CN1063155C - Technology for preparing hydrosol of superfine metal oxide powder - Google Patents
Technology for preparing hydrosol of superfine metal oxide powder Download PDFInfo
- Publication number
- CN1063155C CN1063155C CN97108424A CN97108424A CN1063155C CN 1063155 C CN1063155 C CN 1063155C CN 97108424 A CN97108424 A CN 97108424A CN 97108424 A CN97108424 A CN 97108424A CN 1063155 C CN1063155 C CN 1063155C
- Authority
- CN
- China
- Prior art keywords
- metal oxide
- powder
- aqueous solution
- colloidal sol
- superfine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims abstract description 54
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 21
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 229910001566 austenite Inorganic materials 0.000 claims description 6
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000013268 sustained release Methods 0.000 claims description 4
- 239000012730 sustained-release form Substances 0.000 claims description 4
- 229910017563 LaCrO Inorganic materials 0.000 claims description 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 18
- 238000001354 calcination Methods 0.000 abstract description 6
- 238000000498 ball milling Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- -1 electrons Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 238000012805 post-processing Methods 0.000 abstract 1
- 238000000859 sublimation Methods 0.000 abstract 1
- 230000008022 sublimation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- 239000000693 micelle Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention relates to a preparation method for superfine powder, particularly to a preparation technique for the superfine powder of metal oxides in the industries of ceramics, electrons, chemical industry, etc. The soluble inorganic salt of the corresponding metals of metal oxides to be prepared is prepared into a predecessor aqueous solution. A dispersing agent and a precipitation slow-releasing agent having sublimation or decomposition characteristics are added to the predecessor aqueous solution, the temperature of the predecessor aqueous solution is kept at 50 to 90 DEG C for 1 to 10 hours, and the predecessor aqueous solution forms colloidal sol; then, the colloidal sol is directly calcined for 0.5 to 4 hours at the temperature of 400 to 1200 DEG C, and the nanometer-level superfine powder of the metal oxide can be prepared. Post processing working procedures of ball milling, etc. are not needed. The obtained nanometer-level superfine powder has the characteristics of no agglomeration, high purity, high calcining property, etc.
Description
The present invention relates to a kind of preparation method of superfine powder, refer in particular to the preparation method of the superfine metal oxide powder of industries such as being widely used in pottery, electronics, chemical industry.
In known prior art, the preparation method's of superfine metal oxide powder research report, seen by retrieval: " Chinese invention patent communique " CN1088559A, " the cubic system nanocrystalline ceramics powder technology of polyoxyethylene glycol gel method synthesizing stable " and " functional materials " 1995,26 (5) P427 " ultra-fine BaTiO
3With mix yttrium and partly lead BaTiO
3The colloidal sol of pottery---gel method preparation and sign thereof ".The former adopts the organic solution of metal in its preparation process in above-mentioned public technology, carries out gelation process in organic medium, and its final product superfine metal oxide powder exists the some shortcomings part in oxide compound kind and other characteristic.The latter exists powder reuniting and needs just to obtain through post-treatment steps such as ball millings the superfine powder of the satisfactory metal oxide of particle diameter.
The objective of the invention is to study the technology of preparing of the superfine metal oxide powder that a kind of novelty is provided, it can prepare the gained powder does not have agglomeration and has high purity and high coking property feature, and powder granularity reaches nano level (nm).In preparation process, do not adopt metallorganics as precursor, do not need to carry out post-treatment steps such as ball milling yet to overcome the deficiencies in the prior art part.
Embodiment of the present invention are the precursor aqueous solution that the soluble inorganic salt of selecting for use desire to prepare the respective metal of superfine powder metal oxide is mixed with suitable concn, add the dispersion agent that 0.5～5 times of precursor equivalent has distillation or resolution characteristic: NH
4Cl, NH
4NO
3, (NH
4)
2SO
4, (NH
4)
2CO
3Or NH
4HCO
3, add precipitation sustained release dosage CO (NH with the precursor equivalent
2)
2Or NH
4OH is incubated 1～10 hour between 50～90 ℃, make it form colloidal sol, directly colloidal sol is calcined 0.5～4 hour at 400～1200 ℃ then, promptly makes the superfine powder of metal oxide.
Described metal oxide is: ZrO
2, adulterated alkaline-earth metal oxide compound and rare-earth oxide multicomponent ZrO
2, CeO
2And H
fO
2, YBaCaO and other superconducting ceramic oxide, γ-Fe
2O
3, AL
2O
3, LaCrO
3, BaTiO
3, SnO
2, TiO
2Or MgO.
Advantage of the present invention has provided a kind of simple and novel technology of preparing of method that is used for unit or multicomponent metal oxide superfine powder, the powder that obtains with the inventive method has characteristics such as no reunion, high purity and high coking property, the particle diameter that makes powder reaches nano level (nm), and can select appropriate parameters according to the different purposes of powder, obtain desired powder, no longer need through post-treatment processes such as ball millings.Because the present invention selects to have the dispersion agent of distillation or resolution characteristic, guarantee that the later powder of calcining has polymolecularity and high purity.Method of the present invention changed present prior art general in precipitation process for making steps such as the dispersed adding organic dispersing agent that better adopts of micelle, removing ionogen.Do not have the post precipitation colloidal to clean and drying process in the method for the present invention, thereby eliminated bunching, the agglomeration of the micelle that causes therefrom.
Embodiment 1:
Present embodiment is stably-doped dose of Y
2O
3The preparation of ZrO superfine powder.Be used for structured material and high temperature magnetohydrodynamic generator machine electrode and oxygen ion conductor.
With 1 part of (equivalent) ZrOCl
28H
2O (contains YCl
3, its add-on can be by powder Y
2O
3Composition converts and gets) be mixed with the aqueous solution of 0.5～4N, add 1 part of (equivalent) precipitation agent CO (NH therein
2)
2, the dispersion agent NH of 2～3 parts (equivalents)
4Cl places 90 ℃ of insulations of thermostatical water bath 1～5 hour with the reaction soln of preparing thus, can be converted into colloidal sol by gelatinization process.Colloidal sol contained in the process furnace that directly places 600～800 ℃ in crucible calcined 0.5～2 hour, the colloidal sol in the crucible promptly is decomposed into ZrO
2(Y
2O
3) powder, powder is not reunited for having, and the median size of ultra-fine grain diameter powder is less than 10nm.With this powder sintering pottery, normal pressure-sintered in 0.5 hour air through 1300 ℃, density is up to 99%, and densification temperature is than low 300～500 ℃ of common powder.
The present invention is equally applicable to prepare the ZrO of adulterated alkaline-earth metal oxide compound and rare-earth oxide
2, CeO
2And H
5O
2Ceramic powder.
Embodiment 2:
Present embodiment is preparation YBaCuO high-temperature superconductivity ceramics superfine powder, and typical oxide high-temperature superconductivity ceramics is YBa
2Cu
3O
7-x(0＜X＜1), superconduction critical temperature are greater than 77K, and its powder manufacturing processed takes by weighing YCl respectively for the stoichiometry composition by superconductivity ceramics
3, BaCl
2, CuCl
2Precursor adds the mixing solutions that water is mixed with 2～4N, adds 1 part of (equivalent) precipitation agent CO (NH in solution
2)
2, the dispersion agent NH of 1～5 part (equivalent)
4Cl.This solution is placed thermostatical water bath, 60～90 ℃ are incubated 5～10 hours, the colloidal sol that generates after reacting after 0.5～2 hour, can obtain the YBaCuO superfine powder (diameter of particle is less than 50nm) of stoichiometry composition in 600～900 ℃ of calcinings in process furnace.This powder can get high-temperature superconductor through 980 ℃ of sintering.
Present embodiment is equally applicable to the preparation of the superconducting ceramic oxide powder of other type.
Embodiment 3:
Present embodiment is preparation γ-Fe
2O
3The ferrite superfine powder.
With 1 part of (equivalent) FeCl
3Be precursor, be mixed with the solution of 2～4N, and add 1～3 part of (equivalent) NH
4The Cl dispersion agent, 1 part of (equivalent) CO (NH
2)
2Precipitation agent.Be placed on subsequently and keep in 60～90 ℃ the thermostatical water bath forming solution through gelatinization process in 5～10 hours, with colloidal sol 400～900 ℃ of scopes calcinings 1～4 hour in process furnace, can obtain high-purity γ-Fe that median size is lower than 8nm then
2O
3Powder, specific surface area is greater than 120m
2/ g, this powder is particularly suitable for making γ-Fe
2O
3Gas detecting element and the γ-Fe that is used for high performance tape
2O
3Ferrite powder.
Use the same method, can be used for preparing the ferrite powder of multiple multicomponent.
Embodiment 4:
Present embodiment is a preparation MgO superfine powder.
With MgCl
2Be precursor, be mixed with the aqueous solution of 0.5～2N concentration, in solution, add ammonium salt dispersion agent, (NH
4)
2CO
3Or NH
4NO
3, add-on is MgCl
21～5 part (equivalent).In mixed solution, add and MgCl
2Ammoniacal liquor (the NH of equivalent
4OH) precipitation agent is along with the Mg (OH) that generates
2The precipitation micelle increases, and solution forms colloidal sol gradually, places 400～600 ℃ of stoves to calcine colloidal sol and can get the MgO powder in 0.5～1 hour, and the gained diameter of particle is in 5～50nm scope, and powder does not have reunion.
Embodiment 5:
Present embodiment is preparation TiO
2Superfine powder.
With liquid TiCl
4Be precursor, adding distil water is mixed with the aqueous solution of 1N, adds ammonium salt dispersion agent (NH in solution
4)
2SO
4, add-on is TiCl
40.5～2 part (equivalent).Treat that it dissolves the back gradual slow fully and splashes into and TiCl
4The NH of equivalent
4The OH precipitation agent, Ti to be formed (OH)
4Behind the colloidal sol of micelle, colloidal sol contained in crucible place 250～900 ℃ air furnace calcining more than 0.5 hour, take out crucible and promptly get TiO
2Powder, powder reuniting intensity are less than 100MPa, and particle diameter is monodisperse system in 5～100nm scope, can be used to prepare TiO
2Pottery, BaTiO
3The interpolation constituent element of the raw material of pottery and various structural ceramics, matrix material, electronic material.
Embodiment 6:
Present embodiment is applicable to preparation Al
2O
3, LaCrO
3, BaTiO
3Or SnO
2Etc. multiple different superfine powders.
The primary process for preparing above powder is: choose suitable soluble inorganic salt (villaumite or nitrate etc.) 1 part (equivalent) and be mixed with the aqueous solution that concentration is 2～4N, add the NH of 1～5 part (equivalent)
4Cl or NH
4HCO
3CO (the NH of dispersion agent and 1 part (equivalent)
2)
2The precipitation sustained release dosage generates colloidal sol through 1～10 hour gelatinization process of 50～90 ℃ of constant temperature, and colloidal sol is carried out 400～1200 ℃ of calcinings 0.5～4 hour, can obtain nano level (nm) superfine powder.
Present embodiment is applicable to the metal oxide of such quasi-metal oxides or multicomponent: their oxyhydroxide should be water insoluble or be slightly soluble in water.
Claims (2)
1, a kind of preparation method of superfine metal oxide powder, it is characterized in that: it is that soluble inorganic salt with the respective metal of metal oxide is made into the precursor aqueous solution, add dispersion agent and precipitation sustained release dosage, between 50～90 ℃, be incubated 1～10 hour, make it form colloidal sol, directly colloidal sol was calcined 0.5～4 hour at 400～1200 ℃ then, promptly made the superfine powder of metal oxide;
Described dispersion agent is NH
4Cl, NH
4NO
3, (NH
4)
2SO
4, (NH
4)
2CO
3Or NH
4HCO
3, its add-on is the normal 0.5-5 of precursor times;
Described precipitation sustained release dosage is CO (NH
2)
2Or NH
4OH, its add-on and precursor equivalent.
2, the preparation method of superfine metal oxide powder as claimed in claim 1 is characterized in that, described metal oxide is: ZrO
2, adulterated alkaline-earth metal oxide compound and rare-earth oxide multicomponent ZrO
2, CeO, and H
fO
2, YBaCaO and other superconducting ceramic oxide, γ-Fe
2O
3, AL
2O
3, LaCrO
3, BaTiO
3, SnO
2, TiO
2Or MgO.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108424A CN1063155C (en) | 1997-02-05 | 1997-02-05 | Technology for preparing hydrosol of superfine metal oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108424A CN1063155C (en) | 1997-02-05 | 1997-02-05 | Technology for preparing hydrosol of superfine metal oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1190077A CN1190077A (en) | 1998-08-12 |
| CN1063155C true CN1063155C (en) | 2001-03-14 |
Family
ID=5170409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97108424A Expired - Fee Related CN1063155C (en) | 1997-02-05 | 1997-02-05 | Technology for preparing hydrosol of superfine metal oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1063155C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1092164C (en) * | 2000-02-16 | 2002-10-09 | 中国科学院上海硅酸盐研究所 | Preparation of superfine lead zirconate-titanate powder |
| CN1309797C (en) * | 2000-06-13 | 2007-04-11 | 广东工业大学 | Composite inorganic salt/ceramic-base heat-accumulating material and its preparing process |
| CN1328156C (en) * | 2005-10-27 | 2007-07-25 | 上海大学 | Process for preparing powder material of nano oxide |
| CN101269971B (en) * | 2007-08-06 | 2012-09-12 | 深圳市德方纳米科技有限公司 | Method of preparing nano-particle |
| CN104445393A (en) * | 2014-11-10 | 2015-03-25 | 湖北亿佳欧电子有限公司 | Organic network preparation method of ferrozirconium red zirconia nano-composite ceramic powder |
| CN104925853B (en) * | 2015-06-04 | 2016-07-06 | 天津市职业大学 | A kind of stable nano antimony-doped tin dioxide hydrosol and preparation method thereof |
| CN107555473A (en) * | 2017-09-28 | 2018-01-09 | 洛阳理工学院 | A kind of nanometer BaTiO3Raw powder's production technology |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062122A (en) * | 1990-11-08 | 1992-06-24 | 索尔维公司 | The production technique of blended metal oxide powder |
| WO1993006040A1 (en) * | 1991-09-27 | 1993-04-01 | Kodak-Pathe | Method for preparing particles of metal oxide |
| CN1124227A (en) * | 1994-03-02 | 1996-06-12 | 张振逵 | Technology and equipment for producing ultramicro metallic oxide |
-
1997
- 1997-02-05 CN CN97108424A patent/CN1063155C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062122A (en) * | 1990-11-08 | 1992-06-24 | 索尔维公司 | The production technique of blended metal oxide powder |
| WO1993006040A1 (en) * | 1991-09-27 | 1993-04-01 | Kodak-Pathe | Method for preparing particles of metal oxide |
| CN1124227A (en) * | 1994-03-02 | 1996-06-12 | 张振逵 | Technology and equipment for producing ultramicro metallic oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1190077A (en) | 1998-08-12 |
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