CN111847515A - Preparation method of zirconium tungstate - Google Patents
Preparation method of zirconium tungstate Download PDFInfo
- Publication number
- CN111847515A CN111847515A CN202010620769.9A CN202010620769A CN111847515A CN 111847515 A CN111847515 A CN 111847515A CN 202010620769 A CN202010620769 A CN 202010620769A CN 111847515 A CN111847515 A CN 111847515A
- Authority
- CN
- China
- Prior art keywords
- temperature
- oxide powder
- zirconium
- tungsten oxide
- stirring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of zirconium tungstate, belonging to the technical field of inorganic nonmetallic materials, and the preparation method of zirconium tungstate comprises the following steps: stirring and mixing: adding zirconium oxide powder and tungsten oxide powder into a stirring device for stirring and mixing or manually stirring and mixing; and (3) heat treatment: the method comprises the steps of adding mixed zirconium oxide powder and tungsten oxide powder into a container, putting the mixed zirconium oxide powder and tungsten oxide powder into a heat treatment furnace together with the container, dividing the heat treatment temperature into three stages, sintering the mixed zirconium oxide powder and tungsten oxide powder through a specific sintering process, introducing not less than one temperature mutation in the process of generating zirconium tungstate through reaction at a temperature range of 1105-1257 ℃, rapidly increasing the temperature to a liquid phase point, and rapidly cooling to a solid phase reaction temperature after keeping the temperature for a short time, wherein the temperature mutation aims to tamp the density of a sintered body by utilizing generated liquid phase, reduce pores generated by sintering reaction and promote diffusion among raw materials.
Description
Technical Field
The invention relates to the technical field of inorganic non-metallic materials, in particular to a preparation method of zirconium tungstate.
Background
The inorganic non-metallic material is a material composed of oxides, carbides, nitrides, halogen compounds, borides of certain elements, silicates, aluminates, phosphates, borates and the like. Is a general term for all materials except organic polymer materials and metal materials. The extraction of inorganic non-metallic materials was that after the 40 th 20 th century, it evolved from traditional silicate materials with the development of modern science and technology. The inorganic non-metallic material is one of three materials which are juxtaposed with an organic polymer material and a metal material.
Zirconium oxide (ZrO2) and tungsten oxide (WO3) can generate chemical reaction in a temperature range of 1105-1257 ℃, and the product is single zirconium tungstate (ZrW2O 8). The process for preparing zirconium tungstate by solid-phase sintering of powder zirconium oxide and powder tungsten oxide is simple, but the reaction speed and the product purity are restricted by the mixing uniformity and the diffusion speed of raw materials, so that the problems of long preparation time and high energy consumption exist. For example, a common solid phase preparation method is sintering at 1200 ℃ for 24 hours, followed by quenching; or sintering and grinding at 800 deg.C, 900 deg.C, 1000 deg.C, 1100 deg.C, etc. by so-called stepwise solid phase method, and sintering at 1200 deg.C for no more than 24 hr. The stepwise solid phase method, while reducing the sintering time at 1200 c, increases intermediate steps and overall time. Many studies have desired to increase the reaction temperature to increase the reaction rate. However, under the highest temperature of 1257 ℃ in solid phase sintering, although increasing the temperature can accelerate the reaction speed, because the inevitable mixture is unevenly distributed, zirconium oxide and tungsten oxide need to cross the reaction product and pores generated by solid phase sintering through diffusion, and certain reaction time and higher energy consumption are still needed to prepare zirconium tungstate with higher purity. There have been studies to try to prepare under the condition of containing liquid phase over 1257 ℃, but because the composition of liquid phase zirconium tungstate is complicated, eutectic reaction occurs even at 1231 ℃ to generate zirconium oxide and zirconium tungstate. The eutectic zirconia needs to react with the tungsten oxide through diffusion, and the tungsten oxide is easy to sublimate due to long high temperature time, so that the content is deviated from the stoichiometric ratio, and the purposes of accelerating the reaction speed and preparing the high-purity zirconium tungstate cannot be realized by simply increasing the temperature.
Disclosure of Invention
The invention aims to provide a preparation method of zirconium tungstate, which aims to solve the problem of how to quickly and effectively prepare high-purity zirconium tungstate by using lower cost in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of zirconium tungstate comprises the following steps:
s1: preparing materials: zirconium oxide powder and tungsten oxide powder;
s2: stirring and mixing: adding zirconium oxide powder and tungsten oxide powder into a stirring device for stirring and mixing or manually stirring and mixing;
s3: and (3) heat treatment: adding the mixed zirconium oxide powder and tungsten oxide powder into a container, putting the mixed zirconium oxide powder and tungsten oxide powder into a heat treatment furnace together with the container, wherein the heat treatment temperature is divided into three stages, and sintering the mixed zirconium oxide powder and tungsten oxide powder by a specific sintering process;
s4: quenching: taking out the container filled with the reaction powder from the thermal treatment furnace at the temperature of the third stage, and putting the container into water for quenching;
s5: grinding: and drying and grinding the quenched reaction product into powder.
Preferably, the stoichiometric ratio of the zirconium oxide powder to the tungsten oxide powder in step S1 is 1: 2-4.
Preferably, the stirring speed of the stirring device in the step S2 is 50 rpm, and the stirring time is 10-15 minutes.
Preferably, the container in step S3 is a quartz container with a cover.
Preferably, the temperature change parameters of the heat treatment furnace in step S3 are:
the temperature is raised from room temperature to 300 ℃ within 1 hour, then the temperature is raised to 1180-1230 ℃ within 3 hours, and the temperature is kept for 1-4 hours;
step two, the temperature rises to 1257-1300 ℃ within 2-5 minutes, the temperature is kept for 0-2 minutes, and then the temperature is rapidly cooled to 1180-1230 ℃ within 2-5 minutes;
and step three, keeping the temperature at 1180-1230 ℃ for 1-4 hours, and repeating the step 1-5 times according to the temperature change process from the step two to the step three after the step one, the step two and the step three.
Compared with the prior art, the invention has the beneficial effects that: in the process of generating zirconium tungstate by reaction at the temperature range of 1105-1257 ℃, at least one temperature mutation is introduced, the temperature mutation is that the temperature rapidly rises above a liquid phase point in a short time, and is rapidly cooled to a solid phase reaction temperature after heat preservation for a short time, the temperature mutation aims to utilize the density of a generated liquid phase rammed sintered body, reduce pores generated by sintering reaction, promote diffusion among raw materials, rapidly prepare high-purity zirconium tungstate, and effectively reduce preparation cost.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for preparing zirconium tungstate, which can rapidly prepare high-purity zirconium tungstate and effectively reduce the preparation cost, please refer to figure 1,
the preparation method of the zirconium tungstate comprises the following steps:
s1: preparing materials: zirconium oxide powder and tungsten oxide powder, wherein the stoichiometric ratio of the zirconium oxide powder to the tungsten oxide powder is 1: 2-4;
s2: stirring and mixing: adding zirconium oxide powder and tungsten oxide powder into a stirring device for stirring and mixing or manually stirring and mixing, wherein the stirring speed of the stirring device is 50 revolutions per minute, and the stirring time is 10-15 minutes;
s3: and (3) heat treatment: adding mixed zirconium oxide powder and tungsten oxide powder into a container and putting the mixed zirconium oxide powder and tungsten oxide powder into a heat treatment furnace together with the container, wherein the heat treatment temperature is divided into three stages, the mixed zirconium oxide powder and tungsten oxide powder are sintered by a specific sintering process, the container is a quartz container with a cover, and the temperature change parameters of the heat treatment furnace are respectively as follows: the temperature is increased to 300 ℃ from room temperature within 1 hour, then the temperature is increased to 1180-1230 ℃ within 3 hours, the temperature is kept for 1-4 hours, in the second stage, the temperature is increased to 1257-1300 ℃ within 2-5 minutes, the temperature is kept for 0-2 minutes, then the temperature is quickly cooled to 1180-1230 ℃ within 2-5 minutes, in the third stage, the temperature is kept for 1-4 hours at 1180-1230 ℃, and after the first stage, the second stage and the third stage, the temperature change process from the second stage to the third stage is repeated for 1-5 times;
S4: quenching: at the temperature of 1180-1230 ℃ in the third stage, taking out the container filled with the reaction powder from the thermal treatment furnace, and putting the container into water for quenching;
s5: grinding: and drying and grinding the quenched reaction product into powder.
Example 1
Commercially available zirconia powder 50g and commercially available tungsten oxide powder 188.2 were weighed, and the weighed powders were mechanically mixed uniformly and then poured into a quartz crucible. And placing the crucible into a heat treatment furnace to wait for high-temperature sintering reaction. The temperature change parameters of the heat treatment furnace are respectively set as follows: stage one, increasing the temperature from room temperature to 300 ℃ in 1 hour, then increasing the temperature to 1230 ℃ in 3 hours and holding for 1 hour, stage two, increasing the temperature to 1300 ℃ in 2 minutes, then not holding, rapidly cooling to 1230 ℃ in 2 minutes, stage three, holding for 1 hour at 1230 ℃. Finally, at the temperature of 1230 ℃ in the third stage, taking out the crucible filled with the reaction powder from the thermal treatment furnace, and putting the crucible into water for quenching; the reaction product is dried and ground into powder.
Example 2
Commercially available zirconia powder (50 g) and commercially available tungsten oxide powder (188.2 g) were weighed, and the weighed powders were mechanically mixed to be uniform and then poured into a quartz crucible. And placing the crucible into a heat treatment furnace to wait for high-temperature sintering reaction. The temperature change parameters of the heat treatment furnace are respectively set as follows: stage one, raising the temperature from room temperature to 300 ℃ within 1 hour, then raising the temperature to 1230 ℃ within 3 hours and keeping the temperature for 1 hour, stage two, raising the temperature to 1300 ℃ within 2 minutes, then not keeping the temperature, rapidly cooling to 1230 ℃ within 2 minutes, stage three, keeping the temperature for 1 hour at 1230 ℃; and repeating the processes of the second stage and the third stage. Finally, at the temperature of 1230 ℃ in the third stage, taking out the crucible filled with the reaction powder from the thermal treatment furnace, and putting the crucible into water for quenching; the reaction product is dried and ground into powder.
Example 3
Commercially available zirconia powder (50 g) and commercially available tungsten oxide powder (188.2 g) were weighed, and the weighed powders were mechanically mixed to be uniform and then poured into a quartz crucible. And placing the crucible into a heat treatment furnace to wait for high-temperature sintering reaction. The temperature change parameters of the heat treatment furnace are respectively set as follows: stage one, raising the temperature from room temperature to 300 ℃ within 1 hour, then raising the temperature to 1200 ℃ within 3 hours, and preserving the temperature for 3 hours, stage two, raising the temperature to 1280 ℃ within 5 minutes, then not preserving the temperature, rapidly cooling to 1200 ℃ within 2 minutes, stage three, and preserving the temperature for 3 hours at 1200 ℃; and repeating the processes of the second stage and the third stage. Finally, at the temperature of three stages of 1200 ℃, taking out the crucible filled with the reaction powder from the thermal treatment furnace, and putting the crucible into water for quenching; the reaction product is dried and ground into powder.
Example 4
Commercially available zirconia powder (50 g) and commercially available tungsten oxide powder (188.2 g) were weighed, and the weighed powders were mechanically mixed to be uniform and then poured into a quartz crucible. And placing the crucible into a heat treatment furnace to wait for high-temperature sintering reaction. The temperature change parameters of the heat treatment furnace are respectively set as follows: stage one, raising the temperature from room temperature to 300 ℃ within 1 hour, then raising the temperature to 1180 ℃ within 3 hours, preserving the temperature for 4 hours, stage two, raising the temperature to 1260 ℃ within 5 minutes, preserving the temperature for 1 minute, then rapidly cooling to 1200 ℃ within 5 minutes, and preserving the temperature for 4 hours at 1180 ℃; and repeating the processes of the second stage and the third stage. Finally, at the temperature of 1180 ℃ in the third stage, taking out the crucible filled with the reaction powder from the thermal treatment furnace, and putting the crucible into water for quenching; the reaction product is dried and ground into powder.
Example 5
Commercially available zirconia powder (50 g) and commercially available tungsten oxide powder (188.2 g) were weighed, and the weighed powders were mechanically mixed to be uniform and then poured into a quartz crucible. And placing the crucible into a heat treatment furnace to wait for high-temperature sintering reaction. The temperature change parameters of the heat treatment furnace are respectively set as follows: stage one, raising the temperature from room temperature to 300 ℃ within 1 hour, then raising the temperature to 1200 ℃ within 3 hours, and preserving the temperature for 1 hour, stage two, raising the temperature to 1280 ℃ within 2 minutes, then not preserving the temperature, rapidly cooling to 1200 ℃ within 2 minutes, stage three, and preserving the temperature for 1 hour at 1200 ℃; repeating the processes of the second stage and the third stage; and repeating the processes of the second stage and the third stage for the second time. Finally, at the temperature of three stages of 1200 ℃, taking out the crucible filled with the reaction powder from the thermal treatment furnace, and putting the crucible into water for quenching; the reaction product is dried and ground into powder.
In conclusion, in the process of generating zirconium tungstate by reaction in the temperature range of 1105-1257 ℃, at least one temperature mutation is introduced, the temperature mutation is that the temperature rapidly rises above a liquid phase point in a short time, and is rapidly cooled to a solid phase reaction temperature after heat preservation for a short time, the temperature mutation aims to utilize the density of a generated liquid phase rammed sintered body, reduce pores generated by sintering reaction, promote diffusion among raw materials, rapidly prepare high-purity zirconium tungstate, and effectively reduce preparation cost.
While the invention has been described above with reference to an embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the various features of the embodiments disclosed herein may be used in any combination, provided that there is no structural conflict, and the combinations are not exhaustively described in this specification merely for the sake of brevity and conservation of resources. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (5)
1. A preparation method of zirconium tungstate is characterized by comprising the following steps: the preparation method of the zirconium tungstate comprises the following steps:
s1: preparing materials: zirconium oxide powder and tungsten oxide powder;
s2: stirring and mixing: adding zirconium oxide powder and tungsten oxide powder into a stirring device for stirring and mixing or manually stirring and mixing;
s3: and (3) heat treatment: adding the mixed zirconium oxide powder and tungsten oxide powder into a container, putting the mixed zirconium oxide powder and tungsten oxide powder into a heat treatment furnace together with the container, wherein the heat treatment temperature is divided into three stages, and sintering the mixed zirconium oxide powder and tungsten oxide powder by a specific sintering process;
S4: quenching: taking out the container filled with the reaction powder from the thermal treatment furnace at the temperature of the third stage, and putting the container into water for quenching;
s5: grinding: and drying and grinding the quenched reaction product into powder.
2. The preparation method of zirconium tungstate as set forth in claim 1, wherein: the stoichiometric ratio of the zirconium oxide powder to the tungsten oxide powder in the step S1 is 1: 2-4.
3. The preparation method of zirconium tungstate as set forth in claim 1, wherein: the stirring speed of the stirring device in the step S2 is 50 revolutions per minute, and the stirring time is 10-15 minutes.
4. The preparation method of zirconium tungstate as set forth in claim 1, wherein: the container in the step S3 is a quartz container with a cover.
5. The preparation method of zirconium tungstate as set forth in claim 1, wherein: the temperature change parameters of the heat treatment furnace in the step S3 are respectively:
the temperature is raised from room temperature to 300 ℃ within 1 hour, then the temperature is raised to 1180-1230 ℃ within 3 hours, and the temperature is kept for 1-4 hours;
step two, the temperature rises to 1257-1300 ℃ within 2-5 minutes, the temperature is kept for 0-2 minutes, and then the temperature is rapidly cooled to 1180-1230 ℃ within 2-5 minutes;
And step three, keeping the temperature at 1180-1230 ℃ for 1-4 hours, and repeating the step 1-5 times according to the temperature change process from the step two to the step three after the step one, the step two and the step three.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010620769.9A CN111847515B (en) | 2020-06-30 | 2020-06-30 | Preparation method of zirconium tungstate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010620769.9A CN111847515B (en) | 2020-06-30 | 2020-06-30 | Preparation method of zirconium tungstate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111847515A true CN111847515A (en) | 2020-10-30 |
| CN111847515B CN111847515B (en) | 2022-06-03 |
Family
ID=72988930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010620769.9A Active CN111847515B (en) | 2020-06-30 | 2020-06-30 | Preparation method of zirconium tungstate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111847515B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406905A (en) * | 2001-08-24 | 2003-04-02 | 钜频光电股份有限公司 | Preparation of zirconium tungstate ceramic body products thereby and optical fiber grating temperature compensator |
| US20050101133A1 (en) * | 2003-11-10 | 2005-05-12 | Tzeng Der L. | Method for making negative thermal expansion material zirconium tungstate |
| CN1923705A (en) * | 2006-09-08 | 2007-03-07 | 郑州大学 | Synthesis method of zirconium tungstate with minus thermal-expansion coefficient |
| CN105110377A (en) * | 2015-08-05 | 2015-12-02 | 哈尔滨工业大学 | Method for using solid phase reaction sintering method to prepare negative thermal expansion material of zirconium tungstate |
| CN109437898A (en) * | 2018-12-17 | 2019-03-08 | 安徽升鸿电子有限公司 | A kind of preparation process of negative thermal expansion material tungsten wire array |
-
2020
- 2020-06-30 CN CN202010620769.9A patent/CN111847515B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1406905A (en) * | 2001-08-24 | 2003-04-02 | 钜频光电股份有限公司 | Preparation of zirconium tungstate ceramic body products thereby and optical fiber grating temperature compensator |
| US20050101133A1 (en) * | 2003-11-10 | 2005-05-12 | Tzeng Der L. | Method for making negative thermal expansion material zirconium tungstate |
| CN1923705A (en) * | 2006-09-08 | 2007-03-07 | 郑州大学 | Synthesis method of zirconium tungstate with minus thermal-expansion coefficient |
| CN105110377A (en) * | 2015-08-05 | 2015-12-02 | 哈尔滨工业大学 | Method for using solid phase reaction sintering method to prepare negative thermal expansion material of zirconium tungstate |
| CN109437898A (en) * | 2018-12-17 | 2019-03-08 | 安徽升鸿电子有限公司 | A kind of preparation process of negative thermal expansion material tungsten wire array |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111847515B (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108383530B (en) | ZrB2Preparation process of-SiC ceramic composite powder by precursor conversion method | |
| CN109796209B (en) | (Ti, Zr, Hf, Ta, Nb) B2High-entropy ceramic powder and preparation method thereof | |
| CN106297904B (en) | UO2The preparation method of SiC fuel pellets and using UO made of the preparation method2SiC fuel pellets | |
| CN105198478A (en) | Mullite-whisker-reinforced anorthite porous ceramic and preparation method thereof | |
| CN110156468A (en) | A kind of ZrC-ZrB2The presoma conversion method preparation process of SiC ceramic composite granule | |
| CN111499387A (en) | High-strength silicon nitride composite silicon carbide ceramic and preparation method and application thereof | |
| CN104810072B (en) | A kind of preparation method of sulfur-bearing high activity liquid waste glass ceramics curing substrate | |
| CN101429031B (en) | Macromolecule network preparation method for high-purity ultra-fine aluminum nitride ceramic | |
| CN101956088B (en) | Method for preparing molybdenum doped alloy | |
| CN111847515B (en) | Preparation method of zirconium tungstate | |
| CN102249235A (en) | Method for preparing high-temperature resistant silicon carbide | |
| CN102060544B (en) | Quick crystallization method for realizing amorphous silicon nitride powder by taking silica powder as additive | |
| CN109081705A (en) | The method that v-ti magnetite tailing prepares seepage brick | |
| CN113788480A (en) | Preparation method of high-purity silicon carbide and corresponding high-purity silicon carbide | |
| CN108585040B (en) | CeVO4Quick preparation method of functional material | |
| CN209741305U (en) | mould for growing rare earth ion doped crystal by heterogeneous high-melting point arc seed crystal | |
| CN105858673A (en) | Method for synthesizing Yb2Si2O7 powder by adopting two-step process | |
| CN110255512A (en) | A kind of preparation method of cubic boron nitride | |
| CN108911794B (en) | Improve Ti3B2Method for processing purity of N material | |
| CN105948783B (en) | A kind of Si2N2O-Si3N4The preparation method of-TiN porous ceramics | |
| CN108862301B (en) | High purity Ti3B2Preparation method of N material | |
| CN108147821A (en) | A kind of high-purity nitride porous aluminium crystallite material source preparation method | |
| LU503139B1 (en) | Method for preparing single-crystal spessartine under high-temperature and high-pressure condition | |
| CN117225445A (en) | Preparation method and application of reinforced zirconia graphite phase carbon nitride composite photocatalyst | |
| LU503141B1 (en) | Method for preparing high-nickel, high-zinc and high-water single-crystal diopside under high-temperature and high-pressure condition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |