a chemical nickel plating solution of graphite micropowder, the chemical nickel plating solution is safe and environment-friendly, the nickel plating reaction is carried out under the conditions of normal pressure and medium and low temperature, the formula is accurately designed, when the coating is complete, the nickel concentration in the waste liquid can reach the milligram level, the difficulty of waste liquid treatment is greatly reduced, and the waste liquid generated in the nickel plating process only contains ammonia salt, sulfate, phosphite and trace carbohydrate. The application also provides a method for judging the nickel plating reaction end point of the chemical nickel plating solution, which can accurately judge the reaction end point, has small error, realizes accurate control of the end point, realizes complete coating of graphite micropowder, has complete nickel ion reaction, and reduces pollution to the environment.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and those skilled in the art can make various modifications and variations. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The chemical nickel plating solution of graphite micropowder is characterized by comprising the following components:
the main salt is one or more of nickel sulfamate, nickel chloride, nickel acetate or nickel sulfate;
the reducing agent is one or more of sodium hypophosphite, sodium borohydride, methyl ammonia borane, nickel powder and zinc powder;
the complexing agent is one or more of ammonia water and citric acid;
the buffer is one or more of boric acid, ammonium chloride and sodium acetate;
and a combination additive;
wherein the mass ratio of the main salt to the reducing agent to the complexing agent to the buffering agent to the combined additive is 2 to 1.8 to 2.2.
2. The electroless nickel plating solution of graphite micropowder according to claim 1, characterized in that the combined additive comprises:
distilled water;
the wetting agent is one or more of 2-ethylhexyl sulfate sodium salt, dioctyl sodium sulfosuccinate and sodium dodecyl sulfate;
the stabilizer is one or more of pyridine compounds, butynes compounds, propynes compounds and propylene compounds;
the accelerator is one or more of thiourea, ATPN and UPS.
3. The electroless nickel plating solution for graphite micropowder according to claim 2, wherein the mass ratio of distilled water, wetting agent, stabilizer, accelerator in the combined additive is 96.
4. The electroless nickel plating solution of graphite micropowder according to claim 1, wherein the main salt is nickel sulfate, the reducing agent is sodium hypophosphite, the complexing agent is ammonia water, and the buffering agent is ammonium chloride.
5. The method for judging the nickel plating reaction end point is characterized by comprising the following steps:
step S1, stirring and mixing graphite micro powder and chemical nickel plating solution without adding a reducing agent to obtain graphite powder mixed solution;
s2, stopping stirring after the graphite is fully wetted, adding the coated nickel-carbon powder, and then adding part of reducing agent solution at one time to obtain a nickel plating reaction solution;
and S3, when a large amount of bubbles appear in the nickel plating reaction solution, slowly dripping the residual reducing agent solution, continuously stirring, reaching the end point of the nickel plating reaction when the nickel plating reaction solution is clear and the color of the solution is changed from light blue to colorless, and dripping excessive reducing agent solution to obtain a product mixed solution.
6. The method for judging the end point of a nickel plating reaction according to claim 5, wherein in the step S1, the concentration of the main salt in the graphite powder mixed solution is 200 to 600g/L, and the loading capacity of the graphite micropowder is 45 to 90g/L.
7. The method of claim 5, wherein the amount of the coated nickel-carbon powder added in step S2 is 0.5 to 2g.
8. The method of determining an end point of a nickel plating reaction according to claim 5, wherein a concentration of the reducing agent solution is 1000g/L.
9. The method of claim 8, wherein the amount of the reducing agent solution added in step S2 is 10 to 20mL per liter of the graphite powder mixed solution.
10. The method of claim 8, wherein the excess amount of the reducing agent solution added in step S3 is 10 to 20mL.
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| CN103817323A (en) * | 2014-03-17 | 2014-05-28 | 杨福河 | Nickel-coated graphite electric conduction powder used for electric conduction rubber and manufacturing method thereof |
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| CN108295778A (en) * | 2018-04-24 | 2018-07-20 | 中国工程物理研究院激光聚变研究中心 | A kind of noble metal aeroge and preparation method thereof |
| CN111286976A (en) * | 2020-03-04 | 2020-06-16 | 盐城工学院 | Preparation method and product of super-hydrophobic oil-water separation polyester fabric based on chemical nickel plating |
| CN111424266A (en) * | 2020-03-19 | 2020-07-17 | 西安工程大学 | Preparation method of nickel-coated graphite composite particles |
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2022
- 2022-10-11 CN CN202211238613.XA patent/CN115415519B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1820876A (en) * | 2006-03-23 | 2006-08-23 | 北京科技大学 | Method for preparing nickel and cobalt coated inorganic powder particle coated material |
| CN1821443A (en) * | 2006-03-23 | 2006-08-23 | 北京科技大学 | Method and device for preparing hollow nickel, cobalt, nickel-cobalt fiber and hollow ball |
| CN103817323A (en) * | 2014-03-17 | 2014-05-28 | 杨福河 | Nickel-coated graphite electric conduction powder used for electric conduction rubber and manufacturing method thereof |
| CN104195532A (en) * | 2014-07-03 | 2014-12-10 | 天津大学 | Preparation method of graphite sheet surface chemical plating iron-nickel alloy layer |
| CN108295778A (en) * | 2018-04-24 | 2018-07-20 | 中国工程物理研究院激光聚变研究中心 | A kind of noble metal aeroge and preparation method thereof |
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| CN111424266A (en) * | 2020-03-19 | 2020-07-17 | 西安工程大学 | Preparation method of nickel-coated graphite composite particles |
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