阅读说明：本技术 一种导电浮力材料及其制备方法 (Conductive buoyancy material and preparation method thereof ) 是由 赵健伟 于晓辉 庄再裕 孙志 程娜 于 2019-12-31 设计创作，主要内容包括：本发明公开了一种导电浮力材料及其制备方法,涉及浮力材料技术领域。本发明通过采用硅烷偶联剂对空心玻璃微珠粉材进行表面改性处理,提高无机填料与环氧树脂间界面作用力,增强空心玻璃微珠与环氧树脂相容性；同时在空心玻璃微珠粉材表面以化学镀银方式镀膜得到表面镀银的空心玻璃微珠粉材,使得抗压强度高、密度小的空心玻璃微珠粉材兼具高性能导电填料特性,将表面镀银空心玻璃微珠粉材与环氧树脂共同制备得到导电浮力材料可达到工业导电性要求,并具备低密度、高强度的特点,从而解决固体浮力材料导电性能、浮力性能与力学性能无法兼顾的技术问题,使得固体浮力材料同时具备优异导电性能、浮力性能和力学性能综合素质的技术效果。(The invention discloses a conductive buoyancy material and a preparation method thereof, and relates to the technical field of buoyancy materials. According to the invention, the silane coupling agent is adopted to carry out surface modification treatment on the hollow glass bead powder, so that the interface acting force between the inorganic filler and the epoxy resin is improved, and the compatibility of the hollow glass beads and the epoxy resin is enhanced; meanwhile, the hollow glass bead powder with the silver-plated surface is obtained by plating a film on the surface of the hollow glass bead powder in a chemical silver plating mode, so that the hollow glass bead powder with high compressive strength and low density has the characteristic of high-performance conductive filler, the conductive buoyancy material prepared by the hollow glass bead powder with the silver-plated surface and epoxy resin can meet the industrial conductivity requirement, and has the characteristics of low density and high strength, thereby solving the technical problem that the conductivity, the buoyancy and the mechanical property of the solid buoyancy material cannot be considered simultaneously, and ensuring that the solid buoyancy material has the technical effects of excellent comprehensive properties of conductivity, buoyancy and mechanical property.)

1. The preparation method of the conductive buoyancy material is characterized by comprising the following steps of:

(1) adopting NaOH saturated ethanol solution to carry out surface cleaning and drying on the uniformly dispersed hollow glass bead powder material to obtain the deoiled hollow glass bead powder material;

(2) putting the deoiled hollow glass bead powder material into 0.1-1.0mol/L NaOH solution, stirring at 50-80 ℃ for 30-90min, taking out, then carrying out surface cleaning by using deionized water and drying to obtain the surface hydroxylated hollow glass bead powder material;

(3) putting the hollow glass bead powder with the surface hydroxylated into SnCl₂Stirring the/HCl mixed solution for 10-60min, and taking out to obtain the sensitized hollow glass bead powder material, namely SnCl₂The component proportion of the/HCl mixed solution comprises 40g SnCl₂·2H₂O, 100mL HCl and 2L deionized water;

(4) putting the sensitized hollow glass bead powder into 3-5g/L silver ammonia activation solution, stirring for 10-60min, taking out, then carrying out surface cleaning by using deionized water, and drying to obtain the activated hollow glass bead powder;

(5) putting the activated hollow glass microsphere powder and 0.2-0.4mol/L reducing liquid into a reaction container together, then dropwise adding 0.1-0.2mol/L silver ammonia solution into the reaction container, carrying out chemical silver plating treatment for 2-6h at the reaction temperature of 20-60 ℃ to obtain the surface silver-plated hollow glass microsphere powder, and then putting the surface silver-plated hollow glass microsphere powder at 80 ℃ for drying treatment;

(6) putting the dried hollow glass bead powder with the silver-plated surface into deionized water, adding a silane coupling agent, and stirring at 50-100 ℃ for 1-3h to obtain the silver-plated hollow glass bead powder with the silane coupling agent coated on the surface, wherein the mass of the silane coupling agent is 1-6% of the total mass of the hollow glass bead powder with the silver-plated surface;

(7) and putting the silver-plated hollow glass bead powder material coated with the silane coupling agent on the surface into epoxy resin glue, uniformly stirring for 10-30min, continuously adding a curing agent, stirring for 10-30min to obtain a mixed colloid, pouring the mixed colloid into a mold, and feeding the mold into an oven at 80 ℃ for curing for 5-12h to form, thus preparing the conductive buoyancy material.

2. The method according to claim 1, wherein the mass ratio of the epoxy resin glue to the silver-plated hollow glass bead powder is lower than 5:1.

3. the method according to claim 1, wherein the ratio of the hollow glass bead powder to each reaction reagent is as follows: SnCl₂HCl mixed solution: NaOH solution: silver ammonia activating solution: reducing liquid: silver ammonia solution: silane coupling agent =10 g: 100-500 mL: 100-500 mL: 100-500 mL: 100 and 1000 mL: 100 and 1000 mL: 100 and 1000 mL.

4. The method as claimed in claim 1, wherein the dropping speed of the silver ammonia solution is 100-1000 mL/1.5 h.

5. The method of claim 1, wherein the components of the reducing fluid include at least one of glucose, sodium borohydride, sodium potassium tartrate, and sodium phosphite.

6. The method of claim 1, wherein the epoxy glue comprises at least one of bisphenol a epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, and aliphatic glycidyl ether epoxy resin.

7. The method of claim 1, wherein the curing agent comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine.

8. The method as claimed in claim 1, wherein the electrically conductive and buoyant material has an electrical conductivity of 700-900S/m and a density of 0.80-0.85 g/cm³The compressive strength is 35-40 MPa.

9. The conductive buoyancy material is characterized by being prepared by the preparation method of the conductive buoyancy material according to any one of claims 1 to 8, the conductive buoyancy material comprises epoxy resin glue and silver-plated hollow glass bead powder coated with a silane coupling agent on the surface, the conductivity of the conductive buoyancy material is 700-900S/m, and the density of the conductive buoyancy material is 0.80-0.85 g/cm³The compressive strength is 35-40 MPa.

Technical Field

The invention relates to the technical field of buoyancy materials, in particular to a conductive buoyancy material and a preparation method thereof.

Background

China has 300 ten thousand square kilometers of ocean land area and the ocean resource reserves are abundant. In the development process of carrying out ocean resources, often need fix ocean detection equipment through ocean buoyancy material, avoid ocean detection equipment to receive external environment influences such as ocean current and take place to remove, lead to receiving the influence to the regional ocean detection data accuracy of target detection, wherein, the solid buoyancy material that possesses the buoyancy compensation function is important ocean buoyancy material. The solid buoyancy material adopted in the prior art is mainly formed by compounding hollow glass beads and a thermosetting resin system, and has no conductivity completely, and in the process of matching the solid buoyancy material with ocean detection equipment, an extra conductive cable needs to be configured to supply power to the ocean detection equipment, so that the solid buoyancy material is high in bearing capacity.

In the process of implementing the invention, the inventor finds that the related art has at least the following problems:

Disclosure of Invention

The invention mainly aims to provide a conductive buoyancy material and a preparation method thereof, which are used for solving the technical problem that the conductivity, the buoyancy performance and the mechanical property of the existing solid buoyancy material cannot be considered at the same time, so that the solid buoyancy material has the technical effect of comprehensive quality of excellent conductivity, buoyancy performance and mechanical property. The technical scheme of the invention is as follows:

according to a first aspect of the embodiments of the present invention, there is provided a method for preparing an electrically conductive buoyant material, comprising the steps of:

(1) adopting NaOH saturated ethanol solution to carry out surface cleaning and drying on the uniformly dispersed hollow glass bead powder material to obtain the deoiled hollow glass bead powder material;

(2) putting the deoiled hollow glass bead powder material into 0.1-1.0mol/L NaOH solution, stirring at 50-80 ℃ for 30-90min, taking out, then carrying out surface cleaning by using deionized water and drying to obtain the surface hydroxylated hollow glass bead powder material;

(3) putting the hollow glass bead powder with the surface hydroxylated into SnCl₂Stirring the/HCl mixed solution for 10-60min, and taking out to obtain the sensitized hollow glass bead powder material, namely SnCl₂The component proportion of the/HCl mixed solution comprises 40g of SnCl₂·2H₂O, 100mL HCl and 2L deionized water;

(4) putting the sensitized hollow glass bead powder into 3-5g/L silver ammonia activation solution, stirring for 10-60min, taking out, then carrying out surface cleaning by using deionized water, and drying to obtain the activated hollow glass bead powder;

(5) putting the activated hollow glass microsphere powder and 0.2-0.4mol/L reducing liquid into a reaction container together, then dropwise adding 0.1-0.2mol/L silver ammonia solution into the reaction container, carrying out chemical silver plating treatment for 2-6h at the reaction temperature of 20-60 ℃ to obtain the surface silver-plated hollow glass microsphere powder, and then putting the surface silver-plated hollow glass microsphere powder at 80 ℃ for drying treatment;

(6) putting the dried hollow glass bead powder with the silver-plated surface into deionized water, adding a silane coupling agent, and stirring at 50-100 ℃ for 1-3h to obtain the silver-plated hollow glass bead powder with the silane coupling agent coated on the surface, wherein the mass of the silane coupling agent is 1-6% of the total mass of the hollow glass bead powder with the silver-plated surface;

(7) and putting the silver-plated hollow glass bead powder material coated with the silane coupling agent on the surface into epoxy resin glue, uniformly stirring for 10-30min, continuously adding a curing agent, stirring for 10-30min to obtain a mixed colloid, pouring the mixed colloid into a mold, and feeding the mold into an oven at 80 ℃ for curing for 5-12h to form, thus preparing the conductive buoyancy material.

In a preferred embodiment, the mass ratio of the epoxy resin glue to the silver-plated hollow glass bead powder is lower than 5:1.

in a preferred embodiment, the ratio of the hollow glass bead powder to each reaction reagent is as follows: SnCl₂HCl mixed solution: NaOH solution: silver ammonia activating solution: reducing liquid: silver ammonia solution: silane coupling agent =10 g: 100-500 mL: 100-500 mL: 100-500 mL: 100 and 1000 mL: 100 and 1000 mL: 100 and 1000 mL.

In a preferred embodiment, the dropping speed of the silver ammonia solution is 100-1000 mL/1.5 h.

In a preferred embodiment, the components of the reducing liquid include at least one of glucose, sodium borohydride, sodium potassium tartrate and sodium phosphite.

In a preferred embodiment, the epoxy resin glue comprises at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin.

In a preferred embodiment, the curing agent comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.

In a preferred embodiment, the conductivity of the conductive buoyancy material is 700-900S/m, and the density is 0.80-0.85 g/cm³The compressive strength is 35-40 MPa.

According to a second aspect of the embodiment of the invention, the conductive buoyancy material is characterized by being prepared by any preparation method of the conductive buoyancy material, the conductive buoyancy material comprises epoxy resin glue and silver-plated hollow glass bead powder coated with a silane coupling agent on the surface, the epoxy resin glue is coated with the silver-plated hollow glass bead powder, the conductivity of the conductive buoyancy material is 700-900S/m, and the density of the conductive buoyancy material is 0.80-0.85 g/cm³The compressive strength is 35-40 MPa.

Compared with the prior art, the conductive buoyancy material and the preparation method thereof provided by the invention have the following advantages:

according to the conductive buoyancy material and the preparation method thereof, aiming at the characteristics of large specific surface area and ultra-light weight of the hollow glass bead powder, after multiple pre-treatments, the hollow glass bead powder with the silver-plated surface is obtained by plating a film on the surface of the hollow glass bead powder in a chemical silver plating manner, so that the hollow glass bead powder with high compressive strength and low density has excellent conductivity; meanwhile, silane coupling agent is adopted to carry out surface modification treatment on the silver-plated hollow glass bead powder, so that the interface acting force between the inorganic filler and the epoxy resin is improved, and the compatibility of the silver-plated hollow glass beads and the epoxy resin is further enhanced; the conductive buoyancy material is prepared by the surface-modified silver-plated hollow glass bead powder and the epoxy resin with high stability, so that the conductive buoyancy material meets the requirements of conductivity in industry and research, and has the characteristics of low density and high strength, the technical problem that the conductivity, the buoyancy performance and the mechanical property of the existing solid buoyancy material cannot be considered at the same time is solved, and the solid buoyancy material has the technical effects of excellent conductivity, buoyancy performance and mechanical property comprehensive quality.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.

FIG. 1 is a method flow diagram illustrating a method of making an electrically conductive buoyant material according to an exemplary embodiment.

FIG. 2 is a microscopic view of the hollow glass bead powder provided by the present invention.

FIG. 3 is a microscopic schematic view of a hollow glass bead powder with silver-plated surface according to the present invention.

FIG. 4 shows a schematic diagram of a method for generating a signal m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The I-V curve of the conductive buoyancy material is shown as 5:1.

FIG. 5 shows a schematic diagram of a method of manufacturing a semiconductor device_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The I-V curve of the conductive buoyancy material is shown as 5: 1.5.

FIG. 6 shows a graph of m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The I-V curve of the conductive buoyancy material is shown as 5:2.

FIG. 7 shows a graph of m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The I-V curve of the conductive buoyancy material is shown as 5: 2.5.

FIG. 8 shows a graph of m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The I-V curve of the conductive buoyancy material is shown as 5:3.

FIG. 9 shows a schematic diagram of a method of manufacturing a semiconductor device_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The I-V curve of the conductive buoyancy material is shown as 5: 3.5.

FIG. 10 is a schematic view of a lamp of the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The microscopic view of the conductive buoyancy material is 5:1.

FIG. 11 is a drawing of the present inventionm_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The microscopic view of the conductive buoyancy material is 5: 1.5.

FIG. 12 shows a schematic view of a structure m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The microscopic view of the conductive buoyancy material is 5:2.

FIG. 13 shows a schematic view of a structure m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The microscopic view of the conductive buoyancy material is 5: 2.5.

FIG. 14 shows a graph of m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The microscopic view of the conductive buoyancy material is 5:3.

FIG. 15 shows a schematic view of a structure m according to the present invention_{Epoxy resin}:m_{Silver-plated glass micro-bead powder material}The microscopic view of the conductive buoyancy material is 5: 3.5.

Detailed Description

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

Fig. 1 is a method flow diagram illustrating a method of manufacturing an electrically conductive buoyant material according to an exemplary embodiment, the method of manufacturing the electrically conductive buoyant material, as shown in fig. 1, comprising the steps of:

step (1): and (3) carrying out surface cleaning and drying on the uniformly dispersed hollow glass bead powder by adopting NaOH saturated ethanol solution to obtain the deoiled hollow glass bead powder.

In one possible embodiment, the number of times of cleaning the hollow glass bead powder in the step (1) can be 2, and the drying time after cleaning is 10-30 min.

The hollow glass bead powder is a light nonmetal multifunctional material and has the unique characteristics of high compressive strength, small density, large specific surface area, small thermal shrinkage coefficient and the like. It is necessary to remove impurities and oils from the surface by a method having a stronger cleaning power. For convenience of explanation, a microscopic view of the hollow glass bead powder at a magnification of 500 is shown in fig. 2.

The impurities such as dust, solid particles and the like on the surface of the pretreated hollow glass bead powder material can be removed preliminarily.

It should be noted that, the hollow glass bead powder material is easy to agglomerate in the actual storage and transportation process due to small density, small size and large specific surface area, so as to affect the further treatment of the hollow glass bead powder material.

Step (2): and (3) putting the deoiled hollow glass bead powder into 0.1-1.0mol/L NaOH solution, stirring at 50-80 ℃ for 30-90min, taking out, then carrying out surface cleaning by using deionized water, and drying to obtain the surface hydroxylated hollow glass bead powder.

Hydroxyl is introduced into the surface of the hollow glass bead powder material without reactive groups, so that the surface structure of the hollow glass bead powder material can be changed, and a reactive center is formed on the surface of the hollow glass bead powder material, so that the hydrophilic capacity of the surface of the hollow glass bead powder material is improved, conditions are provided for subsequent deposition of silver on the surface of the hollow glass bead powder material, and meanwhile, the binding force between a silver coating and the hollow glass bead powder material is improved.

And (3): putting the hollow glass bead powder material with the surface hydroxylated into SnCl₂Stirring the/HCl mixed solution for 10-60min, and taking out to obtain the sensitized hollow glass microsphere powder material, namely SnCl₂The component proportion of the/HCl mixed solution comprises 40g SnCl₂·2H₂O, 100mL HCl, and 2L deionized water.

Wherein, SnCl₂the/HCl mixed solution acts as a sensitizing solution.

The purpose of sensitization is to make the surface of the hollow glass microsphere powder material carry Sn which is easy to be reduced²⁺So as to be carried out on the surface of the hollow glass bead powder material through the subsequent oxidation-reduction reactionCarrying a silver coating; the addition of hydrochloric acid to the sensitizing solution is to suppress Sn²⁺Oxidation takes place.

And (4): and (3) putting the sensitized hollow glass bead powder material into 3-5g/L silver ammonia activation solution, stirring for 10-60min, taking out, then carrying out surface cleaning by using deionized water, and drying to obtain the activated hollow glass bead powder material.

The purpose of activation is to form silver particles on the surface of the hollow glass bead powder material, provide catalytic action and provide crystal nuclei for silver crystallization.

And (5): putting the activated hollow glass bead powder and 0.2-0.4mol/L reducing liquid into a reaction container together, then dropwise adding 0.1-0.2mol/L silver ammonia solution into the reaction container, carrying out chemical silver plating treatment for 2-6h at the reaction temperature of 20-60 ℃ to obtain the hollow glass bead powder with silver-plated surface, and then placing the hollow glass bead powder with silver-plated surface at 80 ℃ for drying treatment.

In one possible embodiment, the dropping speed of the silver ammonia solution is 100-1000 mL/1.5 h.

Wherein, a microscopic schematic diagram of the hollow glass bead powder material with silver-plated surface under 500 magnifications is shown in fig. 3.

And (6): and (3) putting the dried hollow glass bead powder with the silver-plated surface into 500mL of 100-fold deionized water, then adding a silane coupling agent, and stirring at 50-100 ℃ for 1-3h to obtain the silver-plated hollow glass bead powder with the surface coated with the silane coupling agent, wherein the mass of the silane coupling agent is 1-6% of the total mass of the hollow glass bead powder with the silver-plated surface.

The addition of the silane coupling agent can improve the chemical reactivity and compatibility between the silver-plated hollow glass bead powder and the epoxy resin adhesive in the step (7), and increase the interface connection performance between the silver-plated hollow glass bead powder and the matrix.

And (7): and putting the silver-plated hollow glass bead powder material coated with the silane coupling agent on the surface into epoxy resin glue, uniformly stirring for 10-30min, continuously adding a curing agent, stirring for 10-30min to obtain a mixed colloid, pouring the mixed colloid into a mold, and feeding the mold into an oven at 80 ℃ for curing for 5-12h to form, thus preparing the conductive buoyancy material.

The epoxy resin adhesive is rich in reactive groups, so that the cured epoxy resin adhesive has extremely high bonding performance, the high stability is another important characteristic of the epoxy resin, and the cured epoxy resin has excellent chemical corrosion resistance.

It should be noted that the coating of a layer of metal on the surface of the non-metal powder is a core-shell type composite powder with a core of non-metal such as glass, ceramic and the like and a surface of metal, which not only can make the non-metal powder have special electric, magnetic and optical properties, but also can keep the original properties of the non-metal powder. According to the invention, the practical application requirements of the buoyancy material in various deep sea environments are explored, the hollow glass bead powder material with small density, stable chemical property and high compressive strength is used as a main body, and the low-density hollow glass bead powder material is endowed with conductivity through the simple process to prepare the conductive buoyancy material, so that the settlement problem of the buoyancy material is favorably solved, the high conductivity of the buoyancy material is realized, the prepared conductive buoyancy material has the characteristics of low density, controllable density, high compressive strength and mechanical processability, and the application requirements of deep sea detection can be met.

According to the invention, the epoxy resin adhesive and the prepared hollow glass bead powder with the silver-plated surface are mixed together to prepare the conductive buoyancy material, so that the excellent performances of the epoxy resin adhesive and the hollow glass bead powder with the silver-plated surface can be synthesized to the greatest extent on the premise of not influencing the performances of the epoxy resin adhesive and the hollow glass bead powder with the silver-plated surface.

In a preferred embodiment, the ratio of the hollow glass bead powder to each reaction reagent is as follows: SnCl₂HCl mixed solution: NaOH solution: silver ammonia activating solution: reducing liquid: silver ammonia solution: silane coupling agent =10 g: 100-500 mL: 100-500 mL: 100-500 mL: 100 and 1000 mL: 100 and 1000 mL: 100 and 1000 mL.

In a preferred embodiment, the components of the reducing liquid include at least one of glucose, sodium borohydride, sodium potassium tartrate and sodium phosphite.

In a preferred embodiment, the epoxy resin glue comprises at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, polyphenol type glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin.

In a preferred embodiment, the curing agent comprises at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine.

In a preferred embodiment, the conductivity of the conductive buoyancy material is 700-900S/m, and the density is 0.80-0.85 g/cm³The compressive strength is 35-40 MPa.

In terms of conductivity, the conductivity (750-^-7S/m) is greatly improved. In the aspect of density, the density (0.80-0.85 g/cm) of the conductive buoyancy material provided by the invention³) Compared with the density (0.53-0.55 g/cm) of the solid buoyancy material added with the same mass ratio of the glass bead powder³) Slightly higher, because the density of the hollow glass beads is increased after silver plating, but the conductivity of the solid buoyancy material added with the glass bead powder is extremely low; under the condition of the same amount of the glass bead powder material filling material, the compression strength (35-40 MPa) of the conductive buoyancy material is not reduced compared with the compression strength (35 MPa) of the solid buoyancy material. Obviously, the conductive buoyancy material provided by the invention has the characteristics of low density and high strength while the conductivity meets the requirement of industrial conductivity.

To better illustrate the beneficial effects of the present invention, the following examples 1-6 are shown for illustration: