Pre‐thermal treatment in binary solvent systems promoting β crystalline phase of electrospun poly(vinylidene fluoride) nanofibers

Poly(vinylidene fluoride) (PVDF) nanofibers were fabricated via electrospinning with an investigation of various ratios of binary solvents at different temperatures. The amount of acetone influenced the morphology. Scanning electron microscopy showed a PVDF membrane composed of smooth and unblemished fibers without beads and dark spots with small diameters of 201 ± 54 nm at a dimethylformamide‐to‐acetone ratio of 4:6. The temperature of pre‐thermal treatment from room temperature to 120 °C was investigated to promote the β crystalline phase in electrospun PVDF nanofibers. The result was characterized using Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD). PVDF solution prepared at 80 °C was used to increase the β crystalline phase of the electrospun PVDF nanofibers due to the transformation of α to β phase occurring during the spinning process and also bead‐free PVDF nanofibers were obtained. Differential scanning calorimetry revealed crystallization behavior corresponding with that determined using FTIR spectroscopy and XRD. Therefore, the solvent proportion and pretreatment temperature were observed to affect ultrafine nanofiber and crystalline structure of PVDF, respectively. © 2020 Society of Chemical Industry     

Crystal phase transition dependence of the energy storage performance of poly(vinylidene fluoride) and poly(vinylidene fluoride‐hexafluoropropene) copolymers

Large‐scale mechanical stretching has been performed to modify the crystal phase structures of the pristine poly(vinylidene fluoride) (PVDF) and its copolymer poly(vinylidene fluoride‐hexafluoropropylene) [P(VDF‐HFP)] with various molar contents HFP in an attempt to improve their energy storage performances. It is found that the physical stretched PVDF and P(VDF‐HFP) 95.5/4.5 mol % films have a phase transition from the nopolar α‐phase to highly polar β‐phase, which is different from the P(VDF‐HFP) films with relative high HFP molar contents (α to γ phases). The following results show that the phase transition in these PVDF‐based polymers has a significant effect on their dielectric and energy storage performances. On account of the reformation of the crystalline property and elimination of the impurity defects, an ultra‐high breakdown electric field of ∼900 MV/m has been obtained in all the stretched samples. Consequently, the higher discharged energy densities of 27.1 and 27.7 J/cm³ are calculated from the D–E loops of the β‐PVDF and β‐P(VDF‐HFP) 95.5/4.5 mol % films, respectively. Regarding their excellent discharging energy density of ∼10 J/cm³ under 600 MV/m for thousands of times, the stretched PVDF and its copolymer P(VDF‐HFP)s are promising candidates for high power capacitors applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46306.     

Influence of the coagulation‐bath temperature on the phase‐separation process of poly(vinylidene fluoride)‐graft‐poly(N‐isopropylacrylamide) solutions and membrane structures

A poly(vinylidene fluoride)‐graft‐poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) copolymer was synthesized, and flat‐sheet membranes were prepared via the phase‐inversion method with N,N‐dimethylformamide (DMF) as the solvent and water as the coagulation bath. The effects of the coagulation‐bath temperature on poly(vinylidene fluoride) (PVDF)/DMF/water and PVDF‐g‐PNIPAAm/DMF/water ternary systems were studied with phase diagrams. The results showed that the phase‐separation process could be due to the hydrophilicity/hydrophobicity of poly(N‐isopropylacrylamide) at low temperatures, and the phase‐separation process was attributed to crystallization at high temperatures. The structures and properties of the membranes prepared at different coagulation‐bath temperatures were researched with scanning electron microscopy, porosity measurements, and flux measurements of pure water. The PVDF‐g‐PNIPAAm membranes, prepared at different temperatures, formed fingerlike pores and showed higher water flux and porosity than PVDF membranes. In particular, a membrane prepared at 30°C had the largest fingerlike pores and greatest porosity. The water flux of a membrane prepared in a 25°C coagulation bath showed a sharp increase with the temperature increasing to about 30°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Modification of electrospun poly(vinylidene fluoride‐co‐hexafluoropropylene) membranes through the introduction of poly(ethylene glycol) dimethacrylate

For the modification of an electrospun poly (vinylidene fluoride‐co‐hexafluoropropylene) (PVDF–HFP) membrane for its potential use as an electrolyte or separator in lithium batteries, poly(ethylene glycol) dimethacrylate (PEGDMA) was introduced into a polymer solution for electrospinning. A post heat treatment of the as‐electrospun membrane at an elevated temperature was performed for PEGDMA polymerization, and this was verified by Fourier transform infrared spectroscopy. The results showed that no significant variations in the membrane morphology were detected when a small amount of PEGDMA (PVDF–HFP/PEGDMA mass ratio = 4/1) was incorporated. This electrospun membrane after heat treatment at 130°C for 2 h exhibited a significantly higher tensile strength (6.26 ± 0.22 MPa) than that of an electrospun PVDF–HFP membrane (3.28 ± 0.35 MPa) without PEGDMA. The porosity and liquid absorption of the electrospun PVDF–HFP/PEGDMA (4/1) membrane were 70.0 ± 1.6% and 267 ± 11%, respectively, lower than those of the electrospun PVDF–HFP membrane (76.5 ± 0.3% and 352 ± 15%) because of the introduction of PEGDMA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Influence of processing conditions on polymorphic behavior,crystallinity, and morphology of electrospun poly(VInylidene fluoride) nanofibers

The polymorphism and crystallinity of poly(vinylidene fluoride) (PVDF) membranes, made from electrospinning of the PVDF in pure N,N‐dimethylformamide (DMF) and DMF/acetone mixture solutions are studied. Influence of the processing and solution parameters such as flow rate, applied voltage, solvent system, and mixture ratio, on nanofiber morphology, total crystallinity, and crystal phase content of the nanofibers are investigated using scanning electron microscopy, wide‐angle X‐ray scattering, differential scanning calorimetric, and Fourier transform infrared spectroscopy. The results show that solutions of 20% w/w PVDF in two solvent systems of DMF and DMF/acetone (with volume ratios of 3/1 and 1/1) are electrospinnable; however, using DMF/acetone volume ratio of 1/3 led to blockage of the needle and spinning process was stopped. Very high fraction of β‐phase (～79%–85%) was obtained for investigated nanofiber, while degree of crystallinity increased to 59% which is quite high due to the strong influence of electrospinning on ordering the microstructure. Interestingly, ultrafine fibers with the diameter of 12 and 15 nm were obtained in this work. Uniform and bead free nanofiber was formed when a certain amount of acetone was added in to the electrospinning solution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42304.     

Effect of coagulation bath temperature on formation mechanism of poly(vinylidene fluoride) membrane

Effects of coagulation bath temperature on the membrane formation mechanism and the morphologies of the formed membranes were studied. The binodal and spinodal lines in the phase diagrams of water/DMAc/Poly(vinylidene fluoride) (PVDF) were calculated based on the thermodynamics equations of membrane formation, and the gel phase boundaries of the systems at 25°C and 60°C were determined via cloud point measurement. The obtained ternary phase diagrams of water/DMAc/PVDF contain three regions: the one‐phase region, the liquid–liquid two‐phase region, and the gel region. In the phase diagrams, the liquid–liquid demixing line (binodal) is located inside the gelation line. At low temperature, there exists a wide region between gelation line and binodal line. Gelation could occur in the absence of liquid–liquid demixing, and becomes the dominant membrane formation mechanism. At high temperatures (60°C), however, the gelation line approaches the binodal line, which results in a much smaller gelation zone. The kinetics of the solvent out‐flux and water influx were enhanced, liquid–liquid demixing is the dominant mechanism. The membrane formation mechanisms at different temperature were confirmed by the light transmission measurements during membrane forming process and the morphologies of the membranes examined by SEM imaging. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

Role of poly(lactic acid) in the phase transition of poly(vinylidene fluoride) under uniaxial stretching

The effect of poly (lactic acid) (PLA) on the crystalline phase transition of poly (vinylidene fluoride) (PVDF) from α‐ to β‐phase under uniaxial stretching for immiscible PVDF/ PLA blends was investigated. The typical sea‐island structure in the blends was found to facilitate the necking of PVDF and the transition from α‐ to β‐phase due to the local stress distribution during stretching. The crystalline phase transition of PVDF in the blends is temperature‐dependent and is affected by the content of PLA. The highest content of β‐phase, F(β), was achieved in the samples stretched at 60°C, while the effect of PLA content on the crystalline phase transition of PVDF is more complex. F(β) increases slightly when the sample with a PLA content no more than 15 wt % is stretched at 60, 80, and 100°C, and decreases sharply for the sample containing 20 wt % PLA; in addition, the sample containing 10 wt % PLA exhibits the highest F(β) no matter what the stretching temperature is. The mechanism of the crystalline phase transition of PVDF during the stretching is interpreted from energy barrier of the transition from α‐ to β‐phase and the morphological structures in the blends. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

A novel β‐nucleating agent for isotactic polypropylene

The nucleating ability of p‐cyclohexylamide carboxybenzene (β‐NA) towards isotactic polypropylene (iPP) was investigated by differential scanning calorimetry, X‐ray diffraction, polarized optical microscopy and scanning electron microscopy. β‐NA is identified to have dual nucleating ability for α‐iPP and β‐iPP under appropriate kinetic conditions. The formation of β‐iPP is dependent on the content of β‐NA. The content of β‐phase can reach as high as 96.96% with the addition of only 0.05 wt% β‐NA. Under non‐isothermal crystallization the content of β‐iPP increases with increasing cooling rate. The maximum β‐crystal content is obtained at a cooling rate of 40 °C min^–1. The supermolecular structure of the β‐iPP is identified as a leaf‐like transcrystalline structure with an ordered lamellae arrangement perpendicular to the special surface of β‐NA. Under isothermal crystallization β‐crystals can be formed in the temperature range 80–140 °C. The content of β‐crystals reaches its maximum value at a crystallization temperature of 130 °C. © 2012 Society of Chemical Industry     

Effect of hot‐press on electrospun poly(vinylidene fluoride) membranes

Poly(vinylidene fluoride) (PVDF) was electrospun into ultrafine fibrous membranes from its solutions in a mixture of N,N‐dimethylformamide and acetone (9:1, v/v). The electrospun membranes were subsequently treated by continuous hot‐press at elevated temperatures up to 155°C. Changes of morphology, crystallinity, porosity, liquid absorption, and mechanical properties of the membranes after hot‐press were investigated. Results of scanning electron microscopy showed that there were no significant changes in fibrous membrane morphology when the hot‐press temperature varied from room temperature to 130°C, but larger pores were formed because of fibers melting and bonding under higher temperatures. Analyses of X‐ray diffraction and differential scanning calorimeter exhibited that the crystalline form of PVDF could transfer from β‐type to α‐type during hot‐press at temperatures higher than 65°C. Tensile tests suggested that the mechanical properties of the electrospun PVDF membranes were remarkably enhanced from 25 to 130°C, whereas the porosity and the liquid absorption decreased. The hot‐press at 130°C was optimal for the electrospun PVDF membranes. The continuous hot‐press post‐treatment could be a feasible method to produce electrospun membranes, not limited to PVDF, with suitable mechanical properties as well as good porosity and liquid absorption for their applications in high‐quality filtrations or battery separators. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Improving the dielectric performance of poly(vinylidene fluoride)/polyaniline nanorod composites by stretch‐induced crystal transition

The introduction of conductive polyaniline (PANI) can significantly improve the dielectric constant of polymer‐based materials. However, there is a drawback of high dielectric loss. Herein, a simple and efficient stretching process was applied to improve the dielectric performance of poly(vinylidene fluoride)/PANI (PVDF/PANI) nanorod films through the stretch‐induced crystal transition from non‐polar α‐crystal to polar β‐crystal in PVDF and the oriented distribution of PANI nanorods. XRD, DSC and Fourier transform IR analyses indicate that the stretched PVDF and stretched PVDF/PANI films possess a high content of β‐crystal at the stretching temperature of 135 °C under a stretching ratio of 200%–400%. Furthermore, the stretched PVDF/PANI film with 10 wt% PANI displays a high dielectric constant of 338 at 100 Hz, which is increased by 20% compared to non‐stretched PVDF/PANI film (281). More importantly, the corresponding dielectric loss is reduced from 0.31 for the non‐stretched film to 0.17 for the stretched film. © 2018 Society of Chemical Industry     

Electrospun nanofiber‐coated separator membranes for lithium‐ion rechargeable batteries

Nanofiber‐coated composite membranes were prepared by electrospinning polyvinylidene fluoride‐co‐chlorotrifluoroethylene (PVDF‐co‐CTFE) and PVDF‐co‐CTFE/polyvinylidene fluoride‐co‐hexafluoropropylene (PVDF‐co‐HFP) onto six different Celgard® microporous battery separator membranes. Application of a PVDF‐based copolymer nanofiber coating onto the surface of the battery separator membrane provides a method for improving the electrolyte absorption of the separator and the separator‐electrode adhesion. Peel tests showed that both PVDF‐co‐CTFE and PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber coatings have comparable adhesion to the membrane substrates. Electrolyte uptake capacity was investigated by soaking the nanofiber‐coated membranes in a liquid electrolyte solution. PVDF‐co‐CTFE and PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber‐coated membranes exhibited higher electrolyte uptake capacities than uncoated membranes. It was also found that PVDF‐co‐CTFE nanofiber‐coated membranes have higher electrolyte uptakes than PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber‐coated membranes due to the smaller diameters of PVDF‐co‐CTFE nanofibers and higher polarity of PVDF‐co‐CTFE. The separator–electrode adhesion properties were also investigated. Results showed PVDF‐co‐CTFE and PVDF‐co‐CTFE/PVDF‐co‐HFP nanofiber coatings improved the adhesion of all six membrane substrates to the electrode. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Isothermal phase diagrams and phase‐inversion behavior of poly(vinylidene fluoride)/solvents/additives/water systems

Isothermal ternary phase diagrams of poly(vinylidene fluoride) (PVDF)/solvents/nonsolvent systems were produced using four different solvents, N,N‐dimethylacetamide (DMAc), 1‐methyl‐2‐pyrrolidinone (NMP), N,N‐dimethylformamide (DMF), and triethyl phosphate (TEP), and using water as a nonsolvent. The effects of the additives polyvinylpyrrolidone (PVP, M_w = 10,000), ethanol, and lithium perchlorate (LiClO₄) on the phase‐inversion behavior of PVDF/DMAc/water ternary system were investigated, with additive concentrations of 2 and 6 wt %, at temperatures of 25 and 70°C, respectively. Ethanol, glycerol, and water were used to study the cloud points of 10, 15, and 20 wt % PVDF/DMAc concentrations, at solution temperatures ranging from 30 to 70°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2150–2155, 2003     

The β‐δ‐Phase Transition and Thermal Expansion of Octahydro‐1,3,5,7‐Tetranitro‐1,3,5,7‐Tetrazocine

Phase behavior of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) is investigated by X‐ray powder diffraction (XRD). The XRD patterns at elevated temperature show that there is a co‐existing temperature range of β‐ and δ‐phase during the phase transition process. Additionally, mechanical forces can catalyze the conversion from δ‐ back to β‐phase. Based on the diffraction patterns of β‐ and δ‐phase at different temperatures, we calculate the coefficients of thermal expansion by Rietveld refinement. For β‐HMX, the linear coefficients of thermal expansion of a‐axis and b‐axis are about 1.37×10⁻⁵ and 1.25×10⁻⁴ °C⁻¹. A slight decrease in c‐axis with temperature is also observed, and the value is about −0.63×10⁻⁵ °C⁻¹. The volume coefficient of thermal expansion is about 1.60×10⁻⁴ °C⁻¹, with a 2.2% change from 30 to 170 °C. For δ‐HMX, the linear coefficients of thermal expansion of a‐axis and c‐axis are found to be 5.39×10⁻⁵ and 2.38×10⁻⁵ °C⁻¹, respectively. The volume coefficient of thermal expansion is about 1.33×10⁻⁴ °C⁻¹, with a 2.6% change from 30 to 230 °C. The results indicate that β‐HMX has a similar volume coefficient of thermal expansion compared with δ‐HMX, and there is about 10.5% expansion from β‐HMX at 30 °C to δ‐HMX at 230 °C, of which about 7% may be attributed to the reconstructive transition.     

Investigation of the physico‐mechanical properties of electrospun PVDF/cellulose (nano)fibers

The electro‐activity and mechanical properties of PVDF depends mainly on the β‐phase content and degree of crystallinity. In this study, cellulose fibers were used to improve these characteristics. This could be achieved because the hydroxyl groups on cellulose would force the fluorine atoms in PVDF to be in the trans‐conformation, and the cellulose particles could act as nucleation centers. Electrospinning was used to prepare the PVDF/cellulose (nano)fibrous films, and this improved the total crystallinity and the formation of β‐crystals. However, the presence and amount of cellulose in PVDF were found to have little influence on the β‐phase content and on the total crystallinity of PVDF. Improvements in the extent of crystallinity and the β‐phase content were primarily brought about by the chain‐ and crystal orientation as a result of electrospinning. The thermal stability of PVDF in the composites slightly increased with increasing cellulose content in the composites up to 1.0 wt %, while the modulus and tensile strength significantly increased up to the same filler level. The dielectric storage permittivity also increased with increasing cellulose content, but the presence of cellulose had no influence on the dynamics of the γ‐ and β‐relaxations of the PVDF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43594.     

Influence of hydroxyl‐terminated polybutadiene additives on the poly(ether sulfone) ultra‐filtration membranes

Hydroxyl‐terminated polybutadiene (HTPB) was blended into a poly(ether sulfone) (PES) casting solution used to prepare ultra‐filtration (UF) membranes via the phase inversion technique. The membranes were then characterized by contact angle (CA) measurements and UF experiments. The CA was increased with the addition of HTPB in the PES membrane and also by lowering the gelation bath temperature. It was observed that the CA was lower for membranes prepared with N‐methyl‐2‐pyrrolidinone (NMP) as the solvent than those using N,N‐dimethylacetamide (DMAc) as solvent. The flux values were higher for membranes made using a 4°C gelation bath when compared with the ambient temperature ((25 ± 1)°C) irrespective of the cast solvents, NMP or DMAc. The flux values were much higher and the solute separations were lower for the HTPB‐based PES membranes than for the pure PES membrane, when the membranes were cast with DMAc as a solvent. On the other hand, both flux and separation values were much lower for the HTPB‐based PES membranes than for the pure PES membrane, when the membranes were cast using NMP. Atomic force microscopy and scanning electron microscopy were used for morphological characterization and the correlation of topography/photography with the performance data was also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2292–2303, 2006     

Properties on novel PVDF‐HFP‐based composite polymer electrolyte with vinyltrimethoxylsilane‐modified ZSM‐5

A kind of novel poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP)‐based composite polymer electrolyte doped with vinyltrimethoxylsilane (DB171 silane)‐modified ZSM‐5 is prepared by phase inversion method (denoted as M‐ZSM‐5 membrane). Physical and chemical properties of M‐ZSM‐5 membrane are studied by SEM, FTIR, TG‐DSC, EIS, and LSV. The results show that thermal and electrochemical stability can reach 400°C and 5 V, respectively; temperature dependence of ionic conductivity follows Vogel–Tamman–Fulcher relation and ionic conductivity at room temperature is up to 4.2 mS/cm; the interfacial resistance reaches a stable value about 325 Ω after 5 days storage at room temperature, which suggests that it can be potentially suitable as electrolyte in polymer lithium ion battery. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Crystallization behavior of PVDF in PVDF‐DMP system via thermally induced phase separation

The crystallization behavior of PVDF (poly (vinylidene) fluoride) in PVDF‐dimethylphthalate(DMP) system was investigated in the liquid–liquid (L–L) phase separation region, solid–liquid (S–L) phase separation region and different quenching conditions via thermally induced phase separation (TIPS). Differential scanning calorimetry (DSC) indicated the crystallinity of PVDF in PVDF‐DMP system increased in the early stage of phase separation and polymer‐rich phase crystallized completely in the late stage of phase separation. The scanning electron microscopy (SEM) showed the different quenching temperatures had effects on the spherulite size of polymer rich phase and the ultimate membrane structure in the different phase separation regions. The wide angle X‐ray diffraction (WAXD) was used to quantify the crystal structure of PVDF in PVDF‐DMP system. The α‐phase PVDF was obtained when the system quenched to different temperatures above 40°C, and the area of diffraction peaks changed when quenching temperatures changed. While the β‐phase PVDF was formed when PVDF‐DMP system was quenched form liquid nitrogen and crystallized for 24 h in 25°C water bath. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3714–3719, 2006     

Mitigating thermal runaway of lithium‐ion battery by using thermally sensitive polymer blend as cathode binder

Thermally sensitive binder (TSB) is developed as an internal safety mechanism of lithium‐ion battery (LIB). The TSB is a polymer blend of poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP). Compared with regular PVDF binder, the softening and swelling of TSB are more pronounced when temperature is above 110 °C. With the TSB, the cycling performance of LIB cell is not affected; upon nail penetration, the heat generation rate is significantly reduced. The crystallinity of TSB is an important factor. This technology may lead to the development of thermal‐runaway‐mitigating LIB cells. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45737.     

Electrospun fiber membranes from blends of poly(vinylidene fluoride) with fouling‐resistant zwitterionic copolymers

Nonwoven super‐hydrophobic fiber membranes have potential applications in oil–water separation and membrane distillation, but fouling negatively impacts both applications. Membranes were prepared from blends comprising poly(vinylidene fluoride) (PVDF) and random zwitterionic copolymers of poly(methyl methacrylate) (PMMA) with sulfobetaine methacrylate (SBMA) or with sulfobetaine‐2‐vinylpyridine (SB2VP). PVDF imparts mechanical strength to the membrane, while the copolymers enhance fouling resistance. Blend composition was varied by controlling the PVDF‐to‐copolymer ratio. Nonwoven fiber membranes were obtained by electrospinning solutions of PVDF and the copolymers in a mixed solvent of N,N‐dimethylacetamide and acetone. The PVDF crystal phases and crystallinities of the blends were studied using wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). PVDF crystallized preferentially into its polar β‐phase, though its degree of crystallinity was reduced with increased addition of the random copolymers. Thermogravimetry (TG) showed that the degradation temperatures varied systematically with blend composition. PVDF blends with either copolymer showed significant increase of fouling resistance. Membranes prepared from blends containing 10% P(MMA‐ran‐SB2VP) had the highest fouling resistance, with a fivefold decrease in protein adsorption on the surface, compared to homopolymer PVDF. They also exhibited higher pure water flux, and better oil removal in oil–water separation experiments. © 2018 Society of Chemical Industry     

Viscoelastic and pressure–volume–temperature properties of poly(vinylidene fluoride) and poly(vinylidene fluoride)–hexafluoropropylene copolymers

The relationship between the pressure, volume, and temperature (PVT) of poly(vinylidene fluoride) homopolymers (PVDF) and poly(vinylidene fluoride)–hexafluoropropylene (PVDF–HFP) copolymers was determined in the pressure range of 200–1200 bar and in the temperature range of 40°C–230°C. The specific volume was measured for two homopolymers having a molecular weight (M_w) of 160,000–400,000 Da and three copolymers containing between 3 and 11 wt % HFP with a molecular weight range of 320,000–480,000 Da. Differential scanning calorimetry (DSC) was used to simulate the cooling process of the PVT experiments and to determine the crystallization temperature at atmospheric pressure. The obtained results were compared to the transitions observed during the PVT measurements, which were found to be pressure dependent. The results showed that the specific volume of PVDF varies between 0.57 and 0.69 cm³/g at atmospheric pressure, while at high pressure (1200 bar) it varies between 0.55 and 0.64 cm³/g. For the copolymers, the addition of HFP lowered its melting point, while the specific volume did not show a significant change. The TAIT state equation describing the dependence of specific volume on the zero‐pressure volume (V₀,T), pressure, and temperature has been used to predict the specific volume of PVDF and PVDF–HFP copolymers. The experimental data was fitted with the state equation by varying the parameters in the equation. The use of the universal constant, C (0.0894), and as a variable did not affect the predictions significantly. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 230–241, 2001