CN115418633A

CN115418633A - Preparation method of continuous aluminum oxide fiber copper interface

Info

Publication number: CN115418633A
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: 2022-12-02
Anticipated expiration: 2042-09-22
Also published as: CN115418633B

Abstract

The invention 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 drying. The method shortens the pretreatment time of the alumina fiber through the sensitization and activation integration, simplifies the pretreatment steps, and then adopts chemical plating to plate copper on the surface of the alumina fiber, 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.

Description

Preparation method of continuous aluminum oxide fiber copper interface

Technical Field

The invention 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-based composite material with excellent performances such as high strength, high wear resistance and the like is widely applied to the fields of aerospace, oil exploitation, electronic packaging and large military weapon products, is well valued by people in various countries, and is abroadResearch has been started as early as 60 s, and at present, foreign technologies are relatively mature and are put into application in great quantity in the United states. For example, the United states has been put into practice with Al ₂ O ₃ The fuel injection part prepared from 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 was put into practice with Al ₂ O ₃ The automobile connecting rod made of the long fiber reinforced aluminum-based composite material greatly improves the strength of the connecting rod, improves the performance of an engine and has a better weight reduction effect.

The metal-based composite material in China starts in the eighties of the last century, and has a great gap compared with developed countries today. For the present research, in the preparation process of the alumina fiber reinforced metal matrix composite material, the temperature of the preparation process is high, the surface energy of the metal melt is large, and Al are mixed ₂ O _3f The poor wettability of the reinforced phase is a key problem for restricting the improvement of the performance of the metal matrix composite. Surface metallization has proven effective in improving the wettability between alumina and metal, where Al ₂ O _3f The surface is too smooth to be plated effectively is a key problem in the prior metallization process.

Al ₂ O _3f The fiber surface metallization can effectively improve the problem of wettability with a metal matrix, and potential metals of the fiber surface metallization are nickel, copper and silver. Electroless plating has been recognized as one of the effective treatment techniques to impart electrical, magnetic and chemical properties to fibers by pretreating the fibers and applying a plating solution to the surface of the fibers to form a desired metal coating. In terms of the present research, many foreign scholars have reported on the metallization of the surface of alumina particles, but the pretreatment time is long and the pretreatment time is long, and Al is used ₂ O _3f Few reports have been made of surface metallization.

The prior 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 copper plating process on the surface of carbon fiber, although the 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 more complicated, so that the industrial production is not facilitated; the palladium salt sensitization and activation are integrated, so that the operation steps are reduced, but the time is still too long, the price of the palladium salt is extremely high, and the large-scale industrial application is not facilitated.

Disclosure of Invention

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

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

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

The specific operation steps are as follows:

s0: alumina fibers were prepared.

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

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

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

S4: and (3) placing the fiber treated in the step (1) in the plating solution prepared in the step (3), heating in a water bath for reaction, controlling the temperature of the water bath to be 50-70 ℃, slowly stirring the plating solution in the reaction process until the plating solution is clear, stopping the reaction, taking out the fiber after copper plating, and naturally drying.

The adhesion mechanism of the continuous alumina fiber surface coating adopted by the invention is different from that of the traditional carbon fiber, and the carbon fiber utilizes pretreatment to make the fiber surface rougher so as to provide adhesion of activated points during subsequent sensitization and activation and achieve the effect of metal deposition. The alumina fiber has larger specific surface area, extremely strong adsorption performance and excellent corrosion resistance, and can still adsorb simple substances even if the surface is smooth, so the invention omits three stages of degumming, deoiling and coarsening in pretreatment aiming at the characteristics of the alumina fiber, combines sensitizing and activating solutions together, and adds proper hydrochloric acid to stabilize the activating solution, so that the silver simple substances can be stably separated out and adsorbed on the surface by the fiber to form nucleation particles, thereby achieving the purpose of reducing metal deposition in the later period. In the preparation process, the key point influencing the metal deposition quality is that the pretreatment step at the early stage is important except the components and the concentration of plating at the later stage. The invention omits three steps of degumming, degreasing and coarsening through process improvement, reduces sensitization activation into one step, greatly shortens pretreatment time, and obtains ideal effect on the premise of greatly simplifying the process. In the method provided by the invention, 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 be deposited on the surface of the fiber to form nucleation spots. Hydrochloric acid serves to prevent the stannous chloride from hydrolyzing too quickly to cause failure.

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

the method has the advantages that the pretreatment time of the alumina fiber is shortened through sensitization and activation integration, the pretreatment steps are simplified, then the surface of the alumina fiber is plated with copper through 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 consumed time is short, 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 interfacial surface elements and their contents for the alumina fiber of example 1.

FIG. 4 is the 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 manner in which the above recited objects, features and advantages of the present invention are obtained will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.

Example 1

A plurality of alumina fibers with the length of 8cm are taken, and the alumina fibers in the embodiment are derived from the following sources: domestic Moron 996 (Morlion 996, trade mark: ML996, manufacturer: national New Material technology (Jiangsu) Co., ltd.) continuous alumina fiber. 7g/L stannous chloride solution 60mL,2g/L silver nitrate solution 30mL and 37wt% HCl solution 10mL are mixed uniformly. Then the fiber is added into the mixed solution to be soaked for 15min. Weighing 15g of copper sulfate, adding deionized water to prepare a solution of 0.1mol/L, and stirring to dissolve the copper sulfate to obtain a clear and transparent copper sulfate solution. Sequentially adding complexing agent sodium potassium tartrate with the concentration of 10g/L and reducing agent formaldehyde with the concentration of 4wt% into copper sulfate solution, and adding potassium hydroxide to adjust the pH value of the plating solution to 12; wherein the copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 20:5:0.2: and 30, obtaining the plating solution. Adding the alumina fiber after the soaking pretreatment into a plating solution, heating in water bath, controlling the temperature at 50 ℃ for reaction, slowly stirring the plating solution in the reaction process until the clarification reaction of the plating solution stops, taking out the plated fiber, and naturally drying to obtain the copper-plated alumina fiber.

FIGS. 1 to 4 are SEM photograph, EDS pattern, surface element and content thereof, and XRD pattern of copper interface of copper-coated alumina fiber prepared in this example, respectively.

As can be seen from FIG. 1, the copper interface of the copper-plated alumina fiber is uniform and dense, and as can be seen from FIGS. 2-4: the surface elements of the plating layer comprise C \ O \ Cu, wherein the content of Cu is the most, the mass fraction accounts for 76.25wt%, and the other elements are basic elements. Further, as can be seen from the XRD pattern analysis of fig. 4, the characteristic diffraction peak of the copper phase is more obvious, and the characteristic peaks of the (111) (200) (220) crystal planes appear at 2 θ of 43.1 °, 50.3 ° and 73.9 °, and the peak width is narrower, and the peak shape is sharper, which indicates that the crystal grains are better crystallized, wherein the intensity of 2 θ is highest at 43.1 °.

Example 2

A plurality of alumina fibers with the length of 10cm are taken, and 10mL of stannous chloride solution 60ml,5g/L silver nitrate solution 30mL and 37wt% HCl solution 10mL are uniformly mixed. Then adding the fiber into the mixed solution to be soaked for 10min. Weighing a proper amount of copper nitrate, adding deionized water to prepare a solution of 0.1mol/L, and stirring to dissolve the copper nitrate. Sequentially adding 30g/L complexing agent tartaric acid and 7wt% reducing agent glucose into a copper nitrate solution, adding potassium hydroxide, and adjusting the pH value of the plating solution to 11; wherein the copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 10:5:0.4:20, obtaining the plating solution. Adding the alumina fiber after the soaking pretreatment into a plating solution, heating in water bath, controlling the temperature at 60 ℃ for reaction, slowly stirring the plating solution in the reaction process until the clarification reaction of the plating solution stops, taking out the plated fiber, and naturally drying to obtain the copper-plated alumina fiber. The detection shows that the plating effect of the fiber of the embodiment is not much different from that of the embodiment 1.

Example 3

A plurality of alumina fibers with the length of 12cm are taken, and 20g/L stannous chloride solution 60mL,10g/L silver nitrate solution 30mL and 37wt% HCl solution 10mL are mixed uniformly. Then the fiber is added into the mixed solution to be soaked for 20min. Weighing a plurality of copper chloride to prepare a solution of 0.1mol/L, stirring to dissolve the copper chloride, sequentially adding a complexing agent EDTA-2Na with the concentration of 60g/L and 10wt% of reducing agent glucose into the copper chloride solution, adding potassium hydroxide, and adjusting the pH value of the plating solution to 13; wherein the copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 30:5:0.6:50, obtaining the plating solution. Adding the alumina fiber after the soaking pretreatment into a plating solution, heating in water bath, controlling the temperature at 70 ℃ for reaction, slowly stirring the plating solution in the reaction process until the clarification reaction of the plating solution stops, taking out the plated fiber, and naturally drying to obtain the copper-plated alumina fiber. The detection shows that the plating effect of the fiber of the embodiment is not much different from that of the embodiment 1.

Comparative example 1

This comparative example, which is not specifically described, corresponds to example 1.

The comparative example was compared to example 1 with the modification of the fiber pretreatment parameters, specifically increasing the stannous chloride and silver nitrate concentrations to examine the effect of the activation fluid concentration on the product.

A plurality of alumina fibers with the length of 10cm are taken, and 30g/L stannous chloride solution 60mL,15g/L silver nitrate solution 30mL and 37wt% HCl solution 10mL are uniformly mixed. Then adding the fiber into the mixed solution to be soaked for 10min. Weighing 15g of copper sulfate, adding deionized water to prepare a solution of 0.1mol/L, and stirring to dissolve the copper sulfate to obtain a clear and transparent copper sulfate solution. Sequentially adding complexing agent sodium potassium tartrate with the concentration of 10g/L and reducing agent formaldehyde with the concentration of 4wt% into copper sulfate solution, and adding potassium hydroxide to adjust the pH value of the plating solution to 12; wherein the copper salt solution: complexing agent: reducing agent: the volume ratio of the deionized water is 20:5:0.2: and 30, obtaining the plating solution. Adding the alumina fiber after the soaking pretreatment into a plating solution, heating in water bath, controlling the temperature at 50 ℃ for reaction, slowly stirring the plating solution in the reaction process until the clarification reaction of the plating solution stops, taking out the plated fiber, and naturally drying 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 the deposition of copper particles is not uniform and that the non-plated regions are locally present. The effect is significantly reduced compared to example 1. The condition that the pretreatment process parameters of the fiber seriously affect the quality of a plating layer is demonstrated.

Comparative example 2

The comparative example changes the fiber plating parameters, adjusts the concentration of the sodium potassium tartrate to 70g/L, the concentration of the formaldehyde to 15wt percent, the PH to 14 and the plating temperature to 40 ℃.

A plurality of alumina fibers with the length of 8cm are taken, and 7g/L stannous chloride solution 60mL,2g/L silver nitrate solution 30mL and 37wt% HCl solution 10mL are mixed uniformly. Then the fiber is added into the mixed solution to be soaked for 15min. Weighing copper sulfate, adding deionized water, stirring to prepare a clear 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 sodium potassium 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 adjusting the pH of the plating solution to 14. Wherein the copper salt solution: complexing agent: reducing agent: the volume ratio of the deionized water is 20:5:0.2:30. and (3) placing the pre-activated fibers in a plating solution, heating in water bath, controlling the temperature at 40 ℃ for reaction, slowly stirring the plating solution in the reaction, taking out the fibers after copper plating when the clarification reaction of the plating solution is stopped, and naturally drying to obtain the copper-plated aluminum oxide fibers.

Fig. 6 is an SEM photograph of the copper interface of the alumina fiber prepared in this example, which shows that the copper grain size is relatively uniform, but the non-plated area is locally present. The effect is reduced compared to example 1. The fiber plating parameters also have great influence on the appearance of the plating layer.

Comparative example 3

A plurality of alumina fibers with the length of 8cm are taken, and 7g/L stannous chloride solution 60mL,2g/L silver nitrate solution 30mL and 37wt% HCl solution 10mL are uniformly mixed. Then the fiber is added into the mixed solution to be soaked for 15min. Weighing 15g of copper sulfate, adding deionized water to prepare a solution of 0.1mol/L, and stirring to dissolve the copper sulfate to obtain a clear and transparent copper sulfate solution. Sequentially adding 10g/L complexing agent sodium potassium tartrate and 4wt% reducing agent formaldehyde into a copper sulfate solution, and adding potassium hydroxide to adjust the pH value of the plating solution to 12; wherein the copper salt solution: complexing agent: reducing agent: deionized water: the volume ratio is 20:5:0.8: and 30, obtaining the plating solution. Adding the alumina fiber after the soaking pretreatment into a plating solution, heating in water bath, controlling the temperature at 50 ℃ for reaction, slowly stirring the plating solution in the reaction process until the clarification reaction of the plating solution stops, taking out the plated fiber, and naturally drying to obtain the copper-plated alumina fiber.

Changing the volume ratio of the plating components shows that the increase of the volume ratio of formaldehyde can cause the plating solution to react quickly, cause the failure of the plating solution and then cause no effective particle deposition on the surface of the fiber.

The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.

Claims

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

s1: mixing a stannous chloride solution, a silver nitrate solution and a hydrochloric acid solution to obtain an activation solution, then soaking the alumina fiber in the activation solution, and flushing after soaking;

s2: preparing a copper salt solution;

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

s4: placing the aluminum oxide fiber treated in the step S1 in a plating solution of the step S3 for copper plating, heating in a water bath, slowly stirring until the plating solution is clear, taking out the fiber after copper plating, and airing; the temperature of the water bath is 50-70 ℃.

2. The method for preparing the copper interface of the continuous alumina fiber according to claim 1, wherein the concentration of each component in the activating solution of the step S1 is as follows: 5-20g/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, and washing with deionized water.

3. The method for preparing the copper interface of the 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.

4. The method for preparing the copper interface of the continuous alumina fiber according to claim 1, wherein the complexing agent in step S3 is one or two of tartaric acid, potassium sodium tartrate and EDTA-2 sodium, and the concentration is 10-60g/L, and the reducing agent is one or more of formaldehyde, sucrose and glucose, and the concentration is 2-10wt%.