CN102030523A - Method for preparing stannic oxide-based low-residual voltage ratio voltage-sensitive ceramic material - Google Patents
Method for preparing stannic oxide-based low-residual voltage ratio voltage-sensitive ceramic material Download PDFInfo
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Abstract
The invention relates to a method for preparing a stannic oxide-based low-residual voltage ratio voltage-sensitive ceramic material, and belongs to the technical field of semiconductor materials. In the method, the voltage-sensitive ceramic material is prepared by doping Co2O3, Cr2O3 and Nb2O5 in SnO2 complexly and by a preparation process of ceramics and a preparation process of the voltage-sensitive ceramic material, wherein the residual voltage ratio is 1.86, the non-linear coefficient is 42.6, and the voltage gradient is 364.6 V/mm. Compared with the conventional SnO2-base voltage-sensitive ceramics in the prior art, the residual voltage ratio of the voltage-sensitive ceramic material is low, and the voltage-sensitive ceramic material has the high non-linear coefficient and appropriate voltage gradient; and the voltage-sensitive ceramic material has electrical characteristics such as the comparable residual voltage ratio, non-linear coefficient, the voltage gradient and the like with commercial ZnO-base voltage-sensitive ceramics, and has a simple microstructure and excellent stability simultaneously.
Description
Technical field
The present invention relates to a kind of preparation method of the low residual voltage ratio pressure-sensitive ceramic material based on tindioxide, belong to technical field of semiconductor.
Background technology
Pressure-sensitive ceramic material is meant a kind of semiconductor ceramic material that has nonlinear I-V characteristic in a certain particular voltage range.Its electrical properties can be described with following formula: J=kE
αJ is a current density in the formula; E is a strength of electric field; k is the constant relevant with material; α is that the piezoresistor that nonlinear factor (α＞1) is made according to this nonlinear I-V characteristic can be used to suppress surge current, overvoltage protection, is widely used in protecting power equipment safety, ensures the normal steady operation of electronics.
At present most widely used is the zno varistor that grows up late 1960s.The ZnO voltage-sensitive ceramic is widely used in the devices such as overvoltage protection and surge current absorption because of having good I-V non-linear character and shock-resistant ability.But because doping is big, the ZnO pressure sensitive comprises heterogeneous structure, and his temperature stability and problem of aging never obtain basic improvement, and the application in the high pressure field also is restricted.In order to seek the better pressure sensitive of performance, scientific workers are also constantly exploring new material.
Nineteen ninety-five, people such as S.A.Pianaro find a small amount of adulterated SnO first
2Stupalith have good compactness and electricity non-linear.SnO
2It is a kind of n N-type semiconductorN with rutile structure.Far different with the heterogeneous structure of ZnO pressure sensitive complexity, this material has only a kind of phase structure, has stability preferably.Only need a spot of doping, just can increase substantially its density and voltage-dependent characteristic.Compare it with ZnO and also have some other advantage simultaneously, as discovering by doping vario-property, when improving electric property, SnO
2The voltage gradient of pressure sensitive can improve tens of times by the acceptor doping of minute quantity, and this miniaturization for pressure-active element provides prerequisite, SnO
2The thermal conductivity of pressure sensitive is close to and is the twice of ZnO pressure sensitive, can improve the heat dispersion and the life-span of device, also can be because of the inequality cracking destruction under the effect of thermal stresses that is heated when releasing surge current.Scientific workers are to SnO
2The performance of voltage-sensitive ceramic has been carried out extensive, deep research, SnO in the document
2The nonlinear factor α of voltage-sensitive ceramic is many between 8～50.Though SnO
2The pressure-sensitive character of voltage-sensitive ceramic can have been accomplished with the ZnO voltage-sensitive ceramic comparable, but its surge receptivity mainly is because its residual voltage ratio is excessive not as good as the latter.The defined formula of residual voltage ratio is K
R=U
R/ U
N, promptly under specified waveform (8/20 μ s standard impulse current), pulse current density 550A/cm
2Under the ratio of residual voltage and direct current 1mA voltage.Residual voltage ratio can reflect the ability of voltage dependent resistor over-voltage more intuitively, shows the non-linear to voltage characteristic of material in big galvanic areas, and residual voltage ratio answers≤3 generally speaking, and is the smaller the better.The residual voltage ratio of the general commercial ZnO varistor that uses is about 1.7, and most of SnO
2The residual voltage ratio of voltage-sensitive ceramic is widely used in 2 research work of above residual voltage ratio at pressure sensitive, is the important indicator of investigating lightning protection voltage dependent resistor, arrester valve piece made and high-performance varistor valve performance.
In sum, also there is not SnO at present
2Pressure-sensitive ceramic material satisfies high non-linearity and two targets of low residual voltage simultaneously, also is not enough to satisfy the needs or the alternative ZnO varistor of practical application.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of the low residual voltage ratio pressure-sensitive ceramic material based on tindioxide, at existing SnO
2Pressure-sensitive ceramic material residual voltage ratio problem of higher is improved prescription, to reduce the residual voltage ratio of pressure-sensitive ceramic material, makes preparation technology simple simultaneously, easily operation.
The preparation method based on the low residual voltage ratio pressure-sensitive ceramic material of tindioxide that the present invention proposes may further comprise the steps:
(1) preparation during pressure-sensitive ceramic material in the raw material molar percentage of each component be:
SnO
2 99.39％～99.42％
Co
2O
3 0.5％
Cr
2O
3 0.02％～0.04％
Nb
2O
5 0.06％～0.07％
(2) weigh back the mixing by prescription by above-mentioned each component, in mixture, add an amount of dehydrated alcohol, ball milling 8 hours;
(3) slurry behind ball milling oven dry is 12 hours, crosses 80 mesh sieves, and the powder that obtains depresses to the disk of diameter 11.5mm, thick about 1mm at the pressure of 160MPa, obtains ceramic body;
When (4) above-mentioned ceramic body being heated to 900 ℃, be incubated 80 minutes, continue to be heated to 1300 ℃, sintering 1 hour.
The preparation method based on the low residual voltage ratio pressure-sensitive ceramic material of tindioxide that the present invention proposes is by SnO
2Composite mixed Co
2O
3, Cr
2O
3, Nb
2O
5, by ceramic preparation technology, the residual voltage ratio of the pressure-sensitive ceramic material that makes is 1.86, and nonlinear factor is 42.6, and voltage gradient is 364.6V/mm.Performance test to the stupalith of the inventive method preparation shows, than existing SnO
2Base voltage-sensitive ceramic residual voltage ratio is low, has higher non-linearity coefficient and suitable voltage gradient; Have electrology characteristics such as comparable residual voltage ratio, nonlinear factor, voltage gradient with commercial ZnO base voltage-sensitive ceramic, have simple microtexture and better stable simultaneously.Thereby its advantage at aspects such as microstructure, thermal conductivitys is manifested.
Description of drawings
Fig. 1 is the XRD figure spectrum of embodiment one to four, all has only SnO
2Crystalline phase.
Fig. 2 is the I-V curve of embodiment one to four.
Embodiment
The preparation method based on the low residual voltage ratio pressure-sensitive ceramic material of tindioxide that the present invention proposes may further comprise the steps:
(1) preparation during pressure-sensitive ceramic material in the raw material molar percentage of each component be:
SnO
2 99.39％～99.42％
Co
2O
3 0.5％
Cr
2O
3 0.02％～0.04％
Nb
2O
5 0.06％～0.07％
(2) weigh back the mixing by prescription by above-mentioned each component, in mixture, add an amount of dehydrated alcohol, ball milling 8 hours;
(3) slurry behind ball milling oven dry is 12 hours, crosses 80 mesh sieves, and the powder that obtains depresses to the disk of diameter 11.5mm, thick about 1mm at the pressure of 160MPa, obtains ceramic body;
When (4) above-mentioned ceramic body being heated to 900 ℃, be incubated 80 minutes, continue to be heated to 1300 ℃, sintering 1 hour.
In the inventive method, each raw material adopts analytically pure SnO
2(99.5%), Co
2O
3(99.0%), Nb
2O
5(99.99%), Cr
2O
3(99.5%) powder.
Below introduce the embodiment of the inventive method.
Embodiment one
Preparation during pressure-sensitive ceramic material in the raw material molar percentage of each component be:
SnO
2 99.42％
Co
2O
3 0.5％
Cr
2O
3 0.02％
Nb
2O
5 0.06％
Prepare according to following steps:
(1) raw material after balance weighs up by analysis, adds an amount of dehydrated alcohol according to prescription, with polyester jar, ZrO
2Ball was in planetary mills ball milling 8 hours;
(2) oven dry of the slurry behind the ball milling is 12 hours, crosses 80 mesh sieves, and the powder that obtains depresses to the disk of diameter 11.5mm, thick about 1mm at the pressure of 160MPa;
(3) the ceramic body Al that packs into
2O
3Crucible buries powder, adds a cover, at 1300 ℃ of following sintering 1h.
Wherein, the compressing tablet process of step (2) must not add binding agent can be dry-pressing formed, and the sintering process of step (3) must the binder removal process, and insulation 80 minutes in the time of 900 ℃, so that Co
2O
3Decomposition reaction fully carry out.
Test its performance, the XRD figure spectrum shows to have only SnO
2The principal crystalline phase structure does not have second phase, as shown in Figure 1; Residual voltage ratio is 1.82, and nonlinear factor is 13.5, and voltage gradient is 364.9V/mm, as shown in Figure 2.
Embodiment two
Preparation during pressure-sensitive ceramic material in the raw material molar percentage of each component be:
SnO
2 99.41％
Co
2O
3 0.5％
Cr
2O
3 0.03％
Nb
2O
5 0.06％
Prepare according to following steps:
(1) raw material after balance weighs up by analysis, adds an amount of dehydrated alcohol according to prescription, with polyester jar, ZrO
2Ball was in planetary mills ball milling 8 hours;
(2) oven dry of the slurry behind the ball milling is 12 hours, crosses 80 mesh sieves, and the powder that obtains depresses to the disk of diameter 11.5mm, thick about 1mm at the pressure of 160MPa;
(3) the ceramic body Al that packs into
2O
3Crucible buries powder, adds a cover, at 1300 ℃ of following sintering 1h.
Wherein, the compressing tablet process of step (2) must not add binding agent can be dry-pressing formed, and the sintering process of step (3) must the binder removal process, and insulation 80 minutes in the time of 900 ℃, so that CO
2O
3Decomposition reaction fully carry out.
Test its performance, the XRD figure spectrum shows to have only SnO
2The principal crystalline phase structure does not have second phase, as shown in Figure 1; Residual voltage ratio is 1.68, and nonlinear factor is 15.9, and voltage gradient is 391.2V/mm, as shown in Figure 2.
Embodiment three
Preparation during pressure-sensitive ceramic material in the raw material molar percentage of each component be:
SnO
2 99.39％
Co
2O
3 0.5％
Cr
2O
3 0.04％
Nb
2O
5 0.07％
Prepare according to following steps:
(1) raw material after balance weighs up by analysis, adds an amount of dehydrated alcohol according to prescription, with polyester jar, ZrO
2Ball was in planetary mills ball milling 8 hours;
(2) oven dry of the slurry behind the ball milling is 12 hours, crosses 80 mesh sieves, and the powder that obtains depresses to the disk of diameter 11.5mm, thick about 1mm at the pressure of 160MPa;
(3) the ceramic body Al that packs into
2O
3Crucible buries powder, adds a cover, at 1300 ℃ of following sintering 1h.
Wherein, the compressing tablet process of step (2) must not add binding agent can be dry-pressing formed, and the sintering process of step (3) must the binder removal process, and insulation 80 minutes in the time of 900 ℃, so that Co
2O
3Decomposition reaction fully carry out.
The performance of the stupalith of test present embodiment preparation, the X-ray collection of illustrative plates shows to have only SnO
2The principal crystalline phase structure does not have second phase, as shown in Figure 1; Residual voltage ratio is 1.86, and nonlinear factor is 42.6, and voltage gradient is 364.6V/mm, as shown in Figure 2.
Claims (1)
1. preparation method based on the low residual voltage ratio pressure-sensitive ceramic material of tindioxide is characterized in that this method may further comprise the steps:
(1) preparation during pressure-sensitive ceramic material in the raw material molar percentage of each component be:
SnO
2 99.39％～99.42％
Co
2O
3 0.5％
Cr
2O
3 0.02％～0.04％
Nb
2O
5 0.06％～0.07％
(2) weigh back the mixing by prescription by above-mentioned each component, in mixture, add an amount of dehydrated alcohol, ball milling 8 hours;
(3) slurry behind ball milling oven dry is 12 hours, crosses 80 mesh sieves, and the powder that obtains depresses to the disk of diameter 11.5mm, thick about 1mm at the pressure of 160MPa, obtains ceramic body;
When (4) above-mentioned ceramic body being heated to 900 ℃, be incubated 80 minutes, continue to be heated to 1300 ℃, sintering 1 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643087A (en) * | 2012-04-28 | 2012-08-22 | 河南科技大学 | SnO2-Zn2SnO4 composite voltage-sensitive ceramics and preparation method thereof |
| CN102643086A (en) * | 2012-02-22 | 2012-08-22 | 中国地质大学（北京） | Stannic oxide based piezoresistor material and preparation method thereof |
| CN110668808A (en) * | 2019-10-17 | 2020-01-10 | 新疆大学 | SnO with high nonlinearity, low residual voltage and large through-current capacity for power transmission of power system2Piezoresistor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531507A (en) * | 2009-04-10 | 2009-09-16 | 孙丹峰 | High energy type zinc oxide piezoresistor composite powder and method for manufacturing piezoresistor |
| JP2010173888A (en) * | 2009-01-29 | 2010-08-12 | Tdk Corp | METHOD FOR PRODUCING MnZn FERRITE |
-
2010
- 2010-11-05 CN CN 201010532613 patent/CN102030523A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010173888A (en) * | 2009-01-29 | 2010-08-12 | Tdk Corp | METHOD FOR PRODUCING MnZn FERRITE |
| CN101531507A (en) * | 2009-04-10 | 2009-09-16 | 孙丹峰 | High energy type zinc oxide piezoresistor composite powder and method for manufacturing piezoresistor |
Non-Patent Citations (1)
| Title |
|---|
| 《Journal of Physics: Conference Series》 20091231 Jiwei FAN等 Investigation of the effect of different dopants on the trap states of ZnO-based and SnO2-based varistors 1-6 1 第152卷, * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102643086A (en) * | 2012-02-22 | 2012-08-22 | 中国地质大学（北京） | Stannic oxide based piezoresistor material and preparation method thereof |
| CN102643086B (en) * | 2012-02-22 | 2014-06-04 | 中国地质大学（北京） | Stannic oxide based piezoresistor material and preparation method thereof |
| CN102643087A (en) * | 2012-04-28 | 2012-08-22 | 河南科技大学 | SnO2-Zn2SnO4 composite voltage-sensitive ceramics and preparation method thereof |
| CN102643087B (en) * | 2012-04-28 | 2013-08-14 | 河南科技大学 | Method for preparing SnO2-Zn2SnO4 composite voltage-sensitive ceramics |
| CN110668808A (en) * | 2019-10-17 | 2020-01-10 | 新疆大学 | SnO with high nonlinearity, low residual voltage and large through-current capacity for power transmission of power system2Piezoresistor and preparation method thereof |
| CN110668808B (en) * | 2019-10-17 | 2022-07-22 | 新疆大学 | SnO with high nonlinearity, low residual voltage and large through-current capacity for power transmission of power system2Preparation method of piezoresistor |
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Application publication date: 20110427 |