Department of Polymer Engineering, University of Akron, Akron, OH 44325, USA.
Nanoscale. 2013 Dec 21;5(24):12440-7. doi: 10.1039/c3nr03591c.
Ordered mesoporous carbons exhibit appealing properties for many applications, but their function and performance can depend critically on their structure. The in-plane orientation of 2D cylinders from the cooperative assembly of Pluronic P123 and resol has been controlled by application of cold zone annealing (CZA). By varying the moving rate, the preferential in-plane orientation of the self-assembled cylinders can be tuned through the entire 180° range possible from ϕ = 50° to ϕ = -130° (relative to the moving direction). At a moving rate of 2 μm s(-1), this simple and easy CZA process leads to cylinders that are well aligned parallel to the moving direction with a high orientational factor of S = 0.98. Moreover, the in-plane oriented cylinders can be nearly perfectly aligned transverse to the moving direction (S = 0.95) by simply decreasing the moving velocity to 0.5 μm s(-1). We attribute the parallel alignment to the flow that develops from the motion of the thermal gradients, while the transverse alignment is related to flow cessation (inertial effect). The preferential orientation is retained through the carbonization process, but there is some degradation in orientation due to insufficient crosslinking of the resol during CZA; this effect is most prominent for the higher moving rates (less time for crosslinking), but can be overcome by post-CZA annealing at uniform elevated temperatures to further crosslink the resol. CZA is a simple and powerful method for fabricating well-aligned and self-assembled mesoporous carbon films over large areas.
有序介孔碳因其在许多应用中的诱人性质而备受关注,但它们的功能和性能可能严重依赖于其结构。通过施加冷区退火(CZA),可以控制 Pluronic P123 和 resol 协同组装的 2D 圆柱的面内取向。通过改变移动速率,可以在可能的整个 180°范围内(相对于移动方向,ϕ = 50°至ϕ = -130°)调节自组装圆柱的优先面内取向。在移动速率为 2 μm s(-1)的情况下,这种简单易行的 CZA 工艺导致圆柱沿移动方向很好地平行排列,取向因子 S 高达 0.98。此外,通过将移动速度降低至 0.5 μm s(-1),可以使面内取向的圆柱几乎完全垂直于移动方向(S = 0.95)排列。我们将平行排列归因于热梯度运动产生的流动,而横向排列与流动停止(惯性效应)有关。优先取向在碳化过程中得以保留,但由于 CZA 过程中 resol 的交联不足,取向会有一定程度的降解;这种效应在较高的移动速率(交联时间较短)下更为明显,但可以通过 CZA 后的高温均匀退火来克服,以进一步交联 resol。CZA 是一种简单而强大的方法,可以在大面积上制备良好排列和自组装的介孔碳膜。