CN101830700B - Barium titanate-based thermosensitive resistance material with low B value and high resistivity and preparation method thereof - Google Patents
Barium titanate-based thermosensitive resistance material with low B value and high resistivity and preparation method thereof Download PDFInfo
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- CN101830700B CN101830700B CN201010131358A CN201010131358A CN101830700B CN 101830700 B CN101830700 B CN 101830700B CN 201010131358 A CN201010131358 A CN 201010131358A CN 201010131358 A CN201010131358 A CN 201010131358A CN 101830700 B CN101830700 B CN 101830700B
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Abstract
The invention relates to the field of electronic ceramic materials, and relates to a barium titanate-based thermosensitive resistance material with low B value and high resistivity and a preparation method thereof. The thermosensitive resistance material is characterized in that the chemical general formula is (Ba0.5Pb0.5)TiO3 + 0.25mol%Y2O3 + 2mol%PbO + xmol%BN + ymol%MnO2, wherein x is more than or equal to 2 and less than or equal to 20, and y is more than or equal to 0.0 and less than or equal to 0.06. The method for preparing the barium titanate-based thermosensitive resistance material with negative temperature coefficient by using a solid phase reaction method comprises the following steps of: weighing barium titanate, titanium dioxide, lead dioxide, yttrium oxide, boron nitride and manganese oxide serving as raw materials based on the proportion in the chemical general formula; and performing a ceramic process, namely blending, ball-milling, crushing and drying the raw materials, pre-sintering the mixture for 2 hours at the temperature of 900 DEG C, then performing secondary ball milling and crushing on the mixture, adding adhesive into the mixture, granulating and shapingthe mixture, preserving the heat for 2 hours at the temperature of 1,200 DEG C, and treating the sintered sample by an electrode to form the thermosensitive resistance material.
Description
Technical field
The present invention relates to field of electronic ceramic materials, relate to negative temperature coefficient heat-sensitive resistance material and technology of preparing, especially a kind of barium phthalate base hangs down B value, high resistivity thermistor material.
Background technology
The fundamental characteristics of existing negative temperature coefficient heat-sensitive resistance material has determined the significant parameter of thermistor element; Normally used thermistor material is formulated by different ratios by the oxide compound of transition metal Mn, Fe, CO, Ni, Cu; Resistivity by several ohmcms to several kilohms centimetres; The B value is several ohm of extremely several megohms from 2000-6000K in order to the thermistor element resistance value of making.
According to the theoretical B=Δ of oxide semiconductor E/2K
In the formula, K is Boltzmann constant (8.62*10
5Ev), Δ E is the intensity of activation of material, and it is to carry atom to be energized into the energy that free state needs by bound state, and the relation of it and resistivity of material ρ is:
ρ＝ρ
0*exp(B/T)＝ρ
0*exp(ΔE/2KT)＝(1/n
0eμ)*exp(ΔE/2KT)
Following formula shows that the material of high resistivity must have high B value.In other words, obtain low B value, high resistivity material is difficult.Along with the thermistor application and development; The element of some special usefulness; Like Internet of Things, automotive electronics with thermistor, military project and space industry with thermistor and various electronic devices and components and semi-conductor; Thermistor is used in the temperature compensation of various transmitters (like pressure, humidity sensor), requires thermistor to have lower temperature sensitivity and higher nominal resistance.Adopt conventional NTC thermistor material prescription to realize.Low B value, high resistivity thermistor material have become a great problem that current negative tempperature coefficient thermistor is made.Therefore developing the New NTC pottery has very important meaning.
Once there was the people in prescription, to add precious metal (R, Pd, Au etc.) particle, resistivity of material is sharply descended, and simultaneously the B value was reduced significantly, be difficult to realize desired low B value, high resistivity material.Had the people in prescription, to introduce metal (K, Na, Ca etc.) oxide compound at a low price afterwards again, the result is similar with the effect that adds metallics.Someone's material that will have low B value, a low-resistivity is compound with the material with high B value, high resistivity recently; Consequently resistivity is both weighted means; The B value is then got Schwellenwert, can not obtain the material of low B value, the requirement of high resistance thermistor equally.Energy band structure and electrical conduction mechanism according to oxide semiconductor; Low B value, high resistivity thermistor material must adopt composite structure; Utilize " the adduction effect " of different structure; Make and form assorted level energy level in the material forbidden band, with level density that reduces conduction band (or valence band) end and the height that improves crystal boundary gesture amount.Experiment shows with spinel structure and the compound negative temperature coefficient heat-sensitive resistance material that can prepare low B value, high resistivity of calcium titanium ore structure (or rutile structure).Conventional in addition high-curie temperature ptc material ((Ba
1-x-yPb
xY
y) TiO
3+ zmol%TiO
2+ umol%SiO
2+ vmol%MnO
2Be called for short BPT-AST system), sintering character is very poor when being higher than more than 300 ℃ at high-curie temperature, and the sample electrical property of making is very unstable, does not have practical value.There are a lot of Chinese invention patents to report the preparation method of negative temperature coefficient material in addition, like No. 200910013607.2 disclosed a kind of B value changeable negative temperature coefficient thermistor compositions of Chinese invention patent application and preparation method thereof.Relevant BT-BN series negative temperature coefficient resistor ceramic does not still have patent report at present.Therefore, be badly in need of a kind of preparation method of BT-BN series negative temperature coefficient resistor ceramic, promptly a kind of barium phthalate base hangs down B value, high resistivity thermistor material and preparation method thereof.
Fig. 1 is the low B value of barium phthalate base, high resistivity thermo-sensitive material ρ-T typical plot.Among Fig. 1, X-coordinate is a temperature T, and unit is ℃, and ordinate zou is a resistivity, and unit is Ω cm.As can be seen from the figure reducing with the temperature rising at resistance below 350 ℃ is NTC (NTC) electricresistance effect.
Summary of the invention
The objective of the invention is to remedy the deficiency of prior art, provide a kind of barium phthalate base to hang down B value, high resistivity thermistor material.
The present invention realizes through following technical scheme:
A kind of barium phthalate base of the present invention hangs down B value, high resistivity thermistor material, is in barium titanate-SP 1 system, to adopt Y
2O
3Semiconductor doping and excess PbO configuration can obtain the excellent PTC stupalith of high curie point and sintering character easily.Doping ratio through regulating SP 1 ratio and control manganese and, can obtain different B values, different resistivity.The B value and the resistivity of the back barium phthalate base material that mixes are all changed to some extent.
A kind of barium phthalate base of the present invention hangs down B value, high resistivity thermistor material, it is characterized in that chemical general formula is:
(Ba
0.5Pb
0.5) TiO
3+ 0.25mol%Y
2O
3+ 2mol%PbO+xmol%BN+ymol%MnO
2(being called for short BT-BN system), wherein 2≤x≤20; 0.0≤y≤0.06;
A kind of barium phthalate base of the present invention hangs down B value, high resistivity thermistor material, is to prepare barium titanate-based negative temperature coefficient resistance material with solid reaction process, and raw material is barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide.
A kind of barium phthalate base of the present invention hangs down B value, high resistivity thermistor material; Solid reaction process with existing ceramic technology is synthetic, is raw material with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide at first, according to chemical general formula through the weighing proportioning; Again batch mixing, with ball mill pulverizing, oven dry; Through 900 ℃ of pre-burnings 2 hours, carry out the ball mill pulverizing second time then, add the tackiness agent granulation, moulding, through 1200 ℃ of insulations two hours, the sample that sinters is carried out by electrode; Carry out performance parameter test then, obtain thermo-sensitive material.
According to the resistivity of the thermistor material of material prescription provided by the present invention and the preparation method preparation scope at 1000-60000 Ω cm, B value=1000-3000K belongs to and typically hangs down B value, high resistivity material.
The present invention has negative temperature coefficient heat-sensitive resistance material and compares with traditional NTC thermistor material, and preparation cost is lower.Its resistivity at room temperature is higher than 1000 Ω cm, B value=1000-3000K, and its Tc is about 350-365 ℃; Maximum operation (service) temperature can reach 300 ℃, can be made into all kinds of TPs, restrictor, time delay unit, is widely used in fields such as sensing net, telecommunications, aerospace, automotive industry, household electrical appliance.
Compare with aforementioned existing like product, a kind of barium phthalate base of the present invention hangs down B value, high resistivity thermistor material, and it is lower to have lower temperature sensitivity and higher nominal resistance and a preparation cost, has remedied the deficiency of existing negative temperature coefficient resister pottery.
Content of the present invention combines following examples to do explanation further, but content of the present invention is not limited only to content related among the embodiment.
Description of drawings
Fig. 1 is the low B value of barium phthalate base, high resistivity thermo-sensitive material ρ-T typical plot.
Embodiment
Embodiment 1: shown in 1# in the table 1, a kind of barium phthalate base described in the present embodiment hangs down the B value, the high resistivity thermistor material is according to chemical general formula:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
X=2, the y=0.00 proportioning, synthetic with the solid reaction process of existing ceramic process; Be raw material at first with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide, through the weighing proportioning, again batch mixing, use ball mill pulverizing; Oven dry through 900 pre-burnings 2 hours, is carried out ball mill pulverizing second time then, is added the tackiness agent granulation, moulding, is incubated 2 hours through 1200; The sample that sinters is carried out by electrode, carry out performance parameter test then, obtain thermo-sensitive material.Test result is seen 1# in the table 1.
Table 1 is the proportioning and the test result of BT-BN series negative temperature coefficient resistor ceramic of the present invention, from table, can find out the collocation that can obtain different resistivity and B value through adjusting and control BN, Mn02.
Embodiment 2: shown in 2# in the table 1, present embodiment is similar with embodiment 1, according to chemical general formula:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
X=2, the y=0.04 proportioning, synthetic with the solid reaction process of existing ceramic process; Be raw material at first with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide, through the weighing proportioning, again batch mixing, use ball mill pulverizing; Oven dry through 900 ℃ of pre-burnings 2 hours, is carried out ball mill pulverizing second time then, is added the tackiness agent granulation, moulding, is incubated two hours through 1200 ℃; The sample that sinters is carried out by electrode, carry out performance parameter test then, obtain thermo-sensitive material.Test result is seen 2# in the table 1.
Embodiment 3: shown in 6# in the table 1, present embodiment is similar with embodiment 1, according to chemical general formula:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
X=2, the y=0.06 proportioning, synthetic with the solid reaction process of existing ceramic process; Be raw material at first with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide, through the weighing proportioning, again batch mixing, use ball mill pulverizing; Oven dry through 900 ℃ of pre-burnings 2 hours, is carried out ball mill pulverizing second time then, is added the tackiness agent granulation, moulding, is incubated two hours through 1200 ℃; The sample that sinters is carried out by electrode, carry out performance parameter test then, obtain thermo-sensitive material.Test result is seen 6# in the table 1.
Embodiment 4: shown in 3# in the table 1, present embodiment is similar with embodiment 1, according to chemical general formula:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
X=5, the y=0.04 proportioning, synthetic with the solid reaction process of existing ceramic process; Be raw material at first with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide, through the weighing proportioning, again batch mixing, use ball mill pulverizing; Oven dry through 900 ℃ of pre-burnings 2 hours, is carried out ball mill pulverizing second time then, is added the tackiness agent granulation, moulding, is incubated two hours through 1200 ℃; The sample that sinters is carried out by electrode, carry out performance parameter test then, obtain thermo-sensitive material.Test result is seen 3# in the table 1.
Embodiment 5: shown in 4# in the table 1, present embodiment is similar with embodiment 1, according to chemical general formula:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
X=10, the y=0.04 proportioning, synthetic with the solid reaction process of existing ceramic process; Be raw material at first with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide, through the weighing proportioning, again batch mixing, use ball mill pulverizing; Oven dry through 900 ℃ of pre-burnings 2 hours, is carried out ball mill pulverizing second time then, is added the tackiness agent granulation, moulding, is incubated two hours through 1200 ℃; The sample that sinters is carried out by electrode, carry out performance parameter test then, obtain thermo-sensitive material.Test result is seen 4# in the table 1.
Embodiment 6: shown in 5# in the table 1, present embodiment is similar with embodiment 1, according to chemical general formula:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
X=20, the y=0.04 proportioning, synthetic with the solid reaction process of existing ceramic process; Be raw material at first with barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide, through the weighing proportioning, again batch mixing, use ball mill pulverizing; Oven dry through 900 ℃ of pre-burnings 2 hours, is carried out ball mill pulverizing second time then, is added the tackiness agent granulation, moulding, is incubated two hours through 1200 ℃; The sample that sinters is carried out by electrode, carry out performance parameter test then, obtain thermo-sensitive material.Test result is seen 5# in the table 1.
Table 1 material mixture ratio and test result
Claims (1)
1. a barium phthalate base hangs down B value, high resistivity thermistor material, it is characterized in that chemical general formula is:
(Ba
0.5Pb
0.5)TiO
3+0.25mol％Y
2O
3+2mol％PbO+xmol％BN+ymol％MnO
2
2≤x≤20 wherein; 0.0≤y≤0.06;
The preparation method is: prepare the barium titanate-based negative temperature coefficient thermistor material with solid reaction process; Raw material is barium carbonate, titanium oxide, plumbous oxide, yttrium oxide, SP 1, manganese oxide; According to chemical general formula weighing proportioning; Carry out through ceramic process: batch mixing, ball mill pulverizing, oven dry, through 900 ℃ of pre-burnings 2 hours; Carry out the ball mill pulverizing second time then, add the tackiness agent granulation, moulding, through 1200 ℃ of insulations two hours, the sample that sinters is carried out being processed thermistor material by electrode.
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| CN201010131358A CN101830700B (en) | 2010-03-24 | 2010-03-24 | Barium titanate-based thermosensitive resistance material with low B value and high resistivity and preparation method thereof |
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| CN102568723B (en) * | 2012-01-09 | 2015-06-24 | 深圳顺络电子股份有限公司 | NTC (negative temperature coefficient) thermistor chip, resistor and manufacturing method thereof |
| CN115101274B (en) * | 2022-07-27 | 2024-07-09 | 成都顺康三森电子有限责任公司 | Functional material composition of linear temperature sensor and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108454A (en) * | 1985-11-23 | 1987-06-03 | 华中工学院 | High temperature positive temperature coefficient heat-sensitive semiconductor ceramic material and manufacture method thereof |
| CN101357844A (en) * | 2008-09-02 | 2009-02-04 | 周金平 | PTC thermal sensitive ceramic material and method for preparing the same |
-
2010
- 2010-03-24 CN CN201010131358A patent/CN101830700B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85108454A (en) * | 1985-11-23 | 1987-06-03 | 华中工学院 | High temperature positive temperature coefficient heat-sensitive semiconductor ceramic material and manufacture method thereof |
| CN101357844A (en) * | 2008-09-02 | 2009-02-04 | 周金平 | PTC thermal sensitive ceramic material and method for preparing the same |
Non-Patent Citations (1)
| Title |
|---|
| 陈建利等.低温烧结锶系PTC材料的研制.《电子元件与材料》.2008,第27卷(第8期),30-32. * |
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