CN101284731B - Leadless positive temperature coefficient resistance material of high use temperature and stability and method for making same - Google Patents

Leadless positive temperature coefficient resistance material of high use temperature and stability and method for making same Download PDF

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CN101284731B
CN101284731B CN200810037779A CN200810037779A CN101284731B CN 101284731 B CN101284731 B CN 101284731B CN 200810037779 A CN200810037779 A CN 200810037779A CN 200810037779 A CN200810037779 A CN 200810037779A CN 101284731 B CN101284731 B CN 101284731B
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resistance material
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CN101284731A (en
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郑嘹赢
李国荣
李艳艳
冷森林
王天宝
曾江涛
殷庆瑞
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Jiangsu Institute Of Advanced Inorganic Materials
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to a resistor material which has high operating temperature, high stability, no lead and positive temperature coefficient, and belongs to the lead-free semiconductor material field. The material has the general formula as follows: (Na0.5Bi0.5)x1(Ba1-x1-x2Lnx2) Ti1-yMyO3+zmol%N, wherein, x1 is larger than 0 and smaller than 0.5, x2 is larger than 0 and smaller than 0.1, y is larger than 0 and smaller than 0.1, z is larger than or equal to 0 and smaller than or equal to 1; Ln is one or more of Sr, Ca, Y and La, M is one or more of Nb, Ta and Sb, and N is one or more of MnO2, Al2O3, SiO2 and TiO2. The high operating temperature and lead-free PTCR material has the advantages that the operating temperature is higher than 130 DEG C. The resistance kicking ratio of the maximum resistance to the minimum resistance is 100:100000. The resistivity at the room temperature is smaller than 800 ohm.cm. The resistance change rate in the temperature zone ranging from the maximum resistance temperature to the temperature which is 50 DEG C higher than the maximum resistance temperature is smaller than 15 percents and the total content of lead in ceramic bodies is smaller than 50 ppm. The resistor material can be used for manufacturing various temperature sensors, thermostatic heating elements, current limiters, time delayers, etc., and can be widely applied to the fields of electronic communication, aeronautics and astronautics, automobile industries, household appliances, etc.

Description

High use temperature, the unleaded positive temperature coefficient resistance material of high stable and preparation method thereof
Technical field
The present invention relates to a kind of high stable, the unleaded positive temperature coefficient resistor of high use temperature (PTCR) material and preparation method thereof, belong to the lead-free semiconductor field of materials.
Background technology
The PTCR pottery is a kind of characteristic of semiconductor and ferroelectric stupalith of having concurrently, and promptly crystal grain has characteristic of semiconductor, and the crystal boundary area is low in the following potential barrier of Tc, electronics can free movement, and at Tc (T c) near form potential barrier when undergoing phase transition, the block electrons electricity is led, and causes resistance that fierce the variation taken place.The temperature profile of PTCR pottery makes the PTCR pottery have unique resistance-temperature (ρ-T) characteristic, current-voltage (I-V) characteristic and electric current-time (I-t) characteristic.
Use temperature and its Tc of PTCR pottery are closely related.The PTCR pottery overwhelming majority of practical application is with BaTiO 3(T cBe 120 ℃) ferroelectric material for base, obtain through behind semiconductor (alms giver) and the doping vario-property, and add Pb in right amount the PTCR ceramic performance that is lower than 120 ℃ is tended towards stability.Working temperature is lower than 120 ℃ PTCR pottery can also be through stable performanceization behind the Sr displacement Ba, although can make T cDescend, therefore, working temperature is lower than 120 ℃ PTCR pottery and has realized unleaded basically; And working temperature be higher than 120 ℃ PTCR pottery be through Pb displacement Ba reaching the purpose that Tc rises, thereby the overwhelming majority is plumbiferous.There is PbO volatilization in the leaded PTCR pottery of high serviceability temperature in preparation process, not only cause departing from of stoichiometric proportion in the pottery, makes consistency of product and repeatability reduce, and environment has been caused polluted and destroy.In addition, the treating processes of the waste of lead-containing materials also can cause very big pollution to environment.Therefore, the eco-friendly PTCR material of non-lead base of seeking and develop high use temperature has very positive meaning to reducing environmental pollution.
[Tadashi Shiosaki, et al.Applied Phys.Lett., 87,102104,2005] such as Tadashi Shiosaki of Japan are to [Ba 1-x(Bi 1/2Na 1/2) x] 1-yLa yTiO 3Material is studied, and discovery can make Tc greater than 130 ℃, and the resistance kick is than the pottery of the lead-free PTCR between 100-10000.China invention ZL200710048275.2 has proposed a kind of unleaded high curie point PTCR thermistor material, and its component is: (Na 1/2Bi 1/2) (Ba 1-x-y+z) TiO 3+ yM 1+ zM 2O+0.02MnO 2Mol%, the introducing that this material changes element B a, Sr, Ca through the Ba position suppresses the volatilization of BI, thereby reaches the excessive promotion material semiconductor of Ba position and reach the purpose of material production PTC effect.
Although above-mentioned research has obtained to have the PTCR material than low temperature resistance, high electrical resistance kick ratio, from its performance, its resistance reach peak ( Rmax, corresponding temperature is designated as T Max) after, its resistance raises with temperature and descends rapidly, at T MaxTo T MaxThe velocity of variation ρ of+50 ℃ temperature range internal resistance Rmax(remember that the corresponding resistance of Tmax+50 ℃ of temperature is R T1, resistance change rate ρ then Rmax=(R Max-R T1)/Tmax} is generally greater than 50%.In practical application, in a single day because voltage fluctuation causes temperature slightly to rise, will lose original temperature, current balance type greatly owing to the material heating power becomes, thereby material temperature, electric current are further risen, vicious cycle finally causes control fails.The present invention reduces room temperature resistivity, improves resistance kick ratio through not only can realizing the semiconductor of material in the interpolation of Ti position, and has improved material greatly at T MaxTo T MaxThe temperature stability of+50 ℃ of temperature ranges can improve the stability and the safety of unleaded high use temperature PTCR device greatly.
Summary of the invention
The object of the present invention is to provide a kind of high use temperature, the unleaded positive temperature coefficient resistor of high stable (PTCR) material; Can be used for processing all kinds of TPs, constant temperature heating element, restrictor, time delay unit etc., be widely used in fields such as telecommunications, aerospace, automotive industry, household electrical appliance.
The composition general formula of high use temperature of the present invention, high stable lead-free PTCR material does
(Na 0.5Bi 0.5) x1(Ba 1-x1-x2Ln x2)Ti 1-yM yO 3+zmol％N。
0＜x1＜0.5 wherein; 0＜x2＜0.1; 0＜y＜0.1; 0＜z≤1; Ln is one or more among Sr, Ca, Y, the La; M is one or more of Nb, Ta, Sb; N is MnO 2, Al 2O 3, SiO 2, TiO 2One or more.
Wherein, preferred z value is 0.05＜z≤1, and preferred x1 value is 0.01＜x1＜0.5, and preferred x2 value is 0.01＜x1＜0.08, and preferred y value is 0.01＜y＜0.08.
Ln mixes Ba position (A position) as high valence ion, can promote the semiconductor of material, reduces the normal temperature resistance of material, and this generally adopts in general lead-free PTCR pottery preparation.Unique distinction of the present invention is the position through another high valence ion M displacement Ti, has both played the effect that promotes semiconductor, can reduce material simultaneously greatly at T MaxTo T MaxThe resistance change rate ρ of+50 ℃ of temperature ranges RmaxThis is because after at present conventional Ba position replaces at high price because the materials A position is contained Na, Bi, three kinds of ions of Ba simultaneously, although so the A position mix and can make material generation semiconductor; But after doping, possibly produce a certain amount of free Na ion; At normal temperatures, because the grain boundary defects gradient forms the obstruction of potential barrier, be difficult to migration; More than Tc, this ion is easy to take place migration and causes conductivity of electrolyte materials and stability decreases.And the defective that the displacement through the Ti position forms can suppress the A position and produces dissociated ion, especially Na ion in semiconductor.
Additive N effect in the present invention mainly is to purify crystal boundary, thereby further reduces the resistivity at room temperature of material.
The concrete preparation method of stupalith of the present invention comprises batching, synthetic, sintering, comprises the steps:
(1) batching: adopted TiO 2, CaCO 3, SrCO 3, BaCO 3, Na 2CO 3, Bi 2O 3, Y 2O 3, La 2O 3, Nb 2O 5, Ta 2O 5, Sb 2O 5, MnCO 3, Al 2O 3, SiO 2Deng being raw material, (Na 0.5Bi 0.5) X1(Ba 1-x1-x2Ln X2) Ti 1-yM yO 3The stoichiometry weighing of+zmol%N, wherein 0＜x1＜0.5; 0＜x2＜0.1; 0＜y＜0.1; 0＜z≤1.
Above-mentioned preferred z value is 0.05＜z≤1, and preferred x1 value is 0.01＜x1＜0.5, and preferred x2 value is 0.01＜x1＜0.08, and preferred y value is 0.01＜y＜0.08.
(2) synthetic: as medium, ball mill mixing is even with deionized water, oven dry back briquetting.Be placed on the ceramic plate and synthesize in advance under 120-360 minute the condition of 800-1000 ℃ of insulation, after pulverizing then, sieving, fine grinding, oven dry, adding additives, moulding, plastic removal (insulation is more than 120 minutes more than 400 ℃).
(3) sintering: sintering temperature is 1200～1350 ℃, is incubated 1-5 hour, naturally cooling.
With the base sheet behind the sintering through cold working, ultrasonic cleaning, go up Ohm contact electrode, operational PTCR ceramic component.
High use temperature of the present invention, lead-free PTCR material use temperature are higher than 130 ℃; The resistance kick is than (maximum resistance and minimum resistance ratio): 100-100000; Resistivity at room temperature is less than 800 Ω .cm, in the temperature that reaches maximum resistance to the temperature range internal resistance rate of descent ρ that is higher than 50 ℃ of this top temperatures RmaxLess than 15%, the overall lead content of porcelain body is less than 50ppm.This shows special-effect of the present invention.
Description of drawings
Fig. 1 is the resistivity-temperature characteristic curve of the PTCR material in the embodiment of the invention 1
Embodiment
Further specify content of the present invention through embodiment below, obvious, embodiment only explains goal of the invention, limits the present invention absolutely not.
Embodiment 1:
Get x=0.2, Ln is La, and x2=0.05, M are Nb, y=0.05, and z=0 then forms molecular formula and is (Na 0.5Bi 0.5) 0.2(Ba 0.75La 0.05) Ti 0.95Nb 0.05O 3Pottery form.Adopt impurity lead content to receive the TiO of strict control 2, BaCO 3, Na 2CO 3, Bi 2O 3, La 2O 3, Nb 2O 5Be raw material, by 1350 ℃/2 hours air atmosphere sintering, cold working, ultrasonic cleaning, go up Ohm contact electrode, operational PTCR ceramic component.Its resistance-temperature characteristic is seen Fig. 1, and concrete performance is listed in table 1.
Embodiment 2-16:
The room temperature resistivity, Tc, resistance kick of regulating material through the variation that changes different displacement compositions and additive than and the resistance change rate ρ in 50 ℃ of temperature ranges more than the Tc RmaxAdopted TiO 2, CaCO 3, SrCO 3, BaCO 3, Na 2CO 3, Bi 2O 3, Y 2O 3, La 2O 3, Nb 2O 5, Ta 2O 5, Sb 2O 5, MnCO 3, Al 2O 3, SiO 2, etc. be raw material, press chemical constitution listed in the table 1, press chemical formula (Na 0.5Bi 0.5) X1(Ba 1-x1-x2Ln X2) Ti 1-yM yO 3The stoichiometry weighing of+zmol%N.Other processing condition are with embodiment 1, and its performance is listed in table 1.
The composition of table 1 embodiment 1-16 and performance table
Figure S2008100377799D00041
11 0.2 La 0.05 Nb∶Ta ＝1∶1 0.02 MnO 2 0.1 119 150 4.1 6.5
12 0.2 La 0.05 Nb∶Ta∶ Sb＝1∶ 2∶1 0.04 MnO 2 0.1 175 140 4.2 5.4
13 0.3 Y 0.05 Nb∶Sb ＝1∶3 0.05 Al 2O 3 0.1 365 165 3.2 6.4
14 0.2 La 0.05 Ta 0.05 SiO 2 0.5 86 135 4.5 8.9
15 0.2 La 0.05 Ta 0.05 Al 2O 3∶ SiO 2∶T iO 2＝1 ∶2∶1 1.0 80 132 4.5 9.1
16 0.2 La 0.05 Ta 0.05 Al 2O 3∶ TiO 2＝ 1∶5 0.8 25 132 4.2 5.2

Claims (8)

1. high use temperature, the unleaded positive temperature coefficient resistance material of high stable is characterized in that chemical formula is (Na 0.5Bi 0.5) X1(Ba 1-x1-x2Ln X2) Ti 1-yM yO 3+ zmol%N;
0＜x1＜0.5 wherein; 0＜x2＜0.1; 0＜y＜0.1; 0＜z≤1;
Wherein Ln is one or more among Sr, Ca, Y, the La; M is one or more of Nb, Ta, Sb; N is MnO 2, Al 2O 3, SiO 2, TiO 2One or more.
2. by the described high use temperature of claim 1, the unleaded positive temperature coefficient resistance material of high stable, it is characterized in that said z value is 0.05＜z≤1.
3. press claim 1 or 2 described high use temperatures, the unleaded positive temperature coefficient resistance material of high stable, it is characterized in that described x 1 value is 0.01＜x1＜0.5, the x2 value is 0.01＜x2＜0.08.
4. press claim 1 or 2 described high use temperatures, the unleaded positive temperature coefficient resistance material of high stable, it is characterized in that described y value is 0.01＜y＜0.08.
5. by the preparation method of the described high use temperature of claim 1, the unleaded positive temperature coefficient resistance material of high stable, comprise batching, mixing, briquetting, synthesize in advance, pulverize, sieve, oven dry, moulding, plastic removal, sintering, it is characterized in that:
The raw material of batching is TiO 2, CaCO 3, SrCO 3, BaCO 3, Na 2CO 3, Bi 2O 3, Y 2O 3, La 2O 3, Nb 2O 5, Ta 2O 5, Sb 2O 5, MnCO 3, Al 2O 3, SiO 2, press stoichiometric equation (Na 0.5Bi 0.5) X1(Ba 1-x1-x2Ln X2) Ti 1-yM yO 3+ zmol%N weighing, wherein 0＜x1＜0.5; 0＜x2＜0.1; 0＜y＜0.1; 0＜z≤1;
Synthesis condition is 800-1000 ℃ of insulation 120-360 minute in advance;
Sintering condition is 1200～1350 ℃ of insulations 1-5 hour.
6. by the preparation method of the described high use temperature of claim 5, the unleaded positive temperature coefficient resistance material of high stable, it is characterized in that the z value is 0.05＜z≤1.
7. press the preparation method of claim 5 or 6 described high use temperatures, the unleaded positive temperature coefficient resistance material of high stable, it is characterized in that the x1 value is 0.01＜x1＜0.5, the x2 value is 0.01＜x2＜0.08.
8. press the preparation method of claim 5 or 6 described high use temperatures, the unleaded positive temperature coefficient resistance material of high stable, it is characterized in that the y value is 0.01＜y＜0.08.
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JP5327556B2 (en) * 2008-12-12 2013-10-30 株式会社村田製作所 Semiconductor ceramic and positive temperature coefficient thermistor
CN101565305B (en) * 2009-03-27 2013-04-17 郜长福 High-temperature lead-free PTC material and production process thereof
CN101624284B (en) * 2009-08-05 2013-01-02 中国科学院上海硅酸盐研究所 Doped BKT-BT series lead-free PTCR ceramic material and preparation method thereof
CN101628810B (en) * 2009-08-12 2012-05-30 中国科学院上海硅酸盐研究所 High transparent and high electro-optical property doped PMN-PT electro-optic ceramic material and preparation method thereof
CN101830698B (en) * 2010-03-15 2013-02-13 华中科技大学 High-Curie-point low-resistivity lead-free PTCR (Positive Temperature Coefficient of Resistance) ceramic material and preparation method thereof
JPWO2013051486A1 (en) * 2011-10-03 2015-03-30 日立金属株式会社 Semiconductor porcelain composition, PTC element, and heating module
CN104370539A (en) * 2013-09-12 2015-02-25 铜仁学院 High use temperature lead-free PTCR (positive temperature coefficient resistance) ceramic and preparation method thereof
CN104692794A (en) * 2015-02-07 2015-06-10 铜仁学院 Lead-free PTCR (Positive Temperature Coefficient Resistor) piezoelectric ceramic material and preparation method thereof
CN107226694B (en) * 2017-06-14 2020-06-16 铜仁学院 PTCR ceramic material, preparation method and application thereof

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CN1541979A (en) * 2003-11-07 2004-11-03 四川大学 Bismuth sodium titanate barium titanate strontium titanate calcium titanate based lead-free piezoelectric ceramics

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