CN103626229B - Method for preparing copper antimonate nano powder - Google Patents
Method for preparing copper antimonate nano powder Download PDFInfo
- Publication number
- CN103626229B CN103626229B CN201310702721.2A CN201310702721A CN103626229B CN 103626229 B CN103626229 B CN 103626229B CN 201310702721 A CN201310702721 A CN 201310702721A CN 103626229 B CN103626229 B CN 103626229B
- Authority
- CN
- China
- Prior art keywords
- solution
- analytical pure
- degrees celsius
- nano powder
- sol
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000010949 copper Substances 0.000 title claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title abstract description 8
- 239000011858 nanopowder Substances 0.000 title abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 12
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 abstract description 5
- 239000000919 ceramic Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000000843 powder Substances 0.000 abstract description 4
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 3
- 229910000410 antimony oxide Inorganic materials 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- VMKYLARTXWTBPI-UHFFFAOYSA-N copper;dinitrate;hydrate Chemical compound O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O VMKYLARTXWTBPI-UHFFFAOYSA-N 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a method for preparing copper antimonate nano powder. The method comprises the following steps: mixing antimony oxide with ethylene glycol monomethyl ether to prepare a transparent solution; dissolving copper nitrate hydrate in methanol or distilled water to prepare a solution; simultaneously and slowly adding the two solutions into a citric acid aqueous solution according to a proportion, and stirring to form sol; drying the sol in a vacuum drying box to obtain dry gel; and heat treating the dry gel in a muffle furnace to obtain the copper antimonate nano powder. The method disclosed by the invention is used for preparing the copper antimonate nano powder through a sol-gel process, the material is uniformly mixed on an atom level, the powder is prepared at a low temperature, so that the sintering temperature of copper antimonate ceramic can be reduced to be lower than 900 DEG C so as to be co-fired with silver. Furthermore, since the ceramic is sintered at a low temperature, the deformation, dispersion and oxygen vacancy defects are effectively inhibited and the electrical properties are excellent.
Description
Technical field
The present invention relates to a kind of preparation method of metaantimmonic acid copper nano body, belong to process for electroceramics field.
Background technology
Along with the develop rapidly of science and technology, the microwave ceramics of multilayered structure is applied in wave filter, duplexer, and as forming the dielectric medium of multilayer ceramic, needs lower sintering temperature, less conduction loss, and have and can apply relatively inexpensive copper or the ability of silver electrode.Recently, according to the research of people, the stibnate of binary has embodied good microwave property, has lower sintering temperature, less conduction loss, and can use relatively inexpensive electrode, is a kind of very promising microwave ceramic material.But the method preparing this stibnate powder is generally solid phase synthesis process, and the powder granularity of acquisition is larger, uneven components, and under high temperature, the valency of copper becomes unstable, causes the dielectric loss of material sharply to increase.Therefore low-temperature fabrication has become to improve the effective ways of metaantimmonic acid copper physicals.
Sinter technology of preparing with conventional high-temperature, sol gel process can realize the synthesis of material at a lower temperature, and moreover, all right crystal grain thinning, obtains the good nano-powder of purity.
Summary of the invention
The object of this invention is to provide a kind of preparation method of metaantimmonic acid copper nano body.
Concrete steps are:
(1) analytical pure weisspiessglanz is mixed according to mass ratio 1:3 ~ 10 with analytical pure ethylene glycol monomethyl ether, obtained clear solution.
(2) in the analytical pure methyl alcohol analytical pure Gerhardite of 1 mass parts being dissolved into 5 ~ 12 mass parts or distilled water, obtained solution.
(3) solution that solution obtained for step (1) and step (2) obtain is pressed Cu
2+total ion concentration and Sb
5+total ion concentration stoichiometric ratio is that the ratio of 1:2 slowly joins 65 ~ 85 degrees Celsius simultaneously, mass percent concentration is in the aqueous citric acid solution of 12 ~ 26%, keeps this temperature to stir 2 ~ 6 hours, forms colloidal sol.
(4) colloidal sol that step (3) is obtained is placed in vacuum drying oven to dry 1 ~ 8 hour under 80 ~ 180 degrees Celsius, obtains xerogel.
(5) xerogel that step (4) is obtained is placed in retort furnace, 500 ~ 700 degrees Celsius of thermal treatments 0.5 ~ 3 hour, namely obtained particle mean size was less than the metaantimmonic acid copper powder body of 80 nanometers.
The inventive method adopts sol gel process to obtain metaantimmonic acid copper nano body, the Homogeneous phase mixing of this material is obtained from atom level, and realize the preparation of this powder at a lower temperature, enable the sintering temperature of metaantimmonic acid copper pottery be reduced to less than 900 degrees Celsius, thus realize burning altogether with silver.Moreover, this pottery is owing to sintering at a lower temperature, and distortion, diffusion and Lacking oxygen defect are obtained for effective suppression, and electric property is excellent.
Embodiment
embodiment 1:
(1) analytical pure weisspiessglanz is mixed according to mass ratio 1:10 with analytical pure ethylene glycol monomethyl ether, obtained clear solution.
(2) the analytical pure Gerhardite of 1 mass parts is dissolved in the analytical pure methyl alcohol of 12 mass parts, obtained solution.
(3) solution that solution obtained for step (1) and step (2) obtain is pressed Cu
2+total ion concentration and Sb
5+total ion concentration stoichiometric ratio is that the ratio of 1:2 slowly joins 65 degrees Celsius simultaneously, mass percent concentration is in the aqueous citric acid solution of 12%, keeps this temperature to stir 6 hours, forms colloidal sol.
(4) colloidal sol that step (3) is obtained is placed in vacuum drying oven to dry 1 hour under 180 degrees Celsius, obtains xerogel.
(5) xerogel that step (4) is obtained is placed in retort furnace, 500 degrees Celsius of thermal treatments 3 hours, namely obtained particle mean size was the metaantimmonic acid copper powder body of 30 nanometers.
embodiment 2:
(1) analytical pure weisspiessglanz is mixed according to mass ratio 1:6 with analytical pure ethylene glycol monomethyl ether, obtained clear solution.
(2) the analytical pure Gerhardite of 1 mass parts is dissolved in the analytical pure distilled water of 8 mass parts, obtained solution.
(3) solution that solution obtained for step (1) and step (2) obtain is pressed Cu
2+total ion concentration and Sb
5+total ion concentration stoichiometric ratio is that the ratio of 1:2 slowly joins 75 degrees Celsius simultaneously, mass percent concentration is in the aqueous citric acid solution of 18%, keeps this temperature to stir 4 hours, forms colloidal sol.
(4) colloidal sol that step (3) is obtained is placed in vacuum drying oven and dries 4 hours at one hundred and twenty degrees centigrade, obtain xerogel.
(5) xerogel that step (4) is obtained is placed in retort furnace, 600 degrees Celsius of thermal treatments 2 hours, namely obtained particle mean size was the metaantimmonic acid copper powder body of 50 nanometers.
embodiment 3:
(1) analytical pure weisspiessglanz is mixed according to mass ratio 1:3 with analytical pure ethylene glycol monomethyl ether, obtained clear solution.
(2) the analytical pure Gerhardite of 1 mass parts is dissolved in the analytical pure distilled water of 5 mass parts, obtained solution.
(3) solution that solution obtained for step (1) and step (2) obtain is pressed Cu
2+total ion concentration and Sb
5+total ion concentration stoichiometric ratio is that the ratio of 1:2 slowly joins 85 degrees Celsius simultaneously, mass percent concentration is in the aqueous citric acid solution of 26%, keeps this temperature to stir 2 hours, forms colloidal sol.
(4) colloidal sol that step (3) is obtained is placed in vacuum drying oven to dry 1 hour under 180 degrees Celsius, obtains xerogel.
(5) xerogel that step (4) is obtained is placed in retort furnace, 700 degrees Celsius of thermal treatments 0.5 hour, namely obtained particle mean size was the metaantimmonic acid copper powder body of 65 nanometers.
Claims (1)
1. a preparation method for metaantimmonic acid copper nano body, is characterized in that concrete steps are:
(1) analytical pure weisspiessglanz is mixed according to mass ratio 1:3 ~ 10 with analytical pure ethylene glycol monomethyl ether, obtained clear solution;
(2) in the analytical pure methyl alcohol analytical pure Gerhardite of 1 mass parts being dissolved into 5 ~ 12 mass parts or distilled water, obtained solution;
(3) solution that solution obtained for step (1) and step (2) obtain is pressed Cu
2+total amount and Sb
5+total amount stoichiometric ratio is that the ratio of 1:2 slowly joins 65 ~ 85 degrees Celsius simultaneously, mass percent concentration is in the aqueous citric acid solution of 12 ~ 26%, keeps this temperature to stir 2 ~ 6 hours, forms colloidal sol;
(4) colloidal sol that step (3) is obtained is placed in vacuum drying oven to dry 1 ~ 8 hour under 80 ~ 180 degrees Celsius, obtains xerogel;
(5) xerogel that step (4) is obtained is placed in retort furnace, 500 ~ 700 degrees Celsius of thermal treatments 0.5 ~ 3 hour, namely obtained particle mean size was less than the metaantimmonic acid copper powder body of 80 nanometers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310702721.2A CN103626229B (en) | 2013-12-19 | 2013-12-19 | Method for preparing copper antimonate nano powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310702721.2A CN103626229B (en) | 2013-12-19 | 2013-12-19 | Method for preparing copper antimonate nano powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103626229A CN103626229A (en) | 2014-03-12 |
| CN103626229B true CN103626229B (en) | 2015-03-11 |
Family
ID=50207729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310702721.2A Expired - Fee Related CN103626229B (en) | 2013-12-19 | 2013-12-19 | Method for preparing copper antimonate nano powder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103626229B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439254A (en) * | 1982-04-05 | 1984-03-27 | Atlas Powder Company | Solid sensitizers in water gel explosives and method |
| US5814584A (en) * | 1995-06-30 | 1998-09-29 | The United States Of America As Represented By The Secretary Of The Army | Compound in the series A2 MeSbO6 for use as substrates barrier-dielectric layers and passivating layers in high critical temperature superconducting devices |
| CN1220551C (en) * | 2000-09-21 | 2005-09-28 | 巴斯福股份公司 | Method for producing multiple-phase multi-metal oxide materials |
| CN101302358A (en) * | 2007-05-09 | 2008-11-12 | 北京有色金属研究总院 | Waterless nano-znic antimonite sol and preparation thereof |
| CN101891460A (en) * | 2010-07-08 | 2010-11-24 | 桂林理工大学 | Method for preparing calcium copper titanium oxide powder by sol-gel method |
| CN102099298A (en) * | 2008-07-17 | 2011-06-15 | 日产化学工业株式会社 | Dispersion sol of anhydrous zinc antimonate colloidal particles in hydrophobic organic solvent and process for production of same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011001413A (en) * | 2009-06-17 | 2011-01-06 | Kuraray Co Ltd | Resin composition and method for producing the same |
-
2013
- 2013-12-19 CN CN201310702721.2A patent/CN103626229B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4439254A (en) * | 1982-04-05 | 1984-03-27 | Atlas Powder Company | Solid sensitizers in water gel explosives and method |
| US5814584A (en) * | 1995-06-30 | 1998-09-29 | The United States Of America As Represented By The Secretary Of The Army | Compound in the series A2 MeSbO6 for use as substrates barrier-dielectric layers and passivating layers in high critical temperature superconducting devices |
| CN1220551C (en) * | 2000-09-21 | 2005-09-28 | 巴斯福股份公司 | Method for producing multiple-phase multi-metal oxide materials |
| CN101302358A (en) * | 2007-05-09 | 2008-11-12 | 北京有色金属研究总院 | Waterless nano-znic antimonite sol and preparation thereof |
| CN102099298A (en) * | 2008-07-17 | 2011-06-15 | 日产化学工业株式会社 | Dispersion sol of anhydrous zinc antimonate colloidal particles in hydrophobic organic solvent and process for production of same |
| CN101891460A (en) * | 2010-07-08 | 2010-11-24 | 桂林理工大学 | Method for preparing calcium copper titanium oxide powder by sol-gel method |
Non-Patent Citations (3)
| Title |
|---|
| Crystal growth and characterization of the magnetic properties of CuSb2O6;A.V. Prokofiev et al.;《Journal of Crystal Growth》;20031231;第247卷;第457-466页 * |
| Crystal structures and cation ordering of Sr2AlSbO6 and Sr2CoSbO6;A. Faik et al.;《Journal of Solid State Chemistry》;20080403;第181卷;第1759-1766页 * |
| On the formation of M2+-Sb3+-alkoxide precursors and sol-gel processing of M-Sb oxides with M= Cr, Mn, Fe, Co, Ni, Cu and Zn;G. WESTIN et al.;《JOURNAL OF MATERIALS SCIENCE》;19921231;第27卷;第1617-1625页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103626229A (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dong et al. | High sintering activity Cu–Gd co-doped CeO2 electrolyte for solid oxide fuel cells | |
| CN104258850A (en) | Ag-doped TiO2 nano thin film and composite material containing thin film | |
| CN112165848A (en) | Composite wave-absorbing material with magnetic metal or oxide thereof loaded on graphene and preparation method thereof | |
| CN102351241B (en) | Synthetic method for giant dielectric constant material copper-calcium titanate | |
| CN103708838A (en) | New method for preparing monoclinic structure ZnZrNb2O8 microwave dielectric ceramic through low temperature sintering | |
| CN103922725B (en) | A kind of low-temperature sintering temperature-stabilized microwave medium ceramic material and preparation method thereof | |
| KR101403370B1 (en) | Manufacturing method of metal particle and metal particle using thereof, and conductive paste and shielding electromagnetic wave containing the same | |
| CN103396117A (en) | Low-temperature sintered strontium titanate energy-storing medium ceramic material and preparation method thereof | |
| CN103693957B (en) | Method for preparing microwave dielectric ceramic material | |
| CN101428856A (en) | Process for producing silver tantalate niobate nano-powder | |
| CN103626229B (en) | Method for preparing copper antimonate nano powder | |
| CN102992377A (en) | Method for preparing nano rare earth oxide through microwave sol-gel technology | |
| CN104230328B (en) | Low dielectric microwave medium ceramic material of a kind of intermediate sintering temperature and preparation method thereof | |
| CN104311003B (en) | Co-precipitation original position prepares nano barium-strontium titanate/magnesia complex phase powder | |
| Singh et al. | Effect of partial substitution of Sn4+ by M4+ (M= Si, Ti, and Ce) on sinterability and ionic conductivity of SnP2O7 | |
| CN102167580A (en) | Dielectric ceramic for high-frequency section and preparation method thereof | |
| CN102910908B (en) | Preparing process of double-perovskite Y2MNCoO6 dielectric ceramic | |
| CN104211383A (en) | Method for sintering Zn2SiO4 microwave medium ceramic at low temperature | |
| Liang et al. | Microwave-plasma induced reconstruction of silver catalysts for highly efficient oxygen reduction | |
| CN104671274A (en) | Preparation method of CuAlO<2> powder | |
| CN108054394A (en) | The synthetic method of solid oxide fuel cell strontium titanate base material | |
| CN102176355B (en) | Nano Ag particle-(Pb0.4Sr0.6)TiO3 solid solution seepage-type composite ceramic film and preparation method thereof | |
| CN107188559B (en) | A kind of high breakdown field strength and the silica-doped copper titanate cadmium giant dielectric ceramic material of energy storage density and preparation method | |
| CN103523815B (en) | A kind of CuAlO that can be adapted to solar cell 2powder making method | |
| CN104496463B (en) | The method that surfactant assisted in situ co-precipitation prepares core-shell structure nanopowder body |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Liu Laijun Inventor after: Li Guizhong Inventor after: Li Lianjing Inventor after: Zheng Shaoying Inventor before: Liu Laijun Inventor before: Li Guizhong Inventor before: Li Lianjing Inventor before: Zheng Shaoying |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150311 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |