Reorientation and translation of individual dye molecules in a polymer matrix

The orientational and translational motion of individual dye molecules embedded in a polymer matrix is studied in the temperature regime above the glass transition. The rotational diffusion close to the glass transition is heterogeneous on the single molecule level and few sudden changes in the reorientational speed of single molecules are found. The exchange between these reorientational speeds is found to be one order of magnitude slower than the reorientational time constant of the molecules. Translational motion can be clearly identified at about 1.2 T_g. However, the translational diffusion shows no signs of heterogeneity on the timescale of our experiments, from which we conclude, that the timescale of the exchange process between microenvironments has become too fast or that no heterogeneity exists at the temperatures above 1.2 T_g.     

Polymer Structures and Glass Transition: A Molecular Dynamics Simulation Study

Full atomistic molecular dynamics (MD) simulations on five polymers with different chain backbone (C—C, Si—O, and C—O) and different side groups (—H, one —CH₃, and two —CH₃) are performed to study the effects of chain flexibility and side groups on the glass transition of polymers. Molecular dynamics simulations of NPT (constant pressure and constant temperature) dynamics are carried out to obtain specific volume as a function of temperature for polyethylene (PE), poly(propylene) (PP), polyisobutylene (PIB), poly(oxymethylene) (POM), and poly(dimethylsiloxane) (PDMS). The volumetric glass transition temperature has been determined as the temperature marking the discontinuity in slope of the plots of V–T simulation data. Various energy components at different temperatures of the polymers are investigated and their roles played in the glass transition process are analyzed. In order to understand the polymer chain conformations above and below the glass transition temperature, dihedral angle distributions of polymer chains at various temperatures are also studied.     

Synthesis, characterization and thermoreversible behaviours of poly(dimethyl siloxane)/poly(N-isopropyl acrylamide) semi-interpenetrating networks

Simultaneous and sequential poly(N-isopropyl acrylamide) (PNIPAAm)/poly(dimethyl siloxane) (PDMS) semi-interpenetrating polymer networks (IPNs) with different linear PDMS contents were prepared by free radical polymerization method. Their phase morphologies have been characterized by FTIR, DSC and SEM. The simultaneous semi-IPNs exhibited phase transition temperatures (T_pt) shifted higher temperature from glass transition temperatures (T_g) of their respective homopolymers, suggesting a heterophase morphology and only physical entanglement between the PNIPAAm network and linear PDMS with high molecular weight (Mn≈9000 g/mol). For sequential semi-IPNs, the shift of T_pts towards lower temperature suggested that the chemical interaction between the constituents of the IPNs increased with increasing PDMS content in the network. In addition, these semi-IPNs were characterized for their thermo-sensitive behaviour by equilibrium swelling studies. The results showed that incorporation of hydrophobic PDMS polymer into the thermo- and pH-sensitive PNIPAAm and P(NIPAAm-co-IA) (itaconic acid) hydrogels by semi-IPN formation decreased swelling degrees of IPNs without affecting their LCSTs whereas addition of acrylated PDMS (Tegomer V-Si 2250) as crosslinker instead of N,N^′-methylenebisacrylamide (BIS) into the structures of these hydrogels changed their LCSTs along with their swelling degrees.     

Study of the glass transition on viscous-forming and powder materials using dynamic mechanical analysis

The investigation of the glass transition in materials that become too viscous or are difficult to prepare in a solid compact form, is not straightforward using dynamic mechanical analysis, DMA. In this work, metallic pockets are used to envelop samples in order to resolve the loss factor peak, tan δ, in the region of T_g. Experiments with indium were carried out at different heating rates in order to correct the temperature in such isochronal measurements. The proof of concept of the utility of such methodology was done by investigating the glass transition dynamics of poly(d,l-lactic acid), PDLLA, a biodegradable amorphous polyester widely investigated for biomedical applications. The glass transition peaks obtained at scanning rates below 4 °C min^?1 shifted to the same temperature region after correction. DMA tests on PDLLA at different frequencies allowed construction of a relaxation plot where the glass transition dynamics followed Vogel–Fulcher–Tamman–Hesse behaviour. Inclusion complexes, ICs, of PDLLA with α-cyclodextrin were obtained, exhibiting a very organized arrangement at the nano-scale level. DMA experiments on the ICs powder packed in the metallic pocket revealed a loss factor peak located at a higher temperature as compared with PDLLA, indicating that the segmental mobility of the polymer chains is highly restricted in this supra-molecular organization.     

Epoxy nanocomposites co-reinforced by two dimensionally different nanoscale particles

Comprehensive high-performance epoxy nanocomposites were prepared by simultaneous incorporating montmorillonite (MMT) and nanoSiO₂ into epoxy. Mechanical tests and thermal analyses showed that the epoxy/MMT/nanoSiO₂ nanocomposites obtained considerable improvement over basic epoxy in tensile modulus, tensile strength, flexural modulus, flexural strength, notch impact strength, glass transition temperature, and thermal decomposition temperature. X-ray diffraction measurements and transmission electronic microscopy observations revealed that the layered structure of MMT was completely exfoliated into two-dimensional nanoscale mono-platelets. These 2D mono-platelets formed intermingled structure with the zero-dimensional nanoSiO₂ spheres in the nanocomposites. This study suggests that employing the synergistic reinforcement effect of two dimensionally different nanoscale particles is one pathway to success in developing comprehensive high-performance polymer nanocomposites.     

Dynamics of α and α′ relaxation in layered silicate/polystyrene nanocomposites studied by anelastic spectroscopy

The dynamics of polymer chains in layered silicate/polystyrene nanocomposites was studied by anelastic spectroscopy. Two thermal activated peaks (α and α′ peaks) appeared when the specimens were heated to a high temperature and they were related to glass transition and liquid-liquid transition, respectively. The activation energy was calculated based on Arrhenius equation and it showed that the activation energy of glass transition (E _g) is much higher than that of liquid-liquid transition (E _ll). Furthermore, the most interesting result for the activation energy was that there were two contrary trends for E _g and E _ll, E _g decreased and E _ll increased with the addition of clay platelets. The fragile parameter was analyzed and the variation of fragile parameters for the two transitions was also contrary to each other with the addition of clay platelets. All the results indicated that the confinement effect of clay platelets on the dynamics of polymer chain was scale dependent, and perhaps, the two transitions were produced by different mechanisms.     

The role of the torsional potential in relaxation dynamics: a molecular dynamics study of polyethylene

The role of the torsional potential in bulk polymer chain dynamics is investigated via molecular dynamics simulation using polyethylene as a model system. A number of three-fold barrier values, both greater and less than the standard one, were invoked. The one-fold potential that determines the gauche vs trans energy difference was also varied. For each of the selected torsional potentials, the MD volumetric glass transition temperature, T_g, was located. It was found that T_g is quite sensitive to the three-fold barrier magnitude, moving from below 100 K to nearly 400 K as the barrier goes from zero to twice the standard value. However T_g was found to be quite insensitive to the gauche trans energy difference. Details of the conformational dynamics were studied for the case of a zero torsional potential. This included the rate and location of conformational transitions, the decay of the torsional angle autocorrelation function (ACF) and the cooperativity of conformational transitions, all as a function of temperature. The temperature dependence of the conformational transition rate remains Arrhenius at all temperatures. The relaxation time characterizing the torsional angle ACF decay exhibits WLF temperature behavior. The conformational transitions are randomly distributed over the bonds at high temperature, but near T_g they become spatially heterogeneous and localized. The transitions show next-neighbor correlation as well as self-correlated forward-backward transitions. All of these features are similar to those found in previous simulations under the standard torsional potential.     

Molecular dynamics study of orientational order and rotational melting in clusters of TeF6

Molecular dynamics simulations of the behavior of molecules in crystalline clusters of TeF₆ were carried out on systems of 100, 150, 250, and 350 molecules. Several diagnostic functions were applied to investigate whether rotational melting occurred before translational melting. These functions included the coefficient of rotational diffusionD _θ(T), the “orientational Lindemann index” δ_θ(T), the “orientational angular distribution function”Q(θ,T), and the “orientational pair-correlation function”g _θ(r, T). All indicators implied that rotational melting occurred before translational melting, that it began with the outermost molecules, and that its onset for smaller clusters was at lower temperatures than for larger clusters. Results also showed that the rotational transition coincided with the transition from a lower symmetry phase (monoclinic) to cubic, a phenomenon that had been noted by others to occur with some regularity for systems of globular molecules.     

Effect of temperature and membrane preparation parameters on gas permeation properties of polymethacrylates

Permeabilities of N₂, Ar, O₂, CO₂, and H₂ gases in PEMA (Polyethylmethacrylate) membranes have been measured above and below glass transition in the temperature range of 25–70 °C. The permeabilities of the gases were observed increasing with temperature. Arrhenius plot of permeability versus temperature data showed that there is a slope discontinuity at near to T_g of PEMA. In addition, the effects of membrane preparation parameters by solvent casting method (percentage of polymer in solvent, annealing temperature, annealing time, evaporation temperature, and evaporation time) have been investigated by using homogenous dense membranes of PEMA. It is observed that membrane preparation parameters strongly affect the membrane performance and the reproducibility of the permeability measurements. On the other hand, the effect of polymer structure on membrane performance has been investigated. Comparison of the permeabilities of N₂, Ar, O₂, CO₂, and H₂ gases in PEMA and PMMA membranes shows that PMMA membranes have smaller permeabilities and higher selectivities than PEMA membranes because of their higher glass transition temperature, T_g. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3025–3033, 2007     

Switchable Guest Molecular Dynamics in a Perovskite‐Like Coordination Polymer toward Sensitive Thermoresponsive Dielectric Materials

A new perovskite‐like coordination polymer [(CH₃)₂NH₂][Cd(N₃)₃] is reported which undergoes a reversible ferroelastic phase transition. This transition is due to varied modes of motion of the [(CH₃)₂NH₂]⁺ guest accompanied by a synergistic deformation of the [Cd(N₃)₃]^? framework. The unusual two‐staged switchable dielectric relaxation reveals the molecular dynamics of the polar cation guest, which are well controlled by the variable confined space of the host framework. As the material switches from the ferroelastic phase to the paraelastic phase, a remarkable increase of the rotational energy barrier is detected. As a result, upon heating at low temperature, this compound shows a notable change from a low to a high dielectric state in the ferroelastic phase. This thermoresponsive host–guest system may serve as a model compound for the development of sensitive thermoresponsive dielectric materials and may be key to understanding and modulating molecular/ionic dynamics of guest molecules in confined space.     

Dynamics and distribution of aromatic model drugs in the phase transition of thermoreversible poly(N-isopropylacrylamide) in solution

Employing differently substituted benzaldehydes as model drugs, their dynamics is investigated under the influence of the coil-to-globule transition of poly(N-isopropylacrylamide), which shows lower critical solution temperature behaviour. Using ¹H-NMR spectra, partial incorporation of the model drug into precipitated polymer particles is shown. The fraction of drug, which is rigidly incorporated, is linearly correlated to the shift of the transition temperature, which it induces for the polymer. By ¹H-NMR spin relaxation measurements on ethylvanillin, 3,4-dimethoxybenzaldehyde and salicylaldehyde the influence of the polymer transition on the model drug dynamics is detected. The data are interpreted in terms of different sites of drug localisation, i.e. rigidly incorporated, loosely bound and free in the aqueous phase, which are identified by their different dynamics. Drug molecules strongly interacting with the polymer, as documented by a large shift of the transition temperature, exhibit only strongly bound and free sites, while with decreasing drug–polymer interaction drug an additional loosely bound site occurs.     

Phase- and glass-transition phenomena due to the same configurational order–disorder mechanism in crystalline racemic sec-butylcyclohexane

We report molar heat capacities for racemic sec-butylcyclohexane (s-BCH) measured by the adiabatic calorimetric method within the temperature range from 14 to 200 K. In the crystalline state, we identified the presence of a second-order phase transition and a glass transition phenomenon, both originating from the same configurational degree of freedom. The phase and glass transition temperatures T _trs and T _g were determined to be (136.7 ± 1.0) and (100 ± 1) K, respectively. The entropy of phase transition was estimated to be Δ_trs S _m = 1.4 J K^?1 mol^?1 ≈ (1/4) R ln 2. The phase transition was judged to be of an order–disorder type on the basis of the fact that the glass transition occurred in the low-temperature heat-capacity tail. The entropy was interpreted to suggest that four molecules in the crystalline state constitute a unit for producing two distinct configurations in the coexistence of (d)- and (l)-s-BCH.     

The diverse effect of antiplasticizer in the molecular dynamics of an organic dye-doped polymer observed at different motional lengthscales

Complementary thermal analysis techniques were used to study blending-induced perturbations in polymer dynamics pertaining to different motional lengthscales. The antiplasticizing role of common neutral and apolar fluorescent perylimides on the cooperative relaxation dynamics of poly(methyl methacrylate) (PMMA) chain segments is evidenced by a clear rise of both the glass transition (T_g) and liquid-liquid transition (T_LL) temperatures. Simultaneously, the dielectric strength, Δε_β, of the signal ascribed to restricted rotational movements of lateral groups, shows a substantial reduction. Most aspects of the observed behavior bear analogies with recent experimental observations in nanoconfined PMMAs (e.g., PMMA with homogeneously dispersed SiO₂ nanospheres, in-situ polymerized in silica nanopores or in the form of supported ultrathin films), suggesting that a common mechanism is operational. In our mixtures, confinement effects, such as a modification in the macroconformation of the polymer, and changes in the orientation and packing of the polymer random coil, provide a plausible explanation of the observed changes regardless of the motional lengthscale concerned. Consonant with this scenario are reports of advanced optical properties for perylimide + PMMA blends, ascribed to the high rigidity of the matrix together with weak intercomponent interactions.     

Thermal transitions and dynamics in nanocomposite hydrogels

Hydrogels based on nanocomposites of statistical poly(hydroxyethyl acrylate-co-ethyl acrylate) and silica, prepared by simultaneous copolymerization and generation of silica nanoparticles by sol?Cgel process at various copolymer compositions and silica contents, characterized by a fine dispersion of filler, were investigated with respect to glass transition and polymer dynamics by dielectric techniques. These include thermally stimulated depolarization currents and dielectric relaxation spectroscopy, covering together broad ranges of frequency and temperature. In addition, equilibrium water sorption isotherms were recorded at room temperature (25?°C). Special attention was paid to the investigation of effects of silica on glass transition, polymer dynamics (secondary ?? and ?? _sw relaxations and segmental ?? relaxation), and electrical conductivity in the dry systems (xerogels) and in the hydrogels at various levels of relative humidity/water content. An overall reduction of molecular mobility is observed in the nanocomposite xerogels, in particular at high silica contents. Analysis of the results and comparison with previous work on similar systems enable to discuss this reduction of molecular mobility in terms of constraints to polymeric motion imposed by interfacial polymer?Cfiller interactions and by the formation of a continuous silica network interpenetrated with the polymer network at filler contents higher than about 15?wt%.     

Local dynamics and glass transition

The dynamics of polymer chains in the bulk state are discussed at three different temperature scales: (i) Well above the glass transition temperature where the basic step of motion is the rotameric transition of bonds. In this regime, the dynamics may conveniently be analyzed by the rotational isomeric state model, (ii) In the vicinity of glass transition where friction forces from the environment dominate. In this regime, the dynamics may be modeled according to the cooperative kinematics model, (iii) Well below glass transition. Here, an analogy with a native protein is made, and the mean-squared fluctuations are analyzed by adopting the Gaussian Network Model, which recently proved successful in describing fluctuations in native proteins.     

Water sorption and polymer dynamics in hybrid poly(2-hydroxyethyl-co-ethyl acrylate)/silica hydrogels

This work probes the hydration properties and molecular dynamics of hybrid poly(hydroxyethyl-co-ethyl acrylate)/silica hydrogels. Two series of hybrid copolymers were prepared by simultaneous polymerization and silica preparation by sol-gel method, the first with hydroxyethyl acrylate/ethyl acrylate (HEA/EA) composition at 100/0, 90/10, 70/30, 50/50, 30/70, 10/90 and fixed silica content at 20 wt.%, and the second with fixed HEA/EA organic composition at 70/30 and 0, 5, 10 and 20 wt.% of silica. The hydration properties of these systems were studied at 25 °C by exposure to several controlled water vapor atmospheres (water activities 0-0.98) in sealed jars and by immersion in distilled water. Finally, the molecular dynamics of the hydrated hybrids at several levels of hydration was probed with Thermally Stimulated Depolarization Currents (TSDC) in the temperature interval between −150 and 20 °C. The results indicate that a critical region of silica content between 10 and 20 wt.% exists, above which silica is able to form an inorganic network. This silica network prevents the expansion of water clusters inside the hydrogels and subsequently the total stretching of the polymer network without obstructing the water sorption at the first stages of hydration from the dry state. As concerns the copolymer composition, the presence of EA reduces water sorption and formation of water clusters affecting directly to the hydrophilic regions. The TSDC thermograms reveal the presence of a single primary main broad peak denoted as α_cop relaxation process, which is closely related to the copolymer glass transition, and of a secondary relaxation process denoted as β_sw relaxation, which originates from the rotational motions of the lateral hydroxyl groups with attached water molecules. The single α_cop implies structural homogeneity at the nanoscale in HEA-rich samples (x_HEA > 0.5), while for high EA content (x_EA ? 0.5) phase separation is detected. Both relaxation processes show strong dependence on water content and organic phase composition.     

Studies of molecular dynamics of carboxylated acrylonitrile-butadiene rubber composites containing in situ synthesized silica particles

The molecular dynamics of carboxylated acrylonitrile-butadiene rubber - silica hybrid materials was investigated. Silica hybrids were formed in situ rubber matrix using varied amounts of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (DAMS), serving also as a cross-linker. Filler-filler and filler-rubber interactions were present, due to the specific nature of these materials. It was found that the amounts of added aminosilane determined the cross-linking density of obtained materials and was the highest with 20 phr DAMS used. The cross-links had ionic nature. Dielectric relaxation spectroscopy (DRS) revealed β, α and α′ relaxation processes. The β relaxation, correlated with the mobility of polymer side groups, was influenced by the weak interaction between both acrylonitrile and carboxylic groups of the rubber and silanol groups of silica. The activation energy for that relaxation was similar for all materials (∼32 kJ mol⁻¹). Both DRS and dynamical mechanical analysis (DMA) demonstrated that the amount of in situ formed silica filler did not significantly influence either the temperature of the α relaxation (correlated with glass transition) or its activation energy. Therefore, that relaxation was caused by free polymer chains, not attached to the silica particles. Similar values of glass transition temperature (T_g) for all hybrids were confirmed by DSC. It appeared that the amplitude of tangent delta (DMA) within T_g was dependent on silica amount. Detected at higher temperature α′ relaxation resulted from the presence of domains, where polymer chains were affected by silica network, geometrical restrictions and morphology of the silica-rich domains.     

Investigations on electric properties of polymers—VI: Thermally stimulated depolarization currents from poly(1-vinylnaphthalene)

The thermally stimulated depolarization currents (TSDC) from poly(1-vinyl naphthalene) were studied over the temperature range 220–420°K. Four relaxation peaks were observed. The first three peaks (β₁, β₂ and β₃) appeared below the glass transition temperature of the polymer. The β₁ peaks seems to arise from a single dipolar relaxation process; β₂, and probably β₃, arise from a dipolar relaxation distributed in activation energy. The α peak could be regarded as a result of simultaneous contributions of the dipolar relaxation and conduction processes. On the basis of published work, the molecular origins of the β peaks are suggested.     

Molecular dynamics simulations of the effects of carbon dioxide on the interfacial bonding of polystyrene thin films

Fabrication of nanoscale polymer‐based devices, especially in biomedical applications, is a challenging process due to requirements of precise dimensions. Methods that involve elevated temperature or chemical adhesives are not practicable due to the fragility of the device components and associated deformation. To effectively fabricate devices for lab‐on‐a‐chip or drug delivery applications, a process is required that permits bonding at low temperatures. The use of carbon dioxide (CO₂) to assist the bonding process shows promise in reaching this goal. It is now well established that CO₂ can be used to depress the glass transition temperature (T_g) of a polymer, allowing bonding to occur at lower temperatures. Furthermore, it has been shown that CO₂ can preferentially soften a polymer surface, which should allow for effective bonding at temperatures even below the bulk T_g. However, the impact of this effect on bonding has not been quantified, and the optimal bonding temperature and CO₂ pressure conditions are unknown. In this study, a molecular dynamics model is used to examine the atomic scale behavior of polystyrene in an effort to develop understanding of the physical mechanisms of bonding and to quantify how the process is impacted by CO₂. The final result is the identification of a range of CO₂ pressure conditions which produce the strongest bonding between PS thin films at room temperature. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011