Lee LH
Consultant for Adhesion Science and Polymer Surface Chemistry, 796 John Glenn Blvd., Webster, New York, 14580
J Colloid Interface Sci. 1999 Jun 1;214(1):64-78. doi: 10.1006/jcis.1999.6165.
In this paper, we demonstrate the spreading pressure and interfacial film pressure to be profoundly relevant to interfacial tension, miscibility of liquids, and the Lewis acid-base approach. For immiscible liquid-solid and liquid-liquid systems, we prefer to employ Harkins' spreading model containing the equilibrium spreading pressure pie. With the inclusion of pie, we can also improve the Lewis acid-base approach for hydrogen-bonding, proposed by van Oss, Chaudhury, and Good. We establish an acidity-basicity scale for the initial surface tension by taking pie into account, and we further calculate interfacial tensions for liquid pairs containing formamide or dimethyl sulfoxide (DMSO) with dispersion components cited in Fowkes et al.'s later publication. However, for initially immiscible liquid-liquid systems, the Harkins model does not apply, and we propose, instead, an adsorption model, which requires the interfacial tension to be varying and surface tensions of the bulk liquids at a distance from the interface to remain unchanged. Thus, the difference between the initial and equilibrium interfacial spreading coefficients (Si) equals the equilibrium interfacial film pressure (pii)e, and that difference also equals that of the two interfacial tensions. For liquid-liquid systems, we can choose either of these two models depending on the miscibility of liquids. According to our adsorption model, there should be two interfacial tensions. The initial (or calculated) interfacial tension can be positive or negative, while the equilibrium (experimental) interfacial tension can reach zero. The former has more predictive value than the latter. A negative, initial interfacial tension is delineated to favor miscibility or spontaneous emulsification, but it tends to revert to zero instantaneously. Furthermore, a slightly positive, initial interfacial tension can also lead to miscibility, if (pii)e can help reduce it to a zero equilibrium interfacial tension. We have also found a new important relationship between (pii)e and pie on the basis of the Laplace equation. We also attempt to calculate with our model the (pii)e's for at least 34 liquid pairs, by assuming the published interfacial tensions to be reasonable equilibrium values. Finally, the equilibrium spreading pressure pie for the liquid-solid interface, or the (pii)e for the liquid-liquid interface, appears to be the missing link between the wetting thermodynamics and linear free energy solvatochromic relationship (LFER). We have shown the pie or (pii)e of the former to be the equivalent of the Pi*, polarity/dipolarity parameter, of the latter. Our findings about the correlation between the surface tension component (STC) concept and LFER have provided a new support for the STC theory. Copyright 1999 Academic Press.
在本文中，我们证明了铺展压力和界面膜压力与界面张力、液体的混溶性以及路易斯酸碱方法密切相关。对于不互溶的液 - 固和液 - 液体系，我们更倾向于采用包含平衡铺展压力πe的哈金斯铺展模型。通过引入πe，我们还可以改进由范奥斯、乔杜里和古德提出的用于氢键作用的路易斯酸碱方法。我们通过考虑πe建立了初始表面张力的酸碱标度，并进一步计算了含有甲酰胺或二甲基亚砜（DMSO）的液体对与福克斯等人后来发表的文献中引用的色散成分之间的界面张力。然而，对于初始不互溶的液 - 液体系，哈金斯模型并不适用，相反，我们提出了一种吸附模型，该模型要求界面张力是变化的，并且远离界面的本体液体的表面张力保持不变。因此，初始和平衡界面铺展系数（Si）之间的差值等于平衡界面膜压力（pii）e，并且该差值也等于两种界面张力的差值。对于液 - 液体系，我们可以根据液体的混溶性选择这两种模型中的任何一种。根据我们的吸附模型，应该有两种界面张力。初始（或计算得到的）界面张力可以是正的或负的，而平衡（实验得到的）界面张力可以达到零。前者比后者具有更大的预测价值。负的初始界面张力表明有利于混溶性或自发乳化，但它往往会瞬间恢复到零。此外，如果（pii）e能够帮助将其降低到零平衡界面张力，稍微正的初始界面张力也可以导致混溶性。我们还基于拉普拉斯方程发现了（pii）e和πe之间的一个新的重要关系。我们还尝试用我们的模型计算至少(34)种液体对的（pii）e，假设已发表的界面张力是合理的平衡值。最后，液 - 固界面的平衡铺展压力πe或液 - 液界面的（pii）e似乎是润湿热力学和线性自由能溶剂化显色关系（LFER）之间缺失的环节。我们已经表明前者的πe或（pii）e等同于后者的Pi*，即极性/偶极参数。我们关于表面张力分量（STC）概念与LFER之间相关性的发现为STC理论提供了新的支持。版权所有(1999)，学术出版社。
