CN1962539A - Zinc oxide base high potential gradient pressure-sensitive ceramic material and its preparation method and uses - Google Patents
Zinc oxide base high potential gradient pressure-sensitive ceramic material and its preparation method and uses Download PDFInfo
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Abstract
The invention discloses a zinc oxide base high-potential gradient voltage-sensitive ceramic material and preparing method and application, which comprises the following parts: 100mol ZnO as main component, first accessory ingredient within Bi2O3, Co2O3, MnO2, Cr2O3, Ni2O3 with molar quantity at 0.5-1.2mol respectively, second accessory ingredient with 0.8-1.5mol Sb2O3, third accessory ingredient with 0.2-1.2mol Ho2O3 and or Er2O3, forth accessory ingredient with 0.002-0.005mol Al2O3. The preparing method comprises the following steps: blending each component together to make spraying slurry; spraying; drying; graining; proceeding dry pressing; moulding; sintering. The potential gradient of voltage-sensitive ceramic material is 300-500V/mm with non-linear coefficient is more than 50, which can be applied in the electric lightning arrester or other lightning protection overvoltage protection of electric electronic circuit due to strong pulse attack resistance ability.
Description
Technical field
The present invention relates to pressure-sensitive ceramic material, particularly a kind of Zinc oxide base high potential gradient pressure-sensitive ceramic material and preparation method thereof and application.
Background technology
Pressure-sensitive ceramic material can be used for making the high potential gradient pressure-sensitive resistor disc, and this resistor disc can be used for making thunder arrester or piezoresistor, is applied to absorb in the power electronics circuit abnormal overvoltage with the protection circuit system.Regular meeting causes the circuit abnormal overvoltage because of thunderbolt or load switching in the power electronics circuit, and the ZnO pressure-sensitive ceramic material is used in a large number that the power electronics circuit absorbs or suppress abnormal overvoltage, and the protection power electronic equipment exempts from destruction.
But the ZnO pressure sensitive of now having used, its potential gradient (unit thickness pressure sensitive voltage) is usually less than 250V/mm, for the higher power electronics circuit of operating voltage, bigger or the placed in-line quantity of the thickness of the piezoresistive wafer that is adopted is more, if can improve the potential gradient of pressure sensitive, the piezoresistive wafer thickness of same application scenario can reduce or placed in-line quantity can reduce.The pressure-sensitive ceramic material that for example with potential gradient is 400V/mm in thunder arrester is used replaces used 200V/mm pressure-sensitive ceramic material, the required series connection piezoresistive wafer of thunder arrester (same thickness) quantity can reduce by half, the height of whole thunder arrester can reduce greatly, this not only can reduce the manufacturing cost of thunder arrester itself, and can reduce the gravity load and the windage of thunder arrester application scenario, improve the electrical power trans mission/distribution system reliability.
Application number is 97103063.4, name is called the patent application of " nonlinear resistor, method for producing pressure sensitive nonlinear resistor and thunder arrester ", can make the voltage dependent resistor body that potential gradient is 400～450V/mm though disclose, but cooling rate was 0～5 ℃/hour between its technological process required 700～400 ℃, and this is difficult to realize on producing; And this patent application require oxygen partial pressure greater than 50% atmosphere in cooling or annealing to improve non-linear to voltage, this will increase manufacturing cost greatly.Application number is that 200510025398.5 patent application (preparation of high-potential gradient zinc oxide piezoresistive material and application) discloses the piezoresistive material that can obtain high potential gradient, but its manufacture craft needs repeatedly ball milling, sintering, and the pulse shock tolerance of unexposed institute invention piezoresistive material, and the pulse shock tolerance is the key characteristic of pressure sensitive, and the pressure sensitive that unknown pulse impacts tolerance can not obtain to use.Application number is patent (a kind of ZnO-Bi of doped with rare-earth oxide of 200610042720.X
2O
3The series pressure-sensitive ceramic medium) disclose and to obtain the pressure sensitive that potential gradient reaches 500V/mm, but its nonlinear factor is less, leakage current is bigger.
Summary of the invention
The objective of the invention is to overcome above-mentioned technical disadvantages, provide a kind of potential gradient to reach 300～450V/mm, high potential gradient pressure-sensitive ceramic material that the pulse shock tolerance is high.
Another object of the present invention is to provide the preparation method of above-mentioned high potential gradient pressure-sensitive ceramic material.
A purpose in addition of the present invention is to provide the application of above-mentioned high potential gradient pressure-sensitive ceramic material.
Technical purpose of the present invention is achieved through the following technical solutions.
A kind of Zinc oxide base high potential gradient pressure-sensitive ceramic material, in molfraction, each component concentration is as follows:
Principal constituent ZnO:100mol part
The first minor component Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3And Ni
2O
3, each 0.5～1.2mol part
The second minor component Sb
2O
30.8～1.5mol part;
The 3rd minor component Ho
2O
3And/or Er
2O
30.2～1.2mol part;
Fourth officer composition Al
2O
30.002～0.005mol part.
Described Al
2O
3With Al (NO
3)
39H
2The O form is introduced.Described MnO
2With Mn
3O
4, MnO
2Or MnCO
3Form is introduced.Described Co
2O
3To adopt commercially available Co
3O
4Or the carbonate of cobalt element or organic salt introducing.
The preparation method of Zinc oxide base high potential gradient pressure-sensitive ceramic material comprises the following steps:
(1) by the mole umber, take by weighing first, second, third minor component, mix, ball milling is made the additive slip;
(2) principal constituent and fourth officer composition are added pure water and disperse the back and the additive slip of step (1) gained to mix, and add polyvinyl alcohol and make the spraying slip; By principal constituent and minor component total amount, per 100 grams add the polyvinyl alcohol solution that contains solid polyethylene alcohol 0.9～1.5 gram;
(3) adopt spray-drying tower with step (2) gained spraying slip spray drying granulation;
(4) with the granulation powder of step (3) gained through dry-pressing formed, make disk shape, cylindric or circular blank on demand;
(5) with step (4) gained blank through being sintering under 1100～1250 ℃ of conditions in temperature behind the binder removal, obtain Zinc oxide base high potential gradient pressure-sensitive ceramic material.
Described step (1) can also be after first, second, third minor component is mixed, adds pure water ball milling, oven dry, to be pre-burning under 600～850 ℃ of conditions in temperature, adds the pure water ball mill pulverizing again and makes the additive slip.
Described step (3) can also be the dry back of full composition slip baking to be added the granulation of sieving of polyvinyl alcohol solution mixing obtain the granulation powder.
Utilize Zinc oxide base high potential gradient pressure-sensitive ceramic material of the present invention to make piezoresistive wafer; prepare silver electrode in its both ends of the surface, the welding leading-out end, and adopt insulating resin to seal curing; make the voltage protection element, be applied to the following AC/DC low-voltage system of 1000V.
Utilizing Zinc oxide base high potential gradient pressure-sensitive ceramic material of the present invention to make potential gradient is 300～450V/mm piezoresistive wafer, and at this piezoresistive wafer edge making resistive formation and insulation layer, the resistor disc both ends of the surface are made aluminium-plated electrode, this resistor disc can reduce the volume and weight of thunder arrester greatly as the valve block of electric power thunder arrester.
With respect to prior art, the present invention has following advantage and beneficial effect:
(1) can form or manufacture craft by regulating materials chemistry, obtaining potential gradient is the high-gradient pressure-sensitive ceramic material of 300～500V/mm.
(2) the pressure-sensitive ceramic material nonlinear factor α of Huo Deing is greater than 50, and some embodiment α reaches 100.
(3) manufacture craft is simple relatively, needn't adopt the nano level starting material.
(4) high-gradient pressure sensitive pulse shock tolerance of the present invention is strong, is expected to be applied to the lightning protection overvoltage protection of electric power thunder arrester or other power electronics circuits.
Embodiment
For better understanding the present invention, below in conjunction with embodiment the present invention is done detailed description further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1～16
Adopting commercially available purity is that 99.7% indirect process zinc oxide is a principal constituent, and its median size is less than 1 micron.First minor component adopts commercially available chemical pure Bi
2O
3, Co
3O
4, MnCO
3, Cr
2O
3, Ni
2O
3, SiO
2Second minor component adopts commercially available chemical pure Sb
2O
3The 3rd minor component adopts commercially available analytical pure Ho
2O
3And Er
2O
3The fourth officer composition adopts commercially available analytical pure Al (NO
3)
39H
2O.
Each composition proportion is pressed table 1, makes 18 groups of samples altogether, comprising two groups of contrast samples.Contrast sample 1 is not for adding Ho
2O
3And Er
2O
3General potential gradient based formulas; Contrast sample 2 is excessive Ho
2O
3And Er
2O
3Prescription.
Press the required Bi of table 1 weighing
2O
3, Co
3O
4, MnCO
3, Cr
2O
3, Ni
2O
3, SiO
2, Sb
2O
3, Ho
2O
3, Er
2O
3, add pure water mixing and ball milling to median size and make the additive slip less than 1 μ m.Drop into principal constituent ZnO in agitation vat, add 1% ammonium salt dispersion agent, and with ZnO: the ratio of pure water=1: 0.8 adds pure water and disperses, and adds required deal Al (NO again
3)
39H
2O stirs and makes the principal constituent slip, slowly adds the additive slip when the principal constituent slip stirs, adds polyvinyl alcohol solution subsequently, and the deal of polyvinyl alcohol solution is the 1.2wt% of ZnO by the dry powder add-on.After mixing, brute force makes the spraying slip.The spray-dried acquisition granulation of spraying slip powder.
The granulation powder obtains the disk shape base substrate of diameter 23mm, thickness 2mm through the approximately pressure forming of 100Mpa.The base sheet is removed poly (vinyl alcohol) binder through room temperature to 500 ℃ slow intensification binder removal, obtains the about 20mm black of diameter porcelain body in three hours through 1180 ℃ of sintering again.At black porcelain body both ends of the surface printed silver electrode slurry, obtain the argent electrode layer through 600 ℃ of reduction, promptly make the voltage dependent resistor print.
After voltage dependent resistor print two sides metal electrode welding tinned wird, with print porcelain body dip-coating high-temp epoxy insullac, heat is coated with powder epoxy envelope material again after solidifying, and makes the electric performance test sample after the curing.
Adopt constant current source method specimen pressure sensitive voltage (V
1mA) and V
0.1mA, (voltage is adjusted into 83%V to adopt constant pressure source
1mA) the specimen leakage current, according to the nonlinear factor α value of following formula (1) calculation sample.
Bearing the pulsed current impact capacity is the key that pressure-active element can obtain practical application.Sample pulse shock test waveform of the present invention is 8/20 a μ s simulation lightning wave, the peak point current target value is 5000A, and the pressure sensitive voltage of specimen calculates the pressure sensitive voltage velocity of variation before and after the pulse shock test, and observe the surface structure after judgement sample bears pulse shock, if pressure sensitive voltage V
1mAVelocity of variation in ± 10%, and sample bear pulse shock after surface structure do not see destruction, it is qualified to judge that then this sample bears the pulse shock performance, otherwise judges that this sample was for losing efficacy.
Table 2 is listed the sample electric performance test result of correspondence table 1 each composition." the little current characteristics " listed in the table 2 is the mean value of every group of data recording before the pulse shock test, and " pulse shock failure rate " data are every group and impact failure number in the sum.
First minor component is a basic added ingredients, particularly Bi of realizing the non-linear character of material in table 1 ingredients listed
2O
3, Co
3O
4, MnCO
3Three kinds of compositions, the amount of first minor component is unfavorable for realizing high non-linearity very little, and is too many then can cause excessive grain boundary segregation phase, the paired pulses tolerance is unfavorable, and the amount of first minor component is many can increase the material manufacturing cost.Therefore among the embodiment 1～16 the first minor component total amount minimum be 3.6 (embodiment 13), what total amount was maximum is 5.9 (embodiment 12).
Second minor component is the important added ingredients of middle high-gradient Zinc oxide-base pressure-sensitive ceramic material in table 1 ingredients listed, simultaneously also be the effective constituent of regulating potential gradient, second minor component very little, potential gradient can be very low, but then the potential gradient regulating effect is insensitive gradually too much, and second minor component can form too much spinel phase too much, it is unfavorable that paired pulses impacts tolerance.So what the second minor component total amount was minimum among the embodiment 1～16 is 0.8 (embodiment 13), what total amount was maximum is 1.5 (embodiment 14).
The 3rd minor component is compared with contrast sample 1 (no third minor component) for improving effective added ingredients of pressure sensitive potential gradient in table 1 ingredients listed, and the potential gradient of adding the embodiment 8 of 0.2mol% the 3rd minor component has significantly and improves.But the 3rd minor component addition too much can reduce the anti-impulse of current ability of material, and the 3rd minor component add-on is 1.5% in the contrast sample 2, and it bears failure rate very high (seeing Table 2) after the pulse shock.
The fourth officer composition is used to improve the electric conductivity of stupalith crystal grain, but add-on is too much, the trend (referring to the performance of embodiment in the table 2 14～16) that has leakage current to increase
From the listed test data of table 2 as can be known, the embodiment of the invention can obtain the pressure-sensitive ceramic material that potential gradient is 300～450V/mm, and its little current characteristics is good, and leakage current is less than 1 microampere, voltage nonlinearity is greater than 50, and it is good that sample bears the pulse shock ability.Though several routine pulse shock failure numbers are arranged greater than zero among the embodiment 1～16, can be improved by changing manufacture craft.
Embodiment 17～18
Adopt the chemical constitution of embodiment 9 and 14 groups to make embodiment 17 and 18 groups of samples respectively.
The starting material place of production and the purity that adopt are identical with embodiment 1～16, are the process for making of additive slurry with the difference of embodiment 1～16.
By the required Bi of corresponding chemical ingredients weighing
2O
3, Co
3O
4, MnCO
3, Cr
2O
3, Ni
2O
3, SiO
2, Sb
2O
3, Ho
2O
3, Er
2O
3, add the pure water mixing and ball milling to median size less than 1 μ m, the alumina crucible of packing into after the oven dry 800 ℃ of insulation pre-burnings 2 hours, adds pure water ball milling to median size with the addition material of pre-burning and makes the additive slip less than 1 μ m.Follow-up making method is identical with embodiment 1～16.The sample electric performance test that obtains the results are shown in table 3.Compare with test product corresponding among embodiment 9 and the embodiment 14, the sample over-all properties that embodiment 17～18 obtains makes moderate progress.
Embodiment 19～24
Adopt the chemical constitution of 7 groups of samples of embodiment to make 6 groups of samples respectively.Except that the sintering temperature difference, process for making is identical with embodiment 17～18, adopts different sintering temperatures to make 6 groups of samples and is designated as embodiment 19～24 respectively, and sample test the results are shown in table 4.
From the listed result of table 4 as can be known, pressure sensitive of the present invention can be at 1100～1250 ℃ of temperature range sintering.Sintering temperature improves, and potential gradient reduces, but the too high or too low ability that all can reduce material withstand shock electric current of sintering temperature.19～24 of embodiment obtain the pressure sensitive potential gradient and are about 350～500V/mm.
Table 1
| Numbering | First minor component (mol%) | Second minor component (mol%) | The 3rd minor component (mol%) | Fourth officer composition (mol%) | ||||||
| Bi 2O 3 | Co 2O 3 | MnCO 3 | Cr 2O 3 | Ni 2O 3 | SiO 2 | Sb 2O 3 | Ho 2O 3 | Er 2O 3 | Al 2O 3 | |
| Contrast sample 1 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 0 | 0 | 0.004 |
| Embodiment 1 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 0.3 | 0 | 0.004 |
| Embodiment 2 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 0.75 | 0 | 0.004 |
| Embodiment 3 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 1.2 | 0 | 0.004 |
| Contrast sample 2 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 1.5 | 0 | 0.004 |
| Embodiment 4 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 0 | 0.3 | 0.004 |
| Embodiment 5 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 0 | 0.75 | 0.004 |
| Embodiment 6 | 1.0 | 1.0 | 1.0 | 0.5 | 0.5 | 0.5 | 1.0 | 0 | 1.2 | 0.004 |
| Embodiment 7 | 1.2 | 0.8 | 0.8 | 0.5 | 0.5 | 0.5 | 1.0 | 0.6 | 0.6 | 0.004 |
| Embodiment 8 | 1.0 | 1.0 | 0.8 | 0.5 | 0.5 | 0.5 | 1.0 | 0.1 | 0.1 | 0.004 |
| Embodiment 9 | 1.0 | 1.2 | 0.8 | 0.75 | 0.5 | 0.5 | 1.0 | 0.4 | 0.4 | 0.004 |
| Embodiment 10 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 1.0 | 0.4 | 0.4 | 0.004 |
| Embodiment 11 | 1.0 | 1.2 | 0.8 | 0.5 | 0.5 | 0.5 | 1.0 | 0.4 | 0.4 | 0.004 |
| Embodiment 12 | 1.2 | 1.2 | 1.0 | 0.8 | 1.2 | 0.5 | 1.0 | 0.4 | 0.4 | 0.004 |
| Embodiment 13 | 0.8 | 0.8 | 0.5 | 0.5 | 0.5 | 0.5 | 0.8 | 0.4 | 0.4 | 0.004 |
| Embodiment 14 | 0.8 | 0.8 | 1.0 | 0.5 | 0.5 | 0.5 | 1.5 | 0.4 | 0.4 | 0.004 |
| Embodiment 15 | 1.0 | 0.8 | 0.8 | 0.5 | 0.5 | 0.5 | 1.0 | 0.4 | 0.4 | 0.002 |
| Embodiment 16 | 0.8 | 1.0 | 0.8 | 0.5 | 1.0 | 0.5 | 1.0 | 0.4 | 0.4 | 0.005 |
Table 2
| Numbering | Little current characteristics (before the pulse shock) | Pulse shock failure rate (failure number/always test number) | ||
| V 1mAPotential gradient (V/mm) | Leakage current μ A | Nonlinear factor α | ||
| Contrast sample 1 | 220 | 0.5 | 58 | 0/10 |
| Embodiment 1 | 312 | 0.4 | 68 | 0/10 |
| Embodiment 2 | 391 | 0.4 | 77 | 1/10 |
| Embodiment 3 | 448 | 0.3 | 82 | 3/10 |
| Contrast sample 2 | 515 | 0.3 | 80 | 9/10 |
| Embodiment 4 | 302 | 0.4 | 72 | 0/10 |
| Embodiment 5 | 382 | 0.3 | 78 | 0/10 |
| Embodiment 6 | 435 | 0.3 | 101 | 2/10 |
| Embodiment 7 | 432 | 0.3 | 90 | 3/10 |
| Embodiment 8 | 301 | 0.5 | 69 | 0/10 |
| Embodiment 9 | 388 | 0.4 | 71 | 0/10 |
| Embodiment 10 | 368 | 0.4 | 75 | 0/10 |
| Embodiment 11 | 393 | 0.3 | 80 | 0/10 |
| Embodiment 12 | 398 | 0.3 | 81 | 0/10 |
| Embodiment 13 | 361 | 0.1 | 76 | 0/10 |
| Embodiment 14 | 402 | 0.3 | 83 | 1/10 |
| Embodiment 15 | 385 | 0.3 | 78 | 0/10 |
| Embodiment 16 | 389 | 1.0 | 50 | 0/10 |
Table 3
| Numbering | Little current characteristics (before the pulse shock) | Pulse shock failure rate (failure number/always test number) | ||
| V 1mAPotential gradient (V/mm) | Leakage current μ A | Nonlinear factor α | ||
| Embodiment 17 | 375 | 0.7 | 72 | 0/10 |
| Embodiment 18 | 391 | 0.6 | 78 | 0/10 |
Table 4
| Numbering | Sintering temperature | Little current characteristics (before the pulse shock) | Pulse shock failure rate (failure number/always test number) | ||
| V 1mAPotential gradient (V/mm) | Leakage current μ A | Nonlinear factor α | |||
| Embodiment 19 | 1100℃ | 496 | 0.8 | 73 | 2/10 |
| Embodiment 20 | 1120℃ | 468 | 0.7 | 71 | 0/10 |
| Embodiment 21 | 1150℃ | 447 | 0.6 | 75 | 0/10 |
| Embodiment 22 | 1200℃ | 395 | 0.6 | 67 | 0/10 |
| Embodiment 23 | 1220℃ | 372 | 0.9 | 73 | 0/10 |
| Embodiment 24 | 1250℃ | 346 | 0.8 | 71 | 1/10 |
Claims (9)
1, a kind of Zinc oxide base high potential gradient pressure-sensitive ceramic material is characterized in that, in molfraction, each component concentration is as follows:
Principal constituent ZnO:100mol part
The first minor component Bi
2O
3, Co
2O
3, MnO
2, Cr
2O
3And Ni
2O
3, each 0.5～1.2mol part
The second minor component Sb
2O
3, 0.8～1.5mol part;
The 3rd minor component Ho
2O
3And/or Er
2O
30.2～1.2mol part;
Fourth officer composition Al
2O
30.002～0.005mol part.
2, Zinc oxide base high potential gradient pressure-sensitive ceramic material according to claim 1 is characterized in that: Al
2O
3With Al (NO
3)
39H
2The O form is introduced.
3, Zinc oxide base high potential gradient pressure-sensitive ceramic material according to claim 1 is characterized in that: MnO
2With Mn
3O
4, MnO
2Or MnCO
3Form is introduced.
4, high potential gradient pressure-sensitive ceramic material according to claim 1 is characterized in that: Co
2O
3To adopt commercially available Co
3O
4, the carbonate of cobalt element or organic salt introduces.
5, the preparation method of the described Zinc oxide base high potential gradient pressure-sensitive ceramic material of claim 1 is characterized in that comprising the following steps:
(1) by the mole umber, take by weighing first, second, third minor component, mix, ball milling is made the additive slip;
(2) principal constituent and fourth officer composition are added pure water and disperse the back and the additive slip of step (1) gained to mix, and add polyvinyl alcohol and make the spraying slip; By principal constituent and minor component total amount, per 100 grams add the polyvinyl alcohol solution that contains solid polyethylene alcohol 0.9～1.5 gram;
(3) adopt spray-drying tower with step (2) gained spraying slip spray drying granulation;
(4) with the granulation powder of step (3) gained through dry-pressing formed, make disk shape, cylindric or circular blank on demand;
(5) with step (4) gained blank through being sintering under 1100～1250 ℃ of conditions in temperature behind the binder removal, obtain Zinc oxide base high potential gradient pressure-sensitive ceramic material.
6, the preparation method of Zinc oxide base high potential gradient pressure-sensitive ceramic material according to claim 5, it is characterized in that: described step (1) is after first, second, third minor component is mixed, adds pure water ball milling, oven dry, in temperature is pre-burning under 600～850 ℃ of conditions, adds the pure water ball mill pulverizing again and makes the additive slip.
7, the preparation method of Zinc oxide base high potential gradient pressure-sensitive ceramic material according to claim 5 is characterized in that: described step (3) obtains the granulation powder for granulation that the dry back adding of full composition slip baking polyvinyl alcohol solution mixing is sieved.
8, the application of the described Zinc oxide base high potential gradient pressure-sensitive ceramic material of claim 1; it is characterized in that; utilize Zinc oxide base high potential gradient pressure-sensitive ceramic material to make piezoresistive wafer; prepare silver electrode in its both ends of the surface; the welding leading-out end; and adopt insulating resin to seal curing, and make the voltage protection element, be applied to the following AC/DC low-voltage system of 1000V.
9, the application of the described Zinc oxide base high potential gradient pressure-sensitive ceramic material of claim 1, it is characterized in that, utilizing Zinc oxide base high potential gradient pressure-sensitive ceramic material to make potential gradient is 300～450V/mm piezoresistive wafer, and at this piezoresistive wafer edge making resistive formation and insulation layer, the resistor disc both ends of the surface are made aluminium-plated electrode, and this resistor disc is applied to make the electric power thunder arrester.
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| CN100361238C (en) * | 2004-11-22 | 2008-01-09 | 山东大学 | Multielement doped modified zinc oxide pressure sensitive material for lightning protection |
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