CN1031895C - Process for controlling zinc oxide crystal whisker growth by carbon reducer - Google Patents
Process for controlling zinc oxide crystal whisker growth by carbon reducer Download PDFInfo
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- CN1031895C CN1031895C CN 94111823 CN94111823A CN1031895C CN 1031895 C CN1031895 C CN 1031895C CN 94111823 CN94111823 CN 94111823 CN 94111823 A CN94111823 A CN 94111823A CN 1031895 C CN1031895 C CN 1031895C
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- zinc
- zinc oxide
- crystal whisker
- whisker
- oxide crystal
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Abstract
The present invention relates to a technological method for growing a zinc oxide whisker for metal, ceramic and macromolecule group composite material. The present invention is characterized in that metal zinc powder serves as raw material, coke powder serves as solid reductant, the oxidization reaction speed of zinc vapor is controlled under the atmospheric condition of 950 to 1050 DEG C, and a zinc oxide crystal whisker can be prepared within 10 to 15 minutes; the crystal whisker is formed by needle-shaped single crystals with four intersection angles about 109 degrees, the length of each needle is from 10 to 100 mum, and the root diameter of each needle is from 0.2 to 2 mum. The zinc oxide crystal whisker provided by the present invention can be used for the fields of the electric conduction, the sound absorption, the cushioning, microwave absorption, the abrasion resistant improvement, etc. of metal, ceramic enhancement, macromolecule composite material.
Description
The present invention relates to the investigation of materials field, relate generally to metal, pottery and polymer-based composite preparation and Application Areas.
At present, the whisker of having prepared in the world reaches tens of kinds, and its principal item is SiC, Si
3N
4, Al
2O
3Deng.Because its preparation temperature height, for example, β-SiC whisker preparation temperature is at 1400-1500 ℃, and 2H-SiC whisker is 1900 ℃; The Processes and apparatus complexity; The influence of factors such as productivity is low costs an arm and a leg, and prospects for commercial application is remote.Above-mentioned in addition crystal whisker materials purposes is limited, only can be as the SiC whisker as metal, and the enhancing body of ceramic structure material uses.The ZnOw that PANASONIC industry company succeeds in developing, cost is lower, and has important application prospects on multi-functional field, thereby this kind material is the type material that marketable value is arranged in the present crystal whisker materials most.PANASONIC industry company prepares in the technology of ZnOw; be control ZnO whisker growth speed; metal zinc is carried out special warfare to be handled; for example melt and spray powder with pure Zn silk arc; place ion exchanged water to use mortar type mixing and kneading machine stir process 25 minutes in the Zn powder that makes; in 20 ℃ of water, placed 75 hours then; environment is an air atmosphere; removed moisture in 3 hours in 130 ℃ of dryings again; purpose is to allow the zinc powder surface form the stopping property oxide film; control whisker growth speed obtains the bigger high-quality crystal whisker materials of length-to-diameter ratio.This complex technical process has increased great amount of manpower and equipment input.In addition, PANASONIC was also tested and was adopted the sealing body of heater, and external gas mixer feeds CO
2, N
2Or water vapor and air mixture, the method for control whisker growth.But this device complexity is unsuitable for industrial production and uses.
The purpose of this invention is to provide a kind of process for controlling zinc oxide crystal whisker growth by carbon reducer, it effectively controlled oxidation zinc whisker under atmospheric condition, grow.
Purpose of the present invention is realized by following technical scheme: press 5: 1 proportioning uniform mixing with zinc powder and coke powder, be laid on container bottom, in air atmosphere, be heated to certain temperature (950 ℃～1050 ℃), solid carbon combines with oxygen in the atmosphere and generates carbonic acid gas and carbon monoxide, its reaction consumes a considerable amount of oxygen, form certain oxygen bias condition, the slow oxidation with this understanding of metallic zinc steam reaches the purpose of controlled oxidation zinc whisker growth.
The present invention's advantage compared with prior art is that zinc powder and coke powder directly are mixed into stove, utilize the oxidation in solid carbon and the atmosphere to close oxygen partial pressure in the control stove, going into the stokehold zinc powder does not need through special processing, do not require that there is dense oxidation film on the zinc powder surface, utilize common box-type furnace under atmospheric condition, can carry out in the production process, avoid all gases to go into the mixing device and the sealed stove and accessory of stokehold, thereby simplified production process greatly and reduced production cost, be more conducive to suitability for industrialized production.
The purpose of this invention is to provide a kind of easy processing method of making high-performance four acicular type zinc oxide crystal whisker material.
Technical scheme of the present invention is: with zinc powder and coke powder is mixing raw material, is laid on container bottom, is heated to certain temperature in the atmosphere, and metallic zinc steam is at CO
2, CO, O
2In the mixed atmosphere, under promptly certain oxygen bias condition, slow oxidation, deposition growing, thus form the big four acicular type zinc oxide crystal whisker of length-to-diameter ratio.
The raw material of making the ZnOw use is a metal zinc, and its fusing point is 692.7K (420 ℃).Under comparatively high temps, zinc evaporation equilibrium partial pressure is very high, contacts very easily oxidation with the oxygen of air and grows up into granular zinc oxide rapidly.In the PANASONIC industry corporate system fabrication technique, the stopping property oxide film control zinc velocity of evaporation of utilizing the zinc powder surface to form slow down the speed of growth, but its treatment process is comparatively complicated.The present invention adopts the solid carbon reductive agent, oxygen partial pressure in the control stove, thus obtained better growth effect.
Fig. 1 is the thermodynamic principles figure of ZnO whisker growth of the present invention.
Fig. 2 is a ZnO whisker component X PS collection of illustrative plates.
Fig. 3 is a ZnO whisker polymer SEM shape appearance figure.
Below in conjunction with accompanying drawing the present invention is further described: Fig. 1 is the thermodynamic principles figure of Atmosphere Control, is found out by figure, and solid carbon combines with oxygen and generates carbonic acid gas, and the reactive system free energy is minimum, and reaction expends a considerable amount of oxygen.Secondly, combine the oxidizing reaction ability that the free energy of reaction that generates carbon monoxide also is lower than zinc fume or solid zinc with oxygen at 950 ℃ of above solid carbons of (about 1220K) temperature, so further reduce the oxygen partial pressure in the furnace atmosphere, help the growth of ZnOw.As can be seen from Figure 1, be higher than 950 ℃, solid carbon helps the formation of weak oxide atmosphere, thereby the speed of growth of controlled oxidation zinc whisker obtains the big whisker of length-to-diameter ratio.
Fig. 2 is the whisker composition spectrogram of measuring at XSAM-800 Electron Energy Disperse Spectroscopy (XPS), only occurs strong Zn (2p) peak among the figure, and 0 (IS) peak shows that this material is the ZnOw material of based on very high purity.
Fig. 3 is a ZnO whisker polymer scanning electron microscope shape appearance figure.ZnOw is made up of four whiskers bodies of middle mind-set three-dimensional unfolded as seen from the figure, and the length of every pin is 10-100 μ m, and angle is approximate 109 ° between per two adjacent needles of base diameter 0.2-2 μ m.For improving whisker morphology photograph sharpness, this sample carried out vacuum metallizing to be handled, and the white blocks sheet on the part pin is a gold plaque.
Processing method having thus described the invention can produce high-purity and the big four acicular type zinc oxide crystal whisker of length-to-diameter ratio easily.This material is used to metal-base composites, and reinforced effects is remarkable; Make polymer composite, have strong microwave absorbing effect, have significant damping damping action simultaneously.
Embodiment
Getting 100 gram particle degree is 60-120 purpose zinc powders, sneaks into the coke powder of the same granularity of 20 grams, is laid on the bottom of container, and the container that compound is housed is placed the high temperature cabinet-type electric furnace, and under the atmospheric environment, 950-1050 ℃ were heated 10-20 minutes.Container bottom and cabinet-type electric furnace bottom grow long 20-100 μ m of pin, the ZnOw of base diameter 0.2-2 μ m.About 100 grams of whisker yield, the outward appearance loose powdery accumulation body that is white in color, the about 0.04-0.1g/cm of proportion
3, press volumetric shrinkage on time, flexible sense.Except that container bottom had a little yellow meal, microscopic examination showed that whisker growth is all right, did not have thin part particle and occurred.
Claims (1)
1. process for controlling zinc oxide crystal whisker growth by carbon reducer, be that metallic zinc is melt into granularity is 60～120 purpose zinc powders, it is 60～120 purpose coke powders that coke is ground to form granularity, it is characterized in that zinc powder and coke powder are prepared burden in 5: 1 ratio, mix, be laid on container bottom, under atmospheric condition, be heated to 950 ℃～1050 ℃ of furnace temperature, be fired into ZnOw.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94111823 CN1031895C (en) | 1994-07-05 | 1994-07-05 | Process for controlling zinc oxide crystal whisker growth by carbon reducer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94111823 CN1031895C (en) | 1994-07-05 | 1994-07-05 | Process for controlling zinc oxide crystal whisker growth by carbon reducer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1101952A CN1101952A (en) | 1995-04-26 |
| CN1031895C true CN1031895C (en) | 1996-05-29 |
Family
ID=5035654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94111823 Expired - Fee Related CN1031895C (en) | 1994-07-05 | 1994-07-05 | Process for controlling zinc oxide crystal whisker growth by carbon reducer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1031895C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086211C (en) * | 1999-04-22 | 2002-06-12 | 中国科学院金属研究所 | Process for preparing four-leg crystal whisker of zinc oxide |
| JP4171038B2 (en) * | 2006-10-31 | 2008-10-22 | 株式会社東芝 | Ultrasonic probe and ultrasonic diagnostic apparatus |
| CN105200519B (en) * | 2015-10-20 | 2017-10-31 | 唐山建华科技发展有限责任公司 | The preparation method of sepiolite four acicular type zinc oxide crystal whisker composite |
| CN105543962A (en) * | 2015-12-28 | 2016-05-04 | 江南大学 | Method for preparing zinc oxide whiskers without lead oxide aid |
| CN105926029B (en) * | 2016-05-09 | 2018-11-27 | 郑州云江科技有限公司 | A method of utilizing microwave rapid synthesis ZnOw |
| CN108505120A (en) * | 2018-04-04 | 2018-09-07 | 慈溪市嘉和新材料科技有限公司 | The production technology that zinc oxide composite crystal must be synthesized disposably |
| CN114150380B (en) * | 2021-10-29 | 2023-06-13 | 中广核研究院有限公司 | Zinc oxide crystal and preparation method thereof |
-
1994
- 1994-07-05 CN CN 94111823 patent/CN1031895C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1101952A (en) | 1995-04-26 |
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