WO2017128526A1 - 一种耐高温ptc导电复合材料 - Google Patents
一种耐高温ptc导电复合材料 Download PDFInfo
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- C08K2003/265—Calcium, strontium or barium carbonate
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- the invention relates to the technical field of positive temperature coefficient PTC conductive compositions, in particular to a high temperature resistant PTC conductive composite material.
- the matrix of the polymer-based PTC material is an organic polymer, and then a composite material is formed by adding some inorganic conductive filler therein.
- This material was first discovered by Frydman in 1948, but at that time, people did not attach great importance to it. It was not until the 1960s that carbon black composites and the like also had the PTC effect that attracted the attention of scientific researchers. First, they were actually used and developed in the United States at the end of the 20th century. This material combines the electrical conductivity of inorganic fillers with the good flexibility of polymer materials and has a good overall performance.
- the properties of polymer-based PTC conductive composites show good and comprehensive characteristics. Polymer-based PTC materials have low room temperature resistivity, high PTC strength, low cost and easy processing, etc.
- the PTC has a constant temperature characteristic and can be applied to various heat sources in households, such as heaters, mosquito repellents, and hand warmers.
- the PTC also has a temperature-reducing characteristic, which can be used for self-regulating heating elements, such as heating and heat preservation of gas, liquid conveying pipes and instruments, and the like, and can also be applied to low-temperature heating such as breeding, fermentation, and the like.
- polymer-based PTC conductive composite materials can only meet the requirements of low temperature and medium temperature fields, and it is difficult to meet the requirements of high temperature fields of 120 ° C or higher.
- Some materials are because their Curie temperature does not reach the high temperature requirement, when the temperature exceeds the temperature After the temperature, the resistance increases sharply and the temperature decreases rapidly.
- the Curie temperature of some materials meets the requirements, the heat generation efficiency is low, and it is difficult to meet the heat generation requirements.
- These materials have insufficient reliability under continuous high temperature conditions, and are prone to burning phenomenon.
- the material may have a problem of too fast decay rate. After the material is used for a period of time, its own resistance will increase geometrically, and the heating temperature will drop rapidly.
- the present invention provides a high temperature resistant PTC conductive composite material, which can fully meet the requirements of high temperature fields of 120 ° C or higher.
- a high temperature resistant PTC conductive composite material comprising 54% to 66% organic polymer, 13.9% to 17.1% inorganic filler, 7% to 9% carbon black XC-72, 10% to 14% by weight HAF, 3% to 4% graphene and 0.3% to 0.7% processing aid.
- the organic polymer is one or more selected from the group consisting of ethylene polytetrafluoroethylene ETFE, fluoroethylene propylene copolymer FEP, and ethylene chlorotrifluoroethylene copolymer ECTFE.
- the inorganic filler is one or more selected from the group consisting of calcium carbonate, zinc oxide, calcium oxide, aluminum oxide, silicon dioxide, and magnesium hydroxide.
- ethylene poly 4 60.8% by weight of ethylene poly 4 is included Vinyl fluoride ETFE, 5.7% calcium carbonate, 10.6% zinc oxide, 8.7% carbon black XC-72, 12.4% HAF, 3.8% graphene and 0.4% processing aid.
- the invention has the beneficial effects that the PTC conductive composite material prepared by the formula of the invention has the advantages of high temperature resistance, the heat requirement can meet the heat generation requirement of high temperature, the burning phenomenon does not occur, and the problem that the attenuation rate is too fast does not exist. , can be used continuously and reliably.
- the high temperature resistant PTC conductive composite material of the invention comprises 54% to 66% organic polymer, 13.9% to 17.1% inorganic filler, 7% to 9% carbon black XC-72, 10% by weight. ⁇ 14% HAF, 3% to 4% graphene and 0.3% to 0.7% processing aid.
- the organic polymer is one or more selected from the group consisting of ethylene polytetrafluoroethylene ETFE, fluoroethylene propylene copolymer FEP, and ethylene chlorotrifluoroethylene copolymer ECTFE.
- the inorganic filler is selected from one or more of calcium carbonate, zinc oxide, calcium oxide, aluminum oxide, silicon dioxide, and magnesium hydroxide.
- PTC conductive composite including 60.8% by weight of ethylene polytetrafluoroethylene ETFE, 5.7% of calcium carbonate, 10.6% of zinc oxide, 8.7% of carbon black XC-72, 12.4% of HAF, 3.8% of graphite Alkene and 0.4% processing aid.
- the materials of the above ratio were prepared, mixed by a screw type injection molding machine, and extruded into a flat mold of 7.8 mm x 2.2 mm, and cooled to form a high temperature resistant PTC core tape.
- the heating temperature of the PTC conductive composite material of this embodiment can reach a higher heat requirement at 120 ° C, and the resistance does not increase geometrically at a high temperature, the work is reliable and stable, and has high temperature resistance. advantage.
- the PTC conductive composite material of the present invention effectively fills the gap in the high temperature field.
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Abstract
本发明公开了一种耐高温PTC导电复合材料，按重量计，包括54％～66％的有机聚合物，13.9％～17.1％的无机填料，7％～9％的炭黑XC-72，10％～14％的HAF，3％～4％的石墨烯以及0.3％～0.7％的加工助剂。基于本发明的配方制成的PTC导电复合材料具有耐高温的优点，其发热要求可以满足高温的发热要求，不会发生烧带现象，不存在衰减率过快的问题，能够持续可靠地使用。 `
Description
本发明涉及正温度系数PTC导电组合物技术领域，具体涉及一种耐高温PTC导电复合材料。
聚合物基PTC材料的基体是有机聚合物，然后在其中加入一些无机导电填料而形成的一种复合材料，这种材料最早是Frydman在1948年发现的，但是当时人们对此并不是非常重视，直到60年代报道炭黑复合材料等也具有PTC效应才引起了科学研究者的注意，首先于20世纪末在美国进行了实际使用与开发。这种材料很好地综合了无机填料导电性能及聚合物材料好的柔韧性能，具有很好的综合性能。聚合物基PTC导电复合材料性能表现出良好与综合性特点，聚合物基PTC材料具有较低的室温电阻率、PTC强度较高、成本低廉便宜及容易加工成型等性能，这些特点也是陶瓷基PTC材料所具有的，这些优势特点使聚合物基PTC材料成为了PTC材料研发的热点与重点，聚合物基PTC不仅广泛地使用在卫生医疗、自限温伴热带及各种加热装置中，在过流过压保护、弱电系统温度补偿等方面也有很大的使用与发展前景。
炭黑填充聚合物基PTC导电复合材料的主要应用包括以
下几个方面。
1、用于起动元件及消磁元件。PTC材料在刚开始通电时，冲击电流较大，等待通电比较稳定之后，其稳定电流又非常小，PTC材料因为没有触点、振动、磨损、干扰等等，因此不会产生电弧，具有较高的可靠性与较长寿命，现在这种材料主要使用在制作冷压缩机中起动器、日光灯及彩色电视机中的消磁电阻等等。起动器中使用这种材料有效地取代了以往常用的离心开关，应用在电容运行的单相电动机中，在机器起动运行过程中具有非常好的起动性能，而且当PTC电阻值出现急剧变大时，会出现“断路”，进一步将起动绕组与运行电容串联起来，保证电机在正常工作状态下运行电容。
2、用于加热元件及恒温元件。PTC具有恒温特性，能够应用在家用中的多种热源，例如暖风机、驱蚊器及手暖器等等。
3、用于保护元件及控温元件。PTC还具有阻温特性，能够用于自控温加热元件，例如气体、液体输送管道及仪器的加热保温等等，也可以应用在育种、发酵等的低温加热中。
4、用于温度补偿。
要使得聚合物基PTC导电复合材料能够完全满足上个各个领域的使用要求，必须开发能够满足各种温度环境的材料。目前，聚合物基PTC导电复合材料都只能满足低温和中温领域的使用要求，难以满足120℃甚至更高的高温领域的使用要求。部分材料是因为其居里温度达不到高温要求，当其温度超过居
里温度后电阻急剧增大，温度迅速降低。部分材料虽然居里温度达到了要求，但其发热效率低，难以满足发热要求，这些材料在持续高温条件下可靠性不足，容易发生烧带现象，另外，材料会存在衰减率过快的问题，材料使用一段时间后，本身电阻会成几何倍数增长，发热温度急速下降。
因此，目前并没有一种能够满足使用要求的耐高温PTC复合材料。
发明内容
针对以上技术问题，本发明提供一种耐高温PTC导电复合材料，其可以完全满足120℃甚至更高的高温领域的使用要求
本发明为解决其技术问题所采用的技术方案是：
一种耐高温PTC导电复合材料，按重量计，包括54％～66％的有机聚合物，13.9％～17.1％的无机填料，7％～9％的炭黑XC-72，10％～14％的HAF，3％～4％的石墨烯以及0.3％～0.7％的加工助剂。
作为优选的实施方式，所述有机聚合物选自乙烯聚四氟乙烯ETFE、氟乙烯丙烯共聚物FEP、乙烯三氟氯乙烯共聚物ECTFE中的一种或以上。
作为优选的实施方式，所述无机填料选自碳酸钙、氧化锌、氧化钙、氧化铝、二氧化硅和氢氧化镁中的一种或以上。
作为优选的实施方式，按重量计，包括60.8％的乙烯聚四
氟乙烯ETFE，5.7％的碳酸钙，10.6％的氧化锌，8.7％的炭黑XC-72，12.4％的HAF，3.8％的石墨烯以及0.4％的加工助剂。
本发明的有益效果是：基于本发明的配方制成的PTC导电复合材料具有耐高温的优点，其发热要求可以满足高温的发热要求，不会发生烧带现象，不存在衰减率过快的问题，能够持续可靠地使用。
本发明的一种耐高温PTC导电复合材料，按重量计，包括54％～66％的有机聚合物，13.9％～17.1％的无机填料，7％～9％的炭黑XC-72，10％～14％的HAF，3％～4％的石墨烯以及0.3％～0.7％的加工助剂。有机聚合物选自乙烯聚四氟乙烯ETFE、氟乙烯丙烯共聚物FEP、乙烯三氟氯乙烯共聚物ECTFE中的一种或以上。无机填料选自碳酸钙、氧化锌、氧化钙、氧化铝、二氧化硅和氢氧化镁中的一种或以上。
下面以具体的实施例进行说明。
PTC导电复合材料，按重量计，包括60.8％的乙烯聚四氟乙烯ETFE，5.7％的碳酸钙，10.6％的氧化锌，8.7％的炭黑XC-72，12.4％的HAF，3.8％的石墨烯以及0.4％的加工助剂。
准备上述配比的材料，通过螺杆式注塑机混合后挤出至一7.8mmx2.2mm的扁平模具内，冷却成型后得到耐高温PTC芯带。
取一定单位长度的芯带进行检测，供电使其发热，检测其
阻值、电流大小及温度值，结果如下：
| 电阻Ω | 电流A | 温度℃ |
| 4.18k | 0.13 | 98 |
| 1.56k | 0.27 | 125 |
| 1.17k | 0.32 | 132 |
| 1.03k | 0.37 | 134 |
| 928 | 0.41 | 136 |
| 882 | 0.42 | 138 |
| 843 | 0.43 | 138 |
| 812 | 0.44 | 139 |
| 790 | 0.47 | 140 |
| 765 | 0.46 | 140 |
| 744 | 0.47 | 141 |
| 726 | 0.48 | 142 |
| 722 | 0.47 | 143 |
| 719 | 0.49 | 144 |
| 705 | 0.51 | 145 |
| 667 | 0.52 | 145 |
| 602 | 0.6 | 143 |
| 518 | 0.66 | 145 |
| 597 | 0.58 | 147 |
| 583 | 0.60 | 149 |
| 585 | 0.59 | 151 |
| 591 | 0.58 | 151 |
| 582 | 0.57 | 152 |
| 586 | 0.59 | 153 |
| 591 | 0.59 | 155 |
| 580 | 0.61 | 157 |
表1
从表1可以看出，此实施例的PTC导电复合材料的发热温度可以达到120℃设置更高的发热要求，处在高温状态下电阻不会发生几何倍数增长，工作可靠稳定，具有耐高温的优点。
本发明的PTC导电复合材料有效地填补了高温领域的空白。以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (4)
- 一种耐高温PTC导电复合材料，其特征在于：按重量计，包括54％～66％的有机聚合物，13.9％～17.1％的无机填料，7％～9％的炭黑XC-72，10％～14％的HAF，3％～4％的石墨烯以及0.3％～0.7％的加工助剂。
- 根据权利要求1所述的一种耐高温PTC导电复合材料，其特征在于：所述有机聚合物选自乙烯聚四氟乙烯ETFE、氟乙烯丙烯共聚物FEP、乙烯三氟氯乙烯共聚物ECTFE中的一种或以上。
- 根据权利要求1所述的一种耐高温PTC导电复合材料，其特征在于：所述无机填料选自碳酸钙、氧化锌、氧化钙、氧化铝、二氧化硅和氢氧化镁中的一种或以上。
- 根据权利要求1至3中任一项所述的一种耐高温PTC导电复合材料，其特征在于：按重量计，包括60.8％的乙烯聚四氟乙烯ETFE，5.7％的碳酸钙，10.6％的氧化锌，8.7％的炭黑XC-72，12.4％的HAF，3.2％的石墨烯以及0.4％的加工助剂。
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| CN111647318A (zh) * | 2020-06-04 | 2020-09-11 | 广东康烯科技有限公司 | Ptc石墨烯基导电油墨的制备方法及ptc石墨烯基导电油墨 |
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| CN106455167B (zh) * | 2016-09-08 | 2019-03-22 | 芜湖市旭辉电工新材料有限责任公司 | 一种低温阻燃地热采暖用自限温伴热带 |
| WO2018077968A1 (en) * | 2016-10-26 | 2018-05-03 | Solvay Specialty Polymers Usa, Llc | Fluoropolymer composition comprising calcium oxide or calcium carbonate for thermoformed window shades |
| CN109897261A (zh) * | 2019-03-08 | 2019-06-18 | 中山市君泽科技有限公司 | 一种ptc自限温石墨烯基导电粒子 |
| CN112111093A (zh) * | 2020-09-23 | 2020-12-22 | 芜湖科阳新材料股份有限公司 | 一种用于伴热带的ptc导电复合材料及其制备方法 |
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| CN102558638A (zh) * | 2010-12-10 | 2012-07-11 | 比亚迪股份有限公司 | 一种正温度系数材料及制备方法和含该材料的热敏电阻 |
| CN102598162A (zh) * | 2009-10-30 | 2012-07-18 | 沙伯基础创新塑料知识产权有限公司 | 具有降低的负温度系数效应的正温度系数材料 |
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| CN101560325A (zh) * | 2009-05-26 | 2009-10-21 | 上海科特高分子材料有限公司 | 耐高温ptc导电组合物、包含该组合物的耐高温ptc器件及其制造方法 |
| CN102598162A (zh) * | 2009-10-30 | 2012-07-18 | 沙伯基础创新塑料知识产权有限公司 | 具有降低的负温度系数效应的正温度系数材料 |
| TW201120922A (en) * | 2009-12-10 | 2011-06-16 | Wei-Han Wang | Method for enhancing current-carrying ability of polymer thermistor. |
| CN102558638A (zh) * | 2010-12-10 | 2012-07-11 | 比亚迪股份有限公司 | 一种正温度系数材料及制备方法和含该材料的热敏电阻 |
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| CN111647318A (zh) * | 2020-06-04 | 2020-09-11 | 广东康烯科技有限公司 | Ptc石墨烯基导电油墨的制备方法及ptc石墨烯基导电油墨 |
| CN111647318B (zh) * | 2020-06-04 | 2022-08-09 | 广东康烯科技有限公司 | Ptc石墨烯基导电油墨的制备方法及ptc石墨烯基导电油墨 |
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