阅读说明：本技术 一种磷酸锆钡陶瓷的制备方法 (Preparation method of barium zirconium phosphate ceramic ) 是由 刘瑞祥 王开宇 张磊 隋学叶 周长灵 程之强 王重海 于 2019-12-20 设计创作，主要内容包括：本发明公开了一种磷酸锆钡陶瓷的制备方法,包括以下步骤：步骤(1)将BaCO<Sub>3</Sub>粉末、ZrO<Sub>2</Sub>粉末、NH<Sub>4</Sub>H<Sub>2</Sub>PO<Sub>4</Sub>粉末混合,然后经低温热处理得到粉料A；步骤(2)将所述粉料A再次进行研磨制得粉料B,所述粉料B经高温热处理后压制成坯体；步骤(3)将所述坯体进行高温热处理,即可得到磷酸锆钡陶瓷。选取锆、钡单元组成设计并制备连续的二元固溶体,可以实现平均热膨胀系数的连续可调,并获得平均线膨胀系数接近零的零膨胀陶瓷,得到的磷酸锆钡材料体系具有耐1400℃高温的特点,而且通过用连续干压成型的方式进行材料制备,制备周期短,适合大规模生产。(The invention discloses a preparation method of barium zirconium phosphate ceramic, which comprises the following steps: step (1) BaCO is added 3 Powder, ZrO 2 Powder, NH 4 H 2 PO 4 Mixing the powder, and then carrying out low-temperature heat treatment to obtain powder A; grinding the powder A again to obtain powder B, and pressing the powder B into a blank after high-temperature heat treatment; and (3) carrying out high-temperature heat treatment on the blank to obtain the barium zirconium phosphate ceramic. The zirconium and barium units are selected to form a design and prepare a continuous binary solid solution, so that the continuous adjustment of the average thermal expansion coefficient can be realized, zero-expansion ceramics with the average linear expansion coefficient close to zero are obtained, the obtained barium zirconium phosphate material system has the characteristic of high temperature resistance of 1400 ℃, the material preparation is carried out by using a continuous dry pressing forming mode, the preparation period is short, and the method is suitable for large-scale productionAnd (5) producing a mould.)

1. The preparation method of the barium zirconium phosphate ceramic is characterized by comprising the following steps of:

step (1) BaCO is added₃Powder, ZrO₂Powder, NH₄H₂PO₄Mixing the powder, and then carrying out low-temperature heat treatment to obtain powder A;

grinding the powder A again to obtain powder B, and pressing the powder B into a blank after high-temperature heat treatment;

and (3) carrying out high-temperature heat treatment on the blank to obtain the barium zirconium phosphate ceramic.

2. The method for preparing barium zirconium phosphate ceramic according to claim 1, wherein BaCO is added₃Powder, ZrO₂Powder, NH₄H₂PO₄Powder mixing, comprising:

taking BaCO₃、ZrO₂、NH₄H₂PO₄The solids are respectively ground into powder orGetting BaCO sold in market₃Powder, ZrO₂Powder, NH₄H₂PO₄And mixing the powder, and putting the mixed powder into a ball milling tank for ball milling for 5-8 h.

3. The method for preparing barium zirconium phosphate ceramic according to claim 1, wherein the grinding is performed by ball milling.

4. The method for preparing barium zirconium phosphate ceramic according to claim 1, wherein BaCO in step (1)₃Powder, ZrO₂Powder, NH₄H₂PO₄The powder is BaCO according to the mol ratio₃Powder: ZrO (ZrO)₂Powder: NH (NH)₄H₂PO₄Powder 1: 3-5: 5-7.

5. The preparation method of barium zirconium phosphate ceramic according to claim 1, wherein the low-temperature heat treatment temperature in step (1) is 300-400 ℃, and the temperature is kept for 5-6 h.

6. The method for preparing barium zirconium phosphate ceramic according to claim 1, wherein the grinding time in step (2) is 8-10 h.

7. The method for preparing barium zirconium phosphate ceramic according to claim 1, wherein the powder material B is pressed into a green body after being subjected to high temperature heat treatment, and the method comprises the following steps:

and (3) carrying out high-temperature heat treatment on the powder B at 900-1000 ℃, keeping the temperature for 6-8 h, and carrying out dry pressing to obtain a blank.

8. The method for preparing barium zirconium phosphate ceramic according to claim 7, wherein the dry pressing pressure is 20 to 30MPa, and the pressure is maintained for 10 to 15 min.

9. The preparation method of barium zirconium phosphate ceramic according to claim 1, wherein the high temperature heat treatment temperature in step (3) is 1200-1400 ℃, and the holding time is 1-2 h.

10. The method for preparing a barium zirconium phosphate ceramic according to claim 1, wherein the low-temperature heat treatment and the high-temperature heat treatment are both performed in a muffle furnace.

Technical Field

The invention relates to the technical field of special ceramic materials, in particular to a preparation method of barium zirconium phosphate ceramic.

Background

The matrix of the NZP family phosphate ceramic is NaZr2(PO4)3 (abbreviated as NZP), and the BaZr4(PO4)6 low-thermal expansion ceramic is one of the NZP ceramics. The NZP family ceramic has the designability of thermal expansion coefficient, namely, the average thermal expansion coefficient can be continuously changed from a negative value to a positive value through the adjustment of the composition, thereby obtaining the zero-expansion ceramic with good thermal shock resistance. Based on the excellent characteristics of the NZP materials, the us and japan, etc., have successively conducted basic research on the application of the NZP family materials in various fields, and the us, one of the earliest countries to date, has achieved the commercial production of the NZP family low thermal expansion ceramics.

The research on the NZP ceramic in China starts late, currently, the research is still in the aspect of basic research, the powder preparation is mostly focused, and the research on the preparation of the NZP ceramic is less. The preparation technology of the NZP ceramic is explored, and the NZP ceramic with the adjustable thermal expansion coefficient is prepared, so that the method has important significance for national defense safety and technology promotion in multiple fields.

Disclosure of Invention

In order to solve the above technical problems, an object of the present invention is to provide a method for preparing barium zirconium phosphate ceramic, the method has the characteristics of low cost and suitability for mass production, and the obtained material has a low thermal expansion characteristic, i.e., the low expansion range is 3 to 10 × 10^-6/℃。

According to one aspect of the present invention, there is provided a method for preparing a barium zirconium phosphate ceramic, comprising the steps of:

step (1) BaCO is added₃Powder, ZrO₂Powder, NH₄H₂PO₄Mixing the powder, and then carrying out low-temperature heat treatment to obtain powder A;

grinding the powder A again to obtain powder B, and pressing the powder B into a blank after high-temperature heat treatment;

and (3) carrying out high-temperature heat treatment on the blank to obtain the barium zirconium phosphate ceramic.

Further, BaCO is added₃Powder, ZrO₂Powder, NH₄H₂PO₄Powder mixing, comprising:

taking BaCO₃、ZrO₂、NH₄H₂PO₄Grinding the solid into powder or collecting BaCO sold in market₃Powder, ZrO₂Powder, NH₄H₂PO₄And mixing the powder, and putting the mixed powder into a ball milling tank for ball milling for 5-8 h.

Further, the grinding mode is ball milling.

Further, BaCO in the step (1)₃Powder, ZrO₂Powder, NH₄H₂PO₄The powder is BaCO according to the mol ratio₃Powder: ZrO (ZrO)₂Powder: NH (NH)₄H₂PO₄Powder 1: 4: 6, and mixing.

Further, the temperature of the low-temperature heat treatment in the step (1) is 300-400 ℃, and the heat is preserved for 5-6 h.

Further, the grinding time in the step (2) is 8-10 h.

Further, the powder B is pressed into a blank after high-temperature heat treatment, and the method comprises the following steps: and (3) carrying out high-temperature heat treatment on the powder B at 900-1000 ℃, keeping the temperature for 6-8 h, and carrying out dry pressing to obtain a blank.

Further, the dry pressing pressure is 20-30 MPa, and the pressure is maintained for 10-15 min.

Further, the high-temperature heat treatment temperature in the step (3) is 1200-1400 ℃, and the heat preservation time is 1-2 hours.

Further, the low-temperature heat treatment and the high-temperature heat treatment are both carried out in a muffle furnace.

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

1. the continuous binary solid solution is designed and prepared by selecting the zirconium and barium units, so that the continuous adjustment of the average thermal expansion coefficient can be realized, the zero-expansion ceramic with the average linear expansion coefficient close to zero is obtained, the obtained barium zirconium phosphate material system has the characteristic of 1400 ℃ high temperature resistance, the material preparation is carried out by using a continuous dry pressing forming mode, the preparation period is short, and the method is suitable for large-scale production;

2. the obtained barium zirconium phosphate material is an NZP group compound, the crystal axis thermal expansion coefficient of the NZP group compound is not only shown to be anisotropic, but also has opposite thermal expansion anisotropy, and based on the characteristic, the NZP ceramic material with the continuously adjustable thermal expansion coefficient can be used within the temperature range of 1000-1400 ℃, and has excellent thermal shock resistance.

Drawings

FIG. 1 is a schematic view of the microstructure of barium zirconium phosphate ceramic.

Detailed Description

In order to better understand the technical scheme of the invention, the invention is further explained by combining the drawings and the specific embodiments in the specification.