阅读说明：本技术 一种防静电材料及其制备方法和应用 (Antistatic material and preparation method and application thereof ) 是由 柯善军 田维 马超 赖俊涛 于 2020-12-15 设计创作，主要内容包括：本发明涉及陶瓷材料技术领域,公开了一种防静电材料及其制备方法和应用,该防静电材料包括如下原料组分：氧化锡、三氯化锑和晶种；晶种为锑掺杂氧化锡的纳米粉体。本发明防静电材料电阻率低,具有良好的防静电性,通过采用引入锑掺杂氧化锡的纳米粉体作为晶种,通过晶种诱导,促进锑掺杂氧化锡的形成,提高了产品的产率,同时将氧化锡和三氯化锑溶液通过超细研磨,可使锑均匀地附着在氧化锡颗粒表面,有利于最终产品的组分均匀一致。(The invention relates to the technical field of ceramic materials, and discloses an anti-static material, a preparation method and application thereof, wherein the anti-static material comprises the following raw material components: tin oxide, antimony trichloride and seed crystals; the seed crystal is nanometer powder of antimony doped tin oxide. The antistatic material has low resistivity and good antistatic property, the antimony-doped tin oxide is promoted to be formed by adopting the nano powder introduced with the antimony-doped tin oxide as the seed crystal and inducing the seed crystal, so that the yield of the product is improved, and meanwhile, the antimony can be uniformly attached to the surfaces of tin oxide particles by carrying out superfine grinding on the tin oxide and the antimony trichloride solution, so that the components of the final product are uniform and consistent.)

1. The antistatic material is characterized by comprising the following raw material components: tin oxide, antimony trichloride and seed crystals; the seed crystal is nanometer powder of antimony doped tin oxide.

2. The antistatic material according to claim 1, wherein the average particle size of the tin oxide is 5 to 15 μm; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the antistatic material.

3. The method for preparing the antistatic material as claimed in claim 1 or 2, comprising the steps of:

1) adding water and a dispersing agent into the tin oxide, and grinding to obtain slurry A;

2) adding water into the antimony trichloride, and stirring to obtain an antimony trichloride solution;

3) adding the seed crystal and the antimony trichloride solution into the slurry A, and grinding to obtain slurry B;

4) drying the slurry B to obtain powder;

5) and calcining, cooling, crushing and sieving the powder in sequence to obtain the antistatic material.

4. The preparation method according to claim 3, wherein in the step 1), the dispersant is polyethylene glycol with a molecular weight of 8000-10000, and the mass of the polyethylene glycol accounts for 0.8-1.2% of the mass of the tin oxide.

5. The preparation method according to claim 3, wherein in the step 1), the solid content of the slurry A is 60-65%.

6. The preparation method according to claim 3, wherein in the step 1), the grinding is carried out by using yttrium-stabilized zirconia balls as grinding media; wherein the average grain diameter of the yttrium-stabilized zirconia balls is 0.3-0.5 mm, the filling rate of the yttrium-stabilized zirconia balls is 65-70%, the grinding speed is greater than or equal to 2000 r/min, and the grinding time is 1-2 hours.

7. The preparation method according to claim 3, wherein in the step 3), the grinding is carried out by using yttrium-stabilized zirconia balls as grinding media; wherein the average grain diameter of the yttrium-stabilized zirconia balls is 0.3-0.5 mm, the filling rate of the yttrium-stabilized zirconia balls is 72-75%, the grinding speed is greater than or equal to 3000 r/min, and the grinding time is 1-1.5 hours.

8. The preparation method according to claim 3, wherein the temperature of the hot air for drying in the step 4) is 140 to 160 ℃.

9. The preparation method according to claim 3, wherein in the step 5), the calcination temperature is 600 to 800 ℃ and the calcination time is 2 to 4 hours.

10. Use of the antistatic material according to claim 1 or 2 in a ceramic material.

Technical Field

The invention relates to the technical field of ceramic materials, in particular to an anti-static material and a preparation method and application thereof.

Background

Static electricity is a common discharge phenomenon caused by friction in daily life, and the existence of potential static electricity on the surface of a material can cause potential safety hazards of some special environments such as laboratories, microcomputer rooms and the like. The tin antimony oxide (antimony doped tin oxide) powder has wide application prospect in many fields due to high conductivity, and is a novel antistatic functional material which is rapidly developed in recent years.

At present, the preparation method of the tin antimony oxide powder material mainly comprises a hydrothermal method, a chemical coprecipitation method and a solid phase method, but the hydrothermal method has high cost and is difficult to realize industrial production; the chemical coprecipitation method can generate more waste liquid, so that the environmental protection burden is increased; the solid phase method has slow reaction speed, is difficult to realize uniform mixing, and has low yield of the obtained tin antimony oxide.

Disclosure of Invention

The present invention is directed to an antistatic material, which solves one or more of the problems of the prior art and provides at least one of the advantages of the present invention.

The technical scheme adopted for solving the technical problems is as follows:

an antistatic material comprises the following raw material components: tin oxide, antimony trichloride and seed crystals; the seed crystal is nanometer powder of antimony doped tin oxide.

The seed crystal used in the invention is antimony doped tin oxide nano-powder synthesized by a water-based sol-gel method, and the water-based sol-gel method can be prepared by referring to the preparation method of antimony doped nano-tin oxide powder disclosed in patent CN 106564937A.

Preferably, the average grain diameter of the tin oxide is 5-15 microns; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The second purpose of the present invention is to provide a method for preparing the above antistatic material, comprising the following steps:

1) adding deionized water and a dispersing agent into the tin oxide, and grinding by adopting a medium stirring mill to obtain slurry A;

2) adding water into the antimony trichloride, and stirring and fully dissolving to obtain an antimony trichloride solution;

3) adding the seed crystal and the antimony trichloride solution into the slurry A at the same time, and grinding by adopting a high-medium stirring mill to obtain slurry B;

4) carrying out spray drying on the slurry B to obtain powder;

5) and sequentially carrying out high-temperature calcination, cooling to room temperature, crushing and 200-325-mesh sieve sieving on the powder to obtain the antistatic material.

Preferably, in the step 1), the dispersant is polyethylene glycol with the molecular weight of 8000-10000, and the mass of the polyethylene glycol accounts for 0.8-1.2% of that of the tin oxide.

Preferably, in the step 1), the solid content of the slurry A is 60-65%.

Preferably, in the step 1), the grinding is specifically carried out by using yttrium-stabilized zirconia balls as grinding media; wherein the average grain diameter of the yttrium-stabilized zirconia balls is 0.3-0.5 mm, the filling rate of the yttrium-stabilized zirconia balls is 65-70%, the grinding speed is greater than or equal to 2000 r/min, and the grinding time is 1-2 hours.

Preferably, in the step 3), the grinding is specifically carried out by using yttrium-stabilized zirconia balls as grinding media; wherein the average grain diameter of the yttrium-stabilized zirconia balls is 0.3-0.5 mm, the filling rate of the yttrium-stabilized zirconia balls is 72-75%, the grinding speed is greater than or equal to 3000 r/min, and the grinding time is 1-1.5 hours.

Preferably, in the step 4), the temperature of the hot air for spray drying is 140-160 ℃.

Preferably, in the step 5), the calcining temperature is 600-800 ℃, and the calcining time is 2-4 hours.

The third purpose of the present invention is to provide the application of the above-mentioned antistatic material in ceramic materials.

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

1. the antistatic material has low resistivity and good antistatic property.

2. The invention adopts the nanometer powder body introduced with the antimony doped tin oxide as the seed crystal, promotes the formation of the antimony doped tin oxide through the induction of the seed crystal, and improves the yield of the product.

3. The invention can lead the antimony to be evenly attached to the surfaces of tin oxide particles by carrying out superfine grinding on the tin oxide and the antimony trichloride solution, and is beneficial to the components of the final product to be even and consistent.

4. The invention adopts the steps of superfine grinding, coarse grain coarse grinding and fine grain fine grinding to the raw materials, which is beneficial to improving the grinding efficiency, so that the material components are mixed more uniformly and the product quality is more stable.

5. The preparation method is simple and easy to industrialize.

Detailed Description

The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.

Example 1

An antistatic material comprises the following raw material components: the tin oxide-antimony trichloride crystal seed comprises tin oxide, antimony trichloride and a crystal seed, wherein the crystal seed is antimony-doped tin oxide nano-powder, and the average particle size of the tin oxide is 5-15 micrometers; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The preparation method of the antistatic material comprises the following steps:

1) 147.70 g of tin oxide with the average particle size of 5 microns is weighed, 100 ml of deionized water and 1.77 g of polyethylene glycol-10000 are added, a medium stirring mill is adopted for grinding, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 65%, the rotating speed of the medium stirring mill is adjusted to 2000 r/min, and slurry A is obtained after grinding for 1 hour;

2) weighing 9.12 g of antimony trichloride, adding water, stirring and fully dissolving to obtain an antimony trichloride solution;

3) weighing 0.77 g of antimony-doped tin oxide nano powder, simultaneously adding the antimony-doped tin oxide nano powder and an antimony trichloride solution into the slurry A, and grinding by adopting a high-medium stirring mill, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 75%, the rotating speed of the medium stirring mill is adjusted to 3000 r/min, and grinding is carried out for 1.0 hour to obtain slurry B;

4) spray drying the slurry B, and setting the hot air temperature of the spray drying to be 150 ℃ to obtain powder;

5) calcining the powder at the high temperature of 600 ℃ for 2 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

Example 2

An antistatic material comprises the following raw material components: the tin oxide-antimony trichloride crystal seed comprises tin oxide, antimony trichloride and a crystal seed, wherein the crystal seed is antimony-doped tin oxide nano-powder, and the average particle size of the tin oxide is 5-15 micrometers; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The preparation method of the antistatic material comprises the following steps:

1) 135.64 g of tin oxide with the average particle size of 15 microns is weighed, 100 ml of deionized water and 1.08 g of polyethylene glycol-10000 are added, a medium stirring mill is adopted for grinding, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 70%, the rotating speed of the medium stirring mill is adjusted to 2200 r/min, and slurry A is obtained after grinding for 2 hours;

2) weighing 27.37 g of antimony trichloride, adding water, stirring and fully dissolving to obtain an antimony trichloride solution;

3) weighing 3.83 g of antimony-doped tin oxide nano powder, simultaneously adding the antimony-doped tin oxide nano powder and an antimony trichloride solution into the slurry A, and grinding by adopting a high-medium stirring mill, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.3 mm, the filling rate of the yttrium-stabilized zirconia ball is 72%, the rotating speed of the medium stirring mill is adjusted to 3100 r/min, and grinding is carried out for 1.5 hours to obtain slurry B;

4) spray drying the slurry B, and setting the hot air temperature of the spray drying to be 150 ℃ to obtain powder;

5) calcining the powder at the high temperature of 800 ℃ for 4 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

Example 3

An antistatic material comprises the following raw material components: the tin oxide-antimony trichloride crystal seed comprises tin oxide, antimony trichloride and a crystal seed, wherein the crystal seed is antimony-doped tin oxide nano-powder, and the average particle size of the tin oxide is 5-15 micrometers; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The preparation method of the antistatic material comprises the following steps:

1) 141.25 g of tin oxide with the average particle size of 12 microns is weighed, 100 ml of deionized water and 1.52 g of polyethylene glycol-10000 are added, a medium stirring mill is adopted for grinding, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 68%, the rotating speed of the medium stirring mill is adjusted to 2200 rpm, and grinding is carried out for 1.5 hours to obtain slurry A;

2) weighing 14.55 g of antimony trichloride, adding water, stirring and fully dissolving to obtain an antimony trichloride solution;

3) weighing 1.78 g of antimony-doped tin oxide nano powder, simultaneously adding the antimony-doped tin oxide nano powder and an antimony trichloride solution into the slurry A, and grinding by adopting a high-medium stirring mill, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.3 mm, the filling rate of the yttrium-stabilized zirconia ball is 72%, the rotating speed of the medium stirring mill is adjusted to 3000 r/min, and grinding is carried out for 1.5 hours to obtain slurry B;

4) spray drying the slurry B, and setting the hot air temperature of the spray drying to be 150 ℃ to obtain powder;

5) calcining the powder at the high temperature of 750 ℃ for 3 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

Example 4

An antistatic material comprises the following raw material components: the tin oxide-antimony trichloride crystal seed comprises tin oxide, antimony trichloride and a crystal seed, wherein the crystal seed is antimony-doped tin oxide nano-powder, and the average particle size of the tin oxide is 5-15 micrometers; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The preparation method of the antistatic material comprises the following steps:

1) 145.27 g of tin oxide with the average particle size of 15 micrometers is weighed, 100 ml of deionized water and 1.08 g of polyethylene glycol-10000 are added, a medium stirring mill is adopted for grinding, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 70%, the rotating speed of the medium stirring mill is adjusted to 2000 r/min, and slurry A is obtained after grinding for 1 hour;

2) 15.46 g of antimony trichloride is weighed, water is added, and the mixture is stirred and fully dissolved to form an antimony trichloride solution;

3) weighing 2.71 g of antimony-doped tin oxide nano powder, simultaneously adding the antimony-doped tin oxide nano powder and an antimony trichloride solution into the slurry A, and grinding by adopting a high-medium stirring mill, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.3 mm, the filling rate of the yttrium-stabilized zirconia ball is 75%, the rotating speed of the medium stirring mill is adjusted to 3500 rpm, and grinding is carried out for 1.5 hours to obtain slurry B;

4) spray drying the slurry B, and setting the hot air temperature of the spray drying to be 150 ℃ to obtain powder;

5) calcining the powder at the high temperature of 600 ℃ for 4 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

Comparative example 1 (different from example 1 in that no seed crystal was added)

An antistatic material comprises the following raw material components: the tin oxide and the antimony trichloride are adopted, and the average particle size of the tin oxide is 5-15 micrometers.

The preparation method of the antistatic material comprises the following steps:

1) 147.70 g of tin oxide with the average particle size of 5 microns is weighed, 100 ml of deionized water and 1.77 g of polyethylene glycol-10000 are added, a medium stirring mill is adopted for grinding, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 65%, the rotating speed of the medium stirring mill is adjusted to 2000 r/min, and slurry A is obtained after grinding for 1 hour;

2) weighing 9.12 g of antimony trichloride, adding water, stirring and fully dissolving to obtain an antimony trichloride solution;

3) adding an antimony trichloride solution into the slurry A, and grinding by adopting a high-medium stirring mill, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 75%, the rotating speed of the medium stirring mill is adjusted to 3000 r/min, and grinding is carried out for 1.0 hour to obtain slurry B;

4) spray drying the slurry B, and setting the hot air temperature of the spray drying to be 150 ℃ to obtain powder;

5) calcining the powder at the high temperature of 600 ℃ for 2 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

Comparative example 2 (difference from example 1 in that liquid antimony trichloride was replaced with solid antimony trioxide)

An antistatic material comprises the following raw material components: the tin oxide-antimony trioxide crystal seed comprises tin oxide, antimony trioxide and a crystal seed, wherein the crystal seed is antimony-doped tin oxide nano powder, and the average particle size of the tin oxide is 5-15 micrometers; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The preparation method of the antistatic material comprises the following steps:

1) 147.70 g of tin oxide with the average particle size of 5 microns is weighed, 100 ml of deionized water and 1.77 g of polyethylene glycol-10000 are added, a medium stirring mill is adopted for grinding, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 65%, the rotating speed of the medium stirring mill is adjusted to 2000 r/min, and slurry A is obtained after grinding for 1 hour;

2) weighing 9.12 g of antimony trioxide;

3) weighing 0.77 g of antimony-doped tin oxide nano powder, simultaneously adding the antimony-doped tin oxide nano powder and antimony trioxide into the slurry A, and grinding by adopting a high-medium stirring mill, wherein the average particle size of a grinding medium yttrium-stabilized zirconia ball is 0.5 mm, the filling rate of the yttrium-stabilized zirconia ball is 75%, the rotating speed of the medium stirring mill is adjusted to 3000 r/min, and grinding is carried out for 1.0 hour to obtain slurry B;

4) spray drying the slurry B, and setting the hot air temperature of the spray drying to be 150 ℃ to obtain powder;

5) calcining the powder at the high temperature of 600 ℃ for 2 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

Comparative example 3 (difference from example 1 in that conventional ball milling was used and milling was not carried out stepwise)

An antistatic material comprises the following raw material components: the tin oxide-antimony trichloride crystal seed comprises tin oxide, antimony trichloride and a crystal seed, wherein the crystal seed is antimony-doped tin oxide nano-powder, and the average particle size of the tin oxide is 5-15 micrometers; the mass of the seed crystal accounts for 0.5-2.5% of the mass of the material.

The preparation method of the antistatic material comprises the following steps:

1) 147.70 g of stannic oxide with the average grain diameter of 5 microns is weighed, 9.12 g of antimony trichloride is weighed, 0.77 g of antimony doped stannic oxide nano powder is weighed, 100 ml of deionized water and 1.77 g of polyethylene glycol-10000 are added, and grinding is carried out for 2.5 hours by adopting a common ceramic ball mill to obtain slurry;

2) spray drying the slurry, wherein the hot air temperature of the spray drying is set to be 150 ℃, so as to obtain powder;

3) calcining the powder at the high temperature of 600 ℃ for 2 hours, cooling to room temperature, crushing, and sieving with a 200-325-mesh sieve.

The antistatic materials obtained in examples 1 to 4 and comparative examples 1 to 3 were subjected to a performance test:

respectively weighing 60 g of the antistatic materials prepared in the embodiments 1-4 and the comparative examples 1-3, preparing a wafer with the diameter (D) of 10 mm and the certain thickness (H) under the pressure of 5000N, padding copper sheets on two ends of the wafer, directly contacting probes of a resistance instrument with the copper sheets to test the resistance (R), and obtaining the resistivity (rho) through a calculation formula: resistivity ═ pi RD²and/4H. The calculation results are shown in table 1 below.

TABLE 1

Test sample	Resistivity (ohm/cm)
		Example 1	1.25
Example 2	0.89
		Example 3	2.55
Example 4	2.27
		Comparative example 1	6.48
Comparative example 2	5.97
		Comparative example 3	10.81

As can be seen from the data in Table 1, the resistivity of the antistatic material prepared in the examples 1 to 4 of the invention is between 0.8 and 2.6, which is lower than that of the antistatic material prepared in the comparative examples 1 to 3, and the antistatic performance of the antistatic material prepared in the examples 1 to 4 of the invention is better; comparative example 1 has low product yield due to no seed crystal added, thereby affecting antistatic performance; comparative example 2 because liquid antimony trichloride was replaced with solid antimony trioxide, antimony did not adhere uniformly to the surface of tin oxide particles, thereby affecting antistatic properties; comparative example 3 because the traditional ball milling mode is adopted, grinding is not carried out step by step, the materials are mixed unevenly, and the antistatic performance is influenced.

While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that the present invention is not limited to the details of the embodiments shown and described, but is capable of numerous equivalents and substitutions without departing from the spirit of the invention as set forth in the claims appended hereto.