Kim S, Hewlett S A, Roth C B, Torkelson J M
Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL 60208, USA.
Eur Phys J E Soft Matter. 2009 Sep;30(1):83-92. doi: 10.1140/epje/i2009-10510-y. Epub 2009 Sep 26.
Using ellipsometry, we characterized the nanoconfinement effect on the glass transition temperature (T (g)of supported polystyrene (PS) films employing two methods: the intersection of fits to the temperature (Tdependences of rubbery- and glassy-state thicknesses, and the transition mid-point between rubbery- and glassy-state expansivities. The results demonstrate a strong effect of thickness: T(g) (bulk) - T(g)(23 nm) = 10 degrees C. The T -range needed for accurate measurement increases significantly with decreasing thickness, an effect that arises from the broadening of the transition with confinement and a region below T (g) where expansivity slowly decreases with decreasing T . As determined from expansivities, the T (g) breadth triples in going from bulk films to a 21-nm-thick film; this broadening of the transition may be a more dramatic effect of confinement than the T (g) reduction itself. In contrast, there is little effect of confinement on the rubbery- and glassy-state expansivities. Compared with ellipsometry, T (g) 's from fluorescence agree well in bulk films but yield lower values in nanoconfined films: T (g)(bulk) - T (g)(23 nm) = 15( degrees ) C via fluorescence. This small difference in the T (g) confinement effect reflects differences in how fluorescence and ellipsometry report "average T (g) " with confinement. With decreasing nanoscale thickness, fluorescence may slightly overweight the contribution of the free-surface layer while ellipsometry may evenly weight or underweight its contribution.
我们使用椭偏仪,采用两种方法表征了纳米限域效应对于支撑聚苯乙烯(PS)薄膜玻璃化转变温度(Tg)的影响:一是对橡胶态和玻璃态厚度随温度(T)变化关系的拟合曲线的交点,二是橡胶态和玻璃态膨胀系数之间的转变中点。结果表明厚度具有显著影响:Tg(本体)−Tg(23纳米) = 10℃。准确测量所需的T范围随着厚度减小而显著增加,这种效应源于限域作用下转变的展宽以及低于Tg的一个区域,在该区域膨胀系数随T降低而缓慢减小。由膨胀系数确定,从本体薄膜到21纳米厚的薄膜,Tg的宽度增加了两倍;这种转变的展宽可能是限域作用比Tg降低本身更显著的影响。相比之下,限域对橡胶态和玻璃态膨胀系数的影响很小。与椭偏仪相比,荧光法测得的本体薄膜的Tg值吻合良好,但在纳米限域薄膜中得到的值较低:通过荧光法测得Tg(本体)−Tg(23纳米) = 15℃。Tg限域效应的这种微小差异反映了荧光法和椭偏仪在限域条件下报告“平均Tg”方式的不同。随着纳米尺度厚度减小,荧光法可能会稍微高估自由表面层的贡献,而椭偏仪可能会均匀加权或低估其贡献。