CN109761602A - A kind of low-resistance thermal sensitive ceramic material and the preparation method and application thereof - Google Patents
A kind of low-resistance thermal sensitive ceramic material and the preparation method and application thereof Download PDFInfo
- Publication number
- CN109761602A CN109761602A CN201910153087.9A CN201910153087A CN109761602A CN 109761602 A CN109761602 A CN 109761602A CN 201910153087 A CN201910153087 A CN 201910153087A CN 109761602 A CN109761602 A CN 109761602A
- Authority
- CN
- China
- Prior art keywords
- thermal sensitive
- ceramic material
- sensitive ceramic
- preparation
- obtains
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a kind of low-resistance thermal sensitive ceramic material and preparation method and applications, belong to electronic ceramic component technical field.The chemical formula of the main component of the thermal sensitive ceramic material is ((Bi0.5Q0.5)xBam‑x)TiO3;Wherein Q is alkali metal element Na or K;Wherein the value range of m is 1≤m≤1.007, and the value range of x is 0.001≤x≤0.007.Preparation method is to calcine after mixing bismuth-sodium titanate or bismuth potassium titanate ceramic powders with barium carbonate powder, titanium dioxide powder, then pass sequentially through curtain coating, lamination, tabletting and slice, obtains molding green compact;Molding green compact are decomposed into mixed organic matter in casting processes under the conditions of temperature is more than or equal to 280 DEG C, then are calcined in a reducing atmosphere, ceramic block is obtained;Ceramic block is calcined in oxygen-containing atmosphere again again.Chip barium phthalate base thermal sensitive ceramics made from the method for the present invention has extremely low room temperature resistivity, higher lift resistance ratio, higher temperature coefficient.
Description
Technical field
The invention belongs to electronic ceramic component technical fields, more particularly, to a kind of piece of low-resistivity high lift-drag ratio
Formula thermal sensitive ceramic material and preparation method and application.
Background technique
Barium titanate-based positive temperature coefficient (PTC) ceramic thermal resistance is widely used in mobile communication, fine definition colour TV, office
The fields such as domain net, computer, automotive electronics.As electronic circuit and electric appliance are rapidly to miniaturization, integrated and multifunction hair
Exhibition, thermistor will also realize micromation.Meanwhile in order to adapt to the requirement of surface mounting technology, thermistor also will as resistance,
The passive discrete component such as capacitor, inductance equally realizes chip type, and requires the slice component outer dimension using standard.Through excessive
Year explores and technological progress, and chip barium titanate-based positive temperature coefficient ceramic thermal resistance mostly uses multilayer sheet type ceramic condenser at present
(MLCC) monolithic structure has many advantages, such as that small in size, resistance is low, lift resistance ratio is high.
For barium titanate-based positive temperature coefficient ceramic thermal resistance, PTC effect derives from crystal boundary, it is general for, it is brilliant
Boundary's potential barrier is higher, and lift resistance ratio (temperature coefficient) is bigger, and grain boundary resistance is also bigger.Therefore, it is difficult to by simply adjusting preparation
Parameter reduces room temperature resistivity.Only pass through integrated use blast blending, optimization preparation flow, adjustment preparation technology parameter
Room temperature resistivity could be reduced while not influencing lift resistance ratio.For chip barium titanate-based positive temperature coefficient ceramics temperature-sensitive electricity
Resistance further decreases room temperature resistivity under the premise of keeping compared with high lift-drag ratio, and improving temperature coefficient is a current technology
Problem.
In this respect, Japanese Murata all relates in numerous patents, for example Publication No. CN00136081
The U.S. Patent application of Chinese patent application and Publication No. US2001/003361 A1.Also there are part related patents: example in the country
Such as application No. is the patents of CN201310570899, prepare lamination sheet type barium titanate thermal sensitive ceramics using sol-gal process method, rise
Resistance is than being greater than 103When minimum specific resistance be 74.4 Ω cm;Application No. is the patent of CN200810047300, room temperature resistivity is
348Ω·cm.It also needs to further increase lift resistance ratio, and reduces resistivity simultaneously.The Publication No. of this seminar
In the patent of CN201811135337, using mixing high-purity bismuth-sodium titanate and optimize the method for preparation parameter simultaneously, air (or
Oxygen-containing atmosphere) in prepare the column thermal sensitive ceramic material and temperature-sensitive element that PTC effect is good, temperature coefficient is high, solve tradition
Column PTC ceramic element (without interior electrode) problem that temperature coefficient is low, response speed is slow.Due to sintering process and moulding process
Difference, the summary of the invention are not suitable for the preparation of multilayer sheet type thermal sensitive ceramic material and element, can not solve this application and be proposed
The problem of.
Summary of the invention
The present invention solves the technical problem that resistivity is high in the prior art and lift resistance ratio is low.
It is according to the invention in a first aspect, provide a kind of chip thermal sensitive ceramic material, the thermal sensitive ceramic material it is main
The chemical formula of ingredient is ((Bi0.5Q0.5)xBam-x)TiO3;Wherein Q is alkali metal element Na or K;Wherein the value range of m be 1≤
The value range of m≤1.007, x are 0.001≤x≤0.007.
Preferably, which also contains donor metal ion, and the donor metal ion is+trivalent rare earth gold
Belong to ion, Nb5+Or Ta5+;The donor metal ion is embedded in the lattice of the thermal sensitive ceramic material;Containing main described in 1mol
Donor metal ion described in the thermal sensitive ceramic material of ingredient is wanted to be less than or equal to 0.008mol;
Preferably, described+trivalent rare earth ion is Y3+Or La3+。
Preferably, which also contains acceptor's compound, and acceptor's compound is MnO2;Contain 1mol institute
Acceptor's compound described in the thermal sensitive ceramic material of main component is stated less than or equal to 0.0006mol.
It is another aspect of this invention to provide that providing the preparation method of the chip thermal sensitive ceramic material, contain following step
It is rapid:
(1) bismuth oxide, alkali metal compound and titanium dioxide are mixed, obtains mixture;The mixture is existed again
0.5h-2h is calcined under the conditions of 800 DEG C -840 DEG C, obtains bismuth-sodium titanate or bismuth potassium titanate ceramic powders;The alkali metal compound
For the oxide of sodium, sodium carbonate, potassium oxide or potassium carbonate;
(2) it is according to the ratio between the amount of substance by ceramic powders, barium carbonate powder and titania powder that step (1) obtains
X:(m-x): 1 is mixed, and obtains mixed ceramic powders;The value range of the m is 1≤m≤1.007, the value model of x
It encloses for 0.001≤x≤0.007;
(3) it will be calcined after step (2) the mixed ceramic powders drying, the temperature of the calcining is 1100
DEG C -1200 DEG C, the time of the calcining is 1h-3h;
(4) sintering aid is added into step (3) products therefrom, single layer green sheet is then obtained by curtain coating, then by the list
Layer green sheet successively carries out lamination, tabletting and slice, obtains molding green compact;The molding green compact are being more than or equal to 280 DEG C
Under the conditions of decompose mixed organic matter in the casting processes;
(5) product that step (4) obtains is calcined in a reducing atmosphere, obtains ceramic block;The calcining is with 200
DEG C/heating rate of h-500 DEG C/h rises to 1050 DEG C -1200 DEG C, then keeps the temperature 0.5h-3h, then with 100 DEG C/h-400 DEG C/h's
Cooling rate is down to 600 DEG C -800 DEG C, then natural cooling;
(6) ceramic block that step (5) obtains is calcined in oxygen-containing atmosphere again, the calcining is with 200 DEG C/h-500
DEG C/heating rate of h rises to 700 DEG C -900 DEG C, then keeps the temperature 0.5h-4h, then natural cooling is made pottery to get to the chip temperature-sensitive
Ceramic material.
It preferably, further include that alms giver's powder is added into mixed ceramic powders in step (2), alms giver's powder is
Rare-earth oxide, Nb2O5Or Ta2O5, rare earth metal is+trivalent in the rare-earth oxide;
Preferably, the rare-earth oxide is Y2O3Or La2O3。
It preferably, further include that acceptor's powder is added into mixed ceramic powders in step (2), acceptor's powder is
Manganese nitrate or manganese oxide.
Preferably, the ratio between amount of substance of step (1) bismuth oxide, alkali metal compound and titanium dioxide is (0.98-
1.02): (0.99-1.03): 4.
It preferably, further include that organic monomer, catalyst and initiator are added into mixture in step (1), due to organic
The polymerization of monomer, so that gel state is presented in the mixture, so that each component in mixture comes into full contact with;
Preferably, the organic monomer is the mixture of acrylamide and methylene-bisacrylamide;The catalyst is
Ammonium persulfate;The initiator is tetramethylethylenediamine;
Preferably, the mass ratio of the acrylamide and methylene-bisacrylamide is (20-28): 1.
Preferably, further include electrode in being printed in the single layer green sheet described in step (4), then successively carry out lamination, pressure
Piece and slice;Step (4) sintering aid is barium carbonate or silica.
It is another aspect of this invention to provide that providing application of the chip thermal sensitive ceramic material for thermistor.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) chip barium titanate-based positive temperature coefficient thermal sensitive ceramic material provided by the invention and preparation method thereof, sufficiently
In conjunction with the characteristics of chip thermal sensitive ceramics and demand, the preparation method of thermal sensitive ceramic material is redesigned, by adjusting at
Distribution ratio, heating rate and soaking time, to reduce room temperature resistivity while keeping compared with high lift-drag ratio, improve temperature
Coefficient.According to the chip PTC ceramic element that obtains of the present invention not only room temperature resistance it is low and also there are also biggish lift resistance ratio and compared with
Thus it is not low enough to solve existing chip thermal sensitive ceramic material room temperature resistance for high temperature coefficient, while lift resistance ratio is not high enough
Technical problem.
(2) main component of thermal sensitive ceramic material provided by the invention is titanate, including barium titanate and bismuth-sodium titanate
Or bismuth potassium titanate, wherein bismuth element, sodium and kalium element enter the barium position of barium titanate, donor element enter barium titanate barium position and/or
Titanium position, recipient element are segregated in crystal boundary, and room temperature resistivity is low and lift resistance ratio is higher.
(3) each raw material is mixed in the preparation method of thermal sensitive ceramic material of the present invention with organic monomer, utilizes organic monomer
Polymerization so that various mixtures mixing after obtain gel, each raw material come into full contact with, increase response area, to drop
The synthesis temperature of low bismuth-sodium titanate or bismuth potassium titanate reduces the volatilization of bismuth element in sintering process, it is ensured that bismuth and alkali gold in product
Belong to the atomic ratio of element close to ideal value.
(4) present invention prepare during bismuth-sodium titanate or bismuth potassium titanate used in organic monomer can aoxidize at high temperature point
Solution is gaseous volatilization, does not influence material component, does not introduce exogenous impurity, so as to prepare high-purity single-phase bismuth titanate sodium or high-purity
Single-phase bismuth titanate potassium powder.
(5) the chip thermal sensitive ceramic material of the prior art is usually not include bismuth-sodium titanate (potassium), can not protected at this time
Room temperature resistivity is further decreased under conditions of card element lift resistance ratio.The bismuth-sodium titanate that the present invention is fired by addition liquid phase
(potassium), optimization preparation process while guaranteeing lift resistance ratio substantially reduce room temperature resistivity, finally prepare and have excellent performance
Chip thermal sensitive ceramics element.
(6) thermal sensitive ceramic material that preparation method provided by the invention is prepared is greater than 10 in lift resistance ratio2While, room
Warm resistivity is minimum to can reach 20 Ω cm.Why the thermal sensitive ceramic material that the present invention is prepared can keep compared with high lift-drag ratio
While obtain lower room temperature resistivity, be because bismuth-sodium titanate or the bismuth potassium titanate optimization of addition and play microscopic appearance
Promote the effect of crystal grain carrier concentration.
(7) when burning in nitrogen or inert gas in preparation method of the present invention, preferably with 100 DEG C/h-400 DEG C/h's
Cooling rate is down to 600 DEG C -800 DEG C.Cooling rate will affect the migration of lattice defect in sintering process and freeze, to influence
The electric property of ceramic material.Select different cooling rates according to actual needs to prepare with different performance parameter
Ceramic component.
(8) present invention prepares a kind of chip thermal sensitive ceramics element, preferably may include interior electrode, is reoxidized using reduction
The chip thermal sensitive ceramic material comprising interior electrode is prepared in technique.
Detailed description of the invention
Fig. 1 is the flow chart of the thermal sensitive ceramic material prepared in the embodiment of the present invention 1.
Fig. 2 is the XRD diagram for the thermal sensitive ceramic material being prepared in the embodiment of the present invention 1.
Fig. 3 is the resistance-temperature curve that the present invention implements the barium phthalate base thermistor prepared in 3.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
The present invention provides a kind of thermal sensitive ceramic material, the chemical formula of the main component of the thermal sensitive ceramic material is
((Bi0.5Q0.5)xBam-x)TiO3;Wherein Q is alkali metal element Na or K;Wherein the value range of m is 1≤m≤1.007, and x's takes
Value range is 0.001≤x≤0.007.
The preparation method of the thermal sensitive ceramic material, includes the following steps:
(1) by bismuth oxide, alkali metal oxide or alkali carbonate, titanium dioxide according to molar ratio (0.98-1.02):
(0.99-1.03): 4 mixing are preferably mixed and added into appropriate organic monomer according to molar ratio 1:1:4, utilize the poly- of organic monomer
Cooperation is used, and obtains gelatinous mixture after mixing, will obtain high-purity bismuth-sodium titanate or bismuth titanates after gelatinous mixture calcining
Potassium ceramic powders;The organic monomer is the mixture of acrylamide and methylene-bisacrylamide;Wherein acrylamide and Asia
The mass ratio of bisacrylamide is 20-28:1;The organic monomer polymerize under the action of catalyst and initiator
Reaction;Preferably, the catalyst is ammonium persulfate, and the initiator is tetramethylethylenediamine;Hybrid mode preferably by
Ball milling mixing, when ball milling, use water as ball-milling additive.Calcination temperature is 800-840 DEG C, and calcination time is 1-2 hours.
(2) ceramic powders and industrial high-pruity barium carbonate powder that obtain step (1), industrial high-purity titanium dioxide
Titanium powder, alms giver's ceramic powders, acceptor's ceramic powders are uniformly mixed, and obtain mixed ceramic powders;Alms giver's powder is oxidation
Lanthanum, yttrium oxide and niobium pentaoxide it is one or more, acceptor's powder is manganese nitrate or manganese oxide.
(3) it will be calcined after step (2) the mixed ceramic powders drying, obtain pure phase powder;The calcining
Specifically: it is calcined at 1100 DEG C~1200 DEG C about 1~3 hour
(4) powder described in step (3) is executed after crushing, while the sintering aid of 0.1mol%-0.3mol% is added, then
By being cast, printing interior electrode, lamination, tabletting, slice, dumping (decompose casting processes in mixed organic matter) obtain molding life
Base;
(5) by (N in a reducing atmosphere of molding green compact described in step (4)2/H2Gaseous mixture) calcining, calcination temperature 1050
~1200 DEG C, calcination time is 0.5~2 hour;
(6) ceramic block that step (5) obtains is calcined in oxygen-containing atmosphere again, set temperature is 700~900 DEG C, is forged
Burning the time is 0.5~3 hour, obtains the thermal sensitive ceramic material.
Embodiment 1
S1: by 58.245g bismuth oxide, 13.249g sodium carbonate, 39.94g titanium dioxide and organic monomer (21.395g third
Acrylamide, 0.873g methylene-bisacrylamide) ball milling mixing is uniform.Using the polymerization of organic monomer, obtained after standing
Homogeneous gel.Accelerate gel process using ammonium persulfate and tetramethylethylenediamine in gel process.By gel at a temperature of 820 DEG C
Calcining 1 hour, obtains high-purity bismuth-sodium titanate ceramic powders.
S2: taking 98.470g barium carbonate, 0.244g lanthana, and 39.957g titanium dioxide passes through ball with 0.106g bismuth-sodium titanate
Mill is uniformly mixed.
S3: ceramic slurry is taken out from ball grinder, is taken out after drying 12h in an oven.Block is ground into after taking-up
Powder.Powder is transferred in muffle furnace, be warming up to 1150 DEG C with 300 DEG C/h of speed and keeps the temperature 2 hours, it is then naturally cold
But;
S4: the agglomerated particle after firing is taken out, executes crushing, while 0.326g barium carbonate is added as sintering aid.It will
Smashed powder drying, adds 1.543g dispersing agent and defoaming agent, adds 92.6g dehydrated alcohol, 154.3g toluene, system
Standby curtain coating slurry out.Further, curtain coating, lamination, tabletting, slice are to obtain standard size molding green compact.Molding is given birth to
Base is dumping 48 hours under the conditions of temperature is more than or equal to 280 DEG C.If you need to prepare interior electrode, silk need to be passed through after curtain coating, before lamination
Electrode slurry is printed onto single layer green sheet by the mode of wire mark brush.
S5: by the green compact after dumping in atmosphere furnace (N2/H2Gaseous mixture) in, it is risen to 300 DEG C of heating rates hourly
1075 DEG C, 2 hours are kept the temperature, then be down to room temperature with 200 DEG C of cooling rates hourly;
S6: the ceramic component that S5 is prepared is transferred in muffle furnace, is risen to 800 DEG C with 300 DEG C of speed hourly, is protected
Temperature 2 hours, then cools to room temperature with the furnace.
Preparation flow figure is as shown in Figure 1, the main component for the thermal sensitive ceramic material that the present embodiment is prepared is
((Bi0.5Na0.5)0.001Ba0.999)TiO3.The ingredient determines that XRD spectrum such as Fig. 2 is tested in XRD as shown in Figure 2 by XRD
Under precision, which is perovskite structure, and without other miscellaneous phases or the second phase, Bi and Na enter lattice A.
Barium titanate thermal sensitive ceramics electric parameters manufactured in the present embodiment are as follows: 81 Ω cm of room temperature resistivity, lift resistance ratio
Rmax/Rmin=3.1 × 102, temperature coefficient α10/25=5.07%.
Embodiment 2-7
The present embodiment is identical as 1 preparation step of embodiment, unlike, the carbonic acid of different amounts has been used in step S2
Barium, bismuth-sodium titanate and donor doping amount.Donor doping amount is then according to x, and depending on y value, to this group of example, every 1mol material alms giver adds
Dosage is 0-0.3mol%;Holding temperature is 1125 DEG C in step S5.
The main component for the thermal sensitive ceramic material that the present embodiment is prepared is ((Bi0.5Na0.5)xBa1-x)TiO3, the value of x
With the electric property such as table 1 of completed electronic elements:
Table 1
Fig. 3 is the resistance-temperature curve that the present invention implements the barium phthalate base thermistor prepared in 3.From the figure 3, it may be seen that system
Standby thermal sensitive ceramics element room temperature resistance out is low, and thermal sensitive effect is obvious, excellent combination property.
Embodiment 8
The present embodiment is identical as 1 other conditions of embodiment, unlike, sintering temperature curve used in step S5 is not
It is same: after heat preservation, then to cool to 800 DEG C with 400 DEG C/H, subsequent cooled to room temperature.
The chemical formula of the main component for the thermal sensitive ceramic material thermal sensitive ceramic material that the present embodiment is prepared is
((Bi0.5Na0.5)0.001Ba0.999)TiO3。
The electric parameters for the barium titanate thermal sensitive ceramics that the present embodiment prepares are as follows: 80.7 Ω of room temperature resistivity
Cm, lift resistance ratio Rmax/Rmin=2.4 × 102, temperature coefficient α10/25=3.92%.It is dropped in S5 compared to embodiment 1 as it can be seen that increasing
Warm speed can reduce the lift resistance ratio and temperature coefficient of material.
Embodiment 9
As different from Example 4, sintering temperature curve used in step S5 is different for the present embodiment: heat preservation terminates
Afterwards, 800 DEG C then are cooled to 100 DEG C/H, subsequent cooled to room temperature.
The chemical formula of the main component for the thermal sensitive ceramic material thermal sensitive ceramic material that the present embodiment is prepared is
((Bi0.5Na0.5)0.001Ba0.999)Ti1O3。
The electric parameters for the barium titanate thermal sensitive ceramics that the present embodiment prepares are as follows: 70 Ω cm of room temperature resistivity,
Lift resistance ratio Rmax/Rmin=5.2 × 103, temperature coefficient α10/25=5.45%.Compared to embodiment 1 as it can be seen that reducing the speed that cools down in S5
The lift resistance ratio and temperature coefficient of material can be improved in degree.
Embodiment 10-12
The present embodiment is same as Example 4, unlike, it joined acceptor's powdered ceramic material.
The main component for the thermal sensitive ceramic material that the present embodiment is prepared is ((Bi0.5Na0.5)0.004Ba0.996)TiO3.By
Main (manganese nitrate) doping and final material performance data are included in table 2:
Table 2
Embodiment 13
The present embodiment is same as Example 1, unlike, the bismuth potassium titanate replacement titanium of the amount of substances such as use in step S2
Sour bismuth sodium, other are all the same.
The chemical formula of the main component for the thermal sensitive ceramic material thermal sensitive ceramic material that the present embodiment is prepared is
((Bi0.5K0.5)0.001Ba0.999)TiO3。
The electric parameters for the barium titanate thermal sensitive ceramics that the present embodiment prepares are as follows: 90 Ω cm of room temperature resistivity,
Lift resistance ratio Rmax/Rmin=2.7 × 102, temperature coefficient α10/25=4.61%.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of chip thermal sensitive ceramic material, which is characterized in that the chemical formula of the main component of the thermal sensitive ceramic material is
((Bi0.5Q0.5)xBam-x)TiO3;Wherein Q is alkali metal element Na or K;Wherein the value range of m is 1≤m≤1.007, and x's takes
Value range is 0.001≤x≤0.007.
2. chip thermal sensitive ceramic material as described in claim 1, which is characterized in that the thermal sensitive ceramic material also contains alms giver's gold
Belong to ion, the donor metal ion is+trivalent rare earth ion, Nb5+Or Ta5+;Described in the donor metal ion insertion
In the lattice of thermal sensitive ceramic material;Donor metal ion described in the thermal sensitive ceramic material containing main component described in 1mol is small
In equal to 0.008mol;
Preferably, described+trivalent rare earth ion is Y3+Or La3+。
3. chip thermal sensitive ceramic material as claimed in claim 2, which is characterized in that the thermal sensitive ceramic material also contains acceptorization
Object is closed, acceptor's compound is MnO2;Acceptor's chemical combination described in the thermal sensitive ceramic material containing main component described in 1mol
Object is less than or equal to 0.0006mol.
4. the preparation method of chip thermal sensitive ceramic material as described in claim 1, which is characterized in that contain following steps:
(1) bismuth oxide, alkali metal compound and titanium dioxide are mixed, obtains mixture;Again by the mixture 800
0.5h-2h is calcined under the conditions of DEG C -840 DEG C, obtains bismuth-sodium titanate or bismuth potassium titanate ceramic powders;The alkali metal compound is sodium
Oxide, sodium carbonate, potassium oxide or potassium carbonate;
(2) ceramic powders, barium carbonate powder and the titania powder for obtaining step (1) are x according to the ratio between amount of substance:
(m-x): 1 is mixed, and obtains mixed ceramic powders;The value range of the m is 1≤m≤1.007, the value range of x
For 0.001≤x≤0.007;
(3) it will be calcined after step (2) the mixed ceramic powders drying, the temperature of the calcining is 1100 DEG C-
1200 DEG C, the time of the calcining is 1h-3h;
(4) sintering aid is added into step (3) products therefrom, single layer green sheet is then obtained by curtain coating, then the single layer is raw
Blank successively carries out lamination, tabletting and slice, obtains molding green compact;The molding green compact are being more than or equal to 280 DEG C of condition
It is lower to decompose mixed organic matter in the casting processes;
(5) product that step (4) obtains is calcined in a reducing atmosphere, obtains ceramic block;The calcining is with 200 DEG C/h-
The heating rate of 500 DEG C/h rises to 1050 DEG C -1200 DEG C, then keeps the temperature 0.5h-3h, then with the cooling of 100 DEG C/h-400 DEG C/h
Speed is down to 600 DEG C -800 DEG C, then natural cooling;
(6) ceramic block that step (5) obtains is calcined in oxygen-containing atmosphere again, the calcining is with 200 DEG C/h-500 DEG C/h
Heating rate rise to 700 DEG C -900 DEG C, then keep the temperature 0.5h-4h, then natural cooling is to get arriving the chip thermal sensitive ceramics material
Material.
5. the preparation method of chip thermal sensitive ceramic material as claimed in claim 4, which is characterized in that further include in step (2) to
Alms giver's powder is added in mixed ceramic powders, alms giver's powder is rare-earth oxide, Nb2O5Or Ta2O5, described
Rare earth metal is+trivalent in rare-earth oxide;
Preferably, the rare-earth oxide is Y2O3Or La2O3。
6. the preparation method of chip thermal sensitive ceramic material as claimed in claim 5, which is characterized in that further include in step (2) to
Acceptor's powder is added in mixed ceramic powders, acceptor's powder is manganese nitrate or manganese oxide.
7. the preparation method of chip thermal sensitive ceramic material as claimed in claim 4, which is characterized in that step (1) bismuth oxide,
The ratio between amount of substance of alkali metal compound and titanium dioxide is (0.98-1.02): (0.99-1.03): 4.
8. the preparation method of chip thermal sensitive ceramic material as claimed in claim 4, which is characterized in that further include in step (1) to
Organic monomer, catalyst and initiator are added in mixture, due to the polymerization of organic monomer, so that the mixture is presented
Gel state, so that each component in mixture comes into full contact with;
Preferably, the organic monomer is the mixture of acrylamide and methylene-bisacrylamide;The catalyst is over cure
Sour ammonium;The initiator is tetramethylethylenediamine;
Preferably, the mass ratio of the acrylamide and methylene-bisacrylamide is (20-28): 1.
9. the preparation method of chip thermal sensitive ceramic material as claimed in claim 4, which is characterized in that further include in step (4)
Electrode in being printed in the single layer green sheet, then successively carry out lamination, tabletting and slice;Step (4) sintering aid is carbonic acid
Barium or silica.
10. the application that any chip thermal sensitive ceramic material of claim 1-3 is used for thermistor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910153087.9A CN109761602B (en) | 2019-02-28 | 2019-02-28 | Low-resistance thermal sensitive ceramic material and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910153087.9A CN109761602B (en) | 2019-02-28 | 2019-02-28 | Low-resistance thermal sensitive ceramic material and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109761602A true CN109761602A (en) | 2019-05-17 |
CN109761602B CN109761602B (en) | 2020-11-24 |
Family
ID=66456511
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910153087.9A Active CN109761602B (en) | 2019-02-28 | 2019-02-28 | Low-resistance thermal sensitive ceramic material and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109761602B (en) |
Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20010003361A1 (en) * | 1999-12-09 | 2001-06-14 | Murata Manufacturing Co., Ltd. | Semiconducting ceramic material and electronic part employing the same |
CN101013618A (en) * | 2007-01-16 | 2007-08-08 | 杨敬义 | Leadless PTC thermistor material with high Curie point |
CN101224979A (en) * | 2008-01-18 | 2008-07-23 | 陕西科技大学 | Method for preparing high Curie point leadless PTC ceramic resistance material |
CN101445365A (en) * | 2008-12-26 | 2009-06-03 | 广东工业大学 | Barium titanate-based positive temperature coefficient resistance material and preparation method thereof |
CN101838143A (en) * | 2010-06-01 | 2010-09-22 | 陕西科技大学 | Bi0.5Na0.5TiO3/Ba1-xCaxTiO3-based PTC thermal sensitive ceramic material and preparation method thereof |
CN101910088A (en) * | 2007-12-26 | 2010-12-08 | 日立金属株式会社 | Semiconductor ceramic composition |
CN101959830A (en) * | 2008-03-27 | 2011-01-26 | 日立金属株式会社 | Process for producing semiconductor porcelain composition/electrode assembly |
CN101959829A (en) * | 2008-03-19 | 2011-01-26 | 日立金属株式会社 | Process for producing semiconductor porcelain composition and heater employing semiconductor porcelain composition |
CN102482160A (en) * | 2009-10-06 | 2012-05-30 | 日立金属株式会社 | Semiconductor ceramic composition, method for producing same, PTC element and heat generating module |
CN102503408A (en) * | 2011-10-12 | 2012-06-20 | 华中科技大学 | Preparation method of laminated barium titanate PTC (positive temperature coefficient) ceramic |
CN102887704A (en) * | 2012-10-09 | 2013-01-23 | 天津大学 | Lead-free high-Curie temperature PTCR (positive temperature coefficient resistor) ceramic material and preparation method thereof |
CN103626489A (en) * | 2013-11-13 | 2014-03-12 | 华中科技大学 | Preparation method of low-temperature sintering laminated sheet type barium titanate thermal sensitive ceramic |
CN104245625A (en) * | 2012-04-20 | 2014-12-24 | 日立金属株式会社 | Semiconductor ceramic composition, method for producing same, and ptc element |
CN104496467A (en) * | 2014-12-18 | 2015-04-08 | 天津大学 | BT-BKT lead-free PTCR ceramic material with high curie temperature and preparation and application of BT-BKT lead-free PTCR ceramic material |
CN104725037A (en) * | 2015-02-14 | 2015-06-24 | 湖北大学 | Preparation method of substrate-type PTC superfine ceramic for adjusting barium titanate with Y/Mn substance ratio |
JP2015213116A (en) * | 2014-05-02 | 2015-11-26 | 日立金属株式会社 | Ptc device and exothermic module |
CN105321641A (en) * | 2014-07-03 | 2016-02-10 | Tdk株式会社 | Semiconductor ceramic composition and PTC thermistor |
CN106518052A (en) * | 2015-09-10 | 2017-03-22 | 华中科技大学 | Method for preparing fine-grained barium titanate temperature-sensitive ceramic and product thereof |
CN106866135A (en) * | 2017-03-13 | 2017-06-20 | 中国地质大学(北京) | A kind of unleaded high-curie temperature BaTiO3The preparation method of base positive temperature coefficient thermal sensitive ceramics |
CN107721409A (en) * | 2017-10-09 | 2018-02-23 | 宁夏钜晶电子材料科技有限公司 | Multilayer sheet type thermal sensitive ceramics device preparation method |
CN108264344A (en) * | 2018-01-18 | 2018-07-10 | 华中科技大学 | A kind of nanocrystalline barium titanate barium thermal sensitive ceramics and preparation method thereof |
CN109206135A (en) * | 2018-09-28 | 2019-01-15 | 华中科技大学 | A kind of thermal sensitive ceramic material and preparation method thereof with high-temperature coefficient |
-
2019
- 2019-02-28 CN CN201910153087.9A patent/CN109761602B/en active Active
Patent Citations (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20010003361A1 (en) * | 1999-12-09 | 2001-06-14 | Murata Manufacturing Co., Ltd. | Semiconducting ceramic material and electronic part employing the same |
CN101013618A (en) * | 2007-01-16 | 2007-08-08 | 杨敬义 | Leadless PTC thermistor material with high Curie point |
CN101910088A (en) * | 2007-12-26 | 2010-12-08 | 日立金属株式会社 | Semiconductor ceramic composition |
CN101224979A (en) * | 2008-01-18 | 2008-07-23 | 陕西科技大学 | Method for preparing high Curie point leadless PTC ceramic resistance material |
CN101959829A (en) * | 2008-03-19 | 2011-01-26 | 日立金属株式会社 | Process for producing semiconductor porcelain composition and heater employing semiconductor porcelain composition |
CN101959830A (en) * | 2008-03-27 | 2011-01-26 | 日立金属株式会社 | Process for producing semiconductor porcelain composition/electrode assembly |
CN101445365A (en) * | 2008-12-26 | 2009-06-03 | 广东工业大学 | Barium titanate-based positive temperature coefficient resistance material and preparation method thereof |
CN102482160A (en) * | 2009-10-06 | 2012-05-30 | 日立金属株式会社 | Semiconductor ceramic composition, method for producing same, PTC element and heat generating module |
CN101838143A (en) * | 2010-06-01 | 2010-09-22 | 陕西科技大学 | Bi0.5Na0.5TiO3/Ba1-xCaxTiO3-based PTC thermal sensitive ceramic material and preparation method thereof |
CN102503408A (en) * | 2011-10-12 | 2012-06-20 | 华中科技大学 | Preparation method of laminated barium titanate PTC (positive temperature coefficient) ceramic |
CN104245625A (en) * | 2012-04-20 | 2014-12-24 | 日立金属株式会社 | Semiconductor ceramic composition, method for producing same, and ptc element |
CN104302599A (en) * | 2012-04-20 | 2015-01-21 | 日立金属株式会社 | Method for producing semiconductor ceramic composition |
CN102887704A (en) * | 2012-10-09 | 2013-01-23 | 天津大学 | Lead-free high-Curie temperature PTCR (positive temperature coefficient resistor) ceramic material and preparation method thereof |
CN103626489A (en) * | 2013-11-13 | 2014-03-12 | 华中科技大学 | Preparation method of low-temperature sintering laminated sheet type barium titanate thermal sensitive ceramic |
JP2015213116A (en) * | 2014-05-02 | 2015-11-26 | 日立金属株式会社 | Ptc device and exothermic module |
CN105321641A (en) * | 2014-07-03 | 2016-02-10 | Tdk株式会社 | Semiconductor ceramic composition and PTC thermistor |
CN104496467A (en) * | 2014-12-18 | 2015-04-08 | 天津大学 | BT-BKT lead-free PTCR ceramic material with high curie temperature and preparation and application of BT-BKT lead-free PTCR ceramic material |
CN104725037A (en) * | 2015-02-14 | 2015-06-24 | 湖北大学 | Preparation method of substrate-type PTC superfine ceramic for adjusting barium titanate with Y/Mn substance ratio |
CN106518052A (en) * | 2015-09-10 | 2017-03-22 | 华中科技大学 | Method for preparing fine-grained barium titanate temperature-sensitive ceramic and product thereof |
CN106866135A (en) * | 2017-03-13 | 2017-06-20 | 中国地质大学(北京) | A kind of unleaded high-curie temperature BaTiO3The preparation method of base positive temperature coefficient thermal sensitive ceramics |
CN107721409A (en) * | 2017-10-09 | 2018-02-23 | 宁夏钜晶电子材料科技有限公司 | Multilayer sheet type thermal sensitive ceramics device preparation method |
CN108264344A (en) * | 2018-01-18 | 2018-07-10 | 华中科技大学 | A kind of nanocrystalline barium titanate barium thermal sensitive ceramics and preparation method thereof |
CN109206135A (en) * | 2018-09-28 | 2019-01-15 | 华中科技大学 | A kind of thermal sensitive ceramic material and preparation method thereof with high-temperature coefficient |
Also Published As
Publication number | Publication date |
---|---|
CN109761602B (en) | 2020-11-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5228915B2 (en) | Semiconductor porcelain composition and method for producing the same | |
KR101039951B1 (en) | Method for producing semiconductor porcelain composition | |
CN104513061A (en) | Semiconductor ceramic composition and ptc thermistor | |
CN102674831A (en) | Semiconductor porcelain composition and process for producing the same | |
JP5710077B2 (en) | Method for manufacturing piezoelectric ceramic, piezoelectric ceramic, and piezoelectric element | |
CN105967656B (en) | Novel NTC thermistor material based on nickel oxide | |
CN104302599A (en) | Method for producing semiconductor ceramic composition | |
CN106866135A (en) | A kind of unleaded high-curie temperature BaTiO3The preparation method of base positive temperature coefficient thermal sensitive ceramics | |
JP2006290675A (en) | Dielectric ceramic composition and multilayer ceramic capacitor using the same | |
CN109803941A (en) | Dielectric ceramic composition and ceramic electronic component | |
CN105036734A (en) | High-dielectric-constant X8R type dielectric material for multilayer porcelain capacitor, and preparation method for dielectric material | |
WO2008050877A1 (en) | Semiconductor ceramic composition and method for producing the same | |
CN106518052B (en) | A kind of method and products thereof preparing fine-grained barium titanate thermal sensitive ceramics | |
CN103748056A (en) | Semiconductor porcelain composition, positive temperature coefficient element, and heat-generating module | |
KR20100133905A (en) | Sintered material for dielectric substance and process for preparing the same | |
Ding et al. | Electrical properties of Y-and Mn-doped BaTiO3-based PTC ceramics | |
CN101402524A (en) | Low-resistance, high-overpressure resistance barium titanate based ceramic thermal resistance and method of manufacturing the same | |
CN117645472A (en) | Preparation method of zinc gallate target material and zinc gallate target material | |
CN109206135A (en) | A kind of thermal sensitive ceramic material and preparation method thereof with high-temperature coefficient | |
CN101528632B (en) | Semiconductor ceramic composition and method for producing the same | |
CN109761602A (en) | A kind of low-resistance thermal sensitive ceramic material and the preparation method and application thereof | |
CN107500756A (en) | A kind of high-k low-loss SrTiO3Based dielectric material and preparation method thereof | |
CN101693617A (en) | Negative temperature coefficient resistance material with high resistivity and low B value | |
Silva et al. | Study of La-doped barium titanate ceramics obtained by laser sintering technique | |
CN105198405B (en) | A kind of pressure-sensitive double functional ceramics of electric capacity and preparation method thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |