CN102531575A - Sm2O3-doped BaTiO3 substrate type PTCR (Positive Temperature Coefficient Resistor) ceramic material and preparation method thereof - Google Patents
Sm2O3-doped BaTiO3 substrate type PTCR (Positive Temperature Coefficient Resistor) ceramic material and preparation method thereof Download PDFInfo
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- CN102531575A CN102531575A CN2011104159526A CN201110415952A CN102531575A CN 102531575 A CN102531575 A CN 102531575A CN 2011104159526 A CN2011104159526 A CN 2011104159526A CN 201110415952 A CN201110415952 A CN 201110415952A CN 102531575 A CN102531575 A CN 102531575A
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Abstract
The invention discloses an Sm2O3-doped BaTiO3 substrate type PTCR ceramic material and a preparation method thereof. The structural formula of the ceramic material is as follows: (Bay minus xSmx) TiO3 plus mSiO2 plus nMn (NO3)2 plus pBN; in the formula, x is equal to 0.2 to 0.8 mol percent, y is equal to 1.014 to 1.029, m is equal to 0.05 to 0.6 mol percent, n is equal to 0.005 to 0.02 mol percent, and p is equal to 0 to 4.4 mol percent. The invention adopts the tape-casting method and utilizes tape-cast slurry prepared from Sm2O3-doped BaTiO3-based PTCR powder to prepare green bodies which are laminated and cut; the green sample is sintered in a reducing atmosphere and then oxidated in the air, and the surfaces are coated with electrodes. The invention overcomes the defect of high-Ba/Ti ratio semiconductive ceramic material, i.e. high resistivity, and the PTCR ceramic material has the characteristics of small grain size, low room-temperature resistivity and high PTC (Positive Temperature Coefficient) effect.
Description
Technical field
The invention belongs to the ceramic material technical field, it is specifically related to a kind of Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith and preparation method thereof.
Background technology
The PTCR stupalith generally is meant thermistor material or the components and parts with PTC.The typical PTCR material of tradition mainly is to be the semiconductor ceramic material of base with the barium titanate, is characterized in (Tc T when envrionment temperature rises to a certain temperature
COr be called the switch temperature point) its resistance value several magnitude of will increasing sharply.With this ceramic components as over-current protecting element in the unicircuit; Function with holding circuit; Simultaneously, it extensively is incorporated in military affairs, industry and electronics because of having series of advantages such as volume is little, simple in structure, with low cost and safe and reliable, and field such as unicircuit.
Development along with microelectronics, low temperature co-fired technology and SMT technology; Promoted electronic devices and components to develop, and lamination sheet type PTCR stupalith components and parts direction has become the domestic and international research focus towards miniaturized, microminiaturization, integrated and chip type direction.At first, German Siemens company has initiated slice component, and then, Japan is seized of tangible technical superiority in this field, and there are field, village, Panasonic and the NGK company etc. of Japan in wherein more representational enterprise.Once more, China scientific research personnel has also begun the research of lamination sheet type PTCR components and parts as far back as the nineties in 20th century, and electrode is difficult to body material formation good Ohmic contact in the pure Pd precious metal.Up to nowadays, domestic this field still also exists a lot of technical barriers, still need await solving.The PTCR material that classical way is made during like sintering in air can obtain extraordinary PTCR characteristic, and top classics prescription can't be indiscriminately imitated fully and make lamination sheet type PTCR element.
From the patent of having announced at present, U.S. Pat 20080204187A1, the REE of having produced the 0.1～0.5mol% that mixes is (like Eu
2O
3, Gd
2O
3, Tb
4O
7, Dy
2O
3, Y
2O
3, Ho
2O
3, Er
2O
3, Tm
2O
3, Sm
2O
3) BaTiO
3Base semiconductor stupalith; Wherein Ba position and Ti position atomic ratio are in 0.996～1.008 scope; Adopt water base casting process, through lamination compression molding technology, sample is 1200～1250 ℃ of sintering in reducing atmosphere; The specific density that obtains porcelain body is 70%, room temperature resistance is the chip-type laminated PTCR stupalith element more than 4 one magnitude less than 0.3 Ω and liftdrag; But when Ba/Ti position ratio is 1.008, do not provide the order of magnitude of this sample P TCR effect in this patent, do not spell out simultaneously yet with the variation tendency of a kind of donor doping element resistivity under different dopings and the width degree in semiconductor zone.Because this point has directive significance to our actual making very much.And based on high Ba/Ti than the lacking of related patent U.S. Patent No. comparison of stupalith, wherein U.S. Pat 6359327B1 adopts Hydrothermal Preparation to mix Sm
2+With the barium carbonate powder of BN, through laminating moulding, green compact are lower than 1000 ℃ of sintering in reducing atmosphere, and after reoxidizing through low temperature, obtain PTCR characteristic preferably.He has also carried out the experiment of high Ba/Ti ratio simultaneously, has obtained PTCR effect preferably, but has not provided the size of concrete grain-size.Because the ceramics sample of doping BN shows cubic crystalline form, and crystal boundary is also unintelligible, and a small amount of SiO that mixes
2BaTiO
3The grain size of basic pattern article is evenly distributed.Mix a spot of Mn (NO in the sample that general traditional technology is produced
3)
2Can improve the acceptor concentration N in the sample crystal boundary
d, obtain very high liftdrag, but U.S. Pat 20010003361A1 mixes 0～0.01mol%Mn
2+The liftdrag of semiconductor ceramics sample is about 3.In addition, U.S. Pat 6359327B1 also hints Mn
2+Content PTCR effect to sample in 0.01～0.05mol% scope does not almost have influence.
Summary of the invention
The object of the present invention is to provide a kind of Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith and preparation method thereof, the present invention has overcome the high deficiency of semiconductor stupalith resistivity of high Ba/Ti ratio, and the PTCR stupalith has the advantages that grain-size is little, room temperature resistivity is low and the PTC effect is big.
A kind of Sm provided by the invention
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is characterized in that the structural formula of this material is:
(Ba
y-xSm
x)TiO
3+mSiO
2+nMn(NO
3)
2+pBN ①
X=0.2～0.8mol% in the formula, y=1.014～1.029, m=0.05～0.6mol%, n=0.005～0.02mol%, p=0～4.4mol%.The preferable range of m is 0.05～0.2mol%.
The preparation method of chip PTCR thermistor provided by the invention, this method may further comprise the steps successively:
The 1st step was utilized Sm
2O
3Doping BaTiO
3Base PTCR powder preparing casting slurry;
The 2nd step adopted the flow casting molding method to utilize casting slurry to prepare base substrate, lamination compressing tablet and section;
The 3rd step obtained chip PTCR stupalith to green compact sintering in reducing atmosphere;
The 4th step reoxidized the PTCR stupalith behind the sintering in air;
The 5th step was coated with electrode on the surface of PTCR stupalith.
The present invention has following advantage:
(1) adopt casting method to make a kind of Sm
2O
3Doping BaTiO
3Substrate formula PTCR material prepares chip PTCR stupalith thermistor through the sintering process that reduces-reoxidize.
(2) through alms giver Sm
2+The amount doping vario-property has obtained the PTCR stupalith of low-resistivity, and finds that reducing atmosphere helps broadening sample low resistance semiconductor zone.
(3) produce the chip semiconductor BaTiO of high Ba/Ti than (in 1.014～1.029 scopes)
3Base ceramic material has obtained tiny grain-size, lower room temperature resistance and bigger liftdrag.
(4) when adding a spot of SiO
2(0.05～0.2mol%) time, low sintering sample has better PTCR characteristic.
The BaTiO that the present invention is prepared
3Substrate formula stupalith is particularly useful for lamination sheet type PTCR thermistor.
Description of drawings
Fig. 1 is the PTCR chip ceramics sample actual measurement resistance-temperature characteristics curve among the embodiment 2.
Embodiment
Through embodiment the present invention is described in further detail below, but following examples are illustrative, protection scope of the present invention does not receive the restriction of these embodiment.
Embodiment 1
1 concrete detailed preparation technology is following:
(1) BaTiO
3The preparation of base PTCR ceramic powder
The component of PTCR specimen material is: (Ba
1.022-xSm
x) TiO
3+ 0.6mol%SiO
2, for sample S1, S2, S3 and S4, x is 0.2mol%, 0.4mol%, 0.6mol% and 0.8mol% respectively, and y is 1.022, and m is 0.6mol%, and n and p are 0, in proportion weighing BaCO successively
3, Sm
2O
3, SiO
2And TiO
2, load weighted mixture is put into the urethane ball grinder adds deionized water, with ZrO
2Ball is as ball-milling medium, and wherein expect: ball: the mass ratio of water is 1: 2: 1.5, on planetary ball mill, grinds 4h, and dried powder is at 1150 ℃ of following pre-burning 2h, and ball milling 4h crosses 60 mesh sieves, BaTiO like this after the oven dry again
3Base PTCR ceramic powder has just prepared.
(2) preparation of casting slurry
The powder of preparing in the step (1) (150g) packed into adds dispersion agent (0.45g), skimmer (0.45g), absolute ethyl alcohol (27g) and toluene (45g) in the nylon jar, with ZrO
2Ball is as ball-milling medium, batch mixing 5～8h on ball mill at first, and the rotating speed of ball mill is 120r/min, adds tackiness agent (42g) ball milling 8～10h then, processes the slurry of curtain coating.
(3) formation of cast sheet and green
The casting slurry that step (2) obtains is crossed 300 mesh sieves, remove a small amount of bubble residual in the slurry, curtain coating goes out evenly, stable and imperforate base sheet.Adopting large-scale casting machine to flow out thick is the green sheet of 56 μ m, then with the pressure of 15MPa it is stacked down at 50 ℃ to force together, and (length and width are thick to be respectively: the green compact sample of 10mm * 8mm * 1mm) to be cut into " 1812 " size then.
(4) reduce-reoxidize the method sinter molding
Earlier the sample on the Zr plate is put into baking oven binder removal 32h at a slow speed, removes the organism in the sample, after put it into the inherent 3%H of corundum aluminum oxide tubular type atmosphere furnace
2/ N
21200 ℃ of sintering 30min of reducing atmosphere, gas flow rate is controlled at 200cm under the pressure of 1atm.
3In/the min, intensification and rate of temperature fall are respectively 5 ℃/min and 6 ℃/min, at 1150 ℃ of insulation 30min, reduce to 800 ℃ up to temperature, then furnace cooling in the temperature-fall period.
Sample behind the sintering inserted in the box-type furnace to reoxidize with 800 ℃ handle 1h, heat up and rate of temperature fall is 5 ℃/min.
(5) be coated with electrode and performance test
On the upper and lower surfaces of sample, be coated with the In-Ga electrode, measure its room temperature resistance with digital multimeter, use resistance-temperature characteristics tester to come the resistance-temperature characteristics curve of specimen, rise to 250 ℃ with the speed of 1.6 ℃/min from room temperature, each probe temperature point is incubated 2min.
This Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is at 3%H
2/ N
21200 ℃ of sintering 30min in the reducing atmosphere, 800 ℃ of room temperature resistivities that reoxidize sample behind the 1h are along with doping Sm in air
2+The semiconductor curve of the increase of amount demonstrates and reduces earlier " U " type variation tendency that afterwards increases.Especially, prepare the chip ceramics sample of high Ba/Ti than (Ba/Ti=1.022), doping 0.6mol%Sm through the method for reducing-reoxidizing
2+BaTiO
3The room temperature resistivity of substrate formula ceramics sample is minimum to be 138.9 Ω cm, liftdrag (Lg (R
250/ R
25)) be 2.8 one magnitude, the grain-size size is 1.1 μ m; And doping 0.4mol%Sm
2+The room temperature resistivity of ceramics sample be 152.4 Ω cm, liftdrag is 3.1 one magnitude, the grain-size size is 1.3 μ m.With compare in the air, agglomerating sample semiconductor " U " type curve moves to high donor doping direction in reducing atmosphere, and its semiconductor zone demonstrates wideization significantly.It is as shown in the table for concrete electrical property:
Embodiment 2
(1) BaTiO
3The preparation of base PTCR ceramic powder
The component of PTCR specimen material is: (Ba
Y-0.002Sm
0.002) TiO
3+ 0.6mol%SiO
2Wherein, the y value is respectively 1.014,1.017,1.02,1.023,1.026 and 1.029 among sample S5, S6, S7, S8, S9 and the S10, and x is 0.2mol%, and m is 0.6mol%, and n, p are 0, in proportion weighing BaCO successively
3, Sm
2O
3, SiO
2And TiO
2, load weighted mixture is put into the urethane ball grinder adds deionized water, with ZrO
2Ball grinds 4h as ball-milling medium on planetary ball mill, dried powder is at 1150 ℃ of following pre-burning 2h, and ball milling 4h crosses 60 mesh sieves, BaTiO like this after the oven dry again
3Base PTCR ceramic powder has just prepared.
(2) preparation of casting slurry
The powder of preparing in the step (1) (150g) packed into adds dispersion agent (0.45g), skimmer (0.45g), absolute ethyl alcohol (27g) and toluene (45g) in the nylon jar, with ZrO
2Ball is as ball-milling medium, batch mixing 5～8h on ball mill at first, and the rotating speed of ball mill is 120r/min, adds tackiness agent (42g) ball milling 8～10h then, processes the slurry of curtain coating.
(3) formation of cast sheet and green
The casting slurry that step (2) is obtained sieves, and removes bubble, makes even and stable green sheet.Adopting large-scale casting machine to make thick is the green sheet of 56 μ m, then with the pressure of 15MPa it is overlapped together down at 50 ℃, and (length and width are thick to be respectively: the green sample of 10mm * 8mm * 1mm) to be cut into " 1812 " size then.
(4) reduce-reoxidize the method sinter molding
Earlier sample is put into baking oven binder removal 32h, after put it in the tubular type atmosphere furnace at 3%H
2/ N
21200 ℃ of sintering 30min in the reducing atmosphere, gas flow rate is controlled at 200cm under the pressure of 1atm.
3In/the min, intensification and rate of temperature fall are respectively 5 ℃/min and 3 ℃/min, are incubated 30min, furnace cooling then at 1150 ℃ in the temperature-fall period.
Sample behind the sintering inserted in the box-type furnace to reoxidize with 800 ℃ handle 1h, heat up and rate of temperature fall is 5 ℃/min.
(5) be coated with electrode and performance test
On the upper and lower surfaces of sample, be coated with the In-Ga electrode; Measure its room temperature resistance with digital multimeter; Use resistance-temperature characteristics tester to come the resistance-temperature characteristics curve of specimen, be warming up to 250 ℃ with the speed of 1.6 ℃/min from room temperature, each temperature test point is incubated 2min.
This 0.2mol%Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is at 3%H
2/ N
21200 ℃ of sintering 30min in the reducing atmosphere, 800 ℃ of room temperature resistivities that reoxidize sample behind the 1h are along with the increase of Ba/Ti ratio (y) demonstrates the variation tendency that reduces afterwards to increase earlier in air.When y=1.026, the room temperature resistivity of ceramics sample is minimum to be 108.5 Ω cm, and the grain-size size is about 1 μ m; The liftdrag of ceramics sample is 3.5 one magnitude when y=1.014, and its resistance is as shown in Figure 1 with the variation of temperature curve, and its concrete room temperature resistivity is as shown in the table:
Embodiment 3
(1) BaTiO
3The preparation of base PTCR ceramic powder
The component of PTCR specimen material is: (Ba
Y-0.002Sm
0.002) TiO
3+ 0.6mol%SiO
2, x=0.2mol% among the sample S11, y=1.02, m=0.6mol%, n=p=0 be weighing BaCO successively in proportion
3, Sm
2O
3, SiO
2And TiO
2, load weighted mixture is put into the urethane ball grinder adds deionized water, with ZrO
2Ball grinds 4h as ball-milling medium on planetary ball mill, dried powder is at 1000～1200 ℃ of following pre-burning 2h, and ball milling 4h crosses 60 mesh sieves, BaTiO like this after the oven dry again
3Base PTCR ceramic powder has just prepared.
(2) preparation of casting slurry
The powder of preparing in the step (1) (150g) packed into adds dispersion agent (0.45g), skimmer (0.45g), absolute ethyl alcohol (27g) and toluene (45g) in the nylon jar, with ZrO
2Ball is as ball-milling medium, batch mixing 5～8h on ball mill at first, and the rotating speed of ball mill is 120r/min, adds tackiness agent (42g) ball milling 8～10h then, processes the slurry of curtain coating.
(3) formation of cast sheet and green
Casting slurry sieve with step (2) obtains removes bubble, is convenient to make even and stable green sheet.Adopting large-scale casting machine to make thick is the green sheet of 56 μ m, then at 50 ℃ of pressure with 15MPa it is stacked to force together, and (length and width are thick to be respectively: the green compact sample of 10mm * 8mm * 1mm) to be cut into " 1812 " size at last.
(4) reduce-reoxidize the method sinter molding
Earlier sample is put into baking oven binder removal 32h, after put it in the tubular type atmosphere furnace at 3%H
2/ N
21200 ℃ of sintering 30min in the reducing atmosphere, gas flow rate is controlled at 200cm under the pressure of 1atm.
3In/the min, intensification and rate of temperature fall are respectively 5 ℃/min and 3 ℃/min, are incubated 30min, naturally cooling then at 1150 ℃ in the temperature-fall period.
Burned sample inserted in the box-type furnace to reoxidize with 800 ℃ handle 1h, heat up and rate of temperature fall is 5 ℃/min.
(5) be coated with electrode and performance test
On the upper and lower surfaces of sample, be coated with the In-Ga electrode; Measure its room temperature resistance with digital multimeter; Use resistance-temperature characteristics tester to come the resistance-temperature characteristics curve of specimen, be warming up to 250 ℃ with the speed of 1.6 ℃/min from room temperature, each temperature test point is incubated 2min.
This 0.2mol%Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is at 1000～1200 ℃ of pre-burning 2h, at 3%H
2/ N
21200 ℃ of sintering 30min in the reducing atmosphere, 800 ℃ of room temperature resistivities that reoxidize sample behind the 1h are along with the increase of calcined temperature demonstrates the variation tendency that reduces afterwards to increase earlier in air.When calcined temperature is 1125 ℃, the minimum 38.3 Ω cm that are about of the room temperature resistivity of ceramics sample, concrete room temperature resistivity is as shown in the table; When calcined temperature during at 1000 or 1200 ℃, the liftdrag of ceramics sample is more than 3.1 one magnitude.Its concrete room temperature resistivity is as shown in the table:
Embodiment 4
This instance be high Ba/Ti than the thin chip-type PTCR of low-resistivity stupalith, its composition consists of:
(Ba
y-xSm
x)TiO
3+mSiO
2+nMn(NO
3)
2+pBN
The concrete prescription of sample S12 to S18 such as following table (unit: mol):
(1) BaTiO
3The preparation of base PTCR ceramic powder
The PTCR specimen material is joined seven groups of sample S12 to S18, weighing BaCO successively in the ratio of last table
3, Sm
2O
3, SiO
2, TiO
2, Mn (NO
3)
2And BN, load weighted mixture is put into the urethane ball grinder add deionized water, with ZrO
2Ball grinds 4h as ball-milling medium on planetary ball mill, dried powder is at 1150 ℃ of following pre-burning 2h, and ball milling 4h crosses 60 mesh sieves, BaTiO like this after the oven dry again
3Base PTCR ceramic powder has just prepared.
(2) preparation of casting slurry
The powder of preparing in the step (1) (150g) packed into adds dispersion agent (0.45g), skimmer (0.45g), absolute ethyl alcohol (27g) and toluene (45g) in the nylon jar, with ZrO
2Ball is as ball-milling medium, batch mixing 5～8h on ball mill at first, and the rotating speed of ball mill is 120r/min, adds tackiness agent (42g) ball milling 8～10h then, processes the slurry of curtain coating.
(3) formation of cast sheet and green
Casting slurry sieve with step (2) obtains removes bubble, is convenient to make even and stable green sheet.Adopting large-scale casting machine to make thick is the green sheet of 56 μ m, then at 50 ℃ of pressure with 15MPa it is stacked to force together, and (length and width are thick to be respectively: the green sample of 10mm * 8mm * 1mm) to be cut into " 1812 " size at last.
(4) reduce-reoxidize the method sinter molding
Earlier sample is put into baking oven binder removal 32h, after put it in the tubular type atmosphere furnace at 3%H
2/ N
21200 ℃ of sintering 30min in the reducing atmosphere, gas flow rate is controlled at 200cm under the pressure of 1atm.
3In/the min, intensification and rate of temperature fall are respectively 5 ℃/min and 3 ℃/min, are incubated 30min, naturally cooling then at 1150 ℃ in the temperature-fall period.
Burned sample inserted in the box-type furnace to reoxidize with 800 ℃ handle 1h, heat up and rate of temperature fall is 5 ℃/min.
(5) be coated with electrode and performance test
On the upper and lower surfaces of sample, be coated with the In-Ga electrode; Measure its room temperature resistance with digital multimeter; Use resistance-temperature characteristics tester to come the resistance-temperature characteristics curve of specimen, be warming up to 250 ℃ with the speed of 1.6 ℃/min from room temperature, each temperature test point is incubated 2min.
This 0.2mol%Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is at 1150 ℃ of pre-burning 2h, at 3%H
2/ N
21180 ℃ of sintering 30min in the reducing atmosphere, in air 800 ℃ to reoxidize behind the 1h room temperature resistance and the liftdrag of sample as shown in the table.From table, can find out doping SiO
2Measure fewly more, liftdrag is high more, and this is to reoxidize thermal treatment because glassy phase is fewer in the ceramics sample with regard to being beneficial to more.And the adding of a small amount of BN can reduce the room temperature resistance of sample further.
The above is preferable enforcement row of the present invention, but the present invention should not be confined to the disclosed content of the foregoing description, so everyly do not break away from the equivalence of accomplishing under the disclosed spirit of the present invention or revise, all falls into protection scope of the present invention.
Claims (3)
1., a kind of Sm
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is characterized in that the structural formula of this material is:
(Ba
y-xSmx )TiO
3?+?
mSiO
2?+?
nMn(NO
3)
2?+?
pBN
In the formula
x=0.2 ~ 0.8mol%,
y=1.014 ~ 1.029,
m=0.05 ~ 0.6mol%,
n=0.005 ~ 0.02mol%,
p=0 ~ 4.4mol%.
2. according to the said a kind of Sm of claim 1
2O
3Doping BaTiO
3Substrate formula PTCR stupalith is characterized in that,
m=0.05 ~ 0.2mol%.
3. the preparation method of a chip PTCR thermistor, this method may further comprise the steps successively:
The 1st step was utilized Sm
2O
3Doping BaTiO
3Base PTCR powder preparing casting slurry;
The 2nd step adopted the flow casting molding method to utilize casting slurry to prepare base substrate, lamination compressing tablet and section;
The 3rd step obtained chip PTCR stupalith to green compact sintering in reducing atmosphere;
The 4th step reoxidized the PTCR stupalith behind the sintering in air;
The 5th step was coated with electrode on the surface of PTCR stupalith.
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105026336A (en) * | 2013-03-11 | 2015-11-04 | Tdk株式会社 | PTC thermistor ceramic composition and PTC thermistor element |
| CN111605039A (en) * | 2020-05-25 | 2020-09-01 | 徐州华焰特种陶瓷有限公司 | Preparation method and smelting equipment of high-strength ceramic wafer |
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2011
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| CN1266269A (en) * | 1999-03-05 | 2000-09-13 | 株式会社村田制作所 | Monolithic electronic element made from semiconductor ceramic |
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| Title |
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| HIDEAKI NIIMI ET AL.: "Effects of Ba/Ti Ratio on Positive Temperature Coefficient of Resistivity Characteristics of Donor-doped BaTiO3 Fired in Reducing Atmosphere", 《JAPANESE JOURNAL OF APPLIED PHYSICS》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026336A (en) * | 2013-03-11 | 2015-11-04 | Tdk株式会社 | PTC thermistor ceramic composition and PTC thermistor element |
| US9697935B2 (en) | 2013-03-11 | 2017-07-04 | Tdk Corporation | PTC thermistor ceramic composition and PTC thermistor element |
| CN111605039A (en) * | 2020-05-25 | 2020-09-01 | 徐州华焰特种陶瓷有限公司 | Preparation method and smelting equipment of high-strength ceramic wafer |
| CN111605039B (en) * | 2020-05-25 | 2021-09-10 | 徐州华焰特种陶瓷有限公司 | Preparation method and smelting equipment of high-strength ceramic wafer |
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Application publication date: 20120704 |