CN100420632C - Method for synthesizing zinc oxide nano micro pin - Google Patents
Method for synthesizing zinc oxide nano micro pin Download PDFInfo
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- CN100420632C CN100420632C CNB2007100194153A CN200710019415A CN100420632C CN 100420632 C CN100420632 C CN 100420632C CN B2007100194153 A CNB2007100194153 A CN B2007100194153A CN 200710019415 A CN200710019415 A CN 200710019415A CN 100420632 C CN100420632 C CN 100420632C
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- zinc oxide
- oxide nano
- nano micro
- micro pin
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title abstract description 3
- 230000002194 synthesizing effect Effects 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004246 zinc acetate Substances 0.000 claims abstract description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 21
- 238000010189 synthetic method Methods 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001507 sample dispersion Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000000137 annealing Methods 0.000 abstract description 5
- 239000000843 powder Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- TUVNXTMEJRDYEE-UHFFFAOYSA-N CCC(C)[N+]([O-])=C Chemical compound CCC(C)[N+]([O-])=C TUVNXTMEJRDYEE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001239 high-resolution electron microscopy Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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Abstract
The invention discloses a making method of nanometer micro-pin shaped zinc oxide, which comprises the following steps: dissolving zinc acetate solution into ethandiol to form solution with density at 2-15 mmol/L; stirring through magnetic force; reacting under 130-200 deg.c for 30-120 min; centrifuging to separate product; washing the separated product through abluent for 3-5 times; obtaining the product; allocating abluent with carbinol, alcohol, propanol, water or their composite liquid; reserving sample in the alcohol or at dried powder pattern; annealing to obtain the product powder.
Description
One, technical field
The present invention relates to a kind of chemical synthesis process, a kind of specifically zinc oxide synthetic method that is the nano micro pin form.
Two, background technology
It is " the most promising material of 21 century " that nano material is described as, and has become the focus of current material area research.Wherein nano zine oxide is again a kind of Multifunction, multi-usage, the high performance fine product of developing in recent years, is playing the part of a kind of role of irreplaceable type functional materials in many instances, and market demand also increases thereupon.This mainly is because the size of particles of nano zine oxide (1-100nm) is little, specific surface area is big, has surface effects, volume effect, quantum size effect, thereby nano zine oxide is at magnetic, light,, heat, there is the incomparable property of general zinc oxide product aspects such as sensitivity, physics with a series of excellences, chemical property, at rubber, weaving, daily-use chemical industry, fine ceramics, ultraviolet screener, piezoelectric, photoelectric material, the efficient catalytic material, magneticsubstance, numerous aspects such as transmitter and absorbing material have a wide range of applications, and its application and development prospect is very wide.At present the monocrystalline or the polycrystalline of the nanometer of variform or micron zinc oxide are synthesized out, comprise nanometer rod, nano wire, nanotube, nanometer octahedron, (little) ball etc. of receiving, yet it is synthetic still to find no the zinc oxide of nano micro pin form.
Two, summary of the invention
Technical problem to be solved by this invention provides the processing method that a kind of preparation has good monodispersity and is the zinc oxide of this specific form of nano micro pin.
The synthetic method of zinc oxide nano micro pin of the present invention is characterized in that it may further comprise the steps:
1) zinc acetate is dissolved in formation 2-15 millimolar concentration solution in the ethylene glycol, in airtight vial or in the vial that uncovered water-cooled refluxes, react, adopt magnetic agitation in the reaction process, temperature of reaction is 130-200 ℃, and the reaction times is 30-120 minute;
2) resultant of reaction adopts centrifuging to separate and obtains isolate;
3) use clean-out system to clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample.
Above-mentioned steps 3) clean-out system in is the mixed solution of methyl alcohol or ethanol or propyl alcohol or water or methyl alcohol, ethanol, third alcohol and water.
Above-mentioned steps 3) the zinc oxide nano micro pin sample of Huo Deing can be dispersed in the ethanol and preserve, and also can obtain the zinc oxide nano micro pin powdered sample 60-100 ℃ of oven dry down.Also can obtain the zinc oxide nano micro pin powdered sample of high-crystallinity 300-600 ℃ of annealing 1-2 hour.
The present invention has successfully prepared the zinc oxide nano micro pin with good monodispersity and specific form.The synthesis temperature of this solution method technology is low, technology is simple, synthetic product purity height, safety pin is formed by 5-15 is nanocrystalline, length is between 1-3 μ m, has higher specific surface area, be easy to suitability for industrialized production, have important application prospects in fields such as fine ceramics, ultraviolet screener, piezoelectric, photoelectric material, efficient catalytic material, magneticsubstance, transmitter and absorbing materials.
Four, description of drawings
The pattern of Fig. 1, zinc oxide nano micro pin.Solution reaction is finished SEM that is kept at the zinc oxide in the ethanol (a) and HRTEM (b) photo that obtains after cleaning separation; After high temperature (300 ℃) thermal treatment, SEM of zinc oxide (c) and HRTEM (d) photo.
The X-ray diffraction result of Fig. 2, zinc oxide nano micro pin.60-100 ℃ of oven dry down, the XRD figure that obtains the zinc oxide nano micro pin powdered sample is composed (a); 400 ℃, after the annealing in 1 hour, the XRD figure spectrum (b) of zinc oxide nano micro pin powdered sample.
Five, embodiment
Embodiment 1: zinc acetate is dissolved in the solution that forms 10 millimolar concentrations in the ethylene glycol, solution is reacted in airtight vial, temperature of reaction is 170 ℃, and magnetic agitation was reacted the beginning back about 10 minutes simultaneously, and solution becomes white opacity liquid by clarification.Reaction continues to finish reaction after 120 minutes.Adopt centrifuging (2000-3000rpm) to separate resultant of reaction and obtain isolate; Use methyl alcohol to clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample as clean-out system.Afterwards sample dispersion is preserved in ethanol.
Embodiment 2: zinc acetate is dissolved in the solution that forms 2 millimolar concentrations in the ethylene glycol, solution is reacted in the vial that uncovered water-cooled refluxes, and temperature of reaction is 180 ℃, simultaneously magnetic agitation, about 7 minutes of reaction beginning back, solution becomes white opacity liquid by clarification.Reaction continues to finish reaction after 60 minutes.Resultant of reaction adopts centrifuging (2000-3000rpm) to separate and obtains isolate; Use ethanol to clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample as clean-out system.The sample that obtains is dried down at 60-100 ℃, obtain the zinc oxide nano micro pin powdered sample.
Embodiment 3: zinc acetate is dissolved in the solution that forms 15 millimolar concentrations in the ethylene glycol, solution is reacted in airtight vial, temperature of reaction is 130 ℃, and magnetic agitation was reacted the beginning back about 20 minutes simultaneously, and solution becomes white opacity liquid by clarification.Reaction continues to finish reaction after 120 minutes.Resultant of reaction adopts centrifuging (2000-3000rpm) to separate and obtains isolate; Use propyl alcohol to clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample as clean-out system.The sample that obtains was annealed 2 hours at 300 ℃, obtain the zinc oxide nano micro pin powdered sample of high-crystallinity.
Embodiment 4: zinc acetate is dissolved in the solution that forms 10 millimolar concentrations in the ethylene glycol, solution is reacted in airtight vial, temperature of reaction is 200 ℃, and magnetic agitation was reacted the beginning back about 5 minutes simultaneously, and solution becomes white opacity liquid by clarification.Reaction continues to finish reaction after 30 minutes.Resultant of reaction adopts centrifuging (2000-3000rpm) to separate and obtains isolate; Make water clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample as clean-out system.The sample that obtains was annealed 1 hour at 600 ℃, obtain the zinc oxide nano micro pin powdered sample of high-crystallinity.
Embodiment 5: zinc acetate is dissolved in the solution that forms 5 millimolar concentrations in the ethylene glycol, solution is reacted in airtight vial, temperature of reaction is 150 ℃, and magnetic agitation was reacted the beginning back about 16 minutes simultaneously, and solution becomes white opacity liquid by clarification.Reaction continues to finish reaction after 120 minutes.Resultant of reaction adopts centrifuging (2000-3000rpm) to separate and obtains isolate; Use the mixed solution of methyl alcohol, ethanol, third alcohol and water to clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample as clean-out system.Sample 60-100 ℃ of oven dry down with obtaining obtains the zinc oxide nano micro pin powdered sample.
The sign of zinc oxide nano micro pin
1. pattern characterizes
Adopt scanning electron microscope (SEM), transmission scanning electron microscope (TEM) and high resolution transmission scanning electron microscope (HRTEM) to carry out pattern, structural research.Fig. 1 has provided the pattern of zinc oxide nano micro pin.Fig. 1 a is that solution reaction is finished SEM that is kept at the zinc oxide in the ethanol and the HRTEM photo that obtains after cleaning separates with Fig. 1 b; After Fig. 1 c and Fig. 1 d are high temperature (300 ℃) thermal treatment, the SEM of zinc oxide and HRTEM photo.As can be seen, behind the solution reaction, (Fig. 1 a), the safety pin length L is between 1-3 μ m, and the interval S of safety pin is between 50-100nm, and the width W of safety pin line itself is between 10-30nm just to have obtained the nano micro pin of zinc oxide.HRTEM photo (Fig. 1 b) shows zinc oxide crystallization substantially, is polycrystalline structure, grain size 5-10nm, and there is the zone that crystallization is imperfect, defective is more in the part.
After 300 ℃ of high-temperature heat treatment, the form of zinc oxide nano micro pin remains unchanged (Fig. 1 c) substantially, and corresponding HRTEM photo (Fig. 1 d) shows that the crystalline quality of zinc oxide improves, and grain size is still about 5-10nm.Experimental data shows that behind 300-600 ℃ of high temperature annealing, the form of zinc oxide nano micro pin remains unchanged substantially, and crystalline quality improves.
2. structural characterization
Fig. 2 has provided the X-ray diffraction result of zinc oxide nano micro pin.Fig. 2 a is dried down for 60-100 ℃ for after reacting, and obtains the XRD figure spectrum of zinc oxide nano micro pin powdered sample.As can be seen, reacted zinc oxide nano micro pin is crystallization substantially, and it is good corresponding that the diffraction peak of XRD and standard spectrogram six sides' of zinc oxide zincblende lattce structure have, and do not have other parafacies to be found.Through 400 ℃, after the annealing in 1 hour, Fig. 2 b peak is strong obviously to be increased, and peak width at half height narrows down.According to the result of Fig. 1 high-resolution electron microscopy, the form of zinc oxide nano micro pin does not have considerable change, and grain-size does not significantly increase yet, therefore the strong increase in XRD peak, the main improvement that narrows down of peak width at half height owing to nanocrystalline quality, the minimizing of defective, the raising of the crystal boundary degree of order.According to the analytical results of thermogravimetric-differential thermal, after 400 ℃ of thermal treatments, the Zinc oxide powder sample has 6% weightlessness, this means the 60-100 ℃ of sample of oven dry down, and a small amount of planar water, ethylene glycol solvent and organic matters may also be contained in the inside.These compositions have been removed in thermal treatment, have improved the crystalline quality of zinc oxide nano micro pin powdered sample, and do not destroy its form.
3. performance characterization
The zinc oxide nano micro pin powdered sample is carried out specific surface BET to be measured.At 60-100 ℃ of sample of drying down, its specific surface area is 23-40m
2/ g; Sample after 300-600 ℃ of thermal treatment is 20-35m
2/ g demonstrates it and has higher specific surface area.By the test shows of optical transmittance and excitation spectrum, the zinc oxide nano micro pin powder has the ultraviolet absorption ability and the characteristics of luminescence preferably.
Claims (5)
1. the synthetic method of a zinc oxide nano micro pin is characterized in that it may further comprise the steps:
1) zinc acetate is dissolved in formation 2-15 millimolar concentration solution in the ethylene glycol, in airtight vial or in the vial that uncovered water-cooled refluxes, react, adopt magnetic agitation in the reaction process, temperature of reaction is 130-200 ℃, and the reaction times is 30-120 minute;
2) resultant of reaction adopts centrifuging to separate and obtains isolate;
3) use clean-out system to clean isolate 3-5 time, can obtain the zinc oxide nano micro pin sample.
2. the synthetic method of zinc oxide nano micro pin according to claim 1 is characterized in that clean-out system in the step 3) is the mixed solution of methyl alcohol or ethanol or propyl alcohol or water or methyl alcohol, ethanol, third alcohol and water.
3. the synthetic method of zinc oxide nano micro pin according to claim 1 and 2 is characterized in that the zinc oxide nano micro pin sample dispersion that step 3) obtains is preserved in ethanol.
4. the synthetic method of zinc oxide nano micro pin according to claim 1 and 2 is characterized in that the zinc oxide nano micro pin sample of step 3) acquisition is dried down at 60-100 ℃, obtains the zinc oxide nano micro pin powdered sample.
5. the synthetic method of zinc oxide nano micro pin according to claim 1 and 2 is characterized in that the zinc oxide nano micro pin sample of step 3) acquisition was annealed 1-2 hour at 300-600 ℃, obtains the zinc oxide nano micro pin powdered sample of high-crystallinity.
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| CNB2007100194153A CN100420632C (en) | 2007-01-22 | 2007-01-22 | Method for synthesizing zinc oxide nano micro pin |
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| CNB2007100194153A CN100420632C (en) | 2007-01-22 | 2007-01-22 | Method for synthesizing zinc oxide nano micro pin |
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| CN100420632C true CN100420632C (en) | 2008-09-24 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556040A (en) * | 2004-01-02 | 2004-12-22 | 清华大学 | Preparation method of nano zine oxide particles with uniform size |
| CN1565977A (en) * | 2003-07-08 | 2005-01-19 | 中国科学院过程工程研究所 | Process for preparing nano zinc oxide |
| CN1660485A (en) * | 2004-12-22 | 2005-08-31 | 华南理工大学 | Photocatalyst of zinc oxide possessing visible light activity and preparation method |
| EP1633809A2 (en) * | 2003-05-30 | 2006-03-15 | LANXESS Deutschland GmbH | Solvent-containing compositions based on polychloroprene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1633809A2 (en) * | 2003-05-30 | 2006-03-15 | LANXESS Deutschland GmbH | Solvent-containing compositions based on polychloroprene |
| CN1565977A (en) * | 2003-07-08 | 2005-01-19 | 中国科学院过程工程研究所 | Process for preparing nano zinc oxide |
| CN1556040A (en) * | 2004-01-02 | 2004-12-22 | 清华大学 | Preparation method of nano zine oxide particles with uniform size |
| CN1660485A (en) * | 2004-12-22 | 2005-08-31 | 华南理工大学 | Photocatalyst of zinc oxide possessing visible light activity and preparation method |
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