CN115418633B

CN115418633B - Preparation method of continuous alumina fiber copper interface

Info

Publication number: CN115418633B
Application number: CN202211156300.XA
Authority: CN
Inventors: 张健; 马小民; 王迎春; 蒋世权
Original assignee: Molen Zhuhai New Material Technology Co ltd
Current assignee: Molen Zhuhai New Material Technology Co ltd
Priority date: 2022-09-22
Filing date: 2022-09-22
Publication date: 2023-12-01
Anticipated expiration: 2042-09-22
Also published as: CN115418633A

Abstract

The application belongs to the technical field of special fiber interface treatment, and relates to a preparation method of a continuous aluminum oxide fiber copper interface. The method comprises the steps of preparing an activating solution, soaking fibers, preparing a plating solution, heating in a water bath for reaction, and naturally airing. According to the application, the pretreatment time of the alumina fiber is integrally shortened through sensitization and activation, the pretreatment step is simplified, and then the copper plating treatment is carried out on the surface of the alumina fiber by adopting chemical plating, so that a layer of uniform and compact copper interface can be plated on the surface of the continuous alumina fiber, thereby expanding the application scene of the alumina fiber, and the whole process flow is simple and convenient, consumes less time, has low cost and is suitable for large-scale industrial popularization.

Description

Preparation method of continuous alumina fiber copper interface

Technical Field

The application belongs to the technical field of special fiber interface treatment, and relates to a preparation method of a continuous aluminum oxide fiber copper interface.

Background

Alumina fiber (Al) ₂ O _3f ) The reinforced metal matrix composite is widely applied to the fields of aerospace, petroleum exploitation, electronic packaging and large military weapon products because of excellent performances such as high strength and high wear resistance, is valued by people in all countries, starts to be researched as early as 60 s abroad, is relatively mature in technology at present, and is widely put into application in the United states. For example, the United states has been put into use by Al ₂ O ₃ The fuel injection part prepared by the reinforced aluminum-based composite material has the advantages that the service life of the part is prolonged, and better economic benefit is obtained; japanese Toyota is put into use by Al ₂ O ₃ The long fiber reinforced aluminum-based composite material automobile connecting rod greatly improves the strength of the connecting rod, improves the performance of an engine and has a good weight reduction effect.

The metal matrix composite material in China starts in the eighties of the last century, and is far from date, and has a great gap compared with developed countries. For the current research, in the preparation process of the alumina fiber reinforced metal matrix composite, the preparation process has high temperature, and the surface energy of the metal melt is large, and the metal melt is equal to Al ₂ O _3f Poor enhanced interphase wettability is always a key problem for restricting the improvement of the performance of the metal matrix composite. Surface metallization has been shown to effectively improve wettability problems between alumina and metal, where Al ₂ O _3f The inability of the surface to plate effectively due to excessive smoothness is a critical problem in current metallization processes.

Al ₂ O _3f The fiber has excellent properties of high temperature resistance, corrosion resistance, low deformation, low heat conductivity and the like, meanwhile, the production raw material cost is low, the production process is relatively simple, and the fiber is widely applied to the field of metal-based ceramic matrix composite materials, so that the wettability problem between the fiber and a metal matrix can be effectively improved by fiber surface metallization, and the potential metals are nickel, copper and silver. Electroless plating has been recognized as one of the effective treatment techniques for providing fibers with electrical, magnetic and chemical properties by pretreating the fibers with a plating solution configured to coat the surfaces of the fibers with a desired metal coating. As for the current research, many foreign students report more on the surface metallization of alumina particles, but the pretreatment is longer and the pretreatment is more effective on Al ₂ O _3f Few reports of surface metallization exist.

The existing fiber surface treatment process mainly comprises a thermal reduction method, a traditional pretreatment method and a palladium salt sensitization and activation integrated method, wherein the thermal reduction method is mainly applied to a carbon fiber surface copper plating process, although sensitization and activation steps are reduced, the pretreatment time is long, and the process conditions required by the thermal reduction process are strict; the traditional pretreatment method is long in time consumption, and the plating process is complicated, so that the industrial production is not favored; the palladium salt sensitization and activation are integrated, and although the operation steps are reduced, the time consumption is still too long, the price of the palladium salt and the price of the palladium salt are too high, and the palladium salt is not beneficial to industrial large-scale use.

Disclosure of Invention

The application provides a novel preparation method of a continuous aluminum oxide fiber copper interface aiming at the problems existing in the traditional fiber copper interface preparation.

In order to achieve the above purpose, the application is realized by adopting the following technical scheme:

the preparation method of the continuous alumina fiber copper interface provided by the application comprises the following two steps: pretreatment of the fiber surface and metallization plating of the fiber surface.

The specific operation steps are as follows:

s0: alumina fibers were prepared.

S1 pretreatment: preparing an activating solution, and uniformly mixing stannous chloride solution with the concentration of 5-20g/L, silver nitrate solution with the concentration of 2-10g/L and 37wt% of HCl solution with the concentration of 2-10 ml; and then soaking the fibers in the activating solution for 10-20min, taking out the fibers after the soaking is finished, and fully flushing the fibers with deionized water. Stannous chloride solution: silver nitrate solution: the volume ratio of the HCl solution is 6:3:1, soaking time is 10-20min, and the flushing liquid is deionized water.

S2, preparing copper salt solution: dissolving one or more of copper nitrate, copper sulfate and copper chloride in deionized water to obtain copper salt solution with concentration of 0.1mol/L, and clarifying and transparency.

S3, preparing plating solution: taking a copper salt solution reagent prepared in S2, sequentially adding a complexing agent, a reducing agent and potassium hydroxide, wherein the complexing agent is tartaric acid or one or two of potassium sodium tartrate and EDTA-2 sodium, the concentration is 10-60g/L, the reducing agent is one or more of formaldehyde, sucrose and glucose, the concentration is 2-10wt%, deionized water is a plurality of, potassium hydroxide is a plurality of, the pH of the plating solution is adjusted to 11-13, and the copper salt solution is: complexing agent: reducing agent: the deionized water part ratio is 10-30:5:0.2-0.6:20-50.

S4: and (3) placing the fibers treated in the step (S1) into the plating solution prepared in the step (S3), heating in a water bath for reaction, controlling the temperature of the water bath at 50-70 ℃, slowly stirring the plating solution in the reaction process until the plating solution is clear, stopping the reaction, and taking out the fibers plated with copper and naturally drying.

The continuous alumina fiber surface coating adhesion mechanism adopted by the application is different from that of the traditional carbon fiber, and the carbon fiber uses pretreatment to make the fiber surface rougher, so that the adhesion of activation points is provided during the subsequent sensitization and activation, and the effect of metal deposition is achieved. The alumina fiber has the advantages that the specific surface area is relatively large, the adsorption performance is extremely strong, and the alumina fiber has excellent corrosion resistance, and simple substances can be adsorbed even though the surface is smooth, so that three stages of glue removal, oil removal and coarsening are saved in pretreatment aiming at the characteristics of the alumina fiber, sensitization and activation liquid are combined together, and the activation liquid is stabilized by adding proper hydrochloric acid, so that the silver simple substances can be stably separated out and adsorbed on the surface of the fiber to form nucleation spots, and the aim of reducing metal deposition in the later period is fulfilled. In the preparation process of the application, the key point affecting the metal deposition quality is that the pre-treatment step is important except the components and the concentration of the post plating. The application omits three steps of removing glue, removing oil and roughening by improving the process, shortens the sensitization and activation into one step, greatly shortens the pretreatment time, and obtains ideal effect on the premise of greatly simplifying the process. In the method provided by the application, stannous chloride reacts with water to produce a tin film attached to the surface of the alumina fiber, and tin ions in the tin film react with silver ions to reduce the silver ions into silver simple substances to deposit on the surface of the fiber to form nucleation spots. Hydrochloric acid plays a role therein in preventing the premature hydrolysis of stannous chloride from causing failure.

Compared with the prior art, the application has the advantages and positive effects that:

the pretreatment time of the alumina fiber is shortened through sensitization and activation integration, the pretreatment step is simplified, then the surface of the alumina fiber is plated with copper by adopting chemical plating, and a layer of uniform and compact copper interface can be plated on the surface of the alumina fiber, so that the application scene of the alumina fiber is expanded, the whole process flow is simple and convenient, the time consumption is less, the cost is low, and the method is suitable for large-scale industrial popularization.

Drawings

Fig. 1 is an SEM photograph of the copper interface of the alumina fiber of example 1.

FIG. 2 is an EDS spectrum of the copper interface of the alumina fiber of example 1.

FIG. 3 shows the copper interface surface elements and their contents in the alumina fiber of example 1.

Fig. 4 is a copper interface XRD pattern of the alumina fiber of example 1.

Fig. 5 is an SEM photograph of the copper interface of the alumina fiber of comparative example 1.

Fig. 6 is an SEM photograph of the copper interface of the alumina fiber of comparative example 2.

Detailed Description

In order that the above objects, features and advantages of the application will be more clearly understood, a further description of the application will be provided with reference to specific examples. It should be noted that, without conflict, the embodiments of the present application and features in the embodiments may be combined with each other.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, however, the present application may be practiced otherwise than as described herein, and therefore the present application is not limited to the specific embodiments of the disclosure that follow.

Example 1

Several alumina fibers with a length of 8cm were taken, and the sources of the alumina fibers in this example are as follows: domestic Molon 996 (Morlon 996, brand: ML996, manufacturer: national materials technology (Jiangsu) Co., ltd.) continuous alumina fiber. 7g/L stannous chloride solution 60mL,2g/L silver nitrate solution 30mL, and 37wt% HCl solution 10mL were mixed well. The fibers were then added to the mixed solution and soaked for 15 minutes. 15g of copper sulfate is weighed, deionized water is added to prepare a solution of 0.1mol/L, and the solution is stirred to dissolve the copper sulfate, so that a clear and transparent copper sulfate solution is obtained. Adding complexing agent potassium sodium tartrate with the concentration of 10g/L and reducing agent formaldehyde with the concentration of 4wt% into the copper sulfate solution in sequence, and adding potassium hydroxide to adjust the PH of the plating solution to 12; wherein copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 20:5:0.2:30, obtaining the plating solution. Adding the soaked and pretreated alumina fiber into plating solution, heating in water bath, controlling the temperature to be 50 ℃ for reaction, slowly stirring the plating solution in the reaction process, taking out the plated fiber when the clarification reaction of the plating solution is stopped, and naturally airing to obtain the copper-plated alumina fiber.

FIGS. 1 to 4 are SEM photographs, EDS patterns, surface elements and contents thereof, and XRD patterns, respectively, of copper interfaces of copper-plated alumina fibers prepared in this example.

As can be seen from fig. 1, the copper interface of the copper-plated alumina fiber is uniform and compact, and as can be seen from fig. 2 to 4: the surface element of the plating layer is C\O\Cu, wherein the Cu content is the largest, the mass fraction accounts for 76.25wt%, and the other is the basic element. Further, as shown by XRD pattern analysis of FIG. 4, the characteristic diffraction peaks of copper phases are more obvious, and the characteristic peaks of (111) (200) (220) crystal faces appear at 2 theta of 43.1 degrees, 50.3 degrees and 73.9 degrees, and the peak widths are narrower, the peak type is more pointed, so that the crystal grains are better in crystallization, wherein the 2 theta is highest in strength at 43.1 degrees.

Example 2

Alumina fibers 10cm in length were taken and mixed uniformly with 60mL of stannous chloride solution 10g/L, 30mL of silver nitrate solution 5g/L, and 10mL of 37wt% HCl solution. The fibers were then added to the mixed solution and soaked for 10 minutes. Weighing a proper amount of copper nitrate, adding deionized water to prepare a solution with the concentration of 0.1mol/L, and stirring to dissolve the copper nitrate. Adding 30g/L complexing agent tartaric acid and 7wt% reducing agent glucose into copper nitrate solution in sequence, and adding potassium hydroxide to adjust the pH of the plating solution to 11; wherein copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 10:5:0.4:20, obtaining plating solution. Adding the soaked and pretreated alumina fiber into plating solution, heating in water bath, controlling the temperature to be 60 ℃ for reaction, slowly stirring the plating solution in the reaction process, taking out the plated fiber when the clarification reaction of the plating solution is stopped, and naturally airing to obtain the copper-plated alumina fiber. The effect of the plating of the fibers of the present embodiment was examined to be not much different from that of example 1.

Example 3

Alumina fibers of 12cm in length were taken and mixed uniformly with 60mL of stannous chloride solution of 20g/L, 30mL of silver nitrate solution of 10g/L, and 10mL of 37wt% HCl solution. The fibers were then added to the mixed solution and soaked for 20 minutes. Weighing a plurality of copper chloride, preparing a solution with the concentration of 0.1mol/L, stirring to dissolve the copper chloride, sequentially adding EDTA-2Na serving as a complexing agent with the concentration of 60g/L and glucose serving as a reducing agent with the concentration of 10wt%, adding potassium hydroxide, and adjusting the pH of the plating solution to 13; wherein copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 30:5:0.6:50, obtaining the plating solution. Adding the soaked and pretreated alumina fiber into plating solution, heating in water bath, controlling the temperature to be 70 ℃ for reaction, slowly stirring the plating solution in the reaction process, taking out the plated fiber when the clarification reaction of the plating solution is stopped, and naturally airing to obtain the copper-plated alumina fiber. The effect of the plating of the fibers of the present embodiment was examined to be not much different from that of example 1.

Comparative example 1

This comparative example is identical to example 1, unless otherwise specified.

The conditions of the present comparative example were changed as compared with example 1 in that the fiber pretreatment parameters, specifically, the stannous chloride and silver nitrate concentrations were increased in order to examine the influence of the activation liquid concentration on the product.

Alumina fibers 10cm in length were taken and mixed uniformly with 60mL of stannous chloride solution 30g/L, 30mL of silver nitrate solution 15g/L, and 10mL of 37wt% HCl solution. The fibers were then added to the mixed solution and soaked for 10 minutes. 15g of copper sulfate is weighed, deionized water is added to prepare a solution of 0.1mol/L, and the solution is stirred to dissolve the copper sulfate, so that a clear and transparent copper sulfate solution is obtained. Adding complexing agent potassium sodium tartrate with the concentration of 10g/L and reducing agent formaldehyde with the concentration of 4wt% into the copper sulfate solution in sequence, and adding potassium hydroxide to adjust the PH of the plating solution to 12; wherein copper salt solution: complexing agent: reducing agent: the volume ratio of deionized water is 20:5:0.2:30, obtaining the plating solution. Adding the soaked and pretreated alumina fiber into plating solution, heating in water bath, controlling the temperature to be 50 ℃ for reaction, slowly stirring the plating solution in the reaction process, taking out the plated fiber when the clarification reaction of the plating solution is stopped, and naturally airing to obtain the copper-plated alumina fiber.

Fig. 5 is an SEM image of the copper interface of the alumina fiber prepared in this comparative example, from which it can be seen that copper particles are unevenly deposited and locally appear in the uncoated areas. The effect is significantly reduced compared to example 1. The method shows that the parameters of the fiber pretreatment process seriously influence the quality of the plating.

Comparative example 2

The comparative example was conducted by changing the parameters of the fiber plating, adjusting the concentration of potassium sodium tartrate to 70g/L, the concentration of formaldehyde to 15wt%, the pH to 14, and the plating temperature to 40 ℃.

Alumina fibers of 8cm in length were taken and mixed uniformly with 60mL of 7g/L stannous chloride solution, 30mL of 2g/L silver nitrate solution, and 10mL of 37wt% HCl solution. The fibers were then added to the mixed solution and soaked for 15 minutes. Weighing copper sulfate, adding deionized water, stirring to prepare a clear and transparent solution with the concentration of 0.1mol/L, sequentially adding a complexing agent, a reducing agent and potassium hydroxide, wherein the complexing agent is a potassium sodium tartrate solution with the concentration of 70g/L, the reducing agent is a formaldehyde solution with the concentration of 15wt%, adding deionized water and potassium hydroxide, and regulating the pH of the plating solution to 14. Wherein copper salt solution: complexing agent: reducing agent: the volume ratio of deionized water is 20:5:0.2:30. and (3) placing the fiber after the pre-activation treatment into a plating solution, heating in a water bath, controlling the temperature to be 40 ℃ for reaction, slowly stirring the plating solution in the reaction, taking out the fiber after copper plating when the clarification reaction of the plating solution is stopped, and naturally airing to obtain the copper-plated aluminum oxide fiber.

Fig. 6 is an SEM photograph of the copper interface of the alumina fiber prepared in this example, from which it can be seen that the copper particles are relatively uniform in size, but locally appear in the uncoated areas. The effect was reduced compared to example 1. The fiber plating parameters are also greatly influenced on the plating morphology.

Comparative example 3

Alumina fibers of 8cm in length were taken and mixed uniformly with 60mL of 7g/L stannous chloride solution, 30mL of 2g/L silver nitrate solution, and 10mL of 37wt% HCl solution. The fibers were then added to the mixed solution and soaked for 15 minutes. 15g of copper sulfate is weighed, deionized water is added to prepare a solution of 0.1mol/L, and the solution is stirred to dissolve the copper sulfate, so that a clear and transparent copper sulfate solution is obtained. Adding complexing agent potassium sodium tartrate with the concentration of 10g/L and reducing agent formaldehyde with the concentration of 4wt% into the copper sulfate solution in sequence, and adding potassium hydroxide to adjust the PH of the plating solution to 12; wherein copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 20:5:0.8:30, obtaining the plating solution. Adding the soaked and pretreated alumina fiber into plating solution, heating in water bath, controlling the temperature to be 50 ℃ for reaction, slowly stirring the plating solution in the reaction process, taking out the plated fiber when the clarification reaction of the plating solution is stopped, and naturally airing to obtain the copper-plated alumina fiber.

Changing the volume ratio of the plating components shows that increasing the volume ratio of formaldehyde can lead to rapid reaction of the plating solution, thereby causing the failure of the plating solution and further leading to no deposition of effective particles on the surface of the fiber.

The present application is not limited to the above-mentioned embodiments, and any equivalent embodiments which can be changed or modified by the technical content disclosed above can be applied to other fields, but any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical substance of the present application without departing from the technical content of the present application still belong to the protection scope of the technical solution of the present application.

Claims

1. The preparation method of the continuous alumina fiber copper interface is characterized by comprising the following steps:

s1: mixing stannous chloride solution, silver nitrate solution and hydrochloric acid solution to obtain an activating solution, soaking alumina fiber in the activating solution, and flushing after the soaking is completed;

s2: preparing copper salt solution;

s3: adding complexing agent, reducing agent, potassium hydroxide and deionized water into the copper salt solution, and regulating the pH to 11-13 to obtain a plating solution, wherein the copper salt solution in the plating solution is: complexing agent: reducing agent: the volume ratio of deionized water is 10-30:5:0.2-0.6:20-50, adding potassium hydroxide to adjust the PH of the plating solution to 11-13;

s4: placing the alumina fiber treated in the step S1 into an S3 plating solution for copper plating, heating in a water bath, slowly stirring until the plating solution is clear, taking out the fiber subjected to copper plating, and airing; the water bath temperature is 50-70 ℃;

the concentration of each component in the activating solution in the step S1 is as follows: 7-20g/L of stannous chloride solution, 2-10g/L of silver nitrate solution and 37wt% of hydrochloric acid solution; stannous chloride solution: silver nitrate solution: the volume ratio of the HCl solution is 6:3:1, soaking for 10-20min, wherein the flushing fluid is deionized water;

the complexing agent in the step S3 is one of tartaric acid, potassium sodium tartrate and EDTA-2 sodium, the concentration is 10-60g/L, the reducing agent is one or more of formaldehyde, sucrose and glucose, and the concentration is 2-10wt%.

2. The method for preparing a copper interface of continuous alumina fiber according to claim 1, wherein the copper salt in the step S2 is at least one of copper nitrate, copper sulfate and copper chloride; the concentration of the copper salt solution is 0.1mol/L.