Ionic noise measurement in polymer electrolytes

Electrical noise associated with ion transport (termed as “ionic noise”) has been measured at different temperatures, using a lock-in amplifier and dynamic signal analyzer for a polymer electrolyte PEO:NH₄I and its CdS dispersed composite. The ionic noise suddenly increases as the polymer passes through its phase transition at T _g and T _m. The T _g-peak in the noise measurement appears more clearly than what it does in DTA/DSC or conductivity measurements. Therefore, we suggest the noise technique as a good probe for studying phase transitions in ion conducting solid electrolytes. Further, the present noise measurements also confirm the known results of DTA/DSC studies that both T _g and T _m of polymer electrolytes shift on the formation of composites.     

Miscibility and Isothermal Crystallization Behavior of Poly (Butylene Succinate-co-Adipate) (PBSA)/Poly (Trimethylene Carbonate) (PTMC) Blends

Poly(butylene succinate-co-adipate) (PBSA)/poly (trimethylene carbonate) (PTMC) blend samples with different weight ratios were prepared by solution blending. The morphologies after isothermal crystallization and in the melt were observed by optical microscopy (OM). Differential scanning calorimetry (DSC) was used to characterize the isothermal crystallization kinetics and melting behaviors. According to the OM image before and after melting, it was found that the blends formed heterogenous morphologies. When the PTMC content was low (20%), PBSA formed the continuous phase, while when the PTMC contents was high (40%), PBSA formed the dispersed phase. The glass transition temperatures (T_g) of the blends were determined by DSC and the differences of the T_g values were smaller than the difference between those of pure PBSA and PTMC. In addition, the equilibrium melting points were depressed in the blends. According to these results, the PBSA/PTMC blends were determined as being partially miscible blends. The crystallization kinetics was investigated according to the Avrami equation. It was found that the incorporation of PTMC did not change the crystallization mechanism of PBSA. However, the crystallization rate decreased with the increase of PTMC contents. The change of crystallization kinetics is related with the existences of amorphous PTMC, the partial miscibility between PLLA and PTMC, and the changes of phase structures.     

Theoretical analysis of the effect of crystallization temperature on structure formation in flexible-chain polymers

Theoretical analysis of flexible-chain polymer crystallization was carried out over a wide temperature range from glass transition temperature T_g to melting temperature T_m. Temperature dependence of dynamic behavior manifesting in the decrease of crystallizing length with decreasing temperature was taken into account. The dependence of crystallizing length on temperature was obtained using chosen values of it at T_g and T_m. The crystallization with the formation of folded-chain crystals (type I) and uncoiled-chain crystals (type II) was considered. The analysis of thermodynamical favorability of both types of crystals with respect to temperature made it possible to obtain a flexible-chain crystallizing polymer phase diagram. This diagram shows the existence of two ranges where type II crystal formation is more favorable: a narrow range near T_m and the wider one near T_g, separated by the temperature range of crystallization with chain folding. Temperature dependences of type II crystals fraction in the system and their size were calculated. It is shown that the crystallization at considerable supercooling leads to the appearance of a great number of type II small crystals connected by tie chains. The system formed is characterized by a high degree of crystallite interconnection.     

COMPATIBILIZATION OF POLY(ETHYLENE OXIDE)/POLY(STYRENE) BLENDS: EFFECT OF THE MOLECULAR WEIGHT OF THE COMPATIBILIZER

The effect of the molecular weight and concentration of the compatibilizer maleic acid-alt-styrene copolymer (MAaS) on the compatibility behavior of incompatible poly(ethylene oxide)/poly(styrene) (PEO/PS) blends was studied by differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEO with [Mbar] _w = 100,000 (PEO₁₀₀) and PS with [Mbar] _w = 225,000 (PS₂₂₅) were used for this study. DSC measurements showed two T _g values that were shifted relative to those of the pure components. This result should be indicative that MAaS acts as a compatibilizer for the blend. Diminishing of the spherulitic growth rate G was observed as the content and molecular weight of MAaS increased in the blend. This result was confirmed by morphological analysis, by which it was possible to observe that the amorphous component diminished its droplike domains. Contact angle measurements suggest that the wettability of PEO drops on a PS/MAaS surface are larger in the system containing MAaS as the compatibilizer.     

Effect of H<Subscript>3</Subscript>PO<Subscript>2</Subscript> on the mechanical,thermal, and electrical properties of polymers based on poly (vinyl alcohol) (PVA) and chitosan (CS)

A polymer based on poly (vinyl alcohol) (PVA) and chitosan (CS) with a weight ratio of 80:20 was prepared by solvent casting processes, and the effect of H₃PO₂ was investigated. Thermal analysis shows miscibility of the two polymer amorphous phases since a single T_g was located between those of the individual components and the melting point of the crystalline phase was depressed to 189 °C. It was found that the acid acts as a plasticizer for the PVA-CS blends and its T_g is depressed significantly to 23 °C as the acid concentration increases to 50%. Strain-stress tests also corroborate this effect. The DC conductivity of the blends follows an Arrhenius-type thermal activation behavior with activation energy of 0.1 eV in the 30–90 °C temperature range. Moreover, the conductivity increases with increasing acid content up to a maximum value of approximately 1.4 × 10^?2 S/cm for the blend with an acid concentration of 50%.     

Thermal behavior of gamma-irradiated low-density polyethylene/paraffin wax blend

The thermal properties of low-density polyethylene (LDPE)/paraffin wax blends were studied using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and melt flow index (MFI). Blends of LDPE/wax in ratios of 100/0, 98/2, 96/4, 94/6, 92/8, 90/10 and 85/15 (w/w) were prepared by melt-mixing at the temperature of 150°C. It was found that increasing the wax content more than 15% leads to phase separation. DSC results showed that for all blends both the melting temperature (T_m) and the melting enthalpy (ΔH_m) decrease linearly with an increase in wax content. TGA analysis showed that the thermal stability of all blends decreases linearly with increasing wax content. No clear correlation was observed between the melting point and thermal stability. Horowitz and Metzger method was used to determine the thermal activation energy (E_a). MFI increased exponentially by increasing the wax content. The effect of gamma irradiation on the thermal behavior of the blends was also investigated at different gamma irradiation doses. Significant correlations were found between the thermal parameters (T_m, ΔH_m, T₅%, E_a and MFI) and the amount of wax content and gamma irradiation.     

Sorption of Organic Solvents in Poly(Dimethyl Siloxane) Membrane. II. Effect of Sorption on the Polymer Crystals upon Cooling

Polymer crystalline properties in poly(dimethyl siloxane) (PDMS) film after solvation by various solvents was determined using low temperature differential scanning calorimetry (DSC). At various solvent uptake levels, the crystalline thermal properties of the solvated polymer were modified to different extents as revealed by the shifts in crystalline melting point (T_m) and its enthalpy (ΔH_m). Water uptake in PDMS was very limited (<0.01 g/g) and T_m did not significantly change during the sorption process. For toluene and cyclohexane penetrants, T_m moved toward a much lower temperature depending on the sorption levels. At low solvent uptakes, the T_m values decreased linearly with solvent uptakes due to formation of a miscible phase. Beyond a threshold, the T_m remained stable and an additional penetrant fusion peak appeared, implying the onset of a microphase separation phenomenon. The ΔH_m values for the swollen membranes were decreased, with the exception of the water penetrant. This indicates that a lower percentage of polymer chains were involved in the crystalline domain for swollen PDMS.     

Intermacromolecular complexation due to specific interactions. 6. Miscibility and complexation between Poly{Styrene-co-[p-(2-Hydroxypropan-2-yl)Styrene]}and poly[n-butyl Methacrylate-co-(4-vinylpyridine)]

In recent years, considerable attention has been focused on polymer miscibility and Complexation due to hydrogen bonding. Monodisperse, proton-donating polystyrene (PS), that is, poly{styrene-co-[p-(2-hydroxypropan-2-yl)styrene]} [PS(t-OH)], was synthesized via chemical modification of polystyrene. Poly[n-butyl methacrylate-co-(4-vinylpyridine)] (BVPy), as a proton acceptor, was prepared by free-radical copolymerization of the corresponding monomers at low conversion. In organic solutions of PS(t-OH)/BVPy blends, viscometry was employed to study the Complexation behavior. Solvents with different proton-accepting abilities were used and hence proved to exert distinctive effects on solution complexation. In very dilute solutions, the complex aggregate was observed by static and dynamic light scattering (LS). Differential scanning calorimetry (DSC) investigation proved that miscibility could be greatly enhanced when a small amount of hydrogen bonding was introduced into the originally immiscible PS/PBMA (polybutyl methacrylate) system. Although it was found that the T _g of the hydrogen-bonding polymer complexes occurred at higher temperatures with respect to linear weight-average value, DSC measurement alone could not accurately distinguish polymer complexes from ordinary miscible blends. Based on the data of miscibility from DSC and complexation from vis-cometry in 1,2-dichloroethane for a few tens of blends, which cover broad ranges of the contents of interaction sites, a map showing the immiscibility-miscibility-complexation transitions by strengthening the hydrogen bonding for the system of PS(t-OH)/BVPy was successfully constructed.     

Confined Crystallization in Polymer Blends: DSC Studies of the Behavior and Kinetics of Isothermal Crystallization of Polypropylene in Poly(cis-butadiene) Rubber Blends

Thermal properties of polypropylene with poly(cis-butadiene) rubber (iPP/PcBR) blends have been measured by differential scanning calorimetry (DSC), and the melting point T_m, crystallization temperature T_c, enthalpy Δ H (melting enthalpies and crystalline enthalpies), and equilibrium melting point T⁰ _m have been measured and calculated. The variation of T_m, T_c, Δ H and T⁰ _m with composition in the blends was discussed, showing that an interaction between phases is present in iPP/PcBR blends. The degree of supercooling characterizing the interaction between two phases in the blends and the crystallizability of the blends which bears a relationship to the composition of the blends was discussed. The kinetics of isothermal crystallization of the crystalline phase in iPP/PcBR blends was studied in terms of the Avrami equation, and the Avrami exponent n and velocity constant K were obtained. The Avrami exponent n is between 3 and 2, meaning that iPP has a thermal nucleation with two dimensional growths. The variation of the Avrami exponent n, velocity constant K, and crystallization rate G bear a relation to the composition of the blends, n increases with increasing content ofPcBR. K also increased with increasing content of PcBR. All of the K for the blends are greater than for pure iPP. The crystallization rate G (t_1/2) depends on the compositions in the blends; all G of the blends are greater than for iPP.     

Natural rubber blends with epoxidized natural rubber

Blends of NR with ENR have been prepared in full composition following the polymer blend technique. Basic properties (mastication behavior and thermal degradation of each rubber and Mooney viscosity, Flory-Huggins interaction parameters, and cure characteristics of the blends) of the uncured blends were determined, in addition to the reversion, cross-linking density, mechanical and dynamic mechanical properties, rebound, and solvent swell of the blend vulcanizates. It was found that the NR ENR blends are immiscible, showing two glass transition temperatures (T_g's) that showed outward migration in the blends. This was interpreted in terms of preferred migration of the curatives into the ENR phase. Retention of mechanical properties on aging, solvent resistance, and heat buildup were greater in NR-rich blends due probably to the higher cross-link density of the blends.     

Maleic Acid–alt–Styrene Copolymer as Compatibilizer for Poly(Ethylene Oxide)-Poly(Styrene)Blends

Maleic acid-alt-styrene (MAaS) copolymer with number-average molecular weight [Mbar] _n = 2500 was used as a compatibilizer in blends of poly(ethylene oxide) (PEO) and poly(styrene) (PS). PEO with weight-average molecular weight [Mbar] _w = 10⁵ (PEO₁₀₀) and two PS samples with [Mbar] _w = 9 × 10⁴ and 4 × 10⁵, respectively (PS₉₀ and PS₄₀₀, respectively) were used. A depression of the melting temperature T _m of PEO in blends containing MAaS relative to pure PEO and PEO/PS blends was observed. The melting enthalpy ΔH _m for the PEO/PS blends containing MAaS was lower than those of pure PEO and PEO/PS blends without compatibilizer. The crystallization kinetics of PEO and the blends were studied by differential scanning calorimetry (DSC) at different crystallization temperatures T _c. Flory-Huggins interaction parameters χ₁₂ for the blends were estimated. Their values are in good agreement with those obtained for similar systems and suggest that the free energy of mixing ΔG _mix should be negative. Polarized optical microscopy shows differences in the macroscopic homogeneity of the blends containing compatibilizer that could be attributed to a compatibilization process.     

Autoadhesion of High‐Molecular‐Weight Monodisperse Glassy Polystyrene at Unexpectedly Low Temperatures

Abstract

Healing of symmetric interfaces of amorphous anionically polymerized high‐ and ultrahigh‐molecular weight (HMW and UHMW, respectively) polystyrene (PS) in a range of the weight‐average molecular weight M _w from 102.5 (M _w/M _n = 1.05) to 1110 kg/mol (M _w/M _n = 1.15) was followed at a constant healing temperature, T _h, well below the glass transition temperature of the polymer bulk [T _g‐bulk = 105–106°C as measured by differential scanning calorimeter (DSC)]. The bonded interfaces were shear fractured in tension on an Instron tester at ambient temperature. Autoadhesion at symmetric HMW PS–HMW PS and UHMW PS–UHMW PS interfaces was detected mechanically after healing at T _h = 38°C for 107 hr, and even at 24°C (for longer healing times). The occurrence of autoadhesion between the surfaces of the UHMW PS with M _w = 1110 kg/mol at 24°C implies that the glass transition temperature at the interface, T _{g‐interface}, of this polymer was a least lower: by 82°C than its DSC T _g‐bulk, by 30–40°C than the Vogel temperature, T _∞—the lowest theoretical value of a kinetic T _g‐bulk at infinite long time—and by 20°C than T ₂ (a “true” thermodynamic T _g‐bulk corresponding to a second‐order phase transition temperature). To our knowledge, this is the first observation of such nature, which gives further evidence of the lowering of the T _g at polymeric surfaces and the persistence of this effect at early stages of healing of polymer–polymer interfaces.     

Amorphous structure heat: Temperature dependence of heats of solution for polystyrene in toluene and ethylbenzene

When a polymer is dissolved in a solvent, the heat measured is a sum of a polymer-solvent interaction term and a term related to the structure that existed in the solid polymer relative to its amorphous liquid state. This latter contribution, termed the “residual” heat, can have an endothermic contribution due to the fusion of crystalline regions and an exothermic contribution due to the disruption of structure in noncrystalline amorphous regions. For atactic polystyrene between 30 and 110°C, it is shown that the “residual” heat is exothermic, decreases linearly with temperature differences below T_g, and extrapolates to zero in the vicinity of T_g. The existence of an exothermic heat above T_g is probably related to a 160°C transition in polystyrene. This “residual” heat was further observed to be independent of the pressure at which the polystyrene was glassified.     

Studies on biodegradable polymer electrolyte rice starch (RS) complexed with lithium iodide

Biodegradable and natural rice starch (RS) polymer with lithium iodide salt (LiI) was used to prepare polymer electrolytes using solution cast technique. Polymer electrolyte films were characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM). TGA and DSC thermograms demonstrate that decomposition temperature (T_dc) and glass transition temperature (T_g) for rice starch shift upon complexation with lithium iodide salt. Thermolysis studies using TGA show decomposition temperature decreases with the addition of lithium iodide salt. XRD patterns show increase in amorphous behavior with doping of lithium iodide salt. The morphology studies were observed using SEM in terms of smoothness and miscibility.     

The Effect of Epoxidized Natural Rubber and Two Kinds of Organoclay upon Molecular Interaction,Structure and Mechanical Properties of (Styrene-Butadiene Rubber/Acrylonitrile-Butadiene Rubber/Organoclay) Nanocomposites

Epoxidized natural rubber (ENR50) and two different kinds of organoclay (C30B and C15A) were used in blends of styrene-butadiene rubber (SBR) and acrylonitrile butadiene rubber (NBR) and their effects upon interaction between phases, morphology, and mechanical properties of the blends were investigated. The compounds were characterized by means of Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), and differential scanning calorimetry (DSC). The obtained results showed formation of hydrogen bonding between the compounds ingredients due to incorporation of C30B, especially in presence of ENR. AFM and FE-SEM analysis revealed good dispersion of the nanoparticles in the polymer matrix upon addition of ENR as well as better dispersion of C30B than C15A in the NBR phase. XRD results showed a greater expansion of the silicate layers by simultaneous use of organoclay and ENR Incorporation of organoclay alone or in combination with ENR in the blends caused shifting of the SBR T_g toward the NBR T_g. The tensile properties of the blends showed improvement by using nanoparticles in the presence of ENR.     

Isothermal Melt Crystallization Kinetics for Poly(Trimethylene Terephthalate)/Poly(Butylene Terephthalate) Blends

The kinetics of isothermal melt crystallization of poly(trimethylene terephthalate) (PTT)/poly(butylene terephthalate) (PBT) blends were investigated using differential scanning calorimetry (DSC) over the crystallization temperature range of 184–192°C. Analysis of the data was carried out based on the Avrami equation. The values of the exponent found for all samples were between 2.0 and 3.0. The results indicated that the crystallization process tends to be two‐dimensional growth, which was consistent with the result of polarizing light microscopy (PLM). The activation energies were also determined by the Arrhenius equation for isothermal crystallization. The values of ΔE of PTT/PBT blends were greater than those for PTT and PBT. Lastly, using values of transport parameters common to many polymers (U*=6280 J/mol, T _∞=T _g – 30), together with experimentally determined values of T _m ⁰ and T _g, the nucleation parameter, K _g, for PTT, PBT, and PTT/PBT blends was estimated based on the Lauritzen–Hoffman theory.     

Electroconductivity and pressure–temperature states of step shocked C60 fullerite

A study of electrophysical and thermodynamic properties of C₆₀ single crystals under step shock loading has been carried out. The increase and the following reduction in specific electroconductivity of C₆₀ fullerite single crystals at step shock compression up to pressure 30 GPa have been measured. The equations of state for face centred cubic (fcc) C₆₀ fullerite as well as for two-dimensional polymer C₆₀ and for three-dimensional polymer C₆₀ (3D-C₆₀) were constructed. The pressure–temperature states of C₆₀ fullerite were calculated at step shock compression up to pressure 30 GPa and temperature 550 K. The X-ray diffraction studies of shock-recovered samples reveal a mixture of fcc C₆₀ and a X-ray amorphous component of fullerite C₆₀. The start of the formation of the X-ray amorphous component occurs at a pressure P _m≈ 19.8 GPa and a temperature T _m≈ 520 K. At pressures exceeding P _m and temperatures exceeding T _m, the shock compressed fullerite consist of a two-phase mixture of fcc C₆₀ fullerite and an X-ray amorphous component presumably consisting of the nucleators of polymer 3D-C₆₀ fullerite. The decrease in electroconductivity of fullerite can be explained by the percolation effect caused by the change of pressure, size and number of polymeric phase nuclei.     

Microhardness of condensation polymers and copolymers. 1. Coreactive blends of polyethylene terephthalate and polycarbonates

The microhardness of coreactive blends of polyethylene terephthalate (PET) and bisphenol A polycarbonate (PC) was investigated over the whole range of compositions. The occurrence of one single glass transition temperature (T _g) step in the differential scanning calorimetry (DSC) curves indicated that intensive chemical interactions had taken place during melt blending, resulting in formation of copolycondensates with dominating random sequential order. The parallel decrease of microhardness (H) and of T_g with increasing PET content in the blends has been ascribed to the formation of new copolymer molecules enriched in the component characterized by lower H and T _g values. It is emphasized that such noncrystallizable copolymers offer the possibility to evaluate the intrinsic contribution of the repeating units to the H and T _g characteristics of copolymers with various compositions and sequential orders.     

Thermal Properties of Fe-octacarboxyl Acid Phthalocyanine/Polyurethane Blends

The thermal stability of PU has been a critical factor to influence its applications as engineering materials. In this paper, the thermal properties of Fe-octacarboxyl acid phthalocyanine (Fe-OCAP)/polyurethane (PU) blends were investigated. The glass transition temperatures (T_g) of Fe-OCAP/PU blends were analyzed by differential scanning calorimetry (DSC). The results showed that with increasing Fe-OCAP content up to 10% T_g of the samples decreased. Thermal stability of the samples was studied by thermogravimetric analysis (TGA). The decrease of the degradation rate of the samples with increasing Fe-OCAP content indicated an improvement of thermal stability for the modified samples. The activation energy of thermal degradation was calculated by the Freeman and Carroll method. The results showed that the activation energy increased with increasing Fe-OCAP content, which also indicated the improved thermal stability obtained in the modified samples. The thermal properties of the samples were influenced by the incorporation of Fe-OCAP.     

Investigation of the Morphological and Mechanical Properties of Polyethylene Terephthalate (PET)/Ethylene Propylene Diene Rubber (EPDM) Blends in the Presence of Multi-Walled Carbon Nanotubes

In this study the blends of polyethylene terephthalate (PET)/ethylene propylene diene rubber (EPDM) in the presence of multi-walled carbon nanotubes (MWCNT) (1 and 3?wt %) were prepared by melt compounding in an internal mixer. Mechanical and morphological properties of the nanocomposites were investigated. The thermal behaviors of the PET/EPDM nanocomposites were also investigated, by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of the mechanical tests showed that the tensile strength, elastic modulus and the hardness of the blends were increased with increasing CNT, while the impact strength and elongation at break decreased. The DSC and TGA results showed an increase of melting temperature (T_m) and degradation temperature of the nanocomposites with the addition of the carbon nanotubes, because the carbon nanotubes serve both as nucleating agents to increase T_m and prevent the composite from degradation to increase the thermal stability. The microstructure of the composites was evaluated through field emission scanning electron microscopy (FESEM) and the results showed a good distribution of the MWCNT within the polymer blend.