• Title/Summary/Keyword: vinylidene fluoride copolymer.

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Preparation of Anhydrous Crosslinked Graft Copolymer Electrolyte Membrane (무가습 가교 가지형 공중합체 전해질 막의 제조)

  • Roh, Dong-Kyu;Koh, Joo-hwan;Park, Jung-tae;Seo, Jin-ah;Kim, Jong-hak
    • 한국신재생에너지학회:학술대회논문집
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    • 2009.06a
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    • pp.270-273
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    • 2009
  • A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoro-ethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (1H-NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA and the -COOH groups of IDA. Upon doping with phosphoric acid ($H_3PO_4$) to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased with increasing $H_3PO_4$ content. A maximum proton conductivity of 0.015 S/cm was achieved at $120^{\circ}C$ under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/$H_3PO_4$ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to $250^{\circ}C$, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.

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Structural Changes in Isothermal Crystallization Processes of Synthetic Polymers Studied by Time-Resolved Measurements of Synchrotron-Sourced X-Ray Scatterings and Vibrational Spectra

  • Tashiro, Kohji;Hama, Hisakatsu
    • Macromolecular Research
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    • v.12 no.1
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    • pp.1-10
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    • 2004
  • The structural changes occurring in the isothermal crystallization processes of polyethylene (PE), poly-oxymethylene (POM), and vinylidene fluoridetrifluoroethylene (VDFTrFE) copolymer have been reviewed on the basis of our recent experimental data collected by the time-resolved measurements of synchrotron-sourced wide-angle (WAXS) and small-angle X-ray scatterings (SAXS) and infrared spectra. The temperature jump from the melt to a crystallization temperature could be measured at a cooling rate of 600-1,000 $^{\circ}C$/min, during which we collected the WAXS, SAXS, and infrared spectral data successfully at time intervals of ca. 10 sec. In the case of PE, the infrared spectral data clarified the generation of chain segments of partially disordered trans conformations immediately after the jump. These segments then became transformed into more-regular all-trans-zigzag forms, followed by the formation of an orthorhombic crystal lattice. At this stage, the generation of a stacked lamella structure having an 800-${\AA}$-long period was detected in the SAXS data. This structure was found to transfer successively to a more densely packed lamella structure having a 400-${\AA}$-long period as a result of the secondary crystallization of the amorphous region in-between the original lamellae. As for POM, the formation process of a stacked lamella structure was essentially the same as that mentioned above for PE, as evidenced from the analysis of SAXS and WAXS data. The observation of morphology-sensitive infrared bands revealed the evolution of fully extended helical chains after the generation of lamella having folded chain structures. We speculate that these extended chains exist as taut tie chains passing continuously through the neighboring lamellae. In the isothermal crystallization of VDFTrFE copolymer from the melt, a paraelectric high-temperature phase was detected at first and then it transferred into the ferroelectric low-temperature phase at a later stage. By analyzing the reflection profile of the WAXS data, the structural ordering in the high-temperature phase and the ferroelectric phase transition to the low-temperature phase of the multi-domain structure were traced successfully.

Fabrications and Properties of Al/$VF_2$/$n^+$-Si(100) Structures by Dip Coating Methode (Dip Coating 법에 의한 Al/$VF_2$-TrFE/Si(100) 구조의 제작 특성)

  • Kim, Ka-Lam;Jeong, Sang-Hyun;Yun, Hyeong-Seon;Lee, Woo-Seok;Kwak, No-Won;Kim, Kwang-Ho
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2008.11a
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    • pp.20-21
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    • 2008
  • Ferroelectric vinylidene fluoride-trifluoroethylene ($VF_2$-TrFE) copolymer films were directly deposited on degenerated Si ($n^+$, 0.002 $\Omega{\cdot}cm$) using by dip coating method. A 1 ~ 3 wt% diluted solution of purified vinylidene fluoride-trifluoroethylene ($VF_2$:TrFE=70:30) in a dimethylformamide (DMF) solvent were prepared and deposited on silicon wafers using dip coating method for 10 seconds. After Post-Annealing in a vacuum ambient at 100~200 $^{\circ}C$ for 60 min, upper aluminum electrodes were deposited by thermal evaporation through the shadow mask to complete the MFS structure. The ferroelectric $\beta$-phase peak of films, depending on the annealing temperature, started to show up around $125^{\circ}C$, and the intensity of the peak increased with increasing annealing temperature. Above $175^{\circ}C$, the peak started to decrease. The C-V characteristics were measured using a Precision LCR meter (HP 4284A) with frequency of 1MHz and a signal amplitude of 20 mV. The leakage-current versus electric-field characteristics was measured by mean of a pA meter/DC voltage source (HP 4140B).

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Water desalination by membrane distillation using PVDF-HFP hollow fiber membranes

  • Garcia-Payo, M.C.;Essalhi, M.;Khayet, M.;Garcia-Fernandez, L.;Charfi, K.;Arafat, H.
    • Membrane and Water Treatment
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    • v.1 no.3
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    • pp.215-230
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    • 2010
  • Poly(vinylidene fluoride-co-hexafluoropropylene), PVDF-HFP, hollow fiber membranes were prepared by the dry/wet spinning technique using different polyethylene glycol (PEG) concentrations as non-solvent additive in the dope solution. Two different PEG concentrations (3 and 5 wt.%). The morphology and structural characteristics of the hollow fiber membranes were studied by means of optical microscopy, scanning electron microscopy, atomic force microscopy (AFM) and void volume fraction. The experimental permeate flux and the salt (NaCl) rejection factor were determined using direct contact membrane distillation (DCMD) process. An increase of the PEG content in the spinning solution resulted in a faster coagulation of the PVDF-HFP copolymer and a transition of the cross-section internal layer structure from a sponge-type structure to a finger-type structure. Pore size, nodule size and roughness parameters of both the internal and external hollow fiber surfaces were determined by AFM. It was observed that both the pore size and roughness of the internal surface of the hollow fibers enhanced with increasing the PEG concentration, whereas no change was observed at the outer surface. The void volume fraction increased with the increase of the PEG content in the spinning solution resulting in a higher DCMD flux and a smaller salt rejection factor.

Spinodal Phase Separation and Isothermal Crystallization Behavior in Blends of VDF/TrFE(75/25) Copolymer and Poly(1,4-butylene adipate) (I) -Spinodal Phase Separation Behavior-

  • Kim, Kap Jin;Kyu, Thein
    • Fibers and Polymers
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    • v.4 no.4
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    • pp.188-194
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    • 2003
  • Phase behavior and spinodal phase separation kinetics in binary blends of a random copolymer of vinylidene fluoride and trifluoroethylene (75/25) [P(VDF/TrFE)] and poly(l,4-butylene adipate) (PBA) have been investigated by means of optical microscopic observation and time-resolved light scattering. The blends exhibited a typical lower critical solution temperature (LCST)∼${34}^{\circ}C$ above the melting temperature of the P(VDF/TrFE) crystals over the entire blend composition range. P(VDF/TrFE) and PBA were totally miscible in the temperature gap between the melting point of P(VDF/TrFE) and the LCST. Temperature jump experiments of the 3/7 P(VDF/TrFE)/PBA blend were carried out on a light-scattering apparatus from a single-phase melt state (${180}^{\circ}C$) to a two-phase region (205∼${215}^{\circ}C$). Since the late stage of spinodal decomposition (SD) is prevalent in the 3/7 blend, SD was analyzed using a power law scheme. Self-similarity was preserved well in the late stage of SD in the 3/7 blend.

Experimental Evidence for the Existence of a New Transition of a VDF and TrFE Copolymer (P(VDF/TrFE)의 새로운 전이에 대한 실험적 증거)

  • 김갑진;이종순;조항원
    • Proceedings of the Korean Fiber Society Conference
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    • 2002.04a
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    • pp.105-109
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    • 2002
  • vinylidene fluoride(VDF)와 trifluoroethylene(TrFE)의 공중합체 인 P(VDF/TrFE)는 전기활성을 갖는 강유전성 결정이므로 압전성 및 초전성 재료로 PVDF와 더불어 널리 사용되고 있다. 그러나 P(VDF/TrFE)는 어떤 온도 이상에서는 all-trans conformation을 하는 강유전 결정상이 전기적으로 불활성으로 되면서 PVDP의 $\alpha$-결정의 사슬배좌(trans-gauche)와 유사한 상유전 결정상으로 전이하는 상승 Curie 전이 온도 (T$^{\uparrow}$ $_{c}$ )가 존재하기 때문에 P(VDF/TrFF)의 압전재료로서의 적용온도 범위가 넓지 못하다는 단점이 있다. (중략)

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Low Dimensional Electro-optic Properties of Ferroelectric Polymer Films (강유전 고분자 박막의 저차원 전기광학 특성)

  • Park, Chul-Woo;Jung, Chi-Sup
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.27 no.3
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    • pp.184-188
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    • 2014
  • The electro-optic properties in Langmuir Blodgett films of poly (vinylidene fluoride trifluoroethylene) are investigated in the crossover region between two and three dimensions. The absence of finite size effect is observed in the films thinner than 20 nm, which confirms that these films are two dimensional ferroelectrics. The copolymer LB film of P(VDF-TrFE) exhibits the largest electro-optic response(26 pm/V) at 10 layer thickness. The cross-over behavior of electro-optic effect around the 10 layer thickness was discussed with the formation of nanomesa after thermal annealing.

Preparation and Gas Permeability Measurements of PVDF-HFP/Ionic Liquid Gel Membranes (PVDF-HFP/이온성 액체 겔 분리막 제조 및 기체 투과도 측정)

  • Ko, Youngdeok;Park, Doohwan;Baek, Ilhyun;Hong, Seong Uk
    • Applied Chemistry for Engineering
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    • v.25 no.6
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    • pp.559-563
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    • 2014
  • It is well known that $CO_2$ can be dissolved easily in imidazolium-based room temperature ionic liquids (RTILs). Because of the high $CO_2$ solubility in RTILs, membranes containing RTILs can separate easily gas mixtures such as $CO_2/N_2$ and $CO_2/CH_4$. In this study, we prepared poly(vinylidene fluoride)-hexafluoropropyl copolymer (PVDF-HFP) gel membranes with several RTILs and measured permeabilities of several gases. When the anion of ionic liquids was tetrafluoroborate($BF{_4}^-$), both $CO_2$ permeability and selectivities decreased as the carbon number of the cation increased. When the cation of ionic liquids was 1-ethyl-3-methylimidazolium[emim], $CO_2$ permeability of gel membranes containing bis(trifluoromethane) sulfoneimide($Tf_2N^-$) anion was double compared to those containing tetrafluoroborate($BF{_4}^-$) anion. However, $CO_2/N_2$ and $CO_2/CH_4$ selectivities of the $Tf_2N^-$ case were decreased, whereas the $H_2$ selectivity was almost the same for two cases.

Preparation of Poly(vinyl chloride)-graft-poly(styrene sulfonic acid) Composite Nanofiltration Membranes (폴리비닐클로라이드-그래프트-폴리스티렌 술폰산 복합 나노막 제조)

  • Kim, Jong-Hak;Park, Jung-Tae;Koh, Joo-Hwan;Roh, Dong-Kyu;Seo, Jin-Ah
    • Membrane Journal
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    • v.18 no.2
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    • pp.132-137
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    • 2008
  • Nanofiltration membranes were prepared based on coating a sulfonated comb-like copolymer layer on top of a poly(vinylidene fluoride) (PVDF) support. The comb-like copolymer comprising poly(vinyl chloride) backbone and poly(styrene sulfonic acid) side chains, i.e. PVC-g-PSSA was synthesized by atom transfer radical polymerization (ATRP) using direct initiation of the secondary chlorines of PVC. The successful synthesis of graft copolymers were confirmed by nuclear magnetic resonance ($^1H$-NMR), FT-IR spectroscopy and wide angle X-ray scattering (WAXS). Composite nanofiltration membranes consisting PVC-g-PSSA as a top layer exhibited the increase of both rejections and solution flux with increasing PSSA concentration. This performance enhancement is presumably due to the increase of SO3H groups and membrane hydrophilicity. The rejections of composite membranes containing 71 wt% of PSSA were 88% for $Na_2SO_4$ and 33% for NaCl, and the solution flux were 26 and $34L/m^2h$, respectively, at 0.3 MPa pressure.

Nonvolatile Ferroelectric P(VDF-TrFE) Memory Transistors Based on Inkjet-Printed Organic Semiconductor

  • Jung, Soon-Won;Na, Bock Soon;Baeg, Kang-Jun;Kim, Minseok;Yoon, Sung-Min;Kim, Juhwan;Kim, Dong-Yu;You, In-Kyu
    • ETRI Journal
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    • v.35 no.4
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    • pp.734-737
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    • 2013
  • Nonvolatile ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) memory based on an organic thin-film transistor with inkjet-printed dodecyl-substituted thienylenevinylene-thiophene copolymer (PC12TV12T) as the active layer is developed. The memory window is 4.5 V with a gate voltage sweep of -12.5 V to 12.5 V. The field effect mobility, on/off ratio, and gate leakage current are 0.1 $cm^2/Vs$, $10^5$, and $10^{-10}$ A, respectively. Although the retention behaviors should be improved and optimized, the obtained characteristics are very promising for future flexible electronics.