TY - JOUR
T1 - Interfacial nanostructuring of poly(vinylidene fluoride) homopolymer with predominant ferroelectric phases
AU - Fu, Chang
AU - Zhu, Huie
AU - Hoshino, Norihisa
AU - Akutagawa, Tomoyuki
AU - Mitsuishi, Masaya
N1 - Funding Information:
This work was partially supported by a Grant-in-Aid for Young Scientists (19K15625) from the Japan Society for the Promotion of Science (JSPS). This work was also supported by the Cooperative Research Program “Network Joint Research Center for Materials and Devices: Dynamic Alliance for Open Innovation Bridging Human, Environment and Materials (MEXT),” Tohoku University Center for Gender Equality Promotion (TUMUG), and Polymer Hybrid Materials Research (PHyM) Center Project, Tohoku University. The authors are grateful to Professor Hidetoshi Oikawa, IMRAM, Tohoku University, for permitting the use of an X-ray diffractometer. MM appreciates financial support from the Nohmura Foundation for Membrane Structure Technology.
Publisher Copyright:
© 2020 American Chemical Society.
PY - 2020/11/24
Y1 - 2020/11/24
N2 - Facile preparation of poly(vinylidene fluoride) (PVDF) homopolymer nanoparticles (NPs) with monodispersed size distribution and predominant ferroelectric phases was done in an interfacial nonsolvent (water/methanol)-solvent (dimethylformamide (DMF))-polymer (PVDF) ternary system using two interfacial nanoassembly methods. First, a fluidic liquid-liquid interface consisting of two miscible solvents was created by introducing nonsolvent (water) under the PVDF solution. After the interface was created, the interface moved up to the DMF phase direction; PVDF NPs were produced through nonsolvent-induced phase separation. As the water content decreased in the nonsolvent by mixing with methanol, PVDF structures changed from nanoparticles with 252 nm average diameter (PVDF NP-1) to a porous membrane through membrane-wrapped NPs. The phenomena were found to be related to the mutual affinity of solvent, nonsolvent, and PVDF. When an additional external force was introduced to the water-DMF-PVDF system through magnetic stirring (reprecipitation method), smaller PVDF NPs with 61.4 nm diameter were obtained (PVDF NP-2). Both the as-prepared PVDF NPs were demonstrated with the predominant ferroelectric (electroactive (EA)) phase up to 97-98% among crystalline phases, which is apparently the highest value ever reported for PVDF homopolymer NPs. It is noteworthy that PVDF NP-2 showed a higher β phase ratio than that of PVDF NP-1, as proved using Fourier transform infrared (FT-IR) spectroscopy. Also, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements revealed that PVDF NP-1 exhibited higher crystallinity and that PVDF NP-2 underwent a well-separated two-step phase transition under heating. Results suggest that controlling interface formation with DMF and water plays a crucial role in manipulating ferroelectric PVDF nanostructures in terms of crystallinity and the ferroelectric β phase-to-γ phase ratio.
AB - Facile preparation of poly(vinylidene fluoride) (PVDF) homopolymer nanoparticles (NPs) with monodispersed size distribution and predominant ferroelectric phases was done in an interfacial nonsolvent (water/methanol)-solvent (dimethylformamide (DMF))-polymer (PVDF) ternary system using two interfacial nanoassembly methods. First, a fluidic liquid-liquid interface consisting of two miscible solvents was created by introducing nonsolvent (water) under the PVDF solution. After the interface was created, the interface moved up to the DMF phase direction; PVDF NPs were produced through nonsolvent-induced phase separation. As the water content decreased in the nonsolvent by mixing with methanol, PVDF structures changed from nanoparticles with 252 nm average diameter (PVDF NP-1) to a porous membrane through membrane-wrapped NPs. The phenomena were found to be related to the mutual affinity of solvent, nonsolvent, and PVDF. When an additional external force was introduced to the water-DMF-PVDF system through magnetic stirring (reprecipitation method), smaller PVDF NPs with 61.4 nm diameter were obtained (PVDF NP-2). Both the as-prepared PVDF NPs were demonstrated with the predominant ferroelectric (electroactive (EA)) phase up to 97-98% among crystalline phases, which is apparently the highest value ever reported for PVDF homopolymer NPs. It is noteworthy that PVDF NP-2 showed a higher β phase ratio than that of PVDF NP-1, as proved using Fourier transform infrared (FT-IR) spectroscopy. Also, differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements revealed that PVDF NP-1 exhibited higher crystallinity and that PVDF NP-2 underwent a well-separated two-step phase transition under heating. Results suggest that controlling interface formation with DMF and water plays a crucial role in manipulating ferroelectric PVDF nanostructures in terms of crystallinity and the ferroelectric β phase-to-γ phase ratio.
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U2 - 10.1021/acs.langmuir.0c02667
DO - 10.1021/acs.langmuir.0c02667
M3 - Article
C2 - 33147043
AN - SCOPUS:85096762509
SN - 0743-7463
VL - 36
SP - 14083
EP - 14091
JO - Langmuir
JF - Langmuir
IS - 46
ER -