CN101870783B - Polyvinyl PTC thermo-sensitive conductive composite material and manufacturing method thereof - Google Patents
Polyvinyl PTC thermo-sensitive conductive composite material and manufacturing method thereof Download PDFInfo
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- CN101870783B CN101870783B CN2010102118508A CN201010211850A CN101870783B CN 101870783 B CN101870783 B CN 101870783B CN 2010102118508 A CN2010102118508 A CN 2010102118508A CN 201010211850 A CN201010211850 A CN 201010211850A CN 101870783 B CN101870783 B CN 101870783B
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- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title description 4
- 239000000463 material Substances 0.000 claims abstract description 40
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 28
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 28
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract description 10
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims abstract description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract 3
- 229920001684 low density polyethylene Polymers 0.000 claims abstract 3
- 239000004702 low-density polyethylene Substances 0.000 claims abstract 3
- 239000006229 carbon black Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 9
- -1 2-CB compound Chemical class 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims 1
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 3
- 230000000996 additive effect Effects 0.000 abstract 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 abstract 1
- 239000005416 organic matter Substances 0.000 abstract 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000005382 thermal cycling Methods 0.000 description 4
- 238000003466 welding Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Thermistors And Varistors (AREA)
Abstract
The invention relates to a polyvinyl PTC thermo-sensitive conductive composite material, which comprises a base material and an additive, wherein the base material comprises 10-25% of LDPE, 20-40% of TiB2, 0-8% of CB and the balance of HDPE, and the additive comprises 0.1-0.3% of antioxidant1010, 1-3% of stearic acid, 1-2% vinyl trimethoxysilane, 3-5% of Sb2O3 and 8-12% of decabromodiphenyl ethane; and the adding amount of the additive is measured by the mass of organic matter components in the base material. The material has room temperature resistivity of 23.5omega . cm, long-term current capacity flow of greater than 100A and PTC intensity of 7.8, and resistance keeps stable after 100 thermal cycles.
Description
One, technical field
The present invention relates to a kind of high molecular based PTC material and preparation method thereof, exactly is a kind of polyvinyl PTC thermo-sensitive conductive composite material and manufacture method thereof
Two, background technology
Organic positive temperature coefficient (PTC) electro-conductive material that is made of conductive additive and polymkeric substance is current development one of functional high molecule material very rapidly.Ptc material as overheated, overcurrent protection be widely used in communicating by letter from the temperature control heating material, in the various fields such as computer, automobile, Industry Control, household electrical appliance.Present organic PTC material is a conductive filler material with graphite and carbon black mainly, its room temperature resistance wider distribution, and PTC intensity is little, thermotolerance and stability are lower, and yield rate is lower during preparation.The ceramic base ptc material is in aspect better performances such as acting characteristic, little current protection ability, anti-pulse high current impact capacities; but because ceramic base ptc material room temperature resistance is higher; rise relatively slow at its temperature range internal resistance more than Curie temperature with temperature; none is similar to sudden change of resistivity process like the safety fuse, so its total overcurrent protection performance is superior not as the high molecular based PTC material.In addition, the ceramic base ptc material is crisp, and processing and shaping are all difficult, and price is also more expensive.
Three, summary of the invention
Purpose of the present invention is exactly in order to overcome the deficiency that above-mentioned technology exists, and a kind of polyvinyl PTC thermo-sensitive conductive composite material and manufacture method thereof that possesses low room temperature resistivity, high pressure resistant, anti-big electric current, long-term through-flow stable performance, high PTC intensity and high PTC stability is provided.
The alleged polyvinyl PTC thermo-sensitive conductive composite material of the present invention is a kind of polyethylene/TiB2-carbon black (HDPE/LDPE/TiB
2-CB) PTC thermo-sensitive conductive composite material is made of base-material and auxiliary agent, and described base-material has the organic constituents and the inorganics component of following mass percent:
New LDPE (film grade) (LDPE) 10～25%
TiB2 (TiB
2) 20～40%
Carbon black (CB) 0～8%
High density polyethylene(HDPE) (HDPE) surplus;
Contained auxiliary agent is by the mass percent of organic constituents in the base-material, promptly in LDPE and HDPE quality:
Antioxidant 1010 0.1～0.3%
Stearic acid 1～3%
Vinyltrimethoxy silane 1～2%
Antimonous oxide (Sb
2O
3) 3～5%
TDE 8～12%
The preparation method of this polyvinyl PTC thermo-sensitive conductive composite material comprises batch mixing, mold pressing, radiation and freezing, it is characterized in that described batch mixing is exactly at first with the TiB of proportional quantity
2Mix under normal temperature, normal pressure with CB, obtain TiB
2-CB compound powder (when CB content was zero, this go on foot omissions certainly), then with the base-material of proportional quantity in each auxiliary agent of other two kinds of organic constituentses and calculated amount in mixing roll in 160～200 ℃ times mixing mixing materials that evenly obtain; Send in the moulding press under 160 ± 10 ℃, pressure 5～15MPa mold pressing to obtain containing the PTC chip of electrode slice mixing materials; With the PTC chip with gamma-rays or crosslinking electron beam irradiation, dosage 120～160KGy; With the PTC chip thermal treatment behind the irradiation 2～3 hours, thermal treatment temp should be higher than the HDPE melting temperature more than 50 ℃; With the freezing treatment 1～2 hour under-20～-40 ℃ of conditions of the PTC chip after the thermal treatment.
Compared with the prior art, beneficial effect of the present invention is embodied in:
In the matrix material of the present invention with TiB2 (TiB
2) be main conductive filler material, be matrix with the polyethylene, and add carbon black, form polyethylene/TiB2-carbon black (HDPE/LDPE/TiB
2-CB) conducing composite material.TiB2 has excellent properties such as high conduction, high heat conduction, oxidation resistance temperature height, has the effect of strengthening anti-stream, withstand voltage and raising resistance change stability; Carbon black (CB) has the effect that connects the TiB2 conductive chain, improves conductive network and conductivity; Crystallinity polyethylene matrix provides the amorphous phase conduction region, and has the effect that changes the conductive network structure.With polyethylene/carbon ink, polyethylene/graphite and other polymer-based carbon/charcoals in the prior art is that the PTC matrix material is compared, when guaranteeing low room temperature resistivity (minimum observed value is 23.5 Ω cm), has long-term through-flow through-current capability, high PTC intensity (highest measurement value is 7.8) and high PTC stability (thermal cycling 100 times after resistance change keep stablizing) greater than 100A.
Four, embodiment
It is following that the present invention is further illustrated according to embodiment:
Embodiment 1:
Will be as crystallinity high density polyethylene(HDPE) (HDPE, degree of crystallinity surpasses 90%, 130 ℃ of fusing points), the straight chain shape new LDPE (film grade) (110 ℃ of LDPE, fusing points) of polymer matrix and TiB2 powder (TiB with electroconductibility
2Resistivity: 14.4 μ Ω cm) according to 4: 2: 4 ratios (mass ratio) batching and mixing, add oxidation inhibitor, stearic acid, vinyltrimethoxy silane coupling agent, antimonous oxide fire retardant, TDE fire retardant according to 0.1%, 2.0%, 1.0%, 3.0%, 8.0% of organic constituents quality in the base-material respectively, under 180 ℃ on double roll mill mixing 30min, obtain mixing thing.
With resulting mixing thing be added in put into diameter be 18mm foil electrode sheet from molding jig, with being set at 160 ℃, the thermocompressor compression molding of 10MPa, the diameter that obtains comprising electrode is that 22mm, thickness are the disk shape PTC chip of 500 μ m.Again with this composite sheet gamma-rays (Co
60) radiation crosslinking, dosage is 160KGy.Behind compressing tablet, irradiation, chip is placed the heating installation 3 hours of 50 ℃ of the above temperature of high molecular polymer fusing point earlier, rapidly it is transferred to then and makes its cooling 2 hours rapidly in-30 ℃ the refrigerating apparatus.Use lead-free low-temperature welding compound (liquidus line is 204 ℃) that the copper cash of diameter as 0.2mm is welded on its two interarea, obtain the thermistor element sample.
Performance evaluation: room temperature (25 ℃) zero power resistance is 14m Ω, PTC intensity reaches more than 8.3, it is placed 5min on 200 ℃ of hot plates indeformable, its room temperature resistance is still below 30m Ω after thermal cycling between-20 ℃ and 140 ℃ 200 times with it, and the changes in resistance situation is stable in thermal cycling.
Embodiment 2:
Will be as crystallinity high density polyethylene(HDPE) (HDPE, degree of crystallinity surpasses 90%, 130 ℃ of fusing points), the straight chain shape new LDPE (film grade) (110 ℃ of LDPE, fusing points) of polymer matrix and TiB2 powder (TiB with electroconductibility
2, resistivity: 14.4 μ Ω cm) and carbon black (CB) according to 50: 20: 27: 3 ratio (mass ratio) batching.Respectively according to 0.1%, 2.0%, 1.0%, 3.0%, 8.0% batching oxidation inhibitor, stearic acid, vinyltrimethoxy silane coupling agent, antimonous oxide fire retardant, the TDE fire retardant of organic constituents quality, at first with TiB
2Mixed 2 hours down with CB normal temperature, normal pressure, then with other components together under 180 ℃ on double roll mill mixing 30min, obtain mixing thing.
With resulting mixing thing be added in put into diameter be 18mm foil electrode sheet from molding jig, with being set at 160 ℃, the thermocompressor compression molding of 10MPa, the diameter that obtains comprising electrode is that 22mm, thickness are the disk shape PTC chip of 500 μ m.Again with this composite sheet gamma-rays (Co
60) radiation crosslinking, dosage is 160KGy.Behind compressing tablet, irradiation, chip is placed the heating installation 3 hours of 50 ℃ of the above temperature of high molecular polymer fusing point earlier, rapidly it is transferred to then and makes its cooling 2 hours rapidly in-30 ℃ the refrigerating apparatus.Use lead-free low-temperature welding compound (liquidus line is 204 ℃) that the copper cash of diameter as 0.2mm is welded on its two interarea, obtain the thermistor element sample.
It is carried out the evaluation identical with embodiment 1, and consequently the workability of ptc material is better, yield rate higher than among the embodiment 1, and between 20 ℃ and 140 ℃ in the thermal cycling changes in resistance situation more stable.Other performance is identical with embodiment 1.
Embodiment 3:
By weight percentage, the composition of matrix material is (mass percent): 50%HDPE, 20%LDPE, 24%TiB2,6.0%CB, and promoter addition is (auxiliary agent is by accounting for organism constituent mass per-cent): 0.2% oxidation inhibitor, 2.0% stearic acid, 1.5% vinyltrimethoxy silane coupling agent, 3.0% antimonous oxide, 10% TDE.At first TiB2 and CB normal temperature, normal pressure were mixed 2 hours down, then with other components together under 180 ℃ on double roll mill mixing 30min, obtain mixing thing.
With resulting mixing thing be added in put into diameter be 18mm foil electrode sheet from molding jig, with being set at 160 ℃, the thermocompressor compression molding of 10MPa, the diameter that obtains comprising electrode is that 22mm, thickness are the disk shape PTC chip of 500 μ m.With this composite sheet gamma-rays (Co60) radiation crosslinking, dosage is 120KGy again.Then, use lead-free low-temperature welding compound (liquidus line is 204 ℃) that the copper cash of diameter as 0.2mm is welded on its two interarea, obtain the thermistor element sample.
Behind compressing tablet, irradiation, chip is placed the heating installation 3 hours of 50 ℃ of the above temperature of high molecular polymer fusing point earlier, rapidly it is transferred to then and makes its cooling 2 hours rapidly in-30 ℃ the refrigerating apparatus.Use lead-free low-temperature welding compound (liquidus line is 204 ℃) that the copper cash of diameter as 0.2mm is welded on its two interarea, obtain the thermistor element sample.
It is carried out the evaluation identical with embodiment 1, and room temperature resistance has increase slightly than embodiment 3, but more obvious at temperature jump point sudden change of resistivity, and other performance is identical with embodiment 2.
But the matrix material of the present invention also mass percent of according to the form below carries out proportioning and processes by the method for embodiment 1～3:
| Group | New LDPE (film grade) | TiB2 | Carbon black | High density polyethylene(HDPE) |
| 1 | 10 | 20 | 0 | Surplus |
| 2 | 10 | 40 | 0 | Surplus |
| 3 | 15 | 40 | 0 | Surplus |
| 4 | 15 | 30 | 4.0 | Surplus |
| 5 | 15 | 25 | 6.0 | Surplus |
| 6 | 20 | 25 | 6.0 | Surplus |
| 7 | 20 | 20 | 8.0 | Surplus |
| 8 | 25 | 40 | 8.0 | Surplus |
Add auxiliary agent during batch mixing, auxiliary agent with respect to the mass percent of organic constituents in the base-material is:
Antioxidant 1010: stearic acid 0.2%: vinyltrimethoxy silane (coupling agent) 2.0%: 1.5%,
Antimonous oxide: TDE (fire retardant) 4%: 10%.
In the last table first group, TiB
2In material, constitute network, play electric action.Because TiB
2Ratio is little, and CB content is zero, and material room temperature electroconductibility is limited, and PTC intensity is lower.But because organic composition (HDPE/LDPE) ratio height, the material plasticity and toughness are good, and plasticity is good, stable mechanical property.
In the last table second group, TiB
2Amount doubles than first group, because TiB
2Amount is big, and the ptc material plasticity and toughness descend, and tearing tendency increases during preparation.But TiB
2Amount is big, conductive network than first group complete, material electroconductibility obviously is better than first group, PTC intensity height, PTC good stability.
In the last table the 3rd group, the LDPE weight percent increases by 50% than second group.LDPE degree of crystallinity is low, and TiB
2Size distribution is in amorphous phase, and LDPE ratio in the PTC matrix material increases, and helps TiB
2Uniform particles distributes, and can effectively improve electroconductibility, PTC intensity.
In the last table the 4th group, TiB
2Amount reduces 25% than the 3rd group, and the CB amount increases to 4% simultaneously.TiB
2Amount reduces and to help reducing PTC matrix material cost, and CB proportion is little, and structure is the high structural state of fluffy, multi-branched, high hole, and CB helps to form complete conductive network, helps increasing ptc material electroconductibility; Because the conductive particle total amount descends, the ptc material plasticity and toughness improve, and tearing tendency reduces during preparation.
In the last table the 5th group, TiB
2Amount further reduces than the 4th group, and the CB amount increases to 6% simultaneously.TiB
2The amount minimizing helps reducing PTC matrix material cost, increases CB and helps to form complete conductive network, helps increasing ptc material electroconductibility; Because the conductive particle total amount descends, the ptc material plasticity and toughness are than the 4th group of raising, and tearing tendency descends during preparation.
In the last table the 6th group, LDPE weight percent increase by 30% than the 5th group, and corresponding HDPE ratio descends.LDPE degree of crystallinity is low, HDPE degree of crystallinity height, and TiB
2Size distribution is in amorphous phase, and LDPE ratio in the PTC matrix material increases, and helps TiB
2Uniform particles distributes, and can effectively improve electroconductibility, PTC intensity.
In the last table the 7th group, TiB
2Amount further reduces than the 6th group, and the CB amount increases to 8% simultaneously.TiB
2The amount minimizing helps reducing PTC matrix material cost, increases CB and helps to form complete conductive network, helps keeping ptc material electroconductibility.Because the conductive particle total amount descends, the ptc material plasticity and toughness are than the 6th group of raising, and tearing tendency descends during preparation; But because the conductive particle total amount is less, conductivity at room temperature can descend to some extent.
In the last table the 8th group, the LDPE weight percent increases by 30% than the 7th group, and corresponding HDPE ratio descends, and TiB
2Size distribution is in amorphous phase, and LDPE ratio in the PTC matrix material increases, and helps TiB
2Uniform particles distributes, and can effectively improve electroconductibility, PTC intensity.Than the 6th group and the 7th group, TiB
2Percentage composition obviously increases, and the conductive network integrity improves, and the conductivity at room temperature rate improves.But because the conductive particle total amount is higher, the PTC cost increases.In addition, the HDPE ratio reduces, and the degree of crystallinity of PTC matrix material descends, and causes strength degradation, hardness to descend.
Claims (1)
1. polyvinyl PTC thermo-sensitive conductive composite material, it is characterized in that: it is to be made by following preparation method, described preparation method comprises batch mixing, mold pressing, radiation and freezing: described batch mixing is exactly at first the TiB2 and the carbon black of proportional quantity to be mixed, and obtains TiB
2-CB compound powder, then with in the base-material of mixed powder and proportional quantity in addition each auxiliary agent of two kinds of organic constituentses and calculated amount in mixing roll in 160～200 ℃ of mixing mixing materials that evenly obtain down; With mixing materials in moulding press under 160 ± 10 ℃, pressure 5～15MPa mold pressing obtain containing the PTC chip of electrode slice; With the PTC chip with gamma-rays or crosslinking electron beam irradiation, dosage 120～160KGy; With the PTC chip behind the irradiation in being higher than under the temperature of high density polyethylene(HDPE) fusing point more than 50 ℃ thermal treatment 2～3 hours; With the freezing treatment 1～2 hour under-20～-40 ℃ of conditions of the PTC chip after the thermal treatment; Wherein said base-material is made of the organic constituents and the inorganics component of following weight percent:
New LDPE (film grade) 10～25% TiB2s 20～40%
Carbon black 0～8% high density polyethylene(HDPE) surplus;
And described auxiliary agent is by new LDPE (film grade) in the base-material and high density polyethylene(HDPE) quality:
Antioxidant 1010 0.1～0.3% stearic acid 1～3%
Vinyltrimethoxy silane 1～2% antimonous oxide 3～5%
TDE 8～12%.
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| CN102176359A (en) * | 2011-01-26 | 2011-09-07 | 上海长园维安电子线路保护股份有限公司 | Cyclic annular positive temperature coefficient thermosensitive resistor and applications thereof |
| CN102702603A (en) * | 2012-06-20 | 2012-10-03 | 合肥工业大学 | Polyethylene/titanium diboride PTC (Positive Temperature Coefficient) composite material and preparation method thereof |
| CN111978620A (en) * | 2020-09-10 | 2020-11-24 | 合肥金四达科技有限公司 | Polyethylene/titanium diboride/graphene thermosensitive conductive composite material and preparation method thereof |
| CN113621272B (en) * | 2021-10-13 | 2022-01-11 | 清远市简一陶瓷有限公司 | Conductive ink with temperature limiting characteristic, preparation method and heating ceramic tile |
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| WO2001064785A1 (en) * | 2000-03-02 | 2001-09-07 | Ko, Chang-Mo | Ptc conductive polymer compositions, method of controlling the same and electrical device containing the same |
| CN1250637C (en) * | 2003-09-30 | 2006-04-12 | 四川大学 | Polyolefin/carbon black PTC conductive composite material and preparing method thereof |
| CN101633787A (en) * | 2008-07-25 | 2010-01-27 | 上海科特高分子材料有限公司 | Low-resistivity positive temperature coefficient type conductive polymer composite material and preparation method thereof |
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