CN1629215A - Temperature sensing material with negative temperature coefficient effect and method for preparing same - Google Patents
Temperature sensing material with negative temperature coefficient effect and method for preparing same Download PDFInfo
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- CN1629215A CN1629215A CN 200410067588 CN200410067588A CN1629215A CN 1629215 A CN1629215 A CN 1629215A CN 200410067588 CN200410067588 CN 200410067588 CN 200410067588 A CN200410067588 A CN 200410067588A CN 1629215 A CN1629215 A CN 1629215A
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Abstract
The invention provides a temperature sensing material with negative temperature coefficient effect and method for preparing process, wherein the NTC material comprises polymer, temperature-sensitive organic-inorganic composite powder and auxiliary agent, wherein the temperature on certain spot of the temperature-sensitive material changes, the resistance will be lowered substantially, thus the value of resistance of the detecting circuit will be changed greatly. The conductivity process of the temperature-sensitive material is realized through carrier supply by the temperature-sensitive organic-inorganic composite powder.
Description
Technical field
The present invention relates to chemical industry, electronic technology field, be specifically related to a kind of temperature sensing material and preparation method thereof with negative temperature coefficient effect (NTC).0-250 ℃ of this temperature sensing material use temperature scope can be used as restorability alarm cable, heat detector, apparatus overheat protector, temperature regulator etc.
Background technology
General temperature monitoring element such as thermopair, RTD, ceramic thermal resistance etc. are the temperature of energy measurement one narrow and small zone (can abstractly be a point) only.Then need carry out temperature monitoring in some occasion (as the open-air atmosphere of building, rainy nebelwind sand, various industrial site, inflammable and explosive hazardous area, protection tunnel, cable, conveying belt, various pipelines etc.) to big two dimensional surface zone.Big area heat detector commonly used at present can be divided into two classes: a class is destructive heat detector, and another kind of is the nondestructive heat detector.Destructive heat detector is disposable heat detector, the use cost height; Big area nondestructive heat detector mostly is external imported product at present greatly, and material cost is higher.
A kind of temperature sensing material with negative temperature coefficient effect (NTC) of the present invention's preparation belongs to nondestructive heat detection material; have the controlled characteristics of electrical specification such as resistance value, material constant, temperature coefficient of resistance; can in 0-250 ℃ temperature range, use, can be used for restorability alarm cable, heat detector, apparatus overheat protector, temperature regulator of heavy construction, various industrial sites etc.
Summary of the invention
The purpose of this invention is to provide a kind of temperature sensing material and preparation method thereof with negative temperature coefficient effect (NTC).This material can be used for the heat detector, equipment protecting equipment in various large-scale places etc.
The NTC temperature sensing material is a kind of compound-type conducting polymkeric substance, and its conducting process provides current carrier to realize by temperature-sensitive organic and inorganic composite powder.Conductive filler material is scattered in the polymkeric substance, and when temperature raise, polymer segment is lax to be accelerated, and the mutual migratory aptitude of conductive filler material increases, and has increased the chance of filler particles contact, resistivity decreased; When temperature reduced, segment was lax slack-off, and the mutual migratory aptitude of conductive filler material weakens, and resistivity raises.Speed τ=τ that segment is lax
0Exp (Δ E/RT), Δ E is an activation energy, T is a temperature, is directly proportional because conductive filler material movement velocity and segment are lax, so the natural logarithm of NTC compound-type conducting polymer resistive is relevant with inverse temperature.Resistance-temperature characteristic can myopia be represented with formula 1nR=B*1/T+k, wherein R is the resistance of material, B is a material constant, B value size can the visual representation temperature sensing material negative temperature coefficient effect, T is an absolute temperature, k is a constant, by control raw material composition, consumption and processing condition etc., and electrical specification that can control material.
The temperature sensing material that the present invention proposes with negative temperature coefficient effect, form by polymkeric substance, temperature-sensitive organic and inorganic composite powder, softening agent, stablizer, lubricant, processing aid, filler, specifically consist of: (1) polymkeric substance, consumption are 100 parts (weight ratios).This polymkeric substance can be used one or both of polyethylene, polyethylene/vinyl-acetic ester EVA, ethylene-propylene terpolymer EPDM, chloroprene rubber, polypropylene, polyvinyl chloride, polyvinylidene chloride, tetrafluoroethylene, polyvinylidene difluoride (PVDF); (2) temperature-sensitive organic and inorganic composite powder, consumption are 5-50 part, and this composite powder can be obtained by reactions such as metal powder, metal oxide powder, conductive polymers powder, coupling agent, auxiliary agents; (3) softening agent, consumption are 30-80 part.This softening agent can be one or more of phthalic acid ester class, polyester, citric acid ester type, phosphoric acid ester, epoxy soybean oils etc., as dibutyl phthalate, dioctyl phthalate (DOP), dioctyl maleate, polyester, citrate, clorafin, diphenyl octyl phosphate, epoxy soybean oil, epoxy soybean oil dioctyl phthalate, trimellitate; (4) thermo-stabilizers such as one or more lead salts stablizers, metallic soap class stablizer, sulphur-containing stabilizer, consumption is 3-20 part, as tribasic lead sulfate, dibasic lead phosphite, two alkali formula lead stearates, Dythal, Zinc Stearate, calcium laurate, Dodecyl Mercaptan dibutyl tin, dibutyl tin laurate, mercaptoacetate mercaptan antimony etc.; (5) lubricant quantity is 0.5-5 part.This lubricant can be one or more of wax, hard ester acid esters, amides lubricant, as clorafin, polyethylene wax, oxidized polyethlene wax, butyl stearate, octyl stearate, amine hydroxybenzene, stearic acid amide, erucicamide, N, N '-ethylenebis stearic acid amide; (6) processing aid, consumption are 0-10 part, a kind of as polymethyl methacrylate copolymer (ACR) class, a-Methylstyrene Low-Polymer (AMS) class, divinyl and acrylonitrile multipolymer (P83); (7) filler, consumption are 0-10 part, as one or more of lime carbonate, talcum powder, wollastonite, silicon-dioxide.
The above-mentioned preparation method with temperature sensing material of negative temperature coefficient effect that the present invention proposes is: in high-speed mixer, add temperature-sensitive organic and inorganic composite powder, softening agent, 500-1500 rev/min low speed mixing 2-5 minute, add other material (comprising polymkeric substance, stablizer, lubricant, processing aid, filler etc.) again, under 40-120 ℃ of airtight heating condition 2000-5000 rev/min high-speed mixing 5-15 minute; Plasticated 5-20 minute with Banbury mixer or forcing machine, granulation, moulding obtain having the temperature sensing material of negative temperature coefficient effect again.
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, and its used polymkeric substance is one or both in polyethylene, polyethylene/vinyl-acetic ester EVA, ethylene-propylene terpolymer EPDM, chloroprene rubber, polypropylene, polyvinyl chloride, polyvinylidene chloride, tetrafluoroethylene, the polyvinylidene difluoride (PVDF).
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, and its used temperature-sensitive organic and inorganic composite powder is to be obtained by reactions such as metal powder, metal oxide powder, conductive polymers powder, coupling agent, auxiliary agents.
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, and its used softening agent is one or more in dibutyl phthalate, dioctyl phthalate (DOP), dioctyl maleate, polyester, citrate, clorafin, diphenyl octyl phosphate, epoxy soybean oil, epoxy soybean oil dioctyl phthalate, the trimellitate.
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, and its used stablizer is one or more of tribasic lead sulfate, dibasic lead phosphite, two alkali formula lead stearates, Dythal, Zinc Stearate, calcium laurate, Dodecyl Mercaptan dibutyl tin, dibutyl tin laurate, mercaptoacetate mercaptan antimony etc.
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, its used lubricant is clorafin, polyethylene wax, oxidized polyethlene wax, butyl stearate, octyl stearate, amine hydroxybenzene, stearic acid amide, erucicamide, N, one or more in N '-ethylenebis stearic acid amide.
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, and its used processing aid is any of polymethyl methacrylate copolymer (ACR) class, a-Methylstyrene Low-Polymer (AMS) class, divinyl and acrylonitrile multipolymer (P83).
The preparation that the present invention proposes has the method for the temperature sensing material of negative temperature coefficient effect, and its used filler is one or more in lime carbonate, talcum powder, wollastonite, the silicon-dioxide etc.
The temperature sensing material with negative temperature coefficient effect of the present invention preparation need not pyroprocessing, adopts composite conductive polymer to make under normal temperature or low-heat condition, and actual use temperature scope is 0-250 ℃.The NTC temperature sensing material is non-destruction warning temperature sensing material; its conducting process provides current carrier to realize by temperature-sensitive organic and inorganic composite granule; have the controlled characteristics of electrical specification such as resistance value, material constant, temperature coefficient of resistance; simple in structure; can be used as heat detector, alarm cable, apparatus overheat protector, temperature regulator etc., and reusable.
Description of drawings
Fig. 1 is the sem photograph (SEM) of temperature sensing material sample section.
Fig. 2 is a temperature sensing material temperature-resistance relation curve (1nR-1/T) (1), 1mR=7165*1/T-23.3 among the figure, material constant B=7165.
Fig. 3 is a temperature sensing material temperature-resistance relation curve (1nR-1/T) (2), 1nR=5587*1/T-12.7 among the figure, material constant B=5587.
Embodiment
Embodiment 1:
In high-speed mixer, add 5 parts of temperature-sensitive organic and inorganic composite powders, 50 parts of dibutyl phthalates, 20 parts of epoxy soybean oils, mixed 5 minutes at 500 rev/mins, add 100 parts of polyvinyl chloride, 5 parts of tribasic lead sulfates, 5 parts of Dythals, 2 parts of oxidized polyethlene wax, ACR5 part, mixed 15 minutes at 80 ℃, 2500 rev/mins, plasticated 10 minutes with Banbury mixer, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Embodiment 2:
In high-speed mixer, add 45 parts of temperature-sensitive organic and inorganic composite powders, 60 parts of trimellitates, 20 parts of dioctyl maleates, 1000 rev/mins of low speed mixing 5 minutes, add polyethylene/vinyl-acetic ester EVA10 part, 90 parts of polyvinyl chloride, 10 parts of tribasic lead sulfates, 8 parts of dibasic lead phosphites, 2 parts of amine hydroxybenzenes, 3 parts of clorafins, 2 parts of talcum powder, mixed 10 minutes at 100 ℃ 2500 rev/mins, plasticated 20 minutes with forcing machine, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Embodiment 3:
In high-speed mixer, add 20 parts of temperature-sensitive organic and inorganic composite powders, 40 parts of dibutyl phthalates, 10 parts of epoxy soybean oil dioctyl phthalates, mixed 3 minutes at 1500 rev/mins, add 8 parts of 100 parts of chloroprene rubbers, 2 parts of Dodecyl Mercaptan dibutyl tins, 3 parts of Zinc Stearates, 3 parts of calcium laurates, 1 part of butyl stearate, 3 parts of clorafins, 1 part of erucicamide, AMS8 part, lime carbonate, 120 ℃ of 3500 rev/mins of high-speed mixing 12 minutes, plasticated 10 minutes with internal mixer, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Embodiment 4:
In high-speed mixer, add 10 parts of temperature-sensitive organic and inorganic composite powders, 10 parts of polyester, 10 parts of dioctyl phthalate (DOP)s, 10 parts of epoxy soybean oils, mixed 5 minutes at 1000 rev/mins, add 20 parts of ethylene-propylene terpolymers, 80 parts of polypropylene, 3 parts of Dythals, 2 parts of Zinc Stearates, 3 parts of calcium laurates, 3 parts of polyethylene waxs, 120 ℃ of 2500 rev/mins of high-speed mixing 10 minutes, plasticated 5 minutes with internal mixer, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Embodiment 5:
In high-speed mixer, add 30 parts of temperature-sensitive organic and inorganic composite powders, 10 parts of citrates, 30 parts of diphenyl octyl phosphates, 20 parts of dioctyl maleates, 1500 rev/mins of low speed mixing 5 minutes, add 50 parts of polyvinylidene chloride, 50 parts of tetrafluoroethylene, 8 parts of dibasic lead stearates, 8 parts of calcium laurates, 4 parts of stearic amides, 8 parts of silicon-dioxide, mixed 10 minutes at 120 ℃ 4000 rev/mins, plasticated 15 minutes with forcing machine, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Embodiment 6:
In high-speed mixer, add 40 parts of temperature-sensitive organic and inorganic composite powders, 70 parts of trimellitates, 10 parts of citrates, mixed 5 minutes at 1000 rev/mins, add 100 parts of polyethylene/vinyl-acetic esters, 10 parts of dibasic lead phosphites, 3 parts of two alkali formula lead stearates, 3 parts of Dythals, 0.5 part of butyl stearate, 2 parts of octyl stearates, 2 parts of erucicamides, 5 parts of divinyl and acrylonitrile multipolymers, at 100 ℃, 3000 rev/mins were mixed 10 minutes, plasticated 15 minutes with Banbury mixer, granulation, extrusion moulding obtains having the temperature sensing material of negative temperature coefficient effect.
Embodiment 7:
In high-speed mixer, add 15 parts of temperature-sensitive organic and inorganic composite powders, 10 parts of clorafins, 20 parts of citrates, 10 parts of epoxy soybean oils, mixed 4 minutes at 500 rev/mins, add 100 parts of polyvinylidene difluoride (PVDF), 3 parts of oxidized polyethlene wax, N, N '-1 part of ethylenebis stearic acid amide, 3 parts in lime carbonate 120 ℃ of 5000 rev/mins of high-speed mixing 15 minutes, were plasticated 20 minutes with internal mixer, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Embodiment 8:
In high-speed mixer, add 25 parts of temperature-sensitive organic and inorganic composite powders, 70 parts of dioctyl maleates, mixed 3 minutes at 1000 rev/mins, add 10 parts of 40 parts of chloroprene rubbers, 60 parts of polypropylene, 3 parts in mercaptoacetate mercaptan antimony, 1 part of octyl stearate, 1 part of polyethylene wax, ACR10 part, wollastonite, 110 ℃ of 3000 rev/mins of high-speed mixing 5 minutes, plasticated 7 minutes with internal mixer, granulation, extrusion moulding obtain having the temperature sensing material of negative temperature coefficient effect.
Claims (9)
1. the temperature sensing material with negative temperature coefficient effect is characterized in that being made up of through mixing polymkeric substance, temperature-sensitive organic and inorganic composite powder, softening agent, stablizer, lubricant, processing aid, filler, and wherein the weight proportion of each component is as follows:
Form part by weight
Polymkeric substance 100
Temperature-sensitive organic and inorganic composite powder 5-50
Softening agent 30-80
Stablizer 3-20
Lubricant 0.5-5
Processing aid 0-10
Filler 0-10
2. the temperature sensing material with negative temperature coefficient effect according to claim 1 is characterized in that polymkeric substance is one or both in polyethylene, polyethylene/vinyl-acetic ester EVA, ethylene-propylene terpolymer EPDM, chloroprene rubber, polypropylene, polyvinyl chloride, polyvinylidene chloride, tetrafluoroethylene, the polyvinylidene difluoride (PVDF).
3. the temperature sensing material with negative temperature coefficient effect according to claim 1 is characterized in that temperature-sensitive organic and inorganic composite powder is to be obtained by metal powder, metal oxide powder, conductive polymers powder, coupling agent, auxiliary agent reaction.
4. the temperature sensing material with negative temperature coefficient effect according to claim 1 is characterized in that softening agent is one or more of phthalic acid ester class, polyester, citric acid ester type, phosphoric acid ester, epoxy soybean oils.
5. the temperature sensing material with negative temperature coefficient effect according to claim 1 is characterized in that stablizer is one or more of lead salts stablizer, metallic soap class stablizer, sulphur-containing stabilizer.
6. the temperature sensing material with negative temperature coefficient effect according to claim 1 is characterized in that lubricant is one or more in wax, hard ester acid esters, the amides lubricant.
7. the temperature sensing material with negative temperature coefficient effect according to claim 1 is characterized in that processing aid is any of polymethyl methacrylate copolymer class, a-Methylstyrene Low-Polymer class, divinyl and acrylonitrile multipolymer.
8. the temperature sensing material with negative temperature coefficient effect according to claim 1, it is characterized in that filler is one or more in lime carbonate, talcum powder, wollastonite, the silicon-dioxide etc.
9. one kind as the described preparation method with temperature sensing material of negative temperature coefficient effect of one of claim 1～8, it is characterized in that concrete steps are as follows: in high-speed mixer, add temperature-sensitive organic and inorganic composite powder, softening agent, 500-1500 rev/min low speed mixing 2-5 minute, add other material again, under 40-120 ℃ of airtight heating condition 2000-5000 rev/min high-speed mixing 5-15 minute; Plasticated 5-20 minute with Banbury mixer or forcing machine, granulation, moulding obtain having the temperature sensing material of negative temperature coefficient effect again.
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| CN 200410067588 CN1629215A (en) | 2004-10-28 | 2004-10-28 | Temperature sensing material with negative temperature coefficient effect and method for preparing same |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585502A (en) * | 2012-02-23 | 2012-07-18 | 南昌航空大学 | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect |
| CN103122106A (en) * | 2011-11-18 | 2013-05-29 | 滁州格美特科技有限公司 | Modified plastic and manufacturing method and application for same |
| CN104356535A (en) * | 2014-10-24 | 2015-02-18 | 江苏亨通光电股份有限公司 | Composite polyvinyl chloride material with negative temperature coefficient effect and preparation method thereof |
| CN105139949A (en) * | 2015-09-22 | 2015-12-09 | 重庆瑞普电缆有限公司 | Fire-proof and water-proof and temperature sensing cable and manufacturing method thereof |
| CN105199270A (en) * | 2015-10-27 | 2015-12-30 | 苏州宽温电子科技有限公司 | Flame-retardant sheath material for electric wire and preparation method thereof |
| CN105282887A (en) * | 2015-11-20 | 2016-01-27 | 王崇 | A low starting current self-temperature limiting tracing band and a manufacture device and a manufacture method thereof |
| CN113400509A (en) * | 2021-07-09 | 2021-09-17 | 惠州市大义塑胶新材料有限公司 | Preparation method, device and application of modified PVC material with NTC effect |
| CN115873386A (en) * | 2023-02-20 | 2023-03-31 | 广东金驭科技有限公司 | Composite organic temperature sensing material, preparation method thereof and fuse |
-
2004
- 2004-10-28 CN CN 200410067588 patent/CN1629215A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122106A (en) * | 2011-11-18 | 2013-05-29 | 滁州格美特科技有限公司 | Modified plastic and manufacturing method and application for same |
| CN103122106B (en) * | 2011-11-18 | 2016-01-06 | 滁州格美特科技有限公司 | A kind of modified plastics and its production and use |
| CN102585502A (en) * | 2012-02-23 | 2012-07-18 | 南昌航空大学 | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect |
| CN102585502B (en) * | 2012-02-23 | 2013-10-23 | 南昌航空大学 | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect |
| CN104356535A (en) * | 2014-10-24 | 2015-02-18 | 江苏亨通光电股份有限公司 | Composite polyvinyl chloride material with negative temperature coefficient effect and preparation method thereof |
| CN105139949A (en) * | 2015-09-22 | 2015-12-09 | 重庆瑞普电缆有限公司 | Fire-proof and water-proof and temperature sensing cable and manufacturing method thereof |
| CN105199270A (en) * | 2015-10-27 | 2015-12-30 | 苏州宽温电子科技有限公司 | Flame-retardant sheath material for electric wire and preparation method thereof |
| CN105282887A (en) * | 2015-11-20 | 2016-01-27 | 王崇 | A low starting current self-temperature limiting tracing band and a manufacture device and a manufacture method thereof |
| CN105282887B (en) * | 2015-11-20 | 2018-04-13 | 王崇 | A kind of low starting current self-limiting heating cable and its manufacture device and manufacture method |
| CN113400509A (en) * | 2021-07-09 | 2021-09-17 | 惠州市大义塑胶新材料有限公司 | Preparation method, device and application of modified PVC material with NTC effect |
| CN115873386A (en) * | 2023-02-20 | 2023-03-31 | 广东金驭科技有限公司 | Composite organic temperature sensing material, preparation method thereof and fuse |
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