Dielectric relaxation in vinylidene fluoride–hexafluoropropylene copolymers

The molecular mobility in copolymers of vinylidene fluoride–hexafluoropropylene VDF/HFP of 93/7 and 86/14 ratios has been investigated by means of broadband dielectric relaxation spectroscopy (10^?1–10⁷ Hz), differential scanning calorimetry DSC (?100 to 150°C), and of wide angle X‐ray diffraction WAXS. Four relaxation processes and one ferroelectric‐paraelectric phase transition have been detected. The process of the local mobility β‐ (at temperatures below glass transition point) is not affected by chemical composition of the copolymer and the formed structure. Parameters of segmental mobility in the region of glass transition (α_a‐relaxation) depend on the ratio of comonomer with lower kinetic flexibility. α_c‐relaxation is clearly observed only in VDF/HFP 93/7 copolymer, which is characterized by a higher crystallinity and a higher perfection of crystals of α‐ (α_p‐) phase. Diffuse order–disorder relaxor type ferroelectric transition connected with the destruction of the domains in low‐perfect ferroelectric phase in the amorphous regions has been detected for both copolymers. An intensive relaxation process (α‐process) was observed for both copolymers in high‐temperature region. DSC data shows that it falls on the broad temperature region of α‐phase crystals melting. It is considered to be connected with the space charge relaxation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Influence of third monomer on the crystal phase transition behavior of ethylene-tetrafluoroethylene copolymer

Crystal phase transition between the low- and high-temperature phases has been investigated for ethylene (E)-tetrafluoroethylene (TFE) alternating copolymer (ETFE) containing the third monomeric species by the temperature dependent measurements of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) and differential scanning calorimetry. Nonafluoro-1-hexene (NFH) and hexafluoropropylene (HFP) were chosen as the third monomers, where they are different in the side-branch length, -(CF₂)₃CF₃ and -CF₃, respectively. In the case of E/TFE/NFH copolymer (ET-C4F9), the crystal phase transition temperature of the original ETFE two-components copolymer was not very much affected by the existence of NFH in the range of NFH content from 0.7 to 3 mol%. Contrarily, the crystal phase transition temperature of E/TFE/HFP copolymer (ET-CF3) was found to decrease drastically with increasing HFP content. The melting temperature and the higher-order structure were also affected sensitively depending on the HFP content. This difference in phase transition behavior between ET-C4F9 and ET-CF3 copolymers is reasonably interpreted as follows: the short side groups (-CF₃) of HFP monomeric unit are included in the crystal lattice of E/TFE chains and the unit cell is expanded gradually with an increment of the HFP content, resulting in the decrease in phase transition point because of easier thermal motion of the chains. On the other hand, the long side groups [-(CF₂)₃CF₃] of NFH monomeric units are excluded out of the crystal lattice and located on the lamellar surfaces or in the amorphous region and do not affect very much the phase transition temperature even when the NFH content is increased. In association with such a change in crystal structure, the long period of stacked lamellar structure was found to decrease remarkably in the case of NFH, whereas it does not change very much for HFP, consistent with the interpretation of the above-mentioned WAXD data.     

An evaluation of Ce-Pr oxides and Ce-Pr-Nb oxides mixed conductors for cathodes of solid oxide fuel cells: Structure, thermal expansion and electrical conductivity

Ceria doped with praseodymia and niobia has been studied in order to evaluate the possibility of applying these materials as cathodes for solid oxide fuel cells. The content of crystallographic phases and their lattice parameters have been determined by X-ray diffraction, the thermal expansion coefficient has been characterised by the dilatometry technique and the electrical conductivity has been measured by complex impedance spectroscopy and by the four probe DC technique. The results have shown the presence of one fluorite phase in binary compositions (CeO₂-PrO_2−x) for PrO_2−x concentrations up to about 20 mol% and two fluorite phases with different lattice parameters for higher PrO_2−x concentrations. The addition of 3 mol% NbO_2·5 has allowed the stabilisation of a single fluorite phase up to 50 mol% PrO_2−x. The thermal expansion coefficient varies between 0 and 30 × 10⁻⁶/K depending on composition and temperature. The electrical conductivity is mainly electronic and thermally activated. The conductivity exceeds 0·1 S/cm at 800°C for compositions with 40 to 50 mol% PrO_2−x.     

Organo-soluble, segmented rigid-rod polyimide films: 2. Properties for microelectronic applications

The essential properties of polyimide films of importance in microelectronic applications are thermal and thermo-oxidative stability, dimensional stability, glass transition behaviour and the relative permittivity (dielectric constant ′). A segmented rigid-rod polyimide was synthesized from 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB) in order to develop new materials for microelectronic applications. The thermal and thermo-oxidative stability were investigated by determining the thermal degradation activation energy in air (210 kJ mol⁻¹) and in nitrogen (303 kJ mol⁻¹). The thermal stability was further studied through thermogravimetry-mass spectroscopy. The coefficient of thermal expansion, which indicates the dimensional stability, was measured via a tension mode of a thermomechanical analyser and doubly extrapolated to zero stresses, and was 6.98 × 10⁻⁶°C⁻¹ for the BPDA-PFMB films. The glass transition temperature, measured thermomechanically, was found to be 287°C. The dielectric constant for the films, measured after ageing at 50% relative humidity for 48 h at 23°C, was between 2.8 and 2.9 in a frequency range from 0.1 kHz to 1 MHz. The temperature and frequency dependence of the dielectric behaviour is also discussed.     

Ion-exchange copolymers based on tetrafluoroethylene,hexafluoropropylene, and acrylic acid

Peroxide-induced copolymerization of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP) and acrylic acid (AA) at different molar ratios of monomers, reaction time, pressure, and initiator concentration was studied. By means of IR spectroscopy and temperature and phase characteristics of the copolymers obtained it was proved that a ternary copolymer of TFE, HFP, and AA was synthesized. Fluoro-containing polymers with ion-exchange capacities up to 0.8 meq/g were obtained. The composition of binary TFE-HFP and ternary TFE-HFP-AA copolymers and some of their characteristics were determined. Copolymerization takes place mainly in the stationary state with an induction period. Polymerization rate R ～ [In]^0.7, which is presumably connected with chain transfer reaction to AA.     

Effect of glass additions on the sintering and microwave properties of composite dielectric ceramics based on BaO–Ln2O3–TiO2 (Ln = Nd, La)

Ten weight percent BBZS (Bi₂O₃, B₂O₃, ZnO and SiO₂) glass was added to x(Ba₄Nd_9.333Ti₁₈O₅₄) − (1 − x)(BaLa₄Ti₄O₁₅) (BNLT, 0 ≤ x ≤ 1) composite dielectric ceramics to lower their sintering temperature whilst retaining microwave properties useful for low temperature co-fired ceramic and antenna core technology. With the addition of 10 wt% BBZS glass, dense BNLT composite ceramics were produced at temperatures between 950 and 1140 °C, depending on composition (x), an average reduction of sintering temperature by 350 °C. X-ray diffraction, scanning and transmission electron microscopy and Raman spectroscopy studies revealed that there was limited inter-reaction between BLT/BNT and the BBZS glass. Microwave property measurement showed that the addition of BBZS glass to BNLT ceramics had a negligible effect on _r and τ_f, although deterioration in the measured quality factor (Qf) was observed. The optimised composition (xBNT − (1 − x)BLT)/0.1BBZS (x = 0.75) had _r  61, τ_f  38 ppm/°C and Qf  2305 GHz.     

Mikrokalorimetrische studie über die eisbildung in chloridhaltigem zementstein

Differential scanning calorimetry (DSC) of wet porous materials in the temperature range between + 20°C and − 60°C is a sensitive tool to investigate phase transitions and supercooling of pore water. Storage of hydrated cement paste (hcp) in water containing 5 % chloride at an age of 8 months after freeze drying leads to an increase of the enthalpy change between − 10°C and − 25°C (phase transition of free water in capillary pores with r_H > 10 nm) and to a strong reduction of the enthalpy change between − 43°C and − 52°C (3 nm < r_H < 10 nm) in comparison to hcp without addition of chloride.     

Effect of hydrostatic pressure and temperature on the mechanical loss properties of polymers: 3. PET, PVAC and vinyl chloride/vinyl acetate copolymers

A torsion pendulum (1 Hz) has been used to determine the pressure dependence of the glass transition temperatures of poly(ethylene terephthalate) (PET), poly(vinyl acetate) (PVAC) and some vinyl chloride/vinyl acetate copolymers. Their glass transition temperatures are shifted upwards by amounts varying between 11 and 18°C/1000 atmospheres. In the case of PVAC it has proved possible to compare the results with theory and the observed shift is found to be much less than the predicted value. A study of poly(methyl methacrylate) (PMMA) shows the β relaxation to be displaced to a higher temperature at the rate of 4°C/1000 atm. Results are also presented for the temperature dependence of shear modulus, G′, and loss tangent, tan δ for a reinforced crosslinked polymer, Bakelite P17404, at different pressures.     

Esterification of ethylene-vinyl alcohol copolymers in homogeneous phase using N,N′-dimethylpropyleneurea as solvent

Ethylene-vinyl alcohol copolymers (EVAL) were esterified with 3,5-dinitrobenzoyl chloride using the cycled urea N,N′-dimethylpropyleneurea (1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone) (DMPU) as the solvent. Ethylene-vinyl alcohol-vinyl-3,5-dinitrobenzoate terpolymers (EVALVDNB) and ethylene-vinyl-3,5-dinitrobenzoate copolymers (EVDNB) were obtained. Both EVAL copolymers (6-73 mol% VAL) and esterified polymers, EVDNB, and EVALVDNB dissolve in DMPU. The substitution may become total under the experimental conditions. The degree of transformation was determined by ¹H NMR. EVDNB copolymers were characterised by IR spectroscopy and ¹H and ¹³C NMR. Thermal properties were studied by DSC. The glass transition temperature of the EVDNB copolymers having a low VDNB content (up to 14 mol%) is roughly constant, whereas above 50 mol% increases. Melting temperature decreases as the VDNB content is increased, owing to the fact that the VDNB groups are excluded from the polyethylene crystal lattice.     

The formation, structure and properties of urethane-diacetylene copolymers as optical strain-sensitive surface coatings

Segmented copolyurethanes comprising ductile polyether-urethane (PE-U) and rigid diacetylene-urethane (DA-U) phases, have been prepared via a one-shot, bulk polymerisation process. Subsequent thermal treatment (100 °C/40 h) of the as-prepared linear copolymers effected solid-state topochemical reactions within the DA-U phase, producing crosslinked and intensely coloured materials. The cross-polymerised copolymers had values of T_g between −32°C and 70°C depending on composition, and were elastically isotropic with tensile moduli and strengths ranging, respectively, from 20–1800 MPa, and 8–67 MPa. The copolymers exhibited optical properties similar to those of polydiacetylene single crystals, and produced intense resonance Raman spectra. In particular, the CC triple bond stretching Raman band at ˜ 2080 cm⁻¹ was well defined and shifted to lower frequency under the application of tensile stress/strain. The copolyurethanes may be readily applied as surface coatings to various substrates, and their use as optically stress/strain-sensitive materials (optical strain sensors) is demonstrated.     

Viscoelastic properties of cellulose derivatives: 1. Cellulose acetate

The dynamic mechanical spectrum of cellulose acetate (CA) from −130°C to 240°C has been determined at different frequencies (from 0.1 to 30 Hz). Three relaxations, designated , β and γ in order of decreasing temperature, and one shoulder (β*) above room temperature were found. Comparison with calorimetric and thermogravimetric measurements yields the conclusion that the relaxation (197°C at 3 Hz) is related to the glass-to-rubber transition and the β* shoulder (50°C–100°C) is due to loss of moisture. The β relaxation (−38°C at 3 Hz, ΔH = 100 kJ mol⁻¹) is tentatively assigned to local motions of the main chain (glucopyranose rings). The low-temperature γ relaxation (−88°C at 3 Hz, ΔH = 46 kJ mol⁻¹), is humidity-dependent: its intensity decreases when the samples are dried to moisture contents lower than that obtained by normal room conditioning (about 3%). Higher water contents shift the relaxation to lower temperatures without increasing the intensity of the mechanical loss. It is suggested that water associated with the unesterified methylol groups of cellulose acetate is responsible of the dynamic mechanical γ dispersion.     

New crosslinked polymer systems with high and stable optical nonlinearity

Thermo-crosslinkable copolymers (PGMAA and PGMAS) of glycidyl methacrylate containing azobenzene chromophores (20 mol%) and stilbene chromophores (19 mol%) respectively were synthesized and characterized. In order to obtain crosslinked polymers with high and stable second-order nonlinear optical (NLO) property, PGMAA and PGMAS were doped with a reactive nonlinear optical (NLO) dye, 4-nitro-4′-aminobiphenyl (20 mol% of the glydidyl group). In the poled state, these doped polymers systems (PGMAD and PGMSD) can be thermo-crosslinked to yield materials with high second-order (NLO) coefficient (d₃₃) of 4.33×10⁻⁷ esu and 4.74×10⁻⁷ esu respectively. The investigation of SHG decay at room temperature and 100°C showed that the polymer networks much improved the SHG stability.     

Terpolymerization kinetics of N,N‐dimethylaminoethyl methacrylate/alkyl methacrylate/styrene systems

Low conversion kinetics of terpolymerization of N,N‐dimethylaminoethyl methacrylate (DMAEM) and dodecyl methacrylate (DDMA) with methyl methacrylate (MMA) or styrene (ST) was investigated. Reactions were performed at 70°C, in toluene solutions, using peroxide initiator. The interdependence between terpolymer and monomer feed composition was successfully described by Alfrey‐Goldfinger equation and the unitary, binary, and ternary azeotropes were calculated. In MMA‐containing system, the wide pseudoazeotropic region with existence of true azeotropic point was observed and experimentally confirmed at the DMAEM:MMA:DDMA molar ratio of 56:41:3. In the ST‐containing system compositional heterogeneity was significant, more than 10 mol%. Required copolymerization reactivity ratios were determined by linear and nonlinear methods. The glass transition temperatures of synthesized terpolymers are found to be between those of the corresponding homopolymers and relative to their content. Increase in the MMA or ST contents and decrease in the DDMA content in terpolymers results in an increase in their glass transition temperatures. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Microstructure and properties of novel fluorescent pyrene functionalized PANI/P(VDF‐HFP) blend

We herein report the preparation and properties of the first polymer blend using pyrene functionalized polyaniline (pf‐PANI). The pf‐PANI has been synthesized and its blend has been prepared with the copolymer of vinylidene fluoride and hexafluoropropylene P(VDF‐HFP). The FTIR results reveal intermolecular interaction between the polar amide group of pf‐PANI and the polarized CH₂ group of P(VDF‐HFP). The crystalline phase of PVDF of the copolymer revealed a transformation from α to β crystalline form after blending with pf‐PANI, as found from FTIR and XRD measurements. The calorimetric measurements together with DMA results revealed the blend is partially miscible. The SEM measurements showed that the pf‐PANI has been dispersed uniformly in the P(VDF‐HFP) matrix. The solution photoluminescence spectrum of the pf‐PANI exhibited emission in the purple–blue region and is slightly red shifted for the blend. The possible applications of this flexible fluorescent pf‐PANI/P(VDF‐HFP) has been suggested. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40162.     

Segmented block copolymers of natural rubber and 1, 3-butanediol–toluene diisocyanate oligomers

A series of segmented block copolymers of NR and 1,3-butanediol–toluene diisocyanate oligomers have been synthesized with varying hard segment content. The synthesis has been carried out by one-shot and two-shot processes in solution. The products were characterized by spectral analysis, thermal and mechanical analysis, SEM and optical microscopy. They are found to be amorphous materials having no potential for hydrogen bonding between the ‘hard' and ‘soft' segments. Their two-phase morphology has been deduced from SEM and optical micrographs and established by DMA and thermal studies. DSC analysis shows a soft segment glass transition temperature at −62±2°C and hard segment glass transitions between 70° and 100°C, depending on the polyurethane content. The T_g values determined by the dynamic mechanical analysis are significantly higher than these values.

The thermogravimetric analysis indicates a two-stage thermal decomposition of the materials by random nucleation mechanism and corresponds to the two phases present in the block copolymer. Depending on the proportion of the continuous and dispersed phases, the block coolymers behave like quasi-elastomers at lower hard segment concentrations and brittle plastics at higher hard segment contents. This variation in mechanical behaviour is consistent with the sample morphology. Materials synthesized by the two-shot process are found to possess better mechanical properties than the one-shot products, presumably due to a more systematic ordering of the different segments in the former.     

Autocatalytic effect and microstructural development during ageing of 3 mol% Y2O3-TZP

The ageing kinetics of a 3 mol% Y-TZP are different at temperatures of 120–400°C in air and in 0·1 MPa water-vapour atmosphere. In air, a sigmoidal curve is observed while in water, a characteristic exponential curve is obtained. A new phase with d = 0·3027−0·2979 nm appeared after ageing in air and in a water-vapour atmosphere. An indication of the formation of a superlattice was observed by selected area diffraction pattern (SADP); it is suggested that the orthorhombic phase is responsible for the additional reflections.     

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.     

Effect of various electrophoretically deposited nano‐silica contents on the properties of poly(vinylidene fluoride‐co‐hexafluoropropylene)‐based electrospun polymer electrolytes

Poly(vinylidene fluoride‐co‐hexafluoropropylene) (P(VDF‐HFP)) based composite polymer electrolyte (CPE) membranes were successfully prepared by electrospinning followed by electrophoretic deposition processes, and desirable polymer electrolytes were obtained after being activated in liquid electrolytes. The physicochemical properties of the CPEs with different electrophoretically deposited nano‐SiO₂ contents were investigated by SEM, XRD, TGA, linear sweep voltammetry and electrochemical impedance spectroscopy measurements. When the ratio of electrophoretically deposited nano‐SiO₂ to P(VDF‐HFP) is up to 4 wt%, the results show that the CPE membrane presents a very uniform surface with abundant interconnected micropores and possesses excellent mechanical tensile strength with high thermal and electrochemical stability; the ionic conductivity at room temperature can reach 3.361 mS cm^?1 and the reciprocal temperature dependence of the ionic conductivity follows a Vogel ? Tamman ? Fulcher relationship. The interfacial resistance of the assembled Li/CPE/Li simulated cell can rapidly increase to a steady value of about 950 Ω from the initial value of about 700 Ω at 30 °C during 15 days' storage. The battery performance test suggests that the CPE also shows excellent compatible properties with commercial LiCoO₂ and graphite materials. © 2015 Society of Chemical Industry     

Effect of temperature on the structure and density of ammonium chloride particles

The structure and density of individual ammonium chloride particles formed at 0 and −20°C by homogeneous nucleation were studied using electron microscopy and X-ray diffraction. The crystal size apparently increased at the lower temperature and many of the particles formed at −20°C were single crystals or had an oriented polycrystalline structure. These results differ from those reported previously for particles formed at room temperature (23–26°C), which showed an amorphous or randomly-oriented fine crystal structure. Coagulation was more frequently observed as the temperature decreased and the porosity present in the particles appeared to be much finer and more uniform. The density of these particles decreased from about 0.26 g cm⁻³ for particles of size 0.1–0.2 μm to approximately 0.1 g cm⁻³ for particles slightly smaller than 1 μ.     

Grafting of 4‐Hydroxybenzenesulfonic Acid onto Commercially Available Poly(VDF‐co‐HFP) Copolymers for the Preparation of Membranes

The grafting of a phenate bearing sulfonate group in solution onto commercially available poly(VDF‐co‐HFP) copolymers, where VDF and HFP stand for vinylidene fluoride and hexafluoropropene, respectively, is presented. This reaction leads to novel fluoropolymers, bearing aryl sulfonic acid side functions, which are fuel cell membrane precursors. A mechanism similar to the grafting of bisphenol onto VDF‐containing copolymers is discussed. First, the sulfonate phenate is modified to give the didecyldimethylammonium bromide sulfonate phenate salt, in order to promote the substitution onto a fluorine atom in VDF unit adjacent to one HFP unit onto a fluorine atom in the copolymer. The substitution of this salt onto the fluorinated copolymer yields low molar percentages of grafted phenate, ranging from 1.8 to 5.1 mol‐%, whereas it reaches values up to 13 mol‐% grafting when the NH₂‐CH₂‐CH₂‐S‐CH₂‐CH₂‐C₆H₄‐SO₃Na amine is used as the grafting agent. NMR characterization is used to monitor the grafting process. The electrochemical properties of the resulting phenate grafted‐poly(VDF‐co‐HFP) copolymer are studied. The theoretical ion exchange capacities are half that of Nafion®. The proton conductivities are also lower than that of Nafion®, although one conductivity measurement reached a value of 5.1 mS cm^–1, showing a non‐negligible conductivity. The water uptake is lower than these noted for a sulfonated amine‐grafted copolymer, and is of the same order as that for Nafion®. Finally, it is shown that these novel materials start to decompose above 200 °C, showing a similar thermostability as that of an amino‐containing aryl sulfonate‐grafted poly(VDF‐co‐HFP) copolymer.