CN101264926B - Method for preparing nano ITO powder by ammonia salt combustion method - Google Patents
Method for preparing nano ITO powder by ammonia salt combustion method Download PDFInfo
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- CN101264926B CN101264926B CN2008100583279A CN200810058327A CN101264926B CN 101264926 B CN101264926 B CN 101264926B CN 2008100583279 A CN2008100583279 A CN 2008100583279A CN 200810058327 A CN200810058327 A CN 200810058327A CN 101264926 B CN101264926 B CN 101264926B
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- 239000000843 powder Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000009841 combustion method Methods 0.000 title claims description 5
- 239000000243 solution Substances 0.000 claims abstract description 41
- 229910052738 indium Inorganic materials 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 150000003863 ammonium salts Chemical class 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 229930091371 Fructose Natural products 0.000 claims description 6
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 6
- 239000005715 Fructose Substances 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000002184 metal Substances 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000000460 chlorine Substances 0.000 abstract description 2
- 238000001513 hot isostatic pressing Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 abstract 2
- 239000013077 target material Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 7
- 241000370738 Chlorion Species 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a method for preparing nanometer ITO powder by means of ammonia salt combustion process, which comprises the following steps: metals of indium and tin are dissolved into nitric acid solution to prepare nitrate solution, organic complexing agent and dispersant are added into the resultant solution and mixed evenly, and the temperature is controlled between 40 and 70 DEG C; then ammonia water is added into the solution, and the pH value is adjusted between 1 and 3.8; finally, absolute ethyl alcohol is added into the prepared ammonia salt solution as combustion improver, liquid drops of the solution is dripped into a rotary kiln with a temperature of 700-1200 DEG C and sintered for 10 to 30 minutes, thus obtaining the nanometer ITO powder. The preparation method for nanometer ITO powder has the advantages that the powder produced has high purity and a grain size ranging between 10 and 30 nm, and the powder is of a regular spherical grain, and has no other impurities, especially chloridion; therefore, the problems of sever cracks occurring on the target material during the ITO target material preparation process by means of sintering method and hot isostatic pressing method due to the abundant chlorine in the ITO powder; moreover, the process cycle is short, the production efficiency is high, and continuous feeding and powder production are possible, thus realizing mass production and causing no pollution to the environment.
Description
Technical field
The present invention relates to a kind of preparation method of high purity indium tin oxide nanometer powder, belong to wet method and prepare a kind of of nano-ITO powder.
Background technology
Indium tin oxide (Indium Tin Oxides, english abbreviation are ITO) nanometer powder is meant 90% In
2O
3With 10% SnO
2The oxide material of forming is a kind of novel specific function material, the deep processing new high-tech product of indium metal.Ito powder is mainly used in preparation ITO target and ito thin film.Ito thin film has the visible light transmissivity height, the reflectivity height in infrared light district, the specific absorption height of ultraviolet region, good electrical conductivity, good matrix tack and chemical stability.The above-mentioned characteristic of ITO has a very wide range of applications it in a lot of fields, becomes the transparent conductive material that present stage has important application and researching value.Usually, have only high-quality ito powder just can prepare the ITO target of perfect performance.Therefore, the development of ITO nanometer powder is one of focus of domestic and international material subject research.
(NONFERROUS METALS such as the old generation post of Central South University, 2000,52, be raw material 88-90) with indium metal and tin, be equipped with nano-ITO powder by the spray burning legal system, this method is highly efficient in productivity, is fit to produce in enormous quantities, and the powder purity of preparing is also very high, but need under the high pressure of 10-15MPa, atomize, this demand to equipment is higher, and operation has certain danger, technological operation complexity.People such as Chi-Hwan (Materials Latters 61 (2007) 1701-1703) utilize sol-gel method successfully to prepare the powder of particle diameter in the 16-33 nanometer, (Scripta Mater such as Nam, 2001,44,2047-2050) make the nano level ito powder with coprecipitation method.Sol-gel method and coprecipitation method are the methods of using always for preparing nano-ITO powder, but for sol-gel method, and influence factor is many, all can influence colloidal formation as the concentration of solution, temperature, pH value etc.; And the powder particle particle diameter that coprecipitation method makes is inhomogeneous.(J.Am.Cerama, Soc, 2001 such as Yanagisawa, 84, be that raw material adopts coprecipitation method to obtain the oxyhydroxide presoma of indium, tin with the villaumite 251-253), carry out repetitive scrubbing then and remove chlorion, carry out hydrothermal treatment consists again, heat-treat at last and obtain the ITO powder.In this method, the removal of chlorion is a big key, if the residual meeting of chlorion has influence on the sintering of ITO target, yet, the removal of chlorion is a very time-consuming technological process, often needs to consume a large amount of water, electric power, also can cause a large amount of losses of product simultaneously, the products production cost is increased, and cause serious environmental to pollute.
CN1978323A discloses " a kind of preparation method of high sintering activity ITO powder ", and it is to utilize the organic and inorganic salt of the alkoxide of indium and tin and other to prepare the high sintering activity ITO powder that particle diameter is 6～25 nanometers.Though this method does not directly utilize muriate to be prepared, it is to carry out hydro-thermal reaction 3～24 hours in 130～260 ℃ in reactor that an operation is arranged in this method, and overlong time causes the excessive cycle of entire reaction.CN1301911C discloses " the ito powder preparation method of solid solution tin in a kind of Indium sesquioxide ", it is to be indium nitrate and tin chloride mixing solutions raw material, utilize spray heating decomposition to prepare the nano-ITO powder, the powder that this method makes is for spherical, but, can influence the sintering of target equally owing to contain chlorion.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, provide a kind of grain-size little, specific surface area height, pattern rule, purity height, technical process is simple, the preparation method of the nano level ito powder that preparation cycle is short.Technical process as shown in Figure 1
Ammonium salt combustion method of the present invention prepares the method for nano-ITO powder, comprises the preparation of the nitrate solution of indium and tin, adds organic complexing agent, regulates pH value and sintering circuit with ammoniacal liquor, it is characterized in that, concrete preparation section is as follows:
A is that 99.99% indium and tin are dissolved in the analytically pure salpeter solution with purity, makes the nitrate solution of concentration 1～4mol/L, and wherein the weight ratio of indium and tin is 9.04: 1;
B, in this solution, add organic complexing agent polyvinyl alcohol and polyacrylamide, the volume ratio of the two and solution is respectively 1: (8～15) and 1: (5～10), then add dispersion agent citric acid and fructose again, the volume ratio of the two and solution is 1: (15～20), stir, temperature is controlled at 40～70 ℃;
C, dropping ammonia more constantly stir with magnetic stirring apparatus, and it is fully reacted, and the pH value of regulator solution is 1～3.8;
D, the ammonium salt solution that the C operation is prepared add again with the liquor capacity ratio be 1: the dehydrated alcohol of (10～18), as ignition dope;
E, the ammonium salt solution that at last the C operation is prepared are put into 700～1200 ℃ kiln sintering 10～30 minutes, promptly obtain nano-ITO powder.
Compare with prior art, the present invention has following advantage or positively effect:
1, the nano-ITO powder footpath that makes is between 10～30 nanometers, and granule-morphology is even sphere, narrow particle size distribution.
2, required raw material is easy to get in the preparation process, simple to operate, technical process is short and reduced this link of removal chlorion, fundamentally solved owing to be rich in the chlorine element in the ito powder, sintering process and hot isostatic pressing method prepare the serious rimose problem of the target that occurs in the process of ITO target, and can not produce pollution to environment.
Description of drawings
Fig. 1 prepares the process flow sheet of nanometer TIO powder for the ammonium salt combustion method.
Fig. 2 is the picture of the transmission electron microscope of the prepared powder of embodiment 2.Can see that on scheming this powder is the spheroidal particle of particle diameter 20-35 nanometer, and regular shape, crystalline structure is good.
Fig. 3 is the X ray diffracting spectrum of the prepared powder of embodiment 2.Therefrom can see, the peak position of 11 diffraction peaks occur 20 °～80 ° scopes, contrast PDF card as can be known, spectral line is In
2O
3The crystalline diffract spectral line does not find to have SnO
2And the spectral line of metal Sn and other clutter, this powder is the ito powder of Indium sesquioxide solid solution stannic oxide.
Embodiment
The invention will be further described with example below
Embodiment 1, take by weighing a certain amount of pure metal In10g, (weight ratio is In: Sn=9.04 to Sn1.1062g: 1) be dissolved in 63% HNO
3In, be mixed with the nitrate solution that 80ml concentration is 1.2mol/L, add successively organic complexing agent polyvinyl alcohol 10ml (with the volume ratio of solution be 1: 8) and polyacrylamide 13.3ml (with the volume ratio of solution be 1: 6); Add successively again dispersion agent citric acid 5.3g (with the volume ratio of solution be 1: 15), fructose 5.3g (with the volume ratio of solution be 1: 15), constantly stir, temperature is controlled at 45 ℃, after treating that added complexing agent and dispersion agent dissolve fully, dropping ammonia, regulating the pH value is 3.8, adding in prepared ammonium salt solution with the liquor capacity ratio is 1: 11 dehydrated alcohol 7.3ml, as ignition dope, put into 800 ℃ rotary kiln sintering 10 minutes, promptly obtain ito powder.
Embodiment 2, take by weighing a certain amount of pure metal In10g, (weight ratio is In: Sn=9.04 to Sn1.1062g: 1) be dissolved in 63% HNO
3In, be configured to the nitrate solution that 60ml concentration is 1.6mol/L, add successively organic complexing agent polyvinyl alcohol 5ml (with the volume ratio of solution be 1: 12) and polyacrylamide 7.5ml (with the volume ratio of solution be 1: 8); Add successively again dispersion agent citric acid 3.75g (with the volume ratio of solution be 1: 16), fructose 3.75g (with the volume ratio of solution be 1: 16), constantly stir, temperature is controlled at 60 ℃, after treating that added complexing agent and dispersion agent dissolve fully, dropping ammonia, regulating pH value is 3.5, interpolation and liquor capacity ratio are 1: 12 dehydrated alcohol 5ml in prepared ammonium salt solution, as ignition dope, the rotary kiln sintering of putting into 1000 ℃ obtained ito powder in 20 minutes.
Embodiment 3, take by weighing a certain amount of pure metal In10g, (weight ratio is In: Sn=9.04 to Sn1.1062g: 1) be dissolved in 63%HNO
3In, be configured to the nitrate solution that 50ml concentration is 1.92mol/L, add successively organic complexing agent polyvinyl alcohol 3.6ml (with the volume ratio of solution be 1: 14) and polyacrylamide 5ml (with the volume ratio of solution be 1: 10); Add successively again dispersion agent citric acid 2.8g (with the volume ratio of solution be 1: 18), fructose 2.8g (with the volume ratio of solution be 1: 18), constantly stir, temperature is controlled at 70 ℃, after treating that added complexing agent and dispersion agent dissolve fully, dropping ammonia, regulating pH value is 2.5, and interpolation and liquor capacity ratio are 1: 13 dehydrated alcohol 3.8ml in prepared ammonium salt solution, and the rotary kiln sintering of putting into 1100 ℃ as ignition dope obtained ito powder in 30 minutes.
Embodiment 4, take by weighing a certain amount of pure metal In10g, (weight ratio is In: Sn=9.04 to Sn1.1062g: 1) be dissolved in 63%HNO
3In, be configured to the nitrate solution that 30ml concentration is 3.21mol/L, add successively organic complexing agent polyvinyl alcohol 3.6ml (with the volume ratio of solution be 1: 14) and polyacrylamide 5ml (with the volume ratio of solution be 1: 10); Add successively again dispersion agent citric acid 1.5g (with the volume ratio of solution be 1: 20), fructose 1.5g (with the volume ratio of solution be 1: 20), constantly stir, temperature is controlled at 70 ℃, after treating that added complexing agent and dispersion agent dissolve fully, dropping ammonia, regulating pH value is 1.5, and interpolation and liquor capacity ratio are 1: 15 dehydrated alcohol 2ml in prepared ammonium salt solution, and the rotary kiln sintering of putting into 1200 ℃ as ignition dope obtained ito powder in 30 minutes.
Claims (1)
1. an ammonium salt combustion method prepares the method for nano-ITO powder, comprises the preparation of the nitrate solution of indium and tin, adds organic complexing agent, regulates pH value and sintering circuit with ammoniacal liquor, it is characterized in that, specifically preparation section is as follows:
A, be that 99.99% indium and tin are dissolved in the analytically pure salpeter solution with purity, make the nitrate solution of concentration 1～4mol/L, wherein the weight ratio of indium and tin is 9.04: 1;
B, in nitrate solution, add organic complexing agent polyvinyl alcohol and polyacrylamide, the volume ratio of the two and nitrate solution is respectively 1: (8～15) and 1: (5～10), then add dispersion agent citric acid and fructose again, the two and nitrate solution volume ratio are 1: (15～20), stir, temperature is controlled at 40～70 ℃;
C, dropping ammonia more constantly stir with magnetic stirring apparatus, and it is fully reacted, and the pH value of regulator solution is 1～3.8;
D, the ammonium salt solution that the C operation is prepared add again with the liquor capacity ratio be 1: the dehydrated alcohol of (10～18), as ignition dope;
E, the ammonium salt solution that at last the D operation is prepared are put into 700～1200 ℃ kiln sintering 10～30 minutes, promptly obtain nano-ITO powder.
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| CN2008100583279A CN101264926B (en) | 2008-04-25 | 2008-04-25 | Method for preparing nano ITO powder by ammonia salt combustion method |
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|---|---|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102417203A (en) * | 2011-08-31 | 2012-04-18 | 广西师范大学 | Method for preparing ultrafine ITO powder by combustion synthesis process |
| CN102923765A (en) * | 2012-10-08 | 2013-02-13 | 中山大学 | Indium tin oxide (ITO) nano powder and preparation method thereof |
| JPWO2019138708A1 (en) * | 2018-01-15 | 2021-01-07 | 国立大学法人東北大学 | Method for Producing ITO Particles, Dispersion Solution and ITO Film |
| CN112591787B (en) * | 2021-02-03 | 2022-01-21 | 河南大学 | Method for preparing nano antimony doped tin oxide powder by microexplosion method |
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