Bridgestone Americas, Center for Research and Technology, 1200 Firestone Parkway, Akron, Ohio 44317-0001, USA.
J Chem Phys. 2010 Mar 14;132(10):104904. doi: 10.1063/1.3337910.
The understanding of size-dependent properties is key to the implementation of nanotechnology. One controversial and unresolved topic is the influence of characteristic size on the glass transition temperature (T(g)) for ultrathin films and other nanoscale geometries. We show that T(g) does depend on size for polystyrene spherical domains with diameters from 20 to 70 nm which are formed from phase separation of diblock copolymers containing a poly(styrene-co-butadiene) soft block and a polystyrene hard block. A comparison of our data with published results on other block copolymer systems indicates that the size dependence of T(g) is a consequence of diffuse interfaces and does not reflect an intrinsic size effect. This is supported by our measurements on 27 nm polystyrene domains in a styrene-isobutylene-styrene triblock copolymer which indicate only a small T(g) depression (3 K) compared to bulk behavior. We expect no effect of size on T(g) in the limit as the solubility parameters of the hard and soft blocks diverge from each other. This strongly segregated limiting behavior agrees with published data for dry and aqueous suspensions of small polystyrene spheres but is in sharp contrast to the strong influence of film thickness on T(g) noted in the literature for free standing ultrathin polystyrene films.
对尺寸相关性质的理解是纳米技术实施的关键。一个有争议且尚未解决的话题是特征尺寸对超薄膜和其他纳米级结构的玻璃化转变温度(T(g))的影响。我们表明,对于由含有聚(苯乙烯-co-丁二烯)软段和聚苯乙烯硬段的嵌段共聚物相分离形成的直径为 20 至 70nm 的聚苯乙烯球形畴,T(g)确实取决于尺寸。我们的数据与其他嵌段共聚物体系的已发表结果进行比较表明,T(g)的尺寸依赖性是扩散界面的结果,并不反映固有尺寸效应。这得到了我们在苯乙烯-异丁烯-苯乙烯三嵌段共聚物中 27nm 聚苯乙烯畴的测量结果的支持,与体相行为相比,T(g)仅略有降低(3K)。我们预计,当硬段和软段的溶解度参数彼此发散时,尺寸对 T(g)没有影响。这种强烈分离的极限行为与已发表的关于小聚苯乙烯球的干燥和水悬浮液的数据一致,但与文献中关于自由支撑的超薄聚苯乙烯膜的 T(g)对膜厚度的强烈影响形成鲜明对比。
Nanotechnology. 2010-4-9
J Phys Chem B. 2009-10-22