Miscibility and intermolecular specific interactions in blends of poly(hydroxyether of bisphenol A) and poly(4-vinyl pyridine)

The blends of poly(hydroxyether of bisphenol A) (phenoxy) with poly(4-vinyl pyridine) (P4VPy) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and high-resolution solid-state nuclear magnetic resonance (NMR) spectroscopy. The single, composition-dependent glass transition temperature (T_g) was observed for each blend, indicating that the system is completely miscible. The sigmoid T_g-composition relationship is characteristic of the presence of the strong intermolecular specific interactions in the blend system. FTIR studies revealed that there was intermolecular hydrogen bonding in the blends and the intermolecular hydrogen bonding between the pendant hydroxyl groups of phenoxy and nitrogen atoms of pyridine ring is much stronger than that of self-association in phenoxy. To examine the miscibility of the system at the molecular level, the high resolution ¹³C cross-polarization (CP)/magic angle spinning (MAS) together with the high-power dipolar decoupling (DD) NMR technique was employed. Upon adding P4VPy to the system, the chemical shift of the hydroxyl-substituted methylene carbon resonance of phenoxy was observed to shift downfield in the ¹³C CP/MAS spectra. The proton spin-lattice relaxation time T₁(H) and the proton spin-lattice relaxation time in the rotating frame T_1ρ(H) were measured as a function of the blend composition. In light of the proton spin-lattice relaxation parameters, it is concluded that the phenoxy and P4VPy chains are intimately mixed on the scale of 20-30 Å.     

Physical nature of complex structural relaxation in polysiloxane - PMpTS: α and α′ relaxations

Structural relaxation processes in poly(methyl-para-tolyl-siloxane) (PMpTS) polymers of three molecular weights were studied using dynamic light scattering. Two relaxation processes: the usual α and an additional slow one α′ were observed and studied as function of temperature and molecular weight. Contrary to the structural relaxation, we find that in a plot T-T_g the relaxation times for the α′ process for all molecular weights do not collapse to a single curve. For one of the samples the light scattering correlation functions were compared with the corresponding functions obtained by means of mechanical relaxation, dielectric spectroscopy and computer simulations. The simulations show that the bimodal distribution, i.e. the α relaxation and the slow (α′) process are contained in the correlation functions of most of the probes (optical anisotropy, dipole moment, chain bond, density) in agreement with experimental observations.     

Drug-Biopolymer Dispersions: Morphology- and Temperature- Dependent (Anti)Plasticizer Effect of the Drug and Component-Specific Johari–Goldstein Relaxations

Amorphous molecule-macromolecule mixtures are ubiquitous in polymer technology and are one of the most studied routes for the development of amorphous drug formulations. For these applications it is crucial to understand how the preparation method affects the properties of the mixtures. Here, we employ differential scanning calorimetry and broadband dielectric spectroscopy to investigate dispersions of a small-molecule drug (the Nordazepam anxiolytic) in biodegradable polylactide, both in the form of solvent-cast films and electrospun microfibres. We show that the dispersion of the same small-molecule compound can have opposite (plasticizing or antiplasticizing) effects on the segmental mobility of a biopolymer depending on preparation method, temperature, and polymer enantiomerism. We compare two different chiral forms of the polymer, namely, the enantiomeric pure, semicrystalline L-polymer (PLLA), and a random, fully amorphous copolymer containing both L and D monomers (PDLLA), both of which have lower glass transition temperature (T_g) than the drug. While the drug has a weak antiplasticizing effect on the films, consistent with its higher T_g, we find that it actually acts as a plasticizer for the PLLA microfibres, reducing their T_g by as much as 14 K at 30%-weight drug loading, namely, to a value that is lower than the T_g of fully amorphous films. The structural relaxation time of the samples similarly depends on chemical composition and morphology. Most mixtures displayed a single structural relaxation, as expected for homogeneous samples. In the PLLA microfibres, the presence of crystalline domains increases the structural relaxation time of the amorphous fraction, while the presence of the drug lowers the structural relaxation time of the (partially stretched) chains in the microfibres, increasing chain mobility well above that of the fully amorphous polymer matrix. Even fully amorphous homogeneous mixtures exhibit two distinct Johari–Goldstein relaxation processes, one for each chemical component. Our findings have important implications for the interpretation of the Johari–Goldstein process as well as for the physical stability and mechanical properties of microfibres with small-molecule additives.     

Confinement, composition, and spin-coating effects on the glass transition and stress relaxation of thin films of polystyrene and styrene-containing random copolymers: Sensing by intrinsic fluorescence

The glass transition temperatures (T_gs) of polystyrene (PS) and styrene/methyl methacrylate (S/MMA) random copolymer films are characterized by intrinsic fluorescence, i.e., monomer fluorescence from an excited-state phenyl ring and excimer fluorescence from an excited-state dimer of two phenyl rings. The T_g is determined from the intersection of the rubbery- and glassy-state temperature dependences of the integrated fluorescence intensity measured upon cooling from an equilibrated state. With PS, the effects of nanoconfinement on T_g and the transition strength agree with results from studies using probe fluorescence and ellipsometry. The T_g-nanoconfinement effect is “tuned” by copolymer composition. As S-content is reduced from 100 mol% to 22 mol%, the confinement effect changes from a reduction to an enhancement of T_g relative to bulk T_g. Intrinsic fluorescence is also a powerful tool for characterizing relaxation of residual stresses. Stresses induced by spin coating affect local conformations, which in turn affect excimer and monomer fluorescence and thereby integrated intensity. The heating protocol needed to achieve apparently equilibrated local conformations is determined by equivalence in the integrated intensities obtained upon heating and subsequent cooling. While partial stress relaxation occurs upon heating in the glassy state, full relaxation of local conformations requires that a film be heated above T_g for times that are long relative to the average cooperative segmental relaxation time. For example, in thin and ultrathin films, equilibration is achieved by heating slowly (∼1 K/min) to 15-20 K above T_g. Dilute solution fluorescence of PS and S/MMA copolymers is also characterized and compared to reports in the literature.     

Dielectric relaxations in poly [2,2-propane-bis-(4-phenyl thiocarbonate)]

The dielectric relaxation properties of poly[2,2-propane-bis-(4-phenyl thiocarbonate)] (PTC) have been studied. The existence of crystallinity, which can be eliminated by quenching, is detected. The degree of crystallinity of polymer samples was determined by differential scanning calorimetry in order to investigate the effect of this factor on the dielectric behaviour of this polymer. The thermal degradation of the samples was studied by thermogravimetry. The degradation of the polymer begins before the glass transition temperature T_g. The dielectric spectrum is complex showing several relaxation phenomena. With increasing temperature a γ relaxation can be observed at - 100°C (5 kHz). The activation energy obtained from an Arrhenius plot (lnfvs T^?1) is 6 kcal mol^?1. At 160°C the α relaxation which is associated with the glass transition temperature T_g is detected. The dielectric behaviour of this poly(thiocarbonate) is compared with the corresponding poly(carbonate).     

Molecular dynamics of poly(butylene tert-butyl isophthalate) and its copolymers with poly(butylene terephthalate) as revealed by broadband dielectric spectroscopy

The dynamic behaviour of a set of copolyesters made of 1,4-butanediol, terephthalic acid and 5-tert-butyl isophthalic acid, as well as the two parent homopolymers was studied. Although the insertion of the tert-butyl isophthalate units in the main chain of poly(butylene terephthalate) modified the glass transition, the β relaxation did not change dramatically. By using broadband dielectric spectroscopy we have obtained a detailed picture of the dynamic behaviour of these systems. In all cases, a strong correlation between the α relaxation and the β relaxation above T_g was observed in accordance with recent proposals based on the coupling model.     

Specific interactions in 4‐hydroxybenzoic acid/poly(2‐vinylpyridine)/poly(N‐vinyl‐2‐pyrrolidone) blends

The specific interactions in ternary 4‐hydroxybenzoic acid (HBA)/poly(2‐vinylpyridine) (P2VPy)/poly(N‐vinyl‐2‐pyrrolidone) (PVP) blends were studied by differential scanning calorimetry, Fourier transform infrared (FTIR) spectroscopy, and electron microscopy. FTIR study shows the existence of hydrogen‐bonding interactions between HBA and P2VPy as well as PVP. The addition of a sufficiently large amount of HBA produces a blend showing one glass‐transition temperature (T_g). Microscopic study shows a drastic reduction in domain size in single‐T_g blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 901–907, 2001     

The kinetics of the α relaxation in an amorphous polymer at temperatures close to the glass transition

The kinetics of the α relaxation of a crosslinked copolymer of acrylonitrile and butadiene (T_g = ?7°C) were studied in the temperature range (T_g + 17°C) down to (T_g ? 8°C). The techniques used were shear creep analysed by time-temperature (t-T) superposition and thermal sampling (TS) with correction procedures proposed by McCrum. In this range the kinetics do not follow the compensation rule, as had been proposed in the pioneering TS experiments by Zielinski, Swiderski and Kryszewski and by Lacabanne et al.. The McCrum correction removes a discrepancy between the pioneering TS experiments and the conclusions of classical t-T superposition experiments. The methods of TS and t-T superposition are compared. At low temperatures, below (T_g + 3°C), the TS method is superior: t-T superposition is unreliable due to lack of normalization and to the physical ageing perturbation. At temperatures from (T_g + 3°C) to (T_g + 11°C) t-T superposition is highly reliable since normalization is not required and there is no ageing. At temperatures above (T_g + 11°C) the precision of t-T superposition depends on the validity of the normalization procedure. It has yet to be determined whether or not the compensation rule applies at temperatures below (T_g ? 8°C): the method most likely to settle this important question is TS, mechanical or dielectric variant, with McCrum correction for the distribution of relaxation times.     

Origin of the divergence of the timescales for volume and enthalpy recovery

Although the relationship between the relaxation timescales of thermodynamic, mechanical, viscoelastic, and dielectric properties in amorphous materials has been studied extensively, no general consensus has been reached. In this work, we examine the relationship between the timescales of volume and enthalpy relaxation for polystyrene using the cooling rate dependence of the glass transition temperature (T_g) obtained from capillary dilatometry and differential scanning calorimetry (DSC). Our analysis suggests that both volume and enthalpy exhibit similar relaxation timescales at temperatures above and below T_g. The divergence of the times required to reach equilibrium noted in the literature at temperatures several degrees below the nominal T_g is attributed to the effects of nonlinearity. The relationship between nonlinearity and dynamic heterogeneity is discussed.     

Evaluation of local polarity of polymer solids by a rigid fluorescent probe of carbazole-terephthalate cyclophane

A novel rigid fluorescent probe, carbazole-terephthalate cyclophane (Cz-TP) was applied to evaluate local dielectric constants (ε) of various polymer solids in a wide range of temperatures. For poly(vinylidene fluoride), the ε increased above the glass transition temperature (T_g), due to relaxations of the polar segment -(CH₂CF₂)- of the main chain. For poly(alkyl methacrylate)s, the ε increased above the T_g or the melting temperature of the side chain, where motions of the polar ester groups are activated. For cyanoethylated polymers, the ε increased owing to motions of the polar cyano groups at the end of the side chain and the ε corresponded to the dielectric constant evaluated by dielectric relaxation measurement at a high frequency, because the Cz-TP exciplex has a lifetime of tens of nanoseconds. For a cyanoethylated polymer with a high content of cyano groups, the ε was larger at low temperatures than the dielectric constant obtained by the macroscopic dielectric relaxation measurement. These results show that the Cz-TP molecule is a useful probe for evaluation of the local polarity in polymer solids over a wide temperature range and can detect even a small change in ε at transition temperatures such as glass transition, side-chain melting, and side-chain relaxation.     

Effect of MgO addition on the properties of PbO –TiO2–B2O3 glass and glass–ceramics

Glass samples with composition of (50?X) PbO–X MgO–25 TiO₂–25B₂O₃ (where X=0, 5, 10 and 15 mol%) were prepared using conventional quenching technique. The amorphous nature of glass samples were confirmed by XRD. The glass transition temperature, T_g and crystallization temperature T_c were determined from the DTA. It has been observed that the addition of MgO enhances the T_g. The rise in T_g with MgO content may be attributed to the greater field strength of Mg²⁺ cation (as compared to Pb²⁺) which leads to the formation of stronger bonds. These glass samples were converted to glass–ceramics by following a two-stage heat treatment schedule. It was observed that there was good correlation between the density and CTE results of the glass–ceramics. The XRD results revealed the formation of tetragonal lead titanate as a major crystalline phase in the glass–ceramics. The addition of MgO to the glass contributes to the formation of MgB₄O₇. The dielectric constant for all the glass–ceramic samples was observed to be higher than that of corresponding glass samples. Further, with addition of MgO the room temperature dielectric constant for glass–ceramic samples increases up to 10 mol% of MgO and then decreases for 15 mol%. It has been further observed that the variation of dielectric constant of glass–ceramic samples with MgO content is exactly opposite to the variation of crystallite size of PbTiO₃ embedded in the glass ceramic-samples.     

Miscibility and specific interactions in blends of poly(4-vinylphenol-co-methyl methacrylate)/poly(styrene-co-4-vinylpyridine)

The miscibility and phase behavior of poly(4-vinylphenol-co-methyl methacrylate) (PVPhMMA50) containing 50% of methyl methacrylate with random copolymers of poly(styrene-co-4-vinylpyridine) (PS4VPy) containing 5, 15, 30, 40, and 100% of 4-vinylpyridine, respectively, were investigated by differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). It was shown that for a composition of 4-vinylpyridine less than 30%, all blends of PVPhMMA50/PS4VPy are immiscible, characterized by the apparition of two glass transitions (T_g) over their entire composition range. However, above this composition, a single T_g has been observed in all the blends of PVPhMMA50 and PS4VPy. When the amount of vinylpyridine exceeds to 40% in PS4VPy, the obtained T_gs of PVPhMMA50/PS4VPy blends were found to be significantly higher than those observed for each individual component of the mixture indicating that these blends are able to form interpolymer complexes. FTIR analysis reveals the existence of preferential specific interactions via hydrogen bonding between the hydroxyl and pyridyl groups and intensifies when the amount of 4VPy is increased in PS4VPy copolymers. Furthermore, the quantitative FTIR study carried out for PVPhMMA50/PS4VPy blends was also performed for the vinylphenol and vinylpyridine functional groups. These results were also confirmed by SEM study. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of the cooling rate in the formation of glass on the α and β relaxations of some amorphous polymers

It has been observed in dynamic mechanical measures that the range of temperatures in which relaxation properties are affected by the diminishing of the free volume has, as a lower limit the temperature at which the maximum of G″ or t_gδ, corresponding to the β relaxation, occurs. In dielectric measures on polymers in which the β relaxation is not predominant over the α relaxation, this temperature range is scarcely affected by changes in frequency, whereas the peak shifts according to its activation energy. This fact leads to the conclusion that the decrease in free volume due to a slow cooling from a temperature above T_g mainly affects mobility of the main chains under T_g, without disturbing the groups that give rise to the secondary relaxations.     

Dielectric relaxation in montmorillonite/polymer nanocomposites

We report dielectric relaxation behavior in blends of sodium montmorillonite particles (MM) with a series of polymers (i.e., polyisoprene (PI), poly(propylene glycol) (PPG), and poly(butylene oxide) (PBO)). These polymers are known to exhibit the dielectric normal mode due to the fluctuation of the end-to-end vector as well as the segmental mode due to local, segmental fluctuations. The data indicate that all blend systems exhibit an additional relaxation process at a temperature region below the glass transition temperature, T_g, of the pure polymer component. The intensity of the new relaxation process increases with the content of MM and hence the relaxation process can be assigned to the segmental motion of the chains intercalated in the interlayers of MM. On the other hand, the relaxation time of the normal mode reflecting the fluctuation of the end-to-end vector is the same as the neat polymers but the intensity of the relaxation process increases due to enhancement of the internal electric field by MM.     

Broadband dielectric spectroscopic characterization of the hydrolytic degradation of carboxylic acid-terminated poly(d,l-lactide) materials

Broadband dielectric spectroscopy was used to examine carboxylic acid-terminated poly(d,l-lactide) samples that were hydrolytically degraded in 7.4 pH phosphate buffer solutions at 37 °C. The dielectric spectral signatures of degraded samples were considerably more distinct than those of undegraded samples and a T_g-related relaxation associated with long range chain segmental mobility was seen. For both degraded and undegraded samples, a relaxation peak just beneath a DSC-based T_g was observed, which shifts to higher frequency with increasing temperature. Thus, this feature is assigned as the glass transition as viewed from the dielectric relaxation perspective. Linear segments on log-log plots of loss permittivity vs. frequency, in the low frequency regime, are attributed to d.c. conductivity. An upward shift in relaxation peak maximum, f_max, observed especially after 145 d of immersion in buffer, implies a decrease in the time scale of long range segmental motions with increased degradation time.Permittivity data for degraded and undegraded materials were fitted to the Havriliak-Negami equation with subtraction of the d.c. conductivity contribution to uncover pure relaxation peaks. Parameters extracted from these fits were used to construct Vogel-Fulcher-Tammann-Hesse (VFTH) curves and distribution of relaxation time, G(τ), curves for all samples. It was seen that the relaxation times for the α-transition in both degraded and undegraded samples showed VFTH temperature behavior. G(τ) curves showed a general broadening and shift to lower τ with degradation, which can be explained in terms of a broadening of molecular weight within degraded samples and faster chain motions.     

Diluent effects on carbonate mobility in bisphenol-A polycarbonate in the solid state

The effect of miscible low molecular weight additives on the mobility of the carbonate group in bisphenol-A polycarbonate (BPAPC) has been studied using n.m.r. and dielectric relaxation experiments in the solid state. Proton-enhanced dipolar-decoupled carbon-13 n.m.r. spectra of BPAPC, isotopically enriched at the carbonate position, are obtained without magic-angle sample spinning. The resolved chemical shift anisotropy allows study of nuclear spin relaxation for the carbonate groups in the polymer that have different orientations relative to the static magnetic field in the laboratory frame. The spin-lattice relaxation time in the rotating frame (T_1?) is measured at a motional-probe frequency of 50 kHz for the undiluted polymer and for BPAPC-diluent blends containing either dibutylphthalate or dinitrobiphenyl. The T_1? exhibits some dependence on orientation in all systems studied. In the blend containing dibutylphthalate (DBP), T_1? is decreased by a factor of two for all orientations of the carbonate group. This implies that DBP substantially increases the spectral density of 50 kHz motions in the carbonate region of the polymer at ambient temperature. In contrast, dinitrobiphenyl does not significantly alter the Fourier component of thermal fluctuations at 50 kHz. Dielectric relaxation measurements at 10 kHz reveal that the primary (T_g) and secondary (β) motional processes in BPAPC are affected by low molecular weight additives. An intermediate relaxation process appears in the temperature interval between the glass transition temperature (T_g) and the sub-T_g β-relaxation (T_β) in the polymer-diluent blends. The n.m.r. spin-lattice relaxation rate in the rotating frame, T^?1_1?, correlates well with the relative magnitude of the dielectric dissipation factor (tan δ_ε) between T_g and T_β.     

Significantly improved dielectric properties of TiO2 ceramics through acceptor-doping and Ar/H2 annealing

The acceptor-doped rutile TiO₂ ceramics, x mol% M₂O₃-(1-x) mol% TiO₂ (M = Al³⁺, Ga³⁺, and In³⁺), were prepared by solid state reaction method. The influence of Ar/H₂ annealing on the structural and dielectric properties of the ceramics were systematically investigated. Our results reveal that the dielectric properties of the ceramics can be significantly improved by the Ar/H₂ annealing. Ga³⁺ is found to be the most suitable dopant with the best doping level of 5 mol%. Excellent dielectric properties of colossal and flat dielectric permittivity (~1.2 × 10⁵ (@1 kHz and 25 °C), low dielectric loss (~0.1), and good frequency stability were achieved over the temperature range of -70–150 °C in the Ar/H₂-annealed 5 mol% Ga₂O₃-95 mol% TiO₂ ceramic. This approach of acceptor-doping and Ar/H₂ annealing leads to two thermally activated relaxations in the sample. The low-temperature relaxation is argued to be a Maxwell-Wagner relaxation caused by frozen electrons, while the high-temperature relaxation is a glass-transition-like relaxation associated with the freezing process of the electrons. This work highlights that engineering low-temperature Maxwell-Wagner relaxation paves a new way other than the frequently used acceptor-donor dual doping to design superior dielectric properties in the TiO₂ system.     

Influence of molecular weight on dynamic crossover temperature in linear polymers

Dielectric and light scattering spectra of two linear polymers, polyisoprene (PIP) and polystyrene (PS), were analyzed in broad temperature and frequency range above the glass transition temperature, T_g. The crossover temperature, T_C, was estimated using two approaches: (i) derivative analysis of relaxation times proposed by Stickel and (ii) Mode-Coupling Theory approach. Both estimates provide consistent values. T_C varies with molecular weight (MW) in both polymers, while the ratio T_C/T_g changes significantly with MW in PS only. It appears that the segmental relaxation time at T_C has value τ(T_C) ∼ 10⁻⁷ s for both polymers independent of MW and similar to the value reported for many non-polymeric glass-forming systems. No sign of the dynamic crossover has been observed in the chain relaxation around T_C of the segmental dynamics.     

Factors determining glass transition temperature and relaxation time of poly(vinyl chloride)

Glass transition properties were obtained by measurements of the dilatometric glass transition temperature T_g at elevated pressure by isobaric cooling at a constant rate. The properties include the pressure-volume-temperature (P-V-T) relations of the liquid, the specific heat capacity and the dielectric properties for a single sample of poly(vinyl chloride). From the experimental results, various thermodynamic excess quantities such as the free volumes and the configurational entropy and energies were evaluated as factors determining T_g and the relaxation time τ. Some empirical rules concerning T_g, which have been proposed by Simha and Boyer, and Wunderlich, are also examined. The main conclusions are as follows: (1) the free volume is not an essential factor determining T_g and τ; (2) the Adam-Gibbs parameter is slightly superior to the other excess entropy and energies defined as the difference of the entropy and energies between the liquid and the hypothetical crystal whose thermal expansivity and compressibility are the same as those of the corresponding glasses; and (3) the glass transition may not be treated as a quasi-equilibrium thermodynamic transition to which one of the Ehrenfest relations applies.     

Molecular motion in a copolymer of styrene and maleic anhydride

Dielectric and mechanical relaxation techniques have been applied to the study of the molecular motions exhibited by an alternating copolymer of styrene and maleic anhydride. Three major relaxations were detected by these techniques and shown to correspond to motions already defined in homopolymers of substituted maleimides. A fourth relaxation was detected but insufficient evidence for assignment was obtained. The α relaxation is attributed to gross main chain motion (T_g～475K), the β relaxation (activation energy 103kJ) to local motion about the backbone and the δ relaxation (activation energy 51kJ) to deformation of the substituted succinic anhydride ring.