Li Zhen, Lian Yiwei, Gu Qianlei, Pei Tiehao, Chen Zhen, Hao Weiliang
Department of Applied Chemistry, School of Materials Science and Engineering, Hebei University of Engineering, Handan, Hebei 056038, China.
School of Life Sciences and Food Engineering, Hebei University of Engineering, Handan, Hebei 056038, China.
Langmuir. 2024 Feb 13;40(6):3202-3212. doi: 10.1021/acs.langmuir.3c03671. Epub 2024 Jan 29.
Two dielectric relaxations located at approximately 10 and 300 MHz were analyzed in the microemulsion composed of the polar ionic liquid (PIL) 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF]), the surface-active ionic liquid (SAIL) 1-butyl-3-methylimidazolium 1,4-bis(2-ethylhexyl) sulfosuccinate ([bmim][AOT]), and benzene. The curve of the dc conductivity vs PIL weight fraction shows two inflection points, namely, 16.69 and 27.90 wt %, which are used to divide the PIL/O, bicontinuous (B.C.), and O/PIL subregions. The critical exponents of percolation = 0.75, 0.79, and 0.80 are suggested from the scaling dependence of dc conductivity on the PIL weight fraction, together with frequency dependences of both permittivity and loss angle, which all infer that static percolation occurs in the microemulsion. Only one dielectric relaxation at high frequency was observed in the PIL/O subregion, when the concentration increased to the boundary between the PIL/O and B.C. subregions; the second dielectric relaxation appeared at low frequency. The high-frequency relaxation is caused by interfacial polarization. The low-frequency relaxation is attributed to the dipole-oriented polarization of AOT. When the oil content of the system was reduced, the interface became softer to allow more AOT to rotate, and the cation shifted from moving around its long axis to rotating along its short axis. The static dielectric constant of [bmim][AOT] was given. The dielectric constants and conductivity of the dispersed and continuous phases in the PIL/O and O/PIL subregions were calculated from the dielectric parameters of high-frequency relaxation.
在由极性离子液体(PIL)1-丁基-3-甲基咪唑四氟硼酸盐([bmim][BF])、表面活性离子液体(SAIL)1-丁基-3-甲基咪唑1,4-双(2-乙基己基)磺基琥珀酸盐([bmim][AOT])和苯组成的微乳液中,分析了位于约10和300 MHz处的两种介电弛豫。直流电导率与PIL重量分数的曲线显示出两个拐点,即16.69和27.90 wt%,用于划分PIL/O、双连续(B.C.)和O/PIL子区域。根据直流电导率对PIL重量分数的标度依赖性以及介电常数和损耗角的频率依赖性,提出了渗流的临界指数分别为0.75、0.79和0.80,所有这些都推断微乳液中发生了静态渗流。在PIL/O子区域中,当浓度增加到PIL/O和B.C.子区域之间的边界时,仅在高频观察到一种介电弛豫;第二种介电弛豫出现在低频。高频弛豫是由界面极化引起的。低频弛豫归因于AOT的偶极取向极化。当体系的油含量降低时,界面变得更软,使更多的AOT能够旋转,阳离子从围绕其长轴移动转变为沿其短轴旋转。给出了[bmim][AOT]的静态介电常数。根据高频弛豫的介电参数计算了PIL/O和O/PIL子区域中分散相和连续相的介电常数和电导率。