阅读说明：本技术 一种CuO与陶瓷粉体均匀混合的方法 (Method for uniformly mixing CuO and ceramic powder ) 是由 王艳 张婷 赵卫星 马蓉 赵微微 胡登卫 于 2019-11-27 设计创作，主要内容包括：本发明公开了一种CuO与陶瓷基粉体均匀混合的方法,该方法包括以下步骤：(1)称取陶瓷粉体,超声条件下分散于水中,再加入含Cu<Sup>2+</Sup>离子和乙酸根的物质；(2)将步骤(1)得到的反应体系在30-70℃反应7-11h,反应结束后抽滤、洗涤、干燥,得到蓝色粉末状的Cu<Sup>2+</Sup>均匀包覆陶瓷的粉体物质；(3)将步骤(2)得到的粉体物质经造粒、成型后除胶,得到CuO与陶瓷均匀混合的粉体。本发明在无碱条件下进行,易获取,操作简单,可避免引入杂质,同时CuO与陶瓷粉体更易达到混合均匀,可抑制陶瓷晶粒发生异常长大,最终提高陶瓷的电性能。(The invention discloses a method for uniformly mixing CuO and ceramic-based powder, which comprises the following steps of (1) weighing ceramic powder, dispersing in water under ultrasonic condition, and adding Cu-containing powder 2+ Ionic and acetate species; (2) reacting the reaction system obtained in the step (1) at 30-70 ℃ for 7-11h, and performing suction filtration, washing and drying after the reaction is finished to obtain blue powdered Cu 2+ Uniformly coating ceramic powder substances; (3) and (3) granulating and molding the powder substance obtained in the step (2), and removing glue to obtain powder with the CuO and the ceramic uniformly mixed. The method is carried out under the alkali-free condition, is easy to obtain, is simple to operate, can avoid introducing impurities, is easy to uniformly mix CuO and ceramic powder, can inhibit abnormal growth of ceramic grains, and finally improves the electrical property of the ceramic.)

1, kinds of CuO and ceramic powder homogeneous mixing method, characterized by, the method comprises the following steps:

(1) weighing ceramic powder, dispersing in water under ultrasonic condition, adding Cu²⁺Ion and acetate, the ceramic powder and the Cu²⁺The molar ratio of ions is (7.8-156): 1;

(2) reacting the reaction system obtained in the step (1) at 30-70 ℃ for 7-11h, and performing suction filtration, washing and drying after the reaction is finished to obtain blue powdery Cu²⁺Uniformly coating the ceramic powder;

(3) and (3) granulating and molding the powder substance obtained in the step (2), and removing glue to obtain powder with the CuO and the ceramic uniformly mixed.

2. The method for uniformly mixing the CuO and the ceramic powder according to claim 1, wherein the weight ratio of the ceramic powder to the water in the step (1) is 1: (100-200) and carrying out ultrasonic dispersion for 5-10 min.

3. The method of claim 1, wherein the CuO is uniformly mixed with the ceramic powder, and wherein the Cu is contained in the mixture²⁺The ionic and acetate species is copper acetate or a mixture of a copper salt and an acetate salt.

4. The method for uniformly mixing CuO and ceramic powder according to claim 3, wherein the copper salt is at least selected from the group consisting of copper sulfate, copper nitrate and copper chloride.

5. The method of claim 1, wherein the CuO is uniformly mixed with the ceramic powder, and wherein the Cu is contained in the mixture²⁺Cu in ionic and acetate species²⁺The molar ratio of ions to acetate is 1: (2-5).

6. The method for uniformly mixing CuO and ceramic powder according to claim 1, wherein the reaction system in the step (2) is reacted at 40-60 ℃ for 8-10 h.

7. The method for uniformly mixing the CuO and the ceramic powder according to claim 1, wherein the powder material and the PVA glue are mixed according to a mass ratio of 1: (1-6) mixing and granulating.

8. The method for uniformly mixing the CuO and the ceramic powder according to claim 7, wherein the mass concentration of the PVA glue is 30-40%.

9. The method for uniformly mixing the CuO and the ceramic powder according to claim 1, wherein the step (3) is specifically as follows: mixing Cu²⁺Uniformly coating the ceramic powder, adding PVA glue, granulating, molding, heating to 400-500 ℃, and removing glue at constant temperature for 0.5-2h to obtain composite powder in which CuO and ceramic powder are uniformly mixed.

10. The method for uniformly mixing CuO and ceramic powder of any one of claims 1 to 9 and , wherein the ceramic powder is selected from kinds of BaTiO 3-based powder and (K)_0.5Na_0.5)NbO₃Base powder, BaZn₂Ti₄O₁₁A base powder.

Technical Field

The invention belongs to the technical field of inorganic nonmetallic materials, and particularly relates to a method for uniformly mixing CuO and ceramic powder.

Background

Multilayer ceramic capacitorThe ceramic material of the container (MLCC) and the microwave medium can be made into various electronic components and parts, and is widely used in the fields of aerospace, mobile communication, war industry, electronic and electric appliances, information, petroleum exploration and the like by ₃The base ceramic has the characteristics of high dielectric constant, excellent ferroelectric, piezoelectric and insulating properties, environmental friendliness and the like, so that is widely applied to the MLCC field.

In recent years, MLCC and microwave dielectric materials are continuously developed towards miniaturization, which requires that the grain size of the ceramic dielectric material reaches submicron or even nanometer, the size of the ceramic grain has a larger relation with the sintering temperature, the powder inevitably generates grain growth in the process of sintering into ceramic, so the sintering temperature of the ceramic needs to be reduced as much as possible, CuO is used as common sintering aids, the sintering temperature of the ceramic can be reduced by promoting the generation of liquid phase, and the microstructure and the electrical property of the ceramic are improved_1/2Ti_1/2)O₃，Zn₂TiO₄，BaZn₂Ti₄O₁₁(Mater Lett,2009,63: 103-_0.5Na_0.5)NbO₃The sintering temperature of the piezoelectric and ferroelectric ceramic (Jpn JApplPhys Part 1,2004, (43): 7159-.

In order to improve the performance of functional ceramic materials, reduce sintering temperature and improve sintering quality, the preparation of powder should be aimed at high purity, uniformity and super-fineness. Therefore, how to mix the powder uniformly and prevent pollution is an important issue that must be considered and studied in the functional ceramic preparation process. However, the method adopted by introducing the sintering aid CuO into the ceramic powder at present is mainly a solid-phase ball milling method (mechanical processing method), which is difficult to achieve uniform mixing of the ceramic powder and the sintering aid CuO due to a plurality of factors influencing the mixing efficiency, including the rotating speed of a ball mill; b, the size proportion, the row shape, the hardness and the quality of grinding balls in the ball mill; c, loading capacity of the ball mill; d ratio of raw material, balls, water (dispersion medium); e, grinding aid; f a dispersing medium; and g, selecting the ball milling time (the longer the time is, the more impurities are introduced, the mixing time is usually 4-8 h, and the fine milling time is 20-24 h), inevitably introducing the impurities in the ball milling process, and polluting the finally obtained sample. Therefore, the problems of the prior art are as follows: the solid-phase ball milling method has more factors influencing the mixing efficiency, is difficult to achieve uniform mixing, can introduce impurities, consumes time and energy, and easily causes that partial ceramic grains are easy to grow abnormally, thereby influencing the electrical property of the ceramic.

Disclosure of Invention

In view of the defects of the prior art, the invention aims to provide a method for uniformly mixing CuO and ceramic powder, which has simple process, is more economical and can achieve uniform mixing more easily.

In order to achieve the technical objects of the present invention, the inventors have made extensive experimental studies and diligent efforts to finally obtain a technical solution of a method for uniformly mixing kinds of CuO with ceramic powder, the method comprising the steps of:

(1) weighing ceramic powder, dispersing in water under ultrasonic condition, adding Cu²⁺Ion and acetate, the ceramic powder and the Cu²⁺The molar ratio of ions is (7.8-156): 1;

(2) reacting the reaction system obtained in the step (1) at 30-70 ℃ for 7-11h, and performing suction filtration, washing and drying after the reaction is finished to obtain blue powdery Cu²⁺Uniformly coating the ceramic powder;

(3) and (3) granulating and molding the powder substance obtained in the step (2), and removing glue to obtain powder with the CuO and the ceramic powder uniformly mixed.

, preferably, the method for uniformly mixing the CuO and the ceramic powder comprises the steps of (1), (100) to (200) the weight ratio of the ceramic powder to water in the step (1) and ultrasonically dispersing for 5 to 10 min.

the method for mixing CuO with ceramic powder uniformly as above is further preferable, wherein the Cu-containing powder²⁺The ionic and acetate substance is copper acetate or a mixture of copper salt and acetate

the method for mixing CuO with ceramic powder uniformly is further preferable, wherein the copper salt is at least selected from copper sulfate, copper nitrate and copper chloride.

the method for mixing CuO with ceramic powder uniformly as above is further preferable, wherein the Cu-containing powder²⁺Cu in ionic and acetate species²⁺The molar ratio of ions to acetate is 1: (2-5).

the method for mixing CuO with ceramic powder uniformly is further preferable, wherein the reaction system in step (2) is reacted at 40-60 deg.C for 8-10 h.

, preferably, the method for uniformly mixing the CuO and the ceramic powder comprises the step (3) of granulating, wherein the powder substance and the PVA glue are mixed and granulated according to the mass ratio of 1 (1-6).

, preferably, the mass concentration of the PVA glue is 30-40%.

the method for mixing CuO with ceramic powder uniformly is further preferable, wherein the step (3) is to mix Cu²⁺Uniformly coating the powder material, adding PVA glue, granulating, molding, heating to 400-500 ℃, and removing glue at constant temperature for 0.5-2h to obtain powder with the CuO and the ceramic powder uniformly mixed.

the method for mixing CuO with ceramic powder uniformly is that the ceramic powder is selected from kinds of barium titanate-based powder and (K)_0.5Na_0.5)NbO₃Base powder, BaZn₂Ti₄O₁₁A base powder.

Compared with the prior art, the method for uniformly mixing the CuO and the ceramic powder has the advantages and remarkable progresses that (1) the method is carried out under the alkali-free condition, is easy to obtain, is simple to operate, can avoid introducing impurities, is time-saving and energy-saving, is an green high-efficiency synthesis process, and (2) the CuO and the ceramic powder are more easily uniformly mixed, can inhibit abnormal growth of ceramic grains, and finally improves the electrical property of the ceramic.

Drawings

FIG. 1 shows BaTiO in example 1₃XRD and SEM images of the ceramic powder.

FIG. 2 is a blue powdery Cu of example 1²⁺Uniformly coated BaTiO₃XRD and SEM images of the powder.

FIG. 3 is a schematic representation of the reaction between CuO and BaTiO of example 1₃And (3) a Cu 2p XPS diagram of the mixed ceramic powder.

FIG. 4 is a graph showing that in example 1, CuO and BaTiO are added₃SEM and EDS energy spectrum after ceramic powder is mixed.

Detailed Description

The process of the present invention is now clearly and completely described by way of the following specific examples and the accompanying drawings, which are given by way of illustration only and are not to be construed as limiting the scope of the invention. In addition, the specific technical operation steps or conditions not indicated in the examples are performed according to the technical or conditions described in the literature in the field or according to the product specification. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.