CN102585502B - Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect - Google Patents
Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect Download PDFInfo
- Publication number
- CN102585502B CN102585502B CN 201210042280 CN201210042280A CN102585502B CN 102585502 B CN102585502 B CN 102585502B CN 201210042280 CN201210042280 CN 201210042280 CN 201210042280 A CN201210042280 A CN 201210042280A CN 102585502 B CN102585502 B CN 102585502B
- Authority
- CN
- China
- Prior art keywords
- pps
- ptfe
- powder
- polymer matrix
- conductive filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a preparation method of a high-temperature polymer matrix PTC (positive temperature coefficient) material with a delay NTC (negative temperature coefficient) effect. The materials comprise the following components by weight percent: 3-15% of conductive carbon black (CB), 42.5-67.9% of polymer matrix polyphenylene sulfide (PPS) and 25.5-48.5% of polytetrafluoroethylene (PTFE), wherein the mass ratio of PPS to PTFE is (5/5)-(7/3). The method comprises the following steps of: carrying out coupling agent modification treatment on the CB, dispersing the CB with the PPS powder and the PFE powder in absolute ethyl alcohol, ball-milling uniformly, then volatilizing a solvent, and sintering under hot pressing at a certain temperature so as to obtain a CB/PPS/PTFE compositematerial. The high-temperature polymer matrix PTC material with the delay NTC effect, disclosed by the invention, has the characteristics of eliminating the NTC effect without radiation crosslinking by crosslinking devices, reducing the manufacturing cost, simplifying the production process, the room-temperature resistivity of the composite material can be adjusted by adjusting the CB content andthe weight ratio of PPS to PTFE.
Description
Technical field
The present invention relates to the polymer matrix PTC matrix material in a kind of hyundai electronics and electric works field, relate to a kind of preparation method with the high temperature polymer matrix PTC material that postpones the NTC effect.
Technical background
The at present manufacturing of ptc polymer is mainly take the single component crystallization such as polyethylene (PE), ethylene-vinyl acetate copolymer (EVA), polyvinylidene difluoride (PVDF) (PVDF) or semi-crystalline polymer as body material, the fusing point of these polymer matrix material causes the use temperature of final polymer matrix PTC material not high generally all less than 150 ℃.Simultaneously, this class ptc material could use after often needing radiation crosslinking to eliminate the NTC effect in the course of processing, otherwise material is when in use causing the temperature rising near the fusing point of polymeric matrix because of energising, and polymkeric substance can deform even burn.But the radiation crosslinking treating processes of ptc material need to be used expensive cross-linking apparatus, and this can improve the production cost of material.Along with making rapid progress of modern science and technology, the ptc polymer Application Areas is constantly expanded, and the needs exploitation is easy to process, cheap for manufacturing cost, use temperature is higher (the PTC transition temperature is higher than 200 ℃) and the polymer matrix PTC material of excellent combination property.Present PE, EVA, PP and PVDF single-component polymer matrix PTC material all can't satisfy the requirement of 200 ℃ of applied at elevated temperatures.The basic skills that improves the polymer matrix PTC material use temperature as matrix by using dystectic semicrystalline polymeric material, adopt two or more polymer blendings to form polynary compound system, matrix material had be different from the novel special performance of single polymers matrix, realize the mutual supplement with each other's advantages of each component, even represent the function that makes new advances.Therefore, multipolymer matrix blended compound material more and more receives people's concern in the research and development of polymer matrix PTC material.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with high temperature polymer matrix PTC material of remarkable delay NTC effect.
A kind of preparation method with the high temperature polymer matrix PTC material that postpones the NTC effect of the present invention is characterized in that:
1) raw material: described high temperature polymer matrix PTC material with delay NTC effect has following material to form: conductive filler material CB, polymer matrix material PPS and PTFE; Described CB conductive filler material accounts for 3.0% ~ 15.0% of matrix material total mass; Described polymeric matrix PPS content 42.5% ~ 67.9%, PTFE content 25.5% ~ 48.5%, wherein PPS and PTFE mass ratio are 5/5 ~ 7/3; Described CB conductive filler material median size is 50nm, uses after silane coupling agent is processed, and wherein the mass ratio of silane coupling agent and CB is 100:1; Described polymeric matrix PPS fusing point is 285 ℃, and median size is 20 μ m; Described polymeric matrix PTFE fusing point is 327 ℃, and melt viscosity is 10
10Pas, median size is 25 μ m;
2) surface treatment of CB conductive filler material: make it in dehydrated alcohol, form suspension by ultra-sonic dispersion and stirring in the CB powder under the room temperature, then add and continue behind the coupling agent to stir 10 ~ 30 minutes; Add subsequently deionized water, at 40 ~ 60 ℃ of lower ultra-sonic dispersion and stirred 15 ~ 60 minutes; The centrifugation powder, then use absolute ethanol washing 1 ~ 3 time after, 60 ~ 120 ℃ of lower vacuum-dryings 2 ~ 5 hours, use after naturally cooling to room temperature; Wherein coupling agent is γ-aminopropyl triethoxysilane;
3) compound: take by weighing the silane coupler modified CB powder that obtains in PPS and PTFE powder and the step (2), the quality percentage composition that makes the CB conductive filler material is 3.0 ~ 15.0%; Polymeric matrix PPS quality percentage composition is 42.5% ~ 67.9%; PTFE quality percentage composition is 25.5% ~ 48.5%; Wherein PTFE and PPS mass ratio are 5/5 ~ 7/3; Then CB powder, PPS powder and PTFE powder are disperseed in ethanol, ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
4) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 100 MPa pressure under 330 ~ 380 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm.
The present invention has following beneficial effect: this polymer PTC matrix material has the transition temperature up to 250 ℃, can be as the high-temp PTC materials'use; The NTC effect of matrix material is deferred to about 335 ℃ from 295 ℃, has postponed about 40 ℃, has avoided expensive radiation crosslinking technique, has simplified the manufacturing process of ptc material, has reduced production cost; Composite material by adopting resistant to elevated temperatures polymeric matrix PPS and PTFE, itself does not fire, and has guaranteed the security of materials'use, does not need additionally to add poisonous halogen containing flame-retardant; Matrix material can pass through the electroconductibility of content and PPS and the PTFE weight ratio change matrix material of adjusting CB, therefore can control comparatively accurately the room-temperature conductivity of matrix material.
Description of drawings
Fig. 1 is the process flow sheet that the present invention prepares the polymer PTC matrix material;
Fig. 2 is that CB conductive filler material content is 8 wt%, and polymeric matrix PPS and PTFE mass ratio are respectively 7/3,6/4, the DSC curve of 5/5 o'clock CB/PPS/PTFE matrix material;
Fig. 3 is that CB conductive filler material content is 8wt%, PPS/PTFE=5/5 (w/w), CB/PPS/PTFE matrix material
Resistance-temperature curve;
Fig. 4 is that CB conductive filler material content is 8wt%, PPS/PTFE=7/3 (w/w), CB/PPS/PTFE matrix material
Resistance-temperature curve;
Fig. 5 is that CB conductive filler material content is 12wt%, PPS/PTFE=5/5 (w/w), the resistance-temperature curve of CB/PPS/PTFE composite wood;
Fig. 6 is that CB conductive filler material content is 9wt%, PPS/PTFE=5/5 (w/w), CB/PPS/PTFE matrix material
Resistance-temperature curve;
Fig. 7 is that CB conductive filler material content is 9wt%, PPS/PTFE=6/4 (w/w), CB/PPS/PTFE matrix material
Resistance-temperature curve;
Fig. 8 is that CB conductive filler material content is 9wt%, PPS/PTFE=7/3 (w/w), CB/PPS/PTFE matrix material
Resistance-temperature curve.
Embodiment
Below by the present invention is described in further detail in conjunction with specific embodiments.Embodiment only is to a kind of explanation of the present invention, and is not construed as limiting the invention.Embodiment is the practical application example, is easy to grasp and checking for those skilled in the art.If make certain change on basis of the present invention, its essence does not exceed scope of the present invention so.
Embodiment 1
(1) makes it in dehydrated alcohol, form suspension by ultra-sonic dispersion and stirring in 100 g CB conductive filler material powder under the room temperature, then add rear the continuing of 1 g coupling agent (γ-aminopropyl triethoxysilane) and stirred 10 ~ 30 minutes; Add subsequently deionized water, at 40 ~ 60 ℃ of lower ultra-sonic dispersion and stirred 15 ~ 60 minutes; The centrifugation powder, then use absolute ethanol washing 1 ~ 3 time after, 60 ~ 120 ℃ of lower vacuum-dryings 2 ~ 5 hours, use after naturally cooling to room temperature;
(2) take by weighing silane coupler modified CB powder 0.5438 g that obtains in 3.1269 g PPS and 3.1269 g PTFE powder and the step (1); The quality percentage composition that makes the CB conductive filler material is 8%, and polymeric matrix PPS quality percentage composition is that 46%, PTFE quality percentage composition is 46%, and wherein PPS and PTFE mass ratio are 5/5; CB powder, PPS powder and PTFE powder are disperseed in ethanol, and ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
(3) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 100 MPa pressure under 360 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm;
(4) the composite manufacture schema is seen accompanying drawing 1 among the embodiment 1-6; With the sample 5-10 mg sample that blade cuts step (3) obtains, in nitrogen, temperature rise rate is the DSC curve of measure sample under the 20 ℃/min condition, and it the results are shown in curve c in the accompanying drawing 2; Starch in 100 ℃ of processing 1h at the sample two ends coated with conductive silver that step (3) obtains, naturally stablize 24h after the cooling, make silver slurry and chip material reach ohmic contact, specimen resistance-temperature characteristics then, it the results are shown in accompanying drawing 3: room temperature resistivity is 151 Ω cm; PTC changes since 250 ℃, and to 295 ℃ of end, PTC intensity is 2.5; The NTC effect occurs after being deferred to 335 ℃ from 295 ℃, has postponed 40 ℃.
(1) process of surface treatment of CB conductive filler material powder is with example 1;
(2) take by weighing silane coupler modified CB powder 0.5502 g that obtains in 4.4291 g PPS and 1.8982 g PTFE powder and the step (1); The quality percentage composition that makes the CB conductive filler material is 8%, and polymeric matrix PPS quality percentage composition is that 64.4%, PTFE quality percentage composition is 27.6%, and wherein PPS and PTFE mass ratio are 7/3; CB powder, PPS powder and PTFE powder are disperseed in ethanol, and ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
(3) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 50 MPa pressure under 380 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm;
(4) the DSC curve test condition of sample the results are shown in curve a in the accompanying drawing 2 with embodiment 1; Sample resistance-temperature characteristics testing method is with embodiment 1, and it the results are shown in accompanying drawing 4: room temperature resistivity is 319 Ω cm; PTC changes since about 250 ℃, and to 290 ℃ of end, PTC intensity is 4.7; The NTC effect occurs after being deferred to 335 ℃ from 290 ℃, has postponed 45 ℃.
(1) process of surface treatment of CB conductive filler material powder is with example 1;
(2) take by weighing silane coupler modified CB powder 0.6732 g that obtains in 2.4684 g PPS and 2.4684 g PTFE powder and the step (1); The quality percentage composition that makes the CB conductive filler material is 12%, and polymeric matrix PPS quality percentage composition is that 44%, PTFE quality percentage composition is 44%, and wherein PPS and PTFE mass ratio are 5/5; CB powder, PPS powder and PTFE powder are disperseed in ethanol, and ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
(3) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 100 MPa pressure under 340 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm;
(4) sample resistance-temperature characteristics testing method is with embodiment 1, and it the results are shown in accompanying drawing 5: room temperature resistivity is 30 Ω cm; PTC changes since about 250 ℃, and to 295 ℃ of end, PTC intensity is 0.8; The NTC effect occurs after being deferred to 335 ℃ from 295 ℃, has postponed 40 ℃.
(1) process of surface treatment of CB conductive filler material powder is with example 1;
(2) take by weighing silane coupler modified CB powder 0.5838 g that obtains in 2.9514 g PPS and 2.9514 g PTFE powder and the step (1); The quality percentage composition that makes the CB conductive filler material is 9%, and polymeric matrix PPS quality percentage composition is that 45.5%, PTFE quality percentage composition is 45.5%, and wherein PPS and PTFE mass ratio are 5/5; CB powder, PPS powder and PTFE powder are disperseed in ethanol, and ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
(3) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 80 MPa pressure under 360 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm;
(4) sample resistance-temperature characteristics testing method is with embodiment 1, and it the results are shown in accompanying drawing 6: room temperature resistivity is 102 Ω cm; PTC changes since about 250 ℃, and to 295 ℃ of end, PTC intensity is 2.4; The NTC effect occurs after being deferred to 335 ℃ from 295 ℃, has postponed 40 ℃.
Embodiment 5
(1) process of surface treatment of CB conductive filler material powder is with example 1;
(2) take by weighing silane coupler modified CB powder 0.6124 g that obtains in 3.7152 g PPS and 2.4768 g PTFE powder and the step (1); The quality percentage composition that makes the CB conductive filler material is 9%, and polymeric matrix PPS quality percentage composition is that 54.6%, PTFE quality percentage composition is 36.4%, and wherein PPS and PTFE mass ratio are 6/4; CB powder, PPS powder and PTFE powder are disperseed in ethanol, and ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
(3) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 50 MPa pressure under 340 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm;
(4) the DSC curve test condition of sample the results are shown in curve b in the accompanying drawing 2 with embodiment 1; Sample resistance-temperature characteristics testing method is with embodiment 1, and it the results are shown in accompanying drawing 6: room temperature resistivity is 402 Ω cm; PTC changes since about 250 ℃, and to 285 ℃ of end, PTC intensity is 3.7; The NTC effect occurs after being deferred to 330 ℃ from 285 ℃, has postponed 40 ℃.
(1) process of surface treatment of CB conductive filler material powder is with example 1;
(2) take by weighing silane coupler modified CB powder 0.5428 g that obtains in 3.8418 g PPS and 1.6465 g PTFE powder and the step (1); The quality percentage composition that makes the CB conductive filler material is 9%, and polymeric matrix PPS quality percentage composition is that 63.7%, PTFE quality percentage composition is 27.3%, and wherein PPS and PTFE mass ratio are 7/3; CB powder, PPS powder and PTFE powder are disperseed in ethanol, and ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
(3) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 50 MPa pressure under 340 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm;
(4) sample resistance-temperature characteristics testing method is with embodiment 1, and it the results are shown in accompanying drawing 6: room temperature resistivity is 896 Ω cm; PTC changes since about 250 ℃, and to 300 ℃ of end, PTC intensity is 4.8; The NTC effect occurs after being deferred to 335 ℃ from 300 ℃, has postponed 35 ℃.
Claims (1)
1. preparation method with the high temperature polymer matrix PTC material that postpones the NTC effect is characterized in that method is:
1) raw material: described high temperature polymer matrix PTC material with delay NTC effect has following material to form: conductive filler material CB, polymer matrix material PPS and PTFE; Described CB conductive filler material accounts for 3.0% ~ 15.0% of matrix material total mass; Described polymeric matrix PPS content 42.5% ~ 67.9%, PTFE content 25.5% ~ 48.5%, wherein PPS and PTFE mass ratio are 5/5 ~ 7/3; Described CB conductive filler material median size is 50nm, uses after silane coupling agent is processed, and wherein the mass ratio of silane coupling agent and CB is 1:100; Described polymeric matrix PPS fusing point is 285 ℃, and median size is 20 μ m; Described polymeric matrix PTFE fusing point is 327 ℃, and melt viscosity is 10
10Pas, median size is 25 μ m;
2) surface treatment of CB conductive filler material: make it in dehydrated alcohol, form suspension by ultra-sonic dispersion and stirring in the CB powder under the room temperature, then add and continue behind the coupling agent to stir 10 ~ 30 minutes; Add subsequently deionized water, at 40 ~ 60 ℃ of lower ultra-sonic dispersion and stirred 15 ~ 60 minutes; The centrifugation powder, then use absolute ethanol washing 1 ~ 3 time after, 60 ~ 120 ℃ of lower vacuum-dryings 2 ~ 5 hours, use after naturally cooling to room temperature; Wherein coupling agent is γ-aminopropyl triethoxysilane;
3) compound: take by weighing the silane coupler modified CB powder that obtains in PPS and PTFE powder and the step (2), the quality percentage composition that makes the CB conductive filler material is 3.0 ~ 15.0%; Polymeric matrix PPS quality percentage composition is 42.5% ~ 67.9%; PTFE quality percentage composition is 25.5% ~ 48.5%; Wherein PTFE and PPS mass ratio are 5/5 ~ 7/3; Then CB powder, PPS powder and PTFE powder are disperseed in ethanol, ball milling mixes afterwards evaporating solvent in baking oven, then places dry 1 h under 120 ℃ of conditions of vacuum drying oven, obtains mixed powder;
4) moulding: as in the sintered-carbide die, in hot pressing 15 minutes under 100 MPa pressure under 330 ~ 380 ℃, obtaining diameter behind the cool to room temperature is 20 mm with mixed powder, and thickness is the disc-shaped sample of 1 ~ 3 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210042280 CN102585502B (en) | 2012-02-23 | 2012-02-23 | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210042280 CN102585502B (en) | 2012-02-23 | 2012-02-23 | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102585502A CN102585502A (en) | 2012-07-18 |
| CN102585502B true CN102585502B (en) | 2013-10-23 |
Family
ID=46474772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210042280 Expired - Fee Related CN102585502B (en) | 2012-02-23 | 2012-02-23 | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102585502B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104129148B (en) * | 2014-08-01 | 2016-05-25 | 广东生益科技股份有限公司 | The preparation method of PTFE composite medium substrate for a kind of microwave circuit |
| TWI588161B (en) * | 2016-07-28 | 2017-06-21 | 廣科工業股份有限公司 | Low-k material and precursor thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629215A (en) * | 2004-10-28 | 2005-06-22 | 复旦大学 | Temperature sensing material with negative temperature coefficient effect and method for preparing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8496854B2 (en) * | 2009-10-30 | 2013-07-30 | Sabic Innovative Plastics Ip B.V. | Positive temperature coefficient materials with reduced negative temperature coefficient effect |
-
2012
- 2012-02-23 CN CN 201210042280 patent/CN102585502B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629215A (en) * | 2004-10-28 | 2005-06-22 | 复旦大学 | Temperature sensing material with negative temperature coefficient effect and method for preparing same |
Non-Patent Citations (2)
| Title |
|---|
| 谢鸿峰等.辐射效应对LDPE/CB复合电性能的影响.《辐射研究与辐射工艺学报》.2001,第19卷(第4期),294-297. |
| 辐射效应对LDPE/CB复合电性能的影响;谢鸿峰等;《辐射研究与辐射工艺学报》;20011130;第19卷(第4期);294-297 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102585502A (en) | 2012-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103594214B (en) | Normal temperature thermal control compound ptc material | |
| CN102585502B (en) | Preparation method of high-temperature polymer matrix PTC (positive temperature coefficient) material with delay NTC (negative temperature coefficient) effect | |
| CN104497394A (en) | Polymer based temperature-sensitive resistance material with negative temperature coefficient (NTC) effect and preparation method thereof | |
| CN108503940B (en) | A kind of low Curie point PTC organic composite material and preparation method thereof | |
| CN103554588A (en) | Macromolecular PTC composite material with crystalline polymer as matrix | |
| CN103756103B (en) | Graphene/high density polyethylene(HDPE) thermistor composite material and preparation method | |
| CN104861273A (en) | Composite material for thermistor and preparation method and application of composite material | |
| CN105462478A (en) | Ultraviolet light cured PPTC electrode slurry and preparation method thereof | |
| CN105761777A (en) | Filament silver paste for automobile glass and preparation method of filament silver paste | |
| CN103524868A (en) | Low-temperature-resistant oil-resistant low-smoke halogen-free flame-retardant polyolefin cable material | |
| CN112778769A (en) | Heat-conducting and insulating composite material, preparation method and application thereof | |
| CN102108127A (en) | Method for preparing chitosan nano composite material membrane | |
| CN105139916A (en) | Carbon powder doped molybdenum-based thick film resistance paste and preparation method thereof | |
| CN103854718A (en) | Solar cell front electrode slurry material and preparation method thereof | |
| CN102190830A (en) | High-temperature low-carbon-black-content polymer-based PTC composite material and preparation method thereof | |
| CN103165222A (en) | High temperature sintering conductive silver paste for negative temperature coefficient (NTC) thermistor and preparation method thereof | |
| CN102604281A (en) | Preparation method of crosslinking-free polymer-based high-temperature PTC (positive temperature coefficient) material | |
| CN107731342A (en) | A kind of chip resistor resistance slurry | |
| CN111768889A (en) | Electric power composite grease and preparation method and application thereof | |
| CN103304875B (en) | PTC composite material and preparation method thereof | |
| CN103500654A (en) | Nitrogen-doped graphene/PVDF (Polyvinylidene Fluoride) composite dielectric film and preparation method thereof | |
| CN106145928A (en) | A kind of manufacture method of tubular ZnO electronic ceramics | |
| CN102543257B (en) | Modified silver thick film sizing agent for crystalline silicon solar cell and preparation method thereof | |
| CN103304938B (en) | PTC thermistor base material and preparation method thereof | |
| CN102260074B (en) | High-temperature negative temperature coefficient (NTC) material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131023 Termination date: 20140223 |