CN102557612A - Low-dielectric-constant pressure-sensitive resistor material and preparation method thereof - Google Patents
Low-dielectric-constant pressure-sensitive resistor material and preparation method thereof Download PDFInfo
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- CN102557612A CN102557612A CN2012100073056A CN201210007305A CN102557612A CN 102557612 A CN102557612 A CN 102557612A CN 2012100073056 A CN2012100073056 A CN 2012100073056A CN 201210007305 A CN201210007305 A CN 201210007305A CN 102557612 A CN102557612 A CN 102557612A
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Abstract
The invention discloses a low-dielectric-constant pressure-sensitive resistor material comprising the following components in percent by weight: 90-97 percent of ZnO, 0.1-3 percent of Bi2O3, 0.1-3 percent of Sb2O3, 0.1-2 percent of Cr2O3, 0.1-1.5 percent of MnO2, 0.1-1.5 percent of Co2O3, 0.1-1 percent of Ni2O3, 0.1-0.8 percent of H3BO3, 0.1-0.8 percent of AgNO3 and 0.1-0.3 percent of Al2(NO3)3.9H2O; and the percentage is molar ratio. Compared with the prior art, the dielectric constant of a pressure-sensitive resistor manufactured by utilizing the resistor material can be controlled within 30-120.
Description
Technical field
The present invention relates to piezoresistive material and make the field, relate in particular to a kind of low-k Zinc-oxide piezoresistor powder and preparation method thereof.
Background technology
ZnO varistor is to be the main body with the ZnO powder, and other mental compound additives that add multiple trace are (like Bi
2O
3, Sb
2O
3, MnCO
3, Co
2O
3, Cr
2O
3Deng), through mix, the heterogeneous semiconductive ceramic element of polycrystalline that forms of sintering at high temperature after the moulding.Since its invention, ZnO varistor has obtained using widely in power system and electronic industry just with premium propertiess such as it are cheap, easily manufactured, nonlinear factor is big, the time of response is fast, discharge capacity is big.
Current, along with the development of electronic circuit high frequencyization, various high speed data transmission line road and interface as: HDMI, USB3.0 etc. has obtained use more and more widely.In order to reduce the loss of transmission signal in this type of circuit; Need reduce the wherein electrical capacity of the voltage dependent resistor of using as far as possible; Therefore must use the low-k piezoresistive material and make this type of little electrical capacity voltage dependent resistor, concern, can make that voltage gradient exceeds normal range when reducing specific inductivity but the specific inductivity of voltage dependent resistor and voltage gradient are anti-growth to satisfy the demand; Therefore, the specific inductivity of existing voltage dependent resistor generally all is higher than 300.
Summary of the invention
Technical problem to be solved by this invention is that a kind of low-k Zinc-oxide piezoresistor powder with good over-all properties and preparation method thereof is provided.
Technical problem of the present invention solves by the following technical programs:
A kind of low-k piezoresistive material is characterized in that comprising:
90 ~ 97% ZnO;
0.1 ~ 3% Bi
2O
3
0.1 ~ 3% Sb
2O
3
0.1 ~ 2% Cr
2O
3
0.1 ~ 1.5% MnO
2Or MnCO
3
0.1 ~ 1.5% Co
2O
3
0.1 ~ 1% Ni
2O
3Or NiO;
0.1 ~ 0.8% H
3BO
3Or B
2O
3
0.001 ~ 0.8% AgNO
3
The Al of 0.001-0.3%
2(NO
3) 3.9H
2O;
Aforesaid per-cent is mol ratio.
Preferably, also comprise: mol ratio is 0.1% ~ 2% SiO
2
Preferably, also comprise: mol ratio is 0.1 ~ 1.5% MgO.
Wherein: described MnO
2Be to introduce with the form that contains manganic compound, the said manganic compound that contains comprises MnO
2, Mn
3O
4Or MnCO
3
Described Ni
2O
3Be to introduce with the form that contains nickel oxide, the said nickel oxide that contains comprises NiO or Ni
2O
3
Described H
3BO
3Be to introduce with the form of boron-containing compound, said boron-containing compound comprises H
3BO
3Or B
2O
3
Described AgNO
3, Al
2(NO
3) 3.9H
2O is dissolved in earlier in deionized water or the ethanol by proportioning, and the mode with this solution adds in the remaining ingredient then.
The experiment proof; Compared with prior art; Adopt the voltage dependent resistor of low-k piezoresistive material preparation of the present invention tangible lifting all to be arranged in the performance aspect electrical property, mechanical property and the safety; And can the relative permittivity of voltage dependent resistor porcelain body be controlled in the 30-120, potential gradient also remains between the normal 400-800v/mm, has excellent comprehensive performances.
Embodiment
Below in conjunction with preferred embodiment the present invention being described further.
The low-k piezoresistive material of present embodiment by:
90 ~ 97% ZnO;
0.1 ~ 3% Bi
2O
3
0.1 ~ 3% Sb
2O
3
0.1 ~ 2% Cr
2O
3
0.1 ~ 1.5% MnO
2Or MnCO
3
0.1 ~ 1.5% Co
2O
3
0.1 ~ 1% Ni
2O
3Or NiO;
0.1 ~ 0.8% H
3BO
3Or B
2O
3
0.001 ~ 0.8% AgNO
3
The Al of 0.001-0.3%
2(NO
3) 3.9H
2O;
Form, wherein each percentages of ingredients is mol ratio.
Preferably can add 0.1% ~ 2% SiO2 and/or 0.1 ~ 1.5% MgO in the above-mentioned materials.
Wherein, AgNO
3And Al
2(NO
3) 3.9H
2O all is dissolved in earlier in deionized water or the ethanol by proportioning, and the mode with this solution adds in the remaining ingredient then.
Experiment showed, that the voltage dependent resistor that adopts above-mentioned materials to make remains in potential gradient under the prerequisite of normal range, specific inductivity can be controlled in the scope of 30-120.
The method that adopts above-mentioned materials to prepare former of voltage dependent resistor is preferably:
1) takes by weighing all powders except that zinc oxide as voltage dependent resistor additive powder mix by proportioning; With the Vilaterm jar is ball grinder; Adopting zirconia ball, deionized water is ball-milling medium, and wherein, the mass ratio of zirconia ball, additive powder, deionized water is: 80:1:12; Wet-milling 5-12h in planetary ball mill, rotating speed are 300-500rmp.
2) after above-mentioned grinding is accomplished; In spherical tank, add the oxide powder and zinc of corresponding proportioning and the PVA (Z 150PH of all powder gross weight 1-2%; Mode with the aqueous solution is used), continue mix grinding 24h in planetary ball mill, rotating speed is 300-500rmp; Pour porcelain dish into after mix grinding is accomplished and in baking oven, dry, bake out temperature is 100-120 ℃.
3) the pressure-sensitive powder after the above-mentioned oven dry being crossed 100 mesh sieves, is Φ 12mm at the forming under the pressure of 9MPa, and thickness is the sequin of 1.0 ~ 2.0mm; Sintering in 1100 ~ 1350 ℃ of air; Naturally cool to room temperature, be coated with silver on the clean ceramics two sides of polishing, the silver ink firing temperature is 750-950 ℃; Time is 30 minutes, promptly completes.
Be the objectivity of explanation technique effect of the present invention, hereinafter provides the experimental data of three concrete experiments:
1) by mole per-cent ZnO 95.1%, Bi
2O
30.5%, Sb
2O
31.25%, Cr
2O
30.5%, SiO
20.25%, MnCO
31%, Co
2O
30.5%, Ni
2O
30.3%, MgO 0.5%, AgNO
30.01%, Al
2(NO
3) 3.9H
2O 0.015% takes by weighing all kinds of powders; With the Vilaterm jar is ball grinder; Adopting zirconia ball, deionized water is ball-milling medium; Zirconia ball, additive powder (all the agent powder except that ZnO), deionized water quality ratio are: 80:1:12, wet-milling 12h in planetary ball mill, rotating speed are 350rmp.Add the oxide powder and zinc of corresponding proportioning and the PVA of all powder gross weights 2% (mode with the aqueous solution is used) then; Continuation is mix grinding 24h in planetary ball mill; Rotating speed is 350rmp, pours porcelain dish into after mix grinding is accomplished and in baking oven, dries, and bake out temperature is 100 ℃.Pressure-sensitive powder after the above-mentioned oven dry is crossed 100 mesh sieves, is Φ 12mm at the forming under the pressure of 9MPa, and thickness is the sequin of 1.4mm; Sintering in 1250 ℃ of air naturally cools to room temperature, is coated with silver on the clean ceramics two sides of polishing; The silver ink firing temperature is 800 ℃, and the time is 30 minutes, promptly completes.
Former warp test of the Zinc-oxide piezoresistor of this instance made, voltage gradient 720V/mm, relative permittivity 120, nonlinear factor 38.1, leakage current 1.4 μ A, shock-resistant electric current 1200A.
2) by mole per-cent ZnO 95%, Bi
2O
30.7%, Sb
2O
31.2%, Cr
2O
30.5%, MnCO
30.5%, Co
2O
31.3%, Ni
2O
30.2%, H
3BO
30.57%, AgNO
30.015%, Al
2(NO
3) 3.9H
2O 0.015% takes by weighing all kinds of powders; With the Vilaterm jar is ball grinder; Adopting zirconia ball, deionized water is ball-milling medium; Zirconia ball, additive powder (all the agent powder except that ZnO), deionized water quality ratio are: 80:1:12, wet-milling 12h in planetary ball mill, rotating speed are 350rmp.Add the oxide powder and zinc of corresponding proportioning and 15% the PVA aqueous solution (concentration is 10%) then, continue mix grinding 24h in planetary ball mill, rotating speed is 350rmp, pours porcelain dish into after mix grinding is accomplished and in baking oven, dries, and bake out temperature is 100 ℃.Pressure-sensitive powder after the above-mentioned oven dry is crossed 100 mesh sieves, is Φ 12mm at the forming under the pressure of 9MPa, and thickness is the sequin of 1.4mm; Sintering in 1250 ℃ of air naturally cools to room temperature, is coated with silver on the clean ceramics two sides of polishing; The silver ink firing temperature is 800 ℃, and the time is 30 minutes, promptly completes.
The Zinc-oxide piezoresistor of this instance made is through test, voltage gradient 660V/mm, relative permittivity 71 nonlinear factors 23.2, leakage current 1.7 μ A, shock-resistant electric current 1240A.
3) by mole per-cent ZnO 94.1%, Bi
2O
30.9%, Sb
2O
31.3%, Cr
2O
30.5%, MnCO
30.6%, Co
2O
31.2%, Ni
2O
30.2%, H
3BO
30.5%, MgO 0.4%, AgNO
30.015%, Al
2(NO
3) 3.9H
2O 0.015% takes by weighing all kinds of powders; With the Vilaterm jar is ball grinder; Adopting zirconia ball, deionized water is ball-milling medium; Zirconia ball, additive powder (all the agent powder except that ZnO), deionized water quality ratio are: 80:1:12, wet-milling 12h in planetary ball mill, rotating speed are 350rmp.Add the oxide powder and zinc of corresponding proportioning and 15% the PVA aqueous solution (concentration is 10%) then, continue mix grinding 24h in planetary ball mill, rotating speed is 350rmp, pours porcelain dish into after mix grinding is accomplished and in baking oven, dries, and bake out temperature is 100 ℃.Pressure-sensitive powder after the above-mentioned oven dry is crossed 100 mesh sieves, is Φ 12mm at the forming under the pressure of 9MPa, and thickness is the sequin of 1.4mm; Sintering in 1250 ℃ of air naturally cools to room temperature, is coated with silver on the clean ceramics two sides of polishing; The silver ink firing temperature is 800 ℃, and the time is 30 minutes, promptly completes.
The Zinc-oxide piezoresistor of this instance made is through test, voltage gradient 690V/mm, relative permittivity 101 nonlinear factors 29.2, leakage current 3.7 μ A, shock-resistant electric current 1140A.
Above content is to combine concrete preferred implementation to the further explain that the present invention did, and can not assert that practical implementation of the present invention is confined to these explanations.For person of ordinary skill in the field of the present invention, do not breaking away under the prerequisite of the present invention design, can also make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be regarded as belonging to protection scope of the present invention.
Claims (4)
1. low-k piezoresistive material is characterized in that comprising:
90 ~ 97% ZnO;
0.1 ~ 3% Bi
2O
3
0.1 ~ 3% Sb
2O
3
0.1 ~ 2% Cr
2O
3
0.1 ~ 1.5% MnO
2Or MnCO
3
0.1 ~ 1.5% Co
2O
3
0.1 ~ 1% Ni
2O
3Or NiO;
0.1 ~ 0.8% H
3BO
3Or B
2O
3
0.001 ~ 0.8% AgNO
3
The Al of 0.001-0.3%
2(NO
3) 3.9H
2O;
Aforesaid per-cent is mol ratio.
2. low-k piezoresistive material according to claim 1 is characterized in that, also comprises: mol ratio is 0.1% ~ 2% SiO
2
3. low-k piezoresistive material according to claim 1 and 2 is characterized in that, also comprises: mol ratio is 0.1 ~ 1.5% MgO.
4. low-k piezoresistive material according to claim 1 is characterized in that: said AgNO
3And Al
2(NO
3) 3.9H
2O all is dissolved in earlier in deionized water or the ethanol by proportioning, and the mode with this solution adds in the remaining ingredient then.
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|---|---|---|---|
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|---|---|---|---|
| CN2012100073056A CN102557612A (en) | 2012-01-11 | 2012-01-11 | Low-dielectric-constant pressure-sensitive resistor material and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681223A (en) * | 2014-12-29 | 2015-06-03 | 广西新未来信息产业股份有限公司 | Lightning and surge protection composite pressure sensitive resistor and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844044A (en) * | 2006-04-24 | 2006-10-11 | 西安交通大学 | ZnO-Bi2O3 pressure-sensitive ceramic dielectric doped with rare-earth oxide |
| CN1962539A (en) * | 2006-11-30 | 2007-05-16 | 华南理工大学 | Zinc oxide base high potential gradient pressure-sensitive ceramic material and its preparation method and uses |
| CN102030522A (en) * | 2010-11-17 | 2011-04-27 | 西安交通大学 | Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric |
-
2012
- 2012-01-11 CN CN2012100073056A patent/CN102557612A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1844044A (en) * | 2006-04-24 | 2006-10-11 | 西安交通大学 | ZnO-Bi2O3 pressure-sensitive ceramic dielectric doped with rare-earth oxide |
| CN1962539A (en) * | 2006-11-30 | 2007-05-16 | 华南理工大学 | Zinc oxide base high potential gradient pressure-sensitive ceramic material and its preparation method and uses |
| CN102030522A (en) * | 2010-11-17 | 2011-04-27 | 西安交通大学 | Low-equilibrium temperature ZnO-Bi2O3 series voltage-sensitive ceramic dielectric |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104681223A (en) * | 2014-12-29 | 2015-06-03 | 广西新未来信息产业股份有限公司 | Lightning and surge protection composite pressure sensitive resistor and manufacturing method thereof |
| CN104681223B (en) * | 2014-12-29 | 2018-07-13 | 广西新未来信息产业股份有限公司 | A kind of compound piezoresistor of lightning protection surge and preparation method thereof |
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Application publication date: 20120711 |