Department of Materials and Interfaces, Weizmann Institute of Science, Rehovot, 76100, Israel.
Phys Chem Chem Phys. 2012 Apr 28;14(16):5551-7. doi: 10.1039/c2cp23000c. Epub 2012 Mar 8.
It has recently been reported that Teflon and polyethylene (PE) if rubbed by polymethylmethacrylate (PMMA) or Nylon as well as non-rubbed PMMA and Nylon induce "redox" reactions, including those of the reduction of Pd(+2) and Cu(+2) ions. On this basis, it was deduced that these dielectric materials may hold ≅10(13)-10(14) of "hidden" electrons cm(-2), a value at least three orders of magnitude higher than the charge that a dielectric surface can accumulate without being discharged in air. The "hidden" electrons were termed "cryptoelectrons". In variance to these reports, we offer here an alternative interpretation. Our model is supported by X-ray photoelectron spectroscopy, contact angle and vibrating electrode (modified Kelvin probe) measurements performed on representative examples. Rubbing of the polymers was found to transfer polymer fragments between the rubbed surfaces altering their physical properties. The transferred polymer fragments promote adsorption of Cu(2+) and Pd(2+) ions. It was found that Teflon and PE rubbed with PMMA and Nylon, and non-rubbed PMMA and non-rubbed Nylon do not induce "redox" reactions of Cu(2+) and Pd(2+) ions but adsorb these ions on their surfaces. Furthermore, the earlier reported reduction of Pd(2+) to Pd(0) by electrons, as detected by catalytic activity of Pd(0) in a Cu-plating bath, can be alternatively explained by reduction of adsorbed Pd(2+) by the reducing agents of the bath itself. Based on these findings, we support the hypothesis that charging of dielectric polymers is due to ions or free radicals rather than electrons and there is no evidence to invoke a hypothesis of "cryptoelectrons".
最近有报道称,聚四氟乙烯(Teflon)和聚乙烯(PE)如果与聚甲基丙烯酸甲酯(PMMA)或尼龙摩擦,以及未经摩擦的 PMMA 和尼龙都会引起“氧化还原”反应,包括还原 Pd(+2)和 Cu(+2)离子。在此基础上,推断这些介电材料可能含有 ≅10(13)-10(14)个“隐藏”电子/cm(-2),这个值至少比介电体表面在空气中不放电就能积累的电荷高出三个数量级。这些“隐藏”电子被称为“隐电子”。与这些报道相反,我们在这里提供了另一种解释。我们的模型得到了 X 射线光电子能谱、接触角和振动电极(改良的 Kelvin 探针)测量的支持,这些测量是在代表性实例上进行的。聚合物的摩擦被发现会在摩擦表面之间转移聚合物碎片,从而改变它们的物理性质。转移的聚合物碎片促进 Cu(2+)和 Pd(2+)离子的吸附。研究发现,用 PMMA 和尼龙摩擦的 Teflon 和 PE,以及未经摩擦的 PMMA 和未经摩擦的尼龙不会引起 Cu(2+)和 Pd(2+)离子的“氧化还原”反应,而是将这些离子吸附在其表面上。此外,先前报道的通过电子检测到的 Pd(2+)还原为 Pd(0)的反应,即在 Cu 电镀浴中的 Pd(0)催化活性,可以通过浴本身的还原剂还原吸附的 Pd(2+)来替代解释。基于这些发现,我们支持这样的假设,即介电聚合物的充电是由于离子或自由基而不是电子引起的,没有证据支持“隐电子”假说。