CN114606482A - Method for preparing Cu @ ZrC core-shell complex-phase particle material by chemical plating - Google Patents

Abstract

The invention discloses a method for preparing Cu@ZrC core-shell composite particulate material by chemical plating, and belongs to the technical field of powder metallurgy material manufacturing. The method includes the following steps: performing degreasing treatment, roughening treatment, sensitization treatment, activation treatment, and dispersion treatment on the ZrC powder in sequence to obtain the ZrC powder to be plated with copper, and then chemically conducting chemical treatment on the ZrC powder to be plated with copper. Copper plating treatment is performed to obtain the Cu@ZrC core-shell composite particle material. The method of the invention can effectively improve the bonding between the ZrC ceramic phase and the metal matrix, and then can be used as a reinforcement to improve the mechanical properties of the metal matrix composite material, and provide a new reinforcement phase particle selection for the preparation of the metal matrix composite material MMCs.

Description

A method for preparing Cu@ZrC core-shell composite particle material by electroless plating

technical field

The invention belongs to the technical field of powder metallurgy material manufacturing, and in particular relates to a method for preparing Cu@ZrC core-shell composite particulate material by chemical plating.

Background technique

Metal matrix composites (MMCs) are composite materials made of metals and their alloys as the matrix and artificially combined with one or several metal or non-metal reinforcements. MMCs have the characteristics of high strength and high elasticity, and also have excellent properties such as wear resistance and high temperature resistance. Metal matrix composites are mainly divided into particle reinforced metal matrix composites and fiber reinforced metal matrix composites. Compared with fiber reinforced metal matrix composites, particle reinforced metal matrix composites have more advantages in production process and cost. And the performance is more uniform. Therefore, in the actual production process, reinforcement particles are often used to strengthen metal matrix composites. ZrC is a high-temperature structural ceramic material with excellent performance. It has high hardness, high strength, high wear resistance and high temperature resistance. It is very suitable as a reinforcing phase particle for metal matrix composites. However, due to its small atomic diffusion coefficient, it is very Difficult to sinter, so the bond with the base metal is poor, which limits its application. Therefore, it is necessary to modify ZrC to improve the dispersibility of ZrC particles and the binding property to the matrix metal.

SUMMARY OF THE INVENTION

In order to solve the above-mentioned problems existing in the prior art, the purpose of the present invention is to provide a method for preparing Cu@ZrC core-shell composite particulate material by electroless plating. The @ZrC core-shell composite particles can effectively improve the bonding between the ZrC ceramic phase and the metal matrix.

To achieve the above object, the present invention provides the following technical solutions:

One of the technical solutions of the present invention is a method for preparing Cu@ZrC core-shell composite particulate material by electroless plating, comprising the following steps: sequentially performing degreasing treatment, roughening treatment, sensitization treatment, activation treatment on ZrC powder, The ZrC powder to be plated with copper is obtained by dispersion treatment, and then the ZrC powder to be plated with copper is subjected to chemical copper plating treatment to obtain the Cu@ZrC core-shell composite particle material.

Further, the ZrC powder is submicron ZrC powder.

Further, the specific operation of the degreasing treatment is as follows: soaking the ZrC powder in NaOH solution, filtering, cleaning and drying.

Further, the concentration of the NaOH solution is 15 vol.%.

Further, the drying temperature in the degreasing treatment is 50°C, and the time is 10h.

Further, the specific operation of the roughening treatment is as follows: ultrasonically treating the degreasing ZrC powder in a HNO ₃ solution, filtering, cleaning, and drying, and the concentration of the HNO ₃ solution is 40 vol.%.

Further, the drying temperature in the roughening treatment is 50°C, and the time is 10h.

Further, the specific operation of the sensitization treatment is as follows: ultrasonically treat the roughened ZrC powder in a sensitization solution, wash and filter, and the sensitization solution is a mixed solution of SnCl ₂ and HCl.

Further, the concentration of SnCl ₂ in the sensitizing solution is 20 g/L, and the concentration of HCl is 20 g/L.

Further, the specific operation of the activation treatment is as follows: ultrasonically treat the sensitized ZrC powder in an AgNO ₃ solution, filter, and clean to neutrality, and the concentration of the AgNO ₃ solution is 5 g/L.

Further, the specific operation of the dispersing treatment is: using a dispersing agent to disperse the ZrC powder after the activation treatment to obtain the ZrC powder to be plated with copper, and the dispersing agent is a mixed solution of sodium pyrophosphate and water glass, The concentration of sodium pyrophosphate in the dispersant was 0.5 wt.%.

Further, the specific operation of the dispersion treatment is as follows: adding the activated ZrC powder into the dispersant, and performing ultrasonic dispersion treatment for 0.5 h, and the power of the ultrasonic dispersion treatment is 40 kHz.

Further, the mass volume ratio of the ZrC powder after the activation treatment to the dispersant is 1g:10ml.

Further, the specific operation of the electroless copper plating treatment is as follows: adding copper sulfate, complexing agent, buffering agent and catalyst in sequence in water to obtain a mixed solution, adjusting the pH value of the mixed solution to 11, and then adding ZrC to be copper-plated in sequence powder and a reducing agent to obtain an electroless copper plating reaction system, the electroless copper plating reaction system is reacted at a temperature of 60 ° C, and after the reaction is completed, it is filtered, cleaned and dried to obtain the Cu@ZrC core-shell composite particulate material .

Further, the complexing agent is trisodium citrate, the buffering agent is boric acid, the catalyst is nickel chloride hexahydrate, and the reducing agent is sodium hypophosphite. By mass ratio, copper sulfate: to be Copper-plated ZrC powder: sodium hypophosphite=40:20:15; the pH value of the electroless copper-plating reaction system was maintained at 10.5-11.5 during the entire reaction process.

Further, in terms of mass ratio, copper sulfate: trisodium citrate: boric acid: nickel chloride hexahydrate: ZrC powder to be plated copper: sodium hypophosphite=40:258:15:23.8:20:15.

Further, the mass-volume ratio of the copper sulfate to water is 40g:300-700ml.

The reaction principle of electroless copper plating is:

The reaction of electroless copper plating is relatively violent. At the same time of the reaction, the pH value of the solution gradually decreases, and the hydroxide ions in the system gradually decrease. As a result, the rate of the electroless copper plating reaction is slowed down due to the lack of hydroxide ions, or even cannot be carried out. Therefore, it is necessary to continuously Add sodium hydroxide solution to adjust the pH to keep the pH of the plating solution around 11.

Further, the reaction time is 1-4h.

The second technical solution of the present invention is a Cu@ZrC core-shell composite particulate material prepared according to the above-mentioned method for preparing a Cu@ZrC core-shell composite particulate material by electroless plating.

Further, the inner core of the Cu@ZrC core-shell composite particle material is ZrC particles, and the outer shell is a Cu layer.

The third technical solution of the present invention is an application of the above-mentioned chemical plating to prepare the Cu@ZrC core-shell composite particle material in a metal matrix composite material.

Further, the Cu@ZrC core-shell composite particle material prepared by the electroless plating is used as the reinforcement of the metal matrix composite material, and the addition amount in the metal matrix composite material is 20 vol.% of the metal matrix composite material, so The volume ratio of zirconium carbide to copper metal in the Cu@ZrC core-shell composite particle material is 1:2.

Compared with the prior art, the present invention has the following beneficial effects:

(1) In the present invention, Cu@ZrC core-shell composite particles are prepared by uniformly plating copper on the surface of ZrC powder through degreasing treatment, roughening treatment, sensitization treatment, activation treatment, dispersion treatment and chemical copper plating treatment. Oil treatment and roughening treatment can remove impurities such as oil stains on the surface of ZrC powder, improve the specific surface area and roughness of ZrC powder, thereby improving the adhesion of copper plating layer on ZrC powder, sensitization treatment, activation treatment, dispersion The treatment can prevent the agglomeration of ZrC powders and improve the uniformity and quality of the copper plating layer. Each step cooperates to prepare Cu@ZrC core-shell composite particle reinforced materials with high dispersibility and high uniformity. The method of the invention can effectively improve the bonding between the ZrC ceramic phase and the metal matrix, and then can be used as a reinforcement to improve the mechanical properties of the metal matrix composite material, and provide a new reinforcement phase particle selection for the preparation of the metal matrix composite material MMCs.

(2) The excellent properties of MMCs not only depend on the structure and properties of each component, but also are largely affected by the interfacial state characteristics. In order to obtain metal matrix composites with excellent properties that can meet various requirements, a suitable interface is required to enable good physicochemical and mechanical compatibility between the reinforcement and the matrix. The invention can improve the interface wettability and chemical compatibility between the ZrC ceramic particle reinforcement and the matrix by coating copper on the surface of the reinforcing particles and modifying them to form core-shell composite particles, so as to achieve the realization of different phase particles between the particles. The uniform dispersion of the particles can give full play to the excellent characteristics of particles of different phases.

(3) The present invention adopts the method of electroless plating to plate copper on the surface of ZrC ceramic particles. Compared with electroplating, electroless plating does not require an external power supply, and the reducing agent in the solution is used to reduce metal ions to metal and deposit on the surface of the substrate to form a coating , easy to operate, simple process, uniform coating, small porosity, good appearance. Compared with the conventional electroless plating process, the method of the present invention avoids the use of highly toxic HF to erode the components to be plated, and is safe and environmentally friendly.

Description of drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the accompanying drawings required in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some of the present invention. In the embodiments, for those of ordinary skill in the art, other drawings can also be obtained according to these drawings without any creative effort.

Fig. 1 is the SEM image of ZrC powder without surface copper plating;

Fig. 2 is the SEM image of Cu@ZrC core-shell composite particles prepared in Example 1 after surface copper plating treatment;

3 is a schematic view of the microstructure of the Cu@ZrC core-shell composite particles prepared in Example 1 after surface copper plating treatment.

Detailed ways

Various exemplary embodiments of the present invention will now be described in detail, which detailed description should not be construed as a limitation of the invention, but rather as a more detailed description of certain aspects, features, and embodiments of the invention.

It should be understood that the terms described in the present invention are only used to describe particular embodiments, and are not used to limit the present invention. Additionally, for numerical ranges in the present disclosure, it should be understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in that stated range is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates. Although only the preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing the methods and/or materials in connection with which the documents are referred. In the event of conflict with any incorporated document, the content of this specification controls.

It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present invention without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the present invention. The description and examples of the present invention are exemplary only.

As used herein, "comprising," "including," "having," "containing," and the like, are open-ended terms, meaning including but not limited to.

Example 1

(1) Degreasing treatment: Add 20g of submicron ZrC powder (particle size is 3-5μm) into 100ml of NaOH solution with a concentration of 15vol..%, soak for 1h, remove the oil stain on the surface of the powder, and use a concentration of 15vol..%. .% NaOH solution was repeatedly filtered and washed for 3 times, then filtered and washed with distilled water for 3 times, and then dried in a vacuum drying oven at 50 °C for 10 h.

( ₂ ) Coarsening treatment: ultrasonically treat the ZrC powder after degreasing treatment in HNO with a concentration of 40Vol.% for 2h (ultrasonic frequency is 40kHz), filter after the powder settles, and repeatedly wash with distilled water for 3 times, Then, it was dried in a vacuum drying oven at 50 °C for 10 h for use; the surface of the ZrC powder after the roughening treatment was relatively rough.

(3) Sensitization treatment: put the roughened ZrC powder into 100ml of mixed sensitization solution with a concentration of 20g/LSnCl ₂ +20g/L HCl, and ultrasonically treat it for 1h (ultrasonic frequency is 40kHz). During the process, the glass rod was continuously stirred to prevent the ZrC powder from being deposited on the bottom of the beaker. After the sensitization treatment was completed, it was filtered and washed with distilled water three times; Coarse, no obvious change in particle size.

(4) Activation treatment: put the sensitized ZrC powder into 100ml AgNO solution with a concentration _of 5g/L for 30min ultrasonic treatment (ultrasonic frequency is 40kHz), wash with distilled water to neutrality, and then put it in a vacuum drying oven Dry at 50℃ for 5h; the morphology and structure of ZrC powder after activation treatment have no obvious change.

(5) Dispersion treatment: The mixed solution of sodium pyrophosphate and water glass (the concentration of sodium pyrophosphate is 0.5wt.%) is used as the dispersant to disperse the submicron ZrC powder. The mass-to-volume ratio of the agent is 1g:10ml; the activated ZrC powder is added to the dispersant, and the ultrasonic dispersion treatment is carried out for 0.5h (ultrasonic frequency is 40kHz). obvious agglomeration.

(6) Electroless copper plating treatment: Weigh 40g of copper sulfate into a beaker with a volume of 1L, add 500ml of distilled water, and then dissolve by mechanical stirring in a constant temperature water bath at 60°C. Add 258g of complexing agent trisodium citrate to the copper sulfate solution, then add 15g of buffering agent boric acid, 23.8g of catalyst nickel chloride hexahydrate (NiCl ₂ ·6H ₂ O), until the above reagents are completely dissolved, add sodium hydroxide The pH value was adjusted to 11, after the adjustment, 20 g of the dispersed ZrC powder was added, and finally 15 g of sodium hypophosphite, a reducing agent, was added to obtain an electroless copper plating reaction system. The temperature of the electroless copper plating reaction system was kept constant at 60 °C, and the reaction was carried out for 3 h. The reaction of electroless copper plating is relatively violent. During the violent reaction, the pH value of the solution gradually decreases. During the process, sodium hydroxide solution is continuously added to adjust the pH value, so that the pH value of the plating solution is maintained at about 11 (10.5-11.5). After the reaction was completed, the stirrer and water bath were turned off, and the copper-plated ZrC powder was washed with distilled water for 6 times, and dried in a blast drying oven with a temperature of 80 °C for 5 h to obtain Cu@ZrC core-shell composite particles.

Take the ZrC powder raw materials that have not been subjected to surface copper plating treatment (also not subjected to degreasing treatment, roughening treatment, sensitization treatment, activation treatment, dispersion treatment, that is, without any treatment) and prepared in Example 1. Surface plating is carried out. The Cu@ZrC core-shell composite particle material after copper treatment was scanned by electron microscope. Figure 1 is the SEM image of the ZrC powder without surface copper plating treatment, and Figure 2 is the surface copper plating treatment prepared in Example 1. SEM images of Cu@ZrC core-shell composite particles, as shown in Figures 1 and 2, ZrC powder still has good dispersibility after copper plating with the addition of dispersant, no obvious agglomeration occurs, and has not undergone surface plating The copper-treated ZrC powder has obvious agglomeration and uneven dispersion.

The schematic diagram of the microstructure of the Cu@ZrC core-shell composite particle material prepared in Example 1 after surface copper plating treatment is shown in Figure 3. It can be seen from Figure 3 that the Cu@ZrC core-shell composite particles prepared in Example 1 For the core-shell structure, a uniform copper layer is formed on the surface of ZrC particles.

Comparative Example 1

The same as Example 1, the difference is that the Cu@ZrC powder after activation treatment is directly used for electroless copper plating without dispersion treatment.

Comparative Example 2

Same as Example 1, the difference lies in that, without activation treatment, the Cu@ZrC powder after sensitization treatment is directly subjected to dispersion treatment and electroless copper plating treatment after drying.

Effect verification

Take the Cu@ZrC core-shell composite particulate materials prepared in Example 1 of the present invention and Comparative Examples 1-2, respectively, and without copper plating on the surface (and without degreasing, roughening, sensitization, and activation). , dispersion treatment, that is, without any treatment) ZrC powder raw material is used as a reinforcement to prepare a titanium matrix composite material, and the addition amount of the reinforcement is 20vol.% of the metal matrix composite material. The specific preparation method is as follows:

First, Ti powder, 6Al-4V alloy powder, ZrC powder without surface copper plating or Cu@ZrC core-shell composite particles were mixed by ball milling according to the formula in a certain proportion, and ball milled at 80 r/min for 20 min. After ball milling, the mixed powder is put into the mold, and pressed into a cylindrical body by ^300MPa cold isostatic pressing. The speed was raised to 1500 °C, and the temperature was kept for 3 h to obtain a powder metallurgy titanium matrix composite block.

The titanium matrix composites prepared by using the Cu@ZrC core-shell composite particles prepared in Example 1 and Comparative Examples 1-2 as reinforcements were taken as the corresponding Example 1 and Comparative Examples 1-2, to use no surface plating. The titanium matrix composite material prepared by copper-treated ZrC powder as the reinforcement was used as the control group 1, and the titanium alloy material prepared without reinforcement was used as the blank control group 2 (the preparation method of the titanium alloy is the same as that of the titanium matrix composite material). , but without adding reinforcements), the following performance tests were performed on the above titanium-based composite materials and titanium alloy materials.

(1) Mechanical property test

Take Example 1, Comparative Examples 1-2, the titanium-based composite material of control group 1 and the titanium alloy material of blank control group 2, and measure sintering according to the method specified in GB/T 10421-2002 (Determination of Density of Sintered Metal Friction Materials) The density of the material is tested according to the GB/T228-2002 room temperature tensile test method for metallic materials, and the Rockwell hardness test is carried out with a digital Rockwell hardness tester. The test results are shown in Table 1:

Table 1

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection scope of the present invention. within.

Claims (10)

1. A method for preparing a Cu @ ZrC core-shell complex-phase particle material by chemical plating is characterized by comprising the following steps: the preparation method comprises the following steps of sequentially carrying out oil removal treatment, coarsening treatment, sensitizing treatment, activating treatment and dispersing treatment on ZrC powder to obtain ZrC powder to be plated with copper, and then carrying out chemical copper plating treatment on the ZrC powder to be plated with copper to obtain the Cu @ ZrC core-shell complex-phase granular material.

2. The method for preparing the Cu @ ZrC core-shell complex phase particle material by the electroless plating process according to claim 1, wherein the oil removing process comprises the following specific operations: soaking ZrC powder in NaOH solution, filtering, cleaning and drying; the specific operation of the coarsening treatment is as follows: the ZrC powder after the oil removal treatment is put in HNO₃Ultrasonic treatment in solution, filtering, cleaning and drying, wherein the HNO is prepared by₃The concentration of the solution was 40 vol.%.

3. The method for preparing the Cu @ ZrC core-shell complex phase particle material by the electroless plating according to claim 1, wherein the specific operations of the sensitization treatment are as follows: carrying out ultrasonic treatment on the coarsened ZrC powder in a sensitizing solution, cleaning and filtering; the sensitizing solution is SnCl₂And HCl.

4. The method for preparing the Cu @ ZrC core-shell complex-phase particle material by electroless plating according to claim 3, wherein SnCl in the sensitizing solution₂The concentration of (2) was 20g/L and the concentration of HCl was 20 g/L.

5. The method for preparing the Cu @ ZrC core-shell complex-phase particle material by electroless plating according to claim 1, wherein the specific operations of the activation treatment are as follows: the sensitized ZrC powder is placed in AgNO₃Ultrasonic treatment in solution, filtering and washing to neutrality, wherein the AgNO is₃The concentration of the solution was 5 g/L.

6. The method for preparing the Cu @ ZrC core-shell complex phase particle material by the electroless plating according to claim 1, wherein the dispersion treatment comprises the following specific operations: and performing dispersion treatment on the activated ZrC powder by using a dispersing agent to obtain the ZrC powder to be plated with copper, wherein the dispersing agent is a mixed solution of sodium pyrophosphate and water glass, and the concentration of sodium pyrophosphate in the dispersing agent is 0.5 wt.%.

7. The method for preparing the Cu @ ZrC core-shell complex-phase granular material by electroless plating according to claim 1, wherein the electroless copper plating treatment comprises the following specific operations: adding copper sulfate, a complexing agent, a buffering agent and a catalyst into water to obtain a mixed solution, adjusting the pH value of the mixed solution to 11, then adding ZrC powder to be plated with copper and a reducing agent to obtain a chemical copper plating reaction system, reacting the chemical copper plating reaction system at the temperature of 60 ℃, filtering, cleaning and drying after the reaction is finished to obtain the Cu @ ZrC core-shell complex-phase granular material.

8. The method for preparing the Cu @ ZrC core-shell complex-phase granular material by electroless plating according to claim 7, wherein the complexing agent is trisodium citrate, the buffering agent is boric acid, the catalyst is nickel chloride hexahydrate, the reducing agent is sodium hypophosphite, and the weight ratio of copper sulfate: and (3) after copper plating of ZrC powder: sodium hypophosphite 40:20: 15; the pH value of the electroless copper plating reaction system is maintained at 10.5-11.5 in the whole reaction process.

9. The Cu @ ZrC core-shell complex-phase particle material prepared by the method for preparing the Cu @ ZrC core-shell complex-phase particle material through electroless plating according to any one of claims 1 to 8.

10. The use of the electroless plating prepared Cu @ ZrC core-shell composite particulate material as defined in claim 9 in a metal matrix composite.

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