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Phase diagram of the polystyrene/near-critical water system

Shibata, Motoki*; Takenaka, Mikihito*; Motokawa, Ryuhei   ; Kumada, Takayuki   ; Ueda, Yuki   ; Miyazaki, Tsukasa*; Nakanishi, Yohei*; Abe, Jun*; Iwase, Hiroki*; Shibayama, Mitsuhiro*; Arima-Osonoi, Hiroshi*; Takata, Shinichi   ; Yamamoto, Katsuhiro*

The development of effective plastic degradation methods is crucial to address environmental pollution. Hydrothermal liquefaction using near-critical water is a promising technology, but the fundamental dissolution and decomposition mechanisms remain poorly understood. This study investigates the thermodynamics of a polystyrene (PS)/water system under near-critical conditions to elucidate this mechanism. We performed in situ small-angle neutron scattering (SANS) to observe the swelling of PS particles in deuterated water (D$$_{2}$$O) at various temperatures under pressures of 10 MPa and 25 MPa. By applying the $${Flory-Huggins-Staverman}$$ (FHS) theory to the swelling data, We quantitatively determined the Flory-Huggins interaction parameter as a function of temperature and pressure by applying the FHS theory to the swelling data. Based on these results, we constructed a phase diagram of the PS/D$$_{2}$$O system. The diagram reveals that miscibility increases with increasing pressure. This work provides a thermodynamical properties of water solutions of polymers under near-critical conditions for optimizing industrial hydrothermal recycling processes.

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