Thermomechanical and optical characteristics of stretched polyvinylidene fluoride

The thermomechanical and optical characteristics of polyvinylidene fluoride (PVDF) are investigated using a thermomechanical, a nanoindentation, anda photometric analyzer for flexible electronic applications. Experimental results show that thermomechanical characteristics, thermal elongation, and expansion, are greatly influenced at stretching ratios of over four in the stretching direction. Consequently, shrinking occurs because of higher cohesion at the tie chains of the amorphous regions. Additionally, there are almost uniform hardness and Young's modulus of about 0.25 ± 0.01 and 3.44 ± 0.14 GPa when the penetration depth is about 1000 nm. Unstretched PVDF films have a higher absorbance in the ultraviolet light range than stretched films do. PVDF films stretched over three times their original length have transmittance of above 90% at near infrared light. In addition, PVDF films stretched at lower temperatures show a lower transmittance because the films easily whitened during α to β phase transformations. The results provide information to optimize PVDF films for applications in flexible designs. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 949–958, 2008     

Phase transformation to β-poly(vinylidene fluoride) by milling

Cryogenic mechanical milling successfully converted α-phase poly(vinylidene fluoride) (PVDF) powder into β-phase PVDF, as measured by wide-angle X-ray diffraction. The presence of β-phase PVDF became more pronounced with increased milling times over the limited time range evaluated. This was the first recorded instance of β-phase powders forming from the α phase through milling. These β-phase powders maintained their crystal structure during compression molding at 70 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 91–97, 2004     

Change in free volume of polyvinylidene fluoride

Measurement of positron lifetime was carried out on polyvinylidene fluoride as a function of temperature ranging from 193 to 293 K. The local molecular motion, the cooperative motion of long chain, and the thermal expansion are discussed based on the change in free volume concluded with the use of positron lifetime. The different temperature dependence of motions is suggested for an amorphous area constrained by crystalline regions and a free amorphous area.     

Elasto-viscoplastic behaviour of a polyvinylidene fluoride (PVDF) in tension

The present paper is concerned with the plasticity of a polyvinylidene fluoride (PVDF) in tension. Strain rate strongly influences the plastic behaviour, but the variation of the elastic properties is almost negligible within the range of strain rates considered in the study (from 1.6 × 10⁻⁴ s⁻¹ up to 1.6 × 10⁻¹ s⁻¹). In particular, the yield stress and the ultimate tensile strength are strongly rate-dependent. A one-dimensional elasto-viscoplastic phenomenological model is proposed and analysed. Despite the nonlinearity of the model equations, only one tensile test performed with variable strain rate is sufficient to identify all material parameters. Model predictions are compared with experiments showing good agreement.     

Deformation and failure kinetics of polyvinylidene fluoride: Influence of crystallinity

The present study investigates the effect of processing conditions on the yield kinetics, such as rate dependence of the yield stress and creep rupture, of polyvinilidene fluoride. Samples were compression molded with cooling rates varying from 100°C/s to 0.5°C/min, or isothermally crystallized at temperatures varying from 20 to 120°C. Deformation kinetics were studied over a wide range of strain rates and temperatures. It is shown that for all conditions the yield response is well represented by the Ree–Eyring model. Moreover, the activation volumes and activation energies are independent from the processing conditions. The effect of processing is fully covered by a simple relationship between the rate factors and the degree of crystallinity. Subsequently, the versatility of this relationship is demonstrated by experimental validation.     

Metal Salt‐Induced Ferroelectric Crystalline Phase in Poly(vinylidene fluoride) Films

In this Communication, the effect of varying mass fractions (0–20 wt.‐%) of calcium chloride (CaCl₂) salt on the α‐ and β‐phase content of poly(vinylidene fluoride) (PVDF) as‐cast films were investigated. Spectral and X‐ray studies revealed the maximum ferroelectric β‐phase for the addition of 15 wt.‐% of CaCl₂ in PVDF compared to neat PVDF samples. The dense β‐phase dominant PVDF–CaCl₂ (15 wt.‐%) thick film used as a ferroelectric insulator in one‐capacitor (1C) type random access memory device exhibited a remnant polarization of 3.1 µC · cm², and is a good indication that the unoriented PVDF–CaCl₂ films can be used in electronic applications without further stretching process.

     

聚偏氟乙烯膜蒸馏技术在水处理中的应用研究进展

膜蒸馏是一种以膜为介质,利用传统蒸发工艺开发的新型膜分离技术。随着高分子材料行业的进步和制膜工艺的成熟,膜蒸馏技术取得了巨大的进展,在水处理领域拥有十分广阔的市场前景。膜蒸馏技术的核心是膜的通量和使用寿命,而性能优良的膜材料是膜蒸馏技术发展的关键。聚偏氟乙烯(PVDF)因具有成膜性能好、表面张力大、化学稳定性强等优点,在膜蒸馏技术应用研究中备受青睐。同时PVDF与其他聚合物具有良好的相容性,为膜的改性研究奠定了基础,极大地扩展了应用范围。本文介绍了膜蒸馏技术的工作原理及工艺特点以及PVDF膜材料的特点及改性方法,重点对PVDF膜蒸馏技术在水处理领域的应用进行了梳理和总结,讨论了该技术亟待研究和解决的问题,以期为该工艺技术的进一步发展提供科学支撑和理论依据。     

Grafting of hydroxymethylacrylamide and acrylic acid copolymer onto polyvinylidene fluoride membrane by supercritical carbon dioxide and its application in dye separation

We report a thermally induced graft copolymerization of acrylic acid and N‐hydroxymethylacrylamide onto polyvinylidene fluoride microporous membrane by using supercritical carbon dioxide as a solvent and carrier agent. The effects of monomer mole ratio, pressure, reaction temperature, time, and initiator concentration on the degree of grafting were investigated. The morphology of the grafted membrane was studied via scanning electron microscopy. Attenuated total reflectance infrared spectroscopy spectroscopy and X‐ray diffraction proved the existence of grafting monomers. The results of contact angle measurement and water filtration at different pH levels indicated pronounced pH‐sensitive behavior and increased hydrophilicity of the polyvinylidene fluoride grafted membrane. In particular, the grafted membrane was applied to the removal of methylene blue with a relative rejection of 98.1% compared with 30.5% of rejection observed from the pristine polyvinylidene fluoride membrane. Copyright © 2014 John Wiley & Sons, Ltd.     

Alteration of the morphology of polyvinylidene fluoride membrane by incorporating MOF-199 nanomaterials for improving water permeation with antifouling and antibacterial property

MOF-199@PVDF composite membranes are prepared by blending with different amounts of ultrasonic synthesized MOF-199 nanomaterials for improving the pure water flux (PWF) and achieving better antifouling and antibacterial performance. The membrane morphology, elemental composition, and surface properties are analyzed by various means of characterizations, including scanning electron microscopy, energy-dispersive X-ray spectroscopy, and water contact angle measurements. The performance of the modified membranes is also determined from the perspective of the PWF, bovine serum albumin rejection, as well as antifouling and antibacterial properties. Due to the variation in the viscosity of dope solution, the composite membranes possess remarkably different morphology, and the M5 membrane, which exhibited a sponge-like structure, the largest surface pore size, and the highest porosity, shows the highest PWF, reaching up to 185.05 L/m²h. Moreover, with the incorporation of MOF-199 nanocrystals, the antifouling property, together with the antibacterial property, toward both gram-negative bacteria and gram-positive bacteria, based on M5 and M7 membranes, increases dramatically compared with the pristine polyvinylidene fluoride membrane. In addition, the long-term permeation performance and copper leakage of the membrane are investigated. As a result, the composite membrane, M5, shows great potential in real water treatment.     

Investigation of the dielectric,mechanical, and thermal properties of noncovalent functionalized MWCNTs/polyvinylidene fluoride (PVDF) composites

To improve the dispersion of multi‐walled walled carbon nanotubes (MWCNTs) and investigate the effect of dispersant for MWCNTs functionalization on the dielectric, mechanical, and thermal properties of Polyvinylidene fluoride (PVDF) composites, two different dispersants (Chitosan and TritonX‐100) with different dispersion capability and dielectric properties were used to noncovalently functionalize MWCNTs and prepare PVDF composites via solution blending. Fourier transform infrared, X‐Ray diffraction, and Raman spectroscopy indicated that TritonX‐100 and Chitosan were noncovalent functionalized successfully on the surface of MWCNTs. With the functionalization of Chitosan and TritonX‐100, the dispersion of MWCNTs changed in different extent, which was investigated by dynamic light scattering and confocal laser scan microscopy. The dielectric, mechanical, and thermal properties of PVDF composites were also improved. Meanwhile, it was also found that the dielectric properties of PVDF composites are closely related to the dielectric properties of dispersant. High dielectric constant of dispersant contributes to the grant dielectric constant of PVDF composites. The mechanical and thermal properties of MWCNTs/PVDF composites largely depend on the dispersion of MWCNTs in PVDF, interfacial interactions and the residual solvent. Copyright © 2016 John Wiley & Sons, Ltd.     

The quartz-cristobalite transformation in heated chert rock composed of micro and crypto-quartz by Micro-Raman and FT-IR spectroscopy methods

The quartz-cristobalite transformation in heated natural chert (flint) rock composed of micro- and ?ypto-quartz was investigated in the temperature interval of 1000–1300°C by micro-Raman spectroscopy, FT-IR spectroscopy, X-ray diffraction and Scanning Electron Microscopy. A small amount of crystobalite was first observed in the chert after heating at 1000°C for 1 h and the transformation was almost completed after heating at 1300°C for 24 h. On the other hand, cristobalite was not detected in well-crystallized pure quartz after heating under the same conditions. The transformation occurs as a solid state nucleation and crystal growth of cristobalite replacing quartz at high-temperatures. The chert rock is naturally rich in crystal defects and boundaries which serve as nucleation sites and enable an earlier quartz-cristobalite transformation.     

Crystallization‐Induced Phase Segregation Based on Double‐Crystalline Blends of Poly(3‐hexylthiophene) and Poly(ethylene glycol)s

Crystallization‐induced vertical stratified structures were constructed based on double‐crystalline poly(3‐hexylthiophene) (P3HT)/poly(ethylene glycol)s (PEG) systems at room temperature, in which the P3HT crystallinity and the mechanism were investigated. Vertical stratified microstructures with highly crystalline P3HT network on the surface were formed when depositing from marginal solvents, while lateral phase‐separated structures or low P3HT crystallinity were observed for good solvents. The morphological differences came from the solvent effect. In marginal solvents, p‐xylene and dichloromethane, P3HT large‐scale microcrystallites were generated in solution, which ensured the priority of P3HT crystalline sequence, and phase separation began in the liquid states. When the PEG matrix began to crystallize, great energy from which the second phase separation was induced drove P3HT crystallites to the surface, resulting in the formation of vertical stratified microstructures with highly crystalline P3HT network on the surface. The method, crystallization‐induced phase segregation of crystalline–crystalline blends in marginal solvent, provides a facile way to construct vertically stratified structures, in which P3HT highly crystalline network is favored.

     

Morphology and crystallization behavior of poly(vinylidene fluoride)/poly(methyl methacrylate)/methyl salicylate,and benzophenone systems via thermally induced phase separation

Poly(vinylidene fluoride) (PVDF) blend microporous membranes were prepared by PVDF/poly(methyl methacrylate) blend (with mass ratio = 70/30) via thermally induced phase separation. Benzophenone (BP) and methyl salicylate (MS) were used as diluents. The phase diagram calculations were carried out in terms of a pseudobinary system, considering the PVDF blend to be one component. The crytallization behaviors of PVDF in the dilutions were detected by differential scanning calorimetry measurement. In these two systems, the melting and crystallization temperatures leveled off in the low polymer concentration (<40 wt %), but shifted to a higher temperature when the polymer concentration >40 wt %. The calculated crystallinity of PVDF for samples with low polymer concentrations was greater than those with high polymer concentrations, because of the limited mobility of polymer chains at a high polymer concentration. The membrane structure as determined by scanning electron microscopy depended on the phase separation mechanism. The quenched samples mainly illustrated the occurrence of crystallization on the same time scale as the liquid–liquid phase separated, resulting in the obvious spherulitic structure with small pores in the spherulites. As the polymer concentration increased, the size of the spherulites and pores within the spherulite was decreased. The evaluated porosity for BP diluted system was higher than that for MS diluted system, and decreased with the increased polymer concentration. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 248–260, 2009     

Improving waterproof/breathable performance of electrospun poly(vinylidene fluoride) fibrous membranes by thermo‐pressing

Facing the ever‐increasing demand for waterproof/breathable materials, a rapid and efficient fabrication method of these functional materials with excellent performance as well as robust mechanical properties remains challenging. Herein, a simple and scalable strategy referred to as thermo‐pressing is introduced to improve the waterproof/breathable performance and mechanical properties of electrospun PVDF fibrous membranes. The synergistic effect of temperature and pressure acted on the electrospun PVDF membranes on the fiber morphology and crystal structure was investigated, which can be able to effectively enhance waterproof performance and mechanical properties, endowing the as‐prepared membranes with a modest breathability. The membranes thermo‐pressed at 150 °C with a pressure of 8.27 MPa exhibit robust tensile strength of 40.65 MPa, which is superior to those of the previous reports (below 32.8 MPa). Notably, the optimized membranes enable to show a high hydrostatic pressure of 102 kPa, good WVTR of 10.87 kg m⁻² d⁻¹ and excellent abrasion resistance, which implies that the thermo‐pressing is an efficient and facile way to steer the fiber morphology and crystal structure of electrospun membranes to improve their application performance. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 36–45     

Experimental characterization of the volume strain of poly(vinylidene fluoride) in the region of homogeneous plastic deformation

Damage to poly(vinylidene fluoride) was studied under uniaxial tension testing at different temperatures and strain rates. A satisfactory accuracy was reached with an original procedure for the assessment of the principal strains and volume strain. The semicrystalline polymer exhibited an increase in the volume strain with the true axial strain caused by material damage. This damage depended on the temperature and strain rate and was related to the whitening phenomenon generally observed. The use of the general ideas of Bucknall's model, based on the decomposition of the whole volume strain into three components, allowed the extraction of the component of the volume strain corresponding to microstructural mechanisms of plastic deformation other than shearing. Therefore, nucleation and growth stages of cavitation were revealed. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2516–2522, 2002     

Morphologies and crystalline forms of polyvinylidene fluoride membranes prepared in different diluents by thermally induced phase separation

We have studied the morphologies and crystalline forms of polyvinylidene fluoride (PVDF) membranes separately prepared in four different diluents bearing >C?O groups, namely 1,2‐propylene glycol carbonate (PGC), dimethyl phthalate (DMP), diphenyl ketone (DPK), and dibutyl phthalate (DBP), by the thermally induced phase separation (TIPS) method. The permittivities of the diluents and PVDF were measured to compare the different PVDF–diluent systems. The results showed the permittivity of PGC to be much greater than that of PVDF, and those of DMP and DBP to be lower than that of PVDF. The permittivity difference between DPK and PVDF was not apparent above 120 °C. On cooling mixtures with a PVDF concentration of 10 wt %, PVDF crystallization was observed in the PVDF–DMP, PVDF–DBP, and PVDF–PGC systems, while liquid–liquid phase separation occurred in the PVDF–DPK system. A cross‐section of the PVDF–PGC membrane presented smooth PVDF particles in the β‐phase crystalline form. Those of the PVDF–DMP and PVDF–DBP membranes presented PVDF particles consisting of a fibrillar network in the α‐phase. The PVDF–DPK membrane preferentially adopted an α‐phase bicontinuous channel structure. When the concentration of PVDF was 60 wt %, the cross‐sections of the above four membranes revealed PVDF polyhedra, among which the PVDF–DMP, PVDF–DBP, and PVDF–DPK membranes retained the α‐phase crystalline form, and the diffraction peak of the α‐phase became visible in the X‐ray diffraction (XRD) spectrum of the PVDF–PGC membrane. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

The Phase Control of Transition Metallic Elements via Facile Chemical and Physical Syntheses

The crystal phases of metals are important factors to tune the properties of metals, and therefore received extensive attention. Traditionally, phase control is performed within limited numbers of elements by harsh conditions, such as face-centered cubic Fe by high temperature. This review summarizes most reports in metal phase control area, including elements of Fe, Co, Ni, Cu, Ru, Pd, Rh, Os and Au. For every metallic element, the facile phase control methods are systematically introduced, such as epitaxial growth, ball milling, chemical reduction, etc. Their corresponding applications and the mechanisms for phase control are thoroughly discussed.     

Positron annihilation lifetime spectroscopy study of polyvinylpyrrolidone-added polyvinylidene fluoride membranes: Investigation of free volume and permeation relationships

Polyvinylidene fluoride (PVDF) membranes were prepared via the phase inversion method from casting solutions containing PVDF, dimethylformamide (DMF), and polyvinylpyrrolidone (PVP) as pore former. PVP was used in the casting solution in a range of 0–5 wt % and extracted. The effect on membranes of using PVP in the casting process was analyzed by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, viscosity, and water permeability techniques. With an increase of PVP from 0 to 5 wt %, the PVDF casting solution viscosities increased from 858 to 1148 cP; the resulting PVDF membrane thickness increased; and the crystallinity of PVDF membranes decreased from 40.0 to 33.3%, which indicates that the addition of PVP inhibits the degree of crystallization in the PVDF membranes. SEM results revealed the shape and size of macropores in the membranes; these macropores changed after PVP addition to the casting solutions. The impact of structural changes on free-volume properties was evaluated using positron annihilation lifetime spectroscopy (PALS) studies. PALS analysis indicated no effect on the average radius (~3.4 Å) of membrane free-volume holes from the addition of PVP to the casting solution. However, the percentage of o-Ps pick-off annihilation intensity, I₃, increased from 1.7 to 5.1% with increased PVP content. Further, increasing the PVP content from 0.5 to 5% resulted in an increased final pure water permeability flux. For instance, the 210 min flux for a 14% PVDF + 0.5% PVP membrane was found to be 3.3 times greater than a control membrane having the same PVDF concentration. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 589–598     

Preferential formation of electroactive crystalline phases in poly(vinylidene fluoride)/organically modified silicate nanocomposites

The role of organically modified silicate (OMS), Lucentite STN on the formation of β‐crystalline phase of poly(vinylidene fluoride) (PVDF) is investigated in the present study. The OMS was solution blended with PVDF and cast on glass slide to form PVDF‐OMS nanocomposites. Solution cast samples were subjected to various thermal treatments including annealing (AC‐AN), melt‐quenching followed by annealing (MQ‐AN), and melt‐slow cooling (MSC). Fourier‐transform infrared spectroscopy (FT‐IR), wide angle X‐ray diffraction (WAXD), and differential scanning calorimetry (DSC) were used to investigate the crystalline structure of thermally treated samples. As a special effort, the combination of in situ thermal FT‐IR, WAXD, and DSC studies was utilized to clearly assess the thermal properties. FT‐IR and WAXD results of MQ‐AN samples revealed the presence of β‐phase of PVDF. Ion‐dipole interaction between the exfoliated clay nanolayers and PVDF was considered as a main factor for the formation of β‐phase. Melt‐crystallization temperature and subsequent melting point were enhanced by the addition of OMS. Solid β‐ to γ‐crystal phase transition was observed from in situ FT‐IR and WAXD curves when the representative MQ‐AN sample was subjected to thermal scanning. Upon heating, β‐phase was found to disappear through transformation to the thermodynamically stable γ‐phase rather than melting directly. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2173–2187, 2008     

Conformational changes and phase transformation mechanisms in PVDF solution‐cast films

The supramolecular crystal structure in poly(vinylidene fluoride) (PVDF) solution‐cast films is studied through changing crystallization conditions in two solvents of different structures and polarities. The crystalline‐state chain conformations of isothermally solution‐crystallized PVDF in N, N‐dimethylacetamide (DMAc), and cyclohexanone are studied through the specific FTIR absorption bands of α, β, and γ phase crystals. There are no changes in the FTIR spectra of cyclohexanone solution‐crystallized films in the temperature range of 50–120 °C. In the case of DMAc solution‐crystallized films, low temperature crystallization mainly results in formation of trans states (β and γ phases), whereas at higher temperatures gauche states become more populated (α phase). This is due to the variations in solvent polarity and ability to induce a specific conformation in PVDF chains, through the changes in chain coil dimensions. This indicates that in spite of cyclohexanone solutions, the intermolecular interactions between PVDF and DMAc are temperature‐sensitive and more important in stabilizing conformations of PVDF in crystalline phase than temperature dependence of PVDF chain end‐to‐end distance <r²>. The high‐resolution ¹⁹F NMR spectroscopy also showed little displacement in PVDF characteristic chemical shifts probably due to changes in PVDF chain conformation resulting from temperature variations. Upon uniaxial stretching of the prepared films under certain conditions, contribution of trans state becomes more prominent, especially for the originally higher α phase‐containing films. Due to formation of some kink bands during film stretching and phase transformation, α phase absorption bands are still present in infrared spectra. Besides, uniaxial stretching greatly enhances piezoelectric properties of the films, maybe due to formation of oriented β phase crystals, which are of more uniform distribution of dipole moments. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3487–3495, 2004