CN107903052A - A kind of crystal whisker of hexa potassium titanate porous ceramics and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of crystal whisker of hexa potassium titanate porous ceramics and preparation method thereof.Its technical solution is：By titaniferous waste material in 1000 ~ 1300 DEG C of heat treatments, grinding, obtains grinding material A.The thermosetting resin of the grinding material A of 50 ~ 70wt%, the titanium dioxide of 10 ~ 20wt% and 10 ~ 30wt% are mixed, shaping, is heat-treated, grinding, obtains grinding material B in 1200 ~ 1400 DEG C and neutral atmosphere.The potassium acetate of the grinding material B of 40 ~ 60wt%, the Anhydrous potassium carbonate of 10 ~ 30wt% and 10 ~ 30wt% are mixed, grinding, obtains abrasive.The thermosetting resin of the grinding material B of 10 ~ 20wt%, the abrasive of 30 ~ 50wt%, the limestone particle of 10 ~ 30wt%, the Anhydrous potassium carbonate of 1 ~ 10wt%, the natrium carbonicum calcinatum of 1 ~ 10wt% and 1 ~ 10wt% are mixed, shaping；Successively through 600 ~ 800 DEG C and 900 ~ 1100 DEG C heat treatments 1 ~ 3 it is small when, obtained crystal whisker of hexa potassium titanate porous ceramics.Whisker size is uniform in the made product of the present invention, and the compressive resistance of product is big and porosity is high.

Description

A kind of potassium hexatitanate whisker porous ceramic and preparation method thereof

technical field

The invention belongs to the technical field of porous ceramics. In particular, it relates to a potassium hexatitanate whisker porous ceramic and a preparation method thereof.

Background technique

The unique interlocking tunnel structure of potassium hexatitanate whiskers makes it have excellent characteristics such as high strength, high temperature resistance, chemical stability, insulation and high infrared reflectivity, so it is used in heat insulation materials, reinforcing materials, friction materials, filtration Materials and other fields have been widely used. At present, the preparation methods of potassium hexatitanate whiskers mainly include flux method, melting-quenching method, combustion method, hydrothermal method and sintering method, etc., although they have their own advantages, there are some shortcomings, such as: flux Although the aspect ratio of the whiskers prepared by the method is large and the size is controllable, the impurities introduced by the flux are easy to be included in the product, which is difficult to remove and affects the performance of the whiskers; the melting-quenching method needs to melt the raw materials at high temperature , After quenching, the subsequent materials are calcined at high temperature for many times, the whiskers produced are easy to agglomerate and form blocks during the crystallization process, which consumes a lot of energy and the production cost is too high; the hydrothermal method requires high temperature and high pressure, and the conditions are harsh ; The sintering method has problems such as difficult control of whisker size and difficulty in whisker separation.

Porous potassium hexatitanate whisker ceramics is a material prepared from potassium hexatitanate whisker as the main raw material. Although it has well-known advantages, it also has some shortcomings: (1) There are many additives, binders or fillers introduced in the preparation process. It is an organic substance, which will be decomposed and oxidized during product preparation or high-temperature use to produce toxic or polluting gas emissions, which will affect the environment; It is easy to have side reactions with whiskers and produce impurity phases, which affect the performance of materials; (3) whiskers are difficult to disperse evenly in the system during the process of mixing, molding and firing with other raw materials, and are easy to agglomerate, and in the process of mixing or stirring Among them, the whiskers are easily broken by mechanical devices, which affects the performance of the material; (4) In the process of product preparation, the size and distribution of the whiskers formed in situ are difficult to effectively control, and thus the performance of porous ceramic materials cannot be optimized.

In recent years, with the rapid development of chemical and biological industries, titanium and its compounds have become more and more widely used, and more and more titanium-containing wastes are produced in the process of product production and use. How to efficiently use titanium-containing wastes, Become a very important and urgent research work. At present, there are many recycling methods for titanium-containing waste, such as recycling titanium through co-melting, chemical leaching, crystallization and calcination. Although considerable development has been achieved, most of the existing technologies are complex and require After titanium, secondary waste will still be generated.

Contents of the invention

The present invention aims to overcome the deficiencies in the prior art, and the purpose is to provide a method for preparing potassium hexatitanate whisker porous ceramics with low production cost, simple process and no secondary waste. The potassium hexatitanate prepared by this method The whisker porous ceramic has uniform whisker size, and the potassium hexatitanate whisker porous ceramic has high compressive strength and high porosity.

For achieving the above object, the steps of the technical solution adopted in the present invention are:

In the first step, the titanium-containing waste is heat-treated at 1000-1300°C for 2-4 hours, and ground to a particle size of less than 0.045mm to obtain grinding material A.

The second step is to mix 50~70wt% of the said grinding material A, 10~20wt% titanium dioxide and 10~30wt% thermosetting resin evenly, press molding under the condition of 50~100MPa; Heat treatment in a neutral atmosphere for 1 to 3 hours, crush and grind until the particle size is less than 0.088mm, and obtain powder and abrasive material B.

In the third step, 40-60wt% of said grinding material B, 10-30wt% of anhydrous potassium carbonate and 10-30wt% of potassium acetate were uniformly mixed, and ground for 0.5-1 hour to obtain grinding material.

The 3rd step, the described grinding material B of 10～20wt%, the grinding material of 30～50wt%, the limestone particle of 10～30wt%, the anhydrous potassium carbonate of 1～10wt%, the anhydrous carbonic acid of 1～10wt% Sodium and 1-10wt% thermosetting resin are mixed evenly, and pressed under the condition of 50-100MPa; then heat-treated at 600-800°C for 1-3 hours, and then heat-treated at 900-1100°C for 1-3 hours, and the Porous potassium hexatitanate whisker ceramics were obtained.

The titanium-containing waste material: the Ti content is greater than 52wt%, and the sum of the Al, Ni, V, Co, Cr, Ca, and Si contents is less than 0.9wt%; the particle size of the titanium-containing waste material is less than 0.088mm.

The particle size of the titanium dioxide is less than 0.088mm, and the _TiO2 content in the titanium dioxide is greater than 99wt%.

The neutral atmosphere is a nitrogen atmosphere or an argon atmosphere.

The particle size of the anhydrous potassium carbonate is less than 0.088mm, and the content of K ₂ CO ₃ in the anhydrous potassium carbonate is greater than 99wt%.

The particle size of the potassium acetate is less than 0.088mm, and the purity of the potassium acetate is greater than 99wt%.

The particle size of the limestone particles is 0.088-0.25mm, and the CaO content in the limestone particles is greater than 54wt%.

The particle size of the anhydrous sodium carbonate is less than 0.088mm, and the content of Na ₂ CO ₃ in the anhydrous sodium carbonate is greater than 99wt%.

Owing to adopting above-mentioned technical scheme, the present invention has following positive effect compared with prior art:

(1) On the basis of the research on the composition, structure and temperature evolution of titanium-containing waste, the present invention controls the product preparation process step by step: adjusting the properties of raw materials, forming the mesophase and forming the microstructure of the material. By strictly limiting the technical parameters of the preparation process, such as the particle size of raw materials, the particle size of intermediate products, treatment temperature, treatment time and atmosphere, the necessary conditions are provided for the formation and uniform distribution of potassium hexatitanate whiskers in the structure, so that the prepared The whisker size in the potassium hexatitanate whisker porous ceramic is uniform, and the manufactured product has high compressive strength and high porosity.

(2) The present invention uses titanium-containing waste as the main raw material, and then mixes common industrial raw materials such as titanium dioxide, thermosetting resin, anhydrous potassium carbonate, anhydrous sodium carbonate, and limestone, and controls the preparation process step by step, which not only reduces the high-temperature treatment. The energy consumption and material loss of the product are precisely adjusted, and the different stages corresponding to the formation of the porous ceramic microstructure are precisely adjusted to achieve a balanced control of product performance, energy consumption in the preparation process, and material cost. Therefore, not only the raw materials used have a wide range of sources, but also the production process is simple, the production cost is low and no secondary waste is produced.

The potassium hexatitanate whisker porous ceramic prepared by the present invention is tested: the diameter of the potassium hexatitanate whisker is 0.5-2 μm, the length of the potassium hexatitanate whisker is 3-20 μm; the potassium hexatitanate whisker porous ceramic The compressive strength at room temperature is greater than 7MPa, and the porosity is greater than 40%.

Therefore, the present invention has the characteristics of low production cost, simple process and no secondary waste, the prepared potassium hexatitanate whisker porous ceramic has uniform whisker size, and the potassium hexatitanate whisker porous ceramic has high compressive strength and High porosity.

Detailed ways

The present invention will be further described below in combination with specific embodiments, which are not intended to limit the protection scope thereof.

In order to avoid duplication, first the raw materials of this specific embodiment are described as follows, and will not be repeated in each embodiment:

The titanium-containing waste material: the Ti content is greater than 52wt%, and the sum of the Al, Ni, V, Co, Cr, Ca, and Si contents is less than 0.9wt%; the particle size of the titanium-containing waste material is less than 0.088mm.

The particle size of the titanium dioxide is less than 0.088mm, and the _TiO2 content in the titanium dioxide is greater than 99wt%.

The particle size of the anhydrous potassium carbonate is less than 0.088mm, and the content of K ₂ CO ₃ in the anhydrous potassium carbonate is greater than 99wt%.

The particle size of the potassium acetate is less than 0.088mm, and the purity of the potassium acetate is greater than 99wt%.

The particle size of the limestone particles is 0.088-0.25mm, and the CaO content in the limestone particles is greater than 54wt%.

The particle size of the anhydrous sodium carbonate is less than 0.088mm, and the content of Na ₂ CO ₃ in the anhydrous sodium carbonate is greater than 99wt%.

Example 1

A potassium hexatitanate whisker porous ceramic and a preparation method thereof. The steps of the preparation method described in this embodiment are:

In the first step, the titanium-containing waste is heat-treated at 1000-1300°C for 2-4 hours, and ground to a particle size of less than 0.045mm to obtain grinding material A.

The second step is to mix 50~60wt% of said grinding material A, 10~20wt% of titanium dioxide and 20~30wt% of thermosetting resin evenly, press molding under the condition of 50~100MPa; Heat treatment in a neutral atmosphere for 1 to 3 hours, crush and grind until the particle size is less than 0.088mm, and obtain powder and abrasive material B.

In the third step, 40-50wt% of said grinding material B, 20-30wt% of anhydrous potassium carbonate and 20-30wt% of potassium acetate were uniformly mixed, and ground for 0.5-1 hour to obtain grinding material.

The 3rd step, the described grinding material B of 10～20wt%, the abrasive material of 40～50wt%, the limestone particle of 10～20wt%, the anhydrous potassium carbonate of 1～10wt%, the anhydrous carbonic acid of 1～10wt% Sodium and 1-10wt% thermosetting resin are mixed evenly, and pressed under the condition of 50-100MPa; then heat-treated at 600-800°C for 1-3 hours, and then heat-treated at 900-1100°C for 1-3 hours, and the Porous potassium hexatitanate whisker ceramics were obtained.

The neutral atmosphere is a nitrogen atmosphere.

Porous potassium hexatitanate whisker ceramics prepared in this example are tested: the potassium hexatitanate whiskers have a diameter of 0.5-2 μm and a length of 3-20 μm, and the normal-temperature compressive strength of the potassium hexatitanate whisker porous ceramics is greater than 9 MPa ; The porosity is greater than 40%.

Example 2

A potassium hexatitanate whisker porous ceramic and a preparation method thereof. The steps of the preparation method described in this embodiment are:

In the first step, the titanium-containing waste is heat-treated at 1000-1300°C for 2-4 hours, and ground to a particle size of less than 0.045mm to obtain grinding material A.

The second step is to mix 60~70wt% of the said grinding material A, 10~20wt% titanium dioxide and 10~20wt% thermosetting resin evenly, press molding under the condition of 50~100MPa; Heat treatment in a neutral atmosphere for 1 to 3 hours, crush and grind until the particle size is less than 0.088mm, and obtain powder and abrasive material B.

In the third step, 50-60wt% of said grinding material B, 10-20wt% of anhydrous potassium carbonate and 20-30wt% of potassium acetate were uniformly mixed, and ground for 0.5-1 hour to obtain grinding material.

The 3rd step, the described grinding material B of 10～20wt%, the grinding material of 30～40wt%, the limestone particle of 20～30wt%, the anhydrous potassium carbonate of 1～10wt%, the anhydrous carbonic acid of 1～10wt% Sodium and 1-10wt% thermosetting resin are mixed evenly, and pressed under the condition of 50-100MPa; then heat-treated at 600-800°C for 1-3 hours, and then heat-treated at 900-1100°C for 1-3 hours, and the Porous potassium hexatitanate whisker ceramics were obtained.

The neutral atmosphere is a nitrogen atmosphere or an argon atmosphere.

Porous potassium hexatitanate whisker ceramics prepared in this example are tested: the potassium hexatitanate whiskers have a diameter of 0.5-2 μm and a length of 3-20 μm; the normal-temperature compressive strength of the potassium hexatitanate whisker porous ceramics is greater than 7 MPa , porosity greater than 50%.

Example 3

A potassium hexatitanate whisker porous ceramic and a preparation method thereof. The steps of the preparation method described in this embodiment are:

In the first step, the titanium-containing waste is heat-treated at 1000-1300°C for 2-4 hours, and ground to a particle size of less than 0.045mm to obtain grinding material A.

The second step is to mix 50~60wt% of said grinding material A, 10~20wt% of titanium dioxide and 20~30wt% of thermosetting resin evenly, press molding under the condition of 50~100MPa; Heat treatment in a neutral atmosphere for 1 to 3 hours, crush and grind until the particle size is less than 0.088mm, and obtain powder and abrasive material B.

In the third step, 50-60wt% of the grinding material B, 20-30wt% of anhydrous potassium carbonate and 10-20wt% of potassium acetate were uniformly mixed, and ground for 0.5-1 hour to obtain the grinding material.

The 3rd step, the described grinding material B of 10～20wt%, the abrasive material of 40～50wt%, the limestone particle of 10～20wt%, the anhydrous potassium carbonate of 1～10wt%, the anhydrous carbonic acid of 1～10wt% Sodium and 1-10wt% thermosetting resin are mixed evenly, and pressed under the condition of 50-100MPa; then heat-treated at 600-800°C for 1-3 hours, and then heat-treated at 900-1100°C for 1-3 hours, and the Porous potassium hexatitanate whisker ceramics were obtained.

The neutral atmosphere is a nitrogen atmosphere.

The potassium hexatitanate whisker porous ceramic prepared in this example is tested: the diameter of the potassium hexatitanate whisker is 0.5-2 μm, and the length is 3-20 μm; the room temperature compressive strength of the potassium hexatitanate whisker porous ceramic is greater than 8 MPa , porosity greater than 50%.

Example 4

A potassium hexatitanate whisker porous ceramic and a preparation method thereof. The steps of the preparation method described in this embodiment are:

In the first step, the titanium-containing waste is heat-treated at 1000-1300°C for 2-4 hours, and ground to a particle size of less than 0.045mm to obtain grinding material A.

The second step is to mix 60~70wt% of the said grinding material A, 10~20wt% titanium dioxide and 10~20wt% thermosetting resin evenly, press molding under the condition of 50~100MPa; Heat treatment in a neutral atmosphere for 1 to 3 hours, crush and grind until the particle size is less than 0.088mm, and obtain powder and abrasive material B.

In the third step, 40-50wt% of said grinding material B, 20-30wt% of anhydrous potassium carbonate and 20-30wt% of potassium acetate were uniformly mixed, and ground for 0.5-1 hour to obtain grinding material.

The 3rd step, the described grinding material B of 10～20wt%, the grinding material of 30～40wt%, the limestone particle of 20～30wt%, the anhydrous potassium carbonate of 1～10wt%, the anhydrous carbonic acid of 1～10wt% Sodium and 1-10wt% thermosetting resin are mixed evenly, and pressed under the condition of 50-100MPa; then heat-treated at 600-800°C for 1-3 hours, and then heat-treated at 900-1100°C for 1-3 hours, and the Porous potassium hexatitanate whisker ceramics were obtained.

The neutral atmosphere is an argon atmosphere.

The porous potassium hexatitanate whisker ceramics prepared in this example are tested: the potassium hexatitanate whiskers have a diameter of 0.5-2 μm and a length of 3-20 μm; the normal-temperature compressive strength of the potassium hexatitanate whisker porous ceramics is greater than 10 MPa , porosity greater than 40%.

Compared with the prior art, this specific embodiment has the following positive effects:

(1) In this specific embodiment, on the basis of research on the composition, structure and phase evolution of titanium-containing waste, the product preparation process is controlled step by step: raw material properties are adjusted, mesophase is formed, and material microstructure is formed. By strictly limiting the technical parameters of the preparation process, such as the particle size of raw materials, the particle size of intermediate products, treatment temperature, treatment time and atmosphere, the necessary conditions are provided for the formation and uniform distribution of potassium hexatitanate whiskers in the structure, so that the prepared The whisker size in the potassium hexatitanate whisker porous ceramic is uniform, and the manufactured product has high compressive strength and high porosity.

(2) This specific embodiment uses titanium-containing waste as the main raw material, and then mixes it with common industrial raw materials such as titanium dioxide, thermosetting resin, anhydrous potassium carbonate, anhydrous sodium carbonate, and limestone, and controls the preparation process step by step, which not only reduces the high temperature The energy consumption and material loss caused by the treatment, and the different stages corresponding to the formation of the porous ceramic microstructure are precisely adjusted to achieve a balanced control of product performance, energy consumption in the preparation process, and material cost. Therefore, not only the raw materials used have a wide range of sources, but also the production process is simple, the production cost is low and no secondary waste is produced.

The potassium hexatitanate whisker porous ceramic prepared in this specific embodiment is tested: the diameter of the potassium hexatitanate whisker is 0.5-2 μm, the length of the potassium hexatitanate whisker is 3-20 μm; the potassium hexatitanate whisker is porous The room temperature compressive strength of ceramics is greater than 7MPa, and the porosity is greater than 40%.

Therefore, this specific embodiment has the characteristics of low production cost, simple process and no secondary waste generation. The whiskers in the prepared potassium hexatitanate whisker porous ceramics are uniform in size, and the pressure resistance of the potassium hexatitanate whisker porous ceramics is high. High strength and high porosity.

Claims (9)

1. a kind of preparation method of crystal whisker of hexa potassium titanate porous ceramics, it is characterised in that the preparation method comprises the concrete steps that：

The first step, by titaniferous waste material under the conditions of 1000 ~ 1300 DEG C heat treatment 2 ~ 4 it is small when, grinding to granularity is less than 0.045mm, Obtain grinding material A；

Second step, the thermosetting resin mixing by the grinding material A of 50 ~ 70wt%, the titanium dioxide of 10 ~ 20wt% and 10 ~ 30wt% Uniformly, it is compressing under the conditions of 50 ~ 100MPa；Then heat treatment 1 ~ 3 is small under the conditions of 1200 ~ 1400 DEG C and in neutral atmosphere When, crush, grinding to granularity is less than 0.088mm, obtains grinding material B；

3rd step, the potassium acetate of the grinding material B of 40 ~ 60wt%, the Anhydrous potassium carbonate of 10 ~ 30wt% and 10 ~ 30wt% are mixed Uniformly, when grinding 0.5 ~ 1 is small, abrasive is obtained；

3rd step, by the grinding material B of 10 ~ 20wt%, the abrasive of 30 ~ 50wt%, the limestone particle of 10 ~ 30wt%, 1 ~ The thermosetting resin of the Anhydrous potassium carbonate of 10wt%, the natrium carbonicum calcinatum of 1 ~ 10wt% and 1 ~ 10wt% is uniformly mixed, 50 ~ It is compressing under the conditions of 100MPa；Then when heat treatment 1 ~ 3 is small under the conditions of 600 ~ 800 DEG C, under the conditions of 900 ~ 1100 DEG C When heat treatment 1 ~ 3 is small, crystal whisker of hexa potassium titanate porous ceramics is made.

2. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the titaniferous waste material： Ti contents are less than 0.9wt% more than the sum of 52wt%, the content of Al, Ni, V, Co, Cr, Ca, Si；The granularity of the titaniferous waste material is small In 0.088mm.

3. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the titanium dioxide Granularity is less than 0.088mm, TiO in the titanium dioxide₂Content be more than 99wt%.

4. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the neutral atmosphere For nitrogen atmosphere or it is argon gas atmosphere.

5. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the Carbon Dioxide The granularity of potassium is less than 0.088mm, K in the Anhydrous potassium carbonate₂CO₃Content be more than 99wt%.

6. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the potassium acetate Granularity is less than 0.088mm, and the purity of the potassium acetate is more than 99wt%.

7. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the lime stone The granularity of grain is 0.088 ~ 0.25mm, and the content of CaO is more than 54wt% in the limestone particle.

8. the preparation method of crystal whisker of hexa potassium titanate porous ceramics according to claim 1, it is characterised in that the Carbon Dioxide The granularity of sodium is less than 0.088mm, Na in the natrium carbonicum calcinatum₂CO₃Content be more than 99wt%.

9. a kind of crystal whisker of hexa potassium titanate porous ceramics, it is characterised in that the crystal whisker of hexa potassium titanate porous ceramics is will according to right Seek the porous pottery of crystal whisker of hexa potassium titanate any one of 1 ~ 8 prepared by the preparation method of crystal whisker of hexa potassium titanate porous ceramics Porcelain.