CN108675783A - A kind of material and preparation method thereof for zinc oxide varistor - Google Patents

A kind of material and preparation method thereof for zinc oxide varistor Download PDF

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Publication number
CN108675783A
CN108675783A CN201810505084.2A CN201810505084A CN108675783A CN 108675783 A CN108675783 A CN 108675783A CN 201810505084 A CN201810505084 A CN 201810505084A CN 108675783 A CN108675783 A CN 108675783A
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parts
zinc oxide
mixture
preparation
varistor
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汪洋
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Jiangsu Shi Rui Electronic Science And Technology Co Ltd
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Jiangsu Shi Rui Electronic Science And Technology Co Ltd
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Abstract

The invention belongs to field of electronic devices, and in particular to a kind of material and preparation method thereof for zinc oxide varistor.The material includes zinc oxide, V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3、Co3O4, tin oxide, ytterbium oxide, dispersant, binder and deionized water.The material property for zinc oxide varistor obtained by preparation method of the present invention is excellent, and toxic Element Lead is free of in the present invention, environmentally protective, and in preparation process, energy consumption is small, meets energy-saving and environment-friendly requirement.

Description

A kind of material and preparation method thereof for zinc oxide varistor
Technical field
The invention belongs to field of electronic devices, and in particular to a kind of material and its preparation for zinc oxide varistor Method.
Background technology
Varistor is a kind of votage limit type guard period.Using the nonlinear characteristic of varistor, when overvoltage appears in Two interpolars of varistor, varistor can have never been realized by voltage clamping to a relatively-stationary voltage value to rear class The protection of circuit.In recent years, with the rapid development of information technology, the miniaturization of electronic equipment, multifunction, high stability The inexorable trend referred to as developed, the varistor as protection semiconductor element is also correspondingly towards frivolous, low pressure, highly reliable Property direction is developed.
And zinc oxide varistor obtains wide always because having both the features such as simple for process, of low cost, easy to use General application.But now due to auto industry, communication apparatus, railway signal, micromotor and various electronic components needs are frivolous Resistor, resistor element thickness be thinned after, not only element mechanical strength reduce, and discharge capacity reduce, dimension, such as What seeks the pressure-sensitive functional material that a kind of pressure sensitive voltage value of unit thickness is low while leakage current is small, at present zinc oxide system Standby industry problem in urgent need to solve.
Application No. is 201510758001.7 patent of invention disclose a kind of zinc oxide varistor dielectric material and The zinc oxide varistor dielectric material pulse shock tolerance of preparation method, the invention is strong, it is expected to be applied to electric power The lightning protection overvoltage protection of arrester or other power electronic circuits；But the zinc oxide varistor dielectric material of the present invention exists It is sintered at 1000-1100 DEG C, sintering temperature is higher, has been unsatisfactory for energy-saving and environment-friendly requirement.
Invention content
For the deficiencies in the prior art, the present invention provide a kind of material for zinc oxide varistor and its Preparation method, the material property for zinc oxide varistor obtained by the invention preparation method is excellent, and in the present invention not It is environmentally protective containing toxic Element Lead, and in preparation process, energy consumption is small, meets energy-saving and environment-friendly requirement.
In order to achieve the above-mentioned object of the invention, present invention employs following technical schemes：
A kind of material for zinc oxide varistor, including following content of component：80-100 parts of zinc oxide, V2O50.05-1.3 parts, TiO20.05-1.3 parts, Bi2O30.05-1.3 parts, MnO20.05-1.3 parts, MgO0.05-0.6 Part, Nb2O50.05-0.6 parts, BaO0.05-1.3 parts, Cr2O30.05-1.3 parts, SnO20.05-1.3 parts, SiO20.05- 1.3 parts, Ni2O30.05-1.3 parts, 0.05-0.6 parts of boric acid, Sm2O30.05-0.6 parts, Co3O40.05-0.6 parts, tin oxide 30-60 parts of 0.05-1.3 parts, 10-20 parts of ytterbium oxide, 10-15 parts of dispersant, 5-15 parts of binder and deionized water.
Preferably, the material for zinc oxide varistor, including following content of component：98 parts of zinc oxide, V2O50.07 part, TiO20.09 part, Bi2O30.07 part, MnO21.1 parts, MgO0.3 parts, Nb2O50.5 part, BaO1.1 parts, Cr2O31.2 part, SnO20.07 part, SiO20.08 part, Ni2O30.09 part, 0.4 part of boric acid, Sm2O30.35 part, Co3O40.27 part, 45 parts of 0.08 part of tin oxide, 15 parts of ytterbium oxide, 12 parts of dispersant, 12 parts of binder and deionized water.
Preferably, the zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 10-40nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3And Co3O4 It mixes and is dissolved in deionized water and obtain mixture, mixture is put into ball mill and carries out being wet ground, rotating speed 600- 1200rpm, ratio of grinding media to material 5：1-10:1, the first mixture is obtained after wet ground；Step 3, by zinc oxide, tin oxide and oxidation Ytterbium is added in the first mixture, carries out secondary ball milling processing, and being passed through liquid nitrogen in mechanical milling process cools down to mixture, and During secondary ball milling, dispersant is added into mixture in three times and binder, ball-milling treatment 2-4 hours obtain second Mixture；Step 4, the second mixture three-roll rolling is handled and is spray-dried, obtain mix powder；Step 5, by mixture Calcination processing at powder is 780-800 DEG C in temperature, obtains the material for zinc oxide varistor.
Preferably, the wet ground time is 3-6 hours in the step 1.
Compared with prior art, the invention has the advantages that：
The material composition of the present invention is simple, can be sintered at low temperature, not only meets the requirement of environmental protection, prepares simultaneously It is simple for process, greatly reduce production cost；By the pressure-sensitive electricity of the material produced by the present invention for zinc oxide varistor Press high comprehensive performance.
Specific implementation mode
Below by specific implementation mode, invention is further described in detail.But those skilled in the art will manage Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment Art or condition person carry out to specifications according to technology described in document in the art or condition.Agents useful for same or instrument Production firm person is not specified, being can be with conventional products that are commercially available.
Embodiment 1
A kind of material for zinc oxide varistor, including following content of component：100 parts of zinc oxide, V2O51.3 Part, TiO21.3 part, Bi2O31.3 parts, MnO21.3 parts, MgO0.6 parts, Nb2O50.6 part, BaO1.3 parts, Cr2O31.3 parts, SnO21.3 parts, SiO21.3 parts, Ni2O31.3 part, 0.6 part of boric acid, Sm2O30.6 part, Co3O40.6 part, 1.3 parts of tin oxide, oxidation 60 parts of 20 parts of ytterbium, 15 parts of dispersant, 15 parts of binder and deionized water.
The zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 40nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3And Co3O4 It mixes and is dissolved in deionized water and obtain mixture, mixture is put into and carries out being wet ground in ball mill, rotating speed is 1200rpm, ratio of grinding media to material 10:1, the first mixture is obtained after wet ground；Step 3, zinc oxide, tin oxide and ytterbium oxide are added It adds in the first mixture, carries out secondary ball milling processing, being passed through liquid nitrogen in mechanical milling process cools down to mixture, and two In secondary mechanical milling process, dispersant is added into mixture in three times and binder, ball-milling treatment 4 hours obtain the second mixture； Step 4, the second mixture three-roll rolling is handled and is spray-dried, obtain mix powder；Step 5, mix powder is existed Temperature is calcination processing at 800 DEG C, obtains the material for zinc oxide varistor.
The wet ground time is 6 hours in the step 1.
Embodiment 2
A kind of material for zinc oxide varistor, including following content of component：80 parts of zinc oxide, V2O50.05 Part, TiO20.05 part, Bi2O30.05 part, MnO20.05 part, MgO0.05 parts, Nb2O50.05 part, BaO0.05 parts, Cr2O30.05 Part, SnO20.05 part, SiO20.05 part, Ni2O30.05 part, 0.05 part of boric acid, Sm2O30.05 part, Co3O40.05 part, tin oxide 30 parts of 0.05 part, 10 parts of ytterbium oxide, 10 parts of dispersant, 5 parts of binder and deionized water.
The zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 30nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3And Co3O4 It mixes and is dissolved in deionized water and obtain mixture, mixture is put into and carries out being wet ground in ball mill, rotating speed is 600rpm, ratio of grinding media to material 8:1, the first mixture is obtained after wet ground；Step 3, zinc oxide, tin oxide and ytterbium oxide are added Into the first mixture, secondary ball milling processing is carried out, being passed through liquid nitrogen in mechanical milling process cools down to mixture, and secondary In mechanical milling process, dispersant is added into mixture in three times and binder, ball-milling treatment 2 hours obtain the second mixture；Step Rapid 4, the second mixture three-roll rolling is handled and is spray-dried, mix powder is obtained；Step 5, by mix powder in temperature Degree is calcination processing at 790 DEG C, obtains the material for zinc oxide varistor.
The wet ground time is 3 hours in the step 1.
Embodiment 3
A kind of material for zinc oxide varistor, including following content of component：98 parts of zinc oxide, V2O50.07 Part, TiO20.09 part, Bi2O30.07 part, MnO21.1 part, MgO0.3 parts, Nb2O50.5 part, BaO1.1 parts, Cr2O31.2 parts, SnO20.07 part, SiO20.08 part, Ni2O30.09 part, 0.4 part of boric acid, Sm2O30.35 part, Co3O40.27 part, tin oxide 0.08 Part, 15 parts of ytterbium oxide, 12 parts of dispersant, 12 parts of binder and 45 parts of deionized water.
The zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 10nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3And Co3O4 It mixes and is dissolved in deionized water and obtain mixture, mixture is put into ball mill and carries out being wet ground, rotating speed 600- 1200rpm, ratio of grinding media to material 5：1, the first mixture is obtained after wet ground；Step 3, zinc oxide, tin oxide and ytterbium oxide are added It adds in the first mixture, carries out secondary ball milling processing, being passed through liquid nitrogen in mechanical milling process cools down to mixture, and two In secondary mechanical milling process, dispersant is added into mixture in three times and binder, ball-milling treatment 3.5 hours obtain the second mixing Object；Step 4, the second mixture three-roll rolling is handled and is spray-dried, obtain mix powder；Step 5, by mix powder Calcination processing at being 780 DEG C in temperature, obtains the material for zinc oxide varistor.
The wet ground time is 5 hours in the step 1.
Comparative example 1
Step is with embodiment 1, the difference is that being not added with ytterbium oxide.
A kind of material for zinc oxide varistor, including following content of component：100 parts of zinc oxide, V2O51.3 Part, TiO21.3 parts, Bi2O31.3 parts, MnO21.3 part, MgO0.6 parts, Nb2O50.6 part, BaO1.3 parts, Cr2O31.3 parts, SnO21.3 part, SiO21.3 part, Ni2O31.3 parts, 0.6 part of boric acid, Sm2O30.6 part, Co3O40.6 part, 1.3 parts of tin oxide, dispersion 60 parts of 15 parts of agent, 15 parts of binder and deionized water.
The zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 40nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3And Co3O4 It mixes and is dissolved in deionized water and obtain mixture, mixture is put into and carries out being wet ground in ball mill, rotating speed is 1200rpm, ratio of grinding media to material 10:1, the first mixture is obtained after wet ground；Step 3, zinc oxide and tin oxide are added to In one mixture, secondary ball milling processing is carried out, being passed through liquid nitrogen in mechanical milling process cools down to mixture, and in secondary ball milling In the process, dispersant is added into mixture in three times and binder, ball-milling treatment 4 hours obtains the second mixture；Step 4, Second mixture three-roll rolling is handled and is spray-dried, mix powder is obtained；Step 5, it is in temperature by mix powder Calcination processing at 800 DEG C obtains the material for zinc oxide varistor.
The wet ground time is 6 hours in the step 1.
Comparative example 2
Step is with embodiment 2, the difference is that the processing that do not cool down.
A kind of material for zinc oxide varistor, including following content of component：80 parts of zinc oxide, V2O50.05 Part, TiO20.05 part, Bi2O30.05 part, MnO20.05 part, MgO0.05 parts, Nb2O50.05 part, BaO0.05 parts, Cr2O30.05 Part, SnO20.05 part, SiO20.05 part, Ni2O30.05 part, 0.05 part of boric acid, Sm2O30.05 part, Co3O40.05 part, tin oxide 30 parts of 0.05 part, 10 parts of ytterbium oxide, 10 parts of dispersant, 5 parts of binder and deionized water.
The zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 30nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3And Co3O4 It mixes and is dissolved in deionized water and obtain mixture, mixture is put into and carries out being wet ground in ball mill, rotating speed is 600rpm, ratio of grinding media to material 8:1, the first mixture is obtained after wet ground；Step 3, zinc oxide, tin oxide and ytterbium oxide are added Into the first mixture, secondary ball milling processing is carried out, and during secondary ball milling, dispersion is added into mixture in three times Agent and binder, ball-milling treatment 2 hours, obtain the second mixture；Step 4, the second mixture three-roll rolling is handled and is sprayed It is dry, obtain mix powder；Step 5, by mix powder temperature be 790 DEG C at calcination processing, obtain be used for zinc oxide The material of piezoresistor.
The wet ground time is 3 hours in the step 1.
Comparative example 3
Step is with embodiment 2, the difference is that by TiO2Replace with lead oxide.
A kind of material for zinc oxide varistor, including following content of component：98 parts of zinc oxide, V2O50.07 Part, 0.09 part of lead oxide, Bi2O30.07 part, MnO21.1 part, MgO0.3 parts, Nb2O50.5 part, BaO1.1 parts, Cr2O31.2 parts, SnO20.07 part, SiO20.08 part, Ni2O30.09 part, 0.4 part of boric acid, Sm2O30.35 part, Co3O40.27 part, tin oxide 0.08 Part, 15 parts of ytterbium oxide, 12 parts of dispersant, 12 parts of binder and 45 parts of deionized water.
The zinc oxide is nano-zinc oxide powder, and nano-zinc oxide powder grain size is 10nm.
A kind of preparation method of material for zinc oxide varistor, includes the following steps：Step 1, raw material is weighed； Step 2, by V2O5, lead oxide, Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、SiO2、Ni2O3, boric acid, Sm2O3With Co3O4It mixes and is dissolved in deionized water and obtain mixture, mixture is put into and carries out being wet ground in ball mill, rotating speed is 600-1200rpm, ratio of grinding media to material 5：1, the first mixture is obtained after wet ground；Step 3, by zinc oxide, tin oxide and oxidation Ytterbium is added in the first mixture, carries out secondary ball milling processing, and being passed through liquid nitrogen in mechanical milling process cools down to mixture, and During secondary ball milling, dispersant is added into mixture in three times and binder, ball-milling treatment 3.5 hours obtain second Mixture；Step 4, the second mixture three-roll rolling is handled and is spray-dried, obtain mix powder；Step 5, by mixture Calcination processing at powder is 780 DEG C in temperature, obtains the material for zinc oxide varistor.
The wet ground time is 5 hours in the step 1.
The material for zinc oxide varistor obtained by embodiment 1-3 and comparative example 1-3 is tested for the property, institute The results are shown in table below：
As upper table is visible：The material property for zinc oxide varistor obtained by preparation method of the present invention is excellent, and Toxic Element Lead is free of in the present invention, it is environmentally protective, and in preparation process, energy consumption is small, meets energy-saving and environment-friendly requirement.
The above is only preferred embodiments of the present invention, is not intended to limit the scope of the present invention, Therefore every any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, belong to In the range of technical solution of the present invention.

Claims (5)

1. a kind of material for zinc oxide varistor, which is characterized in that including following content of component：Zinc oxide 80- 100 parts, V2O50.05-1.3 parts, TiO20.05-1.3 parts, Bi2O30.05-1.3 parts, MnO20.05-1.3 parts, MgO0.05-0.6 parts, Nb2O50.05-0.6 parts, BaO0.05-1.3 parts, Cr2O30.05-1.3 parts, SnO20.05-1.3 parts, SiO20.05-1.3 parts, Ni2O30.05-1.3 parts, 0.05-0.6 parts of boric acid, Sm2O30.05-0.6 parts, Co3O40.05- 0.6 part, 0.05-1.3 parts of tin oxide, 10-20 parts of ytterbium oxide, 10-15 parts of dispersant, 5-15 parts of binder and deionized water 30- 60 parts.
2. a kind of material for zinc oxide varistor according to claim 1, which is characterized in that including following matter Measure part component：98 parts of zinc oxide, V2O50.07 part, TiO20.09 part, Bi2O30.07 part, MnO21.1 parts, MgO0.3 parts, Nb2O50.5 part, BaO1.1 parts, Cr2O31.2 parts, SnO20.07 part, SiO20.08 part, Ni2O30.09 part, 0.4 part of boric acid, Sm2O30.35 part, Co3O40.27 part, 0.08 part of tin oxide, 15 parts of ytterbium oxide, 12 parts of dispersant, 12 parts of binder and deionization 45 parts of water.
3. a kind of material for zinc oxide varistor according to claim 1, which is characterized in that the zinc oxide For nano-zinc oxide powder, nano-zinc oxide powder grain size is 10-40nm.
4. a kind of preparation method of material for zinc oxide varistor described in claim 1, which is characterized in that including Following steps：Step 1, raw material is weighed；Step 2, by V2O5、TiO2、Bi2O3、MnO2、MgO、Nb2O5、BaO、Cr2O3、SnO2、 SiO2、Ni2O3, boric acid, Sm2O3And Co3O4It mixes and is dissolved in deionized water and obtain mixture, mixture is put into ball mill It carries out being wet ground, rotating speed 600-1200rpm, ratio of grinding media to material 5：1-10:1, the first mixture is obtained after wet ground；Step Rapid 3, zinc oxide, tin oxide and ytterbium oxide are added in the first mixture, secondary ball milling processing is carried out, is passed through in mechanical milling process Liquid nitrogen cools down to mixture, and during secondary ball milling, and dispersant and binder is added into mixture in three times, Ball-milling treatment 2-4 hours, obtains the second mixture；Step 4, the second mixture three-roll rolling is handled and is spray-dried, obtained Mix powder；Step 5, by mix powder temperature be 780-800 DEG C at calcination processing, obtain for zinc oxide pressure-sensitive electricity Hinder the material of device.
5. a kind of preparation method of material for zinc oxide varistor according to claim 4, which is characterized in that The wet ground time is 3-6 hours in the step 1.
CN201810505084.2A 2018-05-24 2018-05-24 A kind of material and preparation method thereof for zinc oxide varistor Pending CN108675783A (en)

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