CN1819070A - Production of conductive nanometer fine powder - Google Patents
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- CN1819070A CN1819070A CN 200610003295 CN200610003295A CN1819070A CN 1819070 A CN1819070 A CN 1819070A CN 200610003295 CN200610003295 CN 200610003295 CN 200610003295 A CN200610003295 A CN 200610003295A CN 1819070 A CN1819070 A CN 1819070A
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Abstract
The method includes: the antimony-doped tin oxide fine powder or indium-doped tin oxide fine powder having 5-50nm gain size is made at condition of hyper gravity, and without adding acid or alkaline solubility for adjusting PH value and volatile solvent. The method for use in making antimony-doped tin oxide fine powder includes: the tin halide salt and antimony halide salt, or tin halide salt and antimony oxide are used to compose the acid liquor A in 1.5-19 mol ratio of tin to antimony, and the sodium hydrate, ammonium bicarbonate or ammonia are used to compose alkaline liquor B; the acid liquor A and alkaline liquor B are proportionally injected into the reaction vessel; after taking an instant reaction under the condition of hyper gravity, acquires yellow tin-antimony aqua mixture past; after washing, filtering, ion-exchanging and making powder by drying, it will be calcined in 550-80 DEG C for 1-6 hours, and then acquires the product with 5-50nm gain size and 102-103 omega/m<2> low surface impedance. The method for making indium-doped tin oxide fine powder is similar with the one for making antimony-doped tine oxide fine powder.
Description
Technical field
The present invention is the manufacture method of relevant a kind of conductive nanometer fine powder, refers to a kind of manufacture method of making particle diameter 5～50nm antimony tin oxide (ATO) fine powder or indium tin oxide (ITO) fine powder under the hypergravity condition especially.
Background technology
The routine fashion of production conductivity antimony tin nanometer fine powder, such as Japan Patent JP156606 (1981) or JP071822 (1982) announcement, be with butter of tin (SnCl
45H
2O) and trichloride antimony (SbCl
3) be main body, under general gravity condition, adopt chemical precipitation technology to obtain, but the granularity of made antimony tin nanometer fine powder is thin inadequately under general gravity condition, and particle size distribution is difficult to control evenly, undried is pulverized and just directly to be calcined again in manufacture process, so cause prepared antimony tin nanometer fine powder that the shortcoming of the reproducibility difference of caking appearance between reaching batch is arranged.Especially, this routine fashion must use methyl alcohol or acetone solvent again in manufacture process, has produced the solvent evaporates pollution problems again.
The routine fashion of another kind of production conductivity antimony tin nanometer fine powder, as the announcement of Japan Patent JP477317 (1992) institute, use dissolving with hydrochloric acid SnCl
45H
2O and SbCl
3, and adopt the traditional chemical depositing technology and under general gravity condition, obtain the antimony tin nanometer fine powder, there are not enough refinement of granularity and particle size distribution to be difficult to control uniform shortcoming equally.And, in processing procedure, need to use ammoniacal liquor (NH
4OH), hydrochloric acid, aqueous sodium carbonate, with the control pH value in reaction or adjust reacted antimony tin hydrate slurry pH value, technology is very loaded down with trivial details.
Conventional hypergravity equipment comprises United States Patent (USP) 4,283, No. 255, the 4th, 382, No. 045, the 4th, 382, No. 900 and the 4th, 400, No. 275, wherein, United States Patent (USP) the 4th, 283 discloses a kind of high speed rotating filling bed type equipment, is applied to alternate contact of solution-air and reaction for No. 255; For another people such as Chen Jianfeng in Chinese patent CN1116185A (1996), announcement is with RPB formula hypergravity equipment, make the method for calcium carbonate fine powder, this method characteristic is the improvement of hypergravity device, shorten the carburizing reagent time, make the refinement of calcium carbonate granule ultra micro, make particle diameter be controlled at 10～100nm.And No. the 00538817th, the novel patent in Taiwan then discloses the supergravity reactor that a plurality of porousness rotating vanes are contained in a kind of inside.
Summary of the invention
Purpose of the present invention is promptly providing a kind of manufacture method of conductive nanometer fine powder, can under the hypergravity condition, make particle diameter 5～50nm antimony tin oxide (ATO) nanometer fine powder or indium tin oxide (ITO) nanometer fine powder, and do not need to add again in addition acid-base solution and adjust the pH value, need not use any volatile solvent yet, can promote productive rate so technology is not only simplified more, and not have the solvent contamination problem of environment.
Antimony tin oxide shown in the present (ATO) nanometer fine powder method for making, be by the halogenation salt of tin and the halogenation salt of antimony, or the halogenation salt of tin and the oxide of antimony, forming tin/antimony mol ratio is 1.5～19 acid solution A, and by NaOH, carbonic hydroammonium or ammoniacal liquor are formed alkali lye B, then acid solution A and alkali lye B are injected in the supergravity reactor, adjust the acid ﹠ alkali liquid charge proportion, and after carrying out the moment reaction under the hypergravity condition, obtain the pH value stabilization at 0.8～4.8 milk yellow antimony tin hydrate slurry, again through washing filtering, ion-exchange and drying, after 1～6 hour, promptly get the low surface impedance 10 of particle diameter 5～50nm and tool 550 ℃～800 ℃ following high-temperature calcinations at last
-2～10
1Ω/m
2Antimony tin oxide (ATO) nanometer fine powder.The present invention also can be applicable to prepare indium tin oxide (ITO) nanometer fine powder.
Description of drawings
Fig. 1 is the manufacturing flow chart of antimony tin oxide (ATO) nanometer fine powder method for making shown in the present.
Fig. 2 is the structure chart of the prepared ATO nanometer fine powder of the present invention under electron microscope.
The structure chart of ATO micron fine powder under electron microscope that Fig. 3 makes for traditional coprecipitation method.
Fig. 4 is the manufacturing flow chart of indium tin oxide (ITO) nanometer fine powder method for making shown in the present.
Fig. 5 is the structure chart of ITO nanometer fine powder under electron microscope shown in the present.
Fig. 6 makes the structure chart of ITO micron fine powder under electron microscope for traditional coprecipitation method.
Fig. 7 is the prepared ATO nanometer fine powder of a present invention X-RAY diffracting spectrum.
Fig. 8 is the prepared ITO nanometer fine powder of a present invention X-RAY diffracting spectrum.
Embodiment
Under the hypergravity environment, molecular diffusion between the different sized molecules of nanometer, the mass transport process between phase and phase, all fast than the normal gravity field, particularly solution-air, liquid-liquid, liquid-solid two alternate reactions are flowed and are contacted, be higher than under hundreds of times in general gravitational field～thousands' times the hypergravity environment, great shear forces can make liquid moment tear into nano level film, silk or drop.
Conductive nanometer fine powder method for making shown in the present is to make conductive nanometer fine powder under 1～3000G hypergravity environment, does not use any volatile solvent in manufacture process, the suitable refinement of made conductive nanometer fine powder, and particle diameter is 5～50nm.
As shown in Figure 1, antimony tin oxide shown in the present (ATO) nanometer fine powder method for making comprises following each step:
A. preparing tin/antimony mol ratio is 1.5～19 acid solution A
Wherein a kind of by halogenation salt, acetate, oxalates or the oxide of tin, forming tin/antimony mol ratio with antimonide is 1.5～19 acid solution A.
For example, can select that to form tin/antimony mol ratio by the halogenation salt of the halogenation salt of tin and antimony be 1.5～19 acid solution A for use, perhaps, forming tin/antimony mol ratio by the oxide of the halogenation salt of tin and antimony is 1.5～19 acid solution A.
Wherein, optional the using of halogenation salt of tin by SnF
2, SnF
4, SnCl
2, SnCl
2.2H
2O, SnCl
4, SnCl
4.5H
2O, SnBr
2, SnBr
4, SnI
2And SnI
4The group of being formed wherein a kind of.The acetate of tin can be selected Sn (O for use
2CCH
3)
4The oxalates of tin can be selected SnC for use
2O
4The oxide of tin can be selected SnO or SnO for use
2
Antimonide comprises the halogenation salt of antimony, the acetic acid salt of antimony, the Sulfates Sb of antimony
2(SO
4)
3, antimony oxide (Sb
2O
3, Sb
2O
5), the sulfuration salt (SbS of antimony
3, Sb
2S
3), K
2(C
4H
2O
6Sb)
2.3H
2O, SbSI or Sb
2Te
3Wherein a kind of.And the optional SbF that uses of the halogenation salt of antimony
3, SbF
5, SbCl
3And SbCl
5Wherein a kind of.
For example, get antimonous oxide (Sb
2O
3) or trichloride antimony (SbCl
3) become the hydrochloric acid solution of 8～25% concentration with dissolving with hydrochloric acid; Other gets the butter of tin (SnCl of purity more than 99%
45H
2O), tri-chlorination Monobutyltin (CH
3(CH
2)
3SnCl
3) or liquid butter of tin (SnCl
4), adding water and be deployed into concentration 15～85%, both being inserted mix even one-tenth tin/antimony mol ratio in the raw material tank again is 1.5～19 acid solution A.
B. prepare alkali lye B
An amount of NaOH, carbonic hydroammonium, ammoniacal liquor, sodium carbonate, sodium acid carbonate or other alkali metal are added pure water, and to be dissolved into weight percent concentration be 10～50% alkali lye B.
C. make acid solution A and alkali lye B under the hypergravity condition, carry out the moment reaction
Respectively acid solution A and alkali lye B are injected in the hypergravity reative cell with pump, through adjusting the acid ﹠ alkali liquid charge proportion, make acid solution A and alkali lye B under the hypergravity condition, carry out the moment reaction, generate the antimony tin slurry of milk yellow, and reacted antimony tin pH value of slurry is stabilized in pH=0.8～4.8, but is preferable with pH=2～3.
D. washing filtering, ion-exchange
After the antimony tin slurry of step c left standstill cooling, add water filtration (as plate compression) circulation and clean, cycle-index is not limit, up to the filtrate electric conductivity value till below the 50 μ S/cm.
E. dry powder process and high-temperature calcination
Take out filter cake, adding water homogenisation disperses the back to remove moisture drying powder process with rotating disk drier, insert again in tube furnace or the block furnace, after being warming up to 550 ℃～800 ℃ gradually with the heating rate of 1～10 ℃/min, held temperature 1～6 hour, with phase same rate cooling cooling, promptly get blue antimony tin nanometer fine powder again.Wherein, be warming up to 700 ℃ gradually with the heating rate of 5 ℃/min after, hold temperature and be preferred embodiment in 1～6 hour, resulting blue oxide antimony sijna rice fine powder, its particle through micro-amplification as shown in Figure 2, average grain diameter is 5～50nm, specific area (BET) is 40～60g/m
2
As shown in Figure 4, indium tin oxide shown in the present (ITO) nanometer fine powder method for making, with foregoing antimony tin oxide (ATO) nanometer fine powder method for making roughly the same, wherein, the acid solution A of stanniferous/indium and alkali lye B, through the slurry pH value that generates behind the hypergravity reative cell internal reaction, do not change in time and change, with pH=7 preferred embodiment.Secondly, through behind the washing filtering, take out filter cake, after adding water homogenisation and disperseing, remove moisture drying powder process with rotating disk drier, insert again and carry out high-temperature calcination in tube furnace or the block furnace, during calcining heating rate, but preferable, 600 ℃ of air calcination of temperature 5 hours with 5 ℃/min with 1～10 ℃/min, and, then under 600～900 ℃ of temperature with N
2Gas reduction 3 hours, but with 800 ℃ be preferred embodiment, promptly make low surface impedance 10
-3～10
1Ω/m
2Blue tin indium oxide nanometer fine powder, the micro-amplification of its particle as shown in Figure 5, average grain diameter is 5～50nm.
Now enumerate following embodiment and comparative example, further illustrate technology contents of the present invention, but claim of the present invention is not only limited to the scope of embodiment.
The test type that uses: low resistance impedometer MCP-T600 (Mitsubishi Chemical)
Surface impedance (Ω/m
2) method of electrical detection: get prepared ATO of 1.0g or ITO nanometer fine powder, slowly boost to 1Kg/cm with hydraulic press
2, hold and pressed 1 minute.With four-point probe formula low resistance impedometer, get at 3 on average.
Embodiment 1
1. get antimonous oxide (Sb
2O
3) or trichloride antimony (SbCl
3) become the hydrochloric acid solution of 8～12% concentration with dissolving with hydrochloric acid; Other gets the butter of tin (SnCl of purity more than 99%
45H
2O), tri-chlorination Monobutyltin (CH
3(CH
2)
3SnCl
3) or liquid butter of tin (SnCl
4), add water and be deployed into concentration 15～85%, make tin/antimony mol ratio be respectively 9.5/0.5; 9.0/1.0; 6.0/4.0 three kinds, both are inserted among the raw material tank A, evenly mixed, become reaction acid solution A respectively
1, A
2, A
3
2. an amount of NaOH sheet alkali is added pure water and be dissolved into 10～50% concentration, inserting becomes reaction aqueous slkali B among the raw material tank B.
With pump respectively with acid solution A
1, A
2, A
3, inject in 1～3000G hypergravity reative cell with alkali lye B, adjust the acid ﹠ alkali liquid charge proportion, make reaction disposed slurry pH value stabilization 0.8.
4. reaction adds water filtration (as plate compression) circulation and cleans after disposed slurry leaves standstill cooling, and cycle-index is not limit, up to the filtrate electric conductivity value till below the 50 μ S/cm.
5. the taking-up filter cake adds water homogenisation and disperses the back to remove moisture drying powder process with rotating disk drier, inserts in tube furnace or the block furnace again, heating rate with 5 ℃/min is warming up to 600 ℃ gradually, and hold temperature after 3 hours, with phase same rate cooling cooling, promptly get blue antimony tin nanometer fine powder again.Perhaps, be warming up to 700 ℃ gradually, and hold temperature after 3 hours, with phase same rate cooling cooling, promptly get blue antimony tin nanometer fine powder again with the heating rate of 5 ℃/min.
6. the obtained antimony tin nanometer fine powder of step 5 is carried out surface impedance (Ω/m
2) electrical detection, its result is as shown in table 1.
Embodiment 2
1. get antimonous oxide (Sb
2O
3) or trichloride antimony (SbCl
3) become the hydrochloric acid solution of 12～18% concentration with dissolving with hydrochloric acid; Other gets the butter of tin (SnCl of purity more than 99%
45H
2O), tri-chlorination Monobutyltin (CH
3(CH
2)
3SnCl
3) or liquid butter of tin (SnCl
4), add water and be deployed into concentration 15～85%, make tin/antimony mol ratio be respectively three kinds of 9.5/0.5,9.0/1.0,6.0/4.0, both are inserted mixed evenly one-tenth reaction acid solution A among the raw material tank A
1, A
2, A
3
2. an amount of NaOH sheet alkali is added pure water and be dissolved into 10～50% concentration, inserting becomes reaction aqueous slkali B among the raw material tank B.
With pump respectively with acid solution A
1, A
2, A
3, inject in 1～3000G hypergravity reative cell with alkali lye B, adjust the acid ﹠ alkali liquid charge proportion, make reaction disposed slurry pH value stabilization 2.6.
4. reaction adds water filtration (as plate compression) circulation and cleans after disposed slurry leaves standstill cooling, and cycle-index is not limit, up to the filtrate electric conductivity value till below the 50 μ S/cm.
5. taking-up filter cake, adding water homogenisation disperses the back to remove moisture drying powder process with rotating disk drier, insert again in tube furnace or the block furnace, heating rate with 5 ℃/min is warming up to 600 ℃ gradually, and hold temperature after 3 hours, with phase same rate cooling cooling, promptly get blue antimony tin (ATO) nanometer fine powder again.Perhaps, be warming up to 700 ℃ gradually, and hold temperature after 3 hours, with phase same rate cooling cooling, promptly get blue antimony tin (ATO) nanometer fine powder again with the heating rate of 5 ℃/min.
6. the obtained antimony tin nanometer fine powder of step 5 is carried out surface impedance (Ω/m
2) electrical detection, its result is as shown in table 1, its particle through micro-amplification as shown in Figure 2, average grain diameter is 5～50nm.
Embodiment 3
1. get antimonous oxide (Sb
2O
3) or trichloride antimony (SbCl
3) become the hydrochloric acid solution of 18～25% concentration with dissolving with hydrochloric acid; Other gets the butter of tin (SnCl of purity more than 99%
45H
2O), tri-chlorination Monobutyltin (CH
3(CH
2)
3SnCl
3) or liquid butter of tin (SnCl
4), add water and be deployed into concentration 15～85%, make tin/antimony mol ratio be respectively 9.5/0.5; 9.0/1.0; 6.0/4.0 three kinds, both are inserted mixed evenly one-tenth reaction acid solution A among the raw material tank A
1, A
2, A
3
2. an amount of NaOH sheet alkali is added pure water and be dissolved into 10～50% concentration, inserting becomes reaction aqueous slkali B among the raw material tank B.
With pump respectively with acid solution A
1, A
2, A
3, inject in 1～3000G hypergravity reative cell with alkali lye B, adjust the acid ﹠ alkali liquid charge proportion, make reaction disposed slurry pH value stabilization 3.8.
4. reaction adds water filtration (as plate compression) circulation and cleans after disposed slurry leaves standstill cooling, and cycle-index is not limit, up to the filtrate electric conductivity value till below the 50 μ S/cm.
5. taking-up filter cake, adding water homogenisation disperses the back to remove moisture drying powder process with rotating disk drier, insert again in tube furnace or the block furnace, heating rate with 5 ℃/min is warming up to 600 ℃ gradually, and hold temperature after 3 hours, with phase same rate cooling cooling, promptly get blue antimony tin (ATO) nanometer fine powder again.Perhaps, be warming up to 700 ℃ gradually, and hold temperature after 3 hours, with phase same rate cooling cooling, promptly get blue antimony tin (ATO) nanometer fine powder again with the heating rate of 5 ℃/min.
6. the obtained antimony tin nanometer fine powder of step 5 is carried out surface impedance (Ω/m
2) electrical detection, its result is as shown in table 1.
Embodiment 4
With the way of embodiment 1, but reaction paste pH value stabilization is 4.8.Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
Embodiment 5
With the way of embodiment 1, but reaction adds water filtration (plate compression) circulation and cleans for 2 times after disposed slurry leaves standstill cooling, and test is as chloride ion (Cl
-) when not removing fully for electrical influence.
Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
Embodiment 6
Except that calcining heat is 550 ℃ and holds warm 1 hour that all the other are with the way of embodiment 2.
Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
Embodiment 7
Except that calcining heat is 550 ℃ and holds warm 6 hours that all the other are with the way of embodiment 2.
Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
Embodiment 8
Except that calcining heat is 800 ℃ and holds warm 1 hour that all the other are with the way of embodiment 2.
Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
Embodiment 9
Except that calcining heat is 800 ℃ and holds warm 6 hours that all the other are with the way of embodiment 2.
Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
Comparative example 1 (coprecipitation method)
1. get antimonous oxide (Sb
2O
3) powder becomes the hydrochloric acid solution of 8～12% concentration with dissolving with hydrochloric acid, gets the noncrystalline attitude butter of tin (SnCl of purity more than 99%
4) be deployed into concentration 15～40%, both are inserted in the reactive tank, mixed is one, speed of agitator 100RPM.
2. an amount of NaOH sheet alkali is added that pure water is dissolved into the aqueous slkali of 10～20% concentration and calculated population is long-pending.This aqueous slkali is splashed in the reactive tank under constant speed with peristaltic pump, and dropwised speed of agitator 100RPM in 2 hours.
3. after dripping off, discharging again behind the continuous stirring reaction 0.5～2 hour (preferable), speed of agitator 100RPM with 1 hour.
4. add an amount of sedimentation agent, speed of agitator 100RPM stirs, and it is clean that centrifugal filtration adds washing, circulation for several times up to the filtrate electric conductivity value till below the 50 μ S/cm.
5. taking-up filter cake, after adding the water homogenisation dispersion, remove moisture drying powder process with rotating disk drier, insert again in tube furnace or the block furnace, after being warming up to 550 ℃～800 ℃ (preferable) gradually with the heating rate of 1 ℃～10 ℃/min (5 ℃ preferable) with 700 ℃, hold 1～6 hour (preferable) of temperature, with phase same rate cooling cooling, promptly get blue antimony tin nanometer fine powder again with 3 hours.
6. the obtained antimony tin micro mist of step 5 is carried out surface impedance (Ω/m
2) electrical detection, its result is as shown in table 1, and the micro-amplification of its particle is as shown in Figure 6.
Comparative example 2 (coprecipitation method)
With the way of comparative example 1, but sintering temperature changes 700 ℃ into, and all the other are identical.
Obtained antimony tin nanometer fine powder is through surface impedance (Ω/m
2) result of electrical detection is as shown in table 1.
(the synthetic ATO powder of 1～3000G) method and chemical co-precipitation method is (impedance, Ω/m electrically for table 1 hypergravity
2) relatively:
| ATO | Synthetic method | pH | Whether variable color of solution? does ICP measure ion? | Sintering temperature ℃ * hour | Impedance Ω/m 2 | ||
| Sn/Sb 9.5/0.5 | ?Sn/Sb ?9.0/1.0 | Sn/Sb 6.0/4.0 | |||||
| Embodiment 1 | Hypergravity | 0.8 | Variable color contains Sn 4+Sb 3+ | 600×3 | 3.1 | ?3.3 | 5.3 |
| Variable color contains Sn 4+Sb 3+ | 700×3 | 2.8 | ?3.0 | 4.9 | |||
| Embodiment 2 | Hypergravity | 2.6 | Do not have | 600×3 | 4.6 | ?5.8 | 6.9 |
| Do not have | 700×3 | 2.9 | ?3.2 | 5.5 | |||
| Embodiment 3 | Hypergravity | 3.8 | Do not have | 600×3 | 7.0 | 7.2 | 8.1 |
| Do not have | 700×3 | 5.1 | 5.9 | 6.7 | |||
| Embodiment 4 | Hypergravity | 4.8 | Do not have | 600×3 | 2.3 | 2.4 | 2.6 |
| Do not have | 700×3 | 2.0 | 2.0 | 2.5 | |||
| Embodiment 5 (Cl -) | Hypergravity | 2.6 | Do not have | 600×3 | 4.9 | 6.1 | 7.2 |
| Do not have | 700×3 | 3.2 | 3.9 | 5.9 | |||
| Embodiment 6 | Hypergravity | 2.6 | Do not have | 550×1 | 5.0 | 6.3 | 7.5 |
| Embodiment 7 | Hypergravity | 2.6 | Do not have | 550×6 | 4.7 | 5.5 | 6.3 |
| Embodiment 8 | Hypergravity | 2.6 | Do not have | 800×1 | 3.0 | 3.2 | 5.6 |
| Embodiment 9 | Hypergravity | 2.6 | Do not have | 800×6 | 2.6 | 3.2 | 5.3 |
| Comparative example 1 | Coprecipitation method | 2.6 | Do not have | 600×3 | 4.9 | 5.3 | 7.3 |
| Comparative example 2 | Coprecipitation method | 2.6 | Do not have | 700×3 | 4.5 | 5.1 | 7.1 |
Comparative result
1. comparison sheet 1 each embodiment, (the ATO nanometer fine powder that makes under 1～3000G) condition through adjusting the charge proportion of acid solution and alkali lye, makes reaction disposed slurry pH value stabilization 3.8 or when following, and the ATO nanometer fine powder has the surface impedance (Ω/m of excellence at hypergravity
2).
2. after embodiment 1 reaction paste leaves standstill 3 hours, supernatant liquid has and turns brown, contain tin, antimony ion composition through instrument (ICP) analysis, after the obviously visible reaction reverse dissolution phenomenon is arranged, this is due to the pH=0.8 strong acid, though its powder surface impedance is lower slightly than embodiment 2, yield is lower than 1/2 amount of embodiment 2.
3. comparison sheet 1 each embodiment, (the ATO nanometer fine powder that makes under 1～3000G) condition, under the condition of identical synthetic pH value, the ATO nanometer fine powder is through surface impedance (Ω/m of 3 hours of 700 ℃ of following sintering of excess temperature at hypergravity
2), be better than through 600 ℃ of following sintering of excess temperature 3 hours.
4. under identical synthesis condition, the embodiment 5 of table 1 is because of washing times deficiency when (containing chloride ion), the surface impedance (Ω/m of prepared ATO nanometer fine powder
2) higher.
5. the embodiment 5 by table 1 learns, under synthesis condition pH=4.8, the surface impedance of prepared ATO nanometer fine powder is higher, and other each embodiment is in synthesis condition pH=2～3 time, the surface impedance (Ω/m of prepared ATO nanometer fine powder
2) preferable.
6. the embodiment 2,5 of comparison sheet 1, and 6～9 can learn the surface impedance (Ω/m of ATO nanometer fine powder
2) be subjected to the influence of sintering temperature and duration, that is, low and duration of sintering temperature more in short-term, the surface impedance (Ω/m of prepared ATO nanometer fine powder
2) higher, higher and duration of sintering temperature is when longer, the surface impedance (Ω/m of prepared ATO nanometer fine powder
2) lower, but sintering temperature and time the surface is merged, form granule, it is big that average grain diameter becomes.
The hypergravity method for making of ITO (Indium Tin Oxide) nanometer fine powder
Embodiment 10
1. dispose acid solution A ': get the above indium grain (In) of purity 4N, and become the In (NO of 8～25% concentration with hot concentrated or dissolving with hydrochloric acid
3)
3Solution or inidum chloride (InCl
3) solution; But to be dissolved into the In (NO of 18% concentration
3)
3Solution or inidum chloride (InCl
3) solution is preferred embodiment;
Other gets the above butter of tin (SnCl of purity 99%
45H
2O), tri-chlorination Monobutyltin (CH
3(CH
2)
3SnCl
3) or liquid butter of tin (SnCl
4), add the butter of tin solution that water is deployed into concentration 15～85% (55% is preferable);
Both are inserted among raw material tank T1, T2, the T3, make the indium/tin mol ratio in each raw material tank be respectively 9.5/0.5; 9.0/1.0; 6.0/4.0 three kinds, evenly mixed, become reaction acid solution A ' respectively
1, A '
2, A '
3
2. configuration alkali lye B: get an amount of NaOH sheet alkali and add pure water and be dissolved into 10～50% concentration, inserting becomes reaction aqueous slkali B among the raw material tank T4.
3. respectively with the acid solution A ' among raw material tank T1, T2, the T3
1, A '
2, A '
3, and alkali lye B among the raw material tank T4, inject simultaneously in 1～3000G hypergravity reative cell with pump, adjust the acid ﹠ alkali liquid charge proportion, make reaction disposed slurry pH value stabilization 5.
4. reaction adds water filtration (as plate compression) circulation and cleans after disposed slurry leaves standstill cooling, and cycle-index is not limit, up to the filtrate electric conductivity value till below the 50 μ S/cm.
5. the taking-up filter cake adds water homogenisation and disperses the back to remove moisture drying powder process with rotating disk drier.
6. insert in the tube furnace, with the heating rate of 1～10 ℃/min (5 ℃ are preferable), 600 ℃ of air calcination 5 hours, 600～900 ℃ of (800 ℃ are preferable) N
21～4 hour (3 hours preferable) of gas reduction promptly gets the synthetic blue oxide indium sijna rice fine powder (ITO) of overweight force method.
7. the obtained ITO micro mist of step 6 is carried out surface impedance (Ω/m
2) electrical detection, its result is as shown in table 2.
Embodiment 11
Adjust the acid ﹠ alkali liquid charge proportion, make reaction disposed slurry pH value stabilization 7, all the other steps together
Embodiment 10.
Embodiment 12
Adjust the acid ﹠ alkali liquid charge proportion, make reaction disposed slurry pH value stabilization 10, all the other steps are with embodiment 10.
The comparative example of embodiment 11 (coprecipitation method)
1. dispose acid solution A ': get indium grain (In is more than the purity 4N) becomes 8～25% concentration with hot concentrated or dissolving with hydrochloric acid indium nitrate In (NO
3)
3Or inidum chloride InCl
3Solution; Other gets the butter of tin (SnCl of purity more than 99%
45H
2O), tri-chlorination Monobutyltin (CH
3(CH
2)
3SnCl
3) or liquid butter of tin (SnCl
4), add water and be deployed into concentration 15～85% butter of tin solution;
Both are inserted among raw material tank T1, T2, the T3, make the indium/tin mol ratio in each raw material tank be respectively 9.5/0.5; 9.0/1.0; 6.0/4.0 three kinds, evenly mixed, become reaction acid solution A ' respectively
1, A '
2, A '
3
2. configuration alkali lye B: get an amount of NaOH sheet alkali and add pure water and be dissolved into 10～50% concentration, inserting becomes reaction aqueous slkali B among the raw material tank T4.
Insert an amount of pure water in the reactive tank earlier, respectively with the acid solution A ' among raw material tank T1, T2, the T3
1, A '
2, A '
3, and alkali lye B among the raw material tank T4, injecting reactive tank simultaneously with peristaltic pump, the reactive tank speed of agitator is 400RPM, adjusts the acid ﹠ alkali liquid charge proportion, makes reaction disposed slurry pH value stabilization 7.
3. after dripping off, discharging again behind the continuous stirring reaction 0.5～2 hour (preferable) with 1 hour, speed of agitator still is 400RPM.
4. reaction adds water filtration (as plate compression) circulation and cleans after disposed slurry leaves standstill cooling, and cycle-index is not limit, up to the filtrate electric conductivity value till below the 50 μ S/cm.
5. the taking-up filter cake adds water homogenisation and disperses the back to remove moisture drying powder process with rotating disk drier.
6. insert tube furnace, with the heating rate of 1～10 ℃/min (5 ℃ are preferable), 600 ℃ of air calcination 5 hours, 600～900 ℃ of N
23 hours (800 ℃ preferable) of gas reduction promptly gets the synthetic blue oxide indium sijna rice fine powder (ITO) of coprecipitation method.
The tin indium oxide nanometer fine powder obtained to step 7 carries out surface impedance (Ω/m
2) electrical detection, its result is as shown in table 2, the micro-amplification of its particle such as Fig. 6.
Table 2
| ITO | Synthetic method | pH | Sintering temperature ℃ * hour | Impedance Ω/m 2 | ||
| ?In/Sn ?9.5/0.5 | ?In/Sn ?9.0/1.0 | ?In/Sn ?6.0/4.0 | ||||
| Embodiment 10 | Hypergravity | 5.2 | 600×5in?air 800×3in?N 2 | ?7.4×10 -3 | ?8.7×10 -1 | ?9.7×10 -1 |
| Embodiment 11 | Hypergravity | 7.3 | 600×5in?air 800×3in?N 2 | ?3.5×10 -3 | ?1.7×10 -1 | ?9.2×10 -1 |
| Embodiment 12 | Hypergravity | 10.1 | 600×5in?air 800×3in?N 2 | ?4.1×10 -3 | ?2.6×10 -1 | ?1.2×10 -2 |
| Embodiment 11 comparative examples | Coprecipitation method | 7.3 | 600×5in?air 800×3in?N 2 | ?8.8×10 -3 | ?7.6×10 -1 | ?2.1×10 -2 |
Claims (9)
1, a kind of manufacture method of conductive nanometer fine powder comprises following each step:
A. allocate tin/antimony mol ratio and be 1.5～19 or indium/tin mol ratio be 1.5～19 acid solution A;
B. after adding pure water dissolving with an amount of NaOH, carbonic hydroammonium, ammoniacal liquor, sodium carbonate, sodium acid carbonate or other alkali metal, be deployed into weight percent concentration and be 10～50% alkali lye B;
C. the alkali lye B that makes the acid solution A of step a and step b generates antimony tin slurry or indium tin slurry after the reaction of following moment of 1～3000G hypergravity condition;
D. after the antimony tin slurry of step c or indium tin slurry being carried out washing filtering, take out filter cake;
E. after the filter cake of steps d being added water homogenisation and disperses, remove moisture and dry powder process with rotating disk drier, insert again and carry out high-temperature calcination in tube furnace or the block furnace, wait to lower the temperature after the cooling, promptly make antimony tin oxide that particle diameter is 5～50nm (ATO) or indium tin oxide (ITO) fine powder.
2, the manufacture method of a kind of antimony tin oxide (ATO) nanometer fine powder, comprise by the halogenation salt of tin and the halogenation salt of antimony, or by the halogenation salt of tin and the oxide of antimony, forming tin/antimony mol ratio is 1.5～19 acid solution A, inject respectively in 1～3000G supergravity reactor with alkali lye B, adjust the acid ﹠ alkali liquid charge proportion, and after carrying out the moment reaction under 1～3000G hypergravity condition, obtain the pH value stabilization at 0.8～4.8 milk yellow antimony tin hydrate slurry, again through washing filtering, ion-exchange and drying, after 1～6 hour, promptly get particle diameter 5～50nm and surface impedance 10 550 ℃～800 ℃ following high-temperature calcinations at last
-2～10
1Ω/m
2The antimony tin oxide nanometer fine powder.
3, manufacture method as claimed in claim 2, indication alkali lye are NaOH, carbonic hydroammonium, ammoniacal liquor, sodium carbonate, sodium acid carbonate or other alkali-metal aqueous solution, and its weight percent concentration is 10～50%.
4, manufacture method as claimed in claim 3, wherein, the pH value stabilization of obtained milk yellow antimony tin hydrate slurry is at pH=2.6, and after washing filtering, ion-exchange and drying, is warming up to 700 ℃ gradually with the heating rate of 5 ℃/min and holds temperature calcining 1～6 hour.
5, as claim 3 or 4 described manufacture methods, wherein, the halogenation salt of tin is selected from SnF
2, SnF
4, SnCl
2, SnCl
2.2H
2O, SnCl
4, SnCl
4.5H
2O, SnBr
2, SnBr
4, SnI
2And SnI
4The group of forming wherein a kind of; The halogenation salt of antimony is selected from by SbF
3, SbF
5, SbCl
3, SbCl
5, K
2(C
4H
2O
6Sb)
2.3H
2O, SbSI and Sb
2Te
3The group of forming wherein a kind of, the oxide of antimony is selected Sb for use
2O
3Or Sb
2O
5
6, the manufacture method of a kind of indium tin oxide (ITO) nanometer fine powder, comprise with strong acid dissolving solid indium, it is 1.5～19 acid solution A that the halogenation salt of this solution of indium and tin is formed indium/tin mol ratio, inject respectively in one 1～3000G supergravity reactor with alkali lye B, adjust the acid ﹠ alkali liquid charge proportion, and after carrying out the moment reaction under 1～3000G hypergravity condition, obtain the pH value stabilization at 5～10 white indium tin hydrate slurry, again through washing filtering, ion-exchange and drying, at last 550 ℃～800 ℃ air calcination 1～6 hour, 600～900 ℃ of N2 gas reduced 1～4 hour, promptly got particle diameter 5～50nm and surface impedance 10
-3～10
1Ω/m
2The indium tin oxide nano powder.
7, manufacture method as claimed in claim 6, indication alkali lye are NaOH, carbonic hydroammonium, ammoniacal liquor, sodium carbonate, sodium acid carbonate or other alkali-metal aqueous solution, and its weight percent concentration is 10～50%.
8, manufacture method as claimed in claim 7, the pH value stabilization of obtained white indium tin hydrate slurry be at pH=7, and after washing filtering and dry powder process, with the heating rate of 5 ℃/min, 600 ℃ of air calcination 5 hours, then under 800 ℃ of temperature with N
2Gas reduction 3 hours promptly gets particle diameter 5～50nm and surface impedance 10
-3～10
1Ω/m
2The indium tin oxide nano powder.
9, as claim 7 or 8 described manufacture methods, wherein, the halogenation salt of tin is optional from SnF
2, SnF
4, SnCl
2, SnCl
2.2H
2O, SnCl
4, SnCl
4.5H
2O, SnBr
2, SnBr
4, SnI
2And SnI
4The group of forming wherein a kind of.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261470A (en) * | 2014-09-25 | 2015-01-07 | 广西纳拓科技有限公司 | Preparation method of tin antimony oxide (ATO) nano powder |
| CN108456445A (en) * | 2018-01-26 | 2018-08-28 | 河北晨阳工贸集团有限公司 | A kind of reflection heat-insulating type automobile finiss and preparation method thereof |
-
2006
- 2006-02-08 CN CNB2006100032953A patent/CN100479071C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104261470A (en) * | 2014-09-25 | 2015-01-07 | 广西纳拓科技有限公司 | Preparation method of tin antimony oxide (ATO) nano powder |
| CN104261470B (en) * | 2014-09-25 | 2016-09-07 | 广西纳拓科技有限公司 | The preparation method of tin antimony oxide nano-powder |
| CN108456445A (en) * | 2018-01-26 | 2018-08-28 | 河北晨阳工贸集团有限公司 | A kind of reflection heat-insulating type automobile finiss and preparation method thereof |
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