阅读说明：本技术 一种复合陶瓷填料的制备方法 (Preparation method of composite ceramic filler ) 是由 葛凯 刘庆辉 钟光维 于 2019-12-02 设计创作，主要内容包括：本发明属于陶瓷填料技术领域,具体涉及一种复合陶瓷填料的制备方法。本发明复合陶瓷填料的制备方法,包括以下步骤：S1)将已处理的陶瓷填料投入混合设备中搅拌3～7min,然后将偶联剂以喷雾的形式注入混合设备中,再搅拌10～15min后,升温至150℃,搅拌10～15min,得到共混物A；S2)将步骤S1中的共混物A、含氟树脂乳液和水进行混合搅拌10～30min,得到共混物B；S3)将步骤S2中的共混物B倒入托盘于80～120℃下烘烤5～60min,升温至250～300℃烘烤5～60min,得到粉末；S4)将步骤S3中的粉末过110目振动筛,在380℃下烧结5～10min后,得到复合陶瓷填料。本发明制备得到的复合陶瓷填料具有三层结构,大大改善了与聚四氟乙烯相混性,具有较好的界面结合性。(The invention belongs to the technical field of ceramic fillers, and particularly relates to a preparation method of a composite ceramic filler. The preparation method of the composite ceramic filler comprises the following steps: s1) putting the treated ceramic filler into mixing equipment, stirring for 3-7 min, then injecting the coupling agent into the mixing equipment in a spraying mode, stirring for 10-15 min, heating to 150 ℃, and stirring for 10-15 min to obtain a blend A; s2) mixing and stirring the blend A, the fluorine-containing resin emulsion and the water in the step S1 for 10-30 min to obtain a blend B; s3) pouring the blend B obtained in the step S2 into a tray, baking for 5-60 min at 80-120 ℃, heating to 250-300 ℃, and baking for 5-60 min to obtain powder; s4) sieving the powder obtained in the step S3 by a 110-mesh vibrating screen, and sintering at 380 ℃ for 5-10 min to obtain the composite ceramic filler. The composite ceramic filler prepared by the invention has a three-layer structure, greatly improves the miscibility with polytetrafluoroethylene, and has better interface binding property.)

1. The preparation method of the composite ceramic filler is characterized by comprising the following steps of:

s1) putting the treated ceramic filler into mixing equipment, stirring for 3-7 min, then injecting the coupling agent into the mixing equipment in a spraying mode, stirring for 10-15 min, heating to 150 ℃, and stirring for 10-15 min to obtain a blend A;

s2) mixing and stirring the blend A, the fluorine-containing resin emulsion and the water in the step S1 for 10-30 min to obtain a blend B;

s3) pouring the blend B obtained in the step S2 into a tray, baking for 5-60 min at 80-120 ℃, heating to 250-300 ℃, and baking for 5-60 min to obtain powder;

s4) sieving the powder obtained in the step S3 by a 110-mesh vibrating screen, and sintering at 380 ℃ for 5-10 min to obtain the composite ceramic filler.

2. The method for preparing the composite ceramic filler according to claim 1, wherein the mass ratio of the ceramic filler treated in the step S1 to the coupling agent is 1000: (5-15).

3. The method for preparing the composite ceramic filler according to claim 1 or 2, wherein the treated ceramic filler is treated by: taking the ceramic filler, the seaweed glycolipid fatty acid monoester and the ethanol for ultrasonic dispersion for 2-5 hours, and then drying for 8-10 hours under vacuum.

4. The preparation method of the composite ceramic filler according to claim 3, wherein the mass ratio of the ceramic filler to the seaweed glycolipid fatty acid monoester to the ethanol is 1 (0.025-0.05): 25.

5. the method for preparing the composite ceramic filler according to claim 4, wherein the ceramic filler comprises at least one of silica, titanium dioxide, barium titanate, glass fiber yarn, graphite, aluminum oxide and silicon micropowder.

6. The method for preparing the composite ceramic filler according to claim 1 or 2, wherein the coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent, and a zirconate coupling agent.

7. The preparation method of the composite ceramic filler according to claim 1, wherein the mass ratio of the blend A, the fluorine-containing resin emulsion and the water in the step S2 is (75-55): (5-25): (20-40).

8. The method of claim 1 or 7, wherein the fluorine-containing resin emulsion comprises at least one of polytetrafluoroethylene emulsion, polyperfluoroethylpropylene emulsion, and polyperfluoroalkylether emulsion.

9. A sheet material made of composite ceramic filler, which is characterized in that the composite ceramic filler according to any one of claims 1 to 8 and polytetrafluoroethylene are mixed according to the mass ratio of 1: 1, preparing the composition.

10. A method of making a sheet, comprising the steps of: mixing the composite ceramic filler and polytetrafluoroethylene, molding into a sheet with the thickness of 1.0mm, and sintering at 100 ℃ for 30min, 300 ℃ for 30min and 380 ℃ for 120min to obtain the sheet made of the composite ceramic filler.

Technical Field

The invention belongs to the technical field of ceramic fillers, and particularly relates to a preparation method of a composite ceramic filler.

Background

The fluororesin is a thermoplastic resin containing fluorine atoms in a molecular structure, has extremely low surface activity, is difficult to blend with other materials, and greatly limits the application of the fluororesin.

At present, the comprehensive performance of the fluororesin is improved by blending inorganic particles and the fluororesin, so that the strength, the hardness, the wear resistance, the thermal conductivity and the like of the fluororesin are improved. Therefore, how to disperse the inorganic particles in the fluororesin organic phase with high uniformity is the key to blending. The prior art includes a dry dispersion method and a wet dispersion method, wherein the dry dispersion method mainly comprises mechanical high-speed stirring, and the wet dispersion method mainly comprises adding inorganic particles into PTFE concentrated dispersion liquid and carrying out mechanical stirring or ultrasonic treatment. The above two methods are used for blending inorganic particles with a fluororesin, but these blends have poor bonding interfaces because the proportion of the inorganic particles in the blend is generally less than 30%, and when the amount of the inorganic particles is continuously increased, there is a defect that the inorganic particles are difficult to be uniformly dispersed or the porosity in the article is increased, which in turn decreases the properties of the blend.

Chinese patent CN106671517A discloses a fluorine-containing resin and compound ceramic filler composition and a high-frequency copper-clad plate manufactured by the same, and specifically discloses a composition comprising: mixing fluorine-containing resin; secondly, premixing a plurality of ceramic fillers with different proportions, particle sizes and morphologies by using a solvent; (III) mixing the fluorine-containing resin with the ceramic filler; fourthly, the glass cloth dipped with the composition of the fluorine-containing resin and the ceramic filler is dried, baked and sintered to prepare dipped cloth; preparing copper foil coated and sintered by fluororesin and compound ceramic filler; and (VI) laminating the high-frequency copper clad laminate. However, the mixing of the fluorine-containing resin and the ceramic filler in the patent is still similar to that of a wet dispersion method, the addition amount of the ceramic filler is limited, and the interface bonding of the blend cannot be improved well.

Disclosure of Invention

The invention aims to provide a preparation method of a composite ceramic filler, the composite ceramic filler prepared by the invention has a three-layer structure, the miscibility with polytetrafluoroethylene is greatly improved, and the composite ceramic filler has better interface bonding property; the sheet obtained by blending the composite ceramic filler and the polytetrafluoroethylene has the advantages of uniform size, low water absorption, high bending strength and good stability.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a composite ceramic filler comprises the following steps:

s1) putting the treated ceramic filler into mixing equipment, stirring for 3-7 min, then injecting the coupling agent into the mixing equipment in a spraying mode, stirring for 10-15 min, heating to 150 ℃, and stirring for 10-15 min to obtain a blend A;

s2) mixing and stirring the blend A, the fluorine-containing resin emulsion and the water in the step S1 for 10-30 min to obtain a blend B;

s3) pouring the blend B obtained in the step S2 into a tray, baking for 5-60 min at 80-120 ℃, heating to 250-300 ℃, and baking for 5-60 min to obtain powder;

s4) sieving the powder obtained in the step S3 by a 110-mesh vibrating screen, and sintering at 380 ℃ for 5-10 min to obtain the composite ceramic filler.

In the invention, the treated ceramic filler is coated with the coupling agent, the coupling agent can be promoted to be completely coated on the surface of the ceramic filler by controlling the temperature to be 150 ℃, when the temperature is lower than 150 ℃, the condensation dehydration reaction of the coupling agent is slow, and when the temperature is higher than 150 ℃, the coupling agent can be evaporated or undergoes a self-condensation reaction. The blend a obtained by coating the ceramic filler with the coupling agent was coated with a fluorine-containing resin emulsion, thereby obtaining a composite ceramic filler having a three-layer structure (ceramic filler + coupling agent layer + fluorine resin layer).

Further, the mass ratio of the ceramic filler treated in the step S1 to the coupling agent is 1000: (5-15).

Further, the treatment method of the treated ceramic filler comprises the following steps: taking the ceramic filler, the seaweed glycolipid fatty acid monoester and the ethanol for ultrasonic dispersion for 2-5 hours, and then drying for 8-10 hours under vacuum. The volume percentage of the ethanol is 25-50%, including 25%, 30%, 35%, 40%, 45% and 50%.

In the invention, the specific mechanism of the method is still analyzed, namely the dispersibility of the ceramic filler is possibly improved, the ceramic filler is more coated by the coupling agent, the ceramic filler is possibly activated, the ceramic filler is more coated by the coupling agent, and the dispersibility and uniformity of the coated composite ceramic filler and polytetrafluoroethylene are possibly improved.

Further, the mass ratio of the ceramic filler to the seaweed glycolipid fatty acid monoester to the ethanol is 1 (0.025-0.05): 25.

further, the ceramic filler comprises at least one of silicon dioxide, titanium dioxide, barium titanate, glass fiber yarn, graphite, aluminum oxide and silicon micropowder.

Further, the coupling agent comprises at least one of silane coupling agent, titanate coupling agent and zirconate coupling agent, and comprises tridecafluorooctane, namely triethoxysilane (F8261), phenyltrimethoxysilane (Z6124) and 3-aminopropyltriethoxysilane (KH 550).

Further, in the step S2, the mass ratio of the blend a, the fluorine-containing resin emulsion, and the water is (75 to 55): (5-25): (20-40).

Further, the fluorine-containing resin emulsion comprises at least one of polytetrafluoroethylene emulsion, polyperfluoroethylene propylene emulsion and polyperfluoroalkyl ether emulsion.

The invention provides a sheet material made of composite ceramic filler, which is prepared from any one of the composite ceramic filler and polytetrafluoroethylene according to the mass ratio of 1: 1, preparing the composition.

The invention also provides a preparation method of the sheet, which comprises the following steps: mixing the composite ceramic filler and polytetrafluoroethylene, molding into a sheet with the thickness of 1.0mm, and sintering at 100 ℃ for 30min, 300 ℃ for 30min and 380 ℃ for 120min to obtain the sheet made of the composite ceramic filler.

In the invention, the composite ceramic filler and the polytetrafluoroethylene are mixed by sectional treatment, so that the phenomenon that the performance of the sheet is changed sharply due to overlarge temperature difference is prevented.

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

(1) the preparation method of the invention carries out surface coating treatment on the fluororesin, so that the surface of the ceramic filler is coated with a complete fluororesin layer, and the composite ceramic filler with a three-layer structure is obtained, thereby greatly improving the blending performance of the composite ceramic filler and the polytetrafluoroethylene, ensuring that the interface bonding of the composite ceramic filler and the polytetrafluoroethylene is good, and increasing the filling amount of the composite ceramic filler.

(2) The sheet obtained by blending the composite ceramic filler and the polytetrafluoroethylene has uniform size, lower water absorption and higher bending strength, and the comprehensive performance of the sheet is integrally improved.

(3) The sheet material obtained by blending the composite ceramic filler and the polytetrafluoroethylene has better dimensional stability and thermal stability.

Drawings

FIG. 1 is a schematic structural view of the composite ceramic packing of the present invention.

Wherein, 1-ceramic filler, 2-coupling agent layer and 3-fluorine resin layer.

Detailed Description

The present invention will be described in further detail with reference to the following examples. It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.