CN1160273A - Medium- and low-temp. sintered combined characteristic thermosensitive resistor material composition and preparing method - Google Patents
Medium- and low-temp. sintered combined characteristic thermosensitive resistor material composition and preparing method Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 title claims description 27
- 239000000654 additive Substances 0.000 claims abstract description 35
- 238000005245 sintering Methods 0.000 claims description 43
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 230000000996 additive effect Effects 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 33
- 238000005516 engineering process Methods 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 23
- 239000002131 composite material Substances 0.000 claims description 19
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 238000009472 formulation Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000009766 low-temperature sintering Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- AJGPQPPJQDDCDA-UHFFFAOYSA-N azanium;hydron;oxalate Chemical compound N.OC(=O)C(O)=O AJGPQPPJQDDCDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000005469 granulation Methods 0.000 claims description 4
- 230000003179 granulation Effects 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 235000013619 trace mineral Nutrition 0.000 claims description 2
- 239000011573 trace mineral Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 229910009973 Ti2O3 Inorganic materials 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 abstract 1
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 18
- 239000012071 phase Substances 0.000 description 17
- 238000001354 calcination Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002241 glass-ceramic Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
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- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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Abstract
A middle- or low-temp sintered thermosensitive resistance material with combined NTC-PTC characteristics contains such main components as (Sr 1-x-yBayPbx) Ti2O3 + w PbmSinO2n+m, where x=0.1-0.9, Y=0-0.9, z=0.8-1.2, w=0.001-1 and m/n=0.1-10. It also contains micro semiconductor elements and less secondary additives. Its preparing process includes solid-phase synthesis or chemical synthesis. Its advantages are excellent properties, low sinter temp and good stability and reproducibility.
Description
The present invention relates to a kind of composition and preparation method of combined characteristic thermosensitive resistor material of low temperature sintering, the combined characteristic thermosensitive resistor material here refers in particular to NTC-PTC composite thermistor material or is called the V-shaped ptc material, belongs to material science.
Traditional posistor material (abbreviation ptc material) mainly refers to BaTiO
3Pottery, pure BaTiO
3Be good insulating body, and when the rare earth element (such as La, Nb, Sb, Ta etc.) of the trace that mixes therein, the resistivity of element can drop to 10
2Below the Ω cm, and near 120 ℃, has positive temperature coefficient (PTC) characteristic.Traditional ptc material also has (Ba, Pb) TiO
3, (Sr, Ba) TiO
3Etc. system.
Traditional negative temperature coefficient heat-sensitive resistance material (being called for short the NTC material) mainly is made up of the composite oxides of transition metals such as Mn, Ni, Co, Fe, Cu and Cr.
The technology of traditional preparation thermistor material generally is to pass through solid-phase synthesis.Processing step comprises: weighing-batch mixing-pre-burning-pulverizing (secondary adds simultaneously)-screening-granulation-moulding-sintering etc.Shortcomings such as there is the component skewness in this technology, is subject to contaminating impurity, reproducibility difference.And sintering temperature is generally all more than 1300 ℃, and the energy consumption height is unfavorable for technology controlling and process.
When the thermal resistor of making of thermistor material uses as the discrete component simple function, there is following shortcoming: for the NTC material, under overvoltage, because self-heating causes resistance to descend gradually, have the possibility of puncture; For ptc material, because resistance is littler under the normal temperature, so the energising self-heating is during as heater, because dash current affects greatly its stability and service life.If realize that the NTC-PTC function is compound, the element of making had both had high temperature limit (self-shield) function, had inhibition impulse current (self-regulation) function again, therefore can realize multi-functionals such as adjustment and overcurrent protection.
At BaTiO
3Be to add Yb in the ptc material
2O
3, WO
3Etc. component, burn till in 1350 ℃, can obtain NTC-PTC composite thermistor material (with reference to day the disclosure special permission clear 54-27555 of communique and a 54-29234), this material sintering temperature very high (1350 ℃).
Japan Patent (with reference to day clear 63-280401 of disclosure special permission communique) and Chinese patent (ZL-92112906.8) utilize the ptc material process for solid phase synthesis, with (Sr, Pb) TiO
3Be matrix material, add a small amount of secondary additive and prepare NTC-PTC composite thermistor material.But there is the difficult control of component in this technology, is subject to problems such as contaminating impurity, process reproducibility difference.
The objective of the invention is to prepare a kind of NTC-PTC composite thermistor material with low temperature sintering of novel composition.Solve or improve the problems referred to above that exist in the traditional handicraft, reduce sintering temperature and the resistivity of material, improve the performance repeatability.
The present invention goes into glassy phase with preparation NTC-PTC composite thermistor material by compound in ceramic material.The NTC-PTC composite thermistor material of the present invention's development refers to contain PbSiO
3(Sr, Pb) TiO
3, (Ba, Pb) TiO
3Or (Sr, Ba) TiO
3In the glass-ceramic composite material, the general expression of system principal component is:
(Sr
1-x-yBa
yPb
x) Ti
zO
3+ wPb
mSi
nO
2n+mX=0.1～0.9 wherein; Y=0～0.9; Z=0.8～1.2; W=0.001～1; M/n=0.1～10
Prescription contains metal element Ti in the principal component, also contains Sr, Ba, and three kinds of metallic elements of Pb or wherein any two kinds, the oxide of above-mentioned metallic element forms ceramic phase, i.e. (Sr
1-x-yBa
yPb
x) Ti
zO
3, its total amount accounts for 50～99.9mol% of total amount of material; Prescription also contains elements such as Si in the principal component, forms glassy phase, i.e. Pb with Pb etc.
mSi
nO
2n+m, its total amount accounts for 0.1～30mol% of total amount of material.
In order to make ceramic phase (Sr
1-x-yBa
yPb
x) Ti
zO
3Semiconducting contains a kind of trace element at least in the prescription, as Y, Yb, La, Sb, Nd, Dy, Bi, Ce, Nb etc., its content accounts for 0.01～5mol% of total amount of material.
Sintering temperature and enhancing PTC effect in order to reduce material also are added with a small amount of secondary additive, such as AST (1/3Al in the prescription
2O
33/4SiO
21/4TiO
2), BaPbO
3, Si
3N
4, in BN and the compounds such as Mn, Fe, Li one or more, its content accounts for 0.001～15mol% of total amount of material.Technology:
Technology 1 and technology 2 adopt solid phase synthesis process, and technology 3 and technology 4 adopt chemical synthesis process.
Technology 1 and technology 2 initial feed are selected from TiO
2, SrCO
3, Sr (NO
3)
2, PbO, Pb
3O
4, PbCO
3, Pb (NO
3)
2, BaCO
3, Ba (NO
3)
2, SiO
2And Si (OC
2H
5)
4In the oxide or salt etc. required element, semiconducting element initial feed is selected from Y
2O
3, Y (NO
3)
3, Yb
2O
3, Yb (NO
3)
3, La
2O
3, La (NO
3)
3, Sb
2O
3, Nd
2O
3, Nd (NO
3)
3, Dy
2O
3, Bi
2O
3, Bi (NO
3)
3, Nb
2O
5, CeO
2And Ce (NO
3)
3In the oxide or salt etc. required element, additive is generally selected the higher synthetic product of purity, such as AST, BaPbO
3, Si
3N
4, BN and Mn (NO
3)
2, Fe (NO
3)
2, Li
2CO
3Deng.
Technology 1: cancelled the screening step of commonly using in the traditional handicraft, in the secondary adding technology, introduced chemical treatment method, namely carried out secondary by chemical means and add.The concrete processing step of preparation is as follows: 1. initial feed and semiconducting element are pressed the formulation ratio weighing; 2. mixing and ball milling (48 hours, alcohol-water blending agent, granularity is less than 1 μ m); 3. oven dry (100～150 ℃, 10～30 hours); 4. pre-burning (800～1000 ℃, 1～2 hour); 5. pulverize (granularity is less than 1 μ m), and add additive simultaneously in proportion; 6. dry (100～150 ℃, 10～30 hours), granulation, moulding (moulding pressure 100～500MPa); 7. sintering (1000～1300 ℃, 5～180 minutes) is the composite thermistor material that the present invention develops.
Technology 2: the characteristics ceramic phase (Sr in the principal component that is to fill a prescription
1-xPb
x) Ti
yO
3Synthetic separately, glassy phase Pb
mSi
nO
2n+mAdd simultaneously with additive.The concrete processing step of preparation is as follows: 1. initial feed and semiconducting element are pressed the formulation ratio weighing; 2. mixing and ball milling (48 hours, alcohol-water blending agent, granularity is less than 1 μ m); 3. oven dry (100～150 ℃, 10～30 hours); 4. pre-burning (800～1000 ℃, 1～2 hour), i.e. synthesize ceramic phase (Sr
1-xPb
x) Ti
yO
35. pulverize ceramic phase (granularity is less than 1 μ m), and additive and glassy phase raw material are pressed formulation ratio and ceramic phase (Sr
1-xPb
x) Ti
yO
3Powder body material evenly mixes; 6. dry (100～150 ℃, 10～30 hours), granulation, moulding (moulding pressure 100～500MPa); 7. sintering (1000～1300 ℃, 5～180 minutes) is the composite thermistor material that the present invention develops.
Technology 3 and technology 4 initial feed are selected from TiCl
4, Ti (OC
4H
9)
4, SrCO
3, Sr (NO
3)
2, PbCO
3, Pb (NO
3)
2, BaCO
3, Ba (NO
3)
2And Si (OC
2H
5)
4In the oxide or salt etc. required element, semiconducting element initial feed is selected from Y
2O
3, Y (NO
3)
3, Yb
2O
3, Yb (NO
3)
3, La
2O
3, La (NO
3)
3, Sb
2O
3, Nd
2O
3, Nd (NO
3)
3, Dy
2O
3, Bi
2O
3, Bi (NO
3)
3, Nb
2O
5, CeO
2, Ce (NO
3)
3In the oxide or salt etc. required element, additive is generally selected the higher synthetic product of purity, such as AST, BaPbO
3, Si
3N
4, BN and Mn (NO
3)
2, Fe (NO
3)
2, Li
2CO
3Deng.
Technology 3: be to adopt chemical method to prepare NTC-PTC composite thermistor material.The concrete processing step of preparation is as follows: 1. initial feed and semiconducting element are pressed the formulation ratio weighing; 2. with the initial feed and the semiconducting element of weighing form mixed solution (the Ti ion concentration is between 0.01～10M in the solution) jointly; 3. be that precipitation reagent carries out co-precipitation (10～80 ℃ of precipitation temperatures) with oxalic acid (or oxalic acid ammonia); 4. with sediment washing (ethanol dehydration is more than three times after the washed several times with water), dispersion (dispersant is a n-butanol), oven dry (100～150 ℃, 10～30 hours); 5. calcine 600～800 ℃, be incubated 0.5～1.5 hour, obtain the main formula powder body material; 6. the secondary additive is evenly mixed with the main formula powder body material; 7. dry (100～150 ℃, 10～30 hours), moulding (moulding pressure 100～500MPa); 8. sintering (1000～1300 ℃, 5～180 minutes) is the composite thermistor material that the present invention develops.
Technology 4: the characteristics ceramic phase (Sr in the principal component that is to fill a prescription
1-xPb
x) Ti
yO
3Synthetic separately, glassy phase Pb
mSi
nO
2n+mAdd simultaneously with additive.The concrete processing step of preparation is as follows: 1. initial feed and semiconducting element are pressed the formulation ratio weighing; 2. with the initial feed and the semiconducting element of weighing form mixed solution (the Ti ion concentration is between 0.01～10M in the solution) jointly; 3. be that precipitation reagent carries out co-precipitation (10～80 ℃ of precipitation temperatures) with oxalic acid (or oxalic acid ammonia); 4. with sediment washing (ethanol dehydration is more than three times after the washed several times with water), dispersion (dispersant is a n-butanol), oven dry (100～150 ℃, 10～30 hours); 5. calcine 600～800 ℃, be incubated 0.5～1.5 hour, obtain ceramic phase (Sr
1-xPb
x) Ti
yO
3Powder body material; 6. additive and glassy phase raw material are pressed formulation ratio and ceramic phase (Sr
1-xPb
x) Ti
yO
3Powder body material evenly mixes; 7. dry (100～150 ℃, 1～30 hour), moulding (moulding pressure 100～500MPa); 8. sintering (1000～1300 ℃, 5～180 minutes) is the composite thermistor material that the present invention develops.
The present invention has designed a kind of glass-ceramic composite material, has prepared the compound thermistor material of NTC-PTC, and the minimum specific resistance of material is low, has strong and adjustable NTC effect and bigger PTC lift-drag ratio.
Because adopt new additives, new synthesizing mean and chemical treatment method, the sintering temperature of material reduces greatly.Sintering temperature of the present invention can be reduced to about 1100 ℃.Simultaneously,, suppressed the Pb volatilization effectively, improved stability by means such as special elements doping and secondary dopings.
Description of drawings l～Fig. 8 is the resistivity-temperature characteristic curve corresponding to each sample of embodiment 1～8.The initial measurement temperature of data is 0 ℃ in the curve.The meaning of each parameter representative is as follows in table 1～table 8: ρ
25 ℃-room temperature resistivity; ρ
Min-minimum specific resistance; α
50 ℃-negative temperature coefficient, α
+ 50 ℃-positive temperature coefficient,
PTC jump-PTC lift-drag ratio; The resistance ratio falls in NTC drop-NTC.
Exemplify below embodiments of the invention
Example 1. is doped to example (seeing Table 1), fixedly additive (MnO with Y element
2) amount be 0.01mol%, the principal component composition formula is (Sr
0.45Pb
0.51) TiO
3+ 4%PbSiO
3Experiment adopting process 4 is got initial feed Ti (OC
4H
9)
4300ml (concentration 1.17M), Sr (NO
3)
233.43 gram, Pb (NO
3)
263.95 gram is respectively with the Y (NO of 0.093M
3)
3Solution 1.88ml, 3.75ml, 7.50ml, 15.00ml, 30.00ml, 60.00ml, 120.00ml form 1500ml mixed solution (counting 7 groups), in seven groups of mixed solutions, drip respectively oxalic acid solution (respectively containing about 115 grams of oxalic acid), the gained precipitation by the washing of technology 4 conditions, dry, calcining, is obtained powder body material.Si (the OC that in powder body material (about 50 grams), adds 0.40M
2H
5)
4Solution 20.00ml, the Mn (NO of 0.256%M
3)
2(raw material of Mn) solution 5.00ml, and so that their even mixing, dry after in 140MPa pressure compacted under, in 1160 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains sees Table 1, and what Fig. 1 curve provided is the resistivity-temperature characteristic curve of sample.
Example 2. principal component composition formulas are (Sr
0.45Pb
0.55-μ) TiO
3+ uPbSiO
3, fixedly semiconducting element (being Y element in this example) and additive (FeO
3/2) amount be respectively 0.8mol% and 0.01mol%, change glassy phase principal component SiO
2Content u=0.3%, 1.0%, 2.0%, 4.0%, 12.0% (seeing Table 2).Experiment adopting process 4 is got initial feed Ti (OC
4H
9)
4300ml (concentration 1.17M), Sr (NO
3)
233.43 gram, Pb (NO
3)
263.95 gram, the Y (NO of 0.093M
3)
3Five groups of each five parts compositions of solution 60.00ml, every group forms respectively the 1500ml mixed solution, in five groups of mixed solutions, drip respectively oxalic acid solution (respectively containing about 115 grams of oxalic acid), the gained precipitation by the washing of technology 4 conditions, dry, calcining, is obtained powder body material.Si (the OC that in five groups of powder body materials (each about 50 gram), adds respectively 0.40M
2H
5)
4Solution 1.50ml, 5.00ml, 10.00ml, 20.00ml, the Fe (NO of 60.00ml and 0.256%M
3)
2(raw material of Fe) solution 5.00ml, and so that their even mixing, dry after in 140MPa pressure compacted under, in 1160 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains sees Table 2, and what Fig. 2 curve provided is the resistivity-temperature characteristic curve of sample.
Example 3. is selected Li
2CO
3As additive, fixing prescription is (Sr
0.45Pb
0.51) TiO
3+ 4%PbSiO
3(seeing Table 3).Experiment adopting process 3 is got initial feed Ti (OC
4H
9)
4300ml (concentration 1.17M), Sr (NO
3)
233.43 gram, Pb (NO
3)
263.95 gram, the Si (OC of 0.40M
2H
5)
4Solution 20.00ml, the Y (NO of 0.093M
3)
3Solution 60.00ml, and form the 1500ml mixed solution, to mixed solution and dripping oxalic acid solution (respectively containing about 115 grams of oxalic acid), the gained precipitation by the washing of technology 3 conditions, dry, calcining, is obtained powder body material.The Li that in powder body material, adds 0.256%M
2CO
3Salpeter solution 2.50ml, and make their even mixing, dry back is in 140MPa pressure compacted under, respectively at 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains is seen table 3 and Fig. 3, and as seen, the performance of sample can be regulated according to sintering temperature.
Example 4. selects Mn as additive, and fixing prescription is (Sr
0.45Pb
0.43) TiO
3+ 12%PbSiO
3(seeing Table 4).Experiment adopting process 4 is got initial feed Ti (OC
4H
9)
4300ml (concentration 1.17M), Sr (NO
3)
233.43 gram, Pb (NO
3)
263.95 gram, the Y (NO of 0.093M
3)
3Solution 60.00ml, and form the 1500ml mixed solution, to mixed solution and dripping oxalic acid solution (respectively containing about 115 grams of oxalic acid), the gained precipitation by the washing of technology 4 conditions, dry, calcining, is obtained powder body material.Si (the OC that in powder body material, adds 0.40M
2H
5)
4Solution 60.00ml, the Mn (NO of 0.256%M
3)
2(raw material of Mn) solution 5.00ml, and so that their even mixing are dry rear in 140MPa pressure compacted under, respectively at 1100 ℃, 1110 ℃, 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains is seen table 4 and Fig. 4, and as seen, the performance of sample is relatively stable with sintering temperature.
The powder body material (seeing Table 5) of 5. pairs of embodiment of the invention 3 of example and example 4 preparations, in 140MPa pressure compacted under, respectively with 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, the speed of 25 ℃/min is warming up to 1150 ℃, sintering 60 minutes.The performance parameter of the sample that obtains sees Table 5, and Fig. 5 a and Fig. 5 b curve have provided the resistivity-temperature characteristic curve of sample (corresponding example 3 and example 4 respectively).
Example 6. fixing prescriptions are (Sr
0.45Pb
0.43) TiO
3+ 12%PbSiO
3, and fixing additive (FeO
3/2) amount be 0.01mol%, be semiconducting element (seeing Table 6) with Bi, Nd, Dy, Sb, Nb, La, Yb and Ce etc.Experiment adopting process 2 is got initial feed TiO
228.04 gram, SrCO
323.32 eight groups of gram and each eight parts compositions of PbO 43.09 grams, every group of Bi, Nd, Dy, Sb, Nb, La, Yb and Ce solution 30.00ml that adds respectively 0.093M (this solution chatted by technology 2 semiconducting element raw material formulated), ball milling was dried 24 hours in 120 ℃ after 48 hours respectively, in 860 ℃ of calcinings 90 minutes, the Si (OC of 0.40M will be added simultaneously respectively after the powder after the calcining (the about 50 grams) pulverizing again
2H
5)
4Fe (the NO of solution 60.00ml and 0.256%M
3)
25.00 milliliters of solution evenly mix, dry after in 140MPa pressure compacted under, in 1160 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains sees Table 6, and what Fig. 6 curve provided is the resistivity-temperature characteristic curve of sample.
Example 7. fixing prescriptions are (Sr
0.45Pb
0.51) TiO
3+ 4%PbSiO
3, and fixing semiconducting element (Bi
2O
3) amount be 0.8mol% (seeing Table 7).Experiment adopting process 2 is got initial feed TiO
228.04 gram, SrCO
323.32 four groups of gram and each four parts compositions of PbO43.09 gram, every group of Bi (NO that adds respectively 0.093M
3)
3Solution 60.00ml, difference ball milling in 120 ℃ of oven dry 24 hours, again in 860 ℃ of calcinings 90 minutes, will add respectively the Si (OC of 0.40M after 48 hours after the powder after the calcining (the about 50 grams) pulverizing
2H
5)
4Solution 20.00ml, and add respectively successively Si
3N
4, AST, BaPbO
3With each 0.15 gram of BN, evenly mix, dry after in 140MPa pressure compacted under, in 1160 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains sees Table 7, and what Fig. 7 curve provided is the resistivity-temperature characteristic curve of sample.
Example 8. fixing prescriptions are (Sr
0.45Pb
0.43) TiO
3+ 12%PbSiO
3, and fixing semiconducting element (Nd
2O
3) amount be 0.8mol% (seeing Table 8).Experiment adopting process 1 is got TiO
228.04 gram, BaCO
348.48 each five parts of grams, SrCO
3With each five parts of PbO, quality is respectively: SrCO
34.664 gram, 3.498 grams, 2.332 grams, 1.166 and 0 gram; The PbO4.309 gram, 6.464 restrain, 8.618 grams, 10.773 grams and 12.927 grams are pressed five groups of the corresponding compositions of table 8, every group of Nd (NO that adds simultaneously respectively 0.093M
3)
3Si (the OC of solution 60.00ml and 0.40M
2H
5)
4Solution 60.00ml, difference ball milling in 120 ℃ of oven dry 24 hours, again in 860 ℃ of calcinings 90 minutes, will add respectively the Mn (NO of 0.256%M after 48 hours after the powder after the calcining (the about 50 grams) pulverizing
3)
25.00 milliliters of solution evenly mix, dry after in 140MPa pressure compacted under, in 1160 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The performance parameter of the sample that obtains sees Table 8, and what Fig. 8 curve provided is the resistivity-temperature characteristic curve of sample.
Example 9. can add part semiconducting element and segment glass phase constituent PbO in order to improve stability in the secondary adding technology.Be (Sr such as fixing prescription
0.45Pb
0.43) TiO
3+ 12%PbSiO
3, experiment adopting process 2 is got TiO
228.04 gram, SrCO
323.32 gram and PbO 40.00 grams, the Nd (NO of adding 0.093M
3)
3Solution 20.00ml ball milling in 120 ℃ of oven dry 24 hours, again in 860 ℃ of calcinings 90 minutes, will add respectively PbO 2.09 grams, the Nd (NO of 0.093M after the powder after the calcining (the about 50 grams) pulverizing after 48 hours simultaneously
3)
3Solution 40.00ml, the Si (OC of 0.40M
2H
5)
4Mn (the NO of solution 60.00ml and 0.256%M
3)
25.00 milliliters of solution evenly mix, dry after in 140MPa pressure compacted under, in 1160 ℃ of sintering 60 minutes (20 ℃ of heating rates/min).The stable performance of the sample that obtains, reproducibility is good.
Above-mentioned experimental example explanation is adjusted by prescription, can be so that the room temperature resistivity (ρ of sample
25 ℃) be lower than 20 Ω cm, negative temperature coefficient (α
-50 ℃) be lower than-5.0%/℃, the NTC resistivity decreased surpasses 3 orders of magnitude, positive temperature coefficient (α
+ 50 ℃) be higher than+5.0%/℃, PTC resistivity rises and surpasses 4 orders of magnitude.It is low to utilize composition and engineering of the present invention to obtain sintering temperature, and performance is adjustable, and stability and the good NTC-PTC composite thermistor material of repeatability.
(table 1)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | ||||||||||
| ??SrO | ??PbO | ??TiO 2 | ??SiO 2 | ??Y 2O 3 | ???MnO 2 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ??ρ 25℃??(Ω·cm) | ??ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ?????NTC ?????drop | ??PTC ??jump | |
| ???1-1 | ??45 | ??55 | ??100 | ??4.0 | ???0.025 | ????0.01 | ????1160 | ????60 | ????20 | ??4.17E10 | ??4.20E8 | ????-5.31 | ???0.90 | ????10 2.0 | ??10 0.47 |
| ???1-2 | ??45 | ??55 | ??100 | ??4.0 | ???0.05 | ????0.01 | ????1160 | ????60 | ????20 | ??4.20E10 | ??3.27E8 | ????-5.10 | ???2.32 | ????10 2.0 | ??10 0.73 |
| ???1-3 | ??45 | ??55 | ??100 | ??4.0 | ????0.1 | ????0.01 | ????1160 | ????60 | ????20 | ??1.69E10 | ??1.21E9 | ????-6.39 | ???1.72 | ????10 1.5 | ??10 0.62 |
| ???1-4 | ??45 | ??55 | ??100 | ??4.0 | ????0.2 | ????0.01 | ????1160 | ????60 | ????20 | ??4.34E10 | ??4.27E9 | ????-4.99 | ???1.00 | ????10 1.2 | ??10 0.50 |
| ???1-5 | ??45 | ??55 | ??100 | ??4.0 | ????0.4 | ????0.01 | ????1160 | ????60 | ????20 | ??2.37E3 | ??3.34E2 | ????-1.67 | ???7.60 | ????10 1.1 | ??10 4.22 |
| ???1-6 | ??45 | ??55 | ??100 | ??4.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??4.05E4 | ??4.61E2 | ????-3.54 | ???6.60 | ????10 2.7 | ??10 4.70 |
| ???1-7 | ??45 | ??55 | ??100 | ??4.0 | ????1.6 | ????0.01 | ????1160 | ????60 | ????20 | ??9.64E8 | ??4.13E5 | ????-5.88 | ???7.59 | ????10 4.4 | ??10 2.55 |
(table 2)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | ||||||||||
| ??SrO | ??PbO | ??TiO 2 | ??SiO 2 | ???Y 2O 3 | ???FeO 3/2 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ?ρ 25℃?(Ω·cm) | ??ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ??NTC ??drop | ??PTC ??jump | |
| ???2-1 | ??45 | ??55 | ??100 | ??0.3 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??1.07E2 | ???6.06E1 | ????0.80 | ????5.62 | ??10 0.37 | ??10 2.58 |
| ???2-2 | ??45 | ??55 | ??100 | ??1.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??4.15E5 | ???9.12E4 | ????1.99 | ????8.42 | ??10 0.90 | ??10 3.81 |
| ???2-3 | ??45 | ??55 | ??100 | ??2.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??8.98E2 | ???8.48E1 | ????2.58 | ????6.46 | ??10 1.41 | ??10 4.11 |
| ???2-4 | ??45 | ??55 | ??100 | ??4.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??4.05E4 | ???4.61E2 | ????3.33 | ????6.00 | ??10 2.37 | ??10 4.61 |
| ???2-5 | ??45 | ??55 | ??100 | ??12.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??1.48E4 | ???3.85E2 | ????2.86 | ????5.98 | ??10 2.02 | ??10 5.02 |
(table 3)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | ||||||||||
| ??SrO | ??PbO | ??TiO 2 | ??SiO 2 | ???Y 2O 3 | ??LiO 1/2 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ρ 25℃(Ω·cm) | ???ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ???NTC ???drop | ???PTC ???jump | |
| ???3-1 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1100 | ????60 | ????20 | ??6.02E2 | ???6.37E1 | ????2.11 | ?????4.00 | ???10 1.27 | ??10 3.45 |
| ???3-2 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1110 | ????60 | ????20 | ??9.00E2 | ???7.29E1 | ????2.21 | ?????4.49 | ???10 1.33 | ??10 3.60 |
| ???3-3 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1120 | ????60 | ????20 | ??2.00E3 | ???1.07E2 | ????2.47 | ?????4.64 | ???10 1.68 | ??10 3.85 |
| ???3-4 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1130 | ????60 | ????20 | ??4.50E3 | ???1.44E2 | ????2.70 | ?????5.62 | ???10 1.76 | ??10 4.10 |
| ???3-5 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1140 | ????60 | ????20 | ??1.65E4 | ???2.50E2 | ????3.01 | ?????5.7 | ???10 2.17 | ??10 4.33 |
| ???3-6 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1150 | ????60 | ????20 | ??1.00E5 | ???4.91E2 | ????3.37 | ?????5.93 | ???10 2.37 | ??10 4.72 |
| ???3-7 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??1.65E5 | ???1.09E3 | ????3.90 | ?????6.89 | ???10 2.81 | ??10 4.69 |
| ???3-8 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1170 | ????60 | ????20 | ??3.60E5 | ???2.51E3 | ????4.00 | ?????6.96 | ???10 2.80 | ??10 4.52 |
| ???3-9 | ???45 | ???55 | ??100 | ???4.0 | ????0.8 | ????0.01 | ????1180 | ????60 | ????20 | ??1.77E6 | ???4.80E3 | ????4.44 | ?????6.78 | ???10 3.36 | ??10 4.26 |
(table 4)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | ||||||||||
| ???SrO | ???PbO | ??TiO 2 | ????SiO 2 | ????Y 2O 3 | ????MnO 2 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ??ρ 25℃?(Ω·cm) | ???ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ??NTC ??drop | ????PTC ????jump | |
| ??4-1 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1100 | ????60 | ????20 | ??1.17E5 | ??3.34E3 | ????2.71 | ????4.78 | ??10 1.88 | ???10 4.05 |
| ??4-2 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1110 | ????60 | ????20 | ??1.50E5 | ??3.40E3 | ????2.77 | ????5.44 | ??10 1.92 | ???10 4.38 |
| ??4-3 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1120 | ????60 | ????20 | ??1.91E5 | ??3.82E3 | ????2.80 | ????5.32 | ??10 1.97 | ???10 4.62 |
| ??4-4 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1130 | ????60 | ????20 | ??8.00E4 | ??1.67E3 | ????2.77 | ????5.64 | ??10 2.06 | ???10 4.84 |
| ??4-5 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1140 | ????60 | ????20 | ??7.00E4 | ??1.27E3 | ????3.02 | ????5.55 | ??10 2.19 | ???10 4.95 |
| ??4-6 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1150 | ????60 | ????20 | ??1.83E4 | ??3.85E2 | ????3.11 | ????6.27 | ??10 2.26 | ???10 4.90 |
| ??4-7 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1160 | ????60 | ????20 | ??3.09E4 | ??4.44E2 | ????3.09 | ????5.09 | ??10 2.25 | ???10 4.89 |
| ??4-8 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1170 | ????60 | ????20 | ??3.15E4 | ??5.08E2 | ????3.15 | ????5.27 | ??10 2.28 | ???10 4.47 |
| ??4-9 | ????45 | ????55 | ???100 | ????12.0 | ????0.8 | ????0.01 | ????1180 | ????60 | ????20 | ??4.95E4 | ??5.72E2 | ????3.31 | ????4.16 | ??10 2.41 | ???10 3.95 |
(table 5)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | ||||||||||
| ???SrO | ??PbO | ??TiO 2 | ???SiO 2 | ????Y 2O 3 | Li or Mn | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ???ρ 25℃??(Ω·cm) | ??ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ???NTC ???drop | ??PTC ??jump | |
| ??5-1 | ???45 | ???55 | ???100 | ????4.0 | ????0.8 | ??Li0.01 | ??1160 | ????60 | ????5 | ??4.55E2 | ???5.08E1 | ????2.07 | ?????3.85 | ???10 1.21 | ??10 2.77 |
| ??5-2 | ???45 | ???55 | ???100 | ????4.0 | ????0.8 | ??Li0.01 | ??1160 | ????60 | ????10 | ??3.00E3 | ???1.50E2 | ????2.56 | ?????4.55 | ???10 1.57 | ??10 3.41 |
| ??5-3 | ???45 | ???55 | ???100 | ????4.0 | ????0.8 | ??Li0.01 | ??1160 | ????60 | ????15 | ??1.33E4 | ???3.23E2 | ????3.20 | ?????6.17 | ???10 2.04 | ??10 4.45 |
| ??5-4 | ???45 | ???55 | ???100 | ????4.0 | ????0.8 | ??Li0.01 | ??1160 | ????60 | ????20 | ??1.00E5 | ???4.91E2 | ????3.37 | ?????5.93 | ???10 2.37 | ??10 4.72 |
| ??5-5 | ???45 | ???55 | ???100 | ????4.0 | ????0.8 | ??Li0.01 | ??1160 | ????60 | ????25 | ??1.39E5 | ???1.03E3 | ????3.91 | ?????7.33 | ???10 2.77 | ??10 4.79 |
| ??5-6 | ???45 | ???55 | ???100 | ????12.0 | ????0.8 | ??Mn0.01 | ??1160 | ????60 | ????5 | ??5.32E4 | ???1.23E3 | ????2.94 | ?????5.34 | ???10 2.04 | ??10 4.44 |
| ??5-7 | ???45 | ???55 | ???100 | ????12.0 | ????0.8 | ??Mn0.01 | ??1160 | ????60 | ????10 | ??3.28E4 | ???6.89E2 | ????2.97 | ?????5.77 | ???10 2.08 | ??10 4.72 |
| ??5-8 | ???45 | ???55 | ???100 | ????12.0 | ????0.8 | ??Mn0.01 | ??1160 | ????60 | ????15 | ??2.56E4 | ???5.20E2 | ????3.08 | ?????6.11 | ???10 2.18 | ??10 4.85 |
| ??5-9 | ???45 | ???55 | ???100 | ????12.0 | ????0.8 | ??Mn0.01 | ??1160 | ????60 | ????20 | ??1.83E4 | ???3.85E2 | ????3.11 | ?????6.27 | ???10 2.26 | ??10 4.90 |
| ??5-0 | ???45 | ???55 | ???100 | ????12.0 | ????0.8 | ??Mn0.01 | ??1160 | ????60 | ????25 | ??6.02E4 | ???6.78E2 | ????3.31 | ?????5.49 | ???10 2.47 | ??10 4.46 |
(table 6)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | ||||||||||
| ??SrO | ???PbO | ??TiO 2 | ???SiO 2 | ??FeO 3/2 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ?ρ 25℃?(Ω·cm) | ???ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ???NTC ???drop | ??PTC ??jump | ||
| ???6-1 | ???45 | ???55 | ???100 | ???12.0 | ????Bi0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??3.99E3 | ??1.46E1 | ????4.47 | ????5.39 | ??10 2.95 | ??10 4.36 |
| ???6-2 | ???45 | ???55 | ???100 | ???12.0 | ????Nd0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??1.00E4 | ??2.65E1 | ????4.52 | ????5.41 | ??10 3.16 | ??10 4.12 |
| ???6-3 | ???45 | ???55 | ???100 | ???12.0 | ????Dy0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??6.82E3 | ??3.20E1 | ????4.48 | ????5.11 | ??10 2.89 | ??10 3.47 |
| ???6-4 | ???45 | ???55 | ???100 | ???12.0 | ????Sb0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??1.99E4 | ??5.31E1 | ????4.71 | ????5.56 | ??10 3.14 | ??10 3.78 |
| ???6-5 | ???45 | ???55 | ???100 | ???12.0 | ????Nb0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??9.01E4 | ??1.37E2 | ????5.22 | ????5.22 | ??10 3.43 | ??10 3.44 |
| ???6-6 | ???45 | ???55 | ???100 | ???12.0 | ????La0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??1.72E5 | ??2.74E2 | ????5.21 | ????5.19 | ??10 3.49 | ??10 3.43 |
| ???6-7 | ???45 | ???55 | ???100 | ???12.0 | ????Yb0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??6.99E5 | ??3.43E2 | ????4.49 | ????4.49 | ??10 2.83 | ??10 3.47 |
| ???6-8 | ???45 | ???55 | ???100 | ???12.0 | ????Ce0.4 | ???0.01 | ???1160 | ????60 | ????20 | ??3.26E5 | ??6.64E2 | ????4.70 | ????4.71 | ??10 3.26 | ??10 3.36 |
(table 7)
[notes] additive a, b, c, d represent Si respectively
3N
3, AST, BaPbO
3And BN, content is the weight percentage with respect to principal component
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (wt.%) | Technological parameter | Performance parameter | ||||||||||
| ???SrO | ???PbO | ??TiO 2 | ??SiO 2 | ??Bi 2O 3 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ???ρ 25℃??(Ω·cm) | ??ρ min??(Ω·cm) | ??α -50℃??(％/℃) | ??α +50℃??(％/℃) | ???NTC ???drop | ??PTC ??jump | ||
| ??7-1 | ???45 | ???55 | ??100 | ??4.0 | ????0.8 | ????a0.3 | ????1160 | ????60 | ????20 | ??8.71E3 | ??2.91E1 | ????5.23 | ????5.39 | ??10 3.07 | ??10 4.16 |
| ??7-2 | ???45 | ???55 | ??100 | ??4.0 | ????0.8 | ????b0.3 | ????1160 | ????60 | ????20 | ??2.51E4 | ??1.14E2 | ????4.49 | ????5.10 | ??10 2.90 | ??10 3.47 |
| ??7-3 | ???45 | ???55 | ??100 | ??4.0 | ????0.8 | ????c0.3 | ????1160 | ????60 | ????20 | ??6.60E4 | ??1.31E2 | ????4.73 | ????5.56 | ??10 3.31 | ??10 3.36 |
| ??7-4 | ???45 | ???55 | ??100 | ??4.0 | ????0.8 | ????d0.3 | ????1160 | ????60 | ????20 | ??1.80E5 | ??2.76E2 | ????5.22 | ????4.41 | ??10 3.47 | ??10 3.44 |
(table 8)
| The sample sequence number | Principal component (mol%) | Semiconducting element (mol%) | Additive (mol%) | Technological parameter | Performance parameter | |||||||||||
| ???SrO | ???BaO | ???PbO | ???TiO 2 | ???SiO 2 | ???Nd 2O 3 | ???MnO 2 | Sintering temperature (℃) | Sintering time (min) | Heating rate (℃/min) | ??ρ 25℃??(Ω·cm) | ??ρ min(Ω·cm) | ?α -50℃?(％/℃) | ??α +50℃??(％/℃) | ?????NTC ????drop | ?????PTC ????jump | |
| ??8-1 | ???20 | ???70 | ???10 | ???100 | ???12.0 | ????0.8 | ???0.01 | ????1160 | ????60 | ????20 | ??9.98E2 | ??3.02E2 | ????2.44 | ????7.89 | ???10 0.82 | ???10 4.57 |
| ??8-2 | ???15 | ???70 | ???15 | ???100 | ???12.0 | ????0.8 | ???0.01 | ????1160 | ????60 | ????20 | ??2.73E3 | ??1.98E2 | ????2.85 | ????7.61 | ???10 1.54 | ???10 4.50 |
| ??8-3 | ???10 | ???70 | ???20 | ???100 | ???12.0 | ????0.8 | ???0.01 | ????1160 | ????60 | ????20 | ??1.20E4 | ??1.07E2 | ????3.85 | ????6.40 | ???10 2.48 | ???10 4.57 |
| ??8-4 | ???5 | ???70 | ???25 | ???100 | ???12.0 | ????0.8 | ???0.01 | ????1160 | ????60 | ????20 | ??4.11E4 | ??4.99E1 | ????4.43 | ????5.89 | ???10 3.48 | ???10 4.53 |
| ??8-5 | ???0 | ???70 | ???30 | ???100 | ???12.0 | ????0.8 | ???0.01 | ????1160 | ????60 | ????20 | ??1.83E5 | ??2.48E1 | ????4.79 | ????4.47 | ???10 4.53 | ???10 4.10 |
Claims (5)
1. the combined characteristic thermosensitive resistor material of a low temperature sintering is characterized in that the principal component of this material consists of:
(Sr
1-x-yBa
yPb
x) Ti
zO
3+ wPb
mSi
nO
2n+mX=0.1～0.9 wherein; Y=0～0.9; Z=0.8～1.2; W=0.001～1; M/n=0.1～10
Prescription contains metal element Ti in the principal component, contains Sr, Ba, and three kinds of metallic elements of Pb or wherein any two kinds, the oxide of above-mentioned metallic element forms ceramic phase, i.e. (Sr
1-x-yBa
yPb
x) Ti
zO
3, its total amount accounts for 50～99.9mol% of total amount of material; Prescription contains the Si element in the principal component, forms glassy phase, i.e. Pb with Pb etc.
mSi
nO
2n+mIts total amount accounts for 0.1～30mol% of total amount of material; At least contain a kind of trace element in the prescription, be among Y, Yb, La, Sb, Nd, Dy, Bi, Ce, the Nb one or more, its content accounts for 0.01～5mol% of total amount of material; Be added with a small amount of secondary additive in the prescription, be AST (1/3Al
2O
33/4SiO
21/4TiO
2), BaPbO
3, Si
3N
4, in BN and Mn, Fe, the Li compound one or more, its content accounts for 0.001～15mol% of total amount of material.
2. a method for preparing the combined characteristic thermosensitive resistor material of low temperature sintering as claimed in claim 1 is characterized in that initial feed is selected from TiO
2, SrCO
3, Sr (NO
3)
2, PbO, Pb
3O
4, PbCO
3, Pb (NO
3)
2, BaCO
3, Ba (NO
3)
2, SiO
2And Si (OC
2H
5)
4In the oxide or salt etc. required element, semiconducting element initial feed is selected from Y
2O
3, Y (NO
3)
3, Yb
2O
3, Yb (NO
3)
3, La
2O
3, La (NO
3)
3, Sb
2O
3, Nd
2O
3, Nd (NO
3)
3, Dy
2O
3, Bi
2O
3, Bi (NO
3)
3, Nb
2O
5, CeO
2And Ce (NO
3)
3In the oxide or salt etc. required element, additive is generally selected the higher synthetic product of purity, is AST, BaPbO
3, Si
3N
4, BN and Mn (NO
3)
2, Fe (NO
3)
2, Li
2CO
31. this technology comprise the steps: initial feed and semiconducting element by the formulation ratio weighing; 2. mixing and ball milling (48 hours, alcohol-water blending agent, granularity is less than 1 μ m); 3. oven dry (100～150 ℃, 10～30 hours); 4. pre-burning (800～1000 ℃, 1～2 hour); 5. pulverize (granularity is less than 1 μ m), and add in proportion additive simultaneously; 6. drying (100～150 ℃, 10～30 hours), granulation, moulding (typed pressure 100～500MPa); 7. sintering (1000～1300 ℃, 5～180 minutes) namely obtains the composite thermistor material.
3. a method for preparing the combined characteristic thermosensitive resistor material of low temperature sintering as claimed in claim 1 is characterized in that initial feed is selected from TiO
2, SrCO
3, Sr (NO
3)
2, PbO, Pb
3O4, PbCO
3, Pb (NO
3)
2, BaCO
3, Ba (NO
3)
2, SiO
2And Si (OC
2H
5)
4In the oxide or salt etc. required element, semiconducting element initial feed is selected from Y
2O
3, Y (NO
3)
3, Yb
2O
3, Yb (NO
3)
3, La
2O
3, La (NO
3)
3, Sb
2O
3, Nd
2O
3, Nd (NO
3)
3, Dy
2O
3, Bi
2O
3, Bi (NO
3)
3, Nb
2O
5, CeO
2And Ce (NO
3)
3In the oxide or salt etc. required element, additive is generally selected the higher synthetic product of purity, is AST, BaPbO
3, Si
3N
4, BN and Mn (NO
3)
2, Fe (NO
3)
2, Li
2CO
31. this technology comprise the steps: initial feed and semiconducting element by the formulation ratio weighing; 2. mixing and ball milling (48 hours, alcohol-water blending agent, granularity is less than 1 μ m); 3. oven dry (10～150 ℃, 10～30 hours); 4. pre-burning (800～1000 ℃, 1～2 hour), i.e. synthesize ceramic phase (Sr
1-xPb
x) Ti
yO
35. pulverize ceramic phase (granularity is less than 1 μ m), and additive and glassy phase raw material are pressed formulation ratio and ceramic phase (Sr
1-xPb
x) Ti
yO
3Powder body material evenly mixes; 6. drying (10～150 ℃, 10～30 hours), granulation, moulding (typed pressure 100～500MPa); 7. sintering (1000～1300 ℃, 5～180 minutes) namely obtains the composite thermistor material.
4. a method for preparing the combined characteristic thermosensitive resistor material of low temperature sintering as claimed in claim 1 is characterized in that initial feed is selected from TiCl
4, Ti (OC
4H
9)
4, SrCO
3, Sr (NO
3)
2, PbCO
3, Pb (NO
3)
2, BaCO
3, Ba (NO
3)
2And Si (OC
2H
5)
4In the oxide or salt etc. required element, semiconducting element initial feed is selected from Y
2O
3, Y (NO
3)
3, Yb
2O
3, Yb (NO
3)
3, La
2O
3, La (NO
3)
3, Sb
2O
3, Nd
2O
3, Nd (NO
3)
3, Dy
2O
3, Bi
2O
3, Bi (NO
3)
3, Nb
2O
5, CeO
2, Ce (NO
3)
3In the oxide or salt etc. required element, additive is generally selected the higher synthetic product of purity, is AST, BaPbO
3, Si
3N
4, BN and Mn (NO
3)
2, Fe (NO
3)
2, Li
2CO
31. this technology comprise the steps: initial feed and semiconducting element by the formulation ratio weighing; 2. with initial feed and the semiconducting element of weighing form mixed solution (the Ti ion concentration is between 0.01～10M in the solution) jointly; 3. carry out co-precipitation (10～80 ℃ of precipitation temperatures) take oxalic acid (or oxalic acid ammonia) as precipitating reagent; 4. with sediment washing (ethanol dehydration is more than three times after the washed several times with water), dispersion (dispersant is n-butanol), oven dry (10～150 ℃, 10～30 hours); 5. calcine 600～800 ℃, be incubated 0.5～1.5 hour, obtain the main formula powder body material; 6. the secondary additive is evenly mixed with the main formula powder body material; 7. dry (100～150 ℃, 10～30 hours), moulding (typed pressure 100～500MPa); 8. sintering (1000～1300 ℃, 5～180 minutes) namely obtains the composite thermistor material.
5. a method for preparing the combined characteristic thermosensitive resistor material of low temperature sintering as claimed in claim 1 is characterized in that initial feed is selected from TiCl
4, Ti (OC
4H
9)
4, SrCO
3, Sr (NO
3)
2, PbCO
3, Pb (NO
3)
2, BaCO
3, Ba (NO
3)
2And Si (OC
2H
5)
4In the oxide or salt etc. required element, semiconducting element initial feed is selected from Y
2O
3, Y (NO
3)
3, Yb
2O
3, Yb (NO
3)
3, La
2O
3, La (NO
3)
3, Sb
2O
3, Nd
2O
3, Nd (NO
3)
3, Dy
2O
3, Bi
2O
3, Bi (NO
3)
3, Nb
2O
5, CeO
2, Ce (NO
3)
3In the oxide or salt etc. required element, additive is generally selected the higher synthetic product of purity, is AST, BaPbO
3, Si
3N
4, BN and Mn (NO
3)
2, Fe (NO
3)
2, Li
2CO
31. this technology comprise the steps: initial feed and semiconducting element by the formulation ratio weighing; 2. with initial feed and the semiconducting element of weighing form mixed solution (the Ti ion concentration is between 0.01～10M in the solution) jointly; 3. carry out co-precipitation (10～80 ℃ of precipitation temperatures) take oxalic acid (or oxalic acid ammonia) as precipitating reagent; 4. with sediment washing (ethanol dehydration is more than three times after the washed several times with water), dispersion (dispersant is n-butanol), oven dry (100～150 ℃, 10～30 hours); 5. calcine 600～800 ℃, be incubated 0.5～1.5 hour, obtain ceramic phase (Sr
1-xPb
x) Ti
yO
3Powder body material; 6. additive and glassy phase raw material are pressed formulation ratio and ceramic phase (Sr
1-xPb
x) Ti
yO
3Powder body material evenly mixes; 7. dry (100～150 ℃, 10～30 hours), moulding (typed pressure 100～500MPa); 8. sintering (1000～1300 ℃, 5～180 minutes) namely obtains the composite thermistor material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100777A CN1047457C (en) | 1997-02-26 | 1997-02-26 | Medium- and low-temp. sintered combined characteristic thermosensitive resistor material composition and preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97100777A CN1047457C (en) | 1997-02-26 | 1997-02-26 | Medium- and low-temp. sintered combined characteristic thermosensitive resistor material composition and preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1160273A true CN1160273A (en) | 1997-09-24 |
| CN1047457C CN1047457C (en) | 1999-12-15 |
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ID=5165311
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97100777A Expired - Fee Related CN1047457C (en) | 1997-02-26 | 1997-02-26 | Medium- and low-temp. sintered combined characteristic thermosensitive resistor material composition and preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047457C (en) |
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| CN101894641A (en) * | 2010-06-23 | 2010-11-24 | 深圳市三宝创业科技有限公司 | Method for improving thermosensitive resistor production efficiency |
| CN101962294A (en) * | 2010-07-15 | 2011-02-02 | 上海大学 | W-type low-and-medium temperature NTC-PTC binary composite thermistor material and preparation method thereof |
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|---|---|---|---|---|
| CN1029761C (en) * | 1992-11-12 | 1995-09-13 | 清华大学 | Composite charicteristic thermistor and its making method |
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1997
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| CN105236970A (en) * | 2015-09-28 | 2016-01-13 | 桂林理工大学 | High Curie point positive temperature coefficient resistor material Ba5LiTiNb3O15and preparation method thereof |
| US11340121B2 (en) | 2016-03-02 | 2022-05-24 | Watlow Electric Manufacturing Company | Heater element having targeted decreasing temperature resistance characteristics |
| JP7238176B2 (en) | 2016-03-02 | 2023-03-13 | ワットロー・エレクトリック・マニュファクチャリング・カンパニー | How the heater system works |
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| CN1047457C (en) | 1999-12-15 |
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