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单击此处编辑母版标题样式,单击此处编辑母版文本样式,第二级,第三级,第四级,第五级,*,高聚物的介电常数,8,高聚物的电性能,总论,高聚物具有体积电阻率高(,10,16,10,20,cm,)、介电常数小(,2,)、介质损耗低,(,10,4,)等半导体特殊优良的电性能,同时某些高聚物还具有优良的导电性能。另外,,由于高聚物成型加工容易,品型多,故在电器方法应用广泛。,8-1,高聚物的介电性,一、高聚物分子的极化,定义,高聚物的介电性是指高聚物在电场的作用下,表现出对静电能的储蓄的损耗的性质。,高聚物的极性与类别,高聚物的极化(,polarization,),是电解质在电场的作用下分子内束缚电荷产生弹性位移或偶极子沿电场的从优取向,,在电场方向的电解质两端呈现异号电荷的现象。,强极性高聚物,(,PVA,、,PAN,、,PET,、酚醛树脂、氨基树脂等),高聚物的极性类别,非极性高聚物(,PE,、,PP,、,PTFE,等,),弱极性高聚物(,PS,、,PIP,等),极性高聚物(,PVC,、,PA,、,PVAC,、,PMMA,等),介电性的表示方法,介电常数,介电损耗,影响高聚物介电性的因素,高聚物的极性,高聚物的极化,8-1,高聚物的介电性,高聚物的极化形式,极化形式,极化机理,特点,适用对象,电子极化,电子云的变形,极快,,10,12,10,15,s,;无能量损耗;不依赖温度和频率,所有高聚物,原子极化,各原子之间的相对位移,稍快,,10,12,s,;损耗微量能量;不依赖温度,所有高聚物,偶极极化,极性分子(或偶极子)沿电场方向转动,从优取向,慢,,10,9,s,以上;损耗较大能量;依赖温度和频率,极性高聚物,界面极化,载流子在界面处聚集产生的极化,极慢,几分之一秒至几分钟、几小时,共混、复合材料,高聚物在电场中极化示意图,8-1,高聚物的介电性,二、高聚物的介电性,高聚物的介电常数(,dielectric constant,),定义,显然,高聚物极化程度越大,极板感应产生的电荷,Q,越大,介电常数越大。,常见高聚物的介电常数,高聚物,计算值,实验值,高聚物,计算值,实验值,聚乙烯(外推到无定型),聚丙烯(无定型),聚氯化苯乙烯,聚四氟乙烯(无定型),聚氯乙烯,聚醋酸乙烯酯,聚甲基丙烯酸甲酯,聚,-,氯代丙烯酸甲酯,2.20,2.15,2.55,2.82,2.0,3.20,2.94,3.45,2.3,2.2,2.55,2.6,2.1,2.25,2.6/3.7,3.4,聚,-,氯代丙烯酸乙酯,聚甲基丙烯酸乙酯,聚丙烯腈,聚甲醛,聚苯醚,聚对苯二甲酸乙二酯,(,无定型,),聚碳酸酯,聚已二酰已二胺,3.20,2.80,3.26,2.95,2.65,3.40,3.00,4.14,3.1,2.7/3.4,3.1,3.1,2.6,2.9/3.2,2.6/3.0,4.0,8-1,高聚物的介电性,高聚物的介电损耗(,dielectric loss,),定义,是电介质在交变电场的作用下,将一部分电能转变为,热能而损耗的现象。一般用损耗角的正切值表示。,式中实验测得的介电常数;,高聚物将电能转变为热能损耗的程度。,介电损耗的原因,对非极性高聚物,在交变电场中,所含的杂质产生的漏导电流,载流子流动时,克服,内摩擦阻力而作功,使一部分电能转变为热能,属于欧姆损耗。,对极性高聚物,在交变电场中极化时,由于黏滞阻力,偶极子的转动取向滞后于交变,电场的变化,致使偶极子发生强迫振动,在每次交变过程中,吸收一部分电能成热能而释,放出来,属于偶极损耗。损耗的大小取决于偶极极化的松弛特性。,V,V,I,Ic,a,b,高聚物介电损耗示意图,8-1,高聚物的介电性,部分高聚物的介电损耗,高聚物,介电损耗(,tan,),60Hz,103Hz,106Hz,高密度聚乙烯,低密度聚乙烯,聚丙烯,聚苯乙烯,聚四氟乙烯,聚碳酸酯,聚已内酰胺,聚已二酰已二胺,聚甲基丙烯酸甲酯,聚氯乙烯,聚偏乙烯,ABS,聚甲醛,0.0002,0.0005,0.0005,0.0001,0.0003,0.0002,0.0009,0.014,0.04,0.010,0.06,0.04,0.06,0.08,0.15,0.007,0.02,0.004,0.034,0.004,0.002,0.0005,0.0002,0.0008,0.0001,0.0003,0.0002,0.0021,0.02,0.04,0.011,0.06,0.03,0.05,0.07,0.16,0.009,0.017,0.002,0.012,0.0003,0.0005,0.0001,0.0005,0.0001,0.0004,0.0002,0.010,0.03,0.04,0.03,0.04,0.02,0.03,0.04,0.140,0.006,0.019,0.007,0.026,0.004,8-1,高聚物的介电性,三、影响高聚物介电性的因素,高聚物分子结构对介电性的影响,规律:,与,T,一定,,极性,、极性基团密度,介电常数与介电损耗。,实例,前两表,频率对高聚物介电性的影响,影响高聚物介电性的因素,高聚物的分子结构,交变电场的频率,温度,湿度,增塑剂,(T,1,),(T,1,),(T,1,),(T,1,),(T,1,),(T,1,),随频率增加而降低,并且在较低和较高时为零。,随频率增加存在极大值,并且,频率较高和较低时为零。,T,1,T,2,T,3,8-1,高聚物的介电性,温度对高聚物介电性的影响,对非极性高聚物,温度升高,介电常数下降;对极性高聚物,随温度的升高而出现峰,值。,湿度对高聚物介电性的影响,2.00,2.05,2.10,2.30,2.35,2.40,0,20,40,60,80,100,1,2,3,4,温度(),介电常数,非极性高聚物的介电常数与温度的关系,1-PP,;,2-HDPE,;,3-LDPE,;,4-PTFE,50,60,70,80,90,100,3,5,7,9,1,2,1000Hz,1000Hz,60Hz,60Hz,PVAC,的介电性能与温度的关系,温度(),介电性,介电常数(,50Hz,),介电损耗(,50Hz,),相对湿度,酚醛树脂,聚氯乙烯(电缆料),31.7%,63%,97%,9.71,10.4,15.8,7.40,7.50,8.00,31.7%,63%,97%,0.342,0.358,0.448,0.111,0.113,0.136,湿度,,介电常数与介电损耗,8-1,高聚物的介电性,增塑剂对高聚物介电性的影响,规律:,对非极性高聚物,随加入增塑剂量的增加将曲线推向高频率区;对极性高聚,物,随增塑剂量的增加,介电常数和介电损耗增大。,实例,PVC,杂质对高聚物介电性的影响,规律:,导电性或极性杂质的存在,增加高聚物电导电流的极化率,使介电损耗增大。,实例,HDPE,杂质,1.9%,降到,0.03%,时,,tan,从,1410,-4,降到,tan,1410,-4,20,40,60,80,100,T(),0,5,10,15,20,40,60,80,100,T(),0,0.5,1.0,1.5,0,3,9,15,20,0,3,9,15,20,增塑剂加入量对,PVC,介电性能的影响,8-2,高聚物的导电性,一、高聚物的导电类型,导电性,在电场作用下,物体中载流子发生移动的现象。用电导率或电阻率,表示。,在直流电场下,物体的电导率表示为:,式中,电导率;,n,载流子的浓度;,e,电子电荷;,载流子的移动度。,高聚物的导电类型,高聚物的导电类型,电子导电,离子导电,氧化还原导电,8-2,高聚物的导电性,导电高聚物的应用,导电高聚物的应用,电子导电高聚物,导电材料,电极材料,电显示材料,化学反应催化剂,有机分子开关,离子导电高聚物,代替电解质材料,全固态电池,氧化还原导电高聚物,各种电极材料,特种电极修饰材料,8-2,高聚物的导电性,二、高聚物的绝缘电阻,高聚物绝缘电阻的表示形式,表面电阻率,体积电阻率,平等电极,环状电极,测量电极,环电极,对电极,试样,绝缘电阻测定,8-3,高聚物的击穿电压强度,一、,击穿电压与击穿电压强度,介电击穿:,随着电压的不断增加至某极限值后,出现电阻率降低到极小,电流增加,,产生局部导电而使高聚物材料丧失绝缘性能的现象。,击穿电压:,导致高聚物材料击穿的电压。,电流,-,电压曲线,击穿电压强度:,连续对高聚物材料升高电压,当试样被击穿时的电压和试样厚度的比,值称为击穿电压强度。,高电压区,低电压区,绝缘破坏区,I,电压,V,8-3,高聚物的击穿电压强度,介电击穿的形式、原因及决定因素,介电击,穿形式,本征击穿,热击穿,放电引起的击穿,高聚物材料,高压电场,离子,少数自由电子,加速,运动,获能,碰撞,新的,电子,大量自由电子,介电损耗,产生热量,T,导电率,老化变质,气泡,电离放电,电子,离子,放热,老化变质,8-3,高聚物的击穿电压强度,常见高聚物的击穿电压强度,100,0,-100,-200,5,10,15,温度(),1,2,3,4,5,6,击穿电压强度,10,6,(,V/cm,),几种高聚物的击穿电,压强度与温度的关系,1-,聚甲基丙烯酸甲酯,2-,聚乙烯醇,3-,氯代聚乙烯,4-,聚苯乙烯,5-,聚乙烯,6-,聚异丁烯,高聚物,E,b,高聚物,E,b,高聚物,E,b,聚乙烯,聚丙烯,聚甲基丙烯酸甲酯,聚氯乙烯,聚苯乙烯,18-28,20-26,18-22,14-20,16-20,聚砜,酚醛树脂,环氧树脂,聚乙烯醇,聚丙烯薄膜,17-22,12-16,16-20,40-60,100-140,聚苯乙烯薄膜,聚酯薄膜,聚酢亚胺薄膜,芳香聚酰胺薄膜,50-60,100-130,80-110,70-90,8-3,高聚物的击穿电压强度,二、耐电压性与耐电弧性,耐电压性:,指迅速将电压升高到制品标准规定的电压,停留,1min,(或按制品,标准规定的时间),观察制品是否被击穿,若未被击穿,则此电压为该制品的耐,电压值。此数值表示高聚物制品的耐电压能力。,耐电弧性:,在一定的高压电场下,两极间的气体被击穿产生电弧、火花的作,用,致使高聚物表面形成导电层所需要时间的长短表示高聚物对电弧、电火花的,抵抗能力。,8-4,高聚物的静电现象,一、静电现象(,electrostatic effect,),高聚物静电现象的产生,主要产生于高聚物与成型加工设备之间的摩擦、拉幅、拉丝等过程。,A,A,A,B,B,B,电中性,两相电荷,带电,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,|,接触或,摩擦,分离,物体的静电现象,8-4,高聚物的静电现象,高聚物的带电半衰期与带电序列,二、,静电的利与弊,静电的有利之处,静电喷涂、静电印刷、静电照像、静电吸尘等。,静电的不利之处,影响外观、相互黏结、电器准确性、静电火花、磁带杂音等。,高聚物,半衰期,,s,正电荷,负电荷,聚乙烯基咪唑,赛璐璐,聚,N,,,N-,二甲丙烯酰胺,聚丙烯酸,羊毛,棉花,聚,n-,乙烯基吡咯酮,聚丙烯腈,聚已二酰已二胺,聚乙烯醇,0.1,0.3,0.66,1.5,2.5,3.6,41,667,936,8470,0.24,0.3,0.48,0.96,1.55,4.8,15.8,687,720,3770,聚四氟乙烯,聚丙烯,聚苯乙烯,聚乙烯,聚苯醚,聚偏二氯乙烯,氯化聚醚,聚碳酸酯,聚氯乙烯,聚丙烯腈,聚对苯二甲酸乙二酯,维尼纶,聚甲基丙烯酸甲酯,醋酸纤维,纤维素,聚酰胺,8-4,高聚物的静电现象,三、,静电的防止,静电的防止办法,静电消除器,接地导出,环境湿度调节,加入抗静电剂,阳离子型,阴离子型,两性离子型,非离子型,高分子型,静,电,荷,10,7,10,6,10,5,10,4,10,3,10,2,10,1,1,0,5,10,15,20,吸水率(,%,),聚酰胺,木,棉,麻,羊毛,络素纤维,胶粘纤维,醋酸,纤维,1000,500,100,50,10,5,4,3,2,0,0.1,0.2,0.3,0.4
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