• Polymer(Korea)
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• v.28 no.6
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• pp.509-518
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• 2004

Microdomain structures and crystallization behavior of the binary blends consisting of an asymmetric block copolymer and a homopolymer were investigated using small-angle X-ray scattering (SAXS), optical micro scope (OM) and differential scanning calorimetry (DSC). Poly(methyl methacrylate)-block-polystyrene block copolymer (PMMA-b-PS) (weight fraction of PMMA =0.53) was mixed with low molecular weight poly(vinylidene fluoride) (PVDF). As the PVDF concentration was increased, the morphological change from a lamellar to a cylindrical structure occurred. The crystallization of PVDF significantly disturbed the orientation of the pre-existing microdomain structure, resulting in a poorly ordered morphology. In the blends, PVDF exhibited unique crystallization behavior due to the PMMA block which is preferentially miscible to PVDF and the space constraint imposed by the microdomains.

• Macromolecular Research
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• v.17 no.10
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• pp.757-762
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• 2009

The micro domain structures and crystallization behavior of the binary blends of poly(methyl methacrylate)-b-poly(pentafluorostyrene)-b-poly(methyl methacrylate) (PMMA-PPFS-PMMA) triblock copolymer with a low molecular weight poly(vinylidene fluoride) (PVDF) were investigated by small-angle X-ray scattering (SAXS), small-angle light scattering (SALS), transmission electron microscopy (TEM), optical microscopy, and differential scanning calorimetry (DSC). A symmetric, PMMA-PPFS-PMMA triblock copolymer with a PPFS weight fraction of 33% was blended with PVDF in N,N-dimethylacetamide (DMAc). In the wide range of PVDF concentration between 10.0 and 30.0 wt%, PVDF was completely incorporated within the PMMA micro domains of PMMA-PPFS-PMMA without further phase separation on a micrometer scale. The addition of PVDF altered the phase morphology of PMMA-PPFS-PMMA from well-defined lamellar to disordered. The crystallization of PVDF significantly disturbed the domain structure of PMMA-PPFS-PMMA in the blends, resulting in a poorly-ordered morphology. PVDF displayed unique crystallization behavior as a result of the space constraints imposed by the domain structure of PMMA-PPFS-PMMA. The pre-existing microdomain structures restricted the lamellar orientation and favored a random arrangement of lamellar crystallites.

• Korean Membrane Journal
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• v.9 no.1
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• pp.57-63
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• 2007

Amphiphilic graft copolymer from poly(vinylidene fluoride) (PVDF) was synthesized using atom transfer radical polymerization (ATRP) for composite nanofiltration membranes. Direct initiation of the secondary fluorinated site of PVDF facilitates grafting of tert-butyl methacrylate (tBMA). Amphiphilic PVDF-g-PMAA graft copolymer with a 51:49 wt ratio was obtained by hydrolyzing poly(tert-butyl methacrylate) (PtBMA) to poly(methacrylic acid) (PMAA). Wide angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC) confirmed the decrease of crystallinity of PVDF upon graft copolymerization. Composite nanofiltration membranes were prepared from PVDF-g-PMAA as a top layer coated onto PVDF ultrafiltration (UF) support membrane. The morphology and hydrophilicity of membranes were characterized using scanning electron microscopy (SEM) and contact angle measurement. The rejections of composite membranes were 80.2% for $Na_2SO_4$ and 28.4% for NaCl, and the solution flux were 9.5 and $14.5\;L/m^2\;h$ at 1.0 MPa pressure.

• Membrane Journal
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• v.22 no.2
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• pp.104-112
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• 2012

Chemically stable Polyvinylidene fluoride-hexa-fluoropropane (PVDF-HFP) copolymer asymmetric membranes were prepared by the conventional phase inversion process, using Dimethyacetamide (DMAc) as a solvent and water as a non-solvent. To control the pore size and porosity of the PVDF-HFP membranes, tetra-ethoxysilane (TEOS) was used as a pore-forming agent. The prepared membranes were characterized, using several analytical methods such as Fourier Transform Infrared spectroscopy (FTIR), Thermo-gravimetric analyzer (TGA), Field Emission Scanning Electronic Microscopy (FESEM). TEOS turned out to increase porosity and make homogeneous pores on the membranes. Depending on the composition of the dope solutions, the pore size was ranged from 0.1 to 1.0 ${\mu}m$. The flux of the PVDF-HFP membranes prepared by using TEOS as a pore forming agent was increased substantially without much decrease in the rejection. When 15 wt% PVDF-HFP solution was blended with 13 wt% TEOS solution at composition ratio of 70/30 in wt%, the water flux at 2 bars was about 2 $m^3/m^2day$.

• Smart Structures and Systems
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• v.12 no.1
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• pp.55-71
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• 2013

Structural health monitoring (SHM) is vital for detecting the onset of damage and for preventing catastrophic failure of civil infrastructure systems. In particular, piezoelectric transducers have the ability to excite and actively interrogate structures (e.g., using surface waves) while measuring their response for sensing and damage detection. In fact, piezoelectric transducers such as lead zirconate titanate (PZT) and poly(vinylidene fluoride) (PVDF) have been used for various laboratory/field tests and possess significant advantages as compared to visual inspection and vibration-based methods, to name a few. However, PZTs are inherently brittle, and PVDF films do not possess high piezoelectricity, thereby limiting each of these devices to certain specific applications. The objective of this study is to design, characterize, and validate piezoelectric nanocomposites consisting of zinc oxide (ZnO) nanoparticles assembled in a PVDF copolymer matrix for sensing and SHM applications. These films provide greater mechanical flexibility as compared to PZTs, yet possess enhanced piezoelectricity as compared to pristine PVDF copolymers. This study started with spin coating dispersed ZnO- and PVDF-TrFE-based solutions to fabricate the piezoelectric nanocomposites. The concentration of ZnO nanoparticles was varied from 0 to 20 wt.% (in 5 % increments) to determine their influence on bulk film piezoelectricity. Second, their electric polarization responses were obtained for quantifying thin film remnant polarization, which is directly correlated to piezoelectricity. Based on these results, the films were poled (at 50 $MV-m^{-1}$) to permanently align their electrical domains and to enhance their bulk film piezoelectricity. Then, a series of hammer impact tests were conducted, and the voltage generated by poled ZnO-based thin films was compared to commercially poled PVDF copolymer thin films. The hammer impact tests showed comparable results between the prototype and commercial samples, and increasing ZnO content provided enhanced piezoelectric performance. Lastly, the films were further validated for sensing using different energy levels of hammer impact, different distances between the impact locations and the film electrodes, and cantilever free vibration testing for dynamic strain sensing.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.41-48
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• 2011

The wettabilities of the partially fluorinated polymers (ethylene-tetrafluoroethylene copolymer (ETFE), ethylenechlorotrifluoroethylene copolymer (ECTFE), and poly(vinylidene fluoride) (PVDF)) were investigated by contact angle measurements. Zisman plots for ETFE and ECTFE exhibited linear relationships, while the Zisman plot for PVDF showed a slight curvature, which was interpreted to indicate strong non-dispersive interactions between the surface and the contacting liquids. The Lifshitz-van der Waals forces of the fluoropolymers were estimated to increase in the order of ETFE < PVDF $\ll$ ECTFE. An evaluation of the polar or "acid-base" interaction energies showed that PVDF, which possesses the most acidic hydrogens among the examined fluoropolymers, has the strongest acid-base interactions.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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• 2007.11a
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• pp.130-131
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• 2007

In this study, polyvinylidene fluoride/trifluoroethylene (PVDF-TrFE) was investigated. For a metal-ferroelectic-metal (MFM) structure, We obtained that the 70 nm-thick film showed the maximum polarization of $8.24\;{\mu}C/cm^2$, 2Pr of $6\;{\mu}C/cm^2$ and the coercive voltage of ${\pm}3.1\;V$ at 12 V. The 140 nm-thick film showed higher performance. However, the thicker film required a higher voltage. The current density was $10^{-6}{\sim}10^{-7}\;A/cm^2$ under 15 V. We can expect from these results that the electrical properties of the devices particularly ferroelectric thin film transistor using PVDF-TrFE copolymer, be able to be on the trade-off relationship between the remanent polarization and the leakage current.

• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.21 no.10
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• pp.881-884
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• 2008

In this study, polyvinylidene fluoride-trifluoroethylene (PVDF-TrFE) in the composition from 51/49, was deposited on platinum for a metal-ferroelectric-metal structure. From XRD patterns, the 70 nm- and 140 nm-thick PVDF-TrFE films showed the intensity peak of near $20^{\circ}$ connected to a ferroelectric phase. Moreover, the thicker film indicated the higher intensity than thinner one. The difference of the remanent polarization (2Pr) at 0 V is decreased gradually from 10.19 to $5.7{\mu}C/cm^2$ as the thickness decrease from 140 to 70 nm. However, when the thickness decreased to 50 nm, the 2Pr rapidly drop to $1.6{\mu}C/cm^2$ so the minimum critical thickness might be at least 70 nm for device. Both different thickness films, 70 and 140 nm, indicated that the characteristic of current density-voltage was measured for $10^{-6}{\sim}10^{-7}A/cm^2$ below 15 V and the thicker film maintained relatively lower current density than thinner one. From these results, we can expect that the electrical properties for the devices particularly ferroelectric thin film transistor using PVDF-TrFE copolymer were able to be on the trade-off relationship between the remanent polarization with the bias voltage and the leakage current.

• Macromolecular Research
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• v.16 no.3
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• pp.247-252
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• 2008

Lithium gel electrolytes based on a mixed polymer matrix consisting of poly(vinylidenefluoride-hexafluoropropylene) (PVDF-HFP) and cyanoresin type M (CRM) were prepared using an in situ blending process. The CRM used in this study was a copolymer of cyanoethyl pullulan and cyanoethyl poly(vinyl alcohol) (PVA) with a mole ratio of 1:1. The mixed plasticizer was ethylene carbonate (EC) and propylene carbonate (PC) with a volume ratio of 1:1. In this study, the presence of PVDF in the electrolytes helps to form a dimensionally stable film over a broad composition range, and decreases the viscosity. In addition, it provides better rheological properties that are suitable for the extrusion of thin films. However, the presence of HFP has a positive effect on generating an amorphous domain in a crystalline PVDF structure. The ionic conductivity of the polymer electrolytes was investigated in the range 298-333 K. The introduction of CRM into the PVDF-HFP/$LiPF_6$, complex produced a PVDF-HFP/CRM/$LiPF_6$ complex with a higher ionic conductivity and improved thermal stability and dynamic mechanical properties than a simple PVDF-HFP/$LiPF_6$, complex.

• Composites Research
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• v.17 no.4
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• pp.61-67
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• 2004

Nondestructive damage sensitivity on single-basalt fiber/epoxy composites was evaluated by micromechanical technique and acoustic emission (AE). Piezoelectric lead-zirconate-titanate (PZT), polyvinylidene fluoride (PVDF) and poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) copolymer were used as AE sensor, respectively. In single-fiber composite, the damage sensing with different sensor types were compared to each other. Piezoelectric PVDF polymer sensor was embedded in and attached on the composite, whereas PZT sensor was only attached on the surface of specimen. In case of embedded polymer sensors, responding sensitivity was higher than that of the attached case. It can be due to full constraint inside specimen to transfer elastic wave coming from micro-deformation. For both the attached and the embedded cases, the sensitivity of P(VDF-TrFE) sensor was almost same as that of conventional PVDF sensor.