CN109053187A - A kind of zinc oxide piezoresistive material of high-potential gracient and preparation method thereof - Google Patents

A kind of zinc oxide piezoresistive material of high-potential gracient and preparation method thereof Download PDF

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CN109053187A
CN109053187A CN201811198426.7A CN201811198426A CN109053187A CN 109053187 A CN109053187 A CN 109053187A CN 201811198426 A CN201811198426 A CN 201811198426A CN 109053187 A CN109053187 A CN 109053187A
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oxide
parts
zinc oxide
piezoresistive material
potential gracient
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冯婉钰
冯明铎
张家植
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Anhui Silver Point Electronic Technology Co Ltd
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Anhui Silver Point Electronic Technology Co Ltd
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    • C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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Abstract

The present invention relates to a kind of zinc oxide piezoresistive materials of high-potential gracient, it is made of raw material from the following weight: 96-99 parts of zinc oxide, 1-2 parts of bismuth oxide, 1-2 parts of barium carbonate, 0.01-0.03 parts of nickel oxide, 0.3-0.5 parts of manganese carbonate, 0.2-0.4 parts of cobaltosic oxide, 0.1-0.2 parts of strontium titanates, 0.02-0.04 parts of zirconium dioxide, 0.04-0.08 parts of Dawsonite Kompensan, 0.04-0.07 parts of antimony pentoxide, 0.06-0.18 parts of rare-earth compound.Preparation method are as follows: will above-mentioned raw materials be uniformly mixed grinding after 1.8-3.5h is first heated at 900-1100 DEG C in nitrogen atmosphere, 1-2h is then kept the temperature at 650-750 DEG C, after natural cooling.Zinc oxide piezoresistive material of the invention has good comprehensive performance, and electric potential gradient gets a promotion.

Description

A kind of zinc oxide piezoresistive material of high-potential gracient and preparation method thereof
Technical field
The invention belongs to resistance material field more particularly to a kind of high-potential gracient zinc oxide piezoresistive material and its Preparation method.
Background technique
Varistor is to become in certain Current Voltage range internal resistance value with voltage, and alternatively " resistance value is to voltage The resistance device of sensitivity ".English name is abbreviated as " VDR " " Voltage Dependent Resistor ", or is called “Varistor”。
In actual use, piezoresistor and protected electrical equipment or component are used in parallel.When occurring in circuit Lightning surge or when transient operation overvoltage Vs, piezoresistor and protected equipment and component bear Vs simultaneously, by Quickly in piezoresistor response speed, excellent non-linear conductive characteristic is presented rapidly with nsec for it, at this time pressure-sensitive electricity Resistance device both end voltage declines rapidly, far smaller than Vs, and the voltage actually born in equipment protected in this way and component is with regard to remote Lower than overvoltage Vs, to make equipment and component from the impact of overvoltage.Especially in ultra-high voltage AC input transformation system In, in order to realize the miniaturization and lightness of arrester valve piece, manufacturing cost is reduced, a kind of pressure-sensitive electricity of high-potential gracient is developed Hindering material is development trend.
Summary of the invention
It is an object of the invention to: a kind of zinc oxide piezoresistive material and preparation method thereof of high-potential gracient is provided, Solve the problems, such as that existing varistor performance in ultra-high voltage AC input transformation system is insufficient.
To achieve the goals above, the invention provides the following technical scheme:
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
96-99 parts of zinc oxide, 1-2 parts of bismuth oxide, 1-2 parts of barium carbonate, 0.01-0.03 parts of nickel oxide, manganese carbonate 0.3-0.5 parts, 0.2-0.4 parts of cobaltosic oxide, 0.1-0.2 parts of strontium titanates, 0.02-0.04 parts of zirconium dioxide, aluminum carbonate basic 0.04-0.08 parts of sodium, 0.04-0.07 parts of antimony pentoxide, 0.06-0.18 parts of rare-earth compound.
Preferably, a kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
98 parts of zinc oxide, 1.5 parts of bismuth oxide, 1.5 parts of barium carbonate, 0.02 part of nickel oxide, 0.4 part of manganese carbonate, four oxygen Change 0.3 part of three cobalt, 0.15 part of strontium titanates, 0.03 part of zirconium dioxide, 0.05 part of Dawsonite Kompensan, 0.06 part of antimony pentoxide, 0.09 part of rare-earth compound.
Preferably, the zinc oxide is nano zine oxide.
Preferably, the partial size of the nano zine oxide is 50-100 nanometers.
Preferably, the rare-earth compound is one of rare earth oxide or multiple combinations.
Preferably, it according to mass ratio is 1:1:1 mixed that the rare-earth compound, which is yttrium oxide, ytterbium oxide, scandium oxide, It closes.
A kind of preparation method of the zinc oxide piezoresistive material of high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide, rare-earth compound are uniformly mixed, and are added in frequency conversion planetary ball mill and are ground 15-30min；
S2: the raw material after grinding is first heated into 1.8-3.5h at 900-1100 DEG C in nitrogen atmosphere, then in 650- 1-2h is kept the temperature at 750 DEG C, after natural cooling.
Preferably, grinding rate is 300-500r/min in step S1.
The beneficial effects of the present invention are:
Compared with prior art, the present invention has the advantages that:
Zinc oxide piezoresistive material of the invention using nano zine oxide as primary raw material, by be added bismuth oxide, Barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, zirconium dioxide, Dawsonite Kompensan, antimony pentoxide, rare earth Element compound, so that zinc oxide piezoresistive material obtained has good comprehensive performance, electric potential gradient gets a promotion.Separately Outside, zinc oxide piezoresistive material preparation method of the invention is simple, easy to industrialized production.
Specific embodiment
Embodiment 1
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
Zinc oxide 96 part, bismuth oxide 1 part, barium carbonate 1 part, nickel oxide 0.01 part, manganese carbonate of the partial size for 50 nanometers 0.3 part, 0.2 part of cobaltosic oxide, 0.1 part of strontium titanates, 0.02 part of zirconium dioxide, 0.04 part of Dawsonite Kompensan, five oxidations two 0.04 part of antimony, 0.02 part of yttrium oxide, 0.02 part of ytterbium oxide, 0.02 part of scandium oxide.
The preparation method of the zinc oxide piezoresistive material of above-mentioned high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide, yttrium oxide, ytterbium oxide, scandium oxide are uniformly mixed, and frequency conversion planetary ball mill is added Middle grinding 15min, grinding rate 500r/min；
S2: first heating 3.5h for the raw material after grinding at 900 DEG C in nitrogen atmosphere, then keep the temperature 2h at 650 DEG C, After natural cooling.
Embodiment 2
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
Zinc oxide 98 part, bismuth oxide 1.5 part, barium carbonate 1.5 part, nickel oxide 0.02 part, carbon of the partial size for 70 nanometers 0.4 part of sour manganese, 0.3 part of cobaltosic oxide, 0.15 part of strontium titanates, 0.03 part of zirconium dioxide, 0.05 part of Dawsonite Kompensan, five oxygen Change 0.06 part of two antimony, 0.03 part of yttrium oxide, 0.03 part of ytterbium oxide, 0.03 part of scandium oxide.
The preparation method of the zinc oxide piezoresistive material of above-mentioned high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide, yttrium oxide, ytterbium oxide, scandium oxide are uniformly mixed, and frequency conversion planetary ball mill is added Middle grinding 20min, grinding rate 400r/min；
S2: the raw material after grinding is first heated into 2.5h in nitrogen atmosphere at 1000 DEG C, is then kept the temperature at 700 DEG C 1.5h, after natural cooling.
Embodiment 3
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
Zinc oxide 99 part, bismuth oxide 2 part, barium carbonate 2 part, nickel oxide 0.03 part, manganese carbonate of the partial size for 100 nanometers 0.5 part, 0.4 part of cobaltosic oxide, 0.2 part of strontium titanates, 0.04 part of zirconium dioxide, 0.08 part of Dawsonite Kompensan, five oxidations two 0.07 part of antimony, 0.06 part of yttrium oxide, 0.06 part of ytterbium oxide, 0.06 part of scandium oxide.
The preparation method of the zinc oxide piezoresistive material of above-mentioned high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide, yttrium oxide, ytterbium oxide, scandium oxide are uniformly mixed, and frequency conversion planetary ball mill is added Middle grinding 30min, grinding rate 300r/min；
S2: the raw material after grinding is first heated into 1.8h in nitrogen atmosphere at 1100 DEG C, is then kept the temperature at 750 DEG C 1h, after natural cooling.
Comparative example 1
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
Zinc oxide 99 part, bismuth oxide 2 part, barium carbonate 2 part, nickel oxide 0.03 part, manganese carbonate of the partial size for 100 nanometers 0.5 part, 0.4 part of cobaltosic oxide, 0.2 part of strontium titanates, 0.04 part of zirconium dioxide, 0.08 part of Dawsonite Kompensan, five oxidations two 0.07 part of antimony.
The preparation method of the zinc oxide piezoresistive material of above-mentioned high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide are uniformly mixed, and are added in frequency conversion planetary ball mill and are ground 30min, grinding rate is 300r/min；
S2: the raw material after grinding is first heated into 1.8h in nitrogen atmosphere at 1100 DEG C, is then kept the temperature at 750 DEG C 1h, after natural cooling.
Comparative example 2
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
Zinc oxide 99 part, bismuth oxide 2 part, barium carbonate 2 part, nickel oxide 0.03 part, manganese carbonate of the partial size for 100 nanometers 0.5 part, 0.4 part of cobaltosic oxide, 0.2 part of strontium titanates, 0.04 part of zirconium dioxide, 0.08 part of Dawsonite Kompensan, five oxidations two 0.07 part of antimony, 0.06 part of yttrium oxide, 0.06 part of ytterbium oxide.
The preparation method of the zinc oxide piezoresistive material of above-mentioned high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide, yttrium oxide, ytterbium oxide are uniformly mixed, and are added in frequency conversion planetary ball mill and are ground 30min, grinding rate 300r/min；
S2: the raw material after grinding is first heated into 1.8h in nitrogen atmosphere at 1100 DEG C, is then kept the temperature at 750 DEG C 1h, after natural cooling.
Comparative example 3
A kind of zinc oxide piezoresistive material of high-potential gracient, is made of raw material from the following weight:
Zinc oxide 99 part, bismuth oxide 2 part, barium carbonate 2 part, nickel oxide 0.03 part, manganese carbonate of the partial size for 100 nanometers 0.5 part, 0.4 part of cobaltosic oxide, 0.2 part of strontium titanates, 0.04 part of zirconium dioxide, 0.08 part of Dawsonite Kompensan, five oxidations two 0.07 part of antimony, 0.06 part of yttrium oxide, 0.06 part of scandium oxide.
The preparation method of the zinc oxide piezoresistive material of above-mentioned high-potential gracient, the specific steps are as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, titanium dioxide Zirconium, Dawsonite Kompensan, antimony pentoxide, yttrium oxide, scandium oxide are uniformly mixed, and are added in frequency conversion planetary ball mill and are ground 30min, grinding rate 300r/min；
S2: the raw material after grinding is first heated into 1.8h in nitrogen atmosphere at 1100 DEG C, is then kept the temperature at 750 DEG C 1h, after natural cooling.
Embodiment 1-3 and the performance test results of zinc oxide piezoresistive material made from comparative example 1-3 are as shown in the table:
Detection project Electric potential gradient (V/mm) Leakage current (under 0.75V1mA, μ A)
Embodiment 1 1450 2.0
Embodiment 2 1550 1.7
Embodiment 3 1500 2.1
Comparative example 1 1200 3.5
Comparative example 2 1250 2.9
Comparative example 3 1300 3.1
From in above table it can be seen that in piezoresistive material of the invention add mass ratio be 1:1:1 yttrium oxide, When ytterbium oxide, scandium oxide, the electric potential gradient of the piezoresistive material being prepared compared to being improved for comparative example, Leakage current is reduced.In addition, as can be seen that the composition of raw materials effect of embodiment 2 is best from embodiment 1-3.

Claims (8)

1. a kind of zinc oxide piezoresistive material of high-potential gracient, which is characterized in that be made of raw material from the following weight:
96-99 parts of zinc oxide, 1-2 parts of bismuth oxide, 1-2 parts of barium carbonate, 0.01-0.03 parts of nickel oxide, manganese carbonate 0.3-0.5 Part, 0.2-0.4 parts of cobaltosic oxide, 0.1-0.2 parts of strontium titanates, 0.02-0.04 parts of zirconium dioxide, Dawsonite Kompensan 0.04- 0.08 part, 0.04-0.07 parts of antimony pentoxide, 0.06-0.18 parts of rare-earth compound.
2. a kind of zinc oxide piezoresistive material of high-potential gracient according to claim 1, which is characterized in that by following The raw material of parts by weight is made:
98 parts of zinc oxide, 1.5 parts of bismuth oxide, 1.5 parts of barium carbonate, 0.02 part of nickel oxide, 0.4 part of manganese carbonate, four oxidations three 0.3 part of cobalt, 0.15 part of strontium titanates, 0.03 part of zirconium dioxide, 0.05 part of Dawsonite Kompensan, 0.06 part of antimony pentoxide, rare earth 0.09 part of element compound.
3. a kind of zinc oxide piezoresistive material of high-potential gracient according to claim 1 or 2, which is characterized in that institute The zinc oxide stated is nano zine oxide.
4. a kind of zinc oxide piezoresistive material of high-potential gracient according to claim 3, which is characterized in that described The partial size of nano zine oxide is 50-100 nanometers.
5. a kind of zinc oxide piezoresistive material of high-potential gracient according to claim 1 or 2, which is characterized in that institute The rare-earth compound stated is one of rare earth oxide or multiple combinations.
6. a kind of zinc oxide piezoresistive material of high-potential gracient according to claim 5, which is characterized in that described It according to mass ratio is that 1:1:1 is mixed that rare-earth compound, which is yttrium oxide, ytterbium oxide, scandium oxide,.
7. a kind of preparation method of the zinc oxide piezoresistive material of high-potential gracient, which is characterized in that specific step is as follows:
S1: by zinc oxide, bismuth oxide, barium carbonate, nickel oxide, manganese carbonate, cobaltosic oxide, strontium titanates, zirconium dioxide, alkali Formula sodium aluminum carbonate, antimony pentoxide, rare-earth compound are uniformly mixed, and are added in frequency conversion planetary ball mill and are ground 15- 30min；
S2: the raw material after grinding is first heated into 1.8-3.5h at 900-1100 DEG C in nitrogen atmosphere, then at 650-750 DEG C Lower heat preservation 1-2h, after natural cooling.
8. a kind of preparation method of the zinc oxide piezoresistive material of high-potential gracient according to claim 7, feature It is, grinding rate is 300-500r/min in step S1.
CN201811198426.7A 2018-10-15 2018-10-15 A kind of zinc oxide piezoresistive material of high-potential gracient and preparation method thereof Pending CN109053187A (en)

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Publication number Priority date Publication date Assignee Title
US3928245A (en) * 1973-07-09 1975-12-23 Gen Electric Metal oxide voltage-variable resistor composition
CN101239819A (en) * 2007-09-14 2008-08-13 中国南玻集团股份有限公司 Method for preparing sheet type multilayer zinc oxide pressure-sensitive electric resistance ceramic powder
CN101279844A (en) * 2008-05-20 2008-10-08 上海大学 Zinc oxide pressure-sensitive ceramic material doped with composite rare-earth oxide
CN101880157A (en) * 2010-06-24 2010-11-10 中国科学院宁波材料技术与工程研究所 Recipe and preparation method of high-voltage gradient zinc oxide resistance card
CN105198402A (en) * 2015-09-15 2015-12-30 苏州亿馨源光电科技有限公司 Nano zinc oxide voltage-dependent resistor material and preparation method thereof
CN107935582A (en) * 2017-11-18 2018-04-20 四川启兴电子有限公司 A kind of material prepared for zinc oxide varistor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928245A (en) * 1973-07-09 1975-12-23 Gen Electric Metal oxide voltage-variable resistor composition
CN101239819A (en) * 2007-09-14 2008-08-13 中国南玻集团股份有限公司 Method for preparing sheet type multilayer zinc oxide pressure-sensitive electric resistance ceramic powder
CN101279844A (en) * 2008-05-20 2008-10-08 上海大学 Zinc oxide pressure-sensitive ceramic material doped with composite rare-earth oxide
CN101880157A (en) * 2010-06-24 2010-11-10 中国科学院宁波材料技术与工程研究所 Recipe and preparation method of high-voltage gradient zinc oxide resistance card
CN105198402A (en) * 2015-09-15 2015-12-30 苏州亿馨源光电科技有限公司 Nano zinc oxide voltage-dependent resistor material and preparation method thereof
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Application publication date: 20181221