CN117003559A - Piezoresistor ceramic powder and preparation method and application thereof - Google Patents

Piezoresistor ceramic powder and preparation method and application thereof Download PDF

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Publication number
CN117003559A
CN117003559A CN202310950192.1A CN202310950192A CN117003559A CN 117003559 A CN117003559 A CN 117003559A CN 202310950192 A CN202310950192 A CN 202310950192A CN 117003559 A CN117003559 A CN 117003559A
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parts
varistor
ceramic powder
additive
powder
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Inventor
岑权进
金鹿江
任鑫
姚政
宋毅华
李强
陈志华
胡建兵
褚俊华
曹秀华
胡春元
李梅
向湘红
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Guangdong Fenghua Advanced Tech Holding Co Ltd
University of Shanghai for Science and Technology
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Guangdong Fenghua Advanced Tech Holding Co Ltd
University of Shanghai for Science and Technology
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Priority to CN202310950192.1A priority Critical patent/CN117003559A/en
Publication of CN117003559A publication Critical patent/CN117003559A/en
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    • C04B35/01—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
    • 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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    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
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Abstract

The invention discloses varistor ceramic powder and a preparation method and application thereof, and belongs to the technical field of resistor materials. According to the invention, specific parts by weight of Al element and Ba element are introduced into the varistor ceramic powder, rare earth oxide is introduced into the additive, and the parts by weight of each component in the varistor ceramic powder are controlled, so that the prepared varistor sheet can be sintered at low temperature and has high potential gradient and current capacity; the maximum current density of the resistor disc can reach 4000A/cm 2 Above, the performance stability is good, can be used to prepare super high energy chip varistor material, satisfies the use demands such as electronic product protection surge voltage height, surge current is big.

Description

Piezoresistor ceramic powder and preparation method and application thereof
Technical Field
The invention belongs to the technical field of resistance materials, and particularly relates to a piezoresistor ceramic powder and a preparation method and application thereof.
Background
Along with the rapid development of electronic circuit components in Surface Mount Technology (SMT) in the fields of communication modules, program controlled exchanges, automobile electronics and the like, the requirements of smaller volume, faster response speed, no polarity, low limiting voltage and the like are also provided for piezoresistors. The chip varistor is used as an overvoltage protection core element, the performance of the chip varistor directly affects the stability and the safety of the operation of electronic equipment, and the large through-current capacity and the low limiting voltage are important factors for realizing miniaturization and high energy of the varistor.
The zinc oxide (ZnO) piezoresistor has the characteristics of cheap components, simple process, adjustable potential gradient, high nonlinear coefficient and the like, and is widely applied to the fields of electric power systems, rail transit, electric facility protection and the like. ZnO is used as a main component, and a plurality of metal oxides such as bismuth oxide, antimony oxide, manganese oxide, niobium oxide, cobalt oxide and the like are used as additives to form a multi-element semiconductor ceramic material through processes of mixing, grinding, forming, sintering and the like; the ZnO varistor may be classified into a bismuth-based varistor and a praseodymium-based (or rare earth-based) varistor according to the difference of additives. Patent KR20130060127A discloses a method for manufacturing a zinc oxide varistor, wherein zinc oxide crystal grains of non-equivalent ions are respectively doped in advance according to a preset potential gradient of the varistor, and then sintered powder is prepared independently according to the preset potential gradient of a specific zinc oxide varistor. The traditional piezoresistor is not in line with the use requirements of high surge voltage, high surge current and the like of the protection of the current electronic products due to the limitations of low voltage, small current capacity and the like.
Aiming at the problems of the piezoresistor, the development of the piezoresistor ceramic powder with high potential gradient and high through-flow capacity is the focus of research in the technical field of the current resistance material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the varistor ceramic powder, the preparation method and the application thereof, and the varistor sheet prepared by the varistor ceramic powder can be sintered at low temperature and has excellent potential gradient and current capacity.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a varistor ceramic powder, which comprises the following components in parts by weight: 80.0-97.5 parts of ZnO, 0.01-0.06 part of aluminum salt, 0.01-0.05 part of barium salt and 2.0-20.0 parts of additive; the additive comprises the following components: bi (Bi) 2 O 3 、Sb 2 O 3 、Co 3 O 4 、Mn 3 O 4 、SiO 2 、TiO 2 Silver glass powder and rare earth oxide.
The invention adopts the components to compound and prepare the varistor ceramic powder, and the addition of Al element and Ba element in specific parts by weight in the ceramic powder is beneficial to improving the grain boundary barrier and reducing the grain resistance, thereby improving the stability of the varistor in long-term operation, reducing the residual voltage after lightning energy impact and enhancing the protection characteristic of the varistor.
The inventor also discovers that the addition of aluminum salt and barium salt has great influence on the performance of the final piezoresistor porcelain powder in the invention; if the addition amount of the aluminum element is too low, the grain resistance is difficult to reduce, and the protection of the residual voltage ratio is reduced; the addition of the aluminum element is too high, so that the leakage current of the piezoresistor is obviously increased, and the current level of the resistor is reduced. Meanwhile, in the invention, the proper dosage of Ba is favorable for improving the grain boundary stability, and the too high or too low content of Ba element can influence the structure, the components and the properties of a grain boundary phase, thereby negatively influencing the interface properties among grains.
The inventor also found that by introducing rare earth oxide into the additive, the rare earth oxide can be used as a growth inhibitor of ZnO, and is partially pinned at a crystal boundary, so that the mass transfer capability of interstitial zinc ions is reduced, the crystal boundary structure and components of the varistor are improved, and the potential gradient of the varistor is improved under the condition that the prepared varistor keeps higher current passing capability and lower leakage current.
The inventor also finds that the weight parts of the additives in the ceramic powder have great influence on the performance of the final piezoresistor sheet, and if the weight parts of the additives are less than 2.0 parts, the through-flow level, the ageing resistance and the nonlinear coefficient of the piezoresistor are reduced; if the additive is excessively used, the uniformity of the grain size can be affected, so that the leakage current of the piezoresistor is increased, and the voltage change rate is increased.
As a preferred embodiment of the varistor ceramic powder, the varistor ceramic powder comprises the following components in parts by weight: 86.0-95.5 parts of ZnO, 0.015-0.03 part of aluminum salt, 0.016-0.035 part of barium salt and 6.0-15.0 parts of additive; the inventor finds that the final comprehensive performance of the varistor ceramic powder under the preferable conditions is the best through a large number of experiments.
As a preferred embodiment of the varistor ceramic powder, the additive comprises the following components in parts by weight: bi (Bi) 2 O 3 30.0 to 60.0 parts of Sb 2 O 3 6.0-20 parts, co 3 O 4 12.0 to 28.0 parts of Mn 3 O 4 1.0 to 8.0 parts of SiO 2 5.0 to 23.0 portions of TiO 2 0.1-3.0 parts, 0.2-4.0 parts of rare earth oxide and 0.5-2.5 parts of silver glass powder.
As a more preferable embodiment of the varistor ceramic powder, the additive comprises the following components in parts by weight: bi (Bi) 2 O 3 35.0 to 55.0 parts of Sb 2 O 3 8.0-15 parts, co 3 O 4 14.0-25.0 parts, mn 3 O 4 1.0 to 5.0 parts of SiO 2 10.0 to 20.0 parts of TiO 2 0.5-2.0 parts, rare earth oxide 0.5-2.0 parts and silver glass powder 0.8-2 parts.
The inventors have found that when the content of each component in the additive is within the above-described range, particularly within a further preferable range, the potential gradient and the current passing ability of the obtained varistor are more excellent.
As the preferable implementation mode of the piezoresistor porcelain powder, the grain diameter of the silver glass powder is less than or equal to 1 mu m, the silver oxide content in the silver glass powder is more than or equal to 20wt% and the bismuth oxide content is more than or equal to 30wt%; the silver oxide and bismuth oxide content in the silver glass powder are too low, so that the high-current impact resistance test of the piezoresistor is adversely affected.
As a preferred embodiment of the varistor ceramic powder of the present invention, the aluminum salt is aluminum nitrate nonahydrate (Al (NO) 3 ) 3 ·9H 2 O) the barium salt is barium acetate (Ba (AC) 2 )。
As a preferable embodiment of the varistor ceramic powder, the rare earth oxide is Y 2 O 3 、La 2 O 3 、Nd 2 O 3 Or CeO 2 。
As a more preferable embodiment of the varistor ceramic powder of the invention, the rare earth oxide is CeO 2 The method comprises the steps of carrying out a first treatment on the surface of the The inventors found through a large number of experiments that CeO was used 2 The potential gradient and the current capacity of the piezoresistor can be improved to the greatest extent.
As a preferred embodiment of the varistor ceramic powder, the varistor ceramic powder further comprises a dispersing agent and a binder.
In a second aspect, the present invention provides a process for the preparation of the additive, the process comprising the steps of:
s1, mixing an additive and a dispersing agent, pre-dispersing, grinding, filtering and crushing the pre-dispersed slurry, and sieving the slurry with a 30-mesh sieve to obtain powder;
s2, calcining the powder in the step S1 at 650-950 ℃ for 0.5-4 hours, crushing after calcining, and sieving with a 30-mesh sieve;
s3, secondarily refining the powder obtained in the step S2 to obtain the additive.
As a preferred embodiment of the preparation method of the additive, in the step S1, the pre-dispersing speed is 500-3000r/min, and the pre-dispersing time is 10-60min; grinding the dispersed slurry in a horizontal sand mill at a grinding rate of 1000-3000r/min for 1-5h; filtering the ground slurry by adopting a 120-mesh screen, and drying and crushing the filtered additive at the temperature of 100-130 ℃.
As a more preferable embodiment of the preparation method of the additive, in the step S1, the pre-dispersing speed is 800-1500r/min, and the pre-dispersing time is 10-30min; the grinding rate is 1000-2000r/min, and the grinding time is 1-3h.
As a preferred embodiment of the method for preparing the additive according to the present invention, in the step S2, the calcination temperature is 700-900 ℃.
The inventor finds out through a large number of experiments that by adopting the method, under specific preparation parameters, each component in the additive is fully mixed; the gas decomposition product generated by the component reaction is removed through the step S2, and the valence state change of the valence-changing oxide is completed, so that the additive with narrow particle size distribution and small average particle size can be obtained, and becomes a stable additive compound, thereby being beneficial to the subsequent solid phase reaction, reducing the porosity of the ceramic powder and improving the compactness of the ceramic powder; the product is then subjected to a secondary refinement by step S3, which is identical to step S1, with the aim of more thoroughly mixing the components of the additive.
In a third aspect, the present invention provides a method for preparing the varistor ceramic powder, the method comprising the steps of: mixing the piezoresistor porcelain powder, a dispersing agent and a binder, ball milling for 12-48 hours, sieving with a 100-mesh sieve after ball milling, and spray drying to obtain the piezoresistor porcelain powder.
In a fourth aspect, the present invention provides a varistor sheet made from the varistor ceramic powder according to the first aspect.
As a preferred embodiment of the varistor sheet of the present invention, the varistor sheet further comprises a dispersing agent, a defoaming agent and a binder.
As a preferred embodiment of the varistor according to the present invention, the method for preparing the varistor comprises the steps of:
c1, mixing the components, ball milling for 12-24 hours, and press forming to obtain a resistor disc blank;
c2, performing glue discharging, sintering and heat treatment on the blank body obtained in the step C1;
and C3, coating silver on the green body obtained in the step C2, firing silver, and brushing insulating paint to obtain the varistor.
As a preferred embodiment of the varistor sheet of the present invention, in the method for producing a varistor sheet, the green body in the step C1 has a density of 3.2-3.3g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The inventor finds out through a large number of experiments that if the density of the blank is too small, partial pores in the body are difficult to completely discharge in the sintering process, so that the porosity is increased; if the density of the green body is too high, some air holes in the green body can form closed air holes, and the porosity can be increased in the subsequent sintering process.
The inventor finds through a large number of experiments that in the step C2, the residual organic matters in the green body can be removed by glue discharging, sintering and heat treatment are beneficial to stabilizing a grain boundary barrier, and the stability and the current passing capability of the varistor under the action of continuous voltage are improved.
In the step C2, the glue discharging temperature is 400-530 ℃; the sintering parameters are as follows: the temperature is 900-1080 ℃, the time is 1-7h, and the heating rate is 0.5-4.5 ℃/min; the heat treatment parameters are as follows: the temperature is 500-650 ℃ and the time is 1-5h.
As a more preferable embodiment of the preparation method of the resistor disc, in the step C2, the glue discharging temperature is 420-480 ℃; the sintering parameters are as follows: the temperature is 900-1000 ℃ and the time is 2-4 hours; the heat treatment parameters are as follows: the temperature is 520-580 ℃ and the time is 1-3h.
The inventor finds that the piezoresistor sheet prepared under the preparation parameters has good performance stability and the maximum through-flow density can reach 4000A/cm through a large number of experiments 2 The low-temperature sintering can be realized, and the high-potential gradient and the through-flow capability are realized.
Compared with the prior art, the invention has the beneficial effects that:
the invention introduces specific weight parts of Al element and Ba element into the piezoresistor porcelain powder, and introduces rare earth oxide CeO into the additive 2 The weight parts of all components in the varistor ceramic powder are controlled, so that the prepared varistor can be sintered at low temperature and has high potential gradient and current capacity; the maximum current density of the resistor disc can reach 4000A/cm 2 Above, the performance stability is good, can be used to prepare super high energy chip varistor material, satisfies the use demands such as electronic product protection surge voltage height, surge current is big.
Drawings
FIG. 1 is a flow chart of the preparation of the varistor ceramic powder of the invention;
FIG. 2 is a scanning electron microscope image of a pressure sensitive resistor disc according to an embodiment of the present invention;
FIG. 3 is a scanning electron microscope image of a piezoresistor sheet according to an embodiment of the present invention.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
The reagents, methods and apparatus employed in the present invention, unless otherwise specified, are all conventional in the art.
Example 1
The formula of the varistor ceramic powder in the embodiment 1 of the invention is shown in the table 1, and the formula of the additive is shown in the table 2;
the preparation method of the additive comprises the following steps:
s1, mixing the components of the additive, water and a dispersing agent in a stainless steel charging barrel, and pre-dispersing, wherein the pre-dispersing speed is 1000r/min, and the pre-dispersing time is 15min; transferring the pre-dispersed slurry into a horizontal sand mill for grinding by a constant flow pump, wherein the grinding speed is 2000r/min, and the grinding time is 2h; filtering the ground slurry by adopting a 120-mesh screen, drying and crushing the filtered slurry at the temperature of 120 ℃, and fully and uniformly mixing the crushed slurry twice by a 30-mesh screen to obtain powder;
s2, calcining the powder in the step S1 at 850 ℃ for 1h, crushing after calcining, and sieving with a 30-mesh sieve;
s3, carrying out secondary refinement on the powder obtained in the step S2, namely mixing the powder obtained in the step S2, water and a dispersing agent in a stainless steel charging barrel, and pre-dispersing at a rotating speed of 1000r/min for 15min; transferring the pre-dispersed slurry into a horizontal sand mill for grinding by a constant flow pump, wherein the grinding speed is 2000r/min, and the grinding time is 2h; and filtering the ground slurry by adopting a 120-mesh screen, drying and crushing the filtered slurry at the temperature of 120 ℃, and fully and uniformly mixing the crushed slurry through a 30-mesh screen twice to obtain the additive.
The preparation method of the varistor ceramic powder comprises the following steps: mixing and ball milling the components with water, a dispersing agent and a binder in a ball mill for 24 hours, sieving with a 100-mesh sieve after ball milling, and performing spray drying by adopting a spray granulator to obtain the varistor ceramic powder.
The preparation method of the varistor sheet comprises the following steps:
c1, mixing the ceramic powder, water, a dispersing agent, a binder and a defoaming agent, ball-milling for 12 hours in a ball mill, placing for 12 hours, and pressing and forming by a tablet press to obtain a resistor disc blank, wherein the side length of the blank is 26.8mm, the thickness of the blank is 6.4mm, and the density of the blank is 3.25g/cm 3 ；
C2, discharging the gel of the blank body in the step C1 at 500 ℃, sintering for 5 hours at 950 ℃, and then performing heat treatment for 1 hour at 560 ℃;
and C3, coating silver on the green body obtained in the step C2, firing silver, and brushing insulating paint to obtain the varistor, wherein the side length of the varistor is 22.5mm, and the thickness of the varistor is 5.3mm.
Example 2
The formulation of the varistor ceramic powder in this example is shown in table 1, and the formulation of the additive is shown in table 2.
The preparation method of the additive described in this example differs from example 1 only in that: in the step S1, the grinding time is 2.5 hours; in the step S2, the calcining temperature is 780 ℃; the remainder were identical to example 1.
The preparation method of the varistor ceramic powder in the embodiment is the same as that in embodiment 1.
The manufacturing method of the varistor sheet in this embodiment is different from that of embodiment 1 only in that: in the step C1, after being placed for 24 hours, the resistor disc blank is pressed and molded by a tablet press, and the side length of the blank is 24.6mm, and the thickness of the blank is 6.1mm; in the step C2, sintering is carried out at 960 ℃ for 5 hours, and then heat treatment is carried out at 570 ℃ for 1 hour; the remainder was the same as in example 1, and the side length of the resistor sheet in this example was 22.5mm and the thickness was 5.3mm.
Example 3
The formulation of the varistor ceramic powder in this example is shown in table 1, and the formulation of the additive is shown in table 2.
The preparation method of the additive described in this example differs from example 1 only in that: in the step S1, the grinding time is 3 hours; in the step S2, the calcining temperature is 750 ℃; the remainder were identical to example 1.
The preparation method of the varistor ceramic powder in the embodiment is the same as that in embodiment 1.
The manufacturing method of the varistor sheet in this embodiment is different from that of embodiment 1 only in that: in the step C1, after being placed for 24 hours, the resistor disc blank is pressed and molded by a tablet press, and the side length of the blank is 28.6mm, and the thickness of the blank is 6.5mm; in the step C2, sintering is carried out at 960 ℃ for 7 hours, and then heat treatment is carried out at 570 ℃ for 1 hour; the remainder was the same as in example 1, and the side length of the resistor sheet in this example was 24.2mm and the thickness was 5.5mm.
Example 4
The formulation of the varistor ceramic powder in this example is shown in table 1, and the formulation of the additive is shown in table 2.
The preparation method of the additive described in this example differs from example 1 only in that: in the step S1, the pre-dispersion time is 25min, and the grinding time is 4h; in the step S2, the calcining temperature is 750 ℃; the remainder were identical to example 1.
The preparation method of the varistor ceramic powder in the embodiment is the same as that in embodiment 1.
The manufacturing method of the varistor sheet in this embodiment is different from that of embodiment 1 only in that: in the step C1, after being placed for 24 hours, the resistor disc blank is pressed and molded by a tablet press, and the side length of the blank is 26.8mm and the thickness of the blank is 6.7mm; in the step C2, sintering is carried out at 980 ℃ for 6 hours, and then heat treatment is carried out at 570 ℃ for 1 hour; the remainder was the same as in example 1, the side length of the resistor disc in this example was 22.5mm, the thickness was 5.6mm, and the scanning electron microscope of the varistor disc was shown in FIG. 2.
Examples 5 to 8
Examples 5 to 8 of the present invention differ from example 1 only in that: the formulas of the piezoresistor porcelain powder are different, and are shown in table 1.
Examples 9 to 12
Examples 9-12 of the present invention differ from example 1 only in that: the formulations of the additives are different and are shown in Table 2.
Example 13
The only difference between the varistor ceramic powder additive in the embodiment 13 and the varistor ceramic powder additive in the embodiment 1 of the invention is that: in the step S2, the calcining temperature is 650 ℃; the remainder were identical to example 1.
Example 14
The only difference between the varistor ceramic powder additive in embodiment 14 and the varistor ceramic powder additive in embodiment 1 of the present invention is that: in the step S2, the calcining temperature is 950 ℃; the remainder were identical to example 1.
Comparative example 1
This comparative example differs from example 1 only in that: the Al (NO) 3 ) 3 ·9H 2 The weight part of O was 0.005 part, and the rest was the same as in example 1.
Comparative example 2
This comparative example differs from example 1 only in that: the Al (NO) 3 ) 3 ·9H 2 The weight part of O was 0.07 part, and the rest was the same as in example 1.
Comparative example 3
This comparative example differs from example 1 only in that: said Ba (AC) 2 Parts by weight of 0.008, the remainder being identical to example 1.
Comparative example 4
This comparative example differs from example 1 only in that: said Ba (AC) 2 0.060 parts by weight, the remainder being identical to example 1.
Comparative example 5
This comparative example differs from example 1 only in that: the weight of the additive was 1.3 parts, the remainder being identical to example 1.
Comparative example 6
This comparative example differs from example 1 only in that: the weight of the additive was 25.6 parts, the remainder being identical to example 1.
Comparative example 7
This comparative example differs from example 1 only in that: ceO is not added into the additive 2 The remainder were the same as in example 1.
Comparative example 8
The formulation of the varistor ceramic powder and the formulation of the additive in this comparative example are the same as in example 4.
The preparation method of the additive comprises the following steps: grinding the components of the additive, water, a dispersing agent and agate balls in a ball mill at a grinding rate of 4500r/min for 24 hours; and filtering the ground slurry by adopting a 120-mesh screen, drying and crushing the filtered slurry at the temperature of 120 ℃, and fully and uniformly mixing the crushed slurry through a 30-mesh screen twice to obtain the additive.
The preparation method of the varistor ceramic powder in the embodiment is the same as that in embodiment 1.
The preparation method of the varistor sheet comprises the following steps:
c1, mixing the ceramic powder, water, a dispersing agent, a binder and a defoaming agent, ball milling for 24 hours in a ball mill, placing for 24 hours, and pressing and forming by a tablet press to obtain a resistor disc blank, wherein the side length of the blank is 26.8mm, the thickness of the blank is 6.7mm, and the density of the blank is 3.25g/cm 3 ；
Performing glue discharging on the blank body obtained in the step C1 at 500 ℃, sintering for 6 hours at 980 ℃, and performing heat treatment for 1 hour at 570 ℃;
and C3, coating silver on the green body obtained in the step C2, firing silver, and brushing insulating paint to obtain a piezoresistor sheet, wherein the side length of the resistor sheet is 22.5mm, the thickness of the resistor sheet is 5.3mm, and a scanning electron microscope of the piezoresistor sheet is shown in figure 3.
TABLE 1
TABLE 2
Parts by weight of Bi 2 O 3 Sb 2 O 3 Co 3 O 4 Mn 3 O 4 SiO 2 TiO 2 CeO 2 Silver glass powder
Example 1 49.2 12.5 19.3 3.5 10.8 1.7 1.7 1.3
Example 2 47 11.9 18.5 3.3 14.9 1.6 1.6 1.2
Example 3 48.3 11.9 18.5 3.2 13.9 1.5 1.5 1.2
Example 4 52.2 10.3 17.9 2.7 12.5 1.4 1.4 1.2
Example 5 49.2 12.5 19.3 3.5 10.8 1.7 1.7 1.3
Example 6 49.2 12.5 19.3 3.5 10.8 1.7 1.7 1.3
Example 7 49.2 12.5 19.3 3.5 10.8 1.7 1.7 1.3
Example 8 49.2 12.5 19.3 3.5 10.8 1.7 1.7 1.3
Example 9 35.0 15.0 14.0 1.0 10.0 2.0 0.5 2.0
Example 10 55.0 8.0 25.0 5.0 20.0 0.5 2.0 0.8
Example 11 30.0 6.0 28.0 1.0 23.0 0.1 4.0 0.5
Example 12 60.0 20 12.0 8.0 5.0 3.0 0.2 2.5
Performance testing
The varistor sheets prepared in the above examples and comparative examples were subjected to electrical property test, and the results are shown in table 3 below.
TABLE 3 Table 3
The size side length of the finished varistor sheet manufactured by the method is 10-30mm, and the thickness is 2-15mm; table 3 knotAs a result, the voltage gradient range of the varistor sheets in examples 1-14 can reach 300-550V/mm, the nonlinear coefficient is 30-80, and the peak current density can reach 3000-4500A/cm in the lightning impulse test of 8/20 mu s 2 In particular, the peak current densities of examples 1-6, 9-10 are greater.
Comparative examples 1-4 the peak current density of the finally produced varistor in the lightning wave impulse test of 8/20 mus was low because the parts by weight of the aluminum salt or the barium salt were not in the range of the present invention; comparative examples 5 and 6 all properties of the final varistor were not as good as the examples because the parts by weight of the additives were outside the scope of the present invention; comparative example 7 no rare earth oxide was added to the additive, the potential gradient of the final resistive sheet was low, and the peak current density was low.
Comparing example 4 with comparative example 8 alone, it was found that when the additive was prepared in comparative example 8 by conventional ball milling, and the additive was not calcined and secondarily refined, table 3 shows that the resistance sheet of comparative example 8 had a peak current density of only 1950A/cm in the lightning impulse test of 8/20. Mu.s 2 The method comprises the steps of carrying out a first treatment on the surface of the And in comparison of figures 2 and 3, the preparation process of the additive adopts a horizontal grinder to replace the traditional ball milling mode, so that the grinding efficiency of the additive can be improved, and the microstructure uniformity of the piezoresistor can be obviously improved; the method can reduce the porosity of the porcelain body and improve the compactness of the porcelain body, thereby enhancing the electrical capacity of the piezoresistor.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

1. The varistor ceramic powder is characterized by comprising the following components in parts by weight: 80.0-97.5 parts of ZnO, 0.01-0.06 part of aluminum salt, 0.01-0.05 part of barium salt and 2.0-20.0 parts of additive; the additive comprisesThe components are as follows: bi (Bi) 2 O 3 、Sb 2 O 3 、Co 3 O 4 、Mn 3 O 4 、SiO 2 、TiO 2 Silver glass powder and rare earth oxide.
2. The varistor ceramic powder of claim 1, wherein the varistor ceramic powder comprises the following components in parts by weight: 86.0-95.5 parts of ZnO, 0.015-0.03 parts of aluminum salt, 0.016-0.035 parts of barium salt and 6.0-15.0 parts of additive.
3. The varistor ceramic powder of claim 1 wherein the additive comprises the following components in parts by weight: bi (Bi) 2 O 3 30.0 to 60.0 parts of Sb 2 O 3 6.0-20 parts, co 3 O 4 12.0 to 28.0 parts of Mn 3 O 4 1.0 to 8.0 parts of SiO 2 5.0 to 23.0 portions of TiO 2 0.1-3.0 parts, 0.2-4.0 parts of rare earth oxide and 0.5-2.5 parts of silver glass powder.
4. The varistor ceramic powder of claim 1 wherein the additive comprises the following components in parts by weight: bi (Bi) 2 O 3 35.0 to 55.0 parts of Sb 2 O 3 8.0-15 parts, co 3 O 4 14.0-25.0 parts, mn 3 O 4 1.0 to 5.0 parts of SiO 2 10.0 to 20.0 parts of TiO 2 0.5-2.0 parts, rare earth oxide 0.5-2.0 parts and silver glass powder 0.8-2 parts.
5. The varistor ceramic powder of any one of claims 1-4 wherein the rare earth oxide is Y 2 O 3 、La 2 O 3 、Nd 2 O 3 Or CeO 2 ；
Preferably, the rare earth oxide is CeO 2 。
6. The varistor ceramic powder of any one of claims 1-5, wherein the method of preparing the additive comprises the steps of:
s1, mixing the additive according to any one of claims 1-5 with a dispersing agent, pre-dispersing, grinding, filtering and crushing the pre-dispersed slurry, and sieving the slurry with a 30-mesh sieve to obtain powder;
s2, calcining the powder in the step S1 at 650-950 ℃ for 0.5-4 hours, crushing after calcining, and sieving with a 30-mesh sieve;
s3, secondarily refining the powder obtained in the step S2 to obtain the additive.
7. The varistor ceramic powder of claim 6, wherein in the preparation of the additive, the pre-dispersion parameters in step S1 are: the rotating speed is 500-3000r/min, and the time is 10-60min; the grinding parameters are as follows: the speed is 1000-3000r/min, and the time is 1-5h.
8. The method for preparing varistor ceramic powder in accordance with any one of claims 1-7, which comprises the steps of: mixing the varistor ceramic powder according to any one of claims 1-7 with a dispersing agent and a binder, ball-milling for 12-48 hours, sieving with a 100-mesh sieve after ball milling, and drying to obtain the varistor ceramic powder.
9. A varistor sheet, characterized in that the varistor sheet is made of the varistor ceramic powder according to any one of claims 1-8.
10. The varistor as claimed in claim 9, wherein the method of manufacturing the varistor comprises the steps of:
c1, mixing the ceramic powder according to any one of claims 1-8 with a dispersing agent, a binder and a defoaming agent, ball milling for 12-24 hours, and press forming to obtain a resistor disc blank;
c2, performing glue discharging, sintering and heat treatment on the blank body obtained in the step C1;
and C3, coating silver on the green body obtained in the step C2, firing silver, and brushing insulating paint to obtain the varistor.
CN202310950192.1A 2023-07-31 2023-07-31 Piezoresistor ceramic powder and preparation method and application thereof Pending CN117003559A (en)

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