CN106946560A - Y3+、Sn4+Compound donor doping ZnO voltage-sensitive ceramics and preparation method - Google Patents

Y3+、Sn4+Compound donor doping ZnO voltage-sensitive ceramics and preparation method Download PDF

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CN106946560A
CN106946560A CN201710239612.XA CN201710239612A CN106946560A CN 106946560 A CN106946560 A CN 106946560A CN 201710239612 A CN201710239612 A CN 201710239612A CN 106946560 A CN106946560 A CN 106946560A
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庞驰
方超
张宁
周芳
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Guiyang Hi Tec Yige Electronic Co ltd
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Guizhou University
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Abstract

The invention discloses a kind of Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping and preparation method thereof, include base-material and doping is expected, the base-material includes ZnO by weight：87 95 parts, Bi2O3：2.0 4.0 parts, MnO2：0.4 0.7 parts, Sb2O3：1.5 3.5 parts, Co2O3：0.5 1.5 parts, Cr2O3：0.2 1.0 parts, seed crystal doping material：15 parts；The seed crystal doping material is ZnO, SnO2And Y2O3, its mass fraction ratio is ZnO：SnO2：Y2O3=90 95：0.1‑5：0.1‑5.Y of the present invention3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping have the ZnO grain resistance rates that can reduce, and the characteristics of controlling ZnO distortions of lattice again is finally reached the characteristics of low ZnO varistor residual voltage, aging life-span length, strong pulse current tolerance.

Description

Y3+、Sn4+Compound donor doping ZnO voltage-sensitive ceramics and preparation method
Technical field
The present invention relates to a kind of ZnO voltage-sensitive ceramics and preparation method thereof, particularly one kind is without Al3+The Y of doping3+、Sn4+It is multiple Close donor doping ZnO voltage-sensitive ceramics and preparation method thereof.
Background technology
ZnO varistor is, using ZnO as primary raw material, to add a small amount of Bi2O3、Co3O4、MnO2、Sb2O3、Cr2O3Deng raw material, It is prepared from using ceramic sintering process.Piezo-resistance has the advantages that good non-linear and big through-current capability, and it is used as thunder Electric surge protector component is widely used in electronic circuit and power system.It is swift and violent with microelectronics information technology Development, to the minimizing of component, integrated so that modular requirement is more and more urgent.The electronic component sensitivity of miniaturization High, anti overvoltage level is low, and this improves electronic equipment to the demand of lightning protection, it is necessary to which ZnO varistor can have lower Residual voltage level of protection.
When lightning current invades equipment, the ZnO crystal boundaries conducting of ZnO varistor, its performance mainly has ZnO grain resistances to determine It is fixed.Reduce the residual voltage of ZnO varistor, it is necessary to reduce the resistivity of ZnO varistor.
Existing method one：ZnO varistor original is added to as donor ion using Al ions mostly in the industrial production In material.0.005mol%Al ions normally only be with the addition of as donor ion, therefore cause the reduction of ZnO varistor rate not Substantially.But if adding substantial amounts of Al ions as donor ion, Spinel and richness can be entered due to addition Al ions again In Bi phases, interface state density is caused to decline the reduction with barrier height.So that the leakage current of ZnO varistor increased dramatically, Nonlinear factor declines.
Existing method two：In order to which by donor ion Al Effective Dopings, into ZnO crystal grain, some enterprises improve production work Skill, first by ZnO and Al (NO3)3·9H2O is mixed, and in 1200 DEG C~1300 DEG C temperature lower calcinations, seed crystal is made, then again by seed Crystalline substance is added in the dispensing of ZnO varistor, prepares piezo-resistance using ceramic sintering process, Al ions can be avoided by so doing Into in Spinel and richness Bi phases, interface state density is caused to decline the reduction with barrier height.Above method can reach drop The purpose of low residual voltage, while also obtaining certain effect.In order to be able to reduce ZnO grain resistances, except using seed crystal two above Outside stage production technology, often adulterate substantial amounts of donor ion Al.But because Al ionic radius are only 0.0535nm, and Zn ions Radius is 0.074nm, and both ionic radius differences cause ZnO distortions of lattice serious, this must than larger after formation donor doping So cause the performance indications such as ZnO varistor aging life-span, pulse current tolerance to decline to a great extent, commercial Application can not be met Demand.
The content of the invention
It is an object of the invention to develop one kind without Al3+The ZnO voltage-sensitive ceramics formula and preparation method of doping, the present invention Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, which have, can reduce ZnO grain resistance rates, and ZnO lattices can be controlled again The characteristics of distortion, it is finally reached the characteristics of low ZnO varistor residual voltage, aging life-span length, strong pulse current tolerance.
Technical scheme：A kind of Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material With doping material, the base-material includes ZnO by weight：87-95 parts, Bi2O3：2.0-4.0 parts, MnO2：0.4-0.7 parts, Sb2O3：1.5-3.5 parts, Co2O3：0.5-1.5 parts, Cr2O3：0.2-1.0 parts, seed crystal doping material：1-5 parts；The seed crystal doping material For ZnO, SnO2And Y2O3, its mass fraction ratio is ZnO：SnO2：Y2O3=90-95：0.1-5：0.1-5.
Foregoing Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, the base-material includes by weight ZnO：89-92 parts, Bi2O3：2.5-3.5 parts, MnO2：0.5-0.6 parts, Sb2O3：2-3 parts, Co2O3：0.8-1.2 parts, Cr2O3： 0.3-0.8 parts, seed crystal doping material：2-4 parts；The seed crystal doping material is ZnO, SnO2And Y2O3, its mass fraction ratio is ZnO： SnO2：Y2O3=92-94：3-5：1-3.
Foregoing Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, the base-material includes by weight ZnO：90.5 parts, Bi2O3：3.0 parts, MnO2：0.5 part, Sb2O3：2.5 parts, Co2O3：1 part, Cr2O3：0.5 part, seed crystal doping material 2 Part, the seed crystal doping material mass fraction ratio is ZnO：SnO2：Y2O3=94：4.5：1.5.
A kind of foregoing Y3+、Sn4+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, comprises the following steps：
(1) seed crystal is prefabricated：By ZnO：SnO2：Y2O3Mixed in the ratio, SnO2And Y2O3The form of nitrate can be used Add, while adding alcohol or deionized water, ball milling 8-24 hours forms seed crystal suspension, seed crystal suspension is dried, seed is obtained Brilliant batch；
(2) seed crystal is sintered：Seed crystal batch made from step (1) is put at 1200-1350 DEG C and sintered 3-6 hours, is burnt Normal temperature is slowly dropped to stove after knot, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment made from step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：ZnO, Bi are proportionally added into seed crystal made from step (3)2O3、MnO2、Sb2O3、 Co2O3And Cr2O3Mixing, deionized water, poly-vinyl alcohol solution, dispersant are added into mixture, and ball milling 8-12 hours is obtained Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate made from step (4) is put into electric furnace and is warming up to 400 DEG C of progress insulation dumpings, dumping Time 4-6 hour, 1200-1350 DEG C is warming up to after dumping and is sintered, sintering time 18-23 hours is incubated after the completion of sintering 3-6 hours, make its densification into porcelain, be then cooled to normal temperature with stove.
Foregoing Y3+、Sn4+In the preparation method of compound donor doping ZnO voltage-sensitive ceramics, the step (1), Ball-milling Time For 15-17 hours.
Foregoing Y3+、Sn4+It is by step in the preparation method of compound donor doping ZnO voltage-sensitive ceramics, the step (2) (1) seed material made from is put at 1270-1280 DEG C and sintered 4-5 hours.
Foregoing Y3+、Sn4+In the preparation method of compound donor doping ZnO voltage-sensitive ceramics, the step (4), poly- second is added The mass percent of enolate solution is 5%wt, adds the ratio of poly-vinyl alcohol solution to add the poly- second of 50g in every kilogram of mixture Enolate solution.
Beneficial effects of the present invention：The present invention is by compound donor doping Sn ions and Y-ion, because Sn ionic radius are 0.069nm, Y-ion radius is 0.09nm, and Zn ionic radius are 0.074nm.Sn, Y, Zn ionic radius are more or less the same, easily Adulterated in forming instead type, and Sn ions, Y-ion instead of Zn ions lattice site in Pb-Zn deposits structure, Sn ion displacements Doping causes Lattice Contraction, Y-ion displacement doping to cause lattice dilatation, can be by controlling the doping ratio of Sn ions, Y-ion Carry out precise control ZnO distortions of lattice, donor doping reduces grain resistance rate and reduction ZnO varistor residual voltage, inhibits and let out The growth of leakage current, while suppress the decline of nonlinear factor, ZnO varistor aging life-span, pulse current are enhanced again Tolerance, so that the material has higher performance and is more suitable for commercial Application.
This experimental example makes laboratory sample with 3 kinds of different manufacture crafts altogether, and the first is traditional handicraft, and traditional handicraft is not Plus seed crystal doping material；Second of the technique for addition seed crystal, as described in the background art shown in existing method two；The third according to It is prepared by the method for the invention；The pressure sensitive voltage of test sample, leakage current, nominal discharge current, residual voltage, accelerated life, As a result it is as shown in table 1.
The correction data of table 1
Pass through table 1：Using the sample leakage current of patented technology of the present invention preparation is smaller, residual voltage is lower, pulse current Tolerance is stronger, aging life-span is longer, the sample that its electrical property is prepared better than traditional handicraft and existing method two comprehensively.
Embodiment
With reference to embodiment, the present invention is further illustrated, but is not intended as to the foundation of the invention limited.
Embodiments of the invention
Embodiment 1：A kind of Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material and doping is expected, The base-material includes ZnO by weight：90.5 parts, Bi2O3：3.0 parts, MnO2：0.5 part, Sb2O3：2.5 parts, Co2O3：1 Part, Cr2O3：0.5 part, 2 parts of seed crystal doping material, the seed crystal doping material mass fraction ratio is ZnO：Sn(NO3)4:Y(NO3)3= 94：4.5：1.5.
Embodiment 2：A kind of Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material and doping is expected, The base-material includes ZnO by weight：87 parts, Bi2O3：2.0 parts, MnO2：0.4 part, Sb2O3：1.5 parts, Co2O3：0.5 Part, Cr2O3：0.2 part, seed crystal doping material：1 part；The seed crystal doping material is ZnO, SnO2And Y2O3, its mass fraction ratio is ZnO： SnO2：Y2O3=90：0.1：0.1.
Embodiment 3：A kind of Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, include base-material and doping is expected, The base-material includes ZnO by weight：95 parts, Bi2O3：4.0 parts, MnO2：0.7 part, Sb2O3：3.5 parts, Co2O3：1.5 Part, Cr2O3：1.0 parts, seed crystal doping material：5 parts；The seed crystal doping material is ZnO, SnO2And Y2O3, its mass fraction ratio is ZnO： SnO2：Y2O3=95：5：5.
Embodiment 4：Above-mentioned Y3+、Sn4+The preparation method of ZnO voltage-sensitive ceramics prepared by compound donor doping, step is such as Under：
(1) seed crystal is prefabricated：By ZnO, SnO2And Y2O3Mixed in the ratio, add deionized water and alcohol, ball milling 16 is small When, seed crystal suspension is formed, seed crystal suspension is dried, seed crystal batch is obtained；
(2) seed crystal is sintered：Seed crystal batch made from step (1) is put at 1270 DEG C and sintered 4 hours, with stove after sintering Normal temperature is slowly dropped to, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment made from step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：ZnO, Bi are proportionally added into seed crystal sintering feed made from step (3)2O3、MnO2、 Sb2O3、Co2O3And Cr2O3Mixing, deionized water, poly-vinyl alcohol solution, dispersant are added into mixture, and ball milling 10 hours is obtained Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate made from step (4) is put into electric furnace and is warming up to 400 DEG C of progress insulation dumpings, dumping 5 hours time, 1270 DEG C are warming up to after dumping and is sintered, sintering time 20 hours is incubated 4 hours after the completion of sintering, makes it Then densification is cooled to normal temperature into porcelain with stove.
In above-mentioned steps (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, adds poly-vinyl alcohol solution Ratio is addition 50g poly-vinyl alcohol solutions in every kilogram of mixture.
Embodiment 5：Above-mentioned Y3+、Sn4+The preparation method of ZnO voltage-sensitive ceramics prepared by compound donor doping, step is such as Under：
(1) seed crystal is prefabricated：By ZnO, Sn (NO3)4With Y (NO3)3Mixed in the ratio, add deionized water and alcohol, Ball milling 8 hours, forms seed crystal suspension, seed crystal suspension is dried, seed crystal batch is obtained；
(2) seed crystal is sintered：Seed crystal batch made from step (1) is put at 1200 DEG C and sintered 6 hours, with stove after sintering Normal temperature is slowly dropped to, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment made from step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：ZnO, Bi are proportionally added into seed crystal sintering feed made from step (3)2O3、MnO2、 Sb2O3、Co2O3And Cr2O3Mixing, deionized water, poly-vinyl alcohol solution, dispersant are added into mixture, and ball milling 12 hours is obtained Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate made from step (4) is put into electric furnace and is warming up to 400 DEG C of progress insulation dumpings, dumping 4 hours time, 1200 DEG C are warming up to after dumping and is sintered, sintering time 23 hours is incubated 3 hours after the completion of sintering, makes it Then densification is cooled to normal temperature into porcelain with stove.
In above-mentioned steps (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, adds poly-vinyl alcohol solution Ratio is addition 50g poly-vinyl alcohol solutions in every kilogram of mixture.
Embodiment 6：Above-mentioned Y3+、Sn4+The preparation method of ZnO voltage-sensitive ceramics prepared by compound donor doping, step is such as Under：
(1) seed crystal is prefabricated：By ZnO, SnO2And Y2O3Mixed in the ratio, add deionized water and alcohol, ball milling 24 is small When, seed crystal suspension is formed, seed crystal suspension is dried, seed crystal batch is obtained；
(2) seed crystal is sintered：Seed crystal batch made from step (1) is put at 1350 DEG C and sintered 3 hours, with stove after sintering Normal temperature is slowly dropped to, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment made from step (2), seed crystal average grain diameter is less than 5 μm, system Obtain seed crystal standby；
(4) dispensing, granulation, base：ZnO, Bi are proportionally added into seed crystal sintering feed made from step (3)2O3、MnO2、 Sb2O3、Co2O3And Cr2O3Mixing, deionized water, poly-vinyl alcohol solution, dispersant are added into mixture, and ball milling 12 hours is obtained Suspension, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate made from step (4) is put into electric furnace and is warming up to 400 DEG C of progress insulation dumpings, dumping 6 hours time, 1350 DEG C are warming up to after dumping and is sintered, sintering time 18 hours is incubated 6 hours after the completion of sintering, makes it Then densification is cooled to normal temperature into porcelain with stove.
In above-mentioned steps (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, adds poly-vinyl alcohol solution Ratio is addition 50g poly-vinyl alcohol solutions in every kilogram of mixture.

Claims (7)

1. a kind of Y3+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, it is characterised in that：Include base-material and doping expected, The base-material includes ZnO by weight：87-95 parts, Bi2O3：2.0-4.0 parts, MnO2：0.4-0.7 parts, Sb2O3：1.5- 3.5 parts, Co2O3：0.5-1.5 parts, Cr2O3：0.2-1.0 parts, seed crystal doping material：1-5 parts；The seed crystal doping material is ZnO, SnO2 And Y2O3, its mass fraction ratio is ZnO：SnO2：Y2O3=90-95：0.1-5：0.1-5.
2. Y according to claim 13+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, it is characterised in that：It is described Base-material includes ZnO by weight：89-92 parts, Bi2O3：2.5-3.5 parts, MnO2：0.5-0.6 parts, Sb2O3：2-3 parts, Co2O3：0.8-1.2 parts, Cr2O3：0.3-0.8 parts, seed crystal doping material：2-4 parts；The seed crystal doping material is ZnO, SnO2With Y2O3, its mass fraction ratio is ZnO：SnO2：Y2O3=92-94：3-5：1-3.
3. Y according to claim 23+、Sn4+ZnO voltage-sensitive ceramics prepared by compound donor doping, it is characterised in that：It is described Base-material includes ZnO by weight：90.5 parts, Bi2O3：3.0 parts, MnO2：0.5 part, Sb2O3：2.5 parts, Co2O3：1 part, Cr2O3：0.5 part, 2 parts of seed crystal doping material, the seed crystal doping material mass fraction ratio is ZnO：SnO2：Y2O3=94：4.5：1.5.
4. a kind of Y according to claim any one of 1-33+、Sn4+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, It is characterised in that it includes following steps：
(1) seed crystal is prefabricated：By ZnO：SnO2：Y2O3Mixed in the ratio, SnO2And Y2O3It can be added in the form of nitrate, Alcohol or deionized water are added simultaneously, and ball milling 8-24 hours forms seed crystal suspension, seed crystal suspension is dried, seed crystal is obtained and matches somebody with somebody Close material；
(2) seed crystal is sintered：Seed crystal batch made from step (1) is put at 1200-1350 DEG C and sintered 3-6 hours, after sintering Normal temperature is slowly dropped to stove, seed crystal sintering feed is made；
(3) seed crystal ball milling：By seed crystal sintering feed ball-milling treatment made from step (2), seed crystal average grain diameter is less than 5 μm, and seed is made It is brilliant standby；
(4) dispensing, granulation, base：ZnO, Bi are proportionally added into seed crystal made from step (3)2O3、MnO2、Sb2O3、Co2O3 And Cr2O3Mixing, deionized water, poly-vinyl alcohol solution, dispersant are added into mixture, and ball milling 8-12 hours is suspended Liquid, mist projection granulating is pressed into base substrate；
(5) ceramic post sintering：Base substrate made from step (4) is put into electric furnace and is warming up to 400 DEG C of progress insulation dumpings, dumping time 4-6 hours, 1200-1350 DEG C is warming up to after dumping and is sintered, sintering time 18-23 hours is incubated 3-6 small after the completion of sintering When, make its densification into porcelain, be then cooled to normal temperature with stove.
5. Y according to claim 43+、Sn4+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, it is characterised in that： In the step (1), Ball-milling Time is 15-17 hours.
6. Y according to claim 43+、Sn4+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, it is characterised in that： It is that seed material made from step (1) is put at 1270-1280 DEG C to sinter 4-5 hours in the step (2).
7. Y according to claim 43+、Sn4+The preparation method of compound donor doping ZnO voltage-sensitive ceramics, it is characterised in that： In the step (4), the mass percent for adding poly-vinyl alcohol solution is 5%wt, and the ratio for adding poly-vinyl alcohol solution is every 50g poly-vinyl alcohol solutions are added in kilogram mixture.
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