National Institute of Advanced Industrial Science and Technology (AIST), Japan.
Langmuir. 2012 Dec 21;28(51):17681-9. doi: 10.1021/la303829p. Epub 2012 Dec 10.
Alkylsilane-derived monolayer-covered surfaces generally display a reasonably good level of hydrophobicity but poor oleophobicity. Here, we demonstrate that the physical attributes of alkylsilane-derived surfaces (liquid-like or solid-like) are dependent on the alkyl chain length and density, and these factors subsequently have significant influence upon the dynamic dewetting behavior toward alkanes (C(n)H(2n+2), where n = 7-16). In this study, we prepared and characterized hybrid films through a simple sol-gel process based on the cohydrolysis and co-condensation of a mixture of a range of alkyltriethoxysilanes (C(n)H(2n+1)Si(OEt)(3), where n = 3, 6, 8, 10, 12, 14, 16, and 18) and tetramethoxysilane (TMOS). Surprisingly, when the carbon number (C(n)) of alkyl chain was 10 and below, the produced hybrid films were all smooth, highly transparent, and showed negligible contact angle (CA) hysteresis. On these hybrid surfaces, 5 μL drops of alkanes (n-hexadecane, n-dodecane, and n-decane) could move easily at low tilt angles (<5°) without pinning. On the other hand, when the C(n) exceeded 12, both transparency and mobility of probe liquids significantly worsened. In the former case, TMOS molecules played key roles in both forming continuous films (as a binder) and improving flexibility of alkyl chains (as a molecular spacer), resulting in the smooth liquid-like surfaces. Silylation of the hybrid film and subsequent dynamic CA measurements proved the presence of silanol groups on the outermost surfaces and demonstrated that the dynamic dewettability of hybrid films worsened as packing densities increased. Additionally, solvent effects (high affinity) between the alkyl chains and alkane liquids imparted a more liquid-like character to the surface. Thanks to these simple physical effects, the resistance to the alkane droplet motion across tilted surfaces was markedly reduced. With the longer carbon chains, the chain mobility was strictly inhibited by mutual interactions between neighboring alkyl chains even in the presence of TMOS molecules. The achieved surfaces displayed a solid-like nature along with surface defects, leading to inferior dynamic oleophobicity. Therefore, the critical C(n) of alkyl chain used for determining final dynamic dewetting behavior against alkane liquids was 12. Furthermore, our hybrid surfaces exhibited excellent antifingerprint properties, particularly demonstrating low adhesion and easy removal from the surface.
烷基硅烷衍生的单层覆盖表面通常具有相当好的疏水性,但疏油性较差。在这里,我们证明了烷基硅烷衍生表面的物理性质(液态或固态)取决于烷基链的长度和密度,这些因素随后对烷烃(C(n)H(2n+2),其中 n = 7-16)的动态去湿行为有显著影响。在这项研究中,我们通过一种简单的溶胶-凝胶过程制备和表征了混合薄膜,该过程基于一系列烷基三乙氧基硅烷(C(n)H(2n+1)Si(OEt)(3),其中 n = 3、6、8、10、12、14、16 和 18)和四甲氧基硅烷(TMOS)的共水解和共缩合。令人惊讶的是,当烷基链的碳数(C(n))为 10 及以下时,所制备的混合薄膜均光滑、高度透明,且接触角滞后几乎可以忽略不计。在这些混合表面上,5 μL 的烷烃(正十六烷、正十二烷和正癸烷)液滴可以在低倾斜角度(<5°)下轻松移动而不会被卡住。另一方面,当 C(n)超过 12 时,探针液体的透明度和移动性都显著恶化。在前一种情况下,TMOS 分子在形成连续薄膜(作为粘结剂)和提高烷基链的柔韧性(作为分子间隔物)方面发挥了关键作用,从而形成了光滑的液态表面。混合薄膜的硅烷化和随后的动态接触角测量证明了最外层表面上存在硅醇基团,并表明随着堆积密度的增加,混合薄膜的动态去湿能力恶化。此外,烷基链和烷烃液体之间的溶剂效应(高亲和力)赋予了表面更液态的特征。由于这些简单的物理效应,大大降低了抵抗倾斜表面上烷烃液滴运动的阻力。随着碳链的延长,即使存在 TMOS 分子,相邻烷基链之间的相互作用也严格抑制了链的迁移性。所获得的表面表现出固态性质,同时伴有表面缺陷,导致动态疏油性较差。因此,用于确定对烷烃液体最终动态去湿行为的烷基链的临界 C(n)为 12。此外,我们的混合表面表现出优异的抗指纹性能,特别是表现出低附着力和易于从表面去除。