National Institute of Advanced Industrial Science and Technology (AIST) , 2266-98 Anagahora, Shimoshidami, Moriyama-ku, Nagoya 463-8560, Japan.
Langmuir. 2016 Nov 1;32(43):11101-11110. doi: 10.1021/acs.langmuir.5b04703. Epub 2016 Mar 24.
The dynamic equilibrium model for a bulk nanobubble partly covered with hydrophobic material in water is theoretically and numerically studied. The gas diffusion into a bubble near the peripheral edge of the hydrophobic material on the bubble surface balances that out of the bubble from the other part of the uncovered bubble surface. In the present model, gas diffusion in quiescent liquid is assumed and there is no liquid flow. The total changes of energy and entropy are both zero as it is a kind of equilibrium state. The main origin of the dynamic equilibrium state is the gradient of chemical potential of gas near the peripheral edge of the hydrophobic material. It is caused by the permanent attractive potential of a hydrophobic material to gas molecules dissolved in liquid water as there is permanent repulsion of a hydrophobic material against liquid water. Thus, the gas supply will not terminate. It is numerically shown that stable nanobubble could be present when the fraction of surface coverage by hydrophobic material is from about 0.5 to 1. The stable size of a nanobubble changes with the liquid temperature as well as the degree of gas saturation of water. In slightly degassed water, not only a nanobubble but also a microbubble could be stable in mass balance when the fraction of surface coverage for a microbubble is on the order of 10 or less. For hydrophilic materials, however, a bubble could not be stable unless the fraction of the surface coverage is exactly 1. It is suggested that in many experiments of bulk nanobubbles there could be aggregates of nanobubbles.
部分覆盖疏水材料的体相纳米气泡的动力学平衡模型在理论和数值上进行了研究。疏水材料表面的气泡近边缘处的气体扩散与气泡未被覆盖部分的气泡表面的气体逸出达到平衡。在本模型中,假设气体在静止液体中的扩散,没有液体流动。由于这是一种平衡状态,总能量和熵的变化都为零。动态平衡状态的主要原因是疏水材料近边缘处气体化学势的梯度。这是由于疏水材料对溶解在液态水中的气体分子的永久吸引力所致,因为疏水材料对液态水有永久的排斥作用。因此,气体供应不会终止。数值结果表明,当疏水材料的表面覆盖率约为 0.5 到 1 时,可以存在稳定的纳米气泡。纳米气泡的稳定尺寸随液体温度以及水的气体饱和度而变化。在轻微脱气的水中,当微气泡的表面覆盖率分数在 10 或以下时,不仅纳米气泡而且微气泡都可以在质量平衡下稳定存在。然而,对于亲水材料,除非表面覆盖率分数正好为 1,否则气泡就不能稳定存在。这表明在许多体相纳米气泡的实验中,可能存在纳米气泡的聚集体。