PVDF/PMMA/Basalt fiber composites: Morphology,melting and crystallization,structure, mechanical properties,and heat resistance

This paper is to study the effect of basalt fiber on morphology, melting and crystallization, structure, mechanical properties, melting and crystallization of PVDF/PMMA composites using scanning electron microscopy (SEM), X‐ray, differential scanning calorimeter (DSC), dynamical mechanical analysis (DMA), etc. Basalt fiber may disperse well in PVDF/PMMA matrix and form compact fiber network, and this makes tensile and flexural strength of fiber reinforced PVDF/PMMA composites get to the maximum value of 62 and 102 MPa, respectively. However, the mechanical properties begin to decrease when basalt fiber content exceeds 20 wt %. The α and β phase of PVDF can coexist in composites, and basalt fiber and PMMA can induce β phase of PVDF. The melting temperature of PVDF in composites is kept unchanged, but the degree of crystallinity of composites increases as basalt fiber content increase, and then declines when fiber content exceeds 20%. The DSC results confirm that the nucleation ability of PVDF is enhanced by basalt fiber. Also, the heat resistance of PVDF/PMMA composite is improved from 133 to 146.1°C due to basalt fiber. The DMA shows that basalt fiber increases the storage modulus of PVDF/PMMA composite, and the loss peak of PMMA increases from 116.1 to 130°C. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40494.     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

VGCF填充PVDF/PMMA复合材料导电性能的研究

以气相生长碳纤维（VGCF）为导电填料,聚偏氟乙烯（PVDF）、聚甲基丙烯酸甲酯（PMMA）为基体制备复合型导电高分子材料。考察了填料用量、基体种类、配比以及PVDF结晶行为对复合材料导电性能的影响。结果表明,VGCF填充PMMA、PVDF、PVDF／PMMA（50／50）体系的渗滤阔值分别为5、4、3phr的填料用量。VGCF的加入会导致PVDF／PMMA体系发生微观相分离,而且VGCF会选择性富集在PVDF的非晶相中,所以PVDF／PMMA／VGCF体系的导电性呈现双重渗滤现象,该体系的体积电阻率不仅取决于富集相中VGCF的含量,而且还与PVDF相的连续性及其结晶行为密切相关。     

Highly reversible and repeatable PTCR characteristics of PMMA/Ag‐coated glass bead composites based on CTE mismatch phenomena

Positive temperature coefficient of resistivity (PTCR) behavior of poly(methyl methacrylate) PMMA/silver (Ag)‐coated glass bead composites has been investigated with reference to the conventional PMMA/carbon black (CB) composites. The PMMA/CB composites showed a sudden rise in resistivity (PTC trip) at 115°C, close to the glass transition temperature (T _g, 113°C) of the PMMA. However, the PTC trip temperature (92°C) of PMMA/Ag‐coated glass bead composites was appeared well below the T _g of PMMA. The room temperature resistivity and PTC trip temperature of the composites were also very much stable upon thermal cycling. Addition of 1 phr of nanoclay increased the PTC trip temperature of PMMA/CB composites to 120°C, close to the T _g (118°C) of PMMA/clay nanocomposites, while PMMA/clay/Ag‐coated glass bead nanocomposites showed the PTC trip at 98°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between PMMA and glass beads played a key role that led to a disruption in continuous network structure of Ag‐coated glass beads even at a temperature well below the T _g of PMMA. The decrease in dielectric permittivity of PMMA/Ag‐coated glass bead composites on increasing frequency indicated possible use of the PTC composites as dielectric material. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

An Innovative Approach to the Synthesis of PMMA/PEG/Nanobifiller Filled Nanocomposites with Enhanced Mechanical and Thermal Properties

A facile route was adopted to blend the matrix. The PMMA/PEG blend was reinforced with three types of nanofillers, i.e., pristine MWCNT (P-CNT), amine functionalized MWCNT (PDA-EA-CNT) and nanobifiller i.e. nanodiamond functional MWCNT (PDA-EA-CNT-ND) to yield three different types of nanocomposites i.e. PMMA/PEG/P-CNT, PMMA/PEG/PDA-EA-CNT and PMMA/PEG/PDA-EA-CNT-ND. These nanocomposites were reinforced with nanofiller loading (1 wt. %, 3 wt. %, 5 wt. %, 10 wt. %, 30 wt. % and 50 wt. %) by solution casting method. Structure of composite and nanofillers was confirmed by FTIR. FESEM imaging revealed that nanocomposites have micro porous morphology. At high magnification, distribution of functionalized CNT/ND appears to be protruding out of the polymeric matrix. The TGA result suggests that the thermal stability of the nanocomposites was enhanced in comparison to PMMA due to grafting of filler molecules with PMMA/PEG macromolecules. The DTG results showed that the bifiller nanocomposites (PMMA/PEG/PDA-EA-CNT-ND) exhibited improved thermal stability with T_max (431^°C) as compared to P-CNT and amine functionalized CNT (PMMA/PEG/PDA-EA-CNT) with T_max of 395^°C and 418^°C respectively. XRD results showed fine interaction between filler and the polymeric matrix. As the filler loading was increased the composites showed pronounced XRD peak at 25.9^°, corresponding to (002) reflection of nanotubes. Significant improvement in the mechanical properties of composites was recorded with the reinforcement of fillers as compared to the neat matrix. The most significant improvement in tensile strength and elastic modulus was observed for the bifiller nanocomposites with 5 wt. % PDA-EA-CNT-ND. They showed a tensile strength and elastic modulus of 29.9 MPa and 1474.31 MPa respectively as compared to amine functionalized CNT with tensile strength (25.7) and elastic modulus (1466.99 MPa)and P-CNT with tensile strength(25 MPa) and elastic modulus (1155.75 MPa).     

Dielectric and TSC study of semicompatible PVDF/PMMA blends

Summary Dielectric and TSC studies of charged (by stabilized electrical breakdown) and discharged PVDF/PMMA blends have been performed. The relative changes in are found to decrease with increasing PVDF content except for samples with 50 and 70 weight-% of PVDF. The temperature T_max of the TSC maximum is found to be shifted linearly towards lower temperatures with increasing PVDF content up to 30 weight-% of PVDF. For higher concentrations T_max is found to be independent on PVDF content except for samples of 70 weight-% of PVDF. These behaviours indicate that for PVDF concentrations higher than 30 weight-% the system starts to lose its compatibility.     

PVDF/PMMA composite nanofiber fabricated by electrospray deposition: Crystallization of PVDF induced by solvent extraction of PMMA component

The crystallization of poly(vinylidene fluoride) (PVDF) was observed after the poly(methyl methacrylate) (PMMA) component was extracted from the PVDF/PMMA (50/50) composite nanofiber fabricated by electrospray deposition, even though the original composite showed a completely amorphous pattern in the wide‐angle X‐ray diffraction. The content of the β‐crystal form in the crystalline region depended on the PVDF/PMMA composite ratios and the type of solvents used for the extraction of the PMMA component, e.g., chloroform and toluene. Thus, the content of the β‐crystal form can be controlled by selecting the original PVDF/PMMA composition and the solvent used to extract the PMMA component. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology development and exclusion of noncrystalline polymer during crystallization in PVDF/PMMA blends

Morphology development during the crystallization of poly(vinylidene fluoride) (PVDF)/poly(methyl methacrylate) (PMMA) blends was investigated at various crystallization temperatures (T_C) by means of time-resolved light scattering measurements and atomic force microscopy (AFM). A coarse spherulite obtained at a high T_C of 162 °C was found to be developed with a two-step crystallization process. The ordering in the spherulites (Pr) increased with time at the early stages and then decreased at the later stages. The rate of spherulite growth started to decrease when Pr started to decrease. In contrast, in the compact spherulite obtained at a low T_C of 148 °C, Pr decreased monotonously with time while the growth rate was constant. AFM observation revealed that such characteristic crystallization behavior is attributed to the exclusion of PMMA from the crystal growth during the crystallization; i.e., the amount of excluded PMMA becomes larger as the distance from the spherulite center increases and the crystallization temperature rises.     

Nanotube surface functionalization effects in blended multiwalled carbon nanotube/PVDF composites

A mixed fill system of multiwalled carbon nanotubes (MWCNT) and hydroxylated MWCNT (HO‐MWCNT) in a poly(vinylidene fluoride) (PVDF) matrix was investigated to improve nanotube dispersion and enhance electrical percolation for the bulk nanocomposites. Nonfunctionalized MWCNT were blended at various concentrations into dimethylformamide solutions containing PVDF with 0, 5, or 10 wt % HO‐MWCNT. Composite samples prepared from these solutions were examined by four‐point probe resistivity measurements. The percolation threshold decreased from 0.49 wt % MWCNT in binary MWCNT/PVDF composites to 0.25 wt % for ternary composites containing MWCNT/HO‐MWCNT/PVDF, with either 5 or 10 wt % HO‐MWCNT. In the case of the ternary composite with 10 wt % HO‐MWCNT, the lowest fill percent of MWCNT (0.25 wt %) measured a conductivity that was three orders of magnitude higher than the binary MWCNT/PVDF composite containing twice the concentration of MWCNT (0.5 wt %). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of nanoclay on the thermal,mechanical, and crystallization behavior of nanofiber webs of nylon‐6

Nylon‐6 and nanoclay/nylon‐6 composite nanofibers were prepared by electrospinning technique, in which formic acid was used as a solvent for good solubility of nylon‐6. The diameter of nylon‐6 and nanoclay/nylon‐6 nanofibers was below 350 nm and had smooth surfaces. The DSC heating curves of nylon‐6 and composites nanofibers show two endotherm behaviors, T_m1 (about 214°C) and T_m2 (about 220°C), corresponding to the melting events of γ‐form and α‐form crystals, respectively. The WAXs study showed that the γ‐crystalline phase predominantly present in both nylon‐6 and nanoclay/nylon‐6 nanofibers. The mechanical properties of the nanoclay/nylon‐6 composite nanofibers were higher than neat nylon‐6 electrospun nanofibers, which was decreased as the quantity of the clay increased. It might be due to the aggregation of nanoclay at high concentration. The thermal properties of the composite nanofibers were higher than neat nylon‐6 nanofibers. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Polyvinylidenefluoride/Polymethylmethacrylate/Polyphosphazene/Lithium Tantalate Composites: Synthesis and Characterization

This study presents the preparation of poly vinylidene fluoride (PVDF) based polymethyl methacrylate (PMMA), Poly(bis(4-Aminophenoxy)phosphazene)(PPZ) and lithium tantalate (LT) composites films using solution blending process. The fabricated PVDF/PMMA/PPZ/LT composite films were evaluated using Fourier transformed infrared spectroscopy, Scanning electron microscopy, Differential scanning calorimetry and Thermo gravimetric analyses. The changes in microstructure, dielectric, morphological and thermal properties of these films with change in composition of PVDF/PMMA/PPZ/LT have been investigated. The high PMMA content and incorporation of LT favored the PVDF phase transition from ‘α’ to ‘β’ phase as shown by FT-IR analysis. The LT particles were properly dispersed in PVDF/PMMA/PPZ matrix as confirmed by scanning electron micrograph images. The dielectric properties of the PVDF/PMMA/PPZ improved with increasing the concentration of LT. The dielectric constant of the films increased with increase in LT content in the blends. The values of dielectric properties observed were higher at lower frequency at room temperature. The composites having 10, 20, 30 & 40% LT in blend samples showed regular increase in T_ons, T_max and corresponding char yield with increase in the filler content. All the composites demonstrated two steps decomposition due to the interaction of filler with polymers at high temperature leading to oxidative decomposition of polymeric chains.     

Effect of PMMA addition on characterization and morphology of PVDF

Polyvinylidene fluoride and polymethylmethacrylate (PVDF/PMMA) films were blended with different concentrations by casting method. Structural, spectroscopic, and morphological characteristics of both the interface and the surface of the films have been investigated. The blends were characterized using X‐ray diffraction (XRD), Fourier transform infrared (FTIR), UV–visible, differential thermal analysis (DTA), and scanning electron microscopy (SEM). All measurements reveal that the blends take place based on the influence of PMMA content on PVDF. FTIR results indicate the possible interactions between carbonyl group of PMMA and CH₂ groups of PVDF which indicates the formation of blends. Optical absorption spectra suggested the presence of an optical gap (E_g) which decreased with increasing PMMA content. UV/VIS spectra were characterized by a sharp edge and a window of wavelength range 290–350 nm for some blends. The optical window can be used as an optical sensor or band pass filter. The degree of crystallinity was found to decrease with increasing PMMA content, which was confirmed by XRD and DTA analysis. SEM micrograph shows spherulites which increase with the addition of PMMA and it becomes sharper and contains a longitudinal shape. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Grafting of styrene/maleic anhydride copolymer onto PVDF membrane by supercritical carbon dioxide: Preparation,characterization and biocompatibility

Herein we report the surface modification of poly(vinylidene fluoride) (PVDF) microporous membrane via thermally induced graft copolymerization with maleic anhydride (Man)/styrene (St) in supercritical carbon dioxide (SC CO₂). SC CO₂, as a solvent and carrier agent, could accelerate mass transfer of monomers inside polymer matrixes and then facilitate the graft copolymerization on the surface of the membrane and within membrane pores, which were confirmed by FT-IR/ATR and XPS spectra together with SEM photographs. The effects of SC CO₂ pressure and temperature and the monomer concentration on the graft copolymerization were investigated. The modified PVDF membranes containing from 0 to 7 wt.% of grafted St–Man copolymer (SMA) were prepared and analysed in terms of surface microstructure, composition, hydrophilicity and biocompatibility. Solid-state ¹³C CP/MAS NMR and DSC indicated that the grafted SMA on the PVDF membrane had the alternative sequence structure and formed the different phases in the modified membrane, where the grafted SMA was associated with T_g of 122.8 °C and the PVDF matrix with T_m of 161.2 °C. The static contact angle measurements revealed that remarkable and permanent hydrophilicity was obtained upon grafting SMA. The experiments of BSA adsorption and cell growth also showed that the surface of SMA-based PVDF membrane has excellent biocompatibility.     

Morphological evaluation and phase behavior of PVDF/PEO blends in the presence of graphene nanoplatelets through rheological measurements

In this study, graphene nanoplatelets (GNPs) were incorporated into poly(vinylidene fluoride) (PVDF), poly(ethylene oxide) (PEO), and PVDF/PEO blends using solution casting method in order to achieve binary and ternary polymer nanocomposites. The focus of the work is on the compatibilizing effects of the GNPs on partially miscible PVDF/PEO blends. X-ray diffraction method, rheological measurements, scanning electron microscopy (SEM), and atomic force microscopy observations enabled us to track the dispersion state and localization of the graphene nanosheets in the nanocomposites. The results exhibited that the nanoplatelets were preferentially distributed through the PVDF phase and/or at the interface of the PVDF/PEO phases. Evaluation of the wetting parameter for the PVDF/PEO/GNPs nanocomposite also verified better affinity of the selected nanofiller with the PVDF component. Extend of the miscibility in the nanocomposites was studied by a well-known rheological method. A tangible increment in binodal (T_b) and spinodal (T_s) decomposition temperatures by addition of a very low content of the GNPs (0.5 wt %) revealed well-defined compatibilization effects of the graphene on this binary polymer blend. SEM images at different temperatures confirmed the rheologically determined liquid–liquid phase diagram. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48017.     

Formation of core/shell ultrafine fibers of PVDF/PC by electrospinning via introduction of PMMA or BTEAC

Core/shell structured ultrafine fibers of poly(vinylidene fluoride) (PVDF)/polycarbonate (PC) were prepared by electrospinning their dispersions in a mixed solvent of N,N-dimethylformamide and tetrahydrofuran. The morphology of the obtained fibers viewed under a scanning electron microscope and a transmission electron microscope could be adjusted via introduction of poly(methyl methacrylate) (PMMA) or triethylammonium chloride (BTEAC). The viscosity of the dispersions increased with the increasing amount of PMMA in the range of 10-15 wt%, while the diameter of the dispersive spheral phase in the dispersions decreased. A proper amount of PMMA could decrease the resistance of the dispersive phase transformation in PVDF/PC dispersions, so that the uniform fibrous morphology and distinct core/shell structure were easily formed in the electrospun fibers. Because of the significant increase of the conductivity of the PVDF/PC dispersion, addition of 2 wt% BTEAC could also promote formation of the core/shell structure of electrospun PVDF/PC ultrafine fibers. Comparison between electrospun fibers of PVDF/PC, PVDF/PC/PMMA and PVDF/PC with BTEAC etched by chloroform showed that the core/shell structure of PVDF/PC with BTEAC was in the highest quality.     

Study of crystallization behavior of neat poly(vinylidene fluoride) and transcrystallization in carbon fiber/poly(vinylidene fluoride) composite under a temperature gradient

The crystallization behavior of poly(vinylidene fluoride) (PVDF) and transcrystallization in carbon fiber (CF)/PVDF composite were investigated under a temperature gradient. The crystallization temperature (T_c) was controlled in the range of 110–180 °C. For neat PVDF, the results showed that exclusive γ phase formed at T_c above 164 °C, but coexisted with α phase at T_c ranging from 137 to 160 °C. The promotion of γ phase to nucleation of α phase at low T_c was observed for the first time. For CF/PVDF composite, a cylindrical transcrystalline (TC) layer formed on the surface of CF when T_c was between 137 and 172 °C. The TC layer was exclusively composed of γ phase at T_c above 164 °C. The hybrid nucleation was dominated by γ phase though some α phase nuclei emerged on the surface of CF when T_c was in the range of 144–160 °C. As T_c decreased, competition between the hybrid nucleation of α and γ phase became more intense. The γ phase nuclei was soon circumscribed by the rapidly developed α phase when T_c was below 144 °C. Furthermore, some α phase nuclei were induced at the surface of the γ phase TC layer, and developed into α phase TC layer when T_c was in the range of 146–156 °C, which resulted in a doubled TC layer of α and γ phase at the interface of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43605.     

Hydrophilicity and crystallization behavior of PVDF/PMMA/TiO<Subscript>2</Subscript>(SiO<Subscript>2</Subscript>) composites prepared by in situ polymerization

Composites with enhanced hydrophilicity were prepared by adding TiO₂ or SiO₂ nanoparticles during the in situ polymerization of methyl methacrylate (MMA) in poly(vinylidene fluoride) (PVDF). The hydrophilicities of the PVDF/PMMA/TiO₂(SiO₂) composites generated in this manner were characterized by contact angle measurements and atomic force microscopy (AFM). The hydrophilicity was dependent on nanoparticle content; it gradually increased with increasing TiO₂ (or SiO₂) content when the TiO₂ (or SiO₂) content was no more than 4 wt% of PVDF. A homogeneous dispersion of the TiO₂ (or SiO₂) nanoparticles in the composite matrix was observed in scanning electron microscope (SEM) images. Based on Fourier transform infrared (FTIR) spectra and wide angle X-ray diffraction (WAXD) analyses, the crystalline phase composition of PVDF was not influenced by the addition of TiO₂ (or SiO₂); PVDF crystallized predominantly in the α phase after in situ polymerization. Nevertheless, the nanoparticles can promote the formation of the β phase of PVDF in composites; the β-phase content increased with increasing TiO₂ content, while it was almost independent of SiO₂ content.     

A facile route for the synthesis of mechanically strong MWCNTs/NDs nanobifiller filled polyacrylate composites

ABSTRACT

We present here the synthesis of novel Nano-Bifiller filled composites with extremely promising material properties. To achieve this goal, initially, poly (methyl methacrylate) (PMMA) and poly (ethylene glycol) (PEG) blend were formed. Later, the matrix was reinforced with purified carbon (P-CNT), amino modified carbon nanotube (PDA-CNT) and amino modified carbon nanotube nanodiamond (PDA-CNT-ND). In this way, three series of nanocomposites, i.e. PMMA/PEG/P-CNT, PMMA/PEG/PDA-CNT, and PMMA/PEG/PDA-CNT-ND were synthesized with varying P-CNT, PDA-CNT and PDA-CNT-ND loading (i.e., 1 wt.%, 3 wt.%, 5 wt.%, 10 wt.%, 30 wt.% and 50 wt.%) by a solution blending route. The reinforcement and loading effect of these three types of nanofillers on the matrix was studied. Studies were performed using Fourier transform infrared spectroscopy (FTIR), mechanical testing, thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM) and X-ray powder diffraction (XRD) to explore the structural, morphological, mechanical and thermal properties of nanocomposites prepared. The inter-association of poly (methyl methacrylate) and poly (ethylene glycol) (PMMA/PEG) due to hydrogen bonding and covalent attachment of matrix to the sidewalls of nanotubes was confirmed by FTIR spectra. The experimental results showed that a loading of 5 wt. % filler in matrix produced a tensile strength and modulus of 26.4 (MPa) and 1255.75 (MPa) in PMMA/PEG/P-CNT nanocomposites, while 28.8 (MPa) and 1411.04 (MPa) in PMMA/PEG/PDA-CNT nanocomposites and 29.4 (MPa) and 1419.41 (MPa) in PMMA/PEG/PDA-CNT-ND nanocomposites as compared to neat PMMA which has tensile strength and modulus of 21.79 (MPa) and 1083.84 (MPa) respectively. These results depict that bifiller nanocomposites showed better mechanical properties as compared to pristine and amine functionalized MWCNT. Scanning electron microscopy revealed granular morphology with few protruding out carbon nanotubes. Thermal stability of PMMA/PEG/PDA-CNT-ND nanocomposites was found higher than PMMA/PEG/PDA-CNT and PMMA/PEG/P-CNT nanocomposites. The T_o (369^°C) and T₁₀ (515^°C) values for PMMA/PEG/PDA-CNT-ND composites was higher than PMMA/PEG/PDA-CNT [T_o (354^°C) and T₁₀ (420^°C)] and PMMA/PEG/P-CNT composites [T_o (312^°C) and T₁₀ (390^°C)]. These results suggest that the bifiller nanocomposites were thermally more stable. The XRD spectra showed a pronounced XRD peak at 25.9^°, corresponding to (002) reflection of the nanotubes indicating that MWCNT structure was not destroyed during composite formation. The peak appeared at 75.3^° were indexed to (220) reflections due to nanodiamond structure.     

Enhanced electroactive β phase in three phase PVDF/CaCO3/nanoclay composites: Effect of micro‐CaCO3 and uniaxial stretching

In this study, electroactive polar phase transformation and crystallinity of poly(vinylidene fluoride) (PVDF)‐based composites, such as PVDF/CaCO₃/nanoclay, is explored as a function of micro‐CaCO₃ fraction and draw ratio (R) of uniaxial stretching. Composites including PVDF/clay, PVDF/CaCO₃ and most importantly PVDF/CaCO₃/clay with varying fraction of micro‐CaCO₃ were extruded into homogenous and flexible cast films. Characterization via Fourier transform infrared spectroscopy, X‐ray diffraction, and differential scanning calorimetry (DSC) confirmed the presence of β phase in all the composites incorporated with micro‐CaCO₃ and nanoclay either individually (i.e., PVDF/CaCO₃ and PVDF/clay films, respectively) or together (i.e., PVDF/CaCO₃/nanoclay composites). Interestingly, a gradual but significant improvement in this electroactive phase (β phase) was obtained with successive increment in CaCO₃ content into a fixed composition of PVDF and nanoclay (PVDF/CaCO₃/clay composites). Further increment in β phase content was obtained via uniaxial stretching to different draw ratios and at a temperature of 90 °C, where for PVDF/CaCO₃/clay (especially, 100–35‐3 and 100–40‐3) samples almost no α phase was observed irrespective of R. Conversely, the crystallinity of melt extruded samples decreased gradually all the way with CaCO₃ concentration in PVDF/CaCO₃/clay composites compared to the neat PVDF while increased gradually with increasing draw ratio. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44940.     

Generation of microcellular foams of PVDF and its blends using supercritical carbon dioxide in a continuous process

Use of supercritical carbon dioxide (scCO₂) as a blowing agent to generate microcellular polymer foams (MPFs) has recently received considerable attention due to environmental concerns associated with conventional organic blowing agents. While such foams derived from amorphous thermoplastics have been previously realized, semicrystalline MPFs have not yet been produced in a continuous scCO₂ process. This work describes the foaming of highly crystalline poly(vinylidene fluoride) (PVDF) and its blends with amorphous polymers during extrusion. Foams composed of neat PVDF and immiscible blends of PVDF with polystyrene exhibit poor cell characteristics, whereas miscible blends of PVDF with poly(methyl methacrylate) (PMMA) yield foams possessing vastly improved morphologies. The results reported herein illustrate the effects of blend composition and scCO₂ solubility on PVDF/PMMA melt viscosity, which decreases markedly with increasing PMMA content and scCO₂ concentration. Morphological characterization of microcellular PVDF/PMMA foams reveals that the cell density increases as the PMMA fraction is increased and the foaming temperature is decreased. This study confirms that novel MPFs derived continuously from semicrystalline polymers in the presence of scCO₂ can be achieved through judicious polymer blending.