CN109704755A - Energy-saving heating material of a kind of dibit doping and preparation method thereof - Google Patents
Energy-saving heating material of a kind of dibit doping and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of dibits to adulterate energy-saving heating material and preparation method thereof.The dibit doping energy-saving material component ratio is (Ba1‑x‑ySrxCey)Ti1.01‑aNbaO3, wherein 0.32 < x < 0.38,0.0015≤y≤0.0045,0.001≤a≤0.0025.The preparation method comprises the following steps: calculate the weight of each raw material first, in accordance with component ratio, weigh to be placed in ball grinder and mix, drying obtains mixed powder, high temperature pretreatment, and natural cooling obtains main body phase powder, is then separately added into glass ingredient Al according to molar ratio2O3And SiO2, uniformly mix；It is uniformly mixed after drying with adhesive, and is pressed into disc-shaped；1300~1325 DEG C are warming up to through three sections, keeps the temperature 1~4h, the potsherd of firing sputters one layer of aluminium in tow sides, then coat conductive silver glue respectively, obtain final heating material by rubbing down processing, cleaning, drying.The present invention has room temperature Curie temperature and well positive thermo-resistive effect.
Description
Technical field
The invention belongs to technical field of function materials, especially a kind of dibit adulterates energy-saving heating material and its preparation side
Method.
Background technique
At low ambient temperatures, electronic equipment then needs to have capacity of self-regulation to maintain itself operating temperature
Origin of heat.Traditional solution is, by the PID control system of conventional heating piece and auxiliary, realize electronic equipment compared with
It works under low environment temperature, but this method correspondingly increases the complexity of system, is unfavorable for the small of electronic equipment
Type.
Conventional heating methods are replaced using the material for having positive warm resistance characteristic, saving power, simplification high with temperature control performance
The advantages such as system design.The positive temperature resistance material of high score subclass of application is disclosed at present, and after running for a period of time, it is easy that there are agings
Problem on deformation limits its application.And barium-titanate material (the letter of the heating material of the positive temperature resistance characteristic of ceramic-like such as doping strontium element
Claim, BST), have the advantages that temperature limit extensively, prolonged application without aging, have received widespread attention.But BST is ceramic
Curie point be located between 50-300 DEG C mostly, be not able to satisfy the requirement of most electronic equipment thermal control still.In addition, in Curie temperature
After being transferred to room temperature region, good room temperature resistivity and thermo-resistive effect are also needed.
Document 1 (Chinese patent CN101838142A, applying date 2010-05-25) discloses a kind of barium titanate-based PTC temperature-sensitive
Ceramic powder and preparation method thereof, the thermal sensitive ceramic powder general formula are Ba1-x-y-zPbxSryCaZTiO3, x be 0~0.20, y be 0~
0.20, z is 0.1~0.2, although its room temperature resistivity is lower, preparing minimum Curie temperature in resulting sample is
86.3 DEG C, it is much higher than room temperature, therefore, it is impossible to meet the requirement of electronic equipment thermal control at low ambient temperatures.
Document 2 (room temperature PTC heat control material and its thermal control method research, Song Jialiang, Chinese University of Science and Technology's doctoral thesis), it is public
Having opened a kind of group becomes Ba0.7Sr0.3Ti1.01O3Room temperature PTC heat control material, curie point is about 30 DEG C, PTC intensity be 101,
Room temperature resistivity is greater than 105.8Ω cm, room temperature resistivity is excessively high, and PTC intensity is too low, is unable to reach the requirement of application.
Summary of the invention
The purpose of the present invention is to provide a kind of dibits to adulterate energy-saving heating material and preparation method thereof, thus in Curie
While temperature drops to room-temperature zone, the resistive energy of temperature of BST ceramics is improved.
The technical solution for realizing the aim of the invention is as follows: a kind of energy-saving heating material of dibit doping, molecular formula are
(Ba1-x-ySrxCey)Ti1.01-aNbaO3, wherein 0.32≤x≤0.38,0.0015≤y≤0.0045,0.001≤a≤0.0025,
It joined the cerium salt and niobium oxide of impure element in the barium titanate main body phase of heavy doping strontium.
The dibit adulterates the preparation method of energy-saving heating material, includes the following steps:
Step 1, ingredient: first, in accordance with the component ratio (Ba1-x-ySrxCey)Ti1.01-aNbaO3Calculate the weight of each raw material
Amount, weighs to be placed in ball grinder and mixes；Drying obtains mixed powder；
Step 2, it synthesizes main body phase: after the mixed powder that step 1 is obtained crosses 70 meshes, locating in advance at 1160~1200 DEG C
1.5h is managed, natural cooling obtains (Ba1-x-ySrxCey)Ti1.01-aNbaO3Main body phase powder；
Step 3, add auxiliary element: the main body phase powder that step 2 obtains is separately added into glass ingredient according to molar ratio: rubbing
The Al that your percentage is 0mol%~1.5mol%2O3The SiO for being 1mol%~3mol% with molar percentage2, using ball milling
Mode uniformly mixes；It is dry, cross 120 meshes；
Step 4, be granulated and form: the powder that step 3 is obtained is uniformly mixed with adhesive, and is pressed into using tablet press machine
Disc-shaped；
Step 5, it is burnt into: the disk that step 4 obtains being warming up to 1300~1325 DEG C through three sections, keeps the temperature 1~4h；
Step 6, prepare electrode: the potsherd after firing is handled by rubbing down, is cleaned, and drying is splashed respectively in tow sides
One layer of aluminium is penetrated, then coats conductive silver glue, obtains final heating material.
Further, raw material described in step 1 includes: ammonium carbonate, strontium carbonate, barium carbonate, titanium dioxide and contains miscellaneous
The cerium salt and niobium oxide of prime element；
The condition of ball milling are as follows: ball-milling medium is dehydrated alcohol and zirconia ball；
Raw material: ball: the mass ratio of dehydrated alcohol is 1:2.5:2；
The revolving speed of ball mill be 300rmp, incorporation time be 18~for 24 hours.
Further, drying described in step 1 carries out in 95 DEG C of drying boxes.
Further, pretreated temperature described in step 2 is 1160 DEG C.
Further, granulation described in step 4, specifically: the adhesive of addition is the poly-vinyl alcohol solution of 6~8wt%,
Powder and adhesive that step 3 obtains are ground 1.5 hours in the agate mortar, 70 meshes is crossed and obtains graininess powder.
Further, it molding described in step 4: using press machine by the powder after granulation, is pressed between 2~3MPa
Disk.
Further, firing described in step 5, specific as follows:
The disk that step 4 is obtained, when being warming up to 400 DEG C with 2 DEG C/min, stop 40min with after abundant dumping again with 3
DEG C/min is warming up to 1160~1200 DEG C, 1300~1325 DEG C of maximum sintering temperature finally are warming up to 10 DEG C/min, in highest
At a temperature of keep the temperature 1~4h；When then naturally cooling to 860 DEG C, fire door is opened, blasts air, then shut fire door natural cooling.
Further, electrode is prepared described in step 6, it is specific as follows: by potsherd rubbing down at the thin slice of 1~2mm, drying
Afterwards, first on tow sides magnetron sputtering after one layer of aluminium film, re-coating elargol, the burning infiltration 45min in 510 DEG C of vacuum ovens,
Obtain final heating material.
Compared with prior art, the present invention its remarkable advantage are as follows: (1) pass through strontium element for barium titanate ontology Curie temperature tune
It is whole while its A and B to be replaced using cerium and niobium element to room temperature region, it obtains with room temperature Curie temperature
Dibit adulterates energy-saving heating material, and has good positive thermo-resistive effect；(2) Curie temperature of barium-strontium titanate ceramic is mobile
0~40 DEG C of room temperature region has been arrived, the preparation of room temperature curie point material is realized；(3) dibit is used to adulterate so that barium strontium titanate
The room temperature resistivity of ceramics drops to 10000 Ω cm hereinafter, positive thermo-resistive effect meets most of electronics greater than 3 orders of magnitude
Demand of the operation of component at low ambient temperatures to temperature, and there is capacity of self-regulation, traditional thermal control of alternative complexity
System；(4) manufacture craft is simple, curie point is controllable, to specimen size without limitation, be easy to large-scale production, have very big reality
Border application value is applicable to the thermal control and heat management of system and equipment under cold environment, especially suitable in spacecraft
The thermal control of electronic equipment.
Detailed description of the invention
Fig. 1 is the preparation method flow chart that dibit of the present invention adulterates energy-saving heating material.
Fig. 2 is ball milling mixing of barium strontium titanate of the present invention and pretreated scanning electron microscope (SEM) photograph, wherein (a) is titanium
Scanning electron microscope (SEM) photograph after ball milling mixing of sour strontium barium (b) is the pretreated scanning electron microscope (SEM) photograph of barium strontium titanate.
Fig. 3 is the XRD comparison diagram of barium strontium titanate of the present invention and pure barium titanate.
Fig. 4 is the barium strontium titanate doped energy spectrum diagram of dibit of the present invention and corresponding scanning electron microscope (SEM) photograph.
Specific embodiment
By the analysis to existing literature it is found that being due to its crystal knot since ceramic Curie temperature is transferred to room temperature region
Structure variation causes, while also resulting in the raising of its room temperature resistivity, endangers its thermo-resistive effect.On the other hand, if reducing room temperature
Resistivity, Curie temperature and thermo-resistive effect also will receive corresponding influence.Therefore, the present invention is by the research to Doping Mechanism,
Using the advantage of codope element respectively being modified to the structure of compound, thus significant after curie point is transferred to room temperature
Improve its room temperature resistivity and thermo-resistive effect.
A kind of energy-saving heating material of dibit doping, molecular formula are (Ba1-x-ySrxCey)Ti1.01-aNbaO3, wherein 0.32
≤ x≤0.38,0.0015≤y≤0.0045,0.001≤a≤0.0025 joined in the barium titanate main body phase of heavy doping strontium
The cerium salt and niobium oxide of impure element.
The dibit adulterates the preparation method of energy-saving heating material, includes the following steps:
Step 1, ingredient: first, in accordance with the component ratio (Ba1-x-ySrxCey)Ti1.01-aNbaO3Calculate the weight of each raw material
Amount, weighs to be placed in ball grinder and mixes；Drying obtains mixed powder；
Step 2, it synthesizes main body phase: after the mixed powder that step 1 is obtained crosses 70 meshes, locating in advance at 1160~1200 DEG C
1.5h is managed, natural cooling obtains (Ba1-x-ySrxCey)Ti1.01-aNbaO3Main body phase powder；
Step 3, add auxiliary element: the main body phase powder that step 2 obtains is separately added into glass ingredient according to molar ratio: rubbing
The Al that your percentage is 0mol%~1.5mol%2O3The SiO for being 1mol%~3mol% with molar percentage2, using ball milling
Mode uniformly mixes；It is dry, cross 120 meshes；
Step 4, be granulated and form: the powder that step 3 is obtained is uniformly mixed with adhesive, and is pressed into using tablet press machine
Disc-shaped；
Step 5, it is burnt into: the disk that step 4 obtains being warming up to 1300~1325 DEG C through three sections, keeps the temperature 1~4h；
Step 6, prepare electrode: the potsherd after firing is handled by rubbing down, is cleaned, and drying is splashed respectively in tow sides
One layer of aluminium is penetrated, then coats conductive silver glue, obtains final heating material.
As a kind of specific example, raw material described in step 1 include: ammonium carbonate, strontium carbonate, barium carbonate, titanium dioxide with
And cerium salt and niobium oxide containing impurity element；
The condition of ball milling are as follows: ball-milling medium is dehydrated alcohol and zirconia ball；
Raw material: ball: the mass ratio of dehydrated alcohol is 1:2.5:2；
The revolving speed of ball mill be 300rmp, incorporation time be 18~for 24 hours.
As a kind of specific example, drying described in step 1 carries out in 95 DEG C of drying boxes.
As a kind of specific example, pretreated temperature described in step 2 is 1160 DEG C.
As a kind of specific example, granulation described in step 4, specifically: the adhesive of addition is the poly- second of 6~8wt%
Enolate solution grinds powder and adhesive that step 3 obtains 1.5 hours in the agate mortar, crosses 70 meshes and obtains graininess
Powder.
As a kind of specific example, molding described in step 4: using press machine by the powder after granulation, 2~3MPa it
Between be pressed into disk.
As a kind of specific example, firing described in step 5 is specific as follows:
The disk that step 4 is obtained, when being warming up to 400 DEG C with 2 DEG C/min, stop 40min with after abundant dumping again with 3
DEG C/min is warming up to 1160~1200 DEG C, 1300~1325 DEG C of maximum sintering temperature finally are warming up to 10 DEG C/min, in highest
At a temperature of keep the temperature 1~4h；When then naturally cooling to 860 DEG C, fire door is opened, blasts air, then shut fire door natural cooling.
As a kind of specific example, electrode is prepared described in step 6, it is specific as follows: by potsherd rubbing down at 1~2mm's
Thin slice after drying, first on tow sides magnetron sputtering after one layer of aluminium film, is coated with elargol, burns in 510 DEG C of vacuum ovens
45min is seeped, final heating material is obtained.
With reference to the accompanying drawing and specific embodiment present invention is further described in detail.
Embodiment
The present invention, to the position A of BST complex phase ceramic and B progress dibit substitutions, is obtained and is occupied with room temperature using cerium and niobium
In temperature spot energy-saving heating material.This material use high energy ball mill is sufficiently levigate in two times by raw material and mixes, pre-
Adhesive polyethylene alcohol is added in treated powder, after dry-pressing film-making, prepares dibit doping using solid reaction process
(Ba1-x-ySrxCey)Ti1.01-aNbaO3, 0.32≤x≤0.38,0.0015≤y≤0.0045,0.001≤a≤0.0025.It is made
Standby process is as shown in Figure 1.
The solid reaction process is by high-purity (99.95% or more) BaCO3, SrCO3, TiO2, Ce (NO3)3And Nb2O5By change
After metering is learned than the wet-milling mixing in ethyl alcohol ball-milling medium, main body phase BST is obtained after 1160~1200 DEG C of pretreatments.It adds
Glass ingredient Al2O3、SiO2Finally it is burnt into.Fig. 2 (a) shows raw material distribution situation after high-energy ball milling, and superfine powder is equal
It is even to be attached on bulky grain, and mean particle size is not more than 2 μm.Fig. 2 (b) is the SEM of pretreated main body phase.Known to
BST main body has mutually been formed, and particle is less than 1 μm.
Fig. 3 presents the difference of the crystal structure of BST and undoped barium titanate after doping.With undoped BaTiO3
XRD diagram it is the same, the BST after doping still shows perovskite structure, and has good crystal structure.However after adulterating
The XRD diffraction maximum of barium titanate is compared with undoped, and subtle change all has occurred in peak type and peak position, such as: peak (200) point
For two peaks (200) and (002)；(211) peak is mobile etc. to high angle direction.Illustrate curie point to the movement of low temperature direction and impurity
Element has entered in crystal structure.
Testing result as shown in figure 4, and each element in BST proportion as shown in table 1 (wt% be quality percentage
Than at% is atomic percent).As can be seen that impurity element is successfully doped into barium strontium titanate crystal.In addition, Au
In the presence of being since sample has carried out metal spraying pre-treatment before testing.
Table 1
Below raw material needed for each example purity >=99.95%.
1. ingredient: according to stoichiometric ratio (Ba1-x-ySrxCey)Ti1.01-aNbaO3,0.32≤x≤0.38,0.0015≤y
≤0.0045,0.001≤a≤0.0025.The weight of each raw material is calculated, weighs raw material BaCO respectively3, SrCO3, Ce (NO3)3·
6H2O,TiO2, Nb2O5, and (NH4)2CO3, it is placed in ball grinder mixing 18~for 24 hours；Wherein, ball-milling medium be dehydrated alcohol and
Zirconia ball；Raw material: ball: the ratio of dehydrated alcohol is 1:2.5:2；The revolving speed of ball mill is 300rmp.It is dried through 90~100 DEG C
After obtain mixed powder.
As a kind of preferable example, each parameter x=0.35, y=0.003, a=0.002 in component；That is corresponding each original
The weight of material is 42.5597 grams of BaCO3, 17.2235 grams of SrCO3, 0.4341 gram of Ce (NO3)3·6H2O, 26.8349 grams of TiO2, with
And 0.0886 gram of Nb2O5。
2. synthesis main body phase: it after the powder that step 1) is obtained crosses 70 meshes, is placed in alumina crucible, covers,
1.5h, natural cooling are pre-processed at 1160~1200 DEG C.Obtain (Ba1-x-ySrxCey)Ti1.01-aNbaO3Main body phase powder.
3 addition auxiliary elements: the powder that step 2) obtains is separately added into glass ingredient according to molar ratio: 0≤b≤
1.5mol%Al2O3With 1≤c≤3mol%SiO2, b expression Al2O3Molar percentage, c indicate SiO2Molar percentage.Into
Row secondary ball milling, uniformly mix 18~for 24 hours；It is dry；Cross 120 meshes.
4. being granulated and forming: the powder that step 3) obtains being uniformly mixed with 6~8wt% adhesive, in the agate mortar
Grinding 1.5 hours crosses 70 meshes, and is pressed into disk between 2~3MPa using press machine.
5. firing: the disk that step 4) obtains is warming up to 1300~1325 DEG C through three sections.400 are warming up to 2 DEG C/min
DEG C when, stop 40min with after abundant dumping again with 3 DEG C/min to 1160~1200 DEG C, finally with 10 DEG C/min to most high fever
Junction temperature keeps the temperature 1~4h at the maximum temperature.When naturally cooling to 860 DEG C, fire door is opened, air is blasted, then shuts fire door certainly
It is so cooling.
6. preparing electrode: the potsherd after step 5) firing being handled by rubbing down, ultrasonic cleaning 30min, drying, just
Anti- two sides sputters one layer of aluminium film respectively, then coats conductive silver glue.Burning infiltration 45min, naturally cold in 510 DEG C of vacuum ovens
But, sample is obtained.
Table 2 is specific embodiment and corresponding ratio component, and table 3 is the corresponding performance detection data of each embodiment.According to
Data in table can be seen that the barium-strontium titanate ceramic provided by the invention with room temperature Curie temperature, in substitution amount x=
When 0.35, y=0.003, a=0.002, b=1, c=2 (embodiment 5), Ball-milling Time 20h, sintering temperature is 1300 DEG C, sintering
When time is 3h, the properties of sample of acquisition is best, and Curie temperature is 30 DEG C, is located at room-temperature zone.It is located at compared to current curie point
The barium-strontium titanate ceramic of room-temperature zone, performance are greatly improved and improve.
Table 2
Table 3
| Curie temperature (DEG C) | Room temperature resistivity (Ω cm) | Positive temperature effect intensity | |
| Embodiment 1 | 48 | 17023 | 102 |
| Embodiment 2 | 30 | 13200 | 102 |
| Embodiment 3 | 18 | 80050 | 102.8 |
| Embodiment 4 | 31 | 4021 | 103.2 |
| Embodiment 5 | 30 | 8100 | 104.1 |
| Embodiment 6 | 30 | 8450 | 103.5 |
| Embodiment 7 | 32 | 8900 | 103 |
| Embodiment 8 | 30 | 8038 | 102.8 |
| Embodiment 9 | 30 | 8150 | 103 |
| Embodiment 10 | 30 | 9025 | 102 |
| Embodiment 11 | 30 | 8947 | 103.1 |
| Embodiment 12 | 29 | 9544 | 103.9 |
In conclusion the barium strontium titanate doped heating material of dibit of the present invention with and preparation method thereof, solve existing
The problem of barium strontium titanate may not apply to electronic equipment thermal control due to high-Curie-point.Pass through the dibit in barium strontium titanate complex phase ceramic
Cerium and niobium element are adulterated, under the premise of Curie temperature is dropped to room-temperature zone by discovery, room temperature resistivity is controlled in 10000 Ω cm
Within, and PTC intensity is greater than 3 orders of magnitude, and this has huge application prospect in electronic equipment self-regulation thermal control field.
Claims (9)
1. a kind of dibit adulterates energy-saving heating material, it is characterised in that: its molecular formula is (Ba1-x-ySrxCey)Ti1.01- aNbaO3, wherein 0.32≤x≤0.38,0.0015≤y≤0.0045,0.001≤a≤0.0025, the i.e. barium titanate of heavy doping strontium
It joined the cerium salt and niobium oxide of impure element in main body phase.
2. the preparation method that dibit as described in claim 1 adulterates energy-saving heating material, which is characterized in that including walking as follows
It is rapid:
Step 1, ingredient: first, in accordance with the component ratio (Ba1-x-ySrxCey)Ti1.01-aNbaO3The weight of each raw material is calculated, is claimed
It takes to be placed in ball grinder and mix；Drying obtains mixed powder；
Step 2, it synthesizes main body phase: after the mixed powder that step 1 is obtained crosses 70 meshes, being pre-processed at 1160~1200 DEG C
1.5h, natural cooling obtain (Ba1-x-ySrxCey)Ti1.01-aNbaO3Main body phase powder；
Step 3, add auxiliary element: the main body phase powder that step 2 obtains is separately added into glass ingredient according to molar ratio: moles hundred
Divide the Al than being 0mol%~1.5mol%2O3The SiO for being 1mol%~3%mol with molar percentage2, using the side of ball milling
Formula uniformly mixes；It is dry, cross 120 meshes；
Step 4, be granulated and form: the powder that step 3 is obtained is uniformly mixed with adhesive, and is pressed into disk using tablet press machine
Shape；
Step 5, it is burnt into: the disk that step 4 obtains being warming up to 1300~1325 DEG C through three sections, keeps the temperature 1~4h；
Step 6, prepare electrode: the potsherd after firing is handled by rubbing down, is cleaned, and drying sputters respectively in tow sides
One layer of aluminium, then conductive silver glue is coated, obtain final heating material.
3. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 1 institute
The raw material stated includes: ammonium carbonate, strontium carbonate, barium carbonate, titanium dioxide and cerium salt and niobium oxide containing impurity element；
The condition of ball milling are as follows: ball-milling medium is dehydrated alcohol and zirconia ball；
Raw material: ball: the mass ratio of dehydrated alcohol is 1:2.5:2；
The revolving speed of ball mill be 300rmp, incorporation time be 18~for 24 hours.
4. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 1 institute
The drying stated carries out in 95 DEG C of drying boxes.
5. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 2 institute
The pretreated temperature stated is 1160 DEG C.
6. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 4 institute
The granulation stated, specifically: the adhesive of addition is the poly-vinyl alcohol solution of 6~8wt%, the powder that step 3 is obtained and bonding
Agent is ground 1.5 hours in the agate mortar, is crossed 70 meshes and is obtained graininess powder.
7. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 4 institute
The molding stated: using press machine by the powder after granulation, disk is pressed between 2~3MPa.
8. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 5 institute
The firing stated, specific as follows:
The disk that step 4 is obtained, when being warming up to 400 DEG C with 2 DEG C/min, stop 40min with after abundant dumping again with 3 DEG C/min
1160~1200 DEG C are warming up to, is finally warming up to 1300~1325 DEG C of maximum sintering temperature with 10 DEG C/min, at the maximum temperature
Keep the temperature 1~4h；When then naturally cooling to 860 DEG C, fire door is opened, blasts air, then shut fire door natural cooling.
9. the preparation method that dibit according to claim 2 adulterates energy-saving heating material, which is characterized in that step 6 institute
That states prepares electrode, and specific as follows: by potsherd rubbing down at the thin slice of 1~2mm, after drying, elder generation is in tow sides magnetron sputtering
After upper one layer of aluminium film, it is coated with elargol, the burning infiltration 45min in 510 DEG C of vacuum ovens obtains final heating material.
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Citations (2)
| 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 |
| CN105321641A (en) * | 2014-07-03 | 2016-02-10 | Tdk株式会社 | Semiconductor ceramic composition and PTC thermistor |
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2019
- 2019-02-03 CN CN201910109510.5A patent/CN109704755A/en active Pending
Patent Citations (2)
| 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 |
| CN105321641A (en) * | 2014-07-03 | 2016-02-10 | Tdk株式会社 | Semiconductor ceramic composition and PTC thermistor |
Non-Patent Citations (3)
| Title |
|---|
| CHENG, XUXIN等: "Investigation of PTCR effect and microdefects in Nb2O5-doped BaTiO3-based ceramics by positron annihilation techniques", 《INTERNATIONAL JOURNAL OF MODERN PHYSICS B》 * |
| NEMATI, ZA等: "The effects of cerium doping on the resistivity of PTCR barium lead titanate", 《BRITISH CERAMIC TRANSACTIONS》 * |
| PATIL, D. R等: "Studies on electrical and dielectric properties of Ba1-xSrxTiO3", 《MATERIALS CHEMISTRY AND PHYSICS》 * |
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Application publication date: 20190503 |