CN102177105A - Lead free ceramic composition for PTC thermistor and PTC ceramic thermistor thereby - Google Patents

Lead free ceramic composition for PTC thermistor and PTC ceramic thermistor thereby Download PDF

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CN102177105A
CN102177105A CN2009801404461A CN200980140446A CN102177105A CN 102177105 A CN102177105 A CN 102177105A CN 2009801404461 A CN2009801404461 A CN 2009801404461A CN 200980140446 A CN200980140446 A CN 200980140446A CN 102177105 A CN102177105 A CN 102177105A
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ptc
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白钟厚
李荣津
郑暎勋
金喆敏
李愚永
崔真洙
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HIEL CORP
Korea Institute of Ceramic Engineering and Technology KICET
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Korea Institute of Ceramic Engineering and Technology KICET
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Abstract

The present invention relates to a ceramic composition for a lead-free PTC thermistor which does not contain a lead (Pb) component and has a low specific resistance value at room temperature and a Curie temperature (Tc) of 130 DEG C or more. The ceramic composition for a lead free PTC thermistor according to the present invention comprises any one selected from formulas 1-4. [Formula 1] Ba1-x(Bi0.5 Na0.5)xTiO3 + y mol% M1Ow [Formula 2] Ba1-x(Bi0.5Na0.5)xTiO3 + y mol% M12Ow + z wt% M2O2 [Formula 3] Ba1-x(Bi0.5K0.5)xTiO3 + y mol% M1Ow [Formula 4] Ba1-x(Bi0.5K0.5)xTiO3 + y mol% M1Ow + z wt% M2O2 (In formulas 1-4, 0.01<=x<=0.05, 0.00<y<=0.40, 0.00<z<=0.40; M1 is one or more elements selected from the group consisting of Nb, Sb, La, Y; M2 is Mn; and w is 3 when M1 is a trivalent element and is 5 when M1 is a pentavalent element.) In addition, the invention comprises a ceramic composition for a PTC thermistor of the following formula 5 in which Na0.5K0.5NbO3(NKN) is formed as a solid solution of BaTiO3(BT). [Formula 5] (1-x)BT-xNKN (0<x=0.05) The invention provides a PTC ceramic thermistor prepared using the compositions of the formulas.

Description

Unleaded is PTC thermistor ceramic composition and PTC ceramic thermal resistance
Technical field
The present invention relates to ceramic composition, relate to the PTC thermistor ceramic composition that does not comprise lead composition in more detail.
Background technology
(Positive Temperature Coefficient ofresistance: positive temperature coefficient of resistance) thermistor presents the characteristic that resistance increases along with the rising of temperature to PTC, generally with BaTiO 3Be essentially consist.
BaTiO 3(BT) the based semiconductor pottery is as for example ABO 3Etc. representative uhligite (perovskite) is the compound of crystalline structure, present divalence Ba ion and occupy the form that A-site, tetravalence Ti ion occupy B-site, and show (polymorphic) characteristic that conversion (transition) becomes the multiform of trigonal system (rombohedral), rhombic system (orthorhombic), tetragonal spheroidal (tetragonal) and isometric system (cubic) according to the temperature crystalline structure.
Particularly, if at 1.5V DCBelow measure resistance, can obtain resistance-temperature characteristics based on the variation of PTC thermistor peripheral temperature.In this characteristic, the temperature that resistance value is sharply increased is called resistance sudden turn of events temperature (switching Temperature) or Curie temperature (Curie Temperature), be commonly defined as temperature, and become the important parameter (parameter) of material behavior corresponding to the twice of minimum resistance or reference temperature (25 ℃) resistance value.
At BaTiO 3In the pottery, Curie temperature (Tc) is meant 130 ℃ the temperature that is transformed into the isometric system of paraelectric phase from the tetragonal spheroidal of ferroelectric phase, uses the PbTiO that is replaced to lead (Pb) at A-site for the working temperature that makes the PTC thermistor is elevated to more than 130 ℃ 3
Because PbTiO 3Have 490 ℃ Curie temperature (Tc), thereby working temperature is raise.But plumbous (Pb) composition is harmful, and also might cause environmental pollution, and the lead composition that evaporates in element also might become the inhomogeneity major cause of destroying element.
Recently, along with hommization, the raw-material concern of environment-friendly type are increased day by day, be used to develop Curie temperature (Tc) and be higher than BaTiO 3Unleaded be just active expansion of research activities of PTC thermistor compositions, be intended to substitute the PTC thermistor starting material that contain lead (Pb) composition.
As representative candidate substance in this unleaded PTC of the being thermistor with the Curie temperature (Tc) more than 120 ℃, the known Bi that (perovskite) structure that has uhligite is arranged 1/2Na 1/2TiO 3(BiNT), Bi 1/2K 1/2TiO 3(BiKT), NaNbO 3, BiFeO 3Deng.
But, above-mentioned raw-material ptc characteristics is also obtained fully checking, especially the exploitation to the ceramic composition with high-curie temperature (High Tc＞130 ℃) that is used for auto heater also is in the starting phase.
Summary of the invention
The objective of the invention is to, provide a kind of and do not comprise lead (Pb) composition (Lead free), and have low-resistivity value, 10 at normal temperatures 3The PTC thermistor ceramic composition of above PTCR effect, the temperature factor more than 10% and the Curie temperature more than 130 ℃ (Tc).
And, another object of the present invention is to, a kind of PTC ceramic thermal resistance that utilizes above-mentioned ceramic composition to make is provided.
In order to solve above-mentioned purpose, PTC thermistor ceramic composition of the present invention is characterized in that, any one in following by being selected from [Chemical formula 1] to [chemical formula 5] formed,
[Chemical formula 1] Ba 1-x(Bi 0.5Na 0.5) xTiO 3+ y mol%M1O w
[Chemical formula 2] Ba 1-x(Bi 0.5Na 0.5) xTiO 3+ y mol%M1 2O w+ z wt%M2O 2
[chemical formula 3] Ba 1-x(Bi 0.5K 0.5) xTiO 3+ y mol%M1O w
[chemical formula 4] Ba 1-x(Bi 0.5K 0.5) xTiO 3+ y mol%M1O w+ z wt%M2O 2
[chemical formula 5] be BT-xNKN (1-x)
(at above-mentioned [Chemical formula 1] in [chemical formula 4], 0.01≤x≤0.05,0.00＜y≤0.40,0.00＜z≤0.40, M1 is more than one elements that are selected from the group of being made up of Nb, Sb, La, Y, and M2 is Mn, and w is 3 when M1 is tervalent element; When M1 is the element of pentavalent 5;
In above-mentioned [chemical formula 5], 0＜x≤0.03, BT is BaTiO 3, NKN is Na 0.5K 0.5NbO 3, NKN is formed by the sosoloid of BT).
And PTC ceramic thermal resistance of the present invention is characterized in that, is made by above-mentioned ceramic composition.
Here, above-mentioned ceramic composition is characterised in that, also comprises by Nb 2O 5The doping agent of powder constituent (Dopant) material, above-mentioned Nb 2O 5Be characterised in that its addition is in 0 to 0.2mol% scope.
And the manufacture method according to the PTC ceramic thermal resistance of one embodiment of the invention is characterized in that, comprises the steps: to prepare the high purity BaTiO more than 99.9% 3(BT) step; To above-mentioned BaTiO 3(BT) add Na 0.5K 0.5NbO 3(NKN) form sosoloid and make the step of (1-x) BT-xNKN (0＜x≤0.03) ceramic material powder; Above-mentioned ceramic material powder is put into HDPE (High Density Polyethylene: wide-necked bottle (jar) and distilled water is carried out the step of 24 hours first ball millings as dispersion medium high density polyethylene(HDPE)); In 120 ℃ the above-mentioned ceramic material powder through above-mentioned first ball-milling processing carried out drying after, put into mortar and the step pulverized; The above-mentioned ceramic material powder of pulverizing put into alumina crucible and in two hours steps of 1000 ℃ of calcinings; To put into the high density polyethylene(HDPE) wide-necked bottle through the above-mentioned ceramic material powder of incinerating and distilled water will be carried out the step of 24 hours second ball millings as dispersion medium; And will put into mould and apply 1ton/cm through the above-mentioned ceramic material powder of above-mentioned second ball-milling processing 2Pressure and manufacture the step of transmitter form.
According to ceramic composition of the present invention, do not comprise lead (Pb) composition even can make, also can have low-resistivity value, 10 at normal temperatures 3The PTC thermistor of above PTCR effect, the temperature factor more than 10% and the Curie temperature more than 130 ℃ (Tc).
Therefore, the invention provides and to be applied to the effect that auto heater also is applied to require high performance ptc heater, PCT restrictor, PTC air register etc.
Description of drawings
Fig. 1 to Fig. 9 is the graphic representation of the measurement result of the expression ptc characteristics of measuring embodiment 1～embodiment 33;
Figure 10 to Figure 15 is the graphic representation of the measurement result of the expression ptc characteristics of measuring embodiment 34～embodiment 53;
Figure 16 is the graphic representation that expression is measured the resistivity corresponding with the differing temps of (1-x) of the present invention BT-xNKN pottery;
Figure 17 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation measured of the resistivity at room temperature of different concns correspondence;
Figure 18 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation measured of the Curie temperature of different concns correspondence;
Figure 19 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation measured of the PTC jumping characteristic of different concns correspondence;
Figure 20 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation measured of the temperature coefficient of resistance characteristic of different concns correspondence.
Embodiment
In the present invention, used barium bismuth sodium titanium oxide (barium bismuth sodium titanium oxide; Ba 1-x(Bi 0.5Na 0.5) xTiO 3) and barium bismuth potassium titanium oxide (barium bismuth potassium titanium oxide; Ba 1-x(Bi 0.5K 0.5) xTiO 3) be that pottery is as the principal constituent of PTC thermistor with ceramic composition.(0.01≤x≤0.05)
Used M1O here, wAnd M2O 2As substituting agent.
At this moment, M1 is as trivalent or pentad, specifically can use to be selected among Nb, Sb, La, the Y more than one, and M2 specifically can use Mn as dyad.
M1Ow by the ratio that above-mentioned principal constituent replaced fix on greater than 0.00, in the scope below the 0.40mol%, M2O 2By the ratio that above-mentioned principal constituent replaced fix on greater than 0.00, in the scope below the 0.40wt%.
In sum, PTC thermistor of the present invention can be expressed as with ceramic composition and be selected from following Chemical formula 1 any one to the chemical formula 4.
[Chemical formula 1] Ba 1-x(Bi 0.5Na 0.5) xTiO 3+ y mol%M1O w
[Chemical formula 2] Ba 1-x(Bi 0.5Na 0.5) xTiO 3+ y mol%M1 2O w+ z wt%M2O 2
[chemical formula 3] Ba 1-x(Bi 0.5K 0.5) xTiO 3+ y mol%M1O w
[chemical formula 4] Ba 1-x(Bi 0.5K 0.5) xTiO 3+ y mol%M1O w+ z wt%M2O 2
(at above-mentioned [Chemical formula 1] in [chemical formula 4], 0.01≤x≤0.05,0.00＜y≤0.40,0.00＜z≤0.40, M1 is more than one elements that are selected from the group of being made up of Nb, Sb, La, Y, and M2 is Mn, and w is 3 when M1 is tervalent element; Be 5 when M1 is the element of pentavalent).
In [chemical formula 4], be defined as 0.01≤x≤0.05 at above-mentioned [Chemical formula 1], its reason is, if x less than 0.01 or surpass 0.05 then can obtain good sintered compact, so be difficult to be applied to ptc heater, PCT restrictor, PTC air register etc.
At above-mentioned [Chemical formula 1] in [chemical formula 4], be defined as 0.00＜y≤0.40, its reason is, if y surpasses 0.40, resistivity at room temperature then can be increased to the degree that is difficult to measure, so be difficult to be applied to ptc heater, PCT restrictor, PTC air register etc.
In above-mentioned [Chemical formula 2] and [chemical formula 4], be defined as 0.00＜z≤0.40, its reason is, if z surpasses 0.40, resistivity at room temperature then can be increased to the degree that is difficult to measure, so be difficult to be applied to ptc heater, PTC restrictor, PTC air register etc.
Below, by concrete a plurality of embodiment and comparative example, in PTC thermistor ceramic composition of the present invention, why above-mentioned x, y, z value to be described in the reason in the above-mentioned scope.
＜embodiment 1～embodiment 33 〉
Prepare TiO 2, Bi 2O 3, Na 2CO 3, Nb 2O 5, MnO 2, BaTiO 3As starting raw material, and the weighing above-mentioned raw materials, so that meeting, it forms the interior composition of scope that the application proposes.
In each sample, utilize ball mill (Ball mill) that a plurality of initial elements are carried out 24 hours wet ball grinding processes and mix, in 100～120 ℃ of above-mentioned blended samples of drying, and powder put into mortar and put into alumina crucible after pulverizing in 1000 ℃ of calcinings 2 hours.
To put into mortar and utilize Zirconia ball to pass through wet ball grinding 24 hours after pulverizing through the incinerating powder again.Then, after 100～120 ℃ of thorough drying blended samples, utilize 1[ton/cm 2] pressure at round tube type mould (10mm) sample that is equipped with in mortar is carried out the single shaft compacting and makes it be shaped to the test piece of dish (disc) shape.
To having carried out 4 hours sintering through the test piece of single shaft compacting, this moment, rate of rise in temperature was that per minute rises 5.4～5.6 ℃, had heated 4 hours up to rising to 1300～1350 ℃ under 1300～1350 ℃.
Cooling rate is made as 100 ℃/hr, 200 ℃/hr and 600 ℃/hr and makes the PTC element.
At this moment, be added with TiO in order to analyze 2, Bi 2O 3, Na 2CO 3Conductivity BaTiO 3Formation, analyzed XRD.The PTC element of so making has been carried out having measured after electrode is handled ptc characteristicses such as resistance value.
Following table 1 illustrates chemical quantitative detailed content and the ptc characteristics measurement result about a plurality of samples of preparing respectively in embodiment 1～embodiment 33.
And Fig. 1 to Fig. 9 is the graphic representation about described measurement result.
[table 1]
＜embodiment 34～embodiment 53 〉
Except preparing TiO 2, Bi 2O 3, K 2CO 3, Nb 2O 5, MnO 2, BaTiO 3Beyond starting raw material, made the PTC element according to the method identical with the foregoing description 1, following table 2 illustrates and quantitative relevant detailed content and the ptc characteristics measurement result of the chemistry of the sample of preparing at embodiment 34～embodiment 53 respectively.
And Figure 10 to Figure 15 is the graphic representation about described measurement result.
[table 2]
Figure BDA0000054955230000072
Figure BDA0000054955230000081
[table 1] and [table 2], Fig. 1 to Figure 15 show that the sample that satisfies 0.01≤x≤0.05,0＜y≤0.40,0.00＜z≤0.40 described each condition has the low and T of resistivity at room temperature c(Curie temperature) is the excellent characteristic more than 130 ℃.
And, use highly purified BaTiO 3(BT) as the PTC thermistor of one embodiment of the invention principal constituent with ceramic composition, use with the form of solid solution is the Na of piezoelectrics material as non-lead all the time 0.5K 0.5NbO 3(NKN), thus guarantee high-curie temperature (High Tc＞130 ℃).
And, with Nb 2O 5Be used as the additive of the composition of the foregoing description, so that guarantee effective ptc characteristics.
At first, the PTC thermistor of the above embodiment of the present invention satisfies following [chemical formula 5] with the principal constituent of ceramic composition.
[chemical formula 5]
(1-x)BT-xNKN(0＜x≤0.03)
In above-mentioned [chemical formula 5], be defined as 0＜x≤0.03, its reason is, if x then can obtain good sintered compact, so be difficult to be applied to ptc heater, PCT restrictor, PTC air register etc. below 0 or above 0.03.
Be BaTiO 3(BT), under normal temperature, show the isolator characteristic, if to Na as isolator 0.5K 0.5NbO 3(NKN) carry out an amount of solution treatment, then have conductivity owing to the resistance under the normal temperature sharply descends.And, because Na 0.5K 0.5NbO 3(NKN) Curie temperature that is had up to 420 ℃ about, thereby pure BaTiO 3(BT) about 120 ℃ the Curie temperature that is had is along with to Na 0.5K 0.5NbO 3(NKN) solution treatment of carrying out and raising.If but to Na 0.5K 0.5NbO 3(NKN) carry out excessive (surpass 0.03mol%) solution treatment, then fail the Na of solid solution 0.5K 0.5NbO 3(NKN) a part of particle is present in crystal boundary (grain boundary) last and increase grain boundary resistance and then minimizing conductivity, and the resistivity under the normal temperature is sharply increased.Therefore, be preferably the above-mentioned solid solution scope of observing.
Then, can in 0 to 0.05mol% scope, add Nb with ceramic composition to the PTC of the foregoing description thermistor 2O 5Dopant species.Though Nb 2O 5Dopant species has reduced the PTC jumping characteristic slightly, but still can keep effective ptc characteristics.
But owing to surpass under the situation of 0.05mol% at addition, resistivity at room temperature sharply increases and becomes isolator, and then the problem that ptc characteristics disappears might take place, thereby is preferably the above-mentioned interpolation scope of observing.
Secondly, provide a kind of above-mentioned PTC thermistor ceramic composition that utilizes one embodiment of the invention, by the method for solid phase synthesis manufactured PTC ceramic thermal resistance.
At first, the high purity BaTiO of use more than 99.9% 3, Nb 2O 5Powder minimizes the influence of impurity.
To the Nb of (1-x) BT-xNKN (0＜x≤0.03) pottery interpolation as dopant species 2O 5(99.9%), Nb 2O 5Can add 0 to 0.05mol%.At this moment, be preferably and utilize electronic scale raw material powder precision weighing to 10 -4G.
Then, the above-mentioned raw materials powder is put into HDPE (High Density Polyethylene) wide-necked bottle (jar) and utilized Zirconia ball to carry out 24 hours first ball milling operations as dispersion medium distilled water.
Secondly, will under 120 ℃, carry out putting into mortar and pulverizing after the drying by the first ball milling operation blended sample.
Then, the raw material powder of being pulverized being put into alumina crucible calcined 2 hours down at 1000 ℃.
Then, will put into HDPE (High Density Polyethylene) wide-necked bottle (jar) and distilled water will be carried out 24 hours second ball milling operations as dispersion medium according to identical method through the incinerating powder again.
Then, the sample of crushed after being dried is again put into round tube type mould (Φ: 10mm), and apply 1ton/cm 2Pressure and be shaped to discous PTC ceramic thermal resistance.
Then, behind the PTC of moulding ceramic thermal resistance, be used in 4 hours at 1300 ℃ of following sintering.
Below, the characteristic of a plurality of PTC ceramic thermal resistances of making by above-mentioned steps is described.
At first, for ptc characteristics is analyzed, the above-mentioned plate-like PTC ceramic thermal resistance of making is used as test piece.
Then, after the upper and lower face of dish (disc) forms the Ag-Zn electrode respectively, when temperature is promoted to 320 ℃ from normal temperature the resistance of test piece is measured.Use Digital Multimeter (Agilent 34410A), and utilizes following [equation 1] to calculate the electricalresistivity for resistance is measured.
[equation 1]
&rho; = R &times; A d ( &Omega; &CenterDot; cm )
At this, R is a resistance, and d is a thickness of test piece, and A is the test piece area.
Secondly, calculate temperature coefficient of resistance α by following [equation 2], temperature coefficient of resistance α represents the slope along with the resistance of temperature variation.
[equation 2]
Figure BDA0000054955230000111
At this, T 1=Tc, T 2=T 1+ 80 ℃, R 1Be T 1Under resistance, R 2Be T 2Under resistance.
Figure 16 is the graphic representation that the resistivity corresponding with the differing temps of (1-x) of the present invention BT-xNKN pottery is measured.
With reference to Figure 16, used 0.99BaTiO with pottery in order to make the PTC thermistor 3-0.01 (Na 0.5K 0.5) NbO 3-x mol%Nb 2O 5Composition.Because described composition all shows uniform microtexture, thereby can access good sintered compact.
Test piece by 1300 ℃ of following sintering 4 hours (Sintering temp:130 ℃, Sintering time:4h) and with per hour 600 ℃ (Cooling rate:600 ℃/hr) cooling manufacturing forms, and by embodiment 54 no Nb is shown 2O 5The situation (x=0) of addition, by embodiment 55 situation (x=0.025) of having added 0.025mol% is shown, the situation (x=0.05) of having added 0.05mol% is shown by embodiment 56.At this moment, described x be with above-mentioned [chemical formula 5] in the different coefficient of x, it uses in order to show the constant value shown in the x axle easily when analyzing experimental data.
At this, under the situation of embodiment 54, Curie temperature (Tc) has reached 138 ℃, the electricalresistivity 1Presented low electrical resistivity property with 19 Ω cm.
Under the situation of embodiment 55, Curie temperature (Tc) has reached 137 ℃, the electricalresistivity 2Presented low electrical resistivity property with 49 Ω cm.
Under the situation of embodiment 56, Curie temperature (Tc) has reached 138 ℃, the electricalresistivity 3Presented low electrical resistivity property with 136 Ω cm.
Figure 17 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation measured of the resistivity at room temperature of different concns correspondence.
With reference to Figure 17, resistivity at room temperature is along with adding Nb to the 0.99BT-0.01NKN pottery 2O 5Progressively increase.Otherwise with reference to Figure 18 and Figure 19, Curie temperature (Tc) and PTC transition (Jump) characteristic are but reducing.
Figure 18 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation that the Curie temperature of different concns correspondence is measured, Figure 19 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation that the PTC jumping characteristic of different concns correspondence is measured.
With reference to Figure 18 and Figure 19, Nb 2O 5When adding 0.05mol% to, presented ptc characteristics, but Nb 2O 5Add 0.1mol% to when above, resistivity at room temperature sharply increases and is transformed into isolator and then does not show ptc characteristics.0.05mol%Nb has mixed 2O 5The Curie temperature (T of 0.99BT-0.01NKN pottery c) reached about about 136 ℃, and represented this still low resistivity at room temperature of 136 Ω cm, present the ratio (ρ of maximum resistivity and minimum specific resistance Max/ ρ Min) the PTC jumping characteristic represented 3.2 * 10 3
Figure 20 be to the Nb that adds (1-x) of the present invention BT-xNKN pottery to 2O 5The graphic representation measured of the temperature coefficient of resistance characteristic of different concns correspondence.
Show with reference to Figure 20, the PTC ceramic thermal resistance of embodiments of the invention 54 to embodiment 56 show have 7.9,7.0,5.3% respectively/℃ the good PTCR characteristic of temperature coefficient of resistance (Temperature Coefficient of Resistivity).

Claims (7)

1. a PTC thermistor ceramic composition is characterized in that, any one in following by being selected from [Chemical formula 1] to [chemical formula 5] formed,
[Chemical formula 1] Ba 1-x(Bi 0.5Na 0.5) xTiO 3+ y mol%M1O w
[Chemical formula 2] Ba 1-x(Bi 0.5Na 0.5) xTiO 3+ y mol%M1 2O w+ z wt%M2O 2
[chemical formula 3] Ba 1-x(Bi 0.5K 0.5) xTiO 3+ y mol%M1O w
[chemical formula 4] Ba 1-x(Bi 0.5K 0.5) xTiO 3+ y mol%M1O w+ z wt%M2O 2
[chemical formula 5] be BT-xNKN (1-x)
(at above-mentioned [Chemical formula 1] in [chemical formula 4], 0.01≤x≤0.05,0.00＜y≤0.40,0.00＜z≤0.40, M1 is more than one elements that are selected from the group of being made up of Nb, Sb, La, Y, and M2 is Mn, and w is 3 when M1 is tervalent element; Be 5 when M1 is the element of pentavalent;
In above-mentioned [chemical formula 5], 0＜x≤0.03, BT is BaTiO 3, NKN is Na 0.5K 0.5NbO 3, NKN is formed by the sosoloid of BT).
2. PTC thermistor ceramic composition according to claim 1 is characterized in that above-mentioned ceramic composition also comprises by Nb 2O 5The dopant species of powder constituent.
3. PTC thermistor ceramic composition according to claim 2 is characterized in that, adds above-mentioned Nb in the scope below 0.05mol% 2O 5
4. a PTC ceramic thermal resistance is characterized in that, is made by the ceramic composition of claim 1.
5. the manufacture method of a PTC ceramic thermal resistance is characterized in that, comprises the steps:
Prepare the high purity BaTiO more than 99.9% 3(BT) step;
To above-mentioned BaTiO 3(BT) add Na 0.5K 0.5NbO 3(NKN) form sosoloid and make the step of (1-x) BT-xNKN (0＜x≤0.03) ceramic material powder;
Above-mentioned ceramic material powder put into the high density polyethylene(HDPE) wide-necked bottle and distilled water is carried out the step of 24 hours first ball millings as dispersion medium;
Will be after carrying out drying under 120 ℃ through the above-mentioned ceramic material powder of above-mentioned first ball-milling processing, put into mortar and the step pulverized;
The above-mentioned ceramic material powder of pulverizing put into alumina crucible and in two hours steps of 1000 ℃ of calcinings;
To put into the high density polyethylene(HDPE) wide-necked bottle through the above-mentioned ceramic material powder of incinerating and distilled water will be carried out the step of 24 hours second ball millings as dispersion medium; And
To put into mould and apply 1ton/cm through the above-mentioned ceramic material powder of above-mentioned second ball-milling processing 2Pressure and manufacture the step of transmitter form.
6. the manufacture method of PTC ceramic thermal resistance according to claim 5 is characterized in that, also adds by Nb in above-mentioned ceramic material powder 2O 5The dopant species of powder constituent.
7. the manufacture method of PTC ceramic thermal resistance according to claim 6 is characterized in that, adds above-mentioned Nb in the scope below 0.05mol% 2O 5
CN2009801404461A 2008-10-16 2009-07-16 Lead free ceramic composition for PTC thermistor and PTC ceramic thermistor thereby Pending CN102177105A (en)

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