CN104987059A - Novel NTC thermal resistance material based on copper oxide - Google Patents
Novel NTC thermal resistance material based on copper oxide Download PDFInfo
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- CN104987059A CN104987059A CN201510360036.5A CN201510360036A CN104987059A CN 104987059 A CN104987059 A CN 104987059A CN 201510360036 A CN201510360036 A CN 201510360036A CN 104987059 A CN104987059 A CN 104987059A
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Abstract
The invention relates to a semiconductor ceramic material, in particular to a NTC thermal resistance material meeting the preparation of a thermal resistance element with a resistance negative temperature coefficient (NTC) effect. According to the novel NTC thermal resistance material, the indoor temperature resistance value and the material constant value of the thermal resistance element can be adjusted through the change of the content of micro-scale doped elements. The NTC thermal resistance material is mainly composed of the component of simple oxide, the NTC thermal resistance material can be sintered into a ceramic body at the temperature about 1000 DEG C, and the NTC thermal resistance material can be adaptable to the sintering forming of thermal-sensitive ceramic elements, thin film thermal-sensitive elements and low-temperature cofiring lamination thermal-sensitive components. The novel NTC thermal resistance material has the advantages that the stability is good, the consistency is good, the repeatability is good, and the electrical characteristics including the resistance value, the material constant and the resistance temperature coefficient are controllable. The novel NTC thermal resistance material is suitable for temperature measuring, temperature control and circuit compensation, protection of circuit and electronic components, and the instruments and application fields of flow velocity, flow and ray measuring.
Description
Technical field
The present invention relates to the NTC thermistor material that one prepares the thermistor element with resistance negative temperature coefficient (NTC) effect.Be applicable to temperature survey, temperature controls and line build-out, and the protection of circuit and electronic component and flow velocity, flow, the instrument of radionetric survey and Application Areas.
Background technology
Heat sensitive sensor is the device utilizing the temperature variant characteristic of resistivity of material to make, negative temperature coefficient (NTC) thermistor element that positive temperature coefficient (PTC) thermistor increased comprising resistivity raises with temperature or resistivity raise with temperature and reduces.NTC thermistor element and device have been widely used in temperature survey, control, temperature compensation, and the protection of circuit and electronic component and flow velocity, flow, the pertinent instruments of radionetric survey and Application Areas.
In normal temperature NTC themistor, the main spinel structure NTC thermistor element adopting the oxide compound of transition metal manganese, nickel, cobalt, iron, copper to make, they obtain research and apply widely.As, what Chinese invention patent CN1332405C announced is starting material with the nitrate of manganese, nickel, magnesium, aluminium, adopts the NTC thermistor material of liquid-phase coprecipitation synthesis; The CoO-Co that Chinese invention patent CN1006667B announces
2o
3-Fe
2o
3pottery system NTC thermo-sensitive material; The Co-Mn-Fe-O system NTC thermal sensitive ceramic material prepared for raw material with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, manganous nitrate and ferric sulfate that Chinese invention patent CN100395849C announces; Manganese-nickel-cobalt-iron/copper system NTC thermo-sensitive material that U.S. patent Nos 6861622 publication describes.The common trait of these NTC thermistor materials is the oxide compounds containing at least two kinds of transition metal, and with spinel type cubic crystal structure for principal crystalline phase forms.
In the spinel structure NTC thermistor material adopting the oxide compound of transition metal manganese, nickel, cobalt, iron, copper to make, because the volatilization temperature of these transition metal oxides is lower, easily produce the volatilization of composition of raw material in the preparation sintering process of this kind of NTC thermistor element, make the ultimate constituent of product, the consistence of product and the repeatability of producing between different batches restive.The room temperature resistivity of the NTC ceramic of spinel structure is general comparatively large, and resistance value is not easy regulation and control; The resistivity reducing material often can bring the reduction of temperature factor, affects the NTC characteristic of thermal sensing element.Meanwhile, have the manganese-nickel-cobalt based compound of spinel structure, in 200 ~ 400 DEG C of temperature ranges, its tetrahedron and octahedra cationic redistribute slowly in time and cause structure Relaxation.This Relaxation Phenomena causes the instability of NTC ceramic material electric property, easily causes the aging of material, have impact on the performance and used life of material.
In recent years, in order to development of new oxide-base NTC thermistor material, scientific worker also develops some new material systems, as six side BaTiO
3system (Chinese invention patent ZL 2,009 10043274.8; Chinese invention patent ZL 2,009 1 0303525.1), rutile-type SnO
2pottery (electronic component and material, 2009 (6): 56-59; J. Mater. Sci.:Mater. El., 2014,25 (12): 5552-5559), first Feltz finds LaCoO
3based perovskite structural ceramics has excellent NTC characteristic (J. Eur. Ceram. Soc., 2000,20 (14-15): 2367-2376.), following BaSnO
3, BaBiO
3, SrTiO
3, YMnO
3and LaMnO
3all NTC thermal sensitive ceramics (J. Am. Ceram. Soc., 1997,80 (8): 2153-2156 are successfully obtained by means such as doping, compounds Deng material; Appl. Phys. Lett., 2003,82 (14): 2284-2286; Acta Phys. Chim. Sin., 2008,24 (5): 767-771; J. Electroceram, 2008,20 (2): 113-117; Solid State Sci., 2006,8 (2): 137-141; J. Eur. Ceram. Soc., 2002,22 (4): 567-572).Along with the stability requirements of industry to NTC themistor such as air-conditioning, refrigerator, microwave equipment and automobile are more and more higher, improve existing component system or development of new component system just seems very important.For above situation, it is main component with cupric oxide that the present invention adopts, material by micro-doping vario-property, obtain the thermistor material system with good NTC effect, and can usually regulate the room temperature resistivity of thermistor element and the thermal constant of material by changing trace doped unit.
Summary of the invention
The object of this invention is to provide and a kind ofly can manufacture the NTC thermistor material system with negative temperature coefficient of resistance effect.This thermistor material can by changing trace doped element with the thermal constant of the room temperature resistivity and material that regulate thermistor element.
The composition of NTC thermistor material of the present invention consists of: Cu
1-
x-
y y
x b
y o, wherein
x=0.001 ~ 0.09;
y=0.001 ~ 0.05.
The key that the present invention forms NTC material consists of Cu
1-
x-
y y
x b
y o, containing copper, yttrium and boron in system component, its starting material can be the simple substance containing these elements, the compounds such as oxide compound, inorganic salt or organic salt.Wherein, semiconductor Yt is the room temperature resistivity in order to adjust thermistor element, element boron is that the introducing of boron simultaneously also can strengthen the coking property of thermistor owing to regulating the room temperature resistivity of thermistor element and embodying material constant and the temperature factor of sensitive characteristic.
Can obtain high-purity single-phase thing phase composite by preparation method described in the embodiment of the present invention, the stable performance of prepared NTC thermistor element is high, reliability is high.
Primary focus of the present invention is the component prescription of thermistor material, and can adjust accordingly synthetic method and production technique as required in actual application, handiness is large.As, starting material can select the simple substance containing these elements, the compounds such as oxide compound, inorganic salt or organic salt; Synthetic method can adopt the synthetic method of solid state reaction, sol-gel method, coprecipitation method, vapour deposition process or other stupalith to realize.
The detection of thermistor material characteristic of the present invention adopts coating silver slurry to be electrode, the room temperature resistance of measuring sensor and resistance-temperature characteristics.Actual production can select other electrode materials, as aluminium electrode, In-Ga alloy electrode or nickel electrode material.
Characteristic and the Heterosis of the NTC thermistor material that the present invention relates to exist: 1. material composition is simple, and starting material are relatively abundanter, nontoxic, environmental friendliness; 2. in preparation process, sintering temperature is low, and sintering temperature is 1000 ± 50 C, is applicable to the production of ceramic component, film, the NTC thermistor element such as low temperature co-fired; 3. the room temperature resistance value of thermistor element can be adjusted on a large scale by the content of adjustment semiconductor doped element; The content of the boron in 4. consisting of modifying ingredients, can regulate material constant and the temperature factor of thermal sensing element in a big way.
The electrical property of NTC thermistor material of the present invention can realize following parameter request: room temperature resistivity ρ
25=1 Ω cm
-1~ 10 M Ω cm
-1, material constant B=1000 ~ 5000 K.
Content of the present invention is further described with the following Examples.Following examples just meet several examples of the technology of the present invention content, do not illustrate that the present invention is only limitted to the content described in following example.Of the present inventionly focus on component prescription, described starting material, processing method and step can adjust accordingly according to actual production conditions, and handiness is large.
Accompanying drawing explanation
Fig. 1 is the resistance-temperature characteristics curve of different boric acid content in NTC sensitive ceramic resistor material in embodiment.This figure illustrates that all material all presents typical NTC characteristic, and the trace of boric acid introduces resistivity and the NTC material constant that obviously can change material.
Fig. 2 is the room temperature resistivity of NTC sensitive ceramic resistor material in embodiment and the material constant change curve with Boron contents.BO is described
1.5trace introduce and obviously can change resistivity and the NTC material constant of material.
Fig. 3 is the thermistor material (Cu prepared by embodiment 6
0.977y
0.008b
0.015o) from the resistance-temperature relationship figure of room temperature to 300 ° C replicate measurement.Embody this material and there is good temperature cycle stability.
Embodiment
embodiment 1
The present embodiment is by molecular formula Cu
1-
x-
y y
x b
y o prepares burden, wherein
x=0.008,
y=0.Initial raw materials is selected from copper hydroxide Cu (OH)
2, yttrium oxide Y
2o
3.Material preparation is by the processing step of following experiment:
(1) initial feed is pressed Cu
0.992y
0.008o fills a prescription batching, takes Cu (OH)
228.9265 g, Y
2o
30.4516 g;
(2) starting material previous step taken are dissolved in dust technology respectively;
(3) two kinds of solution that previous step is prepared are mixed, and utilize that magnetic agitation well heater is uniformly mixed, heat drying;
(4) calcined by the powder that previous step is obtained, temperature is 830 DEG C, is incubated 3 hours;
(5) powder that previous step is synthesized is carried out granulation, is pressed into base substrate; Base substrate is wafer type, and disk diameter is 15 millimeters, and thickness is 3.5 ~ 4.0 millimeters;
(6) sintered by the base substrate that previous step obtains, sintering temperature is 985 DEG C, is incubated 2 hours, and intensification and rate of cooling are per minute 5 DEG C, so just obtains NTC thermal sensitive ceramics sheet;
(7), after the NTC thermal sensitive ceramics sheet two sides that previous step is obtained being polished, be coated with silver slurry and make electrode through 600 DEG C of solidifications;
(8) the NTC thermistor element that previous step is obtained is carried out resistance-temperature characteristics measurement.
Prepared material property is as shown in table 1, Fig. 1 and Fig. 2.
embodiment 2
The present embodiment is by molecular formula Cu
1-
x-
y y
x b
y o prepares burden, wherein
x=0.008,
y=0.002.Initial raw materials is selected from copper hydroxide Cu (OH)
2, yttrium oxide Y
2o
3, boric acid H
3bO
3.Material preparation is by the processing step of following experiment:
(1) initial feed is pressed Cu
0.99y
0.008b
0.002o fills a prescription batching, takes Cu (OH)
228.8682 g, Y
2o
30.4516 g, H
3bO
30.0618 g;
(2) preparation process is identical with step (2) ~ (8) in embodiment 1.
Prepared material property is as shown in table 1, Fig. 1 and Fig. 2.
embodiment 3
This example is by molecular formula Cu
1-
x-
y y
x b
y o prepares burden, wherein
x=0.008,
y=0.005.Initial raw materials is selected from copper hydroxide Cu (OH)
2, yttrium oxide Y
2o
3, boric acid H
3bO
3.Material preparation is by the processing step of following experiment:
(1) initial feed is pressed Cu
0.987y
0.008b
0.005o fills a prescription batching, takes Cu (OH)
228.7807 g, Y
2o
30.4516 g, H
3bO
30.1546 g;
(2) preparation process is identical with step (2) ~ (8) in embodiment 1.
Prepared material property is as shown in table 1, Fig. 1 and Fig. 2.
embodiment 4
This example is by molecular formula Cu
1-
x-
y y
x b
y o prepares burden, wherein
x=0.008,
y=0.007.Initial raw materials is selected from copper hydroxide Cu (OH)
2, yttrium oxide Y
2o
3, boric acid H
3bO
3.Material preparation is by the processing step of following experiment:
(1) initial feed is pressed Cu
0.985y
0.008b
0.007o fills a prescription batching, takes Cu (OH)
228.7224 g, Y
2o
30.4516 g, H
3bO
30.2164 g;
(2) preparation process is identical with step (2) ~ (8) in embodiment 1.
Prepared material property is as shown in table 1, Fig. 1 and Fig. 2.
embodiment 5
This example is by molecular formula Cu
1-
x-
y y
x b
y o prepares burden, wherein
x=0.008,
y=0.010.Initial raw materials is selected from copper hydroxide Cu (OH)
2, yttrium oxide Y
2o
3, boric acid H
3bO
3.Material preparation is by the processing step of following experiment:
(1) initial feed is pressed Cu
0.982y
0.008b
0.01o fills a prescription batching, takes Cu (OH)
228.6349 g, Y
2o
30.4516 g, H
3bO
30.3092 g;
(2) preparation process is identical with step (2) ~ (8) in embodiment 1.
Prepared material property is as shown in table 1, Fig. 1 and Fig. 2.
embodiment 6
This example is by molecular formula Cu
1-
x-
y y
x b
y o prepares burden, wherein
x=0.008,
y=0.015.Initial raw materials is selected from copper hydroxide Cu (OH)
2, yttrium oxide Y
2o
3, boric acid H
3bO
3.Material preparation is by the processing step of following experiment:
(1) initial feed is pressed Cu
0.977y
0.008b
0.015o fills a prescription batching, takes Cu (OH)
228.4891 g, 0.4516 g Y
2o
3, 0.4637 g H
3bO
3;
(2) preparation process is identical with step (2) ~ (8) in embodiment 1.
Prepared material property is as shown in table 1, Fig. 1, Fig. 2 and Fig. 3.
Table 1 embodiment material performance index
Claims (3)
1. a negative temperature coefficient heat-sensitive resistance material, is characterized in that the composition of this material consists of Cu
1-
x-
y y
x b
y o, wherein
x=0.001 ~ 0.09;
y=0.001 ~ 0.05.
2. a type oxide Cu according to claim 1
1-
x-
y y
x b
y o based negative temperature coefficient thermistor material, is characterized in that: containing Cu, Y, B element in system component.
3. the Cu according to claim 1,2
1-
x-
y y
x b
y o based negative temperature coefficient thermistor material, the starting material preparing this thermistor can be the simple substance containing these elements, the compounds such as oxide compound, inorganic salt or organic salt.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967675A (en) * | 2016-05-06 | 2016-09-28 | 中南大学 | Novel NTC thermistor material suitable for low temperature preparation |
| CN105967677A (en) * | 2016-05-11 | 2016-09-28 | 中南大学 | Novel zinc-nickel oxide NTC (negative temperature coefficient) thermosensitive resistor material |
| CN107389218A (en) * | 2017-06-27 | 2017-11-24 | 苏州楚博生物技术有限公司 | A kind of thermo-sensitive material for sensor |
| CN110304905A (en) * | 2019-06-15 | 2019-10-08 | 山东格仑特电动科技有限公司 | A kind of copper samarium is the NTC thermistor material and preparation method thereof of semiconducting |
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2015
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Patent Citations (5)
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| R.N. JADHAV等: "Studies on the properties of Ni0.6Cu0.4Mn2O4 NTC ceramic due to Fe doping", 《CERAMICS INTERNATIONAL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105967675A (en) * | 2016-05-06 | 2016-09-28 | 中南大学 | Novel NTC thermistor material suitable for low temperature preparation |
| CN105967677A (en) * | 2016-05-11 | 2016-09-28 | 中南大学 | Novel zinc-nickel oxide NTC (negative temperature coefficient) thermosensitive resistor material |
| CN107389218A (en) * | 2017-06-27 | 2017-11-24 | 苏州楚博生物技术有限公司 | A kind of thermo-sensitive material for sensor |
| CN110304905A (en) * | 2019-06-15 | 2019-10-08 | 山东格仑特电动科技有限公司 | A kind of copper samarium is the NTC thermistor material and preparation method thereof of semiconducting |
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| CN104987059B (en) | 2019-10-18 |
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