CN1801400A - In203-Sn02 nano film coating material and its preparing method - Google Patents

Abstract

The nano In2O3-SnO2 film coating material comprises 70~90% In2O3, 0.5~20% SnO2, 0.5~15% ZnCl2, and 0.001~1% REE compound. Wherein, the preparation method comprises: mixing material to prepare solution, heating and holding 50-80Deg with 7.0~10.0 pH value to hydrolyze; filtering, drying, baking, and cutting to obtain the objective product. Compared with prior art, this invention increases utility for material, reduces cost, can control property and particle size on molecular design level, and the product has well transmittance and conductivity.

Description

In2O3-SnO2Nano coating material and preparation method thereof

The invention belongs to the technical field of films, and relates to industrial indium tin oxide transparent conductive paste and a preparation method thereof.

Ito (indium Tin oxide) is widely used in high technology fields because of its excellent opticalproperties, low resistivity and electrode characteristics as an N-type semiconductor material. The transparent conductive glass obtained by using ITO film formation is widely applied to the field of liquid crystal display, such as thin film transistor TFT, flat liquid crystal display LCD and electroluminescent display ELD; the selectivity of the solar energy heat-insulating glass to light waves (the reflectivity of infrared light is up to 80 percent) can be used for collecting and utilizing solar energy and for curtain walls of high-rise buildings, so that the solar energy heat-insulating glass has a good heat-shielding effect, can make external heat difficult to radiate into a room when the external temperature is higher, replaces double-layer heat-insulating glass to a certain extent, and is also applied to the aspects of heat insulation, refrigeration, automatic defogging and defrosting and the like; by utilizing the attenuation of the microwave, the material has good microwave shielding effect, such as radar shielding protection area, electronic computer room, mobile phone electromagnetic wave shielding, invisible material research and the like. At present, the methods for preparing the ITO film are more, the methods are industrially mature such as a magnetron sputtering method, a sol-gel method, a dip coating method, a thermal decomposition method, a thermal hydrolysis method, a micro-emulsion method, a reduced pressure volatilization method and the like, and in the aspect of liquid crystal display, because the requirements on the quality of the ITO film are very high, such as transmittance, chromatic aberration, resistance, aging, temperature stability and combination tightness of a film layer and a substrate, the film is coated by adopting magnetron sputtering. However, magnetron sputtering is high in investment cost, expensive target materials are used, the utilization rate of the target materials is low (less than 40%), the production process is complex, the cost is high, and the application range of the magnetron sputtering is difficult to expand in other fields except liquid crystal display.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a nano coating material for liquid crystal display, energy-saving glass, vehicle windshield and solar energy utilization and a preparation method thereof, so as to improve the utilization rate of raw materials, reduce the cost, simplify the preparation process and control the performance and granularity of the material from the level of molecular design.

In₂O₃-SnO₂The nanometer coating material comprises the following components in percentage by weight: 70-90% of indium oxide, 0.5-20% of tin oxide, 0.5-15% of zinc oxide and 0.001-1% of rare earth element compound, wherein the diameter of the composite oxide is 8-40 nm.

In₂O₃-SnO₂The preparation method of the nano coating material comprises the following steps:

dissolving: preparing indium chloride or indium metal, tin chloride, zinc chloride and rare earth element compound into solution according to the proportion; mixing;

hydrolysis: heating and keeping the temperature at 50-80 ℃, adding ammonia water for hydrolysis, and simultaneously adding a dispersing agent, wherein the adding amount of the ammonia water ensures that the pH value after reaction is 7.0-10.0, and generating a precipitate:

the reaction formula is as follows:

re is rare earth element.

And (3) filtering: carrying out azeotropic distillation on the sol, washing with water, washing with alcohol, and filtering;

and (3) drying: drying the obtained precipitate at 80-100 deg.C for 10h, and protecting with nitrogen gas while drying;

and (3) calcining: calcining the obtained powder at the temperature of 500-900 ℃ for 2 h; the reaction formula is as follows:

shearing: dissolving the obtained powder in an organic solvent, shearing and dispersing by using ethanol at the speed of 3000-4000rpm for 8h, adding an organic anti-agglomeration agent, and shearing.

Ultrasonic dispersion: and dispersing for 10-15 min by using ultrasonic.

Centrifuging: putting the solution into a centrifuge, controlling the rotating speed of 6000-.

The dispersing agent is: polyethylene glycol, triammonium citrate, sodium silicate, sodium dodecyl benzene sulfonate and triton X-100.

The rare earth element is one or more of lanthanum (La), samarium (Sm) and terbium (Tb);

the anti-agglomeration agent is one or more of silane coupling agents KH550, KH560, KH570, KH792, titanate coupling agents 101, 201, TTS, 38S, vinyltriethoxysilane, vinyltris (β -methoxy) silane and gamma-methacrylic acid propyl trimethoxysilane.

Compared with the prior art, the invention can improve the utilization rate of raw materials, reduce the cost, simplify the preparation process, control the performance and the granularity of the material from the level of molecular design, has high light transmittance and good electric conductivity, and is suitable for large-area film coating.

Drawings

FIG. 1: the invention is a process flow diagram.

Detailed Description

Example 1: 37.5g of indium chloride, 18.4g of tin chloride, 8.78 g of dispersant triton X-1000.7g, 5.3g of zinc chloride and 0.08g of rare earth element compound samarium oxide which are completely dissolved in organic alcohol to prepare solution, wherein the organic alcohol can be isopropanol, the heating temperature is 80 ℃, ammonia water is dripped to adjust the pH value to 7.5, precipitate is generated, the precipitate is filtered out and washed with water until no Cl is detected in washing residual liquid^-Then azeotropic distillation is carried out, n-butanol is selected as a solvent, then organic alcohol is used for washing, ethanol is selected as alcohol, the aim is to take away free water, the obtained sol is dried for 8 hours in the nitrogen protection atmosphere, the temperature is 110 ℃, the powder is ground and then calcined for 3 hours at the temperature of 600 ℃, nano ITO powder can be obtained, 15g of ITO powder is taken and added into ethanol, anti-agglomeration agent silane coupling agent KH560 and titanate coupling agent TTS are added, shearing is carried out for 7 hours at the speed of 4000rpm, ultrasonic dispersion is carried out in ultrasonic water bath for 15 minutes, finally the rotating speed is controlled in a centrifuge to be 8000rpm, the centrifugation time is 8 minutes, and after the centrifugation is finished and the bottom layer precipitation is filtered out, the indium tin oxide nano-tube is obtainedThe average particle size of the coating material is about 8 nm.

Example 2: 23.5g of metal indium, 23.1g of tin chloride, 1.2g of dispersant sodium dodecyl benzene sulfonate, 8.4g of zinc chloride and 0.8g of rare earth element compound terbium oxide are completely dissolved in hydrochloric acid to prepare a solution, the temperature is heated to 65 ℃, the PH value is adjusted to 9 by ammonia water to generate a precipitate, and the precipitate is filtered out and washed by water until no Cl exists^-Then, azeotropic distillation is carried out, the solvent is n-butyl alcohol, then organic alcohol is used for washing, the alcohol is ethanol and aims to take away free water, the obtained sol is dried for 11 hours in the nitrogen protective atmosphere, the temperature is 80 ℃, the powder is ground and then calcined for 2 hours at the temperature of 850 ℃, and the nano ITO powder can be obtained. Adding 18.7g of ITO powder into ethanol, adding an anti-agglomeration agent silane coupling agent KH792 and a titanate coupling agent 38S, shearing at the speed of 4000rpm for 8h, performing ultrasonic dispersion in ultrasonic water bath for 12min, finally controlling the rotating speed in a centrifuge to 7000rpm, centrifuging for 9min, filtering out bottom layer precipitates after centrifugation is finished, and obtaining the indium tin oxide nano coating material, wherein the average particle size is distributed at about 16 nm.

Example 3: 17.5g of indium chloride, 7.7g of tin chloride, 0.5g of polyethylene glycol serving as a dispersant, 2.3g of zinc chloride and 0.05g of lanthanum chloride serving as a rare earth element compound are completely dissolved in organic alcohol to prepare a solution, the organic alcohol can be ethanol, the heating temperature is 70 ℃, ammonia water is dripped to adjust the pH value to 7.5-10.0, precipitate is generated, the precipitate is filtered out and washed with water, and no Cl is detected in washing residual liquid^-Performing azeotropic distillation, selecting n-butanol as a solvent, washing with organic alcohol, selecting ethanol as alcohol for taking away free water, drying the obtained sol in a nitrogen protective atmosphere for 10 hours at 100 ℃, grinding the powder, calcining for 2 hours at 750 ℃ to obtain nano ITO powder, taking 5.5g of the ITO powder, adding the ITO powder into ethanol, adding an anti-agglomeration agent silane coupling agent KH550 and vinyl tris (β -methoxy) silane, shearing for 8 hours at the speed of 3000rpm, performing ultrasonic dispersion in an ultrasonic water bath for 12 minutes, controlling the rotating speed in a centrifuge to be 6000rpm, centrifuging for 8 minutes, filtering out bottom layer precipitates after centrifuging is finished, obtaining the indium tin oxide nano coating material, and averaging the indium tin oxide nano coating materialThe particle size distribution is about 24 nm.

Example 4: 26.25g of indium chloride, 11.55g of tin chloride, 0.3g of dispersant triammonium citrate, 4.3g of zinc chloride and 0.04g of rare earth element compound lanthanum chloride, which are completely dissolved in methanol to prepare a solution, the heating temperature is 70 ℃, ammonia water is dripped to adjust the pH value to 8.5, precipitate is generated, and the sol is filtered out and washed with water until no Cl is detected in the washing residual liquid^-Performing azeotropic distillation, selecting n-butyl alcohol as a solvent, performing alcohol washing on the obtained sol after the azeotropic distillation, selecting ethanol as the alcohol for taking away free water, drying theobtained sol in a nitrogen protective atmosphere for 10 hours at the temperature of 90 ℃, grinding the powder, calcining the powder at the temperature of 700 ℃ for 2.5 hours to obtain nano ITO powder, taking 8.4g of the ITO powder, adding the ITO powder into the ethanol, adding an anti-agglomeration agent titanate coupling agent 201 and gamma-methyl acrylic propyl trimethoxy silane, shearing the mixture at the speed of 4000rpm for 6 hours, performing ultrasonic dispersion in an ultrasonic water bath for 10 minutes, finally controlling the rotating speed in a centrifuge to 6000rpm, centrifuging the time to 6 minutes, filtering out bottom layer precipitates after the centrifugation is finished, and obtaining the indium tin oxide nano coating material, wherein the average particle size is about 33 nm.

Claims (3)

1. In₂O₃-SnO₂The nano coating material is characterized in that: the components by weight percentage are as follows: 70-90% of indium oxide, 0.5-20% of tin oxide, 0.5-15% of zinc oxide, 0.001-1% of rare earth element compound and 8-40 nm of diameter.

2. The nanocoating material of claim 1, wherein: the rare earth element is one or more of lanthanum, samarium and terbium.

3. A method for preparing the nano coating material according to claim 1, which is characterized in that: the method comprises the following steps:

dissolving: preparing indium chloride or indium metal, tin chloride, zinc chloride and rare earth element compound into solution according to the proportion; mixing;

hydrolysis: heating and keeping the temperature at 50-80 ℃, adding ammonia water for hydrolysis, and simultaneously adding a dispersing agent, wherein the adding amount of the ammonia water ensures that the pH value after reaction is 7.0-10.0, and generating a precipitate;

and (3) filtering: carrying out azeotropic distillation on the sol, washing with water, washing with alcohol, and filtering;

and (3) drying: drying the obtained precipitate at 80-100 deg.C for 10h, and protecting with nitrogen gas while drying;

and (3) calcining: calcining the obtained powder at the temperature of 500-900 ℃ for 2 h; the reaction formula is as follows:

shearing: dissolving the obtained powder in an organic solvent, shearing and dispersing the powder by using ethanol at the speed of 3000-4000rpm for 8h, and adding an organic anti-agglomeration agent;

centrifuging: putting the solution into a centrifuge, controlling the rotating speed of 6000-;

the dispersing agent is: polyethylene glycol, triammonium citrate, sodium silicate, sodium dodecyl benzene sulfonate and triton X-100;

the anti-agglomeration agent is one or more of silane coupling agents KH550, KH560, KH570, KH792, titanate coupling agents 101, 201, TTS, 38S, vinyltriethoxysilane, vinyltris (β -methoxy) silane and gamma-methacrylic acid propyl trimethoxysilane.

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