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中国物理学会期刊

聚偏氟乙烯分子链旋转时势能的变化

CSTR: 32037.14.aps.48.1930

VARIATION OF INTERCHAIN POTENTIAL DURING MOLECULAR CHAIN ROTATION IN POLY (VINYLIDENE FLUORIDE)

CSTR: 32037.14.aps.48.1930
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  • 计算了聚偏氟乙烯分子链旋转时势能的变化.结果显示,当中心分子链旋转而其它链静止不动时,计算得到的势能曲线有4个很高的势垒,这些势垒来源于中心分子链和最近邻分子链中的氟原子对的“空间位阻”效应.这一结果与“六阱势”模型预言的势能变化存在准六度对称性相矛盾.计算结果表明,如果中心分子链和周围分子链同步旋转,势垒高度将极大地降低.另外,极化反转时晶格常数发生变化.最后得到的势垒高度约为7.5kJ/mol.与室温下的分子势运动的能量(约2.5kJ/mol)相比,这样的“浅”势阱不足以锁定分子偶极矩形成稳定的自发极

     

    The variation of interchain potential in poly (vinylidene fluoride) polymer during chain rotation was calculated.In the case that center chain rotates while all other chains keep static as discussed by “six-site-potential” theory,the potential curves show four high potential barriers owing to the steric effect of fluorine atom from adjacent molecule,which is in contrast to the six-fold sysmmetry pre-dicted by the “six-site-potential” model.It was found that if all chains rotate synchronically, the barrier height will reduce dramatically.The result also indicates that the polarization reversal is ac-complished with the change of lattice constant.The finally obtained barrier height is about 7.5kJ/mol.In comparison with the thermal energy of chain rotation at room temperature (about2.5kJ/mol),the potential well is too shallow to form stable spontaneous polarization.It was specu-lated therefore,the formation of spontaneous polarization in these materials should include some ex-ternal factors.

     

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