Evaluation of piezoelectric PVDF polymers for use in space environments. II. Effects of atomic oxygen and vacuum UV exposure

The effects of atomic oxygen (AO) and vacuum UV radiation simulating low Earth orbit conditions on two commercially available piezoelectric polymer films, poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐trifluoroethylene) P(VDF‐TrFE), have been studied. Surface erosion and pattern development are significant for both polymers. Erosion yields were determined as 2.8 × 10^?24 cm³/atom for PVDF and 2.5 × 10^?24 cm³/atom for P(VDF‐TrFE). The piezoelectric properties of the residual material of both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF‐TrFE) was observed. A lightly cross‐linked network was formed in the copolymer presumably because of penetrating vacuum ultraviolet (VUV) radiation, while the homopolymer remained uncross‐linked. These differences were attributed to varying degrees of crystallinity and potentially greater absorption, and hence damage, of VUV radiation in P(VDF‐TrFE) compared with PVDF. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2503–2513, 2005     

Synthesis of unsaturation containing P(VDF‐co‐TrFE‐co‐CTFE) from P(VDF‐co‐CTFE) in one‐pot catalyzed with Cu(0)‐based single electron transfer living radical polymerization system

Poly(vinylidene fluoride‐co‐trifluoroethylene‐co‐chlorotrifluoroethylene) (P(VDF‐co‐TrFE‐co‐CTFE)) with internal double bond has been reported with high dielectric constant and energy density at room temperature, which is expected to serve as a promising dielectric film in high pulse discharge capacitors. An environmentally friendly one‐pot route, including the controllable hydrogenation via Cu(0) mediated single electron transfer radical chain transfer reaction (SET‐CTR) and dehydrochlorination catalyzed with N‐containing reagent, is successfully developed to synthesize P(VDF‐co‐TrFE‐co‐CTFE) containing unsaturation. The resultant polymer was carefully characterized with ¹H NMR, ¹⁹F NMR, and FTIR. The composition of the resultant copolymer is strongly influenced by reaction conditions, including the reaction temperature, catalyst concentration, the types of ligands and solvents. The kinetics data of the chain transfer and elimination reaction demonstrate their well‐controlled feature of the strategy. By shifting the equilibrium between the CTR and elimination reactions dominated by N‐compounds serving as ligands in SET‐CTR and catalyst in the dehydrochlorination of P(VDF‐co‐CTFE), P(VDF‐co‐TrFE‐co‐CTFE) with tunable TrFE and double‐bond content could be synthesized in this one‐pot route. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3429–3440     

Hydrophobic/hydrophilic P(VDF‐TrFE)/PHEA polymer blend membranes

Polymer blend membranes have been obtained consisting of a hydrophilic and a hydrophobic polymers distributed in co‐continuous phases. In order to obtain stable membranes in aqueous environments, the hydrophilic phase is formed by a poly(hydrohyethyl acrylate), PHEA, network while the hydrophobic phase is formed by poly(vinylidene fluoride‐co‐trifluoroethylene) P(VDF‐TrFE). To obtain the composites, in a first stage, P(VDF‐TrFE) is blended with poly(ethylene oxyde) (PEO), the latter used as sacrificial porogen. P(VDF‐TrFE)/PEO blend membranes were prepared by solvent casting at 70°C followed by cooling to room temperature. Then PEO is removed from the membrane by immersion in water obtaining a P(VDF‐TrFE) porous membrane. After removing of the PEO polymer, a P(VDF‐TrFE) membrane results in which pores are collapsed. Nevertheless the pores reopen when a mixture of hydroxethyl acrylate (HEA) monomer, ethyleneglycol dimethacrylate (as crosslinker) and ethanol (as diluent) is absorbed in the membrane and subsequent polymerization yields hybrid hydrophilic/hydrophobic membranes with controlled porosity. The membranes are thus suitable for lithium‐ion battery separator membranes and/or biostable supports for cell culture in biomedical applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 672–679     

Miscibility and ferroelectric behavior in blends of poly(vinylidene fluoride/trifluoroethylene) and poly(vinyl acetate)

The blend system containing a poly(vinylidene fluoride/trifluoroethylene) [P(VDF/TrFE)] copolymer (68/32 mol %) and poly(vinyl acetate) (PVAc) was miscible from the results of differential scanning calorimetry (DSC) studies that exhibit the presence of a single, composition‐dependent glass transition temperature (T_g) and a strong melting point depression for the semicrystalline P(VDF/TrFE) component. However, differences between the DSC and dielectric measurements, which showed a separate P(VDF/TrFE) T_g peak, suggests that the P(VDF/TrFE)/PVAc blends are actually partially miscible. Because of the lower dielectric constant of PVAc and the reduced sample crystallinity caused by the addition of PVAc, both the dielectric constant and the remanent polarization of the copolymer blends decrease with increasing PVAc content. The presence of a small amount of PVAc stabilized the anomalous ferroelectric behavior of ice–water‐quenched P(VDF/TrFE), and the blend portrayed normal polarization reversal behavior after adding only 1 wt % PVAc. The piezoelectric response suggests small changes with an increasing number of poling cycles. It is believed that PVAc affects the D‐E hysteresis behavior at the interface between crystalline and amorphous phases, although much work remains to be done to confirm this hypothesis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 927–935, 2003     

High‐resolution solid‐state NMR study of the domain structure and molecular motion in drawn films of a vinylidene fluoride and trifluoroethylene copolymer with 73 mol % vinylidene fluoride

The heterogeneous higher order structure and molecular motion in a single crystalline film of a vinylidene fluoride (VDF) and trifluoroethylene (TrFE) copolymer with 73 mol % VDF was investigated with the ¹H–¹³C cross‐polarization/magic‐angle spinning NMR technique. A transient oscillation was observed in plots of the ¹³C peak intensity versus the contact time for the CH₂, CHF, and CF₂ groups. On the basis of the extended cross‐relaxation theory of spin diffusion, we determined that the oscillation behavior was caused by the TrFE‐rich segments in the chain and that the crystal consisted of VDF‐rich and TrFE‐rich domains. The former had TrFE‐rich segments in VDF and TrFE fractions of 0.24 and 0.27, respectively, and the latter had VDF‐rich segments in a VDF fraction of 0.49. The spin–lattice relaxation time T_1ρH in the rotating frame for each group was minimal in the three temperature regions of β, α_b, and α_c (↑) on heating and in the two temperature regions of α_1D and α_c (↓) on cooling. The α_c (↑) and α_c (↓) processes depended on the first‐order ferroelectric phase‐transition regions on heating and cooling, respectively. The motional modes for the other processes were confirmed by the T_1ρH minimum behavior of the VDF and TrFE groups in the TrFE‐rich domain and the VDF‐rich segments in the VDF‐rich domain. The β and α_b processes were attributed to the flip–flop motion of the TrFE‐rich segments and the competitive motion of the TrFE‐ and VDF‐rich segments in the ferroelectric phase, respectively. The α_1D process was due to the one‐dimensional diffusion motion of the conformational defects along the chain in the paraelectric phase, accompanied by the trans and gauche transformation of the VDF conformers of ttg⁺tg^? and g⁺tg^?tt. The effect of the competitive motion of the TrFE‐rich segment on the thermal stability of the VDF‐rich segment in the chain near the Curie temperature was examined. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1026–1037, 2002     

Infrared spectroscopic investigation of chain conformations and interactions in P(VDF‐TrFE)/PMMA blends

The blending between poly(methyl methacrylate) (PMMA) and ferroelectric (vinylidene fluoride‐trifluorethylene) [P(VDF‐TrFE)] copolymer chains has been investigated by Fourier transform infrared (FTIR) spectroscopy over the full range of composition, for the copolymer with 50 mol % of trifluorethylene [TrFE]. The FTIR spectra revealed an absorption band at 1643 cm⁻¹, characteristic of the blend and absent in the individual constituents. We attributed this band to the interaction of the carbonyl group of the PMMA side chains with the disordered helical chains present in the amorphous region of the P(VDF‐TrFE). We investigated the consequences of adding PMMA onto the formation of the all trans conformation of the copolymer chains and we demonstrated that the effects of thermal heating on the spectra are relevant only for the samples where the ferroelectric semicrystalline phase is present. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 34–40, 2000     

STUDIES ON THE CHAIN STRUCTURAL EFFECT OF PVDF AND VDF (52)/TrFE(48) COPOLYMER BY MEANS OF THE METHOD OF DIELECTRIC RELAXATION

Through improvements on a fully commercial and automatic system measuring frequency andtemperature spectra of the complex elastic, dielectric, and piezoelectric constants of polymerfilms, the precision for measuring complex dielectric constants achieved 2‰ from original 1%.The complex dielectric constants of PVDF, VDF (95 )/VF (5), VDF (52)/TrFE (48) and VDF(47. 5)/TrFE(47. 5)/HeFP (5) over a range of-120-140℃, 10-2-10~4Hz were measured bythe described system. The diminution of chain regularity due to 5mol% vinyl fluoride in the chainof PVDF led to disappearing of α-relaxation and increase in T_g (3℃) of VDF (95)/VF (5).Because of the spatial impediment of 5mol% HeFP in copolymer chain, the Curie point of VDF(52)/TrFE(48) decreased by 30℃ and T_g by 3℃. The behavior of dielectric relaxation indicatedthat 5mol% vinyl fluoride and HeFP made the relaxation strength of noncrystalline regionreduced, the activation energy of local relaxation increased and the relaxation time prolonged respectively.     

Enhanced dielectric response in P(VDF‐TrFE) based all‐organic nanocomposites

A nanocomposite with enhanced dielectric response is developed using poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)] as matrix and Chemically modified high dielectric constant organic semiconductor—copper phthalocyanine oligomer (CuPc)—as filler. Transmission electron microscope (TEM)‐observed morphologies reveal that in the nanocomposite the average size of CuPc particles is about 25 nm [1/24 of that of CuPc in physical blend of P(VDF‐TrFE) and CuPc]. The hot‐press nanocomposite film with 15 wt % CuPc can realize a dielectric constant of 540 at 100 Hz. The enhanced dielectric response in the nanocomposite demonstrates the significance of the interface effect in raising the material responses far beyond that expected by simple mixing rules when there is a large dielectric contrast between the polymer matrix and the dielectric filler in the composite. It is also interesting to note that at high frequencies (such as 100 MHz) the nanocomposite has a dielectric constant of ～100 and this value is comparable to those of current materials used in microwave applications. At 105 °C that is near the ferroelectric‐to‐paraelectric phase transition temperature of the P(VDF‐TrFE) ferroelectric, a much higher dielectric constant (about 1200 at 100 Hz) is obtained. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 490–495, 2010     

Dependence of dielectric,ferroelectric, and piezoelectric properties on crystalline properties of p(VDF‐co‐TrFE) copolymers

Thermal processing at various temperatures has been used to fabricate poly(vinylidene fluoride‐co‐trifluoroethylene) [P(VDF‐co‐TrFE)] films with varied crystalline properties in an attempt to improve their piezoelectric properties. Although the dielectric constant of the films annealed at higher temperature is smaller than that of cooled and quenched ones, it has been shown that the annealed films possess larger crystallinity and stacked lamellar crystal grain size. The ferroelectric domains deriving from crystal region in all the samples are effectively improved by hot polarization. As a result, the remnant polarizations (P_r) and coercive electric field (E_c) of the corresponding films are improved at a low frequency due to the response of dipoles in crystal phase, and the largest piezoelectric constant in the longitudinal thickness mode (d₃₃=?25 pC/N) is obtained in an annealed copolymer film. The results illustrate improving the crystal structure of P(VDF‐co‐TrFE) is an effective way to realize high electromechanical properties, which provides broadly applied scenery for this kind of copolymer in piezoelectric components. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

P (VDF‐co‐CTFE)‐g‐P2VP amphiphilic graft copolymers: Synthesis,structure, and permeation properties

A series of amphiphilic graft copolymers of poly (vinylidene fluoride‐co‐chlorotrifluoroethylene)‐g‐poly(2‐vinyl pyridine), P (VDF‐co‐CTFE)‐g‐P2VP, with different degrees of P2VP grafting (from 26.3 to 45.6 wt%) was synthesized via one‐pot atom transfer radical polymerization (ATRP). The amphiphilic properties of P (VDF‐co‐CTFE)‐g‐P2VP graft copolymers allowed itself to self‐assemble into nanoscale structures. P (VDF‐co‐CTFE)‐g‐P2VP graft copolymers were introduced into neat P (VDF‐co‐CTFE) as additives to form blending membranes. When two different solvents, N‐methyl‐2‐pyrrolidone (NMP) and dimethylformamide (DMF), were used, specific organized crystalline structures were observed only in the NMP systems. P (VDF‐co‐CTFE)‐g‐P2VP played a pivotal role in controlling the morphology and pore structure of membranes. The water flux of the membranes increased from 57.2 to 310.1 L m^?2 h^?1 bar^?1 with an increase in the PVDF‐co‐CTFE‐g‐P2VP loading (from 0 to 30 wt%) due to increased porosity and hydrophilicity. The flux recovery ratio (FRR) increased from 67.03% to 87.18%, and the irreversible fouling (R_ir) decreased from 32.97% to 12.82%. Moreover, the pure gas permeance of the membranes with respect to N₂ was as high as 6.2 × 10⁴ GPU (1 GPU = 10^–6 cm³[STP]/[s cm² cmHg]), indicating their possible use as a porous polymer support for gas separation applications.     

Enhanced electrostriction based on plasticized relaxor ferroelectric P(VDF‐TrFE‐CFE/CTFE) blends

The purpose of this work aims at enhancing the electrostrictive strain response and the mechanical energy density under moderate electric field, which is essential for actuator applications. For achieving this, plasticized effects as well as the influence of chlorofluoroethylene and chlorotrifluoroethylene defects on the electromechanical behavior of the copolymer matrix poly(vinylidene fluoride‐trifluoroethylene) (P(VDF‐TrFE)) are investigated. Experimental results showed that the plasticized terpolymer‐based CFE presented better electrical and mechanical performances than the CTFE one. Furthermore, such interesting properties exhibited superior advantages when CFE was combined with (DEHP) plasticizer, resulting in excellent electrostrictive strain response as well as mechanical energy density. Another aspect of this work reports on the influence of the composition, especially the CTFE content, on the electromechanical properties of the neat and plasticized P(VDF‐TrFE‐CTFE). This enables the determination of the desired terpolymer compositions for given applications, which are based on different criteria, such as crystallinity, elastic modulus, dielectric permittivity, and so forth. All the results demonstrated a possibility to realize high performance electroactive polymer actuators while achieving significant improved strain response and energy density under relatively low electric field. Such an investigation allows overcoming the current technological barrier of conventional electroactive polymers that suffer from the high applied electric field usually required to reach sufficient strain. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1368–1379     

Effects of electron irradiation on poly(vinylidene fluoride–trifluoroethylene) copolymers studied by solid‐state nuclear magnetic resonance spectroscopy

The effects of electron irradiation on the molecular chemical structure, conformation, mobility, and phase transition of vinylidene fluoride (VDF) and trifluoroethylene (TrFE) copolymer have been investigated with variable‐temperature, solid‐state ¹⁹F nuclear magnetic resonance (NMR). It has been found that electron irradiation converts all‐trans conformations of both VDF‐rich and TrFE‐containing segments into dynamically mixed trans–gauche conformations accompanied by a simultaneous ferroelectric‐to‐paraelectric (or amorphous) transition. The variable‐temperature ¹⁹F magic‐angle‐spinning spectra results show that the paraelectric phase melts at much lower temperatures in irradiated films than in an unirradiated sample. Moreover, ¹⁹F NMR relaxation data (spin–lattice relaxation times in both the laboratory and rotating frames) reveal that electron irradiation enhances the molecular motion in paraelectric regions, whereas the molecular motion in a high‐temperature amorphous melt (>100 °C) is more constrained in irradiated films. Besides these physical changes, electron irradiation also induces the formation of several CF₃ groups. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1714–1724, 2006     

Liquid phase demixing in ferroelectric/semiconducting polymer blends: An experimental and theoretical study

This article describes a combined experimental and theoretical study on nanophase structure development as a result of liquid phase demixing in solution‐cast blends of the organic semiconductor poly(9,9′‐dioctyl fluorene) (PFO) and the ferroelectric polymer poly(vinylidene fluoride‐co‐trifluoroethylene) (P(VDF‐TrFE)). Blend layers (200 nm) are prepared by spin coating a 1:9 (w/w) PFO:P(VDF‐TrFE) blend solution in a common solvent on a poly(ethylenedioxy thiophene)/poly(styrene sulfonate) substrate. Owing to the pronounced incompatibility between the two polymers, a strong phase‐separated morphology is obtained, characterized by disk‐like nanodomains of PFO embedded in a P(VDF‐TrFE) matrix, as revealed by scanning electron microscopy. By varying the processing conditions, we find the average domain size and standard deviation to increase with spinning time. The considerable increase in domain size suggests the coarsening process not to be impeded by a steep rise in viscosity. This indicates solvent evaporation to be only moderate within the experimental time frame. The evolution of the observed phase morphology is modeled using ternary diffuse interface theory integrated with a modified Flory–Huggins (FH) treatment of the homogeneous (bulk) free energy of mixing, to account for significant molecular differences between the active blend components. Using calculated FH interaction parameters, the model confirms the phase separation to occur via spinodal decomposition of the blend solution during spin coating, as suggested by experimental observations. The simulated phase morphologies as well as the modeled trends in domain growth and standard deviation compare favorably with the experimental data. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1255–1262, 2011     

Structure and properties of semicrystalline polymers via high-frequency acoustic and x-ray measurements. I. Ferroelectric P(VDF/TrFE) copolymer

Acoustic, opto-acoustic, and x-ray investigations have been performed in order to study the influence of irradiation, electrical poling, and mechanical orientation on the morphology of ferroelectric random copolymers of vinylidene fluoride and trifluorethylene {P[VDF/TrFE] (70/30)}. The influences of these different treatments on the molecular orientation distribution of the amorphous and crystalline phases are discussed, as well as their influences on the crystallinity of the material. The elastic stiffness and the related viscosity tensors of P[VDF/TrFE] (70/30), the elastic stiffness modulus of the amorphous matrix, and the hierarchy of stiffness constants of the crystalline state have been determined. © 1993 John Wiley & Sons, Inc.     

Origin of Piezoelectricity in an Electrospun Poly(vinylidene fluoride‐trifluoroethylene) Nanofiber Web‐Based Nanogenerator and Nano‐Pressure Sensor

A single stage electrospinning process can give rise to preferentially oriented induced dipoles in poly(vinylidene fluoride‐trifluoroethylene) [P(VDF‐TrFE)] nanofibers. The piezoelectricity of as‐electrospun P(VDF‐TrFE) nanofiber webs opens up new possibilities for their use as a flexible nanogenerators and nano‐pressure sensors. In this work, the origin of the piezoelectricity has been spotlighted by randomization of the induced dipoles at the Curie temperature and analyzed by polarized FT‐IR spectroscopic techniques as well as by detecting the piezoelectric signal from a nano‐pressure sensor.

     

Effect of biaxial orientation on dielectric and breakdown properties of poly(ethylene terephthalate)/poly(vinylidene fluoride‐co‐tetrafluoroethylene) multilayer films

Polymer films with enhanced dielectric and breakdown properties are essential for the production of high energy density polymer film capacitors. By capitalizing on the synergistic effects of forced assembly nanolayer coextrusion and biaxial orientation, polymer multilayer films using poly(ethylene terephthalate) (PET) and a poly(vinylidene fluoride‐co‐tetrafluoroethylene) [P(VDF‐TFE)] copolymer were produced. These films exhibited breakdown fields, under a divergent field using needle/plane electrodes, as high as 1000 kV mm^?1. The energy densities of these same materials, under a uniform electric field measured using plane/plane electrodes, were as high as 16 J cm^?3. The confined morphologies of both PET and P(VDF‐TFE) were correlated to the observed breakdown properties and damage zones. On‐edge P(VDF‐TFE) crystals induced from solid‐state biaxial stretching enhanced the effective P(VDF‐TFE) layer dielectric constant and therefore increased the dielectric contrast between the PET and P(VDF‐TFE) layers. This resulted in additional charge buildup at the layer interface producing larger tree diameters and branches and ultimately increasing the breakdown and energy storage properties. In addition to energy storage and breakdown properties, the hysteresis behavior of these materials was also evaluated. By varying the morphology of the P(VDF‐TFE) layer, the low‐field dielectric loss (or ion migration behavior) could be manipulated, which in turn also changed the observed hysteresis behavior. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 882–896     

Fluorinated block copolymers containing poly(vinylidene fluoride) or poly(vinylidene fluoride‐co‐hexafluoropropylene) blocks from perfluoropolyethers: Synthesis and thermal properties

PFPE‐b‐PVDF and PFPE‐b‐poly(VDF‐co‐HFP) block copolymers [where PFPE, PVDF, VDF, and HFP represent perfluoropolyether, poly(vinylidene fluoride), vinylidene fluoride (or 1,1‐difluoroethylene), and hexafluoropropylene] were synthesized by radical (co)telomerizations of VDF (or VDF and HFP) with an iodine‐terminated perfluoropolyether (PFPE‐I). Di‐tert‐butyl peroxide (DTBP) was used and was shown to act as an efficient thermal initiator. The numbers of VDF and VDF/HFP base units in the block copolymers were assessed with ¹⁹F NMR spectroscopy. According to the initial [PFPE‐I]₀/[fluoroalkenes]₀ and [DTBP]₀/[fluoroalkenes]₀ molar ratios, fluorinated block copolymers of various molecular weights (1500–30,300) were obtained. The states and thermal properties of these fluorocopolymers were investigated. The compounds containing PVDF blocks with more than 30 VDF units were crystalline, whereas all those containing poly(VDF‐co‐HFP) blocks exhibited amorphous states, whatever the numbers were of the fluorinated base units. All the samples showed negative glass‐transition temperatures higher than that of the starting PFPE. Interestingly, these PFPE‐b‐PVDF and PFPE‐b‐poly(VDF‐co‐HFP) block copolymers exhibited good thermostability. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 160–171, 2003     

Synthesis of poly(vinylidene fluoride)‐b‐poly(styrene sulfonate) block copolymers by controlled radical polymerizations

Block copolymers based on poly(vinylidene fluoride), PVDF, and a series of poly(aromatic sulfonate) sequences were synthesized from controlled radical polymerizations (CRPs). According to the aromatic monomers, appropriate techniques of CRP were chosen: either iodine transfer polymerization (ITP) or atom transfer radical polymerization (ATRP) from PVDF‐I macromolecular chain transfer agents (CTAs) or PVDF‐CCl₃ macroinitiator, respectively. These precursors were produced either by ITP of VDF with C₆F₁₃I or by radical telomerization of VDF with chloroform, respectively. Poly(vinylidene fluoride)‐b‐poly(sodium styrene sulfonate), PVDF‐b‐PSSS, block copolymers were produced from both techniques via a direct polymerization of sodium styrene sulfonate (SSS) monomer or an indirect way with the use of styrene sulfonate ethyl ester (SSE) as a protected monomer. Although the reaction led to block copolymers, the kinetics of ITP of SSS showed that PVDF‐I macromolecular CTAs were not totally efficient because a limitation of the CTA consumption (56%) was observed. This was probably explained by both the low activity of the CTA (that contained inefficient PVDF‐CF₂CH₂? I) and a fast propagation rate of the monomer. That behavior was also noted in the ITP of SSE. On the other hand, ATRP of SSS initiated by PVDF‐CCl₃ was more controlled up to 50% of conversion leading to PVDF‐b‐PSSS block copolymer with an average number molar mass of 6000 g·mol^?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Composite polymer electrolyte membranes comprising P(VDF‐co‐CTFE)‐g‐PSSA graft copolymer and zeolite for fuel cell applications

Hybrid organic/inorganic composite polymer electrolyte membranes based on a poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) grafted membrane and varying concentrations of zeolite were investigated for application in proton exchange membrane fuel cells (PEMFC). A proton conducting comb copolymer consisting of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) backbone and poly(styrene sulfonic acid) (PSSA) side chains, i.e. P(VDF‐co‐CTFE)‐g‐PSSA (graft copolymer) with 47 wt% of PSSA was synthesized using atom transfer radical polymerization (ATRP) and solution blended with zeolite. Upon incorporation of zeolite, the symmetric stretching band of both SO group (1169 cm^?1) and the ? OH group (3426 cm^?1) shifted to lower wavenumbers. The shift in these FT‐IR spectra suggests that the zeolite particles strongly interact with the sulfonic acid groups of PSSA chains. When the weight percent of zeolite 5A is above 7%, the proton conductivity at room temperature was reduced to 0.011 S/cm. The water uptake of the composite membranes decreased from 234 to 125% with an increase of the zeolite 5A weight percent to 10 wt%. The decrease in water uptake is likely a result of the decrease in the number of available water absorption sites because of the hydrogen bonding interactions between the zeolite particles and the graft copolymer matrix. This behavior is successfully investigated by scanning electron microscopy (SEM). The results of thermal gravimetric analysis (TGA) also showed that all the membranes were stable up to 300°C. Copyright © 2009 John Wiley & Sons, Ltd.     

Antifouling poly(vinylidene fluoride) ultrafiltration membranes containing amphiphilic comb polymer additive

An amphiphilic comb polymer consisting of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene) [P(VDF‐co‐CTFE)] main chains and poly(oxyethylene methacrylate) (POEM) side chains was synthesized using direct initiation of the chlorine atoms in CTFE units through atom transfer radical polymerization, as confirmed by ¹H NMR and FTIR spectroscopy. The P(VDF‐co‐CTFE)‐g‐POEM comb polymer was introduced as an additive to prepare poly(vinylidene fluoride) antifouling ultrafiltration membranes. As the contents of comb polymer increased, the mechanical properties of membranes slightly decreased due to the decreased crystallinity of the membranes, as revealed by universal testing machine and X‐ray diffraction. However, water contact angle measurement and X‐ray photoelectron spectroscopy showed that the hydrophilic POEM segments spontaneously segregated on the membrane surfaces. As a result, the antifouling property of the membranes containing P(VDF‐co‐CTFE)‐g‐POEM comb polymer was considerably improved with a slight change of water flux. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 183–189, 2010