Journal
MACROMOLECULES
Volume 46, Issue 15, Pages 6309-6318Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ma400915g
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Funding
- National Natural Science Foundation of China [50930002]
- National Basic Research Program of China (973 Program) [2011CB606005]
- Program for New Century Excellent Talents in University
- SMC project of Shanghai Jiao Tong University
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Dibenzylidene sorbitol (DBS) was chosen as an in situ forming nucleating agent to study ultrahigh molecular weight polyethylene (UHMWPE)/liquid paraffin (LP) physical gel and complex phase separation. The experimental results indicated that DBS self-assembled into fibrils first and the solution became a physical gel before liquid liquid phase separation (LLPS) and crystallization during thermally induced phase separation (TIPS) of UHMWPE/LP/DBS solution. The temperature of DBS self-assembly and viscoelasticity of UHMWPE/LP/DBS gel show a strong dependence on DBS concentration, temperature, and time. By controlling the relative quenching depth and annealing time, the grow rate of the characteristic length showed a crossover from LLPS to crystallization, which was further justified by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD). With decreasing temperature further, crystallization occurred with the aid of DBS fibrils. Those interactions were affected mutually, showed complex phase separation behavior. We proposed a new mechanism of self-assembly assisted liquid liquid phase separation, which explained excellently the relationship of DBS self-assembly and LLPS. On the basis of rheometer and optical microscopy (OM and POM), we obtained the phase diagram of UHMWPE/LP/DBS ternary blends. Meanwhile, DSC indicated the overwhelming changes of crystallization kinetics after the varying LLPS in the double quenching procedure, which was consistent with the fluctuation assisted nucleation mechanism.
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