CN104402038A - Preparation method for monodisperse nanometer ZnO pressure-sensitive ceramic powder - Google Patents
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Abstract
The invention relates to nanometer zinc oxide, especially relates to a preparation method for a monodisperse nanometer ZnO pressure-sensitive ceramic powder, and belongs to the technical field of preparation and application of electronic ceramic. According to the preparation method, sodium dodecanesulphonate (SDS) is mainly employed as a dispersant for synthesizing the nanometer composite ZnO powder so as to prepare the high-performance ZnO pressure-sensitive ceramic powder. By employing sodium dodecanesulphonate (SDS) as a dispersant for synthesizing nanometer composite ZnO, the obtained powder is relatively small in dimension, homogeneous in morphology, uniform in phase dispersion and high in powder purity, and helps to effectively improve the electric performances of the ZnO pressure-sensitive ceramic.
Description
Technical field
The present invention relates to nano zine oxide, refer in particular to a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology, belong to electronic ceramic preparation and applied technical field.
Background technology
Zinc oxide (ZnO) is the direct broad-band gap metal oxide semiconductor material (3.36V) of a kind of n-type, has high exciton binding energy (60meV), good chemistry and thermostability; Voltage-sensitive ceramic prepared by the elements such as Bi, Pr, Co, Cr, Mn of ZnO doping trace has extraordinary non-linear character; Zinc oxide pressure-sensitive ceramic principle of work is based on had volt-ampere (I-V) non-linear character, namely when voltage is lower than a certain threshold value, the resistance of voltage-sensitive ceramic is very high, be equivalent to isolator, when voltage exceedes this threshold value, resistance sharply reduces, close to conductor, because the existence of this effect, piezoresistor is widely used in overvoltage protection and voltage stabilizing aspect; Along with the quickening of industrialization paces, to the Requirement Increases of power system, require to improve, increasing of Highrise buildings and large industry equipment, rises year by year to the demand of high pressure ZnO varistor, it is also proposed higher requirement simultaneously to its performance; The advantage of high pressure ZnO varistor is that voltage gradient is high, large current characteristic good, but energy capacity is little, easily damages, and the effective ways addressed this problem are exploitation high pressure high energy type voltage dependent resistors; The raising of ZnO varistor electrical property depends primarily on the appearance and size of ZnO powder and the degree of scatter of particle, and therefore prepare pattern homogeneous, particle size is little, and the nano combined ZnO powder of good dispersity is the key point of production process.
Current making ZnO pressure-sensitive ceramic material is except solid phase method, and mainly adopt liquid phase method, liquid phase method mainly comprises the precipitator method, hydrothermal method, sol-gel method, microemulsion method etc.; Precipitator method application is the most general in these methods, because the precipitator method have convenient operation, technique is simple, is applicable to the advantages such as large scale industry production; But under normal circumstances when not adopting extra supplementary means, the nano ZnO powder dispersiveness that the precipitator method prepare is poor, and products collection efficiency is lower, granular size is uneven; Therefore, the emphasis of research at present inquires into a kind of new method
Thus obtained high performance ZnO pressure-sensitive ceramic material.
The present invention mainly adopts sodium laurylsulfonate (SDS) as dispersion agent synthesis of nano compound ZnO powder, thus obtained high performance ZnO pressure-sensitive ceramic material, sodium laurylsulfonate (SDS) is a kind of typical anion surfactant, its structure comprises hydrophilic radical sulfonic group and lipophilic group dodecyl simultaneously, this asymmetric amphiphilic structure group gives sodium laurylsulfonate property in the solution, sodium laurylsulfonate (SDS) increased activity in water is subject to the impact of extraneous factor and induced chemical reaction, this change can make surfactant activity strengthen, its oleophilic group and hydrophilic group more easily embody its hydrophilic ability in the solution, strengthen tensio-active agent and reduce capillary ability, adopt sodium laurylsulfonate (SDS) as dispersion agent synthesis of nano compound ZnO, the powder granule size obtained is less, pattern is homogeneous, thing is uniformly dispersed mutually, powder purity is high, effectively raises the electrical property of ZnO voltage-sensitive ceramic.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of ZnO pressure-sensitive ceramic material, overcome the shortcoming of conventional solid-state method and the nano combined ZnO powder existence of Liquid preparation methods, to prepare powder granule size larger with the current ZnO pressure-sensitive ceramic material of solution, and the zinc oxide pattern obtained is uneven, the problem that granular size differs, according to selecting suitable dispersant to improve ZnO powder microtexture, improve the electrical property of ZnO pressure-sensitive ceramic material.
The method applied in the present invention relates to many factors, and as the proportioning, temperature of reaction, reaction times etc. of reactant, it comprises the following steps:
1, the preparation of nano combined ZnO powder
(1) with analytically pure Zn (NO
3)
26H
2o, Bi (NO
3)
25H
2o, Co (NO
3)
26H
2o, SbCl
3,
MnCl
24H
2o, Cr (NO
3)
39H
2o is raw material, configures Zn (NO respectively
3)
2, Bi (NO
3)
2, Co (NO
3)
2, SbCl
3, MnCl
2with Cr (NO
3)
3the aqueous solution, calculates with molar content, according to the ZnO of 97%, and the Sb of 1%
2o
3, the Bi of 0.5%
2o
3, the Co of 0.5%
3o
4, the CrO of 0.5%
3proportioning mixing with the MnO of 0.5%, stirs.
(2) configure sodium dodecyl sulfate aqueous solution, added by sodium dodecyl sulfate aqueous solution in the mixing solutions prepared, heated and stirred is even, SDS and Zn (NO
3)
26H
2the ratio of the amount of O is 1 ~ 10:1.
(3) measure appropriate NaOH solution, add in mixing solutions fast, be precipitated thing, heated and stirred is even, sodium hydroxide and Zn (NO
3)
26H
2the ratio of the amount of O is 2 ~ 4:1.
(4) the powder suction filtration finally will obtained, and fully wash removal impurity with deionized water and ethanol, finally dry in vacuum drying oven.
Zn (the NO of configuration in described step 1
3)
26H
2o, Bi (NO
3)
25H
2o, Co (NO
3)
26H
2o, SbCl
3, MnCl
24H
2o concentration of aqueous solution is 1mol/L.
The concentration configuring sodium dodecyl sulfate aqueous solution in described step 2 is 4mol/L.
In described step 2, Heating temperature is 60 ~ 90 DEG C, and churning time is 30min.
Configuring sodium hydroxide solution in described step 3 is 4mol/L, and Heating temperature is 60 ~ 90 DEG C, and churning time is 2h.
Drying in described step 4 refers to dry 6h at 80 DEG C.
2, the preparation of ZnO voltage-sensitive ceramic
(1) prepare polyvinyl alcohol (PVA) solution that massfraction is 5%, add in nano combined ZnO powder, grind in mortar, with 200 object sieve granulations, under 30 ~ 80MPa, be pressed into sheet.
(2) sintered at 1050 ~ 1200 DEG C by the sheet biscuit that step (1) is obtained, under air atmosphere, be incubated 2h, temperature rate is 5 DEG C/min, and after being cooled to 200 DEG C, naturally cooling under room temperature, obtains ZnO voltage-sensitive ceramic.
(3) by the ZnO voltage-sensitive ceramic surface finish that step (2) is obtained, polishing, silver-colored, make electrode.
Material prescription provided by the invention and the nano combined ZnO powder obtained by preparation method are brown, and ZnO voltage-sensitive ceramic sheet is dark gray solid, shrinking percentage 8% ~ 15%, pressure sensitive voltage V
1mAbe 400 ~ 500V/mm, leakage current J
leakbe 1.25 ± 0.09 μ A, nonlinear factor α be (42.16 ± 0.56); Because potential gradient is relatively high, may be used for the overvoltage protection product etc. manufacturing high pressure, extra-high voltage Force system.
The present invention adopts the advantage of technique scheme to be:
nano combined ZnO particle size prepared by the method is less, and pattern is homogeneous, good dispersity.
adopt ZnO voltage-sensitive ceramic prepared by the present invention, nonlinear factor is comparatively large, and leakage current is little, meets the requirement of the overvoltage protection product of high-voltage power system.
Accompanying drawing explanation
fig. 1 is the TEM figure of nano combined ZnO powder obtained by the present invention, and as can be seen from the figure nano ZnO powder granular size is homogeneous, and better dispersed, powder granule size is 20 ~ 30nm.
Fig. 2 is the SEM figure of the ZnO voltage-sensitive ceramic obtained by the present invention, and the ZnO pressure-sensitive ceramic material compactness in figure is good, and pattern is homogeneous, and granular size is 7 ~ 9 μm.
Fig. 3 (a), (b) is respectively is the XRD figure of ZnO powder obtained by the present invention and ZnO voltage-sensitive ceramic, as can be seen from the figure after Post isothermal treatment, has new Spinel generation and Zn
7sb
2o
12phase.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described, but never limit the scope of the invention:
Embodiment 1
1, the preparation of nano combined ZnO powder
(1) Zn (NO is configured
3)
2, Bi (NO
3)
2, Co (NO
3)
2, SbCl
3, MnCl
2with Cr (NO
3)
3the aqueous solution, (strength of solution is 1M) calculates with molar content, according to the ZnO of 97%, the Sb of 1%
2o
3, the Bi of 0.5%
2o
3, Co
3o
4, CrO
3, the proportioning mixing of MnO, stirs.
(2) measure 20mL sodium laurylsulfonate (SDS) aqueous solution, add in the mixing solutions prepared, 90 DEG C of heated and stirred 30min.
(3) prepare the NaOH solution of 4M, measure 30mL and add fast in mixing solutions, be precipitated thing, 90 DEG C of heating in water bath, continue rapid stirring 2h.
(4) the powder suction filtration will obtained, and fully wash removal impurity with deionized water and ethanol, finally 80 DEG C of dry 6h in vacuum drying oven.
2, the preparation of ZnO voltage-sensitive ceramic
(1) configuration quality mark is the polyvinyl alcohol (PVA) of 5%, adds in nano combined ZnO powder, grinds in mortar, with 200 object sieve granulations, and tabletted under 50MPa.
(2) sintered at 1050 DEG C by the sheet biscuit that step (1) is obtained, under air atmosphere, be incubated 2h, temperature rate 5 DEG C/min, after being cooled to 200 DEG C, naturally cooling under room temperature, obtains ZnO voltage-sensitive ceramic.
Embodiment 2
In the present embodiment, when preparing nano combined ZnO powder, each component weight in the same manner as in Example 1, add 20mL sodium laurylsulfonate (SDS) aqueous solution, 80 DEG C of heated and stirred, add the NaOH solution of 30mL4M fast after 30min, 80 DEG C of heating in water bath, continue rapid stirring 2h, above-mentioned gained throw out filtering and washing is removed impurity, finally 80 DEG C of dry 6h in vacuum drying oven; Above-mentioned materials adopts the processing step identical with embodiment 1, and be prepared into ZnO voltage-sensitive ceramic, its difference is that ceramic sintering temperature is 1100 DEG C.
Embodiment 3
In the present embodiment, when preparing nano combined ZnO powder, each component weight in the same manner as in Example 1, add 20mL sodium laurylsulfonate (SDS) aqueous solution, 70 DEG C of heated and stirred, add the NaOH solution of 30mL4M fast after 30min, 70 DEG C of heating in water bath, continue rapid stirring 2h, above-mentioned gained throw out filtering and washing is removed impurity, finally 80 DEG C of dry 6h in vacuum drying oven; Above-mentioned materials adopts the processing step identical with embodiment 1, and be prepared into ZnO voltage-sensitive ceramic, its difference is that ceramic sintering temperature is 1150 DEG C.
Embodiment 4
In the present embodiment, when preparing nano combined ZnO powder, each component weight in the same manner as in Example 1, add 20mL sodium laurylsulfonate (SDS) aqueous solution, 60 DEG C of heated and stirred, add the NaOH solution of 30mL4M fast after 30min, 60 DEG C of heating in water bath, continue rapid stirring 2h, above-mentioned gained throw out filtering and washing is removed impurity, finally 80 DEG C of dry 6h in vacuum drying oven; Above-mentioned materials adopts the processing step identical with embodiment 1, and be prepared into ZnO voltage-sensitive ceramic, its difference is that ceramic sintering temperature is 1050 DEG C.
Embodiment 5
In the present embodiment, when preparing nano combined ZnO powder, each component weight in the same manner as in Example 1, add 20mL sodium laurylsulfonate (SDS) aqueous solution, 90 DEG C of heated and stirred, add the NaOH solution of 30mL4M fast after 30min, 90 DEG C of heating in water bath, continue rapid stirring 2h, above-mentioned gained throw out filtering and washing is removed impurity, finally 80 DEG C of dry 6h in vacuum drying oven; Above-mentioned materials adopts the processing step identical with embodiment 1, and be prepared into ZnO voltage-sensitive ceramic, its difference is that ceramic sintering temperature is 1200 DEG C.
Claims (8)
1. a dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology, comprises configuration Zn (NO
3)
2, Bi (NO
3)
2, Co (NO
3)
2, SbCl
3, MnCl
2with Cr (NO
3)
3the aqueous solution, carry out being mixed to get the step of mixing solutions, NaOH joined in mixing solutions the step preparing dispersed nano ZnO voltage-sensitive ceramic powder, it is characterized in that: before NaOH is joined in mixing solutions, sodium laurylsulfonate is joined in mixing solutions, make the dispersed nano ZnO voltage-sensitive ceramic powder granule size of follow-up preparation less, be 20 ~ 30nm, pattern is homogeneous, thing is uniformly dispersed mutually.
2. a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology as claimed in claim 1, is characterized in that step is as follows:
(1) Zn (NO is configured respectively
3)
2, Bi (NO
3)
2, Co (NO
3)
2, SbCl
3, MnCl
2with Cr (NO
3)
3the aqueous solution, calculates with molar content, according to the ZnO of 97%, and the Sb of 1%
2o
3, the Bi of 0.5%
2o
3, the Co of 0.5%
3o
4, the CrO of 0.5%
3proportioning mixing with the MnO of 0.5%, stirs;
(2) configure sodium dodecyl sulfate aqueous solution, joined by sodium dodecyl sulfate aqueous solution in the mixing solutions prepared, heated and stirred is even, SDS and Zn (NO
3)
26H
2the ratio of the amount of O is 1 ~ 10:1;
(3) measure appropriate NaOH solution, add in mixing solutions fast, be precipitated thing, heated and stirred is even, sodium hydroxide and Zn (NO
3)
26H
2the ratio of the amount of O is 2 ~ 4:1;
(4) the powder suction filtration finally will obtained, and fully wash removal impurity with deionized water and ethanol, finally dry in vacuum drying oven.
3. a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology as claimed in claim 2, is characterized in that: the Zn (NO of configuration in described step 1
3)
26H
2o, Bi (NO
3)
25H
2o, Co (NO
3)
26H
2o, SbCl
3, MnCl
24H
2o concentration of aqueous solution is 1mol/L.
4. a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology as claimed in claim 2, is characterized in that: configuring sodium dodecyl sulfate aqueous solution concentration in described step 2 is 4mol/L.
5. a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology as claimed in claim 2, it is characterized in that: in described step 2, Heating temperature is 60 ~ 90 DEG C, churning time is 30min.
6. a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology as claimed in claim 2, is characterized in that: configuring sodium hydroxide solution in described step 3 is 4mol/L, and Heating temperature is 60 ~ 90 DEG C, and churning time is 2h.
7. a kind of dispersed nano ZnO voltage-sensitive ceramic raw powder's production technology as claimed in claim 2, is characterized in that: the drying in described step 4 refers to dry 6h at 80 DEG C.
8. adopt the method for dispersed nano ZnO voltage-sensitive ceramic powder making ZnO voltage-sensitive ceramic as claimed in claim 1, described ZnO voltage-sensitive ceramic is dark gray solid, shrinking percentage 8% ~ 15%, pressure sensitive voltage V
1mAbe 400 ~ 500V/mm, leakage current J
leakbe 1.25 ± 0.09 μ A, nonlinear factor α be (42.16 ± 0.56); It is characterized in that step is as follows:
(1) prepare polyvinyl alcohol (PVA) solution that massfraction is 5%, add in nano combined ZnO powder, grind in mortar, with 200 object sieve granulations, under 30 ~ 80MPa, be pressed into sheet;
(2) sintered at 1050 ~ 1200 DEG C by the sheet biscuit that step (1) is obtained, under air atmosphere, be incubated 2h, temperature rate is 5 DEG C/min, and after being cooled to 200 DEG C, naturally cooling under room temperature, obtains ZnO voltage-sensitive ceramic;
(3) by the ZnO voltage-sensitive ceramic surface finish that step (2) is obtained, polishing, silver-colored, make electrode.
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|---|---|---|---|
| CN201410582462.9A CN104402038A (en) | 2014-10-28 | 2014-10-28 | Preparation method for monodisperse nanometer ZnO pressure-sensitive ceramic powder |
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| CN111205084A (en) * | 2020-01-19 | 2020-05-29 | 常州市创捷防雷电子有限公司 | Preparation method of silicon oxide coated modified ZnO voltage-sensitive ceramic material |
| CN111217601A (en) * | 2020-01-19 | 2020-06-02 | 常州市创捷防雷电子有限公司 | Preparation method of monodisperse ZnO composite powder |
| JPWO2021029421A1 (en) * | 2019-08-15 | 2021-09-13 | Ｊｆｅミネラル株式会社 | Zinc oxide powder and zinc oxide sintered body for producing zinc oxide sintered body, and a method for producing these. |
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| CN111205084A (en) * | 2020-01-19 | 2020-05-29 | 常州市创捷防雷电子有限公司 | Preparation method of silicon oxide coated modified ZnO voltage-sensitive ceramic material |
| CN111217601A (en) * | 2020-01-19 | 2020-06-02 | 常州市创捷防雷电子有限公司 | Preparation method of monodisperse ZnO composite powder |
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