CN101046416A - Linear critical NTC thermistor thermometric element and its prepn process - Google Patents
Linear critical NTC thermistor thermometric element and its prepn process Download PDFInfo
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- CN101046416A CN101046416A CN 200710017713 CN200710017713A CN101046416A CN 101046416 A CN101046416 A CN 101046416A CN 200710017713 CN200710017713 CN 200710017713 CN 200710017713 A CN200710017713 A CN 200710017713A CN 101046416 A CN101046416 A CN 101046416A
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Abstract
The present invention discloses one kind of linear thermometric element in use temperature range of 250-500 deg.c and its preparation process. The preparation process includes the first preparation of Ni2O3-Cr2O3-Fe2O3-In2O3 based thermosensitive semiconductor ceramic powder, the subsequent adding adhesive and lubricant, extruding into rod while threading at least one axial electrode wire, drying at 600-1000 deg.c for 0.5-1 hr for setting, setting into metal tube, drawing for 3-5 times and annealing to obtain the linear thermometric element. The linear thermometric element has the electrode wire and the metal tube as two electrodes, and possesses high resistance at normal temperature and rapid lowering resistance at high temperature or in fire. With the temperature switch characteristic, the linear thermometric element may be used in temperature control, alarming and overheat protection.
Description
Technical field
The present invention relates to a kind of temperature sensor and manufacture method thereof, particularly a kind of linear critical NTC thermistor thermometric element and preparation method thereof,
Background technology
The engine system of various large-scale heavy duty vehicles and kinematic train are all worked under harsh working environment; the factor of various inside and outside causes the too high fire that causes of these positions Yin Wendu through regular meeting; be necessary to develop the temperature element that fire alarm detects and protects is carried out in the engines three-dimensional space, guarantee the safety of equipment.But the complex structure in transmission space because vehicle powertrain is unified, remaining space complications, narrow and small, various somes thermometrys, as thermopair, thermal resistance, ceramic thermal resistance etc. be the temperature in a narrow and small zone of energy measurement only, can't effectively monitor total system.The configuration of secondary meter is also very difficult, can't use conventional point thermometric components and parts to realize effective three dimensions fire alarm monitoring.
The distributed temperature measuring system solves the complex three-dimensional space temperature to measure and the effective means of controlling, wherein the ultimate principle of optical fiber type temperature distribution measuring apparatus is that laser pulse is mapped in the optical fiber, according to arriving the stoke in the Returning scattering light everywhere and the ratio of anti-stoke light, try to achieve relevant temperature.But the optical fiber type temperature distribution measuring apparatus is except optical fiber, also comprise temperature measuring device and data processor, wherein temperature measuring device is made up of the system of more complicated, complex structure, bulky, while its resolution of ranging (1m), temperature-measuring range (0～370 ℃) and thermometric time (3min) also can't directly use at narrow space.
It is reported, adopt a kind of wire thermally sensitive temperature exploration cable to be used for distributed temperature measuring abroad.Its basic structure is outer armouring metal tube, and interior is the oxide ceramics thermo-sensitive material, and two of parallel layouts with metal tube or Single lead silk are embedded in the thermal sensitive ceramics.When ambient temperature changes, the thermo-sensitive material resistance value in the cable will change thereupon, and its relation meets R=Ae
B/T, this cable is coupled together the temperature that just can measure, control the large tracts of land scope by certain method.The temperature-sensitive exploration cable that adopts thermal sensitive ceramic material to make can satisfy requirement narrow and small, the complex space three-dimensional temperature measuring, also can work under abominable complex environment, but adopt which kind of ceramic thermo-sensitive material and the technology how to prepare has had no open report.
Domestic Chongqing instrument Research Institute goes out the armouring thermistor temp exploration cable of Fe-Al-Mn-O series, but its usable range is 100-350 ℃, its temperature index can't satisfy the request for utilization of higher temperature, the request for utilization under harsh high-temperature work environment as large-scale heavy duty automotive power and kinematic train.
Summary of the invention
The present invention is directed to the out of use defective of temperature range that present point type and distributed temperature measuring element exist, a kind of wire temperature element that is suitable for 250～500 ℃ of scopes uses of temperature and preparation method thereof is provided.The resistance of this element keeps a quite high order of magnitude at normal temperature, and when in the space that distributes overtemperature or fire condition taking place, its resistance sharply reduces, and undergos mutation, and shows the temperature switch characteristic, to realize control, warning and the overtemperature protection to temperature.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of linear critical NTC thermistor thermometric element, comprise a stainless steel tube, be provided with the resistance core body in this stainless steel tube, in this resistance core body, be embedded with at least one wire electrode, this wire electrode arranges to interting along the resistor core axon from the position, the center of circle of described resistance core body, it is characterized in that described resistance core body is Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the bar-shaped core body of the heat-sensitive semiconductive ceramic of base, described wire electrode is that diameter is the stainless steel wire of 0.2～0.5mm.
A kind of critical subzero temperature thermistor wire temperature element preparation method: prepare earlier Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the synthetic powder of the heat-sensitive semiconductive ceramic of base; In this ceramic powder, add again binding agent and lubricant, extrusion modling is the bar-shaped core body of diameter 2～3mm, during extruding at this position, bar-shaped core body center of circle along the stock core axon to interting the stainless steel electrode silk of at least one 0.2～0.3mm, the bar-shaped core body that will penetrate again wire electrode places the typing in 0.5～1 hour of 600～1000 ℃ of dryings, in the metal tube with its corresponding internal diameter of packing into, at last this is equipped with the metal tube of bar-shaped core body through 3～5 cold-drawns and corresponding annealing in process, finally obtaining external diameter is the negative temperature coefficient resister wire temperature element with high-critical temperature of 2mm.
In the such scheme, the binding agent that adds in the described ceramic powder is kaolin, and lubricant is boiled wood oil; Described Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3For the preparation method of the synthetic powder of the heat-sensitive semiconductive ceramic of base is:
1) presses mass percent: Ni
2O
310～20%, Cr
2O
35～35%, Fe
2O
330～50%, In
2O
310～15%, CuO 5～15%, Al
2O
34～10% proportion scale weighing, mixing;
2) compound is put into ball grinder, use ethanol as medium, wet ball grinding 24 hours;
3) ball milling is good powder was put into 70 ℃ of dryings of baking oven 24 hours;
4) dried feed was ground the sieve that the aperture is 0.075mm;
5) powder after will sieving is put into crucible, places the resistance furnace calcining synthetic, and synthesis temperature is 1000～1100 ℃, is incubated 2～3 hours, cools off with stove;
6) adding mass percent in the synthetic porcelain after coming out of the stove is 15～20% Al
2O
3, and in mortar, mixed after 0.5 hour again dry ball milling 4 hours;
7) the synthetic powder behind the ball milling is crossed the 0.075mm sieve, namely made the synthetic powder of heat-sensitive semiconductive ceramic;
The synthetic powder of critical NTC coefficient heat-sensitive semiconductive ceramic of the present invention added Al again before dry ball milling
2O
3Component can significantly improve the low temperature static resistivity of ceramic powder; The In that adds certain content
2O
3, can regulate and control the critical-temperature transition point of thermistor, and can adjust resistivity of material at the temperature-coefficient of electrical resistance in critical-temperature interval.The wire temperature detection device for preparing has the CRT resistance-temperature curve of good form.
Compare with existing armouring thermistor temp exploration cable, the present invention is owing to adopted Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the synthetic powder of the critical NTC coefficient thermosensitive ceramics of base, therefore the critical-temperature that its resistivity of wire temperature element that makes is undergone mutation is 250～500 ℃ of scopes, its resistivity keeps a quite high order of magnitude (10～15 megohms/centimetre) at low temperature, thereby can be applied to the instructions for use under the harsh working environment of higher temperature of large-scale heavy duty automotive power and transmission system, also can be applicable to temperature monitoring, control and warning under the like environment.
Description of drawings
Fig. 1 is the axial arrangement figure of wire temperature element of the present invention.
Fig. 2 is the longitudinal section view of Fig. 1.
Fig. 3 is the resistance-temperature curve of the wire temperature detection device of the embodiment of the invention 3.
Embodiment
The present invention is described in further detail below in conjunction with drawings and Examples.
As shown in Figure 1, a kind of critical subzero temperature thermistor wire temperature element comprises the stainless steel tube 2 that an external diameter is 2mm, is provided with resistance core body 1 in this stainless steel tube 2, is embedded with at least one wire electrode 3 in this resistance core body 1, and resistance core body 1 is by Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the bar-shaped core body that critical NTC coefficient heat-sensitive semiconductor ceramic material is made, this bar-shaped core body is packed in the stainless steel tube 2 of corresponding internal diameter; Described wire electrode 3 is the stainless steel wire of 0.2～0.3mm, and this wire electrode 3 arranges to interting along the stock core axon from the position, the center of circle of described bar-shaped core body.Described Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3The preparation method who is critical NTC coefficient thermosensitive ceramics powder is:
1) presses mass percent: Ni
2O
39.8～20%, Cr
2O
35～35%, Fe
2O
330～50%, In
2O
38～15%, CuO 5～15%, Al
2O
34～10% proportion scale weighing, mixing, its composition is as shown in table 1;
Table 1 Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3For the heat-sensitive semiconductive ceramic powder of base is formed and synthetic technological condition
| Form code name | Form (quality %) | Calcination condition | Extraneous component (quality %) | ||||||
| Ni 2O 3 | Cr 2O 3 | Fe 2O 3 | In 2O 3 | CuO | Al 2O 3 | Temperature (℃) | Insulation (h) | Al 2O 3 | |
| A | 9.80 | 25.50 | 40.50 | 9.20 | 9.00 | 7.00 | 1000 | 2 | 16.00 |
| B | 20.00 | 20.00 | 30.00 | 10.00 | 10.00 | 10.00 | 1000 | 2 | 15.00 |
| C | 10.00 | 5.00 | 50.00 | 15.00 | 15.00 | 5.00 | 1100 | 2 | 20.00 |
| D | 11.50 | 32.00 | 35.00 | 12.50 | 5.00 | 4.00 | 1100 | 3 | 18.00 |
2) compound is put into ball grinder, use ethanol as medium, wet ball grinding 24 hours;
3) ball milling is good powder was put into 70 ℃ of dryings of baking oven 24 hours;
4) dried feed being ground the aperture is the 0.075mm sieve;
5) powder after will sieving is put into crucible, places resistance furnace, under air conditions calcining synthetic, synthesis temperature is 1000～1100 ℃, is incubated 2～3 hours, cools off with stove;
6) adding mass percent in the synthetic porcelain after coming out of the stove is 15～20% Al
2O
3, and in mortar, mixed after 0.5 hour again dry ball milling 4 hours;
7) the synthetic powder behind the ball milling is crossed the 0.075mm sieve, promptly made the heat-sensitive semiconductive ceramic powder of critical NTC coefficient.
Prepare earlier Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the heat-sensitive semiconductive ceramic powder of base, it consists of the A in the table 1; Add the kaolin of 5% quality as binding agent at this ceramic powder again, the boiled wood oil of 2% quality is as lubricant and an amount of water, evenly mix, mixed 1 hour at mixer or edge runner, ageing mixture after 8 hours extrusion modling be the bar-shaped core body of diameter 2mm, during extruding at this position, bar-shaped core body center of circle along the stock core axon to the parallel stainless steel electrode silk that interts 1 0.2mm, the bar-shaped core body that will penetrate again wire electrode places resistance furnace, slowly be heated to the typing in 0.5 hour of 600 ℃ of dryings under the air, in the stainless steel tube with its corresponding internal diameter of packing into, the stainless steel tube of bar-shaped core body at last this is equipped with through 3 cold-drawns, through 550 ℃ of annealing in process, finally obtaining external diameter is the negative temperature coefficient resister wire temperature element with high-critical temperature of 2mm.
Prepare earlier Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Heat-sensitive semiconductive ceramic powder for base, it consists of the B in the table 1, the diameter of bar-shaped core body extrusion modling is 2.5mm, during extruding at this position, bar-shaped core body center of circle along the stock core axon to interting the stainless steel electrode silk of 2 0.2mm, to penetrate the bar-shaped core body of wire electrode in the typing in 1 hour of 800 ℃ of dryings, the stainless steel tube of bar-shaped core body is housed through 4 cold-drawns, all the other technologies are with embodiment 1, and finally obtaining the stainless steel external diameter is the negative temperature coefficient resister wire temperature element with high-critical temperature of 2mm.
Prepare earlier Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Heat-sensitive semiconductive ceramic powder for base, it consists of the C in the table 1, the diameter of bar-shaped core body extrusion modling is 3mm, during extruding at this position, bar-shaped core body center of circle along the stock core axon to the parallel stainless steel electrode silk that interts 2 0.3mm, to penetrate again the bar-shaped core body of wire electrode in the typing in 1 hour of 1000 ℃ of dryings, the stainless steel tube of bar-shaped core body is housed through 5 cold-drawns, all the other technologies are with embodiment 1, and finally obtaining core diameter is the negative temperature coefficient resister wire temperature element with high-critical temperature of 2mm.
Embodiment 4
Prepare earlier Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Heat-sensitive semiconductive ceramic powder for base, it consists of the D in the table 1, the diameter of bar-shaped core body extrusion modling is 3mm, during extruding at this position, bar-shaped core body center of circle along the stock core axon to the parallel stainless steel electrode silk that interts 2 0.3mm, to penetrate again the bar-shaped core body of wire electrode in the typing in 1 hour of 1000 ℃ of dryings, the stainless steel that bar-shaped core body is housed belongs to pipe through 5 cold-drawns, all the other technologies are with embodiment 1, and finally obtaining core diameter is the negative temperature coefficient resister wire temperature element with high-critical temperature of 2mm.
Table 2 has been listed Ni of the present invention
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3-CuO-Al
2O
3Be the temperature characterisitic of heat-sensitive semiconductive ceramic powder, Fig. 3 shows the resistance-temperature curve of the wire temperature detection device of embodiments of the invention 3, and as can be seen from Figure 3, it has good critical temperature resistor (CRT) relation.
The resistance-temperature characteristic of table 2 thermistor ceramic powder of the present invention
| Form code name | Low temperature static resistivity Ω .cm | Critical-temperature ℃ | High temperature static resistivity Ω .cm |
| A | 10.8M | 250 | 910 |
| B | 13.2M | 290 | 932 |
| C | 15.0M | 480 | 974 |
| D | 10.2M | 395 | 893 |
Claims (7)
1. linear critical NTC thermistor thermometric element, comprise a stainless steel tube, be provided with the resistance core body in this stainless steel tube, in this resistance core body, be embedded with at least one wire electrode, this wire electrode arranges to interting along the resistor core axon from the position, the center of circle of described resistance core body, it is characterized in that described resistance core body is Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the bar-shaped core body of the heat-sensitive semiconductive ceramic of base, described wire electrode is that diameter is the stainless steel wire of 0.2～0.3mm.
2. linear critical NTC thermistor thermometric element as claimed in claim 1 is characterized in that, described Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3The component that comprises following mass percent for the bar-shaped core body of the heat-sensitive semiconductive ceramic of base: Ni
2O
310～20%, Cr
2O
35～35%, Fe
2O
330～50%, In
2O
310～15%, CuO 5～15%, Al
2O
34～10%.
3. the preparation method of linear critical NTC thermistor thermometric element as claimed in claim 1 is characterized in that, prepares earlier Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3Be the synthetic powder of the heat-sensitive semiconductive ceramic of base; In this ceramic powder, add again binding agent and lubricant, being squeezed into diameter is the bar-shaped core body of 2～3mm, during extruding in this bar-shaped core body centre along the stock core axon to interting the stainless steel electrode silk of at least one 0.2～0.3mm, the bar-shaped core body that will penetrate again wire electrode placed 600～1000 ℃ of dryings 0.5～1 hour, in the metal tube with its corresponding internal diameter of packing into, this metal tube that bar-shaped core body is housed is obtained the negative temperature coefficient resister wire temperature element with high-critical temperature that external diameter is 2mm through 3～5 cold-drawns and annealing in process.
4. the preparation method of linear critical NTC thermistor thermometric element as claimed in claim 3 is characterized in that, described Ni
2O
3-Cr
2O
3-Fe
2O
3-In
2O
3For the preparation method of the synthetic powder of the heat-sensitive semiconductive ceramic of base comprises the steps:
1) presses mass percent: Ni
2O
310～20%, Cr
2O
35～35%, Fe
2O
330～50%, In
2O
310～15%, CuO 5～15%, Al
2O
34～10% proportion scale weighing, mixing;
2) compound is put into ball grinder, use ethanol as medium, wet ball grinding 24 hours;
3) ball milling is good powder was put into 70 ℃ of dryings of baking oven 24 hours;
4) dried feed being ground the aperture is the 0.075mm sieve;
5) powder after will sieving is put into crucible, places the resistance furnace calcining synthetic, and synthesis temperature is 1000～1100 ℃, is incubated 2～3 hours, cools off with stove;
6) adding mass percent in the synthetic porcelain after coming out of the stove is 15～20% Al
2O
3, and in mortar, mixed after 0.5 hour again dry ball milling 4 hours;
7) the synthetic powder behind the ball milling is crossed the 0.075mm sieve, namely made the synthetic powder of heat-sensitive semiconductive ceramic.
5. the preparation method of linear critical NTC thermistor thermometric element as claimed in claim 3 is characterized in that, the cementing agent that adds in the described ceramic powder is a porcelain earth, and addition is 5% of a ceramic powder quality.
6. the preparation method of linear critical NTC thermistor thermometric element as claimed in claim 3 is characterized in that, the lubricant that adds in the described ceramic powder is a boiled wood oil, and addition is 2% of a ceramic powder quality.
7.. the preparation method of linear critical NTC thermistor thermometric element as claimed in claim 3 is characterized in that, the temperature of described annealing in process is 550 ℃.
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|---|---|---|---|
| CNB2007100177139A CN100485332C (en) | 2007-04-20 | 2007-04-20 | Linear critical NTC thermistor thermometric element and its preparation process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100177139A CN100485332C (en) | 2007-04-20 | 2007-04-20 | Linear critical NTC thermistor thermometric element and its preparation process |
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| Publication Number | Publication Date |
|---|---|
| CN101046416A true CN101046416A (en) | 2007-10-03 |
| CN100485332C CN100485332C (en) | 2009-05-06 |
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353471A (en) * | 2011-07-06 | 2012-02-15 | 西安交通大学 | Linear temperature sensor and manufacturing method thereof |
| US8840302B2 (en) | 2012-02-09 | 2014-09-23 | Hyundai Motor Company | Composite material for a temperature sensor, and a method of manufacturing a temperature sensor using the same |
| CN104446391A (en) * | 2014-11-28 | 2015-03-25 | 成都德兰特电子科技有限公司 | NTC (negative temperature coefficient) thermistor material with high B value and, high electrical resistivity and preparation method of thermistor material |
-
2007
- 2007-04-20 CN CNB2007100177139A patent/CN100485332C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102353471A (en) * | 2011-07-06 | 2012-02-15 | 西安交通大学 | Linear temperature sensor and manufacturing method thereof |
| US8840302B2 (en) | 2012-02-09 | 2014-09-23 | Hyundai Motor Company | Composite material for a temperature sensor, and a method of manufacturing a temperature sensor using the same |
| US9404805B2 (en) | 2012-02-09 | 2016-08-02 | Hyundai Motor Company | Composite material for a temperature sensor, and a method of manufacturing a temperature sensor using the same |
| CN104446391A (en) * | 2014-11-28 | 2015-03-25 | 成都德兰特电子科技有限公司 | NTC (negative temperature coefficient) thermistor material with high B value and, high electrical resistivity and preparation method of thermistor material |
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| Publication number | Publication date |
|---|---|
| CN100485332C (en) | 2009-05-06 |
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