CN112210176B - 聚偏氟乙烯基导电复合材料及ptc元件 - Google Patents
聚偏氟乙烯基导电复合材料及ptc元件 Download PDFInfo
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- 239000002033 PVDF binder Substances 0.000 title claims abstract description 120
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 4
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Abstract
本发明公开了一种聚偏氟乙烯基导电复合材料及PTC元件。所述的聚偏氟乙烯基导电复合材料，以聚偏氟乙烯(PVDF)基体，具有正温度系数（PTC）效应，环境温度25℃下的电阻率不大于10Ω.cm，包含：所述的PVDF为第一组分聚合物，占所述聚偏氟乙烯基导电复合材料的体积分数的20~70%；预先辐照交联的含氟聚合物，体积分数在1~20%；导电填料，体积分数在25~80%。本发明还包括利用所述聚偏氟乙烯基导电复合材料制备的PTC元件及其制备方法。由本发明聚偏氟乙烯基导电复合材料制备的PTC元件具有突出的电阻再现性，良好的耐电压性能和环境可靠性。
Description
技术领域
本发明涉及一种聚偏氟乙烯基导电复合材料及PTC元件，尤其是一种具有突出的电阻再现性，良好的耐电压性能和环境可靠性的聚偏氟乙烯基导电复合材料及PTC元件和制备方法。
背景技术
由聚合物和导电填料共混得到的聚合物基导电复合材料，其电阻与温度通常具有非线性关系，随着温度的升高，聚合物基体的热膨胀导致导电颗粒间间距增大，使得材料的体积电阻率增大，而当外界温度接近聚合物基体熔点时，此时基体热膨胀最为显著，导电颗粒间距被急剧拉大，因此，导电复合材料的体积电阻率会出现几个数量级的增大，即出现PTC（电阻正温度系数）效应。这类聚合物导电复合材料在电子线路保护元件、加热器、传感器等领域有诸多应用。
PTC保护元件一个非常典型的应用场合，便是应用在车载领域的电子线路。一般来说，在车载领域，希望PTC保护元件具备：在-40～125℃环境范围内正常工作的能力；电压等级≥26V，并且要有较大的耐压等级余量（车载额定电压：乘用车12V、商用车24V）；良好的环境可靠性，可满足AEC-Q200标准；PTC保护元件的保护特性与电阻直接相关，PTC保护元件在连续多次触发动作恢复后，电阻变化率越大，则PTC保护元件的特性衰减越大，其寿命则相应越短，因此，希望PTC保护元件具有较小的电阻变化率，即良好的PTC电阻再现性。完全理想状态下的PTC保护元件电阻变化率是接近于零，但目前实际商业化的车载PTC保护元件，触发一次后电阻变化率达30%以上，连续10000次触发动作后，电阻变化率一般都不小于80%，因此，开发进一步降低电阻变化率的PTC保护元件，具有非常迫切的实际意义。
美国专利号5451919提供了一种聚偏氟乙烯基导电复合材料以及由该材料制备的PTC器件，该材料具有良好的PTC特性。
发明内容
本发明目的在于：提供一种聚偏氟乙烯基导电复合材料，具有优异的PTC特性和电阻再现性。
本发明的再一目的在于：提供使用上述聚偏氟乙烯基导电复合材料的PTC元件。以及，
本发明的又一目的在于：提供一种上述PTC元件的制备方法。
本发明目的通过下述技术方案实现：一种聚偏氟乙烯基导电复合材料以聚偏氟乙烯(PVDF)为基体，具有正温度系数（PTC）效应，环境温度25℃下的电阻率不大于10Ω.cm，包含：
a)所述的PVDF为第一组分聚合物，占所述聚偏氟乙烯基导电复合材料的体积分数的20~70%，优选为25~65%之间，更优为30~60%之间；
b)预先辐照交联的含氟聚合物为第二组分聚合物，为以0~200Mrads的剂量照射交联的聚四氟乙烯（PTFE）、以3.2~200Mrads的剂量照射交联的聚偏氟乙烯、以3.2~200Mrads的剂量照射交联的聚全氟乙丙烯（FEP）、以3.2~200Mrads的剂量照射交联的四氟乙烯-乙烯共聚物（ETFE）中的一种或两种以上的混合物，占所述聚偏氟乙烯基导电复合材料的体积分数的0.5~30%，优选为1~20%，所述第二组份聚合物分散在第一组分聚合物中；
c)导电填料，占所述聚偏氟乙烯基导电复合材料的体积分数的25~75%，优选为30~70%，所述导电填料分散在第一组分聚合物中。
本发明采用预先辐照交联的含氟聚合物为第二组分聚合物，在熔融加工过程中，具有不流动或流动性小的特点，导电填料不会进入第二聚合物本体中，从而电阻稳定性、电压等级、耐候性等方面表现更优异。
进一步的，所述的第二组分聚合物粒径为10nm~20μm，优选为5nm~15μm，与PVDF的共混效果更好。
所述的导电填料可以是炭黑、碳纤维、碳纳米管、石墨、石墨烯、陶瓷粉末、陶瓷纤维、金属粉末和金属纤维中的一种或两种以上的组合物，优选炭黑。
本发明还提供了一种根据上述的聚偏氟乙烯基导电复合材料制备的PTC元件，由聚偏氟乙烯基导电复合材料片材和紧密连接在该复合材料片材二面的金属电极构成，所述的聚偏氟乙烯基导电复合材料片材的厚度为0.01~3.00mm，优选为0.05~2.5mm，被分割成具有平面形状的单个PTC元件，所述PTC元件有与电流流过方向垂直的两个表面，在25℃时，该PTC元件的电阻率不大于10Ω.cm。
本发明PTC元件具有突出的电阻再现性，良好的耐电压性能和环境可靠性。
在上述方案基础上，所述的PTC元件为方形、三角形、圆形、环形、多边形或其他不规则形状的片状结构。
本发明也提供了一种上述的聚偏氟乙烯基导电复合材料制备的PTC元件的制备方法，包括下述步骤：
1）将第一组分聚合物聚偏氟乙烯、预先辐照交联的第二组分聚合物和导电填料在高于第一组分聚合物聚偏氟乙烯熔融温度条件下，进行混合，如在250℃的条件下，投入密炼机、开炼机、双螺杆挤出机或单螺杆挤出机中，进行熔融混合；然后将混合好的聚合物复合材料通过挤出成型、模压成型或压延成型的方式，加工成厚度0.01~3.0mm的聚偏氟乙烯基导电复合材料片材，优选厚度为0.05~2.5mm，为了加工的方便，更优为0.1~2.0mm；
2）聚偏氟乙烯基导电复合材料片材通过滚筒或平板热压合的方式，将金属电极紧密连接在所述片材的上下表面，形成PTC片材；
3）所述的PTC片材通过冲压、划切或激光切割成单个PTC元件，所述PTC元件为片状，即有与电流流过方向垂直的两个表面，且两个表面之间的距离不大于3.0mm，优选的不大于2.5mm，更优选的不大于2.0mm，制备成PTC元件；
4）对PTC元件进行交联和/或热处理。
在上述方案基础上，步骤2）中，为了使金属电极片与聚偏氟乙烯基导电复合材料片材复合的牢固，可在聚偏氟乙烯基导电复合材料片材还处于熔融状态时，通过滚筒或平板热压合的方式，将金属电极紧密连接在该片材的上下表面获得复合片材；
步骤4）中，对PTC元件进行交联和/或热处理，通常可借助交联和/或热处理的方式来使得PTC元件特性稳定，交联可采用化学或高能射线辐照交联，PTC元件辐照交联一般不超过100Mrads，更优的选择1~50Mrads，更优的选择3.2~32Mrads；热处理可以是退火、热循环、高低温交变，例如135℃/40℃高低温交变。
本发明的优越性在于：本发明聚偏氟乙烯基导电复合材料导电性能良好，由其制备的PTC元件，具有突出的电阻再现性，良好的耐电压性能和环境可靠性。
下面结合附图和具体实施例，对本发明作进一步的详细说明。
附图说明
图1为本发明PTC元件的结构示意图；
图2为本发明包括金属导电引脚的PTC元件结构示意图；
图中标号说明：
11——聚偏氟乙烯基导电复合材料片材；
12、13——上、下金属电极；
14、15——上、下金属导电引脚。
具体实施方式
实施例1
一种聚偏氟乙烯基导电复合材料的PTC元件，按下述步骤制备：
1，一种聚偏氟乙烯基导电复合材料，以PVDF为基体，具有PTC效应，由：
a)所述的PVDF为第一组分聚合物，其熔融温度为173℃，密度1.8g/cm3，体积分数为54%；
b)预先辐照交联的含氟聚合物为第二组分聚合物，
第二组分聚合物为未经过照射交联的聚四氟乙烯PTFE，粒径为120nm，密度2.16g/cm3，体积分数为6%；
c)导电填料，为炭黑，体积分数为40%。
2，聚偏氟乙烯基导电复合材料片材制备：
密炼机温度250℃，转速30转/min，先加入第一组份聚合物聚偏们氟乙烯密炼3min，加入1/2重量的第二组分聚合物PTFE和导电填料，密炼5min，再加完另外1/2重量的第二组分聚合物PTFE和导电填料，继续密炼10min，出料，将所得物料通过开练机薄通拉片，制得厚度为0.30-0.34mm的薄片。
3，在薄片的上下表面覆盖金属箔作为金属电极，采用真空压机热压成型，真空压机温度220℃，预热5min，热压压力10MPa，热压时间8min，冷压压力10MPa，冷压时间10min，采用模具冲压成12×8mm的单个PTC元件，其由聚偏氟乙烯基导电复合材料片材11和上、下金属电极12、13构成，如图1所示。
4，将以上PTC元件经过16M的电子束辐射交联，再通过回流焊的方法将上、下金属引脚14、15分别连接在上、下金属电极12、13表面，最后在135℃/1h到40℃/1h的条件下冷热冲击6次，得到最终的PTC元件。
本实施例的PTC元件的电性能如表一所示，成品电阻R0为20.2；电阻再现性(R10000-R0/R0)*100%为36.6%；耐候性(R1000h@85℃/85%RH-R0)/R0*100%为-1.0%；耐电压能力（R36V/50A-R0)/R0*100%为58.9%。
实施例2
一种聚偏氟乙烯基导电复合材料的PTC元件，与实施例1近似，但配方中第二组分聚合物不同，按下述步骤制备：
1，一种聚偏氟乙烯基导电复合材料，以PVDF为基体，具有PTC效应，由：
a)所述的PVDF为第一组分聚合物，其熔融温度为173℃，密度1.8g/cm3，体积分数为54%；
b)第二组分聚合物为经过32Mrads剂量照射交聚偏氟乙烯联，烯密度1.8g/cm3、粒径1μm，体积分数为6%；
c)导电填料，为炭黑，体积分数为40%。
2，聚偏氟乙烯基导电复合材料片材制备、3，PTC元件制备以及4，最终的PTC元件均与实施例1相同。
本实施例的PTC元件的电性能如表一所示：成品电阻R0为17.3，电阻再现性(R10000-R0/R0)*100%为32.4%；耐候性(R1000h@85℃/85%RH-R0)/R0*100%为-0.6%；耐电压能力（R36V/50A-R0)/R0*100%为65.3%。
实施例3
一种聚偏氟乙烯基导电复合材料的PTC元件，与实施例1近似，但第二组分聚合物不同，按下述步骤制备：
1，一种聚偏氟乙烯基导电复合材料，以PVDF为基体，具有PTC效应，由：
a)所述的PVDF为第一组分聚合物，其熔融温度为173℃，密度1.8g/cm3，体积分数为54%；
b)第二组分聚合物为：
经过32Mrads剂量照射交联的聚偏氟乙烯和经过16Mrads剂量照射交联的四氟乙烯-乙烯共聚物的混合物，其中，该经过32Mrads剂量照射交联的聚偏氟乙烯密度1.8g/cm3，粒径1μm，体积分数2%；该经过16Mrads剂量照射交联的四氟乙烯-乙烯共聚物密度1.8g/cm3，粒径1.5μm，体积分数4%；
c)导电填料，为炭黑，体积分数为40%。
2，聚偏氟乙烯基导电复合材料片材制备、3，PTC元件制备以及4，最终的PTC元件均与实施例1相同。
本实施例的PTC元件的电性能如表一所示：成品电阻R0为16.4；电阻再现性(R10000-R0/R0)*100%为32.9%；耐候性(R1000h@85℃/85%RH-R0)/R0*100%为-1.2%；耐电压能力（R36V/50A-R0)/R0*100%为62.8%。
实施例4
一种聚偏氟乙烯基导电复合材料的PTC元件，与实施例1近似，但第二组分聚合物不同，按下述步骤制备：
1，一种聚偏氟乙烯基导电复合材料，以PVDF为基体，具有PTC效应，由：
a)所述的PVDF为第一组分聚合物，其熔融温度为173℃，密度1.8g/cm3，体积分数为56%；
b)预先辐照交联的含氟聚合物为第二组分聚合物，
第二组分聚合物为未经过照射交联的聚四氟乙烯PTFE，粒径为120nm，密度2.16g/cm3，体积分数为4%；
c)导电填料，为炭黑，体积分数为40%。
2，聚偏氟乙烯基导电复合材料片材制备、3，PTC元件制备以及4，最终的PTC元件均与实施例1相同。
本实施例的PTC元件的电性能如表一所示：成品电阻R0为18.2；电阻再现性(R10000-R0/R0)*100%为34.6%；耐候性(R1000h@85℃/85%RH-R0)/R0*100%为-1.6%；耐电压能力（R36V/50A-R0)/R0*100%61.5%。
实施例5
一种聚偏氟乙烯基导电复合材料的PTC元件，与实施例2近似，但第二组分聚合物不同，按下述步骤制备：
1，一种聚偏氟乙烯基导电复合材料，以PVDF为基体，具有PTC效应，由：
a)所述的PVDF为第一组分聚合物，其熔融温度为173℃，密度1.8g/cm3，体积分数为56%；
b)第二组分聚合物为：经过32Mrads剂量照射交联的聚偏氟乙烯4%；
c)导电填料，为炭黑，体积分数为40%。
2，聚偏氟乙烯基导电复合材料片材制备、3，PTC元件制备以及4，最终的PTC元件均与实施例1相同。
本实施例的PTC元件的电性能如表一所示：成品电阻R0为15.2；电阻再现性(R10000-R0/R0)*100%为34.2%；耐候性(R1000h@85℃/85%RH-R0)/R0*100%为-0.7%；耐电压能力（R36V/50A-R0)/R0*100%为60.5%。
实施例6
一种聚偏氟乙烯基导电复合材料的PTC元件，与实施例3近似，但第二组分聚合物不同，按下述步骤制备：
1，一种聚偏氟乙烯基导电复合材料，以PVDF为基体，具有PTC效应，由：
a)所述的PVDF为第一组分聚合物，其熔融温度为173℃，密度1.8g/cm3，体积分数为56%；
b)第二组分聚合物为：
经过32Mrads剂量照射交联的聚偏氟乙烯和经过16Mrads剂量照射交联的四氟乙烯-乙烯共聚物的混合物，其中，该经过32Mrads剂量照射交联的聚偏氟乙烯密度1.8g/cm3，粒径1μm，体积分数1%；该经过16Mrads剂量照射交联的四氟乙烯-乙烯共聚物密度1.8g/cm3，粒径1.5μm，体积分数3%；
c)导电填料，为炭黑，体积分数为40%。
2，聚偏氟乙烯基导电复合材料片材制备、3，PTC元件制备以及4，最终的PTC元件均与实施例1相同。
本实施例的PTC元件的电性能如表一所示：成品电阻R0为21.4；电阻再现性(R10000-R0/R0)*100%为35.0%；耐候性 (R1000h@85℃/85%RH-R0)/R0*100%为-1.4%；耐电压能力（R36V/50A-R0)/R0*100%为56.1%。
比较例1
制备聚偏氟乙烯基导电复合材料及PTC元件的步骤与实施例1相同，但不添加任何第二组分聚合物，第一组份聚合物聚偏氟乙烯的基体分数为60%。
本对比例的PTC元件的电性能如表一所示：成品电阻R0为17.2；电阻再现性(R10000-R0/R0)*100%为271.5%；耐候性为(R1000h@85℃/85%RH-R0)/R0*100%为-4.7%；耐电压能力为NA（R36V/50A击穿）。
比较例2
制备聚偏氟乙烯基导电复合材料及PTC元件的步骤与实施例1相同，但所添加第二组分聚合物为未经过照射交联的四氟乙烯-乙烯共聚物，该未经过照射交联的四氟乙烯-乙烯共聚物密度1.8g/cm3，粒径1.5μm，体积分数6%。
本对比例的PTC元件的电性能如表一所示：成品电阻R0为18.3；电阻再现性(R10000-R0/R0)*100%为134.4%；耐候性为-4.9%；耐电压能力（R36V/50A-R0)/R0*100%为NA（R36V/50A击穿）。
表一为本发明PTC元件实施例和比较例的配方组成及电气性能测试结果。其中，R0表示所述的PTC元件的成品电阻；
R1表示所述的PTC元件在16V/50A通电6s断电60s，通断电1次，然后在25℃环境中放置至少1h后的电阻值；
R10000表示所述的PTC元件在16V/50A通电6s断电60s，连续通断电10000次，然后在25℃环境中放置至少1h后的电阻值；
R1000cycles表示所述的PTC元件在125℃/60min到-40℃/60min冷热冲击环境中进行1000个循环，然后在25℃环境中放置至少1h后的电阻值；
R1000h@125℃表示所述的PTC元件在125℃环境中放置1000h，然后在25℃环境中放置至少1h后的电阻值；
R1000h@85℃/85%RH表示所述的PTC元件在85℃温度和85%RH湿度环境中放置1000h，，然后在25℃环境中放置至少1h后的电阻值；
R32V/50A为PTC在32V/50A通电条件下，耐电压维持24h，然后在25℃环境中放置至少1h后的电阻值；
R36V/50A为PTC在36V/50A通电条件下，耐电压维持24h，然后在25℃环境中放置至少1h后的电阻值；
由实施例1~6和比较例1~2可知，具有相同体积分数的导电填料，但在实施例1~6中，将聚合物分成了第一组分聚合物和第二组分聚合物，实施例1和实施例4的第二组分聚合物为聚四氟乙烯（PTFE）、实施例2和实施例5的第二组分聚合物为由32Mrads剂量照射交联的聚偏氟乙烯、实施例3和实施例6的第二组分聚合物为由32Mrads剂量照射交联的聚偏氟乙烯和由16Mrads剂量照射交联的四氟乙烯-乙烯共聚物的混合物。
通过分别考察实施例和比较例的电阻再现性、耐候性和耐电压能力，得到表一，由表一可知，PTC元件在16V/50A通电6S断电60S，通断电1次和10000次，然后在25℃环境中放置至少1h后的电阻值，实施例1~6的电阻变化率要小，说明具有明显的电阻再现性优势；PTC元件分别在125℃/60min到-40℃/60min冷热冲击环境中进行1000个循环、高温125℃放置1000h、85℃温度和85%RH湿度环境中放置1000h的耐候性评价中，实施例1~6的电阻变化率要小，说明具有明显的耐候性优势；PTC元件分别在32V/50A和36V/50A下耐电压维持24h，其中比较例1~2在36V/50A耐电压条件下出现了击穿失效，而实施例1~6的PTC元件表现正常，说明具有更高的耐电压能力。
表一说明如下：
PTC元件成品的电阻R0；
电阻再现性：
PTC元件在16V/50A通电6s断电60s，通断电1次和10000次，然后在25℃环境中放置至少1h后的电阻值的电阻R1和电阻R10000，通断电1次的电阻变化率为：(R1-R0/R0)*100%；通断电10000次电阻变化率为：(R10000-R0/R0)*100%；
耐候性：
PTC元件分别在125℃/60min-40℃/60min冷热冲击环境中进行1000个循环电阻R1000cycles、高温125℃放置1000h的电阻R1000h@125℃、85℃温度和85%RH湿度环境中放置1000h的电阻R1000h@85℃/85%RH，电阻变化率为：在125℃/60min-40℃/60min冷热冲击环境中进行1000个循环(R1000cycles-R0)/R0*100%，高温125℃放置1000h的电阻变化率(R1000h@125℃-R0)/R0*100%，85℃温度和85%RH湿度环境中放置1000h的电阻变化率(R1000h@85℃/85%RH-R0)/R0*100%；
耐电压能力：
PTC元件分别在26V/50A下耐电压维持24h电阻为R26V/50A和36V/50A下耐电压维持24h电阻为R36V/50A，在26V/50A下耐电压维持24h电阻变化率为（R26V/50A--R0)/R0*100%，36V/50A下耐电压维持24h电阻变化率为（R36V/50A-R0)/R0*100%，
Claims (5)
1.一种聚偏氟乙烯基导电复合材料，其特征在于：以聚偏氟乙烯(PVDF)为基体，具有正温度系数（PTC）效应，环境温度25℃下的电阻率不大于10Ω.cm，包含：
a) 所述的PVDF为第一组分聚合物，占所述聚偏氟乙烯基导电复合材料的体积分数的20~70%；
b) 预先辐照交联的含氟聚合物为第二组分聚合物，为以3.2~200Mrads的剂量照射交联的聚偏氟乙烯、以3.2~200Mrads的剂量照射交联的聚全氟乙丙烯（FEP）、以3.2~200Mrads的剂量照射交联的四氟乙烯-乙烯共聚物（ETFE）中的一种或两种以上的混合物，占所述聚偏氟乙烯基导电复合材料的体积分数的0.5~30%，所述第二组份聚合物分散在第一组分聚合物中；
c) 导电填料，占所述聚偏氟乙烯基导电复合材料的体积分数的25~75%，所述导电填料分散在第一组分聚合物中；其中，
所述的第二组分聚合物粒径为10nm~20μm。
2.根据权利要求1所述的聚偏氟乙烯基导电复合材料，其特征在于：所述的导电填料可以是炭黑、碳纤维、碳纳米管、石墨、石墨烯、陶瓷粉末、陶瓷纤维、金属粉末和金属纤维中的一种或两种以上的组合物。
3.一种根据权利要求1或2所述的聚偏氟乙烯基导电复合材料制备的PTC元件，由聚偏氟乙烯基导电复合材料片材和紧密连接在该复合材料片材二面的金属电极构成，所述的聚偏氟乙烯基导电复合材料片材的厚度为0.01~3.00mm，被分割成具有平面形状的单个PTC元件，所述PTC元件有与电流流过方向垂直的两个表面，在25℃时，该PTC元件的电阻率不大于10Ω.cm。
4.根据权利要求3所述的聚偏氟乙烯基导电复合材料制备的PTC元件，其特征在于：所述的PTC元件为方形、三角形、圆形、环形、多边形或其他不规则形状的片状结构。
5.一种根据权利要求3和4所述的聚偏氟乙烯基导电复合材料制备的PTC元件的制备方法，包括下述步骤：
1）将第一组分聚合物聚偏氟乙烯、预先辐照交联的第二组分聚合物和导电填料在高于第一组分聚合物聚偏氟乙烯熔融温度条件下，进行混合，然后将混合好的聚合物复合材料通过挤出成型、模压成型或压延成型的方式，加工成厚度0.01~3.0mm的聚偏氟乙烯基导电复合材料片材；
2）聚偏氟乙烯基导电复合材料片材通过滚筒或平板热压合的方式，将金属电极紧密连接在所述片材的上下表面，形成PTC片材；
3）所述的PTC片材通过冲压、划切或激光切割成单个PTC元件，所述PTC元件为片状，即有与电流流过方向垂直的两个表面，且两个表面之间的距离不大于3.0mm；
对PTC元件进行交联和/或热处理。
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| CN1794369A (zh) * | 2005-12-30 | 2006-06-28 | 上海维安热电材料股份有限公司 | 改进型高温级高分子ptc热敏电阻器制造方法 |
| CN102140194A (zh) * | 2010-01-29 | 2011-08-03 | 比亚迪股份有限公司 | 一种正温度系数材料及其制备方法及含有该材料的热敏电阻 |
| CN103797548B (zh) * | 2011-12-31 | 2016-12-07 | 上海长园维安电子线路保护有限公司 | 高分子基导电复合材料及ptc元件 |
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