Mok M M, Kim J, Marrou S R, Torkelson J M
Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208, USA.
Eur Phys J E Soft Matter. 2010 Mar;31(3):239-52. doi: 10.1140/epje/i2010-10569-3. Epub 2010 Mar 9.
Bulk films of random, block and gradient copolymer systems were studied using ellipsometry to demonstrate the applicability of the numerical differentiation technique pioneered by Kawana and Jones for studying the glass transition temperature (T (g)) behavior and thermal expansivities of copolymers possessing different architectures and different levels of nanoheterogeneity. In a series of styrene/n -butyl methacrylate (S/nBMA) random copolymers, T (g) breadths were observed to increase from approximately 17( degrees ) C in styrene-rich cases to almost 30( degrees ) C in nBMA-rich cases, reflecting previous observations of significant nanoheterogeneity in PnBMA homopolymers. The derivative technique also revealed for the first time a substantial increase in glassy-state expansivity with increasing nBMA content in S/nBMA random copolymers, from 1.4x10(-4) K-1 in PS to 3.5x10(-4) K-1 in PnBMA. The first characterization of block copolymer T (g) 's and T (g) breadths by ellipsometry is given, examining the impact of nanophase-segregated copolymer structure on ellipsometric measurements of glass transition. The results show that, while the technique is effective in detecting the two T (g) 's expected in certain block copolymer systems, the details of the glass transition can become suppressed in ellipsometry measurements of a rubbery minor phase under conditions where the matrix is glassy; meanwhile, both transitions are easily discernible by differential scanning calorimetry. Finally, broad glass transition regions were measured in gradient copolymers, yielding in some cases extraordinary T (g) breadths of 69- 71( degrees ) C , factors of 4-5 larger than the T (g) breadths of related homopolymers and random copolymers. Surprisingly, one gradient copolymer demonstrated a slightly narrower T (g) breadth than the S/nBMA random copolymers with the highest nBMA content. This highlights the fact that nanoheterogeneity relevant to the glass transition response in selected statistical copolymers can be comparable to or exceed that observed in moderately phase-segregated gradient copolymers.
利用椭偏仪对无规、嵌段和梯度共聚物体系的块状薄膜进行了研究,以证明川奈和琼斯率先提出的数值微分技术在研究具有不同结构和不同纳米非均相程度的共聚物的玻璃化转变温度(Tg)行为和热膨胀系数方面的适用性。在一系列苯乙烯/甲基丙烯酸正丁酯(S/nBMA)无规共聚物中,观察到Tg宽度从富苯乙烯情况下的约17℃增加到富nBMA情况下的近30℃,这反映了之前在聚甲基丙烯酸正丁酯(PnBMA)均聚物中观察到的显著纳米非均相性。该微分技术还首次揭示了S/nBMA无规共聚物中随着nBMA含量增加玻璃态膨胀系数大幅增加,从聚苯乙烯(PS)中的1.4×10⁻⁴K⁻¹增加到PnBMA中的3.5×10⁻⁴K⁻¹。给出了通过椭偏仪对嵌段共聚物Tg及其宽度的首次表征,研究了纳米相分离共聚物结构对玻璃化转变椭偏测量的影响。结果表明,虽然该技术在检测某些嵌段共聚物体系中预期的两个Tg方面是有效的,但在基质为玻璃态的条件下,橡胶态次要相的玻璃化转变细节在椭偏测量中可能会被抑制;同时,通过差示扫描量热法可以很容易地辨别出这两个转变。最后,在梯度共聚物中测量到了宽的玻璃化转变区域,在某些情况下产生了高达69 - 71℃的异常Tg宽度,比相关均聚物和无规共聚物的Tg宽度大4 - 5倍。令人惊讶的是,一种梯度共聚物的Tg宽度比具有最高nBMA含量的S/nBMA无规共聚物略窄。这突出了一个事实,即所选统计共聚物中与玻璃化转变响应相关的纳米非均相性可以与中度相分离梯度共聚物中观察到的相当或超过后者。
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